Abstract Booklet 2006 - Swanson School of Engineering - University ...

TABLE OF CONTENTS
Oral Sessions
Page
Oral Sessions
Page
1: Gasification Technologies: Applications and
Economics – 1
1
2: Synthesis of Liquid Fuels, Chemicals, Materials and
Other Non–Fuel Uses of Coal: Basics, FT/DME
1
3: Combustion Technologies – 1: Advancing PC Plants
to Near-Zero Emissions
2
4: Environmental Control Technologies: Mercury
Absorption – 1
3
5: Hydrogen from Coal: General Topics 4
6: Global Climate Change: Geologic Carbon
Sequestration – 1
5
7: Gasification Technologies: Applications and
Economics – 2
5
8: Synthesis of Liquid Fuels, Chemicals, Materials and
Other Non–Fuel Uses of Coal: Applied FT/CTL
6
9: Combustion Technologies – 2: Mercury Capture
from Flue Gas
7
10: Environmental Control Technologies: Mercury
Absorption – 2
8
11: Hydrogen from Coal: Storage/Syngas to Hydrogen 9
12: Global Climate Change: Geologic Carbon
Sequestration – 2
10
13: Gasification Technologies: Applications and
Economics – 3
11
14: Synthesis of Liquid Fuels, Chemicals, Materials
and Other Non-Fuel Uses of Coal: Coke and 12
Others
15: Combustion Technologies – 3: Oxy-Fuel
Combustion
12
16: Environmental Control Technologies: SO x , NO x ,
Particulate and Mercury – 1
13
17: Hydrogen from Coal: Membrane Separation 14
18: Global Climate Change: Greenhouse Gas
Utilization and Novel Concepts
15
19: Gasification Technologies: Advanced Synthesis
Gas Cleanup – 1
16
20: Gasification Technologies: Fundamentals and
Simulations – 1
17
21: Combustion Technologies – 4: Coal Co-Fired with
Other Fuels
18
22: Environmental Control Technologies: SO x , NO x ,
Particulate and Mercury – 2
19
23: Hydrogen from Coal: Shift Catalyst and
Gasification
19
24: Global Climate Change: CO 2 Capture – 1:
Chemical Sorbents
20
25: Gasification Technologies: Advanced Synthesis
Gas Cleanup – 2
21
26: Gasification Technologies: Fundamentals and
Simulations – 2
22
27: Combustion Technologies – 5: Coal Reactivity and
Kinetic Studies
23
28: Environmental Control Technologies: Mercury
Oxidation/Catalysts
24
29: Gas Turbines and Fuel Cells for Synthesis Gas and
Hydrogen Applications – 1
25
30: Global Climate Change: CO 2 Capture – 2:
Membranes and Solid Sorbents
25
31: Gasification Technologies: Advanced Technology
Development – 1
26
32: Gasification Technologies: Fundamentals and
Simulations – 3
27
33: Combustion Technologies – 6: Combustion Studies 29
34: Environmental Control Technologies: Mercury – 1 29
35: Gas Turbines and Fuel Cells for Synthesis Gas and
Hydrogen Applications – 2
30
36: Coal Production and Preparation – 1 31
37: Gasification Technologies: Advanced Technology
Development – 2
32
38: Coal Chemistry, Geosciences and Resources:
Geosciences
33
39: Materials, Instrumentation, and Controls – 1 34
40: Environmental Control Technologies: Mercury – 2 35
41: Coal Utilization By-Products – 1 36
42: Coal Production and Preparation – 2 37
43: Gasification Technologies: Advanced Technology
Development – 3
37
44: Coal Chemistry, Geosciences, and Resources:
Mineral Matter, Coal Ash, Coal Combustion
38
45: Materials, Instrumentation, and Controls – 2 39
46: Environmental Control Technologies:
Mercury/Others
40
47: Coal Utilization By-Products – 2 41
48: Coal Production and Preparation – 3 42
49: Gasification Technologies: Advanced Technology
Development – 4
43
50: Coal Chemistry, Geosciences, and Resources: Coal
Chemistry
44
51: Materials, Instrumentation, and Controls – 3 45
52: Environmental Control Technologies: General
Topics
46
53: Coal Utilization By-Products – 3 47
54: Coal Production and Preparation – 4 48
Poster Sessions
Page
1: Combustion Technologies 49
2: Gasification Technologies / Hydrogen from Coal 49
3: Gas Turbines and Fuel Cells for Synthesis Gas and
Hydrogen Applications
51
4: Materials, Instrumentation and Controls 52
5: Environmental Control Technologies 52
6: Synthesis of Liquid Fuels, Chemicals, Materials and
Other Non-Fuel Uses of Coal
53
7: Coal Chemistry, Geosciences and Resources 54

A NOTE TO THE READER
This Abstracts Booklet is prepared solely as a convenient reference for the Conference participants.
Abstracts are arranged in a numerical order of the oral and poster sessions as published in the Final
Conference Program. In order to facilitate the task for the reader to locate a specific abstract in a given
session, each paper is given two numbers: the first designates the session number and the second represents
the paper number in that session. For example, Paper No. 25-1 is the first paper to be presented in the Oral
Session #25. Similarly, Paper No. P3-1 is the first paper to appear in the Poster Session #3.
It should be cautioned that this Abstracts Booklet is prepared based on the original abstract that was
submitted, unless the author noted an abstract change. The contents of the Booklet do not reflect late changes
made by the authors for their presentations at the Conference. The reader should consult the Final
Conference Program for any such changes. Furthermore, updated and detailed full manuscripts are published
in the CD-ROM Conference Proceedings, made available to all registered participants at the Conference.
On behalf of the Twenty-Third Annual International Pittsburgh Coal Conference, we wish to express our
sincere appreciation to Ms. Heidi M. Aufdenkamp, Ms. Diane McMartin, and Mr. Yannick Heintz for their
invaluable assistance in preparing this Abstract Booklet.
Badie Morsi
Executive Director
International Pittsburgh Coal Conference
University of Pittsburgh
September 2006
Copyright © 2006 Pittsburgh Coal Conference

1-1
SESSION 1
GASIFICATION TECHNOLOGIES:
APPLICATIONS AND ECONOMICS – 1
The Gasification Industry: Progress & Prospects
James M. Childress, Gasification Technologies Council, USA
The author will review the major factors that have driven the scope of development of
the gasification industry over the immediate past (three years) – energy market,
environmental regulation, technology development and government policies (at the
federal and state level – and offer insights into what the future may hold over the near
and mid term period. The focus will be on the U.S. industry with somewhat less
detailed analysis of international developments in major markets.
1-2
Polygeneration: Market Barriers and Incentives Considered
Lynn L. Schloesser, Eastman Chemical Company, USA
The global market has potential for advances in technological efficiency in the
conversion of coal to energy and materials. Following the rise of “market power” and
the technology deployment of combined heat and power (CHP); gasification as
coproduction, or polygeneration (production of electricity, process steam, chemical
feedstocks or fuels), offers economic opportunity for doubling or tripling efficiency
(extending the life of coal reserves), achieving near-zero emissions, and building a
bridge to the hydrogen economy. Gasification technology as polygeneration is poised
to become commercial, particularly in the natural gas dependent, industrial sectors.
Though industrials are motivated by tight natural gas supply and demand, market
barriers remain. This paper briefly examines the technology, and the market incentives,
opportunities, and barriers to polygeneration, with particular emphasis on electricity
market barriers and economic incentives in North America.
1-3
Quantifying the Real Option Value of Coal Gasification Polygeneration
Gary Leatherman, Booz Allen Hamilton, USA
One of the more promising applications of coal gasification is polygeneration wherein
the technology is configured for the co production of multiple products such as
electricity, fuels and/or chemicals. The inherent optionality provided by coal
gasification polygeneration is an attractive source of potential value. Polygeneration is
a "real" option that can manifest its value in two ways: 1) arbitrage- wherein the
relative quantities of the various products are varied in response to the market to
maximize profits and 2) insurance- wherein a single product gasification plant can be
modified to produce another product should production of the primary product no
longer be financially viable. However, the value of this optionality is constrained by
operational and financial issues. For instance, turn-down ratios, start-up/shut-down
cycle time, impact of product cycling on availability, and base-load nature of IGCC
electricity production can all impact the extent to which the plant operator can modify
production. Among financial constraints are long term power (or other product)
purchase agreements, which are almost mandatory for project financing, and the power
market context (i.e. regulated, deregulated) in which the plant is located. This paper
attempts to quantitatively assess the inherent economic value of polygeneration
optionality and examine the impact of real-world operational and financial constraints
on this value. To this end a simulation model was developed and subsequently used to
assess the incremental value added by polygeneration optionality through both
arbitrage and insurance.
1-4
Global Experience with Coal Gasification Coal-To-Gas,
Coal-To-Liquids, and IGCC Coal-To-Power
Wm. Mark Hart, West Hawk Development Corp., CANADA
Coal gasification is globally a ‘hot’ topic for ultra-clean energy, utilization, and
transportation of fuels and IGCC electric power generation. Amid surging energy
prices, rising domestic demand, and concerns about energy security, many countries
seek coal gasification to develop and diversify domestic resources. Coal gasification
been successfully used in the USA, Europe, Russia, and South Africa with plants that
convert coal to diesel fuel, power, pipeline quality gas, and various other co-products
with economics competitive to refining crude oil. Environmentally sound, proven
technologies to exploit coal more effectively are now being aggressively applied
around the globe with US$ billions in new projects now being advanced. Increasing
demand for petroleum based fuels along with anticipated increases in natural gas prices
will continue to drive this trend. This paper discusses coal-to-liquids (CTL), coal-togas
(CTG), and coal-to-power (CTP/IGCC), projects and technologies around the
world, including from Germany and South Africa and current activities in the USA,
Canada, and Europe.
1
1-5
Environmental Permitting for IGCC Power Plants
Stephen Jenkins, URS Corporate, USA
Over the past 10 years, power company environmental staff and state and federal
environmental agency staff have had extensive experience with the permitting requirements
for hundreds of natural gas-fired combined cycle power plants and some coal-fired power
plants. Due to the costs of natural gas, stricter environmental requirements, and incentives in
the Energy Policy Act of 2005, many power companies are now planning to develop
Integrated Gasification Combined Cycle (IGCC) power plants that will use coal or blends of
coal and other feedstocks. Since there are only two operating IGCC power plants in the U.S.,
with only 10 years of operating history, there is limited information on environmental
profiles and performance, and little hands-on experience in power companies and
environmental agencies with the air, water, and waste permitting requirements for IGCC
power plants.
This paper explains how IGCC technology and environmental profiles are different from
natural gas-fired combined cycle and coal-fired power plant technology, as well as how
permitting procedures are similar to and different from those used for natural gas-fired
combined cycle power plant and coal-fired power plant permitting. The paper also discusses
the specific regulations that now apply to IGCC power plants, and provides a summary of
key guidelines for air, water, and waste permitting. This will promote the use of standardized
approaches and calculation methods in permit applications, making it easier for
environmental agency staff to review the applications. This will help assure that the new
fleet of IGCC power plants will be developed based on permits that have comparable
emission limits and utilize effective compliance assurance methods based on the lessons
learned over the past 10 years of IGCC power plant operation.
SESSION 2
SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND
OTHER NON-FUEL USES OF COAL: BASICS, FT/DME
2-1
Fischer-Tropsch Synthesis in Microstructured Reactors: the Importance of Flow
Distribution on Both the Process and Coolant Streams
Kai Jarosch, Anna Lee Tonkovich, Sean Fitzgerald, Velocys, Inc., USA
To date, synthetic fuel processes have required enormous economies of scale to produce
competitively priced products. Systems based on microchannel technology hold the potential
to significantly reduce overall costs and enable production of synthetic fuels at smaller scales
from a variety of low cost feedstock materials. Reactors using this technology are
characterized by parallel arrays of microchannels, with typical dimensions in the 0.010-inch
to 0.200-inch range. Processes are intensified by reducing heat and mass transfer distances,
thus decreasing transfer resistance between process fluids and channel walls. Overall system
volumes are reduced 10- to 100-fold or more, permitting smaller, lower cost units to produce
commercially significant quantities of synthetic fuel.
At present, several commercial Fischer-Tropsch (FT) processes are used: a tubular fixed bed,
slurry bed, fluid bed, and circulating fluid bed. These conventional processes are limited by
heat and/or mass transfer performance, and are operated with GHSV less than 1000 hr -1 with
selectivity to the undesired methane side product near 10%. Methane production is a strong
function of temperature. As the catalyst temperature increases with the exothermic reaction,
the methane selectivity continues to rise.
The use of microchannel reactors for GTL has demonstrated improved temperature control
and reduced methane selectivity. The scale-up challenge of enhanced FT performance in
large scale microchannel reactors has not yet been addressed in the literature. This work will
describe the importance of flow distribution on both the process channels and cooling
channels to maintain performance as the number of parallel process channels increases from
one to ten to ten thousand and beyond.
FT performance in a single microchannel has been reported in the literature, where CO
conversion approached 70% per pass and methane selectivity less than 11% after more than
1000 hours on stream.
A catalyst similar to those reported above was evaluated in multi-channel microstructured
reactors consisting of more than 10 parallel microchannels interleaved with coolant channels.
Cooling was provided by a cross-flow stream of coolant that was allowed to partially
vaporize thus quickly removing the heat released by the FT reaction. Two reactor designs
were evaluated both with and without tight control of the coolant flow distribution. In both
cases the process stream had a flow mal-distribution of less than 10%.
In the first case, the reactor design did not achieve tight control of the cool flow distribution
and when operated the coolant flow rate from channel-to-channel deviated by more than
30%. This mal-distribution resulted in a steep temperature gradient in the catalyst, of more
than 30°C, at the inlet of the process channels. Due to the poor temperature control, the
selectivity to methane exceeded 30%.
The second case, the multi-channel microstructured reactor was designed to provide a tight
control of the flow distribution on the coolant side, and in operation the coolant flow rate
from channel-to-channel deviated by less than 5%. The resulting process performance
mirrored the performance of the single channel microstructured reactor.
Scale-up of microstructured reactors for FT synthesis requires careful design of the flow
distribution system for both the process channels and the coolant channels. The objective is

to review strategies for designing a flow distribution system for the coolant fluid, where
pressure drop is low and phase change occurs as the exothermic reaction in the process
channel proceeds.
2-2
Selectivity Improvement via Nitriding of Iron-Based Fischer-Tropsch Catalysts
Michael Claeys, Mark E. Dry, Eric van Steen, Centre for Catalysis Research,
University of Cape Town, SOUTH AFRICA
Philip Gibson, Jakobus Visagie, Thato Motjope, Andre van Zyl, Sasol Technology
R&D, SOUTH AFRICA
Iron-based Fischer-Tropsch catalysts have been modified by nitriding at different
conditions in an attempt to affect product selectivity towards valuable chemicals.
Mildly pre-reduced catalyst samples nitrided with ammonia at elevated temperature
showed largely improved formation of oxygenates compared to hydrogen reduced
catalysts. In addition, and in contrast to early work reported by the Bureau of Mines,
nitrided samples in this work also showed increased productivity for long chain 1-
olefins. Nitriding was not found to affect overall catalyst activity, water gas shift
activity, methane selectivity and chain growth. The beneficial effects of nitriding can
however decay at Fischer-Tropsch conditions, possibly due to loss of nitrogen from the
iron nitride phases upon formation of iron carbides.
2-3
The Direct Synthesis of Dimethyl Ether over Hybrid Catalysts Composed of
Cu-Zn Based Catalysts and Solid Acid Catalysts
Tae Jin Lee, Eun Jin Kim, No-Kuk Park, Gi Bo Han, Si Ok Ryu, Yeungnam
University, National Research Laboratory, SOUTH KOREA
Dimethyl ether (DME) is primarily used as an aerosol propellant or industrially important
chemical intermediate because of its attractive physical properties. In view of the
environmental protection, the substitution of DME is unavoidable. Recently, a great attention
has been paid to its applications as a fuel additive for vehicles and household uses. DME can
be not only burned in diesel engine with a modified fuel system at the same efficiency but
also handled like liquefied petroleum gas (LPG). DME has been obtained directly from
syngas. In this study, the direct synthesis of DME over hybrid catalysts was performed in the
temperature range of 270-290°C. Space velocity (GHSV), molar ratio of [H 2 ]/[CO], and
reaction pressure in the experiments were 3000-6000 ml/g-cat.h, 1.0, and 30-50 atm,
respectively. Typically, the hybrid catalysts were composed of methanol dehydration
catalyst and methanol synthesis catalyst, which were made by a physical mixing in various
combinations. A series of hybrid catalysts were characterized by BET surface area and XRD
analysis.
2-4
Performance of a Non-Sulphided Maximum Distillate Catalyst in
Fischer-Tropsch Wax Hydrocracking
Jack C.Q. Fletcher, Athanasios Kotsiopolis, Walter Bohringer, University of Cape
Town, Catalysis Research, SOUTH AFRICA
M. de Boer, Albemarle Catalysts Company B.V., NETHERLANDS
C. Knottenbelt, The Petroleum Oil & Gas Corporation of South Africa Ltd,
SOUTH AFRICA
Fischer-Tropsch (F-T) based Gas-to-Liquids (GTL) processing is recognized as an
industrially proven and economically competitive route to high quality diesel. Furthermore,
it is generally accepted that for this purpose, GTL processing is most effective when
comprising an F-T synthesis driven to wax production, followed by hydrocracking to
produce middle-distillate products. Applying a CoMo/SiO 2 -Al 2 O 3 catalyst, optimised for
hydrocracking crude oil refinery feedstocks in a sulphur-containing environment, to the
processing of a linear paraffin F-T wax model compound, n-tetradecane, shows that a
significant opportunity exists for utilisation of base metal catalyst, having the advantage of
producing less branched hydrocracking products, i.e. high cetane number diesel via a
hydrogenolytic cracking mechanism. A drawback of such a catalyst, if applied in nonsulphided
form and in a non-sulphur containing environment, is the comparably high yield
of light gases, in particular methane. It is shown, and proved by a simple kinetic model, that
methane is formed via ‘methanolysis’, i.e. successive hydrogenolytic demethanisation
reaction of the feed compounds, presumably of islands of metallic cobalt on the catalyst.
2-5
High Temperature Methanation Process-Revisited
Niels Udengaard, Anders N. Olsen, Haldor Topsoe Inc., USA
Christian Wix-Nielsen, Haldor Topsoe A/S, DENMARK
The rising cost of natural gas has resulted in a strong interest in manufacturing of substitute
natural gas (SNG) from the less costly and much more abundant coal.
Methanation of synthesis gas mixtures derived from gasification of coal is an essential step
in the manufacturing of SNG. Technologies and catalysts for the SNG process were
developed and tested extensively during the 1970’s, when the energy costs were expected to
increase to unseen levels. This did not happen and the interest in this technology vanished. A
renewed interest today in shifting more energy consumption to coal has resulted in a revival
of several of these SNG technologies. The knowledge gained over the years has been applied
to the former technologies resulting in improved efficiency and lower investment cost.
SESSION 3
COMBUSTION TECHNOLOGIES – 1:
ADVANCING PC PLANTS TO NEAR-ZERO EMISSIONS
3-1
Deployment of Near-Zero-Emission USC PC Power Plants for CO 2 Reduction
Tony Armor, John Wheeldon, Electric Power Research Institute, USA
Ultra-supercritical PC plants are being built and operated in Europe and Japan with
superheated steam conditions as high as 4100 psia and 1130°F. These plants are built with
ferritic steels and this limits the maximum operating temperature. At US operating
conditions and using bituminous coal, the efficiency of these plants is around 40 percent on a
higher heating value basis. These plants are operating reliably and achieving high
availabilities and low emissions.
The AD700 program in Europe is developing materials and for USC plants with superheated
steam conditions as high as 5000 psia and 1290°F and improving boiler and steam turbine
designs. To exceed the temperature limit imposed by the ferritic steels, high-nickel alloys
have to be used. A similar US-DOE program is investigating high-nickel alloys for
temperatures of 1400°F, which are projected to achieve generating efficiencies as high as 48
percent (HHV). USC plants operating at these conditions will lower CO 2 emissions by 20
percent compared to the current designs. By producing less CO 2 , the new designs lower the
cost of CO 2 capture.
This paper reports on the operation of current USC PC plants, along with their thermal and
environmental performance, and how these designs might be deployed in the US. How the
more advanced USC PC designs might be deployed to achieve near-zero emission power
plants is also discussed.
3-2
Requirements and Issues towards Obtainment of Ultra-Low NO x Levels
Tony Facchiano, EPRI, USA
Several power plants equipped with low-NO x burners and SCR systems are already
obtaining NO x levels under 0.05 lb/MBtu when fired on sub-bituminous coal. However, the
obtainment of near-zero levels, defined as equal or less than 0.01 lb/MBtu, will require
significant development effort for both bituminous and sub-bituminous coals. This paper
will examine the current state of combustion-based and post-combustion NO x control
technologies and their accomplishments, operational and design issues currently precluding
the obtainment of near-zero NO x levels, and the development needed to overcome these
limitations. This paper will draw upon full-scale data and experiences, as well as pilot- and
lab-scale efforts currently underway. Specific issues addressed will include limitations on
pollutants that may be consequential to achieving ultra-low NO x levels (e.g., SO 3 , ammonia
slip, PM-10, etc), instrumentation and control challenges, component reliability, and the
impact of fuel properties and their variability. Consideration will be given to the existing
fleet of coal-fired boilers, where furnace design limits combustion-based NO x mitigation
levels and available access limits SCR reactor sizes. Also discussed will be the design of
new plants with advanced steam conditions, where greater flexibility to reduce NO x
emissions, albeit at increased costs and operational constraints, can be built into the system.
3-3
FGD Designs for High Efficiency: Current Status and Future Challenges
George Offen, Charles Dene, John Wheeldon, Electric Power Research Institute, USA
Robert Keeth, Washington Group International, USA
Performance and field experience with new, high-efficiency flue gas desulfurization (FGD)
systems will be reported. The information presented will be based on recent EPRI visits to
sites that had installed the latest design upgrades at commercial scale or were testing them at
large-scale pilot scale. On-site discussions and observations were used to determine the
impacts that these design upgrades were having on day-to-day performance of emissions
control systems as well as balance-of-plant impacts. Sites in Europe, Japan, and the United
States were visited during the project, and a summary of the major observations will be
provided.
The paper will also present an assessment of the ability of these technologies to achieve Near
Zero Emissions (NZE) goals and suggest additional measures that may be needed to meet
this goal continuously. Qualitatively, NZE is defined as being virtually equivalent to
emissions from gas-fired power plants, with the exception of CO 2 . It will be shown that
state-of-the-art FGD systems achieve very low SO 2 emissions when operated optimally, but
to maintain these levels continuously provisions may be needed to counter temporary
deviations in performance.
3-4
Advanced Ultra-Supercritical Boiler Design and Boiler Materials
James Kutney, The Babcock & Wilcox Company, USA
2

The U.S. pioneered development of supercritical technology with the first boiler
commencing commercial operation in 1957. This 125-MW B&W Universal Pressure
boiler located at Ohio Power Company's Philo plant delivered 675,000 lb/h steam at
4,550 psi. The steam was superheated to 1150°F with two reheats to 1050 and 1000°F.
Also installed in the U.S. are 9 x 1300-MW units, the largest single supercritical units
designed, including one that set a record for 607 continuous days of operation.
B&W are an actively involved in the US-DOE s ultra supercritical boiler materials
research program testing stronger more corrosion-resistant materials, such as highnickel
alloys, necessary to progress to steam temperatures as high as 1400°F. Such
progression is essential to preserving pulverized coal technology as the preferred
choice for power generation. Applying these new materials will increase generating
efficiency beyond that currently possible with ferritic steels and, by producing less
carbon dioxide, new units will have lower the costs for carbon capture and
sequestration.
This paper will present results from the test programs to certify the new materials.
Fire-side and steam-side corrosion data have been collected from a test loop in an
operating boiler as well as from laboratory simulations, and material weldability and
fabrication have been evaluated. The paper will also discuss how the materials under
development will be incorporated into the design of new, more efficient boilers.
3-5
Post-Combustion CO 2 Capture from Pulverized Coal Plants
John Wheeldon, Electric Power Research Institute; USA
In response to concerns over global warming, technologies need to be developed that capture
and store the CO 2 released by fossil-fueled power plants. A study carried out in 2000 and cofunded
by the US-DOE and EPRI investigated the thermal and economic performance of
supercritical pulverized coal (PC) combustion and an E-Gas integrated gasification
combined cycle (IGCC), using bituminous coal both with and without CO 2 removal. The
general conclusion was that for power plants with CO 2 capture, the technology with the
lowest cost of electricity was IGCC with pre-combustion capture. An implied conclusion
was that supercritical PC with post-combustion capture was not an economic or efficient
way to proceed.
Since the publication of that study, several improvements have been identified that enhance
the thermal and economic performance of post-combustion CO 2 capture technology.
Improvements include those to solvents, CO 2 capture plant equipment design, and
integration of the CO 2 capture plant with the power plant to improve heat utilization. Once
these improvements are incorporated into the DOE/EPRI study, it is shown that a PC plant
using post-combustion capture can be competitive with IGCC using pre-combustion capture.
This is especially the case for sub-bituminous coal where post-combustion capture may be
the most economic choice. The latest study also shows a benefit in going to ultrasupercritical
steam conditions. The higher efficiency of these PC plants lowers the amount of
CO 2 produced and so lowers the cost of CO 2 capture. This information justifies continued
effort to develop materials for use with steam cycles operating at higher temperatures and
pressures. Significant benefits are also gained from improvements to CO 2 capture solvents
and equipment design, so both these measures also warrant continued development effort.
The paper reports on the improvements identified for PC plants incorporating postcombustion
CO 2 capture and discusses improvements that may be made in the future.
SESSION 4
ENVIRONMENTAL CONTROL TECHNOLOGIES:
MERCURY ABSORPTION – 1
4-1
Effectiveness of Sulphur-Impregnated Activated Carbons Produced Using
Different Impregnation Methods in Mercury Vapour Adsorption
Laura Fuentes de Maria, Shitang Tong, Donald W. Kirk, Charles Q. Jia, University of
Toronto, CANADA
Adsorption technologies based on sulphur-impregnated activated carbons (SIACs) have
been proven an efficient method for vapour-phase mercury removal at coal-fired power
plants. The enhanced adsorption capacity of SIACs is often attributed to its high specific
surface area and sulphur species. The effect of sulphur-impregnation methods, which can
result in different sulphur species in SIACs, on mercury adsorption, is however not well
understood. The present study evaluates the effectiveness of several SIACs produced from
petroleum coke using different activation methods in the adsorption of vapour-phase
elemental mercury. To analyze the effect of different sulphur species on the adsorption of
mercury, four types of activated carbons are used, a commercially available sulphur-free
activated carbon (VAC), a commercially available SIAC (BARRICK), and two adsorbents
(FC1 and FC2) produced in our laboratory using oil-sands fluid coke as raw material. The
mercury adsorption experiments are conducted using a laboratory scaled fixed-bed quartz
reactor. A permeation device is used as the source of mercury vapour. Concentrations of
mercury vapour are analyzed based on the dual gold amalgamation technique using a Cold
Vapour Atomic Fluorescence Spectrophotometer (CVAFS). The adsorption capacity of the
carbons is determined by analyzing mercury concentrations before and after adsorption. The
effect of the temperature is studied in this work to better understand mercury adsorption
mechanisms by SIACs.
3
4-2
A Novel Process for On-site Production of Mercury Sorbents
Lawrence Bool, Chien-Chung Chao, David R. Thompson, Praxair, USA
Activated carbon injection (ACI) represents a promising method reduce mercury
emissions from coal-fired plants. In recent years Praxair has developed a flexible
process to produce powder activated carbon (PAC) on-site using the plant’s pulverized
coal. The process is very flexible, allowing both undoped and doped carbons to be
easily produced from the same plant. Third party test results from slipstream tests at
We Energies’ Pleasant Prairie Plant and Xcel Energy’s Comanche Station have shown
removals of 90% or greater. Praxair has continued to refine the process to better
understand the process conditions leading to good mercury capture while minimizing
the PAC cost. Several parameters have been explored in detail and will be discussed.
These parameters include the effect of dopant concentration on mercury capture, the
effect of different parent coals on sorbent performance, and the effect of a two-step
activation process. Additional work planned in cooperation with the U.S. DOE to
mitigate the impact of PAC produced with the Praxair process on concrete properties
will also be discussed.
4-3
Feasibility of Activated Char Production for Mercury
Capture from Chicken Waste and Coal
Wei-Ping Pan, Hong Cui, Yan Cao, Institute for Combustion Science and
Environmental Technology, Western Kentucky University, USA
Chicken waste (CW) and its blending samples with a selected high sulfur coal (E-coal)
were used as raw materials for activated char (AC) preparation. Raw samples were
subjected to the preparation procedures of carbonization in a nitrogen atmosphere and
activation in a steam atmosphere. The basic properties of the raw materials, char and
activated char were analyzed by components analysis, surface porosity and TGA
analysis. One AC sample was selected for elemental mercury capture tests in a labscale
drop tube reactor with air flow. The results show that low-cost and effective
activated carbon could be produced by co-process of chicken waste and coal with
benefits to increase char yields. The higher removal efficiency is assumed that some
activated species of chlorine and sulfur contained in the activated carbon can be of
benefit to elemental mercury capture. However, the assumed capture mechanism
should be proved by the further investigation of detailed surface characteristics.
4-4
Characterization Mercury Transport and Deposition in Ohio River Valley Region
Myoungwoo Kim, Kevin Crist, Ohio University, USA
Rao Kotamarthi, Argonne National Laboratory, USA
Ohio University, in collaboration with Argonne National Laboratory, CONSOL Energy,
Advanced Technology Systems, Inc (ATS) as subcontractors, is evaluating the impact of
emissions from coal-fired power plants in the Ohio River Valley region as they relate to the
transport and deposition of mercury, arsenic, and associated fine particulate matter. This
evaluation involves two interrelated areas of effort: ambient air monitoring and regionalscale
modeling analysis. The scope of work for the modeling analysis includes (1)
development of updated inventories of mercury and arsenic emissions from coal plants and
other important sources in the modeled domain; (2) adapting an existing 3-D atmospheric
chemical transport model to incorporate recent advancements in the understanding of
mercury transformations in the atmosphere; (3) analyses of the flux of Hg 0 , RGM, arsenic,
and fine particulate matter in the different sectors of the study region to identify key transport
mechanisms; (4) comparison of cross correlations between species from the model results to
observations in order to evaluate characteristics of specific air masses associated with longrange
transport from a specified source region; and (5) evaluation of the sensitivity of these
correlations to emissions from regions along the transport path. This will be accomplished by
multiple model runs with emissions simulations switched on and off from the various source
regions. The modeling analysis is currently on-going. However an analysis of the base case
runs will be presented including mercury wet-deposition patterns for the Ohio River Valley.
4-5
Field Evaluations of Carbon Sorbents
Nicholas R. Pollack, Calgon Carbon Corporate, USA
Calgon Carbon Corporation has investigated a series of carbon sorbents for the
removal of mercury from flue gas streams of coal-fired power plants. Pilot studies
were conducted at a commercial power plant together with Apogee Scientific, Inc. The
results represent the performance of the sorbents under real conditions using an actual
flue gas stream. A number of parameters were studied: carbon substrate, particle size,
impregnants, pore volume, and surface modifications. A follow-up study was
conducted with the most promising candidates in order to maximize the performance
and minimize the cost of the sorbent. Greater than 90% mercury removal was achieved
with the best sorbents at normal injection rates. Calgon Carbon Corporation will
present the results of these studies.

SESSION 5
HYDROGEN FROM COAL: GENERAL TOPICS
5-3
The Future of Pennsylvania Coal in a Hydrogen Economy
Paul Lemar, Resource Dynamics Corporation, USA
Eileen M. Schmura, Concurrent Technologies Corporation, USA
5-1
US DOE Office of Fossil Energy’s Hydrogen from Coal Activities
Robert Wright, Lowell Miller, Daniel Cicero, US Dept of Energy, USA
Mark Ackiewicz, John Anderson, Technology & Management Services, Inc., USA
Edward Schmetz, John Winslow, Leonardo Technologies, Inc., USA
The Hydrogen from Coal Program is part of the Office of Sequestration, Hydrogen,
and Clean Coal Fuels (OSHCCF) activities in the Department of Energy’s (DOE)
Office of Fossil Energy (FE). The Program manages the Department’s research,
development, and demonstration (RD&D) activities for novel coal-based technologies
designed to produce, deliver, store, and utilize hydrogen from coal. Hydrogen research
is a key element of the Department’s energy research portfolio to meet the
Administration’s energy goals and objectives as defined in the National Energy Policy.
In addition to managing its respective RD&D portfolio, the Program also cooperates
on joint efforts with other DOE and FE offices on large-scale initiatives such as the
Hydrogen Fuel Initiative, FutureGen project, Clean Coal Power Initiative and
Advanced Energy Initiative that were instituted in order to utilize domestic resources,
including coal, to address concerns about energy security and greenhouse gas
emissions. The Hydrogen Fuel Initiative, led by the Office of Energy Efficiency and
Renewable Energy (EERE), coordinates hydrogen-related activities being performed
by EERE, FE, Office of Nuclear Energy, Science and Technology (NE), and the Office
of Science (SC). The Hydrogen from Coal Program is responsible for hydrogen from
coal research activities and participates in joint efforts such as development of the
DOE Hydrogen Posture Plan. This plan outlines DOE’s activities, milestones, and
deliverables to facilitate the United States’ transition to a hydrogen economy.
Additionally, the Hydrogen from Coal Program staff coordinates with the staff of other
DOE offices on joint R&D solicitations and other appropriate activities. Coordinating
efforts and sharing of information and experiences are essential if we are to be
successful in the transition to a hydrogen economy. DOE’s coal RD&D portfolio
contains technology for energy systems that produce multiple products (i.e., electric
power, hydrogen, fuels, and chemicals). These systems perform with near-zero
emissions, including the capture and storage of carbon dioxide (CO 2 ). A key element
of this drive toward zero emissions plants is DOE’s FutureGen project. This project
serves as an integration platform to demonstrate co-production of electricity and
hydrogen with CO 2 sequestration performed at commercial scale.
This paper reviews (1) the key energy and environmental challenges that the program
addresses, (2) the benefits of producing hydrogen from coal while utilizing
sequestration and (3) the advanced technologies that are under development by the
Hydrogen from Coal Program. The goals and milestones of the Program are presented,
along with recent accomplishments and progress since its inception in FY2004.
Finally, key features in the implementation of the program are discussed.
5-2
Hydrogen-Assisted IC Engine Combustion as a
Route to Hydrogen Implementation
Andre Boehman, Daniel Haworth, Elana Chapman, Melanie Fox, Bryan Nese, Saket
Priyadarshi, Gregory Lilik, Yu Zhang, Eugene Kung, Pennsylvania State University,
USA
This research project (Funded under DOE Cooperative Agreement DE-FC25-04FT42233)
focuses on developing the underlying fundamental information to support technologies that
will facilitate the introduction of coal-derived hydrogen into the market. Two paths are
envisioned here for hydrogen utilization in transportation applications. One is to mix
hydrogen with other fuels, specifically natural gas, to enhance performance in existing
natural gas-fueled vehicles (e.g., transit buses) and provide a practical and marketable
avenue to begin using hydrogen in the transportation industry. A second is to use hydrogen
to enable alternative combustion modes, such as homogeneous charge compression ignition,
in order to permit enhanced efficiency and reduced emissions. This project on hydrogenassisted
combustion encompasses two objectives: (1) Optimization of hydrogen-natural gas
mixture composition and utilization through laboratory studies of spark ignition engine
operation on H 2 -NG coupled with numerical simulation of the impact of hydrogen blending
on the physical and chemical processes within the engine. The project makes use of facilities
developed under a DOE-sponsored hydrogen fueling station project (DOE Cooperative
Agreement No. DE-FC04-02AL67613, “Development of a Turnkey Commercial Hydrogen
Fueling Station”) to provide both hydrogen and hydrogen enriched natural gas (HCNG) for
the laboratory studies, and (2) Examination of hydrogen-assisted combustion in advanced
compression-ignition engine processes, such as homogeneous charge compression ignition
(HCCI) engine operation. This includes experiments in a multicylinder engine and
multidimensional modeling of in-cylinder aero-thermo-chemical processes. The project will
provide information on the viability and benefits of using hydrogen in an HCCI engine, will
map out the useful HCCI operating envelope, and will explore the possibilities for
broadening the HCCI operating envelope using direct in-cylinder pilot injection.
The Department of Energy (DOE) Multi-Year Research, Development and Demonstration
Plan’s1 overall program goal is to develop hydrogen delivery technologies that enable the
introduction and long-term viability of hydrogen as an energy carrier for transportation and
stationary power. Concurrent Technologies Corporation (CTC) and other organizations are
performing research and development (R&D) and infrastructure development tasks in order
to assist in meeting this goal. This paper addresses an important objective in this effort to
provide a hydrogen delivery tradeoff study for the State of Pennsylvania. One aspect of the
tradeoff study addresses the future for Pennsylvania coal in a hydrogen economy. Resource
Dynamics Corporation (RDC), in conjunction with CTC and Air Products and Chemical
Inc, completed the study; however, this paper was prepared collaboratively by RDC and
CTC. The hydrogen delivery tradeoff project being lead by CTC for the DOE identifies and
qualifies the most important tradeoffs among hydrogen delivery options for the State of
Pennsylvania. Pennsylvania is a very good case study market because it contains 15 discrete
metropolitan statistical areas (MSA), as well as a variety of potential fossil fuel based and
renewable hydrogen energy sources and delivery infrastructures. This allows for a structured
analysis of a variety of meaningful alternative delivery tradeoff scenarios reflective of many
of the challenges the nation faces in moving towards a hydrogen economy.
The objectives of this project were to show the lowest cost solution for production
location/method and delivery methods, and the tradeoffs between these methods. Given that
the State has abundant coal reserves, examining the use of coal as a feedstock for hydrogen
production was a critical aspect of the study. The study approach was designed to use a
scenario-based methodology. Three hydrogen demand scenarios were constructed and
analyzed: an initial scenario focusing on 1 % of the current population of light duty vehicles
(LDVs) fueled by hydrogen, 10 %, and 30 %. The 1 % case is fleet use and early adopter use
with the 10 % and 30 % cases representing an increased number of early adopters. Within
each of these scenarios, demand centers were identified that in general coincided with the
major MSAs in the State and were used to define volume and distance relationships. With
these parameters defined, a variety of different production and distribution options could be
analyzed and the various tradeoffs identified. For each scenario, the parameters needed for
lowest delivered cost and for lowest infrastructure investment were identified using a
lifecycle cost analysis and the DOE’s H2A model. The sensitivity analysis examined the
potential for the lowest cost options to change based on alternate assumptions and the key
tradeoffs.
1) Hydrogen, Fuel Cells & Infrastructure Technologies Program Multi-Year Research,
Development and Demonstration Plan, US Department of Energy, January 21, 2005
5-4
Hydrogen Production through Coal Gasification in Updraft
Gasifiers with Syngas Treating Sections
Alberto Pettinau, Sotacarbo S.p.A., ITALY
VittorioTola, University of Cagliari, ITALY
Paolo Deiana, ENEA, ITALY
Hydrogen production through coal gasification is becoming one of the most attractive
options for energy production due to the remarkable advantages offered by this
technology in pollution control and greenhouse gases-emissions monitoring.
With this aim, Sotacarbo, Ansaldo Ricerche, ENEA and the University of Cagliari, are
developing a research project to design, construct and test a pilot plant for hydrogen
production from coal gasification (in particular from high-sulphur Sulcis coal). The
project has been funded by the Italian Ministry of Education, University and Research
(MIUR) and by the European Commission and the total cost has been estimated in
about 12 million euros.
The pilot plant, which is currently under construction in the Sotacarbo Research Centre
located in Sardinia (Italy), includes two updraft fixed-bed Wellman-Galusha gasifiers
(a 700 kg/h pilot gasifier and a 35 kg/h laboratory-scale gasifier), fed up with highsulphur
Sulcis Coal and low-sulphur South African coal, and a syngas treating process,
which includes the raw-gas cleaning section, an integrated CO-shift and CO 2 removal
system and the hydrogen separation unit. In particular, the raw gas cleaning sections is
composed by both hot and cold gas desulphurization processes, which can operate in
parallel in order to compare their performances.
This paper reports the main results of the process analysis and performance evaluation,
in particular the analysis of the updraft moving bed gasifiers has been carried out under
the assumption of chemical equilibrium by using two different simulation models,
developed using the Aspen Plus 12.1 and the ChemCad 5.2 software (in both models
the syngas composition has been calculated through the minimization of the Gibbs free
energy). The results obtained with the two gasification models are very similar and
compare favourably with the expected performance specified by the gasifier
manufacturer.
The results obtained with the two gasification models are very similar and compare
favourably with the expected performance specified by the gasifier manufacturer.
As for the syngas treatment line, a detailed simulation dynamic model has been
developed in order to evaluate the performances of each component of the plant (with
particular reference to the hot gas desulphurization process and to the integrated COshift
and CO 2 removal system).
4

5-5
Enhanced Hydrogen Production with in-situ CO 2 Capture
in a Single Stage Reactor
Liang-Shih Fan, Mahesh Iyer, Shwetha Ramkumar, Danny Wong, The Ohio State
University, USA
Enhancement in the production of high purity hydrogen from fuel gas, obtained from coal
gasification, is limited by thermodynamics of the Water Gas Shift Reaction which is used to
shift the carbon monoxide towards hydrogen. However, this constraint can be overcome by
concurrent water-gas shift (WGS) and carbonation reactions to enhance H 2 production by
incessantly driving the equilibrium-limited WGS reaction forward and removing the CO 2
product from the fuel gas mixture in-situ. This not only improves the H 2 yield but also
augments the purity of the product by removing the CO 2 co-product and achieving near
complete conversion of the CO reactant. This process developed at the Ohio State University
can effectively and economically produce a pure H 2 stream, at high temperature and
pressure, via coal gasification while integrating capture of CO 2 emissions, for its subsequent
sequestration. The enhanced water gas shift reaction for H 2 production with insitu
carbonation was studied using the commercial High Temperature Shift (Iron Oxide) catalyst
and calcium sorbents in an integral fixed bed reactor setup. We have identified a high
reactivity patented, mesoporous calcium oxide sorbent for the in-situ CO 2 capture. The
morphological properties of our patented precipitated calcium carbonate sorbent (PCC) can
be tailored using surface modifiers to demonstrate a high CO 2 capture capacity of about 70%
by weight (~700g of CO 2 /kg sorbent ) at elevated temperatures (600-700°C). Experimental
evidence clearly shows that this proprietary calcium sorbent (PCC) performance dominates
over that of commercial limestone sorbents at any given time. Thus, product gas
composition analyses demonstrate complete carbon monoxide conversion as well as CO 2
removal during the initial part of the breakthrough curve, thus demonstrating the synthesis of
pure hydrogen.
6-1
SESSION 6
GLOBAL CLIMATE CHANGE:
GEOLOGIC CARBON SEQUESTRATION – 1
Effects of CO 2 and Aquifer Brine on Well Plugging Cements
Steve Gerdemann, G.E. Rush, Bill O’Connor, NETL, USA
General consensus is that CO 2 at injection pressures in a saline environment will degrade
portland based well plugging cements. Long term exposure, years or decades are typical
time frames mentioned and modeled. Actual cement samples from CO 2 environments such
as oil fields in which CO 2 has been used to extend field production are rare, and actual
brackish to saline aquifer rock with CO 2 exposure still less common. Laboratory experiments
to simulate the saline environments were run with interesting results.
6-2
Using Pinnate Well Patterns for CO 2 Sequestration in
Allison Unit Reservoir Simulation Study
Jalal Jalali, Shahab Mohaghegh, West Virginia University, USA
Concerns about rising concentrations of carbon dioxide (CO 2 ) in the atmosphere and the
necessity of reducing greenhouse gas emissions has led to consideration of large-scale
storage of CO 2 in subsurface. Carbon dioxide is injected into unminable coal seams for
enhancing the coalbed methane recovery, which also has the extra advantage of long-term
CO 2 sequestration. Pilot projects exist in North America and some European countries to
study the feasibility of CO 2 sequestration in depleted oil and gas reservoirs.
Among different well patterns currently used for primary recovery of coalbed methane,
horizontal pinnate wells demonstrate high methane recovery in a short period of time along
with cost reductions and smaller footprints.
In this study, a pinnate well is first used for primary recovery of methane and then converted
into an injector for CO 2 injection to enhance the methane recovery and eventually long term
sequestration. The large contact area between the wellbore and the formation helps fast
dewatering, hence producing the methane, which is desorbed from the coal matrix into the
natural fractures. The pinnate pattern distributes the CO 2 in a large area of the formation
before it reaches the producing wells. Therefore, a larger amount of CO 2 could be stored in
the formation before CO 2 breakthrough occurs.
In this paper, a feasibility study of CO 2 sequestration using pinnate patterns into a coal seam
in the Allison Unit is presented. Several characteristics of the pinnate pattern and the CO 2
injection strategy are studied and optimized using a numerical reservoir simulator in order to
increase the methane recovery and total CO 2 that can be stored before breakthrough. Results
will be compared with the results from the well pattern currently used for CO 2 flooding in
the field.
6-3
Experimental Measurements of the Solubility of CO 2 in
the Oriskany Sandstone Aquifer
Robert M. Dilmore, Patrice Pique, Sheila Hedges, Yee Soong, R. J. Jones,
DOE/NETL, USA
5
Douglas Allen, DOE/NETL, Salem State College, USA
Experiments were conducted to determine the solubility of CO 2 in a natural brine
solution of the Oriskany sandstone formation under elevated temperature and pressure
conditions. These data were collected at pressures between 100 and 450 bars and at
temperatures of 21 and 75ºC. In addition, data on CO 2 solubility in pure water were
collected over the same pressure range as a means of verifying reliability of
experimental technique. Experimentally determined data were compared with CO 2
solubility predictions using a model developed by Duan and Sun (2003). Model results
compare well with Oriskany brine CO 2 solubility data collected experimentally,
suggesting that the Duan and Sun model is a reliable tool for estimating solution CO 2
capacity in high salinity aquifers in the temperature and pressure range evaluated.
6-4
Evaluation of CO 2 Flood on the Geomechanics of Whole Core Samples
Steve Gerdemann, Hank Rush, Bill O'Connor, NETL, USA
Geological sequestration of CO 2 , whether by enhanced oil recovery (EOR), coal-bed
methane (CBM) recovery, or saline-aquifer injection, is a promising near-term sequestration
methodology. While tremendous experience exists for EOR, and CBM recovery has been
demonstrated in existing fields, saline-aquifer-injection studies have only recently been
initiated. Studies evaluating the availability of saline aquifers suitable for CO 2 injection show
great potential.
This study evaluated the physical and chemical effects on Mt. Simon sandstone core from
the Illinois Basin exposed to simulated deep-aquifer brine saturated with super-critical CO 2 .
Conducting these tests on whole core samples rather than crushed core allowed an
evaluation of the impact of the CO 2 flood on the rock-mechanics properties as well as the
geochemistry of the core and brine solution. Preliminary results show an increase in porosity
and a decrease in crushing strength of the core after exposure to CO 2 for 2000 hours.
6-5
Sequestration of CO 2 in Mixtures of Bauxite Residue and Saline Waste Water
with Carbonate Mineral Formation and Caustic Byproduct Neutralization
Robert Dilmore, Yee Soong, Sheila Hedges, Angelo Degalbo, DOE/NETL, USA
Douglas Allen, DOE/NETL, Salem State College, USA
Jaw K. Fu, Charles L. Dobbs, ALCOA, USA
Chen Zhu, Indiana University, USA
Under consideration is a process designed to enhance the CO 2 trapping capacity of
brine solutions through addition of bauxite residue with subsequent carbonation of the
caustic mixture. A set of experiments was conducted to explore the concept of utilizing
mixtures of bauxite residue and brine to sequester carbon dioxide from industrial gas
streams such as flue gas from coal fired electric utility boilers. Factors affecting the
solubility of acid gasses in such mixtures include temperature, pressure, and water
chemistry properties including pH, ionic concentration, and salinity. Bauxite
residue/brine mixture of 90/10 by volume exhibited a CO 2 sequestration capacity of
greater than 9.5 grams per liter when exposed pure CO 2 at 20ºC and 100 psig. Calcite
formation was verified as a product of bauxite/brine mixture carbonation. Data
presented herein provide a preliminary assessment of overall process feasibility and
probe the influence of several variables on treatment efficiency. It is demonstrated that
CO 2 sequestration is augmented by adding bauxite residue as a caustic agent to acidic
brine solutions, and that trapping is accomplished through solubilization and ultimate
mineralization.
SESSION 7
GASIFICATION TECHNOLOGIES:
APPLICATIONS AND ECONOMICS – 2
7-1
The Shell Coal Gasification Process
Hugo T. P. Bos, F.G. van Dongen, Shell Global Solutions International BV, THE
NETHERLANDS
The latest status of the Shell Coal gasification Process (SCGP) is discussed.
Applications of gasification for chemicals production and power production are given.
Projects throughout the world are presented including the status of completion/ startup.
The latest developments of the Shell Coal gasification Process are presented such as
combined oil + coal gasification, biomass/coal to liquids conversion and methods for
CO 2 sequestration.
7-2
The GSP Gasification Process; State-of-the-Art and Further Development
Manfred Schingnitz, Klaus-Dieter Klemmer, Future Energy GmbH, GERMANY
The development of the GSP-Process, a pulverized fuel pressure gasification technology,
was started in 1975 by Deutsches Brennstoffinstitut Freiberg/Sa. (DBI, German Fuel
Research Institute). Main objective for this development was the demand to save crude oil

and natural gas which should be partly replaced by using the available lignite. It was the
intention of the government in the former GDR to build up several gasification plants in the
area of Central Germany to supply major chemical companies through long-distance
pipelines with syngas from lignite. Because of the low rank of lignite and the high salt
content in the ash of this coal the process had special demands to the feeding system and to
the gasifier itself. Passing a period of several owners after the privatization in 1991 the
FUTURE ENERGY GmbH belongs to SIEMENS Power Generation since the 1st January
2006. The first test facility with a thermal capacity of 3 MW, built in 1979, was used to
examine the technical concept and to test the planned lignite and saliferous lignite for the
erection of the large scale demonstration facility in 1984 in the Gaskombinat Schwarze
Pumpe /Germany, where the name of the process “GSP” comes from. In the period 1994 to
1998 further test facilities were erected at FUTURE ENERGY site in Freiberg, among this a
5 MW th cooling screen reactor. Up to now these facilities have been used to gasify more than
90 candidate gasification feeds - among others 35 different coals, 25 sewage sludge’s of
municipal or industrial provenance, petroleum coke, waste oils, bio-oils, bio-slurries and 20
liquid residues, in order to investigate their gasification behavior and to analyze the quality
and the characteristics of the gasification products. By this systematic research and
development the field of application of the GSP Technology was enlarged from
conventional fuels, such as coals and oils, through residual and waste materials and biomass.
7-3
Orlando Gasification Project: Demonstration of
a Nominal 285 MW Coal-Based Transport Gasifier
Frank Morton, Tim Pinkston, Southern Company, USA
Nicola Salazar, KBR, USA
Denise Stalls, Orlando Utilities Commission, USA
Southern Company, the Orlando Utilities Commission (OUC), and KBR are building an
advanced 285-megawatt coal gasification facility near Orlando, Florida with the support of
the Department of Energy (DOE) under the Clean Coal Power Initiative (CCPI). The CCPI
is a cost-sharing partnership between the government and industry designed to accelerate
commercial deployment of advanced technologies to ensure that the United States has clean,
reliable, affordable coal-based electricity, which is essential for a strong U.S. economy and
domestic energy security. The proposed plant will demonstrate an Integrated Gasification
Combined Cycle (IGCC) using an air-blown Transport Gasifier. Southern Company and
KBR are developing the Transport Gasifier and related systems for commercial application
in the power industry in conjunction with the U.S. Department of Energy (DOE). The Power
Systems Development Facility (PSDF) is an engineering scale demonstration of the KBR
Transport Gasifier, a high-temperature, high-pressure syngas filtration system, and gas
cleanup. Built at a sufficient scale to test advanced power systems and components in an
integrated fashion, the PSDF provides data necessary for commercial scale-up of these
technologies.
The Transport Gasifier is an advanced circulating fluidized bed system designed to operate
at higher circulation rates, velocities, and riser densities than a conventional circulating bed
unit. The high circulation rates result in higher throughput, better mixing, and higher mass
and heat transfer rates. Since the gasifier uses a dry feed and does not slag its ash, it is
particularly well-suited for high moisture fuels such as sub-bituminous coal and lignite.
7-4
Energy investment of the future - Nuon Magnum IGCC Power Plant
Leon Pulles, Nuon, NETHERLANDS
Natalie van der Burg, Capgemini, NETHERLANDS
The 21st century is in need of investments in the power generation sector. This article
describes the economic view on investing in this sector. In addition it entails the
project development approach of a current investment project, as illustrated by the
Nuon Magnum IGCC Power Plant project with a generation capacity of 1200 MWe.
Capgemini is working together with Nuon and delivers project management
capabilities.
7-5
The Exergy UCG Technology and its Commercial Applications
Michael S. Blinderman, Ergo Exergy Technologies, Inc., CANADA
Underground Coal Gasification (UCG) is a gasification process carried on in non-mined coal
seams using injection and production wells drilled from the surface, converting coal in situ
into a product gas usable for chemical processes and power generation. The UCG process
developed, refined and practiced by Ergo Exergy Technologies is called the Exergy UCG
Technology or UCG Technology.
The UCG technology is being applied in numerous power generation and chemical projects
worldwide. These include power projects in South Africa (1,200 MWe), India (750 MWe),
Pakistan, and Canada, as well as chemical projects in Australia and Canada. A number of
UCG based industrial projects are now at a feasibility stage in New Zealand, USA, and
Europe. An example of UCG application is the Chinchilla Project in Australia where the
technology demonstrated continuous, consistent production of commercial quantities of
quality fuel gas for over 30 months. The project is currently targeting a 24,000 barrel per day
synthetic diesel plant based on UCG syngas supply. The UCG technology has demonstrated
exceptional environmental performance. The UCG methods and techniques of
environmental management are an effective tool to ensure environmental protection during
6
an industrial application. A UCG -IGCC power plant will generate electricity at a much
lower cost than existing or proposed fossil fuel power plants. CO 2 emissions of the plant can
be reduced to a level 55% less than those of a supercritical coal-fired plant and 25% less than
the emissions of NG CC.
8-1
SESSION 8
SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND
OTHER NON-FUEL USES OF COAL: APPLIED FT/CTL
Coal Conversion - A Rising Star
C. Lowell Miller, DOE, USA
Daniel Cicero, NETL, USA
Mark Ackiewicz, John Anderson, Technology & Management, USA
Edward Schmetz, John Winslow, Leonardo Technologies, Inc., USA
Coal’s primary use has been for electric power production but it can also be used for other
purposes, such as for producing liquid fuels, hydrogen, or chemical intermediates. Coal s
versatility and flexibility as a feedstock is becoming increasingly recognized, with
government and industry, jointly and independently, pursuing opportunities to maximize
coal s potential as a feedstock for purposes other than power generation. For example, the
jointly sponsored, government-industry FutureGen project will develop the world s first
electric power and hydrogen co-production plant that produces near-zero emissions and
captures and stores the carbon dioxide that is produced.
This paper will review current coal conversion activities that are being pursued by the federal
government and industry and the key fundamentals that may be driving these activities.
Representative coal to liquid (CTL) concepts and capital and product costs will be reviewed
including discussion of potential activities which could reduce the uncertainties in cost
estimation.
Recent legislation may be playing a role in the increased interest in coal conversion
technologies. For example, the Energy Policy Act of 2005 (EPACT 2005) contained
provisions related to coal-to-liquid (CTL) technologies or co-production of power and fuels
or chemicals from coal. Additionally, Section 1090 of the National Defense Authorization
Act for Fiscal Year 2006 required the Department of Energy to prepare a development plan
for coal-to-liquid fuels and the Department of Defense to develop a report on how it would
potentially use these fuels. Efforts are also underway by state governments, primarily in
major coal-producing states, to increase the conversion of coal into fuels and chemicals.
Expanded use of coal to produce liquid fuels, hydrogen and chemical intermediates can
increase the security and stability of the nation s liquid fuel supplies, and provide economic
and employment benefits.
8-2
Review of Competitive and Environmental Challenges to US
Coal-to-Liquids (CTL) Industry Development
Tim Cornitius, Syngas Refiner, USA
New construction and expansion of Canadian oilsands projects to increase output of
bitumen-derived synthetic crude oil (SCO) has surpassed the promising potential of
producing transportation fuels from coal as the United States continues to neglect the timely
and vital development of this vast resource. Unlike other oilsands projects, Canadian Natural
Resources Ltd. appears to be staying ahead of budget and it said one move recently “avoided
millions of dollars in additional costs.” The first staged of its Horizon project is proceeding
well and predicted construction will be 44% completed by the end of the September. Its
preplanning is paying off on work for the first stage, budgeted at $6.8 billion with expansion
plans of more than $20 billion over the next dozen years. International oil companies (IOCs)
usually increase production when oil prices are expected to remain high, but a lack of access
to acreage in some key oil-rich countries has forced them to turn to the Canadian oilsands to
increase reserves. The IOCs are using various technologies including gasification to process
bitumen economically that will mean an increased supply of SCO to US refineries.
Alternative fuels production is highly sensitive to crude oil price levels. The US Energy
Information Administration’s Annual Energy Outlook (AEO) 2006 reference case prices
increase from $40.49/bbl in 2004 to $54.08/bbl in 2025 ($21/bbl higher than AEO2005) and
to $56.97/bbl in 2030. Higher prices increase demand for unconventional transportation-fuel
sources and stimulate coal-to-liquids (CTL) production. With even higher oil prices, US gasto-liquids
(GTL) production is also stimulated.
8-3
Use of Cobalt Fischer-Tropsch Catalysts with Coal Derived Synthesis Gas
Steve LeViness, Fischer Tropsch Reactor Technology, USA
Heinz Robota, Syntroleum Corporation, USA
Rafael Espinoza, Rafael Espinoza Consulting, USA
The production of hydrocarbons by the hydro-polymerization of carbon monoxide was
discovered by Fischer and Tropsch in 1923, and – with the exception of 1945-1955 – has
been in commercial use continuously since 1933. The first commercial Fischer-Tropsch
process, practiced in Germany from 1933-1945, employed cobalt based catalysts in fixed
bed reactors using coal derived synthesis gases. Since 1955 Sasol has practiced FT from coal

derived synthesis gases employing iron based catalysts in a variety of different reactors,
including fixed, fluidized, and slurry bed variations. Since the late 1980’s and early 1990’s
Mossgas and Shell have practiced FT synthesis from natural gas derived synthesis gases
employing iron catalysts in fluidized bed reactors, and cobalt catalysts in fixed bed reactors,
respectively. Also since the late 1980’s and early 1990’s, FT synthesis processes from
natural gas (“gas to liquids”, or “GTL”) have been developed by BP, ConocoPhillips,
ENI/IFP/Agip, ExxonMobil, Rentech, Sasol and Sasol Chevron, Shell, Statoil-PetroSA, and
Syntroleum, among other. All of these technologies are based upon cobalt catalyst slurry
phase reactors, with the exceptions of BP and Shell (cobalt catalyst fixed bed reactors) and
Rentech (iron catalyst slurry reactors). The recent dramatic escalation in world-wide
petroleum prices, coupled with the passage of a $21/bbl tax credit in the US, has caused a
sharp increase in interest in production of FT products from coal derived synthesis gases.
Current conventional wisdom appears to be that only iron based FT catalysts are appropriate
for this application, ignoring the fact that the entire German commercial FT industry was in
fact based on cobalt catalysts and coal derived synthesis gases.
The FT reaction consumes H 2 and CO in a ratio slightly higher than 2/1, typically about
2.15. Depending on the synthesis gas source (especially coal vs. natural gas) and the syngas
generation technology, the raw synthesis gas H 2 /CO ratio can be anywhere in the range of
0.6 to 3.0, or higher. Typical coal gasification raw synthesis gas ratios range from about 0.6
to as high as 2.3, again depending on coal source and composition and gasification
technology. For raw syngas H 2 /CO ratios below the required FT stoichiometric usage ratio
of about 2.15, it is necessary to increase the ratio through the use of the water gas shift
(WGS) reaction, either in a separate WGS reactor or in the FT reactor itself through the use
of an FT catalyst with significant WGS activity like iron. In practice, even with iron
catalysts, a feed synthesis gas H 2 /CO ratio of 0.6-1.0 is too low, and external WGS must be
employed to avoid excessive FT catalyst requirements and reactor sizes.
While iron catalysts are preferred for the high temperature FT processes targeting chemical
feedstocks and high octane gasoline, the choice of optimum catalyst type for low
temperature FT synthesis, targeting middle distillates and other paraffinic products from coal
derived syngas is not straightforward, as both cobalt and iron have significant advantages
and disadvantages. In the preferred slurry bed reactors, iron catalysts are characterized by
low cost, moderate syngas cleanup requirements, relatively low particle strengths (leading to
potential catalyst wax separation issues), high deactivation rates and short effective catalyst
life (leading to high catalyst replacement and solids handling volumes), and low methane but
excessive CO 2 selectivities. Cobalt catalysts, on the other hand, are characterized by much
higher costs, extremely high syngas cleanup requirements, high particle strength (relatively
easy catalyst-wax separation), low deactivation rates and long effective life, and somewhat
higher methane but much lower CO 2 selectivities. The major challenge facing the use of
cobalt catalysts is synthesis gas clean-up, which will strongly depend on coal source and
syngas generation (gasification) technology choices. Related coal syngas based catalytic
processes, such as methanation and methanol synthesis, have similar syngas contaminant
specifications and are currently practiced commercially, indicating technical feasibility.
Preliminary results of cobalt catalyzed FT synthesis using a commercial coal gasification
based synthesis gas will be presented.
8-4
The WMPI Coal-To-Liquids Program
James C. Sorensen, Sorensenenergy, LCC, USA; John W. Rich, Jr., WMPI PTY.,
LLC, USA
The Gilberton CTL Project, with plans to begin construction this year, represents the
first step in WMPI’s U.S. Coal-To-Liquids program. In parallel with Gilberton, WMPI
has begun exploratory development work on larger capacity CTL projects of a scale
not requiring Government subsidy. This paper will provide an update on progress at
Gilberton, summarize the efforts underway toward commercial project objectives and
some initial conclusions, as well as outlining WMPI’s basic criteria for project success.
In addition, key drivers behind the current surge of interest in Coal-To-Liquids will be
discussed.
8-5
Selective Coal Liquefaction through Fischer-Tropsch Synthesis
Hans Schulz, Engler-Bunte-Institute, GERMANY
The selectivity of Fischer-Tropsh synthesis to very clean fuels and chemicals makes
the process so attractive today – and also for future application on a coal basis, as
much against direct coal liquefaction by hydrogenation. Coal gasification and the
composition of synthesis gas from coal, in relation to the requirements of the Fischer-
Tropsch synthesis are regarded together with specific process options of FT-synthesis.
Of particular interest is the FT route to diesel fuel as relying strongly on the
combination with “ideal hydrocracking”. But further options are also promising.
The mechanistic basis of Fischer-Tropsch synthesis is then regarded, taking into
account time resolved self-organization of the FT-regime. The fundamental differences
of FT on iron and cobalt are evaluated and the common principle of “frustrated
desorption” is established, as on the basis of detailed selectivity studies, seeing the
highly ordered complexity of product composition. The progress in understanding FTcatalysis
shall be useful also for progress in commercial application of Fischer-Tropsch
synthesis on a coal basis.
7
9-1
SESSION 9
COMBUSTION TECHNOLOGIES – 2:
MERCURY CAPTURE FROM FLUE GAS
The U.S. Department of Energy’s Phase II Mercury Control
Technology Field Testing Program
Thomas Feeley, III, DOE/NETL, USA
Mercury exists in trace amounts in coal. In the United States, coal-fired power plants
emit about 48 tons of mercury and are the largest point source of emissions. The U.S.
Environmental Protection Agency determined the need to control mercury emissions
from power plants and issued regulations on March 15, 2005 under the Clean Air
Mercury Rule. In addition, several states have proposed mercury regulations more
aggressive than the Federal rule.
Recognizing the potential for mercury regulations, the U.S. Department of
Energy/National Energy Technology Laboratory (DOE/NETL) has been carrying out a
comprehensive mercury research and development program since the early 1990s.
Working collaboratively with EPRI, industry, academia, and EPA, DOE/NETL has
helped to advance the understanding of the formation, distribution, and capture of
mercury. However, uncertainty remains, particularly related to the overall cost and
effectiveness of controlling mercury from a diverse population of coal-fired boilers, as
well as the ultimate fate of mercury once it is removed from the flue gas.
This presentation will provide an update on DOE/NETL s Phase II mercury field
testing program directed at full-scale and slip-stream evaluation of sorbent injection
(e.g., activated carbon) and oxidation processes that have the capability to achieve 50
to 70 percent capture of mercury from operating pulverized-coal-fired power plants. In
addition, results from the characterization of mercury in coal combustion by-products
collected from the Phase II field testing program will be presented.
9-2
Control of Mercury Emissions from Clean Coal Power Plants with CO 2 Capture
Kourosh E. Zanganeh, Ahmed Shafeen, Murlidhar Gupta, Robert Dureau, CANMET
Energy Technology Centre, CANADA
Currently, coal-fired power plants provide about 39% of the global electricity demand and
this trend is likely to remain the same in the coming decades. According to the International
Energy Agency’s predictions, the world’s electricity demand will be doubled between now
and 2030. During this period, nearly 1400 GW of new coal-fired power capacity will be
required worldwide. With emission standards becoming more stringent, future coal-fired
power plants will be expected to significantly reduce their emission intensity by utilizing
advanced clean coal technologies. The new generation of clean coal power plants with CO 2
capture, may include integrated energy conversion systems such as gasification with precombustion
capture, ultra-supercritical steam boilers with post-combustion capture, and oxyfuel
combustion systems with integrated capture and compression. The capture component
of these advance systems could be facilitated by a variety of technologies including
membrane separation, absorption, adsorption and cryogenic separation technologies. Some
of these technologies such as post-combustion with amine scrubbing would carry significant
potential for adaptation in the existing fleet of coal-fired power plants through retrofit, while
others such as oxy-fuel combustion and gasification could be effectively deployed in the new
state-of-the-art green-field plants with near-zero emissions.
Controlling the emission of toxic air pollutants such as mercury and other trace metals is one
of several key challenges facing the large-scale deployment of advanced clean coal power
plants in the next two decades. This is further compounded by the imposed timelines, set in
the recent regulations and standards in U.S. and Canada. Currently, there are ongoing
initiatives to demonstrate clean coal technologies for power generation in North America,
Europe and other parts of the world by 2012 and beyond. However, any successful
demonstration of clean coal technologies should also consider the control of primary air
pollutants such as mercury.
In this paper, we present an overview of mercury emissions from clean coal power plants
with CO 2 capture, possible pathways for mercury species in gasification, oxy-coal
combustion and post-combustion capture plants, and potential control technologies for
reducing mercury emissions from these plants. The CANMET’s oxy-fuel combustion group
has been actively pursuing the development of new mercury control technologies for oxycoal
combustion processes in recent years. The focus of this work is on low rank coals,
mainly, sub-bituminous and lignite coals. In this paper, some results from the recent pilotscale
testing at CANMET’s oxy-fuel combustion facility to develop effective mercury
control technologies for the next generation of oxy-coal power plants are presented. The
results obtained to date are very encouraging and further work is under progress to optimize
these processes.
9-3
Mercury Speciation in Exhaust Gases of O 2 -CO 2 Coal Combustion
Achariya Suriyawong, Pratim Biswas, Washington University in St. Louis, USA
Carbon dioxide emissions from coal combustion are of particular concern due to their
potential effects on global warming and climate change. In most coal combustors, however,

carbon dioxide makes up only approximately 15% of the total flue gas by volume; thus,
carbon dioxide control methodologies are usually not cost effective. Recently, there have
been many studies on O 2 -CO 2 combustion, where CO 2 is recycled and used as the diluent
gas. Recycling effluent flue gas would significantly increase the carbon dioxide
concentration- thus, making CO 2 capture become economically feasible. A change in
combustion gas composition may have numerous effects on pollutants associated with coal
combustions. Suriyawong et al. 1 found that the aerosol size distribution characteristics of
ultrafine and submicrometer particles change when N 2 is replaced with CO 2 . The number
concentration and mean size of submicrometer particles are smaller in O 2 -CO 2 coal
combustion. This is due to temperature in the vicinity of burning coal particle is lower in the
O 2 -CO 2 system, leading to slower burning rate of coal and submicrometer particle formation.
The same study also reported no change in mercury speciation measured at the exit of the
combustor for O 2 -CO 2 and conventional air combustion. However, a number of studies
found that mercury transformation occurs mostly at lower temperature zone down stream of
the combustor and depends on flue gas composition, such as Cl 2 , HCl and NO. Since NO x
emission significantly decreases for coal combustion in the O 2 -CO 2 system, mercury
speciation could be affected in the low temperature zone down stream of the combustor. In
this study, the effect of O 2 -CO 2 coal combustion on mercury speciation in the low
temperature zone is investigated. Flue gas compositions used in this study are chosen to
mimic gas compositions that would potentially be in coal combustion system where CO 2 is
recycled. The temperature profile and residence time are selected are based on the typical
full-scale coal combustion systems. Mercury emission is measured using the method
developed by Hedrick et al. 2 .The results are compared with those obtained under
conventional air combustion conditions.
9-4
Impact of NO and SO 2 on Measurement of Mercury Speciation
in a Wet Chemical Conditioning System
Andrew Fry, JoAnn Lightly, Geoffrey D. Silcox, Brydger Cauch, Jost O.L. Wendt,
University of Utah, USA
Constance L. Senior, Reaction Engineering International, USA
The impacts of NO and SO 2 on speciated mercury measurements from a wet chemical
conditioning system were investigated. A reactor previously used to elucidate the impact of
chlorine on mercury oxidation in combustion products was used. NO injected directly into
the KCl impinger of the conditioning system was shown to reduce mercury oxidation by
44% at concentration of 500 ppmv NO and 200 ppmv Cl exactly matching results where the
NO was injected into the reactor burner at the same concentration. SO 2 was shown to
essentially eliminate apparent oxidation at concentrations of 300 ppmv SO 2 and 200 ppmv
Cl when injected into the KCl impinger. The effect of NO and SO 2 on mercury oxidation
were also predicted using a detailed kinetic model for the reactor conditions of interest.
Model results confirm the observed inhibition does not occur as homogeneous oxidation in
the reactor. Reduction of Hg 2+ in the KCl solution of the wet-chemical conditioning system
by SO 2 and NO is likely responsible and is being reported as reduction of oxidation. Due to
this measurement bias, the effects of NO and SO 2 can not be elucidated using a mercury
analysis system of this type. Further investigation is required to determine the nature and
impact of this oxidation-reduction chemistry in the KCl solution.
9-5
Adsorption of Trace Elements and Sulfur Dioxide on Ca-Based Sorbents
Erdem Sasmaz, Jennifer L. Wilcox, Worcester Polytechnic Institute, USA
Ab initio quantum mechanical tools are used to explain the adsorption mechanism of
trace elements on a calcium oxide surface in the gas phase. Density functional theory is
used to calculate binding energies of elemental mercury, oxidized mercury, selenium
dioxide and sulfur dioxide molecules with a calcium oxide sorbent using the software
programs, Gaussian 03 and Vienna Ab initio Simulation Package (VASP). Super cells
with periodic boundary conditions versus cluster approaches are compared to illustrate
the potential mechanisms of adsorption. Further, effects of hydrogen chloride on the
adsorption of oxidized mercury are investigated to determine how hydrogen chloride
plays a role in activating the calcium oxide surface to increase potential trace element
adsorption. Our predictions calculated in the gas phase indicate SO 2 , HgCl 2 and SeO 2
molecules are capable of adsorbing onto calcium oxide surfaces. However, elemental
mercury does not adsorb onto calcium oxide unless it is first oxidized. Moreover, HCl
inhibits the adsorption of HgCl 2 on the calcium oxide surface. These results are in good
agreement with the current data in the literature.
SESSION 10
ENVIRONMENTAL CONTROL TECHNOLOGIES:
MERCURY ABSORPTION – 2
10-1
Predicting Mercury Retention in Utility Gas Cleaning Systems
Stephen Niksa, Balaji Krishnakumar, Chitralkumar V. Naik, Niksa Energy Associates,
USA
This paper presents validations of the Hg speciation predicted by NEA’s
MercuRator package with the NETL field test database for over 20 full-scale utility
gas cleaning systems. It emphasizes SCR/ESP/FGD combinations and activated carbon
injection because these two applications present the best long-term prospects for Hg
control by coal-burning utilities. The satisfactory performance with SCR/ESP/FGD
combinations paves the way for several important applications, including (i) legitimate
comparisons of data from the same system taken at grossly different times; (ii) very
accurate predictions for a wide range of fuel quality at particular SCRs and FGDs,
because the Cl dependence is represented so accurately; and (iii) reliable estimates for
Hg 0 oxidation with and without NH 3 injection. It is now possible to reliably assess the
benefits of adding an SCR and/or an FGD to any commercial gas cleaning system, for
any coal type and the full domain of commercial gas cleaning conditions. The status of
the validation of ACI performance is similar, in that Hg removal can be accurately
estimated for the full domain of coal quality, LOI, and ACI rates.
10-2
Enhanced Absorption of Elemental Mercury by Sulphurized
Activated Lignite HOK ®
Mailk Werner, Wolfgang Heschel, Technical University Bergakademie Freiberg,
GERMANY
Jurgen Wirling, Rheinbraun Brennstoff GmbH, GERMANY
Adsorptive waste gas cleaning with pulverized activated lignite HOK® by an
entrained-phase technique is well-known to reduce elemental and ionogenic mercury
from the gas phase. Because of the specific surface area and the particular pore
structure, the favorably-priced mass sorbent is used to treat waste gases from
metallurgical processes, waste combustion plants and those of coal-fired power plants.
The decisive point of effective mercury retention by activated carbon or HOK® is the
self-doping of the adsorbent by sulfuric acid during the gas cleaning process. This
catalytic mechanism usually takes place with the residual SO 2 and H 2 O content in the
waste gas. Due to the adsorbed accumulated sulfuric acid in the micropores, highly
volatile mercury is separated by means of chemisorption. The objective of this study is
to develop a low cost adsorbent to ensure mercury deposition in waste gases with SO 2 -
reduced and without SO 2 content. For this purpose different sulfurization methods have
been applied to sulfurize activated lignite HOK®. Additives such as elemental sulfur
and sulfuric acid have been used. The effectiveness of the produced HOK® samples
was measured continuously by the adsorption of elemental volatile mercury Hg0 in a
fixed bed reactor with several thin particle layers.
Laboratory tests include the temperature-dependent mercury adsorption (60 - 150°C)
and the influence exerted by the SO 2 , O 2 and H 2 O content in the synthetic waste gas
mixture. Experimental results showed an enhancement of the mercury reduction in
absence of SO 2 by all sulfurized HOK® samples. The adsorption reached its maximum
by using the sulfur-endowed activated lignite at approximately 90°C. Furthermore at
these samples the mercury separation was independent on the presence of oxygen in
the gas stream.
10-3
Mercury Speciation and Emissions from Bituminous Coal-Fired Facilities:
A Compilation of CONSOL’s Test Results Since 1994
Jeffrey A. Withum, CONSOL Energy, Inc., USA
Beginning in 1994, CONSOL Energy Inc., Research & Development (CONSOL), with
support from federal and state agencies, trade organizations and private industry, has
performed mercury sampling and analysis test programs at many bituminous coal-fired
plants equipped with various combinations of NO x , SO 2 , and particulate matter control
devices. With a few exceptions, the Ontario Hydro Flue Gas Mercury Speciation
Method was used simultaneously at up to five locations in each plant. At most of the
plants, solid and liquid samples were collected and mercury mass balances were
calculated to confirm the observed removals. This paper will discuss the results of a
comprehensive analysis of the data base developed from all of these test programs. The
analysis includes an examination of factors that affect mercury speciation in flue gas
and coal-to-stack mercury removal at power plants.
10-4
A New Non-Carbon Sorbent For Removing Mercury
Gokhan Alptekin, Margarita Dubovik, Michael Cesario, TDA Research Inc., USA
The U.S. Environmental Protection Agency (EPA) determined the need to reduce mercury
emissions from power plants by implementing maximum achievable control technology.
Although, substantial reductions will likely be required over the next decade, there are still
uncertainties, particularly related to the cost and effectiveness of existing mercury control
technologies. An ideal mercury abatement system would be easy to retrofit into the existing
coal-fired electric utilities. An attractive approach is dry sorbent injection where the sorbent
injected into the flue gas reacts with gas phase mercury and the mercury-laden sorbent is
removed with the fly ash either by a fabric filter or by an electrostatic precipitator. The
requirements for such a sorbent are straightforward: 1) it should be low cost, 2) it should
remove mercury with high capacity, and 3) it should not present any environmental
problems in its own right. Another less obvious but very important consideration is that the
sorbent collected with the fly ash, must not degrade and limit the potential uses of fly ash.
8

Several physical adsorbents, particularly activated carbons, can remove mercury from flue
gases produced by coal combustion. However, activated carbons are non-selective
adsorbents; most of the flue gas components adsorb on carbon, competing with mercury,
thus, the efficacy of carbon-based sorbents is severely compromised. To improve the
adsorption capacity, it is common to chemically modify the activated carbons with various
chemical promoters including sulfur, iodine, chlorine and nitric acid, although the carbon
treatment processes significantly increase the cost of the sorbent. As a result, both for
promoted and unpromoted carbons, the projected annual cost of abatement is high in the
order of $38,000 per pound of mercury removed (based on the combined operating and
annualized capital costs) or over $4 million per year for a 250 MW power plant4. In fact, all
these estimates understate the difficulties and costs associated with using carbon-based
sorbents. Much of the fly ash collected in the particulate control module is sold as an
extender to Portland cement: fly ash can replace as much as 80% of the cement in some
grades. However, fly ash that contains carbon is not suitable for use in cement. The problem
is much more serious than lost sales. If the fly ash is not salable for concrete, it has no use at
all, and immediately becomes an expensive waste problem.
TDA Research, Inc. is developing a new sorbent to remove all mercury species from flue
gas. The sorbent is made of non-carbon based materials and has a high mercury absorption
capacity, thus will not alter the properties of the fly ash. The sorbent can be produced as an
injectable powder for easy integration into the existing power plant infrastructure
10-5
Feasibility of Generating Sulphur Impregnated Activated Carbon using
Petroleum Coke and Flue Gases from a Copper Smelter
Eric Morris, Charles Q. Jia, University of Toronto, CANADA
Shitang Tong, Wuhan University of Science and Technology, CHINA
Non-ferrous metal smelters are among the largest point-source emitters of gaseous mercury
and sulphur dioxide. It has been shown that Alberta oil-sands fluid coke can be effectively
used to reduce SO 2 to elemental sulphur while simultaneously producing sulphurimpregnated
activated carbon (SIAC). In the capture of mercury from industrial flue gases,
SIAC has proven to be a highly effective adsorbent material. The current research aims at
developing an existing SIAC technology to meet the needs of a copper smelter for mitigating
both mercury and SO 2 emissions while making elemental sulphur as a co-product. The
challenge behind this undertaking is that these flue gases generally contain percent levels of
O 2 and H 2 O vapour (2-12%), and SO 2 concentrations significantly lower than those
previously used for the activation process. Previous work has shown that it is feasible to
reduce SO 2 and produce elemental sulphur in the presence of oxygen and water vapour, but
little work has been done to characterise the SIAC product. The focus of this study is
therefore on the optimisation of the SIAC properties under the conditions of the flue gas of a
copper smelter. Fluid coke samples are reacted with varying concentrations of SO 2 and
oxygen or water vapour in a tubular furnace, and the products are analysed for their specific
surface area, pore size distribution, mass yield, sulphur content, and mercury uptake
capacity. The outlet gases from the reactor are examined using gas chromatography in order
to characterise the reactions taking place within the carbon bed.
SESSION 11
HYDROGEN FROM COAL: STORAGE/SYNGAS TO HYDROGEN
11-1
Hydrogen Production from Coal Derived Syn Gas using
Novel Metal Oxide Particles
L.S. Fan, Luis G. Velazquez-Vargas, Puneet Gupta, Fanxing Li, The Ohio State
University, USA
Syngas Redox process (SGR) is capable of producing H 2 from coal derived syngas while
providing sequestration ready CO 2 stream. A Fe 2 O 3 containing composite particle is used as
oxygen carrier to combust coal derived producing, after condensation of water, a nearly pure
CO 2 stream. This reaction reduces the Fe 2 O 3 to metallic iron which is then oxidized back
with steam in a second reactor. This generates a nearly pure H 2 stream. With this technology,
the cost of energy intensive and expensive CO 2 separation process is avoided. Furthermore,
depending on the syngas composition, both reactors can operate exothermically which
favors the heat integration of the system. The process has a high hydrogen production
efficiency of about 75% as compared to 64% for the current gasification-WGS technology.
In this work, a novel oxygen carrier particle is developed, synthesized and tested. The
recyclability, reactivity, and strength of the pellets were characterized. Fixed bed
experiments for the reduction and oxidation of the pellets ware also performed. It is observed
that the newly developed pellets can maintain satisfactory reactivity for multiples cycles and
are strong enough for operation in the proposed SGR reactors. Moreover, fixed bed
experiments show that particles can be fully oxidized or reduced producing a H 2 stream with
high purity at a reasonable rate.
11-2
Novel Sorption Enhanced Reaction Process for Production of
H 2 and CO 2 from Synthesis Gas
Shivaji Sircar, Hugo Caram, K. B. Lee, M. Beaver, Lehigh University, USA
The feasibility of simultaneously producing essentially pure streams of H 2 and CO 2
from synthesis gas using a novel sorption enhanced reaction process concept is being
evaluated. The concept is designed to simultaneously carry out the thermodynamicallycontrolled
water gas shift reaction (CO + H 2 O ↔ H 2 + CO 2 ) and removal of CO 2 from
the reaction zone using a sorber-reactor packed with an admixture of the shift catalyst
and a CO 2 selective chemisorbent in order to circumvent the thermodynamic limitation
of the reaction and facilitate the rate of forward reaction. K 2 CO 3 promoted hydrotalcite
is initially being tested as the chemisorbent, which selectively sorbs CO 2 in presence of
water. This paper outlines the novel process concept, and reports new CO 2
chemisorption isotherm and column dynamic data for estimating the kinetics of CO 2
chemisorption. The CO 2 chemisorption isotherm is Langmuirian in the low pressure
region with a very large gas-solid interaction parameter. The isotherm deviates from
Langmuir behavior in the high pressure region. A new model to describe the observed
chemisorption isotherm is proposed. The model simultaneously accounts for
Langmuirian chemisorption of CO 2 on the surface of the sorbent and additional
reaction between the gaseous and the sorbed CO 2 . The length of the mass transfer zone
for CO 2 chemisorption is fairly small. The Linear Driving Force Model is adequate to
describe the chemisorption column dynamics.
11-3
Production of Hydrogen and Carbon Nanotubes by Catalytic Non-Oxidative
Dehydrogenation of Hydrocarbon Gases and Liquids
Gerald Huffman, Yuguo Wang, Naresh Shah, Wenquin Shen, Frank Huggins.
University of Kentucky, USA
In this paper, we report on non-oxidative catalytic dehydrogenation of methane or
ethane to produce pure hydrogen and carbon nanotubes in a single reaction. The
catalysts used are binary Fe-Ni (65% Fe, 35% Ni) or Ni nanoparticles supported on
Mg(Al) oxide derived from a hydrotalcite-like precursor Mg 5 Al(OH) 11 CO 3 xH 2 O. The
Ni/Mg(Al)O catalyst exhibited high activity for production of hydrogen and stacked
cone carbon nanotubes(SCNT) from both methane and ethane at approximately 500°C.
However, the activity of the Ni/MgAl(O) catalyst decreased rapidly at a reaction
temperature of 650°C. Conversely, the (Fe-Ni)/Mg(Al)O catalyst exhibited good
activity and a substantially longer life time for methane and ethane decomposition at
650°C. The carbon nanotubes produced were easily purified by dissolving the Mg(Al)
oxide supported catalysts in 6 M nitric acid at room temperature. Preliminary runs
showed that unsupported Ni(Fe)O (Ni/Fe=5/1) exhibited self-reduction and high
activity at 500ºC for the decomposition of ethane for 110 hours. 1 gram of Ni(Fe)O
produced 19.5 grams of SCNT+catalyst. The purity of the SCNT therefore exceeds 95
wt% even before removing the catalyst particles.
11-4
Coproduction of Hydrogen and Methyl Formate by
Dehydrogenation of Methanol
Yulong Zhang, Fan Shi, Xin Fan, John Tierney, Irving Wender, University of
Pittsburgh, USA
Methanol is produced in very large amounts from synthesis gas derived from natural
gas and coal. It is a hydrogen-rich liquid, providing convenience in storage, transport
and handling of hydrogen.
The coproduction of hydrogen and chemicals is of potential industrial value. The
catalytic dehydrogenation of methanol produces hydrogen as well as methyl formate
(MF) according to the following equation:
2CH 3 OH = HCOOCH 3 + 2H 2
MF is a stable liquid which is a source of important chemicals such as formaldehyde,
dimethyl formamide, formamide, ethylene glycol, acetic acid and dimethyl carbonate.
It is an intermediate in a series of reactions so that fast desorption and diffusion are
essential for high selectivity to MF and hydrogen. In this study, work has started on the
gas phase dehydrogenation of methanol to produce hydrogen and MF over a series of
copper-based catalysts. The effects of supports and promoters are under investigation.
Initial results indicate that a Cu/ZrO 2 catalyst shows good activity for the coproduction
of hydrogen and methyl formate.
11-5
Development of Hydrogen Storage Materials
S.G. Sankar, Brian Zande, Advanced Materials Corporation, USA
Long Pan, Jing Li, Rutgers University, USA
Jinchen Liu, Karl Johnson, University of Pittsburgh, USA
US Department of Energy has embarked on a program to develop hydrogen storage
materials for stationary and transportation applications. Hydrogen gas will be derived from a
variety of sources, one of which being the by-product from the Clean Coal Initiative. Future
requirements for the utilization of hydrogen in fuel cell vehicles calls for the development of
on-board storage systems with a capacity of ~ 6 wt% hydrogen in the near term and of ~ 9
wt% by 2015. In this talk, we review the work on three families of materials: (a.) Traditional
rare earth intermetallic compounds such as LaNi 5 , (b.) Light metals such as magnesium and
(c.) Microporous Metal Organic Frameworks. Each of these families of materials possess
distinct advantages and disadvantages; a thorough understanding of the basic properties of
9

these materials is likely to lead to the discovery of new and improved materials for hydrogen
storage that meets the challenging specifications set by the US DOE.
In the traditional rare earth intermetallic compounds, hydrogen is stored in the interstitial
sites of a crystal. The heat of formation of the hydrides is typically about -15 kJ/H, the
plateau pressures can be fine-tuned by modifying the alloy compositions, the kinetics of
hydrogen absorption-desorption are fast ( ~200 sec.) and the volumetric hydrogen capacity is
reasonably high. However, the gravimetric hydrogen storage capacity is only about 1.5 wt%,
far short of DOE goals. Metallic magnesium chemically reacts with hydrogen to form stable
MgH 2 with a heat of formation of ~-37 kJ/H. The theoretical gravimetric capacity is as high
as 7 wt%. However, the kinetics of decomposition even in microcrystalline samples is
extremely slow (several thousand seconds at ~300°C). Our recent research work has shown
that (1) kinetics of decomposition of the hydride increases when the material is reduced to
the nanocrystalline size through mechanical milling technique and (2) Addition of small
amounts (~2 wt%) of, for example, nanocrystalline iron modifies the plateau pressure
significantly. More recently, we have begun synthesis, characterization and hydrogen
adsorption studies of Microporous Metal Organic Frameworks (MMOFs). These materials
are composed of various metals, including selected group-1 and group-2 light elements and
transition metals and sp 2 -carbon based ligands, which form the internal surfaces of the pores.
We have synthesized several MMOF materials with a number of metals and organic ligands,
and studied their hydrogen adsorption properties at room temperature as well as at low
temperatures (78 K). For instance, we found that the hydrogen storage capacity is about 3
w% and 2.25 w% at 78 K and decreases to about 0.29 w% and 0.5 w% at room temperature
for [Co 3 (bpdc) 3 bpy] 4DMF H 2 O (bpdc = biphenyldicarboxylate) and Cu 3 BTC (BTC =
Benzene-1,3,5-tricarboxylate), respectively, at hydrogen pressures of ~30 atm. The hydrogen
uptake appears to be related, in part, to the pore size and pore structure. Thermal stability,
pore structure and hydrogen storage characteristics of these and other related MMOF
materials will be presented. We have performed atomistically-detailed modeling of H 2
adsorption in various MMOF materials and have compared these theoretical predictions with
experimental data. We have computed both the adsorption isotherms and isosteric heats of
adsorption at different temperatures. In general we find qualitative agreement between
simulations and experiments. The simulations indicate that the most attractive sites for
adsorption are near the corners of the frameworks, close to where oxygens are bound to the
metal atoms. Calculations indicate that substantially higher heats of adsorption are needed to
effectively store hydrogen at room temperature.
Supported by: US DOE Grants: DE-FC26-05NT42446 and DE-FG02-04ER83886
12-1
SESSION 12
GLOBAL CLIMATE CHANGE:
GEOLOGIC CARBON SEQUESTRATION – 2
The Use of Water Injection for CO 2 Sequestration in Coalbeds
Miguel Tovar, Shahab Mohaghegh, West Virginia University, USA
Carbon capture and storage in geologic formations has been proposed as a global warming
mitigation strategy that can contribute to stabilize the atmospheric concentration of carbon
dioxide, the anthropogenic gas with the largest greenhouse effect. Particularly in the US, the
storage of CO 2 in unmineable coalbeds is an attractive prospect due to the large amount of
coal reserves and the possibility of enhanced coalbed methane recovery. This study
introduces a new strategy for the prevention of post-sequestration CO 2 seepage to the surface
from the CBM (CoalBed Methane) formations that is named the “Nature’s Sequestration
Technique”. The idea is to retain the adsorbed CO 2 in the coalbed formation by having
formation water filling the cleat system. Coalbed formations have the capacity to retain
methane adsorbed on its surface through the geologic time under an appropriated pressure
condition. This pressure condition is mainly established by water contained in the fracture
network (the cleat system). We can take advantage of this natural occurrence in order to
restore the system’s original conditions by filling the cleat system with water and having
CO 2 adsorbed on the matrix instead of methane. Using a commercial numerical simulator
and data representative of the Appalachian basin region; we investigate whether or not the
presence of water on the cleats helps to sequester CO 2 in a coalbed for a long period of time
without significant seepage. Several scenarios were considered for this study, with variations
of depth, flow mechanism and nature of potential fracture that would work as a conduit for
the seepage of CO 2 to the surface. Results show that water filling the coal cleat system
decreases significantly the amount of CO 2 seeped to the formations above the target
formation.
12-2
Numerical Modeling of CO 2 Sequestration in Unmineable Coal Seams
Guoxiang Liu, Andrei Smirnov, West Virginia University, USA
Numerical modeling of CO 2 sequestration in deep unmineable coal seams can be used
for long term predictions of storage capacity of these reservoirs, as well as enables one
to analyze possible CO 2 escape routes. In addition to this, the computations can
provide estimates on the possibility of residual methane recovery in CO 2 sequestration
operations. The process of CO 2 transport in a coal seam can be influenced by many
factors, such as bounding layers permeabilities, porosities, fracture densities, etc.
In this study a series of computer simulations was conducted with a purpose of
predicting CO 2 transport in a multi-layer environment of typical unmineable coal
seams. The parameters of three typical coal basins were considered as examples: San-
Juan, Appalachian, and Powder River basins. In the majority of cases it was presumed
that the upward migration was limited by the lowest permeability layers. An opensource
OpenFOAM CFD solver (openfoam.org) was used in this study to analyze CO 2
transport in coal seams. Darcy’s diffusion term was added into the solver, and mass
injection was modeled within the framework of compressible flow. To facilitate the
analysis of more complex layer formations in reservoirs a voxel-based geometric
design system was adapted and interfaced with the OpenFOAM and TOUGH2
simulators. The study can provide long term projections for the CO 2 sequestration
operations in known coal seams.
12-3
Determination of Coalbed Methane Potential and Gas
Adsorption Capacity in Western Kentucky Coals
Sarah Mardon, Kathy G. Takacs, James C. Hower, Cortland F.Eble, University of
Kentucky, USA
Maria Mastalerz, Indiana University, USA
The Illinois Basin has not been developed for Coalbed Methane (CBM) production. It is
imperative to determine both gas content and other parameters for the Kentucky portion of
the Illinois Basin if exploration is to progress and production is to occur in this area. This
research is part of a larger project being conducted by the Kentucky Geological Survey to
evaluate the CBM production of Pennsylvanian-age western Kentucky coals in Ohio,
Webster, and Union counties using methane adsorption isotherms, direct gas desorption
measurements, and chemical analyses of coal and gas. This research will investigate
relationships between CBM potential and petrographic, surface area, pore size, and gas
adsorption isotherm analyses of the coals. Maceral and reflectance analyses are being
conducted at the Center for Applied Energy Research. At the Indiana Geological Survey, the
surface area and pore size of the coals will be analyzed using a Micrometrics ASAP 2020,
and the CO 2 isotherm analyses will be conducted using a volumetric adsorption apparatus in
a water temperature bath. The aforementioned analyses will be used to determine site
specific correlations for the Kentucky part of the Illinois Basin. The data collected will be
compared with previous work in the Illinois Basin and will be correlated with data and
structural features in the basin. Gas composition and carbon and hydrogen isotopic data
suggest mostly thermogenic origin of coalbed gas in coals from Webster and Union
Counties, Kentucky, in contrast to the dominantly biogenic character of coalbed gas in Ohio
County, Kentucky.
12-4
Effects of Structural Rearrangements on Sorption Capacity of Coals
Vyacheslav Romanov, Yee Soong, Robert Warzinski, Ronald Lynn, DOE/NETL, USA
Recently, the problems in practical application of experimental data and modeling to
the sequestration of carbon dioxide in coal seams and the concurrent enhanced coalbed
methane (ECBM) recovery have underscored the need for new approaches that take
into account the ability of coal for structural rearrangements. Areas of interest include
plasticization of coal due to CO 2 dissolution, the effect of coal swelling on estimation
of the capacity of a coal-seam to adsorb CO 2 (adsorption isotherm), and the stability of
the CO 2 saturated phase once formed, especially with respect to how it might be
affected by changes in the post-sequestration environment (environmental effects).
Coals are organic macromolecular systems well known to imbibe organic liquids and
carbon dioxide. CO 2 dissolves in coals and swells them. The problems become more
prominent in the region of supercritical CO 2 . We investigated the effects of moisture
content and pressure cycling history on temporal changes in the coal sorptive capacity
for a set of Argonne premium coals. The samples were tested as received, dried at
80°C for 36 hours, and moisture equilibrated at 96-97% RH and 30°C for 48 hours.
The powders were compared to core samples. Additionally, plasticization of coal
powders was studied by high pressure dilatometer.
12-5
Sorption of Gases by Argonne Premium Coals at Supercritical Pressures
Richard Sakurovs, Stuart Day, Steve Weir, Greg Duffy, CSIRO Energy Technology,
AUSTRALIA
Modelling the sorption properties of coals for carbon dioxide under supercritical
conditions is necessary for accurate prediction of the sequestering ability of coals in
seams. We present recent data for sorption curves for three dry Argonne Premium
coals using a gravimetric system, and apply a recently developed model to the fitting
of the excess sorption by these coals of carbon dioxide, methane and nitrogen at two
different temperatures at pressures up to 15MPa. The model is unique in that it uses
gas density rather than pressure as the main variable. It is a modified Dubinin-
Radushkevich (DR) equation, using adsorbed phase density rather than saturation
pressure as the upper limit. The fit of this model is generally around 1% of the sorption
capacity. The sorption capacity of the coal is found to decrease with increasing
temperature, which disagrees with expectations from simple models of coal sorption
that predict a sorption capacity that is independent of temperature. This means that
sorption capacity should not be considered a direct measure of the surface area of coal.
10

13-1
SESSION 13
GASIFICATION TECHNOLOGIES:
APPLICATIONS AND ECONOMICS – 3
GE and Bechtel’s IGCC Reference Plant Update
Rich Rapagnani, GE Energy, USA
For background, GE Energy purchased ChevronTexaco's gasification technology business in
June of 2004, and soon thereafter formed an IGCC alliance with Bechtel Corporation to
jointly develop and commercialize an IGCC reference plant. Rated nominally at 630 MW,
this IGCC Reference Plant provides customers a commercially competitive, cleaner coal
alternative for coal to power. Moreover, the GE and Bechtel IGCC Alliance provides this
IGCC product on a turnkey basis, including commercial guarantees, thus offering the total
package customers need for successful commercialization of their project.
This presentation provides to the conference attendees an update on the GE and Bechtel
IGCC Reference Plant design status, a look at the fuel flexibility benefits inherent in such a
plant design, a preview of the expanded fuel envelope capabilities under development by GE
and a discussion of the business aspects supporting development of IGCC projects.
13-2
Beluga Coal Gasification Feasibility Study Phase 1
Ronald Schoff, Robert Chaney, RDS-Parsons Corporation, USA
The Beluga Coal Gasification study aims to determine the economic feasibility of siting a
coal-based gasification plant in the Cook Inlet region of Alaska for the co-production of
electric power and marketable by-products. The plant products may include synthesis gas,
Fischer-Tropsch (F-T) liquids, fertilizers such as ammonia and urea, alcohols, hydrogen,
nitrogen and carbon dioxide, that would be manufactured for local use or for sale in domestic
and foreign markets. The project was divided into two phases. In Phase 1, the Agrium
fertilizer plant in Nikiski serves as the case study site and customer for product gases
(including hydrogen, nitrogen and carbon dioxide), steam and power from the coal
gasification facility. In Phase 2, an assessment of alternative locations and plant designs
based on local and export markets for the suite of potential products will take place. The
Phase 1 case study results, reported here, will feed into the Phase 2 central Alaska regional
study. The project may be broken into four major subject areas, described below:
Gasification Plant Design: The coal gasification plant investigated in this study is designed
to provide the Kenai Nitrogen Operations (KNO) plant with the following suite of required
products:
• 282 million standard cubic feet per day (MMSCFD) of hydrogen at 400 psig and of
suitable quality for ammonia production.
• Stoichiometric quantity of nitrogen (approximately 100 MMSCFD) at 400 psig and
99.99% purity.
• 1,500,000 lb/hr steam at 1500 psig and a minimum temperature of 825°F.
• 300,000 lb/hr steam at 600 psig and 625°F.
• 2,500 tpd CO 2 suitable for urea production (25 psig)
• Electric power to satisfy the auxiliary power requirements for the gasification plant
and the KNO facility, to make the entire facility electric power independent.
Two cases were considered:
Case 1: Process the syngas from the gasification plant to supply required hydrogen and
nitrogen to the KNO ammonia synthesis loop compressor and produce sufficient steam and
power for the KNO needs. Capital Cost was $1.64 billion.
Case 2: Process the syngas from the gasification plant to supply required hydrogen and
nitrogen to the KNO ammonia synthesis loop compressor, but do not produce power from a
gas turbine. Rather, independently produce the required steam and power for the KNO
facility with a CFB coal-fired boiler. Capital Cost was $1.87 billion.
Financial Analysis - The Power Systems Financial Model Version 5.0 (now the standard
used by NETL for IGCC systems analysis) was used to perform the financial analysis.
Factors in the analysis included: coal and limestone supply and cost, by-product markets,
and impact on local natural gas and electric power markets. Project return on equity
investment (ROI) and a discounted cash flow analysis were key results. Identification of key
model sensitivities also occurred.
Case 1 possesses superior financial potential relative to Case 2. For Case 1, the ROI was
11.1% with a Payback Year of 2023, assuming start-up in 2011. For Case 2, the ROI was
6.0% with a Payback Year of 2031. While both cases produce enough raw materials
necessary for ammonia and urea production at the Agrium facility, Case 2 is more
expensive, produces less export power, and requires slightly more coal feed in order to do so.
Sensitivity analysis was performed on all model inputs in both cases. The items found to
have the greatest impact on the financial results are the plant EPC cost, system availability,
ammonia/urea prices, and coal price.
Environmental Issues The analysis of the design basis indicates that a proposed IGCC
facility at the Agrium Kenai Plant is feasible in terms of current environmental permitting
and compliance requirements imposed by federal, state and local regulations.
Carbon Capture/Use - The potential for use of CO 2 for enhanced oil recovery in regional oil
fields was a major consideration. It was determined that CO 2 floods could economically
produce up to 300 million barrels of oil in Cook Inlet fields with oil prices at $35 to $40/bbl
and CO 2 price at from $0.50 to $1.20/mcf. The production potential is equal to that achieved
locally over the last 25 years by conventional methods.
13-3
2006 Cost and Performance Estimates of Fossil Energy Power Plants
Jared P. Ciferno, RDS-Parsons Corporation, USA
Julianne Klara, NETL, USA
In 1999, the Department of Energy s National Energy Technology Center (NETL)
sponsored a report entitled Market-Based Advanced Coal Power Systems in response to a
newly deregulated power industry. The study, conducted by Parsons Corporation, compared
the performance and economics of power systems that were advanced, yet market-ready
within a 5 year time frame that included Pulverized Coal Boiler (PC), Natural Gas
Combined Cycle (NGCC), Integrated Gasification Combined Cycle (IGCC) and 2nd
Generation Pressurized Fluidized Bed Combustion (PFBC) power plants. In the 7 years
since this report was published, natural gas prices have more than doubled while proposed
emissions regulations such as EPA s Clean Air Interstate Rule (CAIR) and the Proposed
Power Plant Mercury Rule, have forced the potential inclusion of control devices and
operational strategies to lower future power plant emissions. Furthermore, concern over the
potential effect of CO 2 emissions from fossil fuel power plants on the global climate is a key
issue for the future of power generation worldwide. With energy demand projected to rise by
over 60% through 2030, limiting CO 2 emissions from power plants is becoming ever more
pressing. Finally, technological advances such as the anticipated introduction of a synthesis
gas fired gas turbine and expected improvements in the operation of gasifiers will affect the
overall plant performance. As a result of changing economic, regulatory and technological
issues, the 1999 study has become outdated. The effort that is currently underway is the 2006
Market-Based Advanced Coal Power Systems study, expanded to include three competitive
gasifier technologies, with and without CO 2 capture. Economic issues, including the rapid
increase in natural gas prices and the shift in the industry back to coal-based plants, are
considered here. Pollution control technology advances, brought about by anticipated
regulation, result in cleaner plants. Advances in gas turbine, gasifier and other balance of
plant equipment are taken into account. Cost and performance results of the study effort will
be discussed in this paper and at the conference presentation.
13-4
Advanced Clean Coal Technologies for Capture
Minish Shah, Praxair, Inc., USA
In the absence of any regulations on CO 2 emissions in the US, the focus is on building new
power plants that are CO 2 capture ready. This paper compares and contrasts two advanced
clean coal technologies for CO 2 capture: Integrated Gasification Combined Cycle and Oxy-
Coal Fired Boiler. The gasification has been widely promoted and the oxy-fuel combustion
is also gaining support as a viable alternative for CO 2 capture. Both of these technologies are
touted for their potential to capture CO 2 at low cost. There are significant differences in the
commercial readiness and the CO 2 capture readiness. These issues will be highlighted and
the cost and performance with CO 2 capture will be presented for both the technologies. All
the individual components of IGCC plant with CO 2 capture have been demonstrated in large
scale operation in different applications. The main obstacles to commercialization of IGCC
are uncertainties related to costs and reliability. Adding CO 2 capture capability to IGCC will
impact the performance of all the major sub-units (gasification, combined cycle and ASU).
Therefore, to make IGCC CO 2 capture ready, significant preplanning will be required. The
oxy-fuel technology allows utilities to build power plants based on air-fired PC boiler,
technology they are most familiar with and one which requires lower initial investment
compared to IGCC. And for CO 2 capture, two new sub-systems (an air separation unit and a
CO 2 clean-up unit) can be installed only when needed further minimizing up-front
investment. However, there has been no large-scale demonstration of some of the subcomponents
of this technology. Although in theory, the oxy-coal fired boiler can be operated
to mimic the air-coal fired boiler, testing at smaller scale will be necessary to understand
flame and heat transfer characteristics and materials compatibility due to different chemical
environment within the boiler. The learnings from such testing will also be needed to
establish whether any design changes are required for the CO 2 -capture ready plant. The CO 2
clean-up will also require further development to address issues related to impurities such as
SO x and NO x .
13-5
Power Systems Development Facility Update on Six Trig Studies
Luke H. Rogers, Southern Company Services, USA
George S. Booras, Electrical Power Research Institute, USA
Ronald W. Breault, National Energy Technology Center, USA
Nicola Salazar, Kellogg Brown and Root, Inc., USA
The pursuit of more cost-effective and reliable coal technologies with superior
environmental performance continues to drive the development of the Transport Gasifier at
the Power Systems Development Facility (PSDF). This paper presents the results of six
updated system and economic studies of Transport Integrated Gasification (TrIG) plants.
Southern Company and Kellogg Brown and Root (KBR), in conjunction with the U.S.
Department of Energy (DOE) and other partners, are developing the TrIG process at the
PSDF for commercial application in the power industry. The PSDF is an engineering scale
demonstration of the KBR Transport Gasifier along with a high-temperature, high-pressure
11

syngas filter, a gas cleanup process, and related systems. Built at a sufficient scale to test
advanced power systems and components in an integrated fashion, the PSDF provides data
necessary for commercial scale-up of these technologies. To guide future tests and
commercialization of the technologies at the PSDF, a series of conceptual commercial plant
designs has been completed in partnership with the DOE and the Electric Power Research
Institute (EPRI). Six TrIG combined cycle cases ha been developed to investigate the
relative costs and benefits of oxygen-blown or air-blown gasification, of stack gas or syngas
cleanup, and of carbon dioxide capture. These cases are all based on a 2x1 GE7FA+e
combined cycle fueled by syngas from two Transport Gasifiers using Powder River Basin
(PRB) sub-bituminous coal. Detailed performance modeling and cost estimation have shown
that the optimal configuration for power production without carbon dioxide capture includes
air-blown gasification and cold syngas cleanup. Airblown gasification was also shown to be
preferable when carbon dioxide is captured in a TrIG combined cycle system.
SESSION 14
SYNTHESIS OF LIQUID FUELS, CHEMICALS, MATERIALS AND
OTHER NON-FUEL USES OF COAL: COKE AND OTHERS
14-1
Hydrothermal Extraction of Brown Coals for Their Effective Utilization
Kouichi Miura, Hiroyuki Nakagawa, Masato Morimoto, Ryuichi Ashida, Kyoto
University, JAPAN
A novel coal conversion process was proposed: the method combines "a hydrothermal
extraction of brown coal (HT-Extraction, extraction of brown coal by inherent water
under hydrothermal condition)" and "a catalytic hydrothermal gasification of the
extract (CHT-Gasification)" both of which are performed under the exactly same
conditions of less than 350°C and less than 20 MPa. The HT-extraction intends to
increase the amount of organic compounds in the aqueous phase and the CHT-
Gasification gasifies the organic compounds in the aqueous phase using a novel Nisupported
carbon catalyst developed by the authors, producing combustible gas rich in
CH 4 and H 2 . Then the proposed process is expected to be not only a dewatering/
upgrading process of brown coal but also an effective brown coal gasification process.
To elucidate the behaviors on the HT-Extraction, several brown coals were treated in
flowing water or different concentrations of phenol aqueous solutions at temperatures
of 350°C. Experiments combining the extraction and the catalytic reaction process
were also performed using an Australian brown coal to examine the validity of the
proposed concept.
14-2
The Characterization of Cokes from Co-coking of Decant Oil and Coal
Parvana Gafarova Aksoy, Caroline Burgess Clifford, Leslie Rudnick, Harold H.
Schobert, The Pennsylvania State University, USA
Researchers at The Pennsylvania State University have been involved for the last
fifteen years in the development of thermally stable jet fuel. The focus of production of
this fuel is to incorporate coal or coal derived materials into existing oil refinery
operations. Penn State’s researchers have clearly shown that the kinds of chemicals in
the fuel that make it stable at 900°F (hydroaromatics and naphthenes) can be derived in
abundant amounts from coal. The overall objectives of refinery integration project are:
1) Investigate and develop an understanding of the most promising refinery integration
of all process streams resulting from the production of a coal-based jet fuel. 2)
Demonstrate the quality of each of the process streams in terms of refinery
requirements to maintain a stable, profitable refinery operation. 3) Demonstrate the
performance of key process streams in practical testing used for application of these
streams. Therefore, the project focus is to examine the characteristics and quality of the
streams, such as gasoline, diesel fuel, fuel oil, and coke and to determine the effects of
those materials on other unit operations in the refinery. The work presented will focus
on the blending of coal with decant oil as delayed coker feed. The objective of this
work is to evaluate coke from co-coking of decant oil and coal. The affect of coal to
coking of decant oil will be examined. The unique pilot-scale coking unit was used for
performing coking and co-coking experiments. This work mainly focused on
characterization of uncalcined and calcined coke samples. Densities and ash contents
were determined for calcined and uncalcined coke samples. X-ray diffraction
technique was used for evaluation the degree of structural anisotropy in coke samples.
14-3
Co-pyrolysis of Hydrothermally Upgraded Brown Coal
and Wax Formed From Waste Plastics
Susan Roces, De La Salle University, USA
Ryuichi Ashida, Masato Morimoto, Kouichi Miura, Monthicha Pattarapanusak, Kyoto
University, USA
The authors have recently presented a new method that not only removes water from
brown coal but also separates the coal into upgraded coal and extract of low molecular
mass compounds. Brown coals were hydrothermally treated using flowing liquid water
at around 350°C. The treatment of an Australian brown coal, Loy Yang, resulted in
12
obtaining 46% upgraded coal and 46% extract. It was found that the upgraded coal
contained much less oxygen than the raw coal and its elemental composition was close
to higher rank coals. However, the upgraded coal was still not like bituminous coals
and it will need some technique to be utilized more effectively. In this study copyrolysis
of the upgraded coals and waxes formed from waste plastics was investigated
as one of the methods of their effective utilization. Waxes were prepared through
pyrolysis of high density polyethylene, polypropylene, and polyethylene terephtalate.
Upgraded coals were then impregnated with the waxes by treatment in an autoclave at
200°C under pressure. The mixtures of coal and wax were rapidly heated up to 1040°C
at about 3000°C/s using a Curie point pyrolyzer in an inert atmosphere. It was found
that char yield was greatly enhanced by a factor of 1.1 to 1.3 compared to the char
yield of the upgraded coals and waxes when pyrolyzed independently. Even at a slower
heating rate (0.17°C/s) the char yields increased by a factor of 1.2 for all waxes. Since
no such effect was found when using raw brown coal instead of the upgraded coal, it
was suggested that the improvement of the structure of brown coal by our method
could enhance interactions between the coal and the wax when co-pyrolyzed.
14-4
Structural Characterization of Alternative Binder Pitches for Carbon Anodes
Uthaiporn Suriyapraphadilok, David J. Clifford, Caroline E. Clifford, Harold H.
Schobert, The Pennsylvania State University, USA
John M. Andresen, University of Nottingham, UNITED KINGDOM
The demand for coal tar binder pitch in the aluminium industry accounts for about 75% of
the pitch market. Since the production of coal tars is rapidly decreasing in the United States
as well as throughout the world, the development of alternative binders should be
considered. The objective of the present work was to understand the chemistry of alternative
pitches from different origins and processes and compare with the well-developed coal tar
binder pitch. The pitch samples studied included a coal tar pitch, coal-extracted pitch,
gasification pitch, and laboratory-generated co-coking pitch. Coal tar binder pitches are
traditionally obtained from coal tars that are the by-product of bituminous coal coking
process used to make coke for blast furnaces in iron production. Gasification pitches are
distilled by-product tars produced from the coal gasification process. A production of coalextracted
pitches involves a pre-hydrogenation of coal followed by extraction using a dipolar
solvent. The co-coking pitch is a unique material derived from co-carbonization of coal and
decant oil under the conditions simulating a delayed-coker in our laboratory. All samples
were characterized by nuclear magnetic resonance (NMR) spectroscopy and laser desorption
mass spectrometry (LDMS). A comparison of average structure and molecular mass of these
pitch samples will be presented.
14-5
Supercritical Fluid Extraction of Diterpenes from Slovak Brown Coal
Udmila Turcani, Slovak Academy of Science, SLOVAK REPUBLIC
Franciszek Czechowski, Institute of Organic Chemistry, POLAND
Helena Sovava, Institute of Chemical Process Fundamentals AS CR, CZECH
REPUBLIC
Franti ek Verbich, Upper Nitra Mines, SLOVAKIA
Anton Zubrik, Silvia Uvanova, Institute of Geotechnics, SLOVAKIA
The finely powdered Handlova brown coal was extracted under supercritical
conditions at temperature of 323K with CO 2 and at temperatures 573 and 613K with
cyclohexane isopropanol mixture (9:1 v/v). Particles size of the powdered coal used to
extraction (Ad = 7.7%, Cd = 54 %) averaged around 6.5m (planetary mill Molinex).
The coal granularity under 10 m, according to literature, assured highest extract yield.
The extracted material amounted 0.42, 13.95 and 7.99% of raw coal mass at the above
mentioned temperatures, respectively. The supercritical fluid extracts were
preliminarily separated to three fractions by semipreparative HPLC (HP 1090,
Hewlett-Packard, Germany) equipped with UV detector (HP 1090, Series II) using
chromatographic column Lichrosphere 100 RP 18 (mobile phase: acetonitrile-water).
The fraction selected on the base of elution time within narrow range found for elution
time of kaurenoic acid (14.647 minutes, UV wavelength 210 nm) was further analyzed
by GC/MS (Agilent Technologies 6890N - Folsom, USA). This fraction constituted
high abundance of diterpenoic compounds: 16 H kaurane - C 20 H 34 , kaurenoic acid -
C 20 H 30 O 2 , abietatriene C 20 H 30 , ferruginol C 20 H 30 O and others. The data on fungicidal
activity of the terpenoic compounds separated from coal will be presented.
SESSION 15
COMBUSTION TECHNOLOGIES – 3: OXY-FUEL COMBUSTION
15-1
Expanding the Clean Coal Portfolio: Oxyfiring to Enhance CO 2 Capture
Glen Jukkola, Nsakala Nsakala, Greg Liljedahl, Frank Kluger, Alstom Power, USA
A portfolio of Clean Coal power generation technologies are on path to commercialization in
response to the need for near-zero emissions and CO 2 capture for storage/sequestration.
Technology providers are responding to generators needs with innovations ranging from
higher efficiency to post-combustion capture to alternative plant designs. Among the

promising Clean Coal technologies under development to address CO 2 emissions is oxygen
combustion. By firing with nearly pure oxygen, atmospheric nitrogen is not introduced into
the products of combustion and a concentrated CO 2 flue gas stream is produced. This CO 2
stream can be dried and compressed for sequestration, or further processed into a high purity
CO 2 product for varied uses including enhanced oil recover (EOR) or enhanced gas
recovery.
Oxyfiring is an attractive option for coal combustion for a number of reasons, including:
1. It uses proven, reliable, commercially available Pulverized Coal (PC) and Circulating
Fluidized Bed (CFB) technology
2. Oxygen can be readily produced by commercial cryogenic air separation
3. CO 2 cleanup, compression, and liquefaction is proven technology
It is anticipated that initial deployment of oxyfiring would be for commercial EOR
application, with co-production of electricity, use of CO 2 for oil field stimulation, and use of
by-product nitrogen (from oxygen production) for oil field pressurization. Oxyfiring is also a
stepping stone to additional advanced Clean Coal processes, including chemical looping.
ALSTOM is actively participating with the US-DOE as well as European partners, Utilities,
and academia to design and demonstrate oxyfiring utilizing PC and CFB technologies. This
paper will address the key aspects of the design of oxyfired boilers and the timeline for
commercialization. Recent studies have developed important knowledge on heat transfer,
combustion efficiency, and emissions. This data will form the design basis for scale-up for
oxyfired demonstration plants. The next step is to demonstrate oxyfiring at a scale of 10 to
100 MWe. The goal is to provide coal-based power generation options that are clean, cost
competitive, and reliable.
15-2
Comparisons among Different Implementation Options for
Coal-Fired Oxyfuel Power Plants
Xinxin Li, Columbia University, USA
Climate change concerns over carbon dioxide emissions from fossil fuel combustion have
led to the development of carbon dioxide capture technologies for coal fired power plants.
One particularly promising approach known as oxyfuel-combustion replaces air in the
combustion chamber with a mixture of pure oxygen and carbon dioxide rich recycled flue
gas. The resulting concentrated stream of CO 2 can be pressurized and transported from the
plant to a storage site where it is disposed off safely and permanently. Oxyfuel-combustion
based power plants are shown to be a very competitive option for CO 2 capture. This study
evaluates three major strategies for introducing oxyfuel power plants: (1) construction of
new oxyfuel plants; (2) retrofit of existing power plants to oxyfuel plants; (3) construction of
new conventional plants that are designed for a cost-efficient future retrofit. The paper
considers the engineering aspects in the three cases and develops an economic analysis to
compare the three options with each other and with a conventional coal fired power plant
that provides the baseline case. The net present values of the different plants are calculated
and compared; a sensitivity analysis is performed and the implications of different
sensitivities of the key parameters are discussed in the context of long-term investment
decisions. The study suggests that under a wide range of assumptions building new oxyfuel
power plant is the most attractive options for power plant investors. Retrofit options are not
competitive unless the plant has a remaining lifetime of more than twenty years. This is
rarely the case for today s power plant fleet in the United States. The situation changes,
however, if the upgrade can significantly increase the remaining lifetime of the plant. The
sensitivity analysis indicates that the electricity price and CO 2 credit price heavily influence
the choice of plant options. An increase in the price of CO 2 credit makes new oxyfuel plant
even more attractive, the decrease in the price of CO 2 credit makes the base plant more
attractive, the minimum CO 2 credit for oxyfuel power plants to be competitive with the base
plant is $25.30/ton. An increase in the price of electricity also makes the base plant more
attractive; at electricity prices greater than 7.15 c/kWh, new oxyfuel power plant is not
attractive as the loss in additional electricity outweighs the gain from carbon credits. Under
those conditions, the best investment is a conventional coal-fired power plant.
15-3
An Optimized Supercritical Oxygen-Fired Pulverized Coal
Power Plant for CO 2 Capture
Andrew Seltzer, Zhen Fan, Foster Wheeler North America Corp., USA
Timothy Fout, DOE/NETL, USA
The Department of Energy and Foster Wheeler have jointly developed a conceptual
supercritical pulverized coal (PC) boiler plant design that will allow practical carbon dioxide
(CO 2 ) capture for future CO 2 sequestration efforts. CO 2 is a major greenhouse gas, which has
been linked to global climatic change. A novel process for CO 2 sequestration is proposed
utilizing a supercritical oxygen-fired PC boiler, which, as part of a Rankine steam cycle,
forms a high efficiency, zero emission, stackless power station. Coal is combusted in the
furnace where the oxidizer consists of a mixture of O 2 and recycled flue gas, which contains
primarily CO 2 gas. Recycling of the flue gas is utilized to control flame temperature in the
boiler furnace to maintain acceptable waterwall temperatures. NO x formation is minimized
by combustion staging via low NO x burners and over-fire gas ports. Virtually all of the flue
gas sensible and latent heat energy is recovered in the heat recovery area of the boiler where
steam superheaters, steam reheaters, gas recuperators, and water economizers are located.
The effluent of the plant is virtually pure CO 2 , which is condensed, pressurized, and piped
from the plant to the sequestration site. Overall power plant system and component designs
are presented for a 475 MW (gross) supercritical coal-fired plant. The power plant system
cycle was optimized to minimize the overall power plant heat rate and facilitate CO 2
sequestration. Vent gas power recovery and vent gas recycle for O 2 recovery are
incorporated to minimize the CO 2 removal auxiliary power. The furnace and heat recovery
area components were designed to optimize the location and design of the furnace, burners,
over-fire gas ports, and internal radiant surfaces producing a more compact and efficient
design than air-fired furnaces. A detailed thermal/hydraulic design and analysis of the
waterwall geometry was conducted to avoid high metal temperatures due to dryout or
departure from nucleate boiling and to avoid flow instabilities. An investigation of the
improvement in cycle efficiency and the reduction in CO 2 removal penalty due to the
integration of advanced oxygen separation techniques is also presented.
15-4
Numerical Modeling of the Effect of Aerodynamics on NO x Emissions and
Char Burnout for Combustion of Coal in O 2 /CO 2
Sarma V. Pisupati, Prabhat Naredi, The Pennsylvania State University, USA
Combustion of coal in O 2 and Recycled Flue Gas (RFG) medium is one of the approaches to
obtain pure CO 2 stream from an existing power plant that can be sequestered to reduce the
greenhouse gas emissions into the atmosphere. Other advantages of this approach are an
increase in char burnout and reduction in NO x emissions. However, in order to retrofit the
existing boiler, approximately 30% O 2 and 70% CO 2 blend is required in the oxidizer
stream. This leads to a decrease in the volume of combustion gases which subsequently
changes the mixing pattern of oxidizer and coal particles inside the boiler. If coal particles
and oxygen are not well mixed, NO x emissions will be altered due to local fuel rich pockets.
In the present paper, an, axi-symmetric, 2-D computational model was developed using
Fluent CFD code, for a 1,000 lb steam/hr “A-frame”, water-tube research boiler to identify
and optimize the key variables that influence the NO x emissions. Model predictions were
compared with the experimental measurements of gas temperature, particle speed and
gaseous emissions for Upper Freeport (Bituminous) coal fired in air medium. The effects on
gaseous emissions such as NO x , and CO 2 due to change in combustion gas loading and
presence of increased CO 2 are predicted under similar operating conditions. The effect of
swirl number was analyzed to minimize the NO x emissions from the boiler in enriched
O 2 /CO 2 medium.
15-5
Experimental and Modeling Study on Particle Size Distribution
Effects Due to Oxy-Combustion of Coal
Achariya Suriyawong, Scott Skeen, Richard Axelbaum, Pratim Biswas, Washington
University in St. Louis, USA
O 2 -CO 2 coal combustion is a promising technology for mitigating the increase of CO 2
in the atmosphere. Advantages include the potential for CO 2 capture, reduction of NO x
emissions, and improvement in combustion efficiency. This paper presents an
experimental study developed to examine the effects of O 2 -CO 2 combustion on fine
particle formation and flame stability from both a laminar flow drop-tube furnace and a
piloted coal flame reactor. The results were compared with those obtained under
conventional combustion conditions (air) and differences are highlighted.
SESSION 16
ENVIRONMENTAL CONTROL TECHNOLOGIES:
SO x , NO x , PARTICULATE AND MERCURY – 1
16-1
A Multi-Pollutant Wet Scrubber for Capture of SO 2 , NO x and Hg
Nick Hutson, Ravi Srivastava, Brian Attwood, US EPA, USA; Carl Singer, Arcadis,
USA
An enhanced wet scrubber that removes SO 2 , NO x and Hg (both Hg 2+ and Hg 0 ) from coal
combustion flue gas has been developed and tested at the EPA/RTP laboratories. In this
multi-pollutant system, a traditional limestone (or other alkali) scrubber solution is enhanced
with an additive that promotes the capture of NO x and Hg species. In the optimized system,
SO 2 (1800 ppm), NO x (200 ppm) and Hg 0 (30 ppb) were all captured at near 100%
efficiency. Results from this testing will be provided and discussed in the presentation.
16-2
Study on NO Reduction by Coal and Chars in an Entrained Flow Reactor
Ping Lu, Shengrong Xu, Xiuming Zhu, Nanjing Normal University, P.R. CHINA
Rapid pyrolysis and NO reduction efficiency of five Chinese pulverized coals and their chars
produced at the different conditions under coal reburning were systematically carried out in
an entrained flow reactor (EFR). The results indicate that the release of carbon and nitrogen
is almost the same as the coal mass loss, however, hydrogen release fraction is significantly
larger than the coal mass loss and the release fraction of carbon, nitrogen. The NO reduction
efficiency decreases with increasing primary-zone or reburning-zone air: fuel stoichiometry
ratio. The char contributions to total NO reduction efficiency increase with increasing
proximate volatile matters. The relative contribution of char to total NO reduction at the
13

conditions of SR1=1.0 and SR1=1.2 is significantly larger than that at SR1=1.1 for high
volatile coal at a fixed reburning fraction.
16-3
Low-Temperatures Reduction of NO Using V 2 O 5 /AC Catalyst from Flue Gas
Zhanggen Huang, Zhenyu Liu, Pingguang Liu, Xianniu Hong, Zenghou Liu, Jue Ge,
Chinese Academy of Sciences, CHINA
V 2 O 5 /AC catalyst showed higher selective catalytic reduction (SCR) activity of NO in
the presence of SO 2 at lower temperatures. Further study showed the V 2 O 5 /AC catalyst
deactivated easily in the presence of H 2 O and SO 2 , which is due to the excess position
of ammonium-sulfate salts on the catalyst surface. The position rate of ammoniumsulfate
salts is governed by the rate difference between its formation and reaction with
NO. Through decrease in the formation rate of ammonium-sulfate salts or increase in
the reaction rate of ammonium-sulfate salts and NO, such as decrease in V 2 O 5 loading,
mineral content of AC and space velocity, or increase in reaction temperature, the
catalyst can be used stably at a space velocity of below 9000 h -1 and temperature of
250°C in the presence of SO 2 and H 2 O. In the real existing burner system, a fixed bed
reactor, including reaction and regeneration system, is explored and the catalyst shows
higher NO conversion at 150°C and 1000 h -1 for 30 day.
Argonne National Laboratory (ANL) is developing dense cermet (i.e., ceramic-metal
composite) membranes for separating hydrogen from mixed gases, particularly product
streams generated during coal gasification and/or methane reforming. Hydrogen separation
with these membranes does not require electrodes or an external power supply, and
hydrogen separated from the mixed gas stream is of high purity, so post-separation
purification steps are unnecessary. Cermet membranes were prepared by mixing ≈50 vol.%
Pd with Y 2 O 3 -stabilized ZrO 2 . Using several feed gas mixtures, we measured the
nongalvanic hydrogen permeation rate, or flux, for the cermet membranes in the temperature
range of 500-900°C. This rate varied linearly with the inverse of membrane thickness and
reached ≈33 cm 3 [STP]/min-cm 2 at 900°C for an ≈15-μm-thick membrane on a porous
support structure when 100% H 2 at ambient pressure was used as the feed gas. Hydrogen
flux measurements in H 2 S-containing atmospheres showed that the cermet membranes are
stable for up to 1200 h at 900°C in gases that contain 400 ppm H 2 S. We have also measured
the hydrogen flux through the cermet membrane at 500 and 600°C using a feed gas of 73%
H 2 /400 ppm H 2 S/balance He. Because formation of palladium sulfide (Pd 4 S) can seriously
degrade hydrogen permeation though Pd-containing membranes, we evaluated the chemical
stability of the membranes by equilibrating samples in 73% H 2 /400 ppm H 2 S/balance He at
temperatures in the range 400-900°C to determine the conditions under which palladium
sulfide (Pd 4 S) forms. The present status of membrane development at Argonne will be
presented in this paper.
16-4
SCR/SNCR Optimization with In-Situ Ammonium
Bisulfate Fouling Measurement
Charles Lockert, Breen Energy Solutions, USA
17-2
Single Membrane Reactor Configuration for Separation of
Hydrogen, Carbon Dioxide and Hydrogen Sulfide
Shain Doong, Raja Jadhav, Gas Technology Institute, USA
Ammonia slip has long been considered one of the primary variables relating to overall
performance of both SCR and SNCR NO x control processes. However, because ammonium
bisulfate generation is related not only to ammonia slip, but the presence of SO 3 , moisture,
and excess O 2 as well, its presence cannot be accurately predicted by an ammonia slip
instrument alone. A novel technology has been introduced for the direct measurement of
ammonium bisulfate related fouling tendencies. This instrument directly measures and
reports both the formation temperature and the fouling potential of the ammonium bisulfate
based fouling compounds. Data will be presented on the ammonium bisulfate instrument’s
response, under full scale plant conditions, to varying levels of ammonia slip, its sensitivity
to extremely low levels of ammonia, correlation between detected ammonium bisulfate
activity and site specific air heater fouling as well as correlation between detected
ammonium bisulfate activity and ammonia-on-ash concentrations. Further, this
measurement feedback may be used to optimize the operation of SCR and SNCR systems.
The measurement would be used to maximize NO x reduction while minimizing fouling
across various loads and operating conditions. The specific control actions that can be taken
include:
• modifying urea/ammonia injection rates,
• controlling air heater gas outlet temperature by controlling the amount of hot flue gas
air heater bypass to maintain AH cold-end temperature above the AbS dew point, or
• controlling air heater inlet air temperature with air preheating by steam coils to
maintain AH cold-end temperature above the AbS dew point.
A grid of AbS measurements may also be used to monitor SCR catalyst fouling as part of a
catalyst management program. The paper will include performance results from several US
generating stations operating either SCR and/or SNCR post combustion NO x systems.
16-5
Current Status of Development of Sieving Electrostatic Precipitator
Hajrudin Pasic, Zahirul Khan, Ohio University, USA
The paper describes a recently-proposed Sieving Electrostatic Precipitator (SEP)-- a device
suitable for efficient, cost-effective cleaning of polluted gases of both large and ultra fine
particulates in a very broad temperature range. In the last several years, a large number of fly
ash collection-efficiency tests have been conducted, first on a bench-size SEP with 6-by-6
inches screens, at room temperature, high temperature (300-350°F), and several tests at
1500°F. Most recently, the SEP has been demonstrated in a laboratory pilot-scale setting
with 6-by-2 foot screens at room temperature. All the results confirm that this technology
provides high fly ash collection efficiency, including extremely efficient removal of ultra
fine, submicron particulates. Finally, the joint effort of Ohio University (OU), Ohio Coal
Research Office (OCDO), American Electric Power (AEP), and Electric Power Research
Institute (EPRI) is in progress to build and test the SEP pilot unit as a part of a slipstream in
AEP’s Conesville (OH) Power Plant. Some of those preliminary test results will be
presented as well.
SESSION 17
HYDROGEN FROM COAL: MEMBRANE SEPARATION
17-1
Dense Cermet Membranes for Hydrogen Separation from Mixed Gas Streams
U. Balu Balachandran, Tae H. Lee, Ling Chen, Sun-Ju Song, Stephen E. Dorris,
Argonne National Laboratory, USA
The objective of this research project is to develop a novel single membrane reactor process
that can consolidate two or more downstream unit operations of a coal gasification system in
a single module for production of a pure stream of hydrogen and a pure stream of carbon
dioxide. The overall goals are to achieve higher hydrogen production efficiencies, lower
capital costs and a smaller overall footprint than what can be achieved by utilizing separate
components for each required unit process/operation in conventional coal to hydrogen
systems. This novel membrane reactor process that is under development combines
hydrogen sulfide removal, hydrogen separation, carbon dioxide separation and water-gas
shift reaction in a single membrane configuration. The carbon monoxide conversion of the
water-gas-shift reaction from the coal derived syngas stream is enhanced by the
complementary use of two membranes within a single reactor to separate hydrogen and
carbon dioxide. Consequently, hydrogen production efficiency is increased. The single
membrane reactor configuration produces a pure H 2 product and a pure CO 2 permeate
stream that is ready for sequestration. In this work, Gas Technology Institute, partnered with
Arizona State University, is evaluating the technical feasibility of this “one-box” concept by
focusing on membrane material development. A new class of high-temperature nonporous
membranes for separation of CO 2 from coal-derived syngas is being developed. Supported
CO 2 membranes are synthesized using a variety of techniques, including in-situ
impregnation and vacuum infiltration. Additionally, disc-shaped membranes are prepared by
pressure compaction of precursor powders. The prepared membranes are analyzed for
physical and chemical properties and evaluated for CO 2 permeation. This paper will discuss
the simulation results for this novel single membrane reactor process in comparison with the
conventional H 2 -selective or CO 2 -selective membrane reactor process. The modeling
approach is based on thermodynamic analysis using a commercial flowsheet simulator to
calculate the expected performances. The preliminary results from membrane synthesis and
characterization will also be presented. The project is sponsored by DOE’s National Energy
Technology Laboratory and Illinois Clean Coal Institute.
17-3
Alloy Membranes for Hydrogen Permeation
Gokhan Alptekin, Sarah DeVoss, Robert Amalfitano, TDA Research, USA
J. Dough Way, Paul Thoen, Mark Lusk, Colorado School of Mines, USA
U.S. coal reserves nearly equal the total proved world conventional oil reserves – a 250-year
supply of U.S. coal at today’s domestic production rates. Hydrogen represents a clean
alternative fuel and its clean production from coal in tandem with carbon sequestration could
reduce the environmental concerns associated with the widespread use of coal energy in
stationary power applications. Gasification technologies have shown the potential to produce
clean synthesis gas from coal with virtually zero pollutant emissions, including the emissions
of carbon dioxide (CO 2 ). In this approach, coal is first gasified to produce a carbon
monoxide (CO)-rich synthesis gas. In several processing steps the impurities in the syngas
are removed and the CO content of the syngas is reduced by converting CO to hydrogen
(H 2 ) in a two-step water-gas-shift reaction. Finally, the hydrogen is separated from other
compounds, mainly CO, CO 2 and water. Currently, there are no coal-based facilities that
produce both hydrogen and electric power. However, system level studies indicate that the
efficiency of the coal-to-hydrogen plant could be enhanced if the WGS and H 2 separation
were combined into a single step and carried out at temperatures compatible with the
contaminant control step (350-400°C).
The hydrogen separation membrane should provide robust performance, high hydrogen
throughput, high selectivity and recovery and long-life at low cost. Palladium (Pd) alloy
membranes have all these attributes. The hydrogen separation capability of Pd alloy
membranes is well known with applications in hydrogenation/dehydrogenation reactions and
recovery of hydrogen from petrochemical plant streams. Pd alloy membranes provide very
14

high selectivity (theoretically producing a 100% purity H 2 product). Unlike the ceramic
membranes developed to date (which could only achieve up to 90% H 2 selectivity in a single
pass and requires cascades of membrane modules to provide higher purities), Pd alloy
membranes can achieve high selectivity in a single module. Pd alloy membranes also
achieve very high hydrogen flux, with at least an order of magnitude higher flux than the
high temperature dense ceramic membranes. The operating temperature of the Pd alloy
membranes (300-600°C) is also well matched to that of the WGS process (200-600°C),
where the reaction kinetics and the thermodynamic equilibrium both favor formation of
hydrogen. The operating temperature for PSA systems (40-80°C) are too low for good WGS
reaction kinetics and the equilibrium is unfavorable at the high operating temperature of the
dense ceramic membranes (600-800°C). However, in spite of these potential benefits,
several hurdles inhibit commercial implementation of this membrane technology. To be
commercially viable: 1) the robustness of these membranes must be improved, 2) the cost of
the membrane must be reduced, and 3) the sealing problems encountered when integrating
the membrane into the process equipment must be eliminated; a key problem for any
membrane system.
TDA Research Inc., in collaboration with Colorado School of Mines (CSM) is developing a
sulfur and CO-tolerant membrane to produce the clean hydrogen from syngas using Pd
membrane films prepared on a variety of supports (e.g., symmetric ceramic supports and
porous stainless steel supports). This paper summarizes the results of the membrane
development and testing efforts. Membranes that showed superior properties in screening
tests using hydrogen/nitrogen mixtures were further evaluated under representative
conditions (the baseline gas composition used in these evaluations were 51% H 2 , 26% CO 2 ,
21% H 2 O and 2% CO vol.). In general, membranes showed very good stability in water gas
shift environment and were tested for several days with stable permeance and selectivity. We
examined the effect of operating parameters including temperature, pressure and H 2 recovery
on membrane performance. We also investigated the impact of CO, CO 2 and H 2 S
concentration in the reformate gas on the H 2 permeation and selectivity of the membrane.
17-4
High-Pressure Operation of Dense Hydrogen Transport Membranes for
Pure Hydrogen Production and Simultaneous CO 2 Capture
Xiaobing Xie, Carl R. Everson IV, Michael V. Mundschau, Harold A. Wright, Paul J.
Grimmer, Eltron Research Inc., USA
Eltron has developed a family of dense inorganic membranes that enable high H 2 separation
rates with essentially 100% selectivity to H 2 . The membranes are designed to operate at the
same conditions as high-temperature water-gas shift (WGS) reactors (320−440°C) and can
be operated with up to 1,000 psi pressure differential across the membrane. In synthesis gas
systems that incorporate WGS, the membranes facilitate efficient, low cost separation of H 2
and CO 2 at high pressure, enabling efficient capture of CO 2 . The membranes are being
developed to work with refinery waste streams as well as synthesis gas derived from natural
gas, liquid hydrocarbons, coal, petroleum coke and biomass. The membranes may be ideal
for natural gas or coal-based IGCC applications with or without hydrogen export. Compared
to palladium-based membranes, the Eltron membrane exhibits 20 times the flux for a given
set of conditions and costs about 10 times less. The high hydrogen permeability and low cost
of the membrane materials allows the use of relatively thick membranes, which is crucial for
their operation under high pressure differential. This technology has many advantages over
competing hydrogen separation technologies. Advantages are listed as follows: (1) the
membranes allow the capture of CO 2 at high pressure. The CO 2 is essentially captured at
gasification or reforming pressure; (2) the membrane is low cost with long membrane life.
Stability tests have been conducted for over eleven months on line with high flux retained;
(3) the membranes, in principle, will work with synthesis gas generated from any source
including coal, petroleum coke, natural gas, or biomass; (4) essentially 100% pure hydrogen
is separated since the membrane works by transporting dissociated hydrogen across the
membrane material; (5) hydrogen recoveries of 90% or higher are possible; (6) the
membranes can be operated under high permeate pressures of pure hydrogen, and thus the
costs associated with hydrogen compression can be substantially reduced; (7) the
membranes can be integrated with commercial high temperature water-gas shift catalysts.
The integrated membrane/WGS reactor has been demonstrated capable of achieving
significantly higher CO conversion over the thermodynamic equilibrium limitation.
Eltron was recently awarded a program from the United States Department of Energy aimed
at scaling up these membranes for possible use in the FutureGen coal-based power and
hydrogen plant. This paper discusses recent advances in the development of these
membranes including experimental demonstrations of the above mentioned advantages, and
membrane performance.
17-5
Effect of Nanocrystalline Catalysts on the Desorption Temperature of
MgH 2 for Hydrogen Storage Applications
M.S. Seehra, P. Dutta, S. Pal, J. Fortune, West Virginia University, USA
MgH 2 is an attractive hydrogen storage material with 7.6 wt% hydrogen capacity and with a
safe endothermic desorption of hydrogen at Td ≈ 4320°C [1]. However for practical
applications, this Td is too high. In this work, we will report recent results of our experiments
to lower Td. Our approach is based on the use of nanocrystalline Ni to reduce Td. Our recent
experiments using 20 nm Ni nanoparticles mixed ultrasonically in the amount of 1 mol %
with a commercial β-MgH 2 followed by ball milling of the mixture for 15 minutes, have
yielded Td ≈ 2700°C as revealed by thermogravimetric analysis (TGA) and differential
15
scanning calorimetry (DSC). X-ray diffraction (XRD) of the sample at different stages of the
reaction shows that sonicating alone shifts Td to 3400°C, without any chemical changes in
Ni or β-MgH 2 . However, milling converts a part of β-MgH 2 to γ-MgH 2 . Additional
experiments are underway to determine whether the lower Td ≈ 2700°C corresponds to γ-
MgH 2 . From our experiments, it is also evident that lowering the crystalline size of both
MgH 2 and the Ni catalyst and thorough mixing is likely to further reduce Td. An additional
motivation to lower Td is to avoid the formation of Mg 2 Ni which in our experiments forms
at 2700°C. This may be possible if the amount and crystallite size of the Ni catalyst are
further reduced. Results of these experiments, now in progress, will be reported.
* Work supported by U.S Department of Energy, Contract # DE-FC26-05NT42456.
[1] See the review by J. Huot in Nanoclusters and Nanocrystals edited by H.S.Nalwa (Amer.
Sci.Publishers, 2003) pages 53-85.
SESSION 18
GLOBAL CLIMATE CHANGE:
GREENHOUSE GAS UTILIZATION AND NOVEL CONCEPTS
18-1
Use of Coal Mine Methane in a Microturbine at CONSOL Energy’s Bailey Mine
Deborah Kosmack, Richard A. Winschel, CONSOL Energy Inc., USA
Patrick Rienks, Jay Johnson, Ingersoll-Rand Energy Systems, USA
CONSOL Energy Inc Research & Development and Ingersoll Rand Energy Systems, with
partial funding by the Clean Air Fund provided by the Pennsylvania Department of
Environmental Protection, are installing a low-emission 70 kW microturbine generator on a
large underground coal mine in Pennsylvania to reduce emissions of methane by capturing
them and converting them into usable electricity. The generator will be fueled with coal
mine methane that is currently being vented as part of the mine’s ventilation system. Coal
mine methane is one of several major sources of anthropogenic methane, accounting for
about 10% of anthropogenic methane emissions in the United States. Methane is the second
most important non-water greenhouse gas, with a global warming potential 21 times as great
as that of carbon dioxide (CO 2 ) on a mass basis. Thus, any coal mine methane that is emitted
rather than utilized simultaneously represents a lost potential resource and the emission of a
powerful greenhouse gas. The project objectives are to: 1) convert the low and variable
concentrations of methane contained in coal mine methane gas that would otherwise be
vented to the atmosphere to electricity; 2) provide the generated electric power to an existing
electric power grid; 3) donate the value of the electricity generated during the project period
to a local school district; and 4) determine the quantity of useful energy that can be
economically produced when processing coal mine methane from a working coal mine and
perform a techno-economic evaluation of the system. When operating at 95% capacity factor
and a heat rate of 13,550 Btu/kWh HHV (higher heating value), the 70 kW generator will
produce 583 MWh of electricity as it consumes 7,954,000 cubic feet of methane, with a
global warming potential equivalent to 3,522 short tons of carbon dioxide, each year. Startup
and commissioning of the system will be followed by 12 months of operations.
18-2
Green Power Technologies for High Ash Indian Coals-Evaluation of
CO 2 Mitigation Options,
D.N. Reddy, Centre for Energy Technology, INDIA; V.K. Sethi, Rajiv Gandhi
Technological University, INDIA
The Global concern for reduction in emission of green house gases (GHG) especially CO 2
emissions are likely to put pressure on Indian Power System for adoption of improved
generation technologies. Although India does not have GHG reduction targets, it has actively
taken steps to address the climate change issues. Mitigation options for CO 2 reduction which
have been taken up vigorously include GHG emission reduction in power sector through
adoption of Co-generation, Combined cycle, Clean Coal Technologies and Coal
Beneficiation. CO 2 emissions per unit of electricity generated are significantly high in India
as large proportion of power generated comes from low sized, old and relatively inefficient
generating units which constitute over 50% of our total installed capacity of about 103,000
MW. The technology up gradation through life extension of old polluting units is expected to
increase the generating efficiency of these units thereby reducing CO 2 emissions. Presently
about 32 power stations with 106 units of various capacities ranging from 30MW to 200MW
totaling to about 10,400 MW dated capacities are taken-up for Life extension (LE) during
10 th five year plan (2002-07). In addition to above about 60 Thermal Power plants units
(13,900 MW) have been taken up for Renovation and Modernization (R&M) in the country,
which is expected to contribute significantly in terms of CO 2 reduction.
A major thrust on CO 2 reduction on long term and sustainable basis would however come
through adoption of advanced technologies of power generation like Supercritical/Ultrasupercritical
power cycles, Integrated Gasification Combined Cycles (IGCC), Fluidized Bed
Combustion/Gasification Technologies and so on. A beginning towards adoption of super
critical units has already been made in the country and it is foreseen that super critical
technology would almost universally be adopted for all large sized pithead units in the
country. The attained efficiency gains of these technologies are likely to reduce the
environmental emissions especially CO 2 significantly. Adoption of higher parameters for
super critical units after sufficient feedback and operational experience would further reduce
these emissions to a great extent. A total additional efficiency of about 1.5-2% is normally

achieved for adoption of super critical parameters of 246-kg/cm 2 (g) and 537/565°C, chosen
for the first Supercritical Power Plant under planning with unit size of the order of 660 MW.
Adoption of still higher parameters would further enhance the efficiency. Attempts would
also need to be made to further enhance the efficiency of conventional pulverized coal fired
plant by adoption of ultra super-critical parameters. The main constraint being faced for
adoption of these technologies is the availability of requisite material to withstand
combination of high Pressures and temperatures encountered. A consortium of several
equipment manufacturers globally has pooled their resources to develop necessary materials
to overcome the constraints for adoption of ultra super-critical technology.
Another option for CO 2 reduction is increased use of natural gas. This provides improvement
in generation efficiency together with reduction in CO 2 emissions but would facilitate
environmental pollution control only up to a certain extent. With addition of more and more
generation capacity and also increasing CO 2 emissions from transport and other industrial
sectors, progressive de-carbonization of generation resources may have to be adopted in
certain regions/areas. Already, Natural Gas is being used in a big way in the country for
power generation and GT/CCGT stations accounted for about 10% of total generation in the
year 2001. The natural Gas resource crunch being faced at present, even though there is
quest for quick power generation restricts increased use of Natural gas in Combined Cycle
mode, limiting it to some specific priority areas only. Research work in this area to increase
the generation efficiency of Combined Cycle to an extent of 60% is already underway and
this goal is likely to be realized in near future. These technologies can then be adopted as and
when available. A much more efficient methodology of generating electricity from Natural
gas is on the anvil i.e. fuel cell technology which looks more promising source of Energy
option in future.
The present study is dedicated to environmentally benign Clean Coal Technologies for
burning high ash Indian Coals and middling, washery rejects and so on. The paper primarily
focuses on evaluation of various CO 2 mitigation options through use of these Green Power
Technologies.
18-3
Gas Treatment Concepts for IGCC with CO 2 -Separation
Hardy Rauchfuss, Sirko Ogriseck, Mathias Rieger, Bernd Meyer, Technische
Universitat Bergakademie Freiberg, GERMANY
Lignite-based power generation plays an essential role for energy supply in Germany.
Combustion of lignite in conventional PC power plants causes a specific CO 2 -emission up to
1,100 kg/MWh averaged [1]. This exceeds the specific CO 2 -emission of natural gas based
power generation by two or three times. The German government intends a reduction of CO 2
emissions by 21 % by 2012 compared to the year 1990. For a notable reduction of the CO 2 -
emission of power generation new concepts for high efficient power plants with options for
CO 2 -sequestration or polygeneration are essential. A promising possibility is IGCC with
CO 2 -Separation. All concepts in this investigation are determined for lignite gasification
based on fluidized bed gasification which was been developed for industrial scale in the
HTW-process. An IGCC with CO 2 -Separation includes nearly the same process steps as a
conventional IGCC without CO 2 -removal. However, additional equipment is necessary for
CO-conversion, CO 2 -separation and compression. Clean gas and raw gas CO-conversion, as
well as alternative concepts have been investigated in accordance with various concepts for
raw gas cooling and sour gas removal. Thus specific CO 2 -emissions in the range of 110
kg/MWh and 235 kg/MWh are achievable. This means a carbon retention rate of up to 89 %.
The calculations show net efficiencies between 39 and 42 % based on LHV. The costs of
electricity are estimated in the range of 60 to 90 €/MWh.
18-4
Optimal Design for Integrating CO 2 Capture and Fuel Conversion
Technologies in a 500 MWe Coal-Based Power Plant
Nari Soundarrajan, Meredith A. Hill, Jiahua Guo, Lu-Ming Chen, Vasudha Dhar,
Hyun Joe Kim, Ramanathan Sundararaman, Onur Mustafaoglu, Derek Elsworth,
Jonathan P. Mathews, Sarma Pisupati, Chunshan Song, The Pennsylvania State
University, USA
A conceptual study was conducted towards a new design for more efficient fuel conversion
and CO 2 capture in a future 500 MWe power plant that incorporates both new conversion
technologies to optimize plant efficiency and new carbon dioxide (CO 2 ) capture methods.
Conventional means of power generation without CO 2 capture (e.g., air-fired pulverized coal
combustion and fluidized bed combustion) formed base cases to evaluate advanced
combustion technologies with CO 2 capture. The following capture schemes were
investigated: 1) Pre-combustion decarbonization consisting of gasification or reforming
processes with CO 2 separation membranes; 2) Denitrogenation methods such as oxycombustion
and chemical looping combustion; 3) Post-combustion CO 2 recovery using
solvent absorption, membrane separation and solid adsorption. Evaluations were based on:
1) Efficiency of electricity generation; 2) Fuel consumption and CO 2 emitted per unit
electricity; 3) Feasibility of scale-up; and 4) Energy penalty associated with capture. Both the
methods of CO 2 capture and the technology of energy conversion were found to influence
the overall plant efficiency and amount of CO 2 that can be captured. Advanced combustion
technologies enable the production of concentrated CO 2 emission streams, but involve
complex process designs. Gasification-based processes and chemical looping combustion
emerged as efficient options for future coal-based power plants. These power generation
technologies were integrated with selected CO 2 capture technologies to recover a high
percentage of the CO 2 produced (> 90%) while maintaining reasonable power generation
efficiency (> 30%). The integrated combinations were optimized with respect to net power
generation efficiency, fraction of CO 2 captured, and scale-up considerations. An optimized
design balancing those parameters and scale is presented as a solution for a coal-based 500
MWe power plant.
18-5
Utilization of Carbon Dioxide from Coal-Fired Power Plant for the
Production of Value-Added Products
Daniel Van Niekerk, Brandie Markley, Arun Ram Mohan, Victor Rodriguez-Santiago,
David Thompson, Derek Elsworth, Jonathan P. Mathews, Sarma Pisupati, Chunshan
Song, Yan Li,The Pennsylvania State University, USA
This paper discusses a few promising physical and chemical technologies for the utilization
and conversion of CO 2 from a 500 MW coal-fired power plant into viable economic
products. The main areas of interest were microalgae biomass production (pond and
bioreactor production), supercritical CO 2 extraction technology, fixation of CO 2 into organic
compounds (production of various chemical products), and trireforming of CO 2 for synthesis
gas production. The value added products that can be produced from these four main
technologies are: biomass (high and low grade), biomass-derived products (pharmaceutical,
chemical or nutritional), synthesis gas, specialty products (extracted using supercritical
technology), organic carbonates (linear, cyclic or polycarbonates), carboxylates (formic acid,
oxalic acid, etc), salicylic acid and urea. The method employed for CO 2 utilization depends
on the desired products. It can be concluded, however, that chemical conversion and trireforming
are the leading technologies when the aim is to sequester the most possible CO 2 .
Despite the small percentages of CO 2 being utilized by biological and scCO 2 technologies
when compared to the total amount emitted by a 500 MW power plant, the value-added
products and yield are considerable.
19-1
SESSION 19
GASIFICATION TECHNOLOGIES:
ADVANCED SYNTHESIS GAS CLEANUP – 1
Field Testing of a Warm-Gas Desulfurization Process Using a
Pilot-Scale Transport Reactor System with Coal-Based Syngas
Jerry Schlather, Eastman Chemical Company, USA
Brian Turk, Research Triangle Institute International, USA
Current Integrated Gasification Combined Cycle (IGCC) power plant designs employ
amine-based scrubbing systems to desulfurize the syngas prior to the combustion
turbine. Because these systems operate at low temperature relative to the gasifier and
combustion turbine, the overall efficiency of the power plant is reduced by several
points. Research Triangle Institute (RTI) has been developing a competing
desulfurization technology that avoids decreasing overall thermal efficiency by
operating at temperatures 260ºC (500ºF). This desulfurization technology makes use of
an attrition resistant regenerable desulfurization sorbent and a transport reactor. For
temperatures from 260 to 500ºC (500 to 950ºF), RTI has developed a zinc oxide-based
sorbent that has been commercially produced and demonstrated to reduce inlet
concentrations of H 2 S and COS totaling 8,000 ppmv (wet basis) to < 5 ppmv (total
sulfur wet basis) in extensive bench-scale testing with simulated syngas and in actual
testing in a pilot-scale transport reactor with real coal derived syngas. Extended testing
of the pilot plant transport reactor and desulfurization sorbent was conducted with a
slip stream of coal-derived syngas from the commercial gasifier at Eastman Chemical
Company s facility in Kingsport, TN. This paper will present the results from this
extended field test of this pilot-scale desulfurization system and the technical/economic
merits of this technology compared to conventional processes.
19-2
Sulfur Removal from E-Gas Gas Streams with S Zorb Sulfur
Removal Technology (SRT)
Roland Schmidt, Joe Cross, Albert Tsang, Ed Sughrue, ConocoPhillips, USA
Robert Kornosky, DOE/NETL, USA
The SG Solutions (SGS) facility in Terre Haute, IN produces syngas (hydrogen/carbon
monoxide stream) for power generation using ConocoPhillips’ E-Gas Technology to
gasify coal or petroleum coke. The syngas can contain high levels of sulfur
contaminants (>1 weight %). These contaminants must be removed from the gas
stream prior to power generation. ConocoPhillips’ proprietary S ZorbTM sulfur
removal technology (SRT) utilizes proprietary sorbents that can remove these sulfur
contaminants under warm-gas conditions. A slipstream study at the SGS facility
demonstrated sulfur reduction to ppm levels under plant operating conditions. The
work used ConocoPhillips’ proprietary S ZorbTM sorbents as part of a test program
under the “Wabash River Integrated Methanol and Power Production from Clean Coal
Technologies (IMPPCCT)” Project funded by the U.S. Department of Energy
Cooperative Agreement No. DE-FC26-99FT40659, and managed by the National
Energy Technology Laboratory.
16

19-3
Development of Highly Efficient Hot-gas Cleanup Technology for Advanced
IGCC System Involving Coproduction of Hydrogen and Liquid Fuels
Michihiro Ishimori, Yoshiharu Yamaguchi, Koichiro Furusawa, Masafumi Katsuta,
Waseda University, JAPAN
Development studies of hot-gas cleanup system, especially highly efficient desulfurization
technologies have been carried out in order to realize the highly effective coal gasification
power plants such as IGCC and related systems involving coproduction of hydrogen and/or
liquid fuels (GTL or CTL). In continuing our studies of zinc ferrite and related compounds
as desulfurization agents, we have found several excellent sorbent systems for hot reductive
gases such as coal gas produced by an entrained-flow gasifier. The performance tests of the
sorbent systems were carried out at a fixed-bed type bench-scale reactor at 250-600°C under
atmospheric and pressurized conditions, using simple reductive gas containing hydrogen
sulfide and/or related gas. Some sorbent systems composed of zinc ferrite and metal oxides
and/or metal sulfides were found to show excellent desulfurization performance for some
representative sulfur compounds; concentrations of hydrogen sulfide, dimethyl sulfide, and
thiophene involved in the reductive gases were respectively decreased to less than 50 ppbv;
the performance of the desulfurization agents for synthesis gas is satisfactory with respect to
production of high grade hydrogen and/or liquid fuels such as methanol and DME. The
regeneration of the sorbent systems after sulfidation is carried out by oxidation. The feature
of breakthrough curves for the sulfuric gases suggests that deactivation of the sorbent
systems during absorption-regeneration cycles is negligible. The characteristics of zinc
ferrite and related systems will be discussed in relation with sorbent systems for hot-gas
cleanup process of IGCC power generation system involving coproduction of hydrogen
and/or liquid fuels; the coproduction process is integrated with IGCC system in parallel with
the combined cycle of gas turbine and steam turbine.
19-4
Dry Desulfurization of Coal Gas by Partial Oxidation of H 2 S
Dirk Bauersfeld, Prof. Dr.-Ing.B. Meyer, I. Rochner, Technische Universitat
Bergakademie Freiberg, GERMANY
This paper deals with the dry desulfurization of coal gas by partial oxidation of H 2 S on
high temperature brown coal coke (HOK). H 2 S is catalytically oxidized by O 2 :
H 2 S+ 1/8 O 2 → H 2 O + 1/8 S 8
The formed sulfur is adsorbed on the inner surface on HOK. The operation temperature
for this dry desulfurization process ranges from 150 to 250°C. A high operation
pressure is favorable for the achievable desulfurization level, where more than 99 %
can be obtained. The level of desulfurization depends on temperature, pressure and the
formation of COS. The main limiting factor is COS formation:
CO + 1/8 S 8 → COS
This reaction was investigated in a fixed bed reactor, using a typical gasification gas
from brown coal fluidized bed gasification, at a temperature of 180°C, a pressure up to
27 bars and a total volume flow of 1.5 to 3 m 3 /h (STP). The experimental investigation
showed that the reaction between CO and elemental sulfur is not the main one. COS is
mainly produced by reactions of CO and H 2 S on HOK. Furthermore, a reaction (COS-
Hydrolysis) was found at lower COS concentrations in the clean gas. These reactions
were observed with increasing residence time. Finally, we determine the amount of
COS could be reduced while increasing the desulfurization level.
19-5
Selective Catalytic Oxidation of Hydrogen Sulfide - IGCC Applications
Maryanne Alvin, Robert Stevens, DOE/NETL, USA
Richard A. Newby, Dale L. Keairns, Science Applications International Corporation,
USA
Selective catalytic oxidation of hydrogen sulfide (SCOHS) to elemental sulfur using
activated carbon and NETL-processed metal oxide catalyst systems has been
investigated under bench-scale, simulated pressurized IGCC conditions for use in dry
and humid gas cleaning process applications. For this technology to be successful, a
20% cost effective advantage and 1 percentage-point plant efficiency gain over current
commercial technology, and

Power generation by means of Integrated Gasification Combined Cycle is potentially very
efficient and deserves serious attention as a means of making the best use of available coal
resources. Gas solid fluidization is a subject having wide engineering application
overlapping different industries. It is eminently suitable for thermal coal processing and
could in future play a major role in production of liquid and gaseous fuel from coal using
liquefaction and fluidized bed gasification processes. Clean Coal Technologies facilitate the
use of coal in an environmentally, satisfactory and economically viable way. For IGCC
(Integrated Gasification Combined Cycle) further R&D and commercial scale
demonstrations are needed to encourage commercialization of the technology by improving
reliability and availability and reducing costs. Material developments will be important in the
above. BHEL was the first organization to take up development of IGCC systems in phases
using PFBG for power generation systems, which has the potential to result in higher
efficiency owing to the possibility of integrating advanced gas turbines to the gasification
system. Cold model rigs have been set up by BHEL to confirm hydrodynamics adopted in
design of Pressurised fluidized bed gasifier. The purpose of this study is to investigate the
origin of pressure fluctuations in gas solid tapered fluidized beds using cold model studies.
The study will assess the potential for using pressure fluctuations as an indicator of fluidized
bed hydrodynamics in both laboratory scale cold models and industrial scale gasifiers.
Many advantages like uniformity of temperature, uniform mixing have been found in
fluidized beds. However there exits many problems in fluidized operation carried out in
cylindrical columns, such as non-uniform fluidization in large diameter and deep cylindrical
beds, where there is particle size reduction during operation leading to severe entrainment.
Hence there is necessity for the system to have capability of fluidizing particles of different
sizes at the same time. The demerits mentioned above in cylindrical beds can be overcome
by using tapered beds. Hydrodynamic characteristics of fluidization in tapered beds differ
from those in columnar beds due to variation of superficial velocity in the axial direction of
the beds. In the former, fixed and fluidized beds could coexist and the sharp peaking of the
pressure could occur, thereby giving rise to a remarkable pressure drop at high flow rates and
hysterisis loop at incipient fludization. Such high velocity regime in tapered fluidized beds
can offer better gas to solid contact.
In this study, an attempt is made to investigate the various possible regimes in gas solid
tapered fluidized beds. To explore these unique properties, a series of experiments was
carried out in gas solid tapered beds with various tapering angles of 5°, 10°, 15°, 20°, using
particles of different sizes and densities. Detailed visual observations of fluid and particle
behavior and measurements of the pressure drops using Data Acquisition System have led to
the identification of 5 flow regimes. The tapering angle of the beds has been found to
dramatically affect the beds behavior.
Other hydrodynamic characteristics determined experimentally included (peak pressure
drop, minimum fluidization velocity, minimum velocity of full fluidization, maximum
velocity of full defluidization, maximum and minimum expansion ratio, hysterisis). The
work on tapered fluidized bed is carried out using distributors of cone angles 60°, 90°, 120°,
150° and 180° and varying apex angle from 5° to 20° and compared with that of cylindrical
bed. The bed is fixed to a plenum chamber with a distributor. Experiments are conducted in
3-D tapered cold model test rigs. The materials used for the experiments are closely sieved
refractory of density 2965 kg/m 3 , sand of density 2590 kg/m 3 , bottom ash of density 1900
kg/m 3 and mustard of density 1150 kg/m 3 with air as fluidizing medium. In literature,
correlations are proposed for critical fluidization velocity, peak pressure drop. While there
have been no correlations for prediction of other parameters such as minimum fluidization
velocity of tapered bed with effect to the distributor. Hence it is expected the present
predicted correlation for minimum fluidization velocity would be more useful in design and
operation of tapered fluidizers. The proposed correlation is found to agree with the
experimental results within ± 19%.
SESSION 21
COMBUSTION TECHNOLOGIES – 4:
COAL CO-FIRED WITH OTHER FUELS
21-1
Biomass Co-firing in Pulverized Coal-fired Utility Boiler
Marek Sciazko, Jaroslaw Zuwala, Institute for Chemical Processing of Coal, POLAND
Wojciech Zygmanski, Skawina Power Plant, POLAND
Co-firing tests of sawdust and food processing residue with coal have been carried out at
Skawina Power Plant in Poland (1532 MWth in fuel, currently belonging to CEZ Group).
Skawina Power Plant is a tangentially-fired pulverized coal unit with nine boilers (4 boilers
of 210 and five boilers of 230 t/h live steam respectively) that produces 590 MW electricity,
600 MW district heat and process steam.
The paper presents an analysis of energy and ecological effects of biomass co-firing in both
types of coal boilers. Coal and sawdust were blended in the coal yard, and the mixture was
fed into the boiler through coal mills. Full scale co-firing trial tests were carried out for two
weeks during February 2005. In the tests, sawdust mass share of 9.5% and food processing
residue of 6.6% (both mass basis) were examined. The co-firing tests were successful. Based
on the analysis of the test results, the influence of biomass co-firing on specific components
of energy balance (e.g. stack losses and boiler thermal efficiency) was discussed, in
comparison to combustion of coal alone. The emission indices during coal combustion were
calculated and compared to the emission indices for biomass co-firing. It was shown that
biomass co-firing leads to a decrease of CO and SO 2 emissions. Due to the possibility of
18
considering part of the energy generated during co-firing as renewable energy, the procedure
for renewable energy share calculation is presented and illustrated with an example.
21-2
Co-combustion Experiences from the Czech Republic
Dagmar Juchelkova, Helena Raclavska, Bohumir Cech, VSB-Technical University of
Ostrava
Klaus Koppe, Technical University of Dresden, DEUTSCHLAND
The research is focused on the field of combined combustion of coal and waste including
biomass in the fluidized-bed boilers with atmospheric fluidized bed. Special attention will be
given to emissions and possibility of the future utilization on other FCB boilers in the Czech
Republic. Main goals may be outlined in the study of conditions for:
- Potential substitution of fuel with less valuable types of coal simultaneously with the
waste and biomass, sustainability of fluidized bed combustion.
- Actual unit diagnostics development.
- Laboratory studying mechanism for combustion by thermal analysis.
- Raw material input analysis and dependence of combustion solid residues on raw
material input.
- Combustion inaccuracy assessment in Foster Wheeler FCB unit (temperatures,
gaseous and solid components, velocities).
- Studying mechanism for fouling deposits formation and composition.
- Balance of combustion elements including heavy metals.
- Verifying a redistribution mode for choice of elements between the fuel and solid byproducts
of combustion.
- Quantitative phase analysis and structural analysis of substance especially minerals by
employing rtg. diffraction methods.
- Long-term deposit formation on thermal exchanger s walls.
- Saturation sludge dosing as a sorbent.
21-3
Kimberlina - A Zero-Emission Multi-Fuel Power Plant and
Demonstration Facility
Scott MacAdam, Roger Anderson, Fermin Viteri, Keith Pronske, Clean Energy
Systems, USA
Clean Energy Systems, Inc. (CES) has developed a zero-emission power generation
technology by integrating proven aerospace technology into conventional power systems. A
simplified schematic of the process is shown in Figure 1. The core of CES’ process is an
oxy-combustor adapted from rocket engine technology. This combustor burns a clean
gaseous fuel with gaseous oxygen in the presence of water. Fuels include syngas from coal,
refinery residues, or biomass; natural gas; landfill gas; and biodigester gases. The
combustion is performed at near-stoichiometric conditions in the presence of recycled water
to produce a steam/CO 2 mixture at high temperature and pressure. These combustion
products power conventional or advanced steam turbines and may use modified gas turbines
operating at high temperatures for expansion at intermediate-pressures. The gas exiting the
turbines enter a condenser/separator where it is cooled, separating into its components, water
and CO 2 . The recovered CO 2 is conditioned and purified as appropriate and sold or
sequestered. Most of the water is recycled to the gas generator but excess high-purity water
is produced and available for export. Every component in the CES process, except for the
combustor and reheater, is commercially proven and is standard in power generation. The
basic combustor technology has been used successfully in aerospace applications for
decades. CES’ innovation has been to adapt that aerospace technology to power generation,
much like the process by which aircraft jet engines were adapted for aero-derivative gas
turbines in conventional power plants.
21-4
Research on the Suspension Combustion Rate of Coal Water Slurry
Ji Deng-Gao, Taiyuan University of Technology, P.R. CHINA
Wang Zu-Ne, China University of Mining Technology, P.R. CHINA
The atomization suspension combustion of coal water slurry is the extensive technology of
its combustion and gasification. Research on coal-water-slurry atomization suspension
combustion property is very important. Experiment based on traditional single drop
combustion couldn’t reflect true atomization, suspension firing of coal water slurry
atomization suspension firing test device (ASFTD) was adopted and study on the
combustion rate of Shenmu coal water slurry suspension combustion was carried out. The
model of Shenmu slurry suspension combustion rate was proposed under this experiment
condition. The results show that suspension combustion rate gradually increases with the
prolongation of coal water slurry combustion time under different temperature, however,
different temperature results in distinct suspension combustion rate change. The trend shows
that the suspension combustion rate increases with coal water combustion temperature
heightening. It is helpful to design and operation of coal water slurry combustor.
21-5
Utilization of Biomass and Mixtures for the Gas Production
Dagmar Juchelkova, Helena Raclavska, Vaclav Roubicek VSB - Technical University
of Ostrava, CZECH REPUBLIC

The Aim of the project is the improvement of the collaboration in the gas production
and utilization (from various kinds of fuels, incl. biomass and their mixtures).
Collaboration between both universities (VŠB-TU Ostrava a SIU Carbondale) was
started at 1993 and there is interest on various themes. Presently is interest on the
“clean gas” production, the special aspect of this work is environmental improvement
(minimizing of negative people impact to the antroposphere). On the SIU (Southern
Illinois University) Carbondale ware gasification engine – pilot with various output –
which can be use for the experiments. Collaboration intensification in the sphere
“clean gas” production and utilization of the results in the praxis and teaching process
Special interest of the research is given to the estimation of main conditions for the gas
production.
22-1
SESSION 22
ENVIRONMENTAL CONTROL TECHNOLOGIES:
SO x , NO x , PARTICULATE AND MERCURY – 2
Effectiveness of Clean Coal Technology Provisions of EPAct in
Addressing Current Environmental Issues Facing Coal
Ben Yamagata, Coal Utilization Research Council, USA
The Energy Policy Act of 2005 (EPAct) includes the enactment of numerous programs
designed to encourage the research, development, demonstration and deployment of clean
coal technologies. Except for the enactment of certain tax incentives designed to benefit
taxpayers utilizing qualifying clean coal technologies all other clean coal programs included
in last year s national energy legislation are authorizations that require appropriations in
order to become effective. The paper will review the various clean coal technology programs
that are included in EPAct and comment upon the rationale and justification cited by
Congress and industry for enactment of these provisions. With respect to industry s, and
particularly CURC s, rationale for these various programs, a Clean Coal Technology
Roadmap, first developed by EPRI and CURC, in consultation with the Department of
Energy, was a guiding document to define what objectives EPAct programs should be
designed to achieve. The Roadmap will be described as well as a discussion as to how the
EPAct programs might support achievement of the goals and objectives set forth in the
Roadmap. In order to succeed in achieving the goals of EPAct related to clean coal
technologies and to successfully reach the objectives defined in the Roadmap it will be
necessary to fully support the clean coal authorizations of EPAct. That is not happening.
Why and what are the potential consequences of a lack of attention to technology
development especially in light of possible regulation of carbon dioxide The paper will seek
to answer these questions and particularly will focus on the need for successful technology
development if policy makers choose to create a national or international carbon
management regulatory scheme.
22-2
A Novel Ammonia-Based FGD Process: Experiences of a 60MW Demonstration
Wen-De Xiao, East China University of Science and Technology, P.R. CHINA
More than 70% of the energy requirements are met by coal combustion in China, resulting in
severe environmental pollution by huge flue SO 2 discharge over 25 million tones a year. The
well-established and effective procedures to scope with SO 2 and acid rain troubles are flue
gas desulfurization (FGD). But the well-accepted and widely-applied limestone-based FGD
methods have been increasingly blamed where considerable second-hand pollutions
produced. The author and coworkers have been for a decade carried out research for a novel
FGD method, based on ammonia and co-producing a useful fertilizer, ammonium sulfate, as
displayed by: 2NH 3 +SO 2 +H 2 O+0.5O 2 =(NH 4 ) 2 SO 4 It is especially suitable for the Chinese
situations of huge ammonia and fertilizer industry. Furthermore, ammonia-based method is,
but limestone-based one is not, accordant to the green chemical principles.
This paper presents the operation experiences with a 60MW demo of the newly-developed
ammonia-based FGD process, shown in Figure 1, characterized by a multiple functional
column for SO 2 absorption to ammonium sulfite, sulfite oxidation to sulfate, and sulfate
crystallization. It also overcame shortage of the NH 3 slip in the outlet purified gas commonly
appeared in the conventional ammonia-based FGD methods by using two stages in between
NH 3 introduced.
Figure 2 depicts the operational results during a period of 168 hours for the evaluation of the
method when the inlet flue gas SO 2 content fluctuated between 200 and 1200 ppmv as the
result of shifting combusted coal from different mines. The FGD column is very robust for
the SO 2 content variation. The ammonium sulfate resulted met the top-grade fertilizer
specifications.
22-3
Oxy-Firing Flue-Gas Character and Its Effect on FGD -
A Process Study for Integrated Pollutant Removal
Danylo Oryshchyn, Jake Armstrong, Steve Gerdemann, Thomas Ochs, Cathy
Summers, NETL-Albany, USA
The National Energy Technology Laboratory (NETL) is investigating combining oxyfiring
coal, using recirculated flue gas enriched with oxygen, with a unique Integrated
19
Pollutant Removal (IPR) system. Oxy-firing coal produces an exhaust stream
composition dominated by CO 2 and water, with particulate matter and small
contributions of SO x , NO x , O 2 , N 2 , Ar, and Hg. This is followed by the IPR system
which uses compression and intercooling to produce a supercritical, transportationready
CO 2 fluid suitable for sequestration or for purification, as necessary, to obtain
CO 2 for industrial use. Recent theoretical and experimental work at NETL is
examining three aspects of IPR: acid gas and particulate removal with energy recovery;
water treatment for recycle and release; and the enhancement of Hg 0 capture through
oxidation. Because their combination is corrosive, water, associated acid gases and
particulate matter must be removed from the boiler flue gas in the initial stages of IPR
to enable compression of the remaining CO 2 fluid. This study compared air-fired
furnace exhaust and oxy-fired furnace exhaust in flue gas desulfurization experiments.
Tests indicate the largest effect is associated with the greater concentration of SO 2 in
oxy-fired exhaust, despite the high concentration of CO 2 in this flue-gas composition.
22-4
Photocatalytic Decomposition of NO Originated from Coal Analog Compound
Xue Hanling, Li Jianwei, Ge Lingmei, Zhous Anning, Xi’an University of Science &
Technology, P.R. CHINA
Nitric oxide (NO) is the major air pollutant that has to be removed before emitting flue
gas into the atmosphere. Various processes, such as the selective catalytic reduction
(SCR) and selective non-catalytic reduction (SNCR), are under operation to remove
NO from flue gas. However, these processes require high operating temperatures and
costs. Recently, a great deal of research work has been carried out on the
heterogeneous photocatalytic reactions due to lower energy consumption and operating
cost for treatment of polluted water and air. This photocatalytic process has the
advantage of complete breakdown of organic pollutants to yield CO 2 , H 2 O and the
mineral acid. And studies on photocatalytic decomposition of NO have been reported.
It has been found that Cu + /zeolite catalysts exhibit photocatalytic reactivities for the
decomposition of NO x into N 2 and O 2 at 275K. In addition, a mixture of TiO 2 and
activated carbon is found to be an appropriate photocatalyst for the removal of lowconcentration
NO x from air. In the study, the photocatalytic oxidation of nitric oxide,
which was the oxidation product stemed from the mold compound pyridine of azocycle
compound in coal structure, over mesoporous loaded nanometer photocatalyst
containing metal compounds (MCs) has been studied in a fluidized-bed photoreactor.
Stannic oxide (SnO 2 ), zinc oxide (ZnO), cadmium sulfide (CdS), were used as MCs.
Mesoporous molecule sieve MCM-41 was acted as carrier, and TiO 2 was the primary
photocatalyst. The TiO 2 treated with MC over support MCM-41 by sol-gel method and
dipping process, had the greater efficiency as a NO remover under UV irradiation
compared with monocomponent TiO 2 . It is believed that MCM-41 has a high
adsorptivity for nitric oxide (NO) to contribute to photocatalytic reaction. The amount
of NO removed by the loaded photocatalyst including MC showed a tendency to
increase with decreasing initial NO concentration. The reaction rate increased with
reducing UV light wavelength. The NO decomposition activity depended on the
amount of semiconductor photocatalysts deposited in channel of MCM-41, too, and the
TiO 2 loaded with only 10wt%, meanwhile CdS loaded with only 5%, the photocatalyst
had revealed the highest level of activity in the fluidized-bed photoreactor, NO
decomposition reached about 64% at the gas velocity of 200ml/min. Highly dispersed
semiconductor photocatalysts in channel of MCM-41 was effective for the
photocatalytic decomposition of NO.
23-1
SESSION 23
HYDROGEN FROM COAL: SHIFT CATALYST AND GASIFICATION
Robust, Low-Cost Water-Gas Shift Membrane Reactor for
High-Purity Hydrogen Production from Coal-Derived Syngas
Zhijiang Li, Neng Ye, James Torkelson, Aspen Products Group, Inc., USA
In an effort to develop a reliable, low-cost membrane water-gas-shift reactor (WGS)
for hydrogen generation from coal-derived syngas, a sulfur-tolerant transition metal
WGS catalyst and a low-cost, H 2 -selective membrane were developed. Tests conducted
with synthetic syngas containing 3000 ppm sulfur showed that the WGS catalyst is
highly active and capable of converting CO at equilibrium conversions at temperatures
from 300 to 500ºC and pressures from 300 to 500 psig. The catalyst displayed higher
WGS activity than a number of commercial catalysts, especially at lower temperatures.
The stability of the catalyst in the presence of 3000 ppm H 2 S and 350 ppm HCl was
demonstrated for >200 hours. The H 2 -selective, high-temperature membrane is based
on a low-cost, hydrogen-selective material. The surfaces of the membrane were
modified by deposition of catalyst layers of desired compositions. H 2 permeation tests
conducted at 300-500ºC and up to 200 psi H 2 partial pressure showed that the
membrane is highly selective to H 2 with a H 2 permeability in the range of 1×10 -8 to
1×10 -7 mol H 2 /(m·s·Pa 0.5 ), comparable to that of Pd-based membranes. Surface
modification increases not only the membrane’s H 2 permeability but also its tolerance
to H 2 S.

23-2
Gas-Phase Incorporation of Palladium onto Ceria-doped Silica
Aerogel for Water-Gas Shift Catalysis
Gregory C. Turpin, Brian C. Dunn, Yifan Shi, Eric P. Fillerup, Ronald J. Pugmire,
Edward M. Eyring, Richard D. Ernst, University of Utah, USA
Prasanta Dutta, Mohindar Seehra, Vivek Singh, West Virginia University, USA
The Water-Gas Shift (WGS) reaction is a means of producing hydrogen from coal-derived
syngas. Palladium-promoted ceria has been investigated recently and has shown potential for
low-temperature WGS catalysis. One limitation of traditional ceria is an inherent low surface
area. While specialty cerias with surface areas as high as 300 m 2 /g have recently been
prepared, they do not show structural stability at relevant temperatures. Supporting ceria on
the surface of silica aerogel can take advantage of the very high surface area of the silica
aerogel as well as the structural integrity of the support. Starting with a silica aerogel having
an approximate surface area of 700 m 2 /g, ceria can be incorporated onto the surface with
nominal loadings up to 40% (w/w), yielding final surface areas as high as 600 m 2 /g and
generally above 450 m 2 /g.
Palladium was added via the gas-phase incorporation (GPI) of a volatile organometallic
complex, (η 3 -allyl)(η 5 -cyclopentadienyl)palladium, which is air-stable and prepared by a
well-established procedure. Comparisons between GPI and conventional aqueous phase
incorporation indicate increased activity for GPI-derived catalysts. For example, GPI can
increase the WGS activity in excess of 150% for otherwise identical catalysts. This is
presumably due to a higher dispersion of the Pd derived from GPI. A XRD analysis of
catalysts derived from the GPI of Pd failed to show well-defined peaks indicative of
agglomerated Pd particles, which agrees with the interpretation of high dispersion.
23-3
Mesoporous Metal-Promoted Ceria Catalysts for the Water Gas Shift Reaction
Brian Dunn, Jennifer Gasser, Dae-Jung Kim, Eric Fillerup, Gary Hunyh, Gregory C.
Turpin, Richard D. Ernest, Ronald J. Pugmire, Edward M. Eyring, Daniel W. Ramirez,
University of Utah, USA
Metal-promoted ceria catalysts that are active for the Water Gas Shift reaction have
received considerable attention in recent years. One drawback to the ceria catalysts is
the relatively low surface area achievable with traditional preparation methods. Two
new types of ceria has been synthesized which possess high surface area and
significant catalytic activity when palladium is incorporated into the catalyst. High
surface area is attained by either preparing the ceria in an aerogel form or by
combining the ceria with a mesostructured silica, SBA-15. The ceria aerogels have
measured BET surface areas as high as ~300 m 2 /g which is about twice as large as the
highest surface area ceria prepared via traditional methods. Measured BET surface
areas of the ceria/SBA-15 composite material can be as high as 800 m 2 /g, however, the
SBA-15 contributes substantially to this value. Various metals (Pd, Cu, Au) were
incorporated into the ceria and the resulting catalysts were evaluated for Water Gas
Shift activity in a 6-channel, laboratory-scale, packed bed reactor. The reactor was
constructed with 6 parallel catalyst beds to allow for the simultaneous evaluation of up
to 6 catalysts under identical reaction conditions (temperature, reactant flow, etc.).
Each bed was equipped with an internal thermocouple to ensure accurate temperature
measurement and to evaluate thermal cross-talk between reactors that could be caused
by an exothermic reaction in the catalyst bed. No cross-talk was observed. The
catalytic activity was measured at 5 temperatures between 150°C and 350°C for 24
hours at each temperature. At the highest temperature, the Pd/ceria aerogel catalyst
converted 148 g CO / (hr g-Pd) resulting in the production of 11 g H 2 / (hr g-Pd). The
Cu and Au catalysts were less active. The Pd-loaded ceria/SBA-15 based catalysts
were less active than the Pd-loaded ceria aerogel based catalysts at temperatures less
than 300°C, but become more active above 300°C.
23-4
Sulfur Deactivation Studies in the High-Temperature Water-Gas Shift
Reaction over Chromium-Free Iron-Based
Lingzhi Zhang, Umit Ozkan, The Ohio State University, USA
Coal is the most abundant fossil fuel in our nation and how to make an efficient and
environmentally acceptable use of coal has become a hot topic considering the
increasing energy demands. Hydrogen production through integrated gasification
combined-cycle (IGCC) has emerged as a highly promising technology. The
commercialization of these joint power and hydrogen plants needs significant
improvements in some of the steps following gasification to produce hydrogen more
efficiently and economically. Among them is the water gas shift (WGS) reaction.
Development of highly active, sulfur tolerant and chromium free catalysts will bring
about the successful use of coal-derived gas for hydrogen production, resulting in
enhanced use of our vast coal reserves. Sulfur deactivation studies have been carried
on over current Fe-based catalysts prepared with different methods. A series of sulfur
testing with simulated coal gas were run on the catalysts and different characterization
techniques including BET, XRD, DRIFTS and XPS are used to describe catalyst
properties before and after sulfur poisoning. Those characterizations also give us
information about reaction mechanisms and help us explain functions of different
promoters and their relation with reaction activities.
20
23-5
Hydrogen from Coal-Derived Methanol via an Autothermal Reformation Process
Hyung Chul Yoon, Paul A. Erickson, University of California, Davis, USA
This paper reports on an investigation of hydrogen production via reformation of coalbased
methanol. We have proven that coal–derived liquids such as commercially
available methanol can be converted into hydrogen using both steam and autothermal
reforming methods. These studies have taken place at the Hydrogen Production &
Utilization Laboratory at University of California Davis. Through chemical analysis,
coal-based methanol has shown to have slightly higher amounts of trace hydrocarbons
than chemical grade methanol derived from natural gas. While these trace
hydrocarbons are typically inconsequential for some energy conversion devices, fuel
cell applications require ultra pure hydrogen. Steam and autothermal reformers were
investigated to find the optimal hydrogen production method in the existence of such
trace impurities. Based on experimental results, steam-reforming of coal-based
methanol has shown significant catalyst degradation caused by the trace impurities.
Autothermal reformation of coal-derived methanol has demonstrated better
performance with the trace impurities due to its higher operating temperature generated
by the oxidation step. Autothermal reformation can also avoid some of the energy
penalties of steam reformation but generally has a lower concentration of hydrogen due
to the diluent nature of nitrogen by adding air as the oxidizer. This investigation shows
that hydrogen production from coal-based methanol is possible using both reformation
methods when considering fuel cell applications.
SESSION 24
GLOBAL CLIMATE CHANGE:
CO 2 CAPTURE – 1: CHEMICAL SORBENTS
24-1
Carbon Dioxide Removal from Flue Gas of Coal-Fired Power Plants Using Dry
Regenerable Carbonate Sorbents in a Thermal-Swing Process
Thomas Nelson, David Green, Paul Box, Raghubir Gupta, Andreas Weber, RTI
International, USA
The reversible reaction between sodium carbonate, carbon dioxide and water vapor, to
form sodium bicarbonate (or an intermediate salt) can be used in a thermal swing
cyclic process to recover concentrated carbon dioxide from power plant flue gas for
sequestration or reuse. The process is initially targeted for coal-fired power plants
incorporating wet flue gas desulfurization. The process is also suitable for natural gasfired
power plants. Process modeling suggests that a process of this type offers a lower
total energy requirement (and lower overall CO 2 capture costs) than existing liquid
amine- based processes.
Calcined sodium bicarbonate can be used as the sorbent for this process. Alternately,
sodium carbonate incorporated in an attrition resistant support material can be used.
The supported sorbent has demonstrated removal of >90% of the CO 2 present in a
simulated flue gas in a bench-scale co-current down-flow reactor system. The partially
reacted sorbent can be thermally regenerated, releasing CO 2 and H 2 O. Upon
condensation of the H 2 O from the vent stream, a nearly pure CO 2 stream can be
produced for reuse or sequestration. This paper discusses the results of a series of labscale
down-flow reactor tests investigating the impact of gas composition, temperature,
sorbent-to-gas ratio, and other important variables on the reaction of CO 2 with the
sorbent. This paper also highlights results of field tests confirming that complete
sorbent regeneration can be achieved in a heated screw conveyor, with minimal
sorbent attrition. An integrated system incorporating a co-current down-flow absorber,
a heated hollow screw conveyor/regenerator, and a hollow screw conveyor/sorbent
cooler has been designed, constructed and tested
24-2
Developing a New Method for Direct Observation of the
Effects of CO 2 Injection into Coal Seams
Randal E. Winans, Sonke Seifert, Argonne National Laboratory, USA
Tony Clemens, CRL Energy LTD, NEW ZEALAND
Initial investigations to assess the suitability of in situ Small Angle X-Ray Scattering
(SAXS) for directly observing changes in coal structure when injected with pressurized
CO 2 were carried out at 50 bar pressure and ambient temperature on a suite of New
Zealand coals and US coal samples from the Argonne Data Bank. The method requires
the use of the Advanced Photon Source (APS) high energy synchrotron at Argonne.
The high level of beam intensity provides the high levels of resolution and
observational power required.
These initial studies showed that:
• High energy X-ray beams from the APS can be used to directly observe
changes in coal structure as CO 2 is injected into the coal at high pressure.
• The results are very reproducible
• There are clear trends with coal rank.
These initial successes suggest that it may be possible to develop a robust method for
predicting CO 2 sequestration ability of coal seams based on direct observation.

24-3
Development of Fluidizable Lithium Silicate-Based Sorbents for
High Temperature Carbon Dioxide Removal
Weijiong Li, Santosh Gangwal, Raghubir Gupta, Brian S. Turk, RTI International,
USA
One of the key features accelerating the commercial deployment of integrated
gasification combined cycle (IGCC) systems for producing electricity is that the
addition of CO 2 capture and sequestration processes results in the lowest increment in
capital and operating costs of any of the competing technologies. However, the
commercially available technologies require significant cooling of the syngas to
effectively capture the CO 2 that introduces a significant thermodynamic penalty for
CO 2 capture. RTI International (RTI) has been working with regenerable sorbent
materials for CO 2 capture at elevated temperatures with the potential to produce a high
pressure high purity CO 2 product. This process offers the potential to significantly
reduce any thermodynamic penalty associated with the CO 2 capture process. During
the course of this research, RTI has developed Li 2 SiO 4 -based sorbents that have
demonstrated CO 2 capture and regeneration in bench-scale testing. Results from this
testing program were presented at last year’s Pittsburgh Coal Conference.
Over the last year, RTI has built upon this success by conducting R&D for a fluidized
Li 4 SiO 4 -based sorbent. The incentive for this work is the knowledge that a transport
reactor system can be designed to treat high gas throughputs at relatively low capital
costs, which will be required to treat the large CO 2 content of syngas derived from
carbonaceous fuels, especially coal. A CO 2 capture technology that offers lower capital
cost and higher thermal efficiency becomes more commercially attractive with the
potential reward of earlier implementation. The technical challenges for developing a
fluidized Li 4 SiO 4 sorbent are to achieve a high CO 2 reactivity, acceptable
hydrodynamic properties and suitable attrition resistance. This presentation will
describe the progress made in this R&D program.
24-4
Carbon Dioxide Separation through Supported Ionic
Liquids Membranes in Polymeric Matrixes
Jeffery Ilconich, David Luebke, Christina Myers, Henry Pennline, DOE/NETL, USA
As compared to other gas separation techniques, membranes have several advantages which
can include low capital cost, relatively low energy usage and scalability. While it could be
possible to synthesize the ideal polymer for membrane separation of carbon dioxide from
fuel gas, it would be very intensive in terms of money and time. Supported liquid
membranes allow the researcher to utilize the wealth of knowledge available on liquid
properties. Ionic liquids, which can be useful in capturing CO 2 from fuel gas because they
posses high CO 2 solubility in the ionic liquid relative to H 2 , are an excellent candidate for
this type of membrane. Ionic liquids are not susceptible to evaporation due to their negligible
vapor pressure and thus eliminate the main problem typically seen with supported liquid
membranes.
A study has been conducted evaluating the use of the ionic liquid 1-hexyl-3-methylimidazolium
bis(trifuoromethylsulfonyl)imide in supported ionic liquid membranes for the
capture of CO 2 from streams containing H 2 . In a joint project, the ionic liquid was
synthesized and characterized at the University of Notre Dame, incorporated into a
polymeric matrix, and tested at the National Energy Technology Laboratory. Initial results
have been very promising with calculated CO 2 permeabilities as high as 950 barrers and
significant improvements in CO 2 /H 2 selectivity over the unmodified polymer at 37°C along
with promising results at elevated temperatures. In addition to performance, the study
included examining the choice of polymeric supports on performance and membrane
stability in more realistic operating conditions. Also included in this study was an evaluation
of novel approaches to incorporate the ionic liquid into polymer matrices to optimize the
performance and stability of the membranes.
24-5
A Parametric Study for Regenerative Ammonia-Based
Scrubbing for the Capture of CO 2
Kevin Resnik, James T. Yeh, Henry W. Pennline, DOE/NETL, USA
William Garber, Deborah C. Hreha, Parsons Project Services, Inc., USA
A continuous gas and liquid flow, regenerative scrubbing process for CO 2 capture is
currently being demonstrated at the bench-scale level. An aqueous ammonia-based
solution captures CO 2 from simulated flue gas in an absorber and releases a nearly pure
stream of CO 2 in the regenerator. After the regeneration, the solution of ammonium
compounds is recycled to the absorber. The design of the continuous flow unit was
based on earlier exploratory results from a semi-batch reactor, where a CO 2 and N 2 gas
mixture flowed through a well-mixed batch of ammonia-based solution. Recently, a
series of tests have been conducted on the continuous unit to observe the effect of
various parameters on CO 2 removal efficiency and regenerator effectiveness within the
flow system. The parameters that were studied include absorber temperature,
regenerator temperature, initial NH 3 concentration, simulated flue gas flow rate, liquid
solvent inventory in the flow system, and height of the packed-bed absorber. Results
from this current testing campaign conducted in the continuous scrubbing unit as well
as test results from a 5-cycle semi-batch reactor will be discussed.
25-1
SESSION 25
GASIFICATION TECHNOLOGIES:
ADVANCED SYNTHESIS GAS CLEANUP – 2
Synthesis and Reactivity Test of Nanostructure ZnO for
Hot Gas Cleanup on the IGFC
Si Ok Ryu, No-Kuk Park, You Jin Lee, Gi Bo Han, Tae Jin Lee, Yeungnam
University, SOUTH KOREA
Chih Hung Chang, Oregon State University, USA
A nano-size zinc oxide was formulated for the effective removal of a very low concentration
of sulfur compounds (H 2 S, COS) contained in a gasified fuel gas and their reactivity was
also investigated in this study. They were prepared by a matrix-assisted method with various
precursors. An active carbon was used for a matrix and zinc nitrate, zinc acetate, zinc
chloride, and zinc sulfate were selected as precursors. Zinc nitrate was the best precursor for
the formulation of the nano-size zinc oxide in the experiments. The size of the formulated
nano-size zinc oxides was in the range of 20-30 nm and its surface area was about 56.2 m 2 /g.
From TGA(thermal gravity analysis) test, it was found that its sulfur absorption rate was
about 0.363 gS/min·100 g-sorbent. Their reactivity increased with the smaller size and the
larger surface area of the sorbents. Most prepared nano-size zinc oxides showed an excellent
performance for the removal of not only H 2 S but also COS. Their absorption rate was faster
than commercial zinc oxides. In order to investigate the sulfur absorption characteristics of
zinc oxide, a series of experiments for various nano-size zinc oxides formulated from
different precursors were carried out in a packed-bed reactor system over the temperature
500°C. The sulfur capacity was about 5.83 gS/100 g-sorbent for H 2 S. It was concluded that
the zinc oxide prepared by zinc nitrate as a precursor showed the highest sulfur removing
capacity.
25-2
Desulfurization of High-Pressure Gasified Coal Using the
UC Sulfur Recovery Process
Diana Matonis, Howard S. Meyer, Dennis Leppin, Gas Technology Institute, USA
The University of California Sulfur Recovery Process – High Pressure (UCSRP-HP)
provides the potential to treat high-pressure, warm synthesis gas for the removal of
ammonia, hydrogen chloride, and heavy metals including arsenic, mercury, cadmium, and
selenium as well as essentially all of the hydrogen sulfide and carbonyl sulfide in a coalderived
synthesis gas in a compound contacting tower. In the bottom or scrub section of the
tower, the sour gas feed is contacted with a solvent that will absorb some steady state levels
of water, ammonia, and hydrogen sulfide from the gas stream. As a result, the HCl content
of the feed gas will be absorbed very effectively to form highly soluble NH 4 Cl. A small but
significant concentration of NH 4 HS will also be present in the liquid phase, and the heavy
metals As, Cd and Hg, will be absorbed to form their respective, very insoluble sulfides.
Selenium, present in the syngas as H 2 Se, will be absorbed to form highly soluble (NH 4 ) 2 Se.
The solvent is recirculated with a small slipstream being withdrawn, perhaps intermittently,
for filtration and other treatment to remove the accumulated impurities and then returned.
The gas stream leaving the scrub section passes into the reactor section through a chimney
that effectively prevents the mixing of the solvent in the two sections. In the upper or reactor
section of the tower, the UCSRP-HP uses a solvent with high capacity for H 2 S and SO 2 that
also catalyzes the liquid-phase reaction of H 2 S and SO 2 to sulfur and water. Operation is
above the melting point of sulfur, so the sulfur forms a separate liquid phase and is removed
by simple decantation. The now scrubbed, sour gas, mixed with 10% − 20% excess SO 2 , is
contacted at high pressure (the higher the better) with the UCSRP solvent at about 260 −
285°F (125 – 140°C). Substantially all of the H 2 S reacts to form liquid sulfur, leaving the
excess SO 2 in the treated gas. The unreacted SO 2 is recovered in a separate absorber/stripper
system, which may optionally also serve to dry the treated gas. The sulfur-free gas may
optionally also be passed through a second absorber/stripper system for CO 2 recovery. The
recovered SO 2 is combined with SO 2 produced by burning one-third of the liquid sulfur in a
furnace, compressed and perhaps liquefied, and fed to the reactor column. The furnace
employs either air or oxygen. All of the sulfur formed in the reactor is vaporized as it passes
through the furnace; the unburned two-thirds condense in the waste-heat boiler. Any organic
components dissolved in the sulfur will also be burned. The product sulfur has only a small
amount of dissolved SO 2 as impurity. This paper will discuss the experimental and
engineering studies of UCSRP-HP for syngas desulfurization with optional CO 2 recovery
that include laboratory studies on vapor liquid equilibrium, solvent stability, corrosion and
kinetic studies performed in laboratory scale equipment and column scale-up testing in
bench-scale apparatus conducted at GTI and will highlight the potential economic benefits of
the process.
25-3
Sorbents for Mercury Capture from Fuel Gas with
Application to Gasification Systems
Evan Granite, Henry W. Pennline, Christina R. Myers, Dennis C. Stanko, DOE/NETL,
USA
21

In gasification for power generation, the removal of mercury by sorbents at elevated
temperatures preserves the higher thermal efficiency of the integrated gasification combined
cycle system. Unfortunately, most sorbents display poor capacity for elemental mercury at
elevated temperatures. Previous experience with sorbents in flue gas has allowed for
judicious selection of potential high-temperature candidate sorbents. The capacities of many
sorbents for elemental mercury from nitrogen, as well as from four different simulated fuel
gases at temperatures from 204 to 371°C, were determined. The simulated fuel gas
compositions contain varying concentrations of carbon monoxide, hydrogen, carbon dioxide,
moisture, and hydrogen sulfide. Promising high temperature sorbent candidates have been
identified. Palladium sorbents appear the most promising for high temperature capture of
mercury and other trace elements from fuel gases. A collaborative research and development
agreement has been initiated between the Department of Energy’s National Energy
Technology Laboratory and Johnson Matthey for optimization of the sorbents for trace
element capture from high temperature fuel gas. Future directions for mercury sorbent
development for fuel gas application will be discussed. The work presented in this
manuscript was recently accepted for publication in Industrial & Engineering Chemistry
Research.
25-4
A Novel Sorbent-Based Trace Metal Removal from Coal-Derived
Synthesis Gas: Field Demonstration Results
Gokhan Alptekin, Robert Amalfitano, Margarita Dubovik, Michael Cesario, TDA
Research Inc., USA
Gasifiers convert coal into synthesis gas feed streams that can be used in advanced
power cycles to generate electricity and in the production of a wide variety of
chemicals. However, the coal-derived synthesis gas contains a myriad of trace
contaminants that cannot be released to the environment if the syngas is burned to
generate power or may poison the catalysts used in the downstream chemical
manufacturing processes. Therefore, removal of these contaminants is critical for the
widespread and environmentally-friendly utilization of coal. TDA Research Inc.
(TDA) is developing a sorbent that can reduce the concentration of the trace metal
contaminants (i.e., mercury, arsenic, selenium and cadmium) to less than parts per
billion levels in the coal-derived synthesis gas at elevated temperatures (260°C). The
sorbent is the key component of an integrated trace contaminant removal system. The
production of the sorbent is scaled-up under subcontract with a leading U.S. sorbent
manufacturer using commercial manufacturing techniques. The performance
capabilities of the commercially produced sorbent were also confirmed at bench-scale.
As a next step, TDA is building an integrated trace metal contaminant removal
prototype equipped with all essential items, flow systems and auxiliary components to
test the operation of the breadboard system using real coal-derived synthesis gas. The
proof-of-concept tests will be carried out using a real coal-derived synthesis gas at the
University of North Dakota Energy Environmental Research Center (UNDEERC) in
their Transport Reactor Demonstration Unit (TRDU). The performance of the sorbent
will be tested, and the integration of the process components will be shown in the
prototype unit designed to treat 10,000 SCFH coal gas generated from Powder River
Basin coal. This paper discusses the results of the demonstration tests.
25-5
Palladium Sorbents for Arsenic Capture from Fuel Gas with
Application to Gasification Systems
Evan J. Granite, Henry W. Pennline, Christina R. Myers, Dennis C. Stanko
Arsenic is a semi-volatile trace element present in coal at concentrations of around 15
ppm. In the oxidizing environment of flue gas, arsenic forms the oxide As 2 O 3 , whereas
in the reducing environment of fuel gas, it forms arsine, AsH 3 . Arsenic is a well known
poison for many catalysts such as palladium, platinum, and the NO x selective catalytic
reduction (SCR) catalysts employed in coal-burning power plants. Arsenic and its
compounds are highly toxic and may be subject to future regulations. It has been found
that palladium can adsorb arsine from both nitrogen and a simulated fuel gas over a
wide temperature range. Palladium sorbents have significant potential for high
temperature removal of trace metals such as arsenic, mercury, selenium, and cadmium
from coal-derived fuel and flue gases.
26-1
SESSION 26
GASIFICATION TECHNOLOGIES:
FUNDAMENTALS AND SIMULATIONS – 2
Dynamic Simulation and Training for IGCC Power Plants
Michael Erbes, Enginomix, LLC, USA
Stephen E. Zitney, NETL, USA
Integrated Gasification Combined Cycle (IGCC) is emerging as the technology of choice for
providing clean, low-cost electricity for the next generation of coal-fired power plants and
will play a central role in the development of high-efficiency, zero-emissions power plants
such as FutureGen. Several major utilities and developers recently announced plans to build
22
IGCC plants and other major utilities are evaluating IGCC s suitability for base-load capacity
additions. This recent surge of attention to IGCC power generation is creating a growing
demand for experience with the analysis, operation, and control of commercial-scale IGCC
plants. To meet this need, the National Energy Technology Laboratory (NETL) has
launched a project to develop a generic, full-scope, IGCC dynamic plant simulator and
establish a state-of-the-art simulator training center at WVU’s National Research Center for
Coal and Energy (NRCCE).
In a recently completed scoping study, the authors defined the requirements and features for
an IGCC simulator, and identified potential operator training simulator (OTS) suppliers,
R&D technology collaborators, and members of an advisory board for the project. Key
simulator requirements and features identified included:
- High-fidelity, real-time dynamic models of both process (gasification) and power sides
- Full-scope OTS capabilities including startup, shutdown, load following and shedding,
response to fuel and ambient variations, control strategy analysis, malfunctions/trips,
alarms, scenarios, trending and snapshots
- Unified software modeling platform for engineering analysis and training
- Maintainable, flexible, extendable and easy-to-use software and model libraries
- Full distributed control system (DCS) emulation
- Leverage existing NETL equipment/process models and software technology
- Extendable to FutureGen and zero-emission poly-generation plants
The project consists of five phases including: I) Project scoping, II) Detailed planning, III)
Simulator development, IV) Simulator deployment, and V) Establishment and support of an
IGCC Simulator Training Center. The project length from simulator planning through
deployment is about three years.
The IGCC Dynamic Simulator & Training Center will offer much-needed IGCC
demonstration, education, and training services such as IGCC plant operation and control
demonstrations, technology familiarization, computer-based training and on-site train the
trainer programs. Potential users include utilities, engineering firms, technology suppliers,
Department of Energy system analysts and engineers, university engineering and training
R&D community, and others interested in learning more about IGCC plant operations and
control. Because the simulator will be based on a generic IGCC plant design, it is not
intended for training actual plant operators, but IGCC operators may benefit from training on
the generic simulator before moving on to plant-specific simulators.
The IGCC Dynamic Simulator & Training Center project will build on and reach beyond
existing combined-cycle and conventional-coal power plant simulators to combine for the
first time a process/gasification simulator and a combined-cycle simulator together in a
single dynamic simulator framework for use in training applications as well as engineering
studies.
26-2
CO 2 Control Technology Effects on IGCC Plant Performance and Cost
Edward S. Rubin, Chao Chen, Michael B. Berkenpas, Carnegie Mellon University,
USA
As part of the US DOE’s Carbon Sequestration Program, we have developed an
integrated modeling framework to evaluate the performance and cost of alternative
carbon capture and storage (CCS) technologies for fossil-fueled power plants in the
context of multi-pollutant control requirements. The model (called IECM, for
Integrated Environmental Control Model) also allows for explicit characterization of
the uncertainty or variability in any or all input parameters. Power plant options
currently include pulverized coal (PC) combustion plants, natural gas combined cycle
(NGCC) plants, and integrated gasification combined cycle (IGCC) plants. This paper
uses the IECM to analyze the effects of adding CCS to an IGCC system employing a
GE quench gasifier with a water gas shift reactor and Selexol system for CO 2 capture.
Parameters of interest include the effects of varying the CO 2 removal efficiency, the
quality and cost of coal, and selected other factors affecting overall plant performance
and cost. The stochastic simulation capability of the model also is used to illustrate the
effect of uncertainties or variability in key parameters. The potential for advanced
oxygen production and gas turbine technologies to reduce the cost and environmental
impacts of IGCC with CCS also is analyzed.
26-3
Thermodynamic Modeling of Gasification Processes with
Respect to Trace Elements
Stefan Guhl, Philipp Bruggemann, Bernd Meyer, Technical University Bergakademie
Freiberg, GERMANY
Andreas Jockhamann, Sustec Schwarze Pumpe GmbH, GERMANY
Trace elements like Na and K and their compounds are known to evaporate in high
temperature processes such as gasification. The condensation of their compounds in low
temperature areas in gasifiers can cause problems. Therefore, it is important to assess their
thermal behaviour. Thermodynamic models can be an excellent tool to carry out this
assessment. The presented model simulate the BGL-gasification process (British Gas –
Lurgi) using the thermodynamic software SimuSage in connection with FactSage and
Delphi, whereby the Gibbs energy minimisation is used to calculate equilibrium state. The
process data and material samples have been obtained from a BGL-gasifier with 200 MW
thermal input, which is commercially operated by Sustec Schwarze Pumpe GmbH near
Dresden, Germany. The main feedstock is pelletised municipal solid waste and the synthesis
gas is used to generate methanol and electricity. The gasification process itself is similar to

the classical Lurgi-gasifcation process (fixed bed, counter flow, dry ash removal). The major
difference lies in an ash removal by a slag bath, where the liquid slag is tapped by a watercooled
copper-nozzle. Hence the temperatures in the combustion zone are very high and lead
to evaporation of volatile ash components. The model consists of four interacting
equilibrium stages. Three equilibrium stages describe the classical fixed-bed gasifier zones
and include devolatilisation, gasification and combustion. The fourth equilibrium stage
considers the slag bath. Material flows connect all four stages. The following elements are
taken into account: Al, C, Ca, Cu, Cl, Fe, H, K, Mg, N, Na, O, S, Si, Ti, Zn. For the
description of the molten slag, a solution phase is used, which is based on the quasi-chemical
model. It therefore considers real interactions between the slag components in the liquid
state. As a major result of the model, the capture of volatile ash components can be
described. For example the alkalis K and Na evaporate in the hot lower part of the gasifier
(slag bath and combustion zone) and will condense in the upper part (devolatilisation zone)
at the cold solid feedstock. The feedstock will move downward to the hot zones and the
alkalis will evaporate again. Due to the subsequent accumulation of alkali vapours in the gas
phase, the solubility of alkalis in the slag will increase. Finally, capture rates and raw gas
concentrations of volatile slag components are calculated. The evaluation of the model was
done by process data and material samples from the BGL gasifier described above. Practical
experiences from the operation of the BGL-gasifier are also considered.
26-4
Economic Optimization of the Integrated Hot Metal, Heat and
Power Generation Based on the Coal Gasification Process
Marcin Liszka, Andrzej Ziebik, Silesian University of Technology, POLAND
The worldwide consumption of coal for not hot metal and steel production represents a
significant part of total coal demand. On the other hand, the well known possibilities for
integration between hot metal and power generation provide a big potential to increase the
fuel utilization efficiency and decrease environment pollution. However, the key problem of
such integration is cash flow economy. The steel&power plant, fed with coal is thus
analyzed within the frames of this paper from the thermodynamic and economic points of
view.
The system taken into consideration consists of the Corex island, combined cycle power
plant and air separation unit (ASU). The Corex process (trademark of Siemens-VAI) is one
of technologies for cokeless hot metal production belonging to the smelting reduction
family. Coal is gasified by oxygen in the hot metal environment, while the produced gas is
used as reducing agent (for iron ore) in another shaft reactor. From the power generation
point of view the most important feature of this technology is simultaneous production of hot
metal and medium-calorific gas which can be fired in gas turbine combustor. The overall
system (Corex, power island, ASU) can be thus perceived as some kind of multi-product
IGCC.
The case study presented here concerns the location of such an integrated IGCC in southern
Poland, nearby the existing steel mill and medium size city. Thus, the demands for district
heat and process steam have been also considered. The power plant becomes in this light a
CHP facility which, among mentioned above, might produce compressed air for high
pressure ASU and consume nitrogen - waste by product of air separation.
The simultaneous presence of Corex gas fuel (natural gas alternative) and demand for
different type energy carriers (for internal and external usage) provides large freedom for
optimization of the CHP plant structure and operating parameters. It has been assumed that
the Corex export gas is fired in gas turbine (GT) combustor. The GT unit is connected with
heat recovery steam generator (HRSG) and produced steam expands in multi pressure, tapcondensing
steam turbine (ST). The GT structure was assumed as a fixed simple cycle while
the HRSG and ST arrangements are free for optimization from point of view of number of
pressure levels and fractions of appropriate district water heaters in total district heat
production. The examples of other independent variables selected for optimization are:
natural gas to Corex gas admixture ratio, GT pressure ratio, GT firing temperature, minimal
temperature differences in HRSG, flow rate of compressed air form GT compressor to ASU,
ST extraction pressure, rate of supplementary firing in HRSG. Finally, 16 independent
variables have been qualified for optimization. This set of parameters and special techniques
of mathematical modeling, based on theory of superstructure allow for generation of
completely different structures during the optimization process, e.g. it is permissible (for the
model) to build double pressure combined cycle with reheat or GT unit with district heat
exchanger (no ST) or gas fired steam boiler with ST and extraction connected district heat
exchangers. The Net Present Value (NPV) has been adopted as the objective function of
optimization. Even though optimization deals mainly with the parameters of CHP unit, the
NPV has been calculated for cash flows crossing the boundary of whole integrated system.
Such an approach emphasizes the impact of power island parameters on the overall system
performance.
The applied computational strategy can be described in following steps: a) selection of
values of independent variables being optimized, b) design point simulation of CHP plant at
rated conditions, c) off-design simulation including whole year of operation with varying
ambient temperature, machines efficiencies and control procedures, d) calculation of
objective function on the basis of integrated (during a year) values of substance and energy
fluxes, e) selection of new parameters for optimization and return to point a.
All CHP plant facilities have been modeled on the GateCycle software. The off-design
models include, among others, the GT blade cooling and HRSG heat transfer coefficient
analyses. The control procedures and other additional algorithms were integrated as Visual
Basic macros.
23
Two optimization methods - genetic algorithm and Powells conjugate directions have been
coupled in one hybrid procedure to ensure high quality of results and reasonably low
computational effort.
The whole optimization analysis has been repeated several times for different price scenarios
on the coal, iron and electricity markets. In particular, the impact of rapid change of coal and
iron ore prices due to increased Asia demand has been considered.
26-5
Comparison of Thermodynamic Equilibrium Compositions for Indian Coals
Preeti Aghalayam, Anil Khadse, Mohammed Qayyumi, Sanjay Mahajani,
IIT Bombay, INDIA
A simple model is developed that predicts thermodynamic equilibrium compositions using
the ultimate analysis of coals. Coal is represented as CH x O y . The model is validated with the
pure carbon-steam system by comparison with literature. The thermodynamic equilibrium
compositions are predicted for three Indian coals and compared on the basis of product gas
compositions and gross calorific value. The results show that each coal has different
equilibrium compositions at identical set of operating conditions. Coals containing higher
H/C give more H 2 and CH 4 . The coals containing higher H/C give higher gross calorific
value at relatively higher pressures. Thus, high-pressure gasification like Underground Coal
Gasification may have an advantage over other processes in terms of product calorific value.
The inclusion of the energy balance equation in the equilibrium model will enable us to
predict the adiabatic gasification temperature. The model becomes complex due to this, but
the additional benefit is that a set of operating conditions is obtained, while reducing one
degree of freedom.
27-1
SESSION 27
COMBUSTION TECHNOLOGIES – 5:
COAL REACTIVITY AND KINETIC STUDIES
THERMACT - A Revolutionary breakthrough in Fire-Side Technology
Swatantra Kumar, Abhitech Energycon Limited, INDIA
Abhitech Energycon, in association with Indian Institute of Technology, Mumbai, has
developed a solid fuel additive-THERMACT, which when mixed with coal improves
the overall combustion efficiency, thereby reducing coal consumption and pollutants
like SO x , NO x , SPM etc. THERMACT is added in the proportion of 1 KG for 10-15
MT of Coal. Catalysts present in THERMACT convert carbon atoms in coal, into,
allotropes by sharing electrons in SP2 hybridization. These allotropes are in Soccer
ball shapes, known as Buckyballs, each consisting of 60 carbon atoms (C60) linked
together. Tremendous amount of energy is released when they are burnt. The hollow
structure of buckyballs traps other atoms inside them like a molecular cage.
THERMACT breaks the Oxygen and Hydrogen electronic bond in the water molecule
(inherent moisture). This liberated Hydrogen forms transitory methane, which gives
extra heat on combustion. In the presence of THERMACT the buckyballs formed react
with SO 2 to form polymeric compounds, which come down into ash. This prevents SO 3
formation reducing SO x emissions. Sulphur in fly ash is reduced & that in bottom ash
is increased. THERMACT decomposes metal silicates into silica and metal oxides
thereby reducing slag and clinker formation. THERMACT prevents formation of V 2 O 5 .
THERMACT reduces unburnts in fly ash as well as bottom ash and black smoke as a
result of an efficient & complete combustion of coal. THERMACT changes the flame
color to bright whitish yellow from orange indicating optimum combustion of coal.
THERMACT Advantages:
- Improves combustion
- Reduces Coal consumption
- Unburnts in fly and bottom ash
- Emissions
- Excess air consumption
- Continuity in the Plant Operations
- CO 2 emission also comes down due to reduced coal consumption.
THERMACT is presently being used in Power, Cement and Steel Plants in India.
27-2
Coal Characterization in a Drop Tube Furnace
Anne-Lise Brasseur, Anne Neveu-Dubosc, EDF R&D, FRANCE
Severine Pillet, ITG Consultants, FRANCE
A database on the coal characteristics is elaborated in order to provide the input data required
to take into account the fuel flexibility (numerous varieties of coals and mixtures) in the 3D
simulation of pulverized coal boiler. In this frame, the characterization of a series of coals,
from different ranks and origins, has been carried out on a drop tube furnace developed by
EDF R&D. This test facility is particularly suitable to study the parameters of the reactivity
of coal under experimental combustion conditions closest as possible to those of a PC boiler.
Thus this study reports the characterization of a series of coals both under pyrolysis and
combustion conditions, and especially, the coal reactivity constants (Arrhenius constants, Ec
and Ac) evaluated through a combustion model.

27-3
Studies in Pyrolysis and Combustion of Indian Coals
Using Thermogravimetric Analyzer
Preeti Aghalayam, Anil Khadse, Chinmay Ghoroi, Sanjay Mahajani, IIT Bombay,
INDIA
Experiments are performed to study the pyrolysis and combustion reactions for Indian
coals using a Thermogravimetric Analyzer (NETZSCH STA 409 PC/PG). Burning
profiles and volatile release profiles are obtained at various heating rates, in both air
and inert atmospheres, from 25 to 1000°C for three coal samples. Peak temperatures
are obtained and activation energies are calculated. The activation energies are in the
range 68.49-100.29 kJ/mol at a heating rate of 10°C /min, 66-88.13 kJ/mol at 20°C
/min and 52.74-74.93 kJ/mol at 30°C /min, for the combustion reaction. For pyrolysis,
activation energies are in the range 34.79-147.99 kJ/mol at 10°C /min, 38.40-166.74
kJ/mol at 20°C /min and 36.72-167.46 kJ/mol at 30°C /min.
27-4
Study of the Effect of FeCl 3 on the Ignition Point of Coal
Qiaowen Yang, Dongyao Xu, Wei Li, Aiguo Cheng, Jia Cao, Liying Wang, China
University of Mining & Technology, P.R. CHINA
The combustion supporting alternate agent of three coals was selected by Thermal Gravity
Analysis (TG) in this paper, it has been found that FeCl 3 plays great role on reducing the
ignition point of Guangxi Liang-coal, and FeCl 3 could effectively reduce the ignition point
of Xinwen raw coal and Guangxi An-coal also. It also stated that FeCl 3 has a good
combustion supporting action on the coal. At the same time, the relationship of FeCl 3
amount and the ignition point of coal were inspected; the optimum amount of FeCl 3 could be
got. We initially probed into the combustion supporting mechanism of FeCl 3 , during
combustion, the combustion supporting action of FeCl 3 was the results of common action of
chloride and iron in chemicals; The combustion supporting action of FeCl 3 was individually
achieved by reducing the ignition point of Volatile and Fixed Carbon.
27-5
Modeling and Simulation of Single Coal Particle Combustion
Anil Samale, Arvind Latey, College of Engineering Pune, INDIA
In the present study, a mathematical model to describe the combustion of single coal particle
is developed by incorporating improvement in the existing models available in the literature.
This model couples the heat transfer equation with the chemical kinetics equations. The
combustion rate has been simulated by considering the first order reaction (C+O 2 = CO 2 ).
The dependence of the convective heat transfer coefficient on Nusselt number is
incorporated in this model. A finite volume method using a TDMA scheme is used for
solving heat transfer equation and Runge-Kutta fourth order method for the chemical
kinetics equations. The model equation is solved for the spherical coal particle of equivalent
radius ranging from 0.00005 m to 0.0001m and temperature ranging from 300 K to 1000 K.
The simulated results obtained by using the present model are in excellent agreement with
experimental data, much better than the agreement with earlier model reported in the
literature. Simulation results capture expected qualitative trends in nature.
SESSION 28
ENVIRONMENTAL CONTROL TECHNOLOGIES:
MERCURY OXIDATION/CATALYSTS
28-1
Mercury Transformation Reactions on Model Fly Ashes
Sukh Sidhu, Patanjali Varanasi, University of Dayton Research Institute, USA
From results of our previous mercury oxidation study which was conducted using four
different Ohio coal fly ashes, it was observed that the chemical composition of surfaces
plays a very important role in mercury oxidation reactions. To further understand
mercury oxidation and its dependence on the chemical composition of fly ashes, a
series of experiments were conducted using model fly ashes. These model fly ashes
were prepared using flame soot as carbon source and iron oxide as metal oxide
catalyst. Vanadia supported on titania was also used as a catalyst in order to compare
mercury oxidation observed on the surface of model fly ashes with that on SCR
catalyst. To keep catalytic bed characteristic same for all surfaces the catalytic surface
were dispersed on quartz wool. In all experiments, the inlet concentration of Hg 0 (g)
was maintained at 47 µg/m 3 using a permeation device as the source of Hg 0 (g). All
experiments were conducted using 4% O 2 in nitrogen mix as a reaction gas, and other
reactants (HCl, H 2 O) were added as required. The fixed bed catalytic reactor was
operated over a temperature range of 300 to 500°C. In each experiment the reactor
effluent was sampled using modified Ontario-Hydro method. After each experiment,
fixed beds were also analyzed for mercury. It was observed that soot is more active in
mercury oxidation than vanadia/titania and iron oxide catalyst. Results also show that
over the surface of metal oxide catalysts mercury oxidation is only weakly dependent
on temperature.
28-2
Experimental Investigation and Theoretical Calculation on Effect of C12
on Mercury Oxidation in Coal Fire Combustion Process
Wei-Ping Pan, Songgeng Li, Quanhai Wang, Yan Cao, ICSET of Western Kentucky
University, USA
Mercury (Hg) from coal power plants has been identified as the hazardous air pollutant
of greatest public health concern. Hg in the flue gas occurs as three main forms: the
gaseous elemental mercury Hg(0), the gaseous oxidized Hg(2+), and particulate
mercury, Hg(p). Hg(2+) is water soluble, highly absorbable on fly ash and has a low
vapor pressure. Therefore, relative to Hg(0), Hg(2+) is more effectively captured in
conventional Air Pollution Control Devices (APCD) such as wet scrubbers (FGD),
fabric filters (FF) and electrostatic precipitator (ESP). However, Hg(0) is firstly
vaporized in the flue gas at higher temperature zone in combustor, followed by
thermodynamically favored oxidation process to major occurrence of Hg(2+) through
the homogeneous and the heterogeneous reaction routines at downstream flue gas pass
as temperature is cooled down. Thus, identifying the mechanism of mercury oxidation
in the downstream flue gas pass is very important to improve mercury emission control
efficiencies by APCD in the coal-fired boilers. Based on facts that HgCl 2 is the main
Hg(2+) in coal-fired combustion process, as well as enormous previous studies on Hg
oxidation, it has been generally accepted that chlorine-containing species are the most
important factor on the Hg(0) oxidation in coal-fired flue gas. Chlorine is evolved
during coal combustion primarily as hydrochloric acid (HCl), less chance as chlorine
molecule (Cl 2 ) through the Deacon reaction under fly ash available conditions.
However, the possible concentration of Cl 2 is still much higher than request by the Hg
oxidation process. Moreover, the flue gas chemistry may dramatically impact this
oxidation process by the intermediate reactions to affect production of chlorine ion,
which is more active in the Hg oxidation process. In this work, isolated effects of Cl 2
and HCl or their effects including other flue gas species on Hg oxidation under a
largely varied temperature window were investigated in a special designed multi-phase
flow reactor. A thermal-dynamic and kinetics calculation is used to explore the maxim
Hg oxidation rate and possible reaction mechanisms.
28-3
A Theoretical Cluster Approach to Understanding Mercury
Adsorption to Halogen-Embedded Activated Carbon
Bihter Padak, Michael Brunetti, Jennifer Wilcox, Worcester Polytehcnic Institute,
USA
Ab initio methods have been employed for the modeling of activated carbon surface
using a fused-benzene ring cluster approach. Oxygen functional groups have been
investigated for their promotion of effective elemental mercury adsorption on the
activated carbon surface sites. Lactone and carbonyl functional groups yield the
highest mercury binding energies. Additionally, halogen atoms have been added to the
modeled surface, and have found to increase the activated carbon’s mercury adsorption
capacity. The mercury binding energies increase with the addition of the following
halogen atoms, F > Cl > Br > I, with the addition of fluorine being the most promising
halogen for increasing mercury adsorption.
28-4
Survey of Catalysts for Oxidation of Mercury in Flue Gas
Evan J. Granite, Albert A. Presto, DOE/NETL, USA
The United States Environmental Protection Agency issued a regulation in March of
2005 for the emission of mercury from coal-burning power plants. In addition, several
states have also enacted legislation requiring control of mercury emissions from coalburning
plants. Mercury is a neurotoxin and accumulates within the food chain.
Elemental mercury is difficult to capture from a gas stream. Much of the mercury
contained in power plant flue gas is in the elemental form. Elemental mercury is a
semi-noble metal, is insoluble in water, and is not captured efficiently by carbon.
Mercuric chloride is highly soluble in water, and is more readily removed by carbon. A
catalyst that can oxidize elemental mercury to mercuric chloride (or another
compound) would be of tremendous value. A catalyst would enable mercury to be
captured by existing air pollution control devices (APCDs) present in coal-burning
power plants. These existing APCDs include wet scrubbers for acid gas removal, as
well as electrostatic precipitators (ESPs) and baghouse filters for particulate removal.
The mercury oxidation catalyst can be located upstream of the appropriate APCD.
Mercuric chloride is readily removed by the scrubbing solutions employed for acid gas
removal. Mercuric chloride is easily removed by adsorption on unburned carbon in fly
ash captured in ESPs or baghouse filters. Mercuric chloride is also sequestered by
activated carbon sorbents injected upstream of an ESP or baghouse. Several materials
have been proposed as catalysts for oxidation of mercury. These materials include
palladium, gold, iridium, platinum, SCR catalysts, fly ash, activated carbons, Thief
carbons, and halogen compounds. Previous results obtained with these catalysts are
reviewed. Several mechanisms of mercury oxidation are proposed, and future research
directions are suggested. Alternative catalysts and supports will be suggested, and an
extensive list of references will be provided. The work presented in this manuscript
was recently accepted for publication in Environmental Science & Technology.
24

28-5
A Kinetic Approach to Catalytic Oxidation of Mercury in Flue Gas
Evan J. Granite, Albert A. Presto, Henry W. Pennline, Andy Karash, William J.
O’Dowd, Richard A. Hargis, DOE/NETL, USA
Several materials have been examined as catalysts for the oxidation of mercury in a
bench-scale packed-bed reactor located at NETL. The catalysts examined include
activated carbon, Thief carbons, precious metals, fly ash, and halogen compounds.
Slipstreams of flue gas generated by the NETL 500-lb/hr pilot-scale combustion
facility were contacted with the catalysts. An on-line continuous emissions monitor
(CEM) was employed to measure elemental and oxidized mercury entering and exiting
the bed. The apparent activation energy and reaction order for mercury were
determined for several of the catalysts. Future research on catalyst materials will be
conducted in a bench-scale packed-bed reactor employing both simulated and real flue
gas streams generated on-site at NETL. The work presented in this manuscript was
also accepted for publication in Energy & Fuels.
SESSION 29
GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND
HYDROGEN APPLICATIONS – 1
29-1
Coal IGCC Turbine Technology Improvements for Carbon Free Fuels
Ashok Anand, Benjamin Mancuso, Kevin Collins, Greg Wotzak, GE Energy, USA
Reduction of carbon dioxide from Coal-based IGCC Power Plants is rapidly gaining
increased interest in future installations. Studies have shown that IGCC technology is
able to capture and remove carbon dioxide at lower economic penalty as compared to
conventional pulverized coal fired steam plants. Further improvements in IGCC power
plants with carbon capture, is possible though the development of specific gas turbine
cycle designs that increase plant efficiency at reduced costs and emissions. The
performance influence of a typical heavy-duty gas turbine’s cycle parameters on IGCC
plant with carbon capture is presented. An optimization analysis method is described,
which can be successfully applied to select a gas turbine cycle design to achieve plant
level performance goals.
29-2
Advanced Hydrogen Turbine Development
Ed Bancalari, Ihor S. Diakunchak, Pedy Chan, Siemens Power Generation, Inc., USA
The Advanced Hydrogen Turbine Development Project objective is to design and develop a
fuel flexible (coal derived hydrogen or syngas) advanced gas turbine for Integrated
Gasification Combined Cycle (IGCC) and FutureGen type applications that meets the U.S.
Department of Energy (DOE) turbine performance goals. The overall DOE Advanced
Power System goal is to conduct the Research and Development necessary to produce CO 2
sequestration ready coal-based IGCC power systems with high efficiency (45-50% [HHV]),
near zero emissions (< 2 ppm NO x @ 15% O 2 ) and competitive plant capital cost (<
$1000/kW). DOE has awarded Siemens Power Generation a contract for Phases 1 and 2
development work. Phase 1 activities will include identification of advanced technologies
required to achieve the Project goals, detailed Research & Development Implementation
Plan preparation and conceptual designs for the new gas turbine components. In Phase 2, the
identified concepts/technologies will be down selected and a detailed design of the gas
turbine will be completed. Phase 3, which has not yet been awarded, will involve the
advanced gas turbine and IGCC plant construction and validation/demonstration testing. The
end objective is to validate the advanced gas turbine technology by 2015. The starting point
for this development effort is the SGT6-6000G gas turbine. This gas turbine will be adapted
for operation on coal and biomass derived hydrogen and syngas fuels, as well as natural gas,
while achieving high performance levels and reduced capital costs. This paper describes
Phase 1 activities and accomplishments in the first 9 months since the program was initiated.
29-3
Benefits to IGCC Gas Turbines of Advanced Vortex Combustion
Robert Steele, Pete Baldwin, Ramgen Power Systems, USA
Ramgen Power Systems is developing an Advanced Vortex Combustion (AVC) technology
for combustion of hydrogen-based fuels which shows tremendous potential for increased
energy efficiency and improved asset utilization. The fundamentals of the technology and
the potential advantages of incorporating the AVC approach into an IGCC gas turbine will
be presented. The AVC technology can be applied to the efficient and cost-effective
combustion of hydrogen-based fuels with sub-3 ppmv NO x emissions while maintaining or
extending simple cycle efficiencies. The AVC technology has the potential for improved
turbine efficiency, lower NO x
emissions, greater flame stability, high flame speed flexibility, increased durability, and
reduced manufacturing costs. This approach can play an important role in the advancement
of future Integrated Gasification Combined Cycle (IGCC) power plants that will require
hydrogen-enriched fuel burning gas turbines. The flame speed of hydrogen-air mixture is six
times higher than a natural gas-air mixture. Conventional swirl-based combustion systems
25
need customized modifications in order to manage the potential for flame flashback. The
unique insensitivity of the AVC approach to high through-put velocities will reduce
hardware modifications and accommodate the extremely fast burning hydrogen-based fuels.
In addition, Ramgen’s AVC technology is cross-cutting and capable of delivering benefits to
many of the technical areas of concern in zero-emissions combustor-based facilities
including the oxy-fuel Rankine cycle system.
29-4
Catalytic Combustion for Ultra-Low NO x Hydrogen Turbines
Benjamin Baird, S. Etemad, Sandeep Alvandi, William C. Pfefferle, H. Karim,
Precision Combustion, Inc., USA
Kenneth O. Smith, W. Nazeer, Solar Turbines, Inc., USA
Precision Combustion, Inc. (PCI), under sponsorship from the U.S. Department of
Energy, is further developing it’s Rich Catalytic Lean-burn (RCL®) combustion
system for hydrogen fuels. Rich catalytic operation has successfully demonstrated low
single digit ppm NO x and the ability to burn hydrogen fuels in 9 atmosphere subscale
tests. The test data show the potential of using rich catalytic combustion for low single
digit emissions. Areas of further work to commercialize this technology has been
identified. PCI, in collaboration with Solar Turbines Incorporated and other gas turbine
manufacturers, has a 39 month DOE Fossil Energy Turbine Technology R&D program
to develop and demonstrate a low emission rich catalytic combustion system for fuel
flexible ultra-low NO x megawatt-scale gas turbines that can utilize hydrogen fuel,
facilitate high efficiency operation, and be installed or retrofitted into existing turbines.
This paper presents the status of the rich catalytic application from the combustion
point of view for MW size engine application.
29-5
Development of Turbo Machinery for a Zero CO 2 Emissions Oxy-Fuel Cycle
Mohan A. Hebber, Shiv Dinkar, Juan Pablo Gutierrez, Siemens Power Generation, Inc.
Jim Downs, Florida Turbine Technologies, Inc., USA
In 2005 the U.S. Department of Energy-National Energy Technology Laboratory (DOE-
NETL) awarded a program to Siemens Power Generation (SPG), Inc. to develop turbo
machinery powered by oxy-fuel combustion, which generates near zero emissions and
provides for economical CO 2 capture capability. (The combustor for this oxy-fuel cycle is to
be developed separately by Clean Energy Systems (CES), Inc. of Rancho Cordova,
California.). The new working fluid (a mixture of CO 2 and steam) and the desire to
maximize the plant cycle efficiency pose numerous technical challenges not only in
developing the turbine designs and consideration of material systems, but also in the
selection of a plant cycle. The calculation of auxiliary loads for Fuel Processing Plant
(gasifier), Air Separation Unit (ASU), O 2 compression, CO 2 compression, limitations on
metal temperatures and other boundary conditions – all posed difficulties in arriving at
cycles for further consideration. Any turbine design that depends on boundary conditions
higher than the current state-of-the-art poses special challenges in the selection of materials.
Initial studies indicate that materials in the turbine for the “topping” cycle may have to
tolerate a Turbine Inlet Temperature (TIT) well in excess of 1500°C with CO 2 and H 2 O as
working fluid. With regards to the steam turbine in the “bottoming” cycle, major challenges
are anticipated in selecting materials for the turbine casing, rotor, blading, valves, sealing and
bolting. Other challenges include innovative cooling techniques including, but not limited to,
the development of serpentine cooling paths; development of start-up procedures and
algorithms for controls and life consumption. The paper describes approaches planned to
overcome the technical challenges and develop turbine designs that meet the overall
objectives of the program including the efficiency goals. An overall time line is also
identified for key milestones.
SESSION 30
GLOBAL CLIMATE CHANGE: CO 2 CAPTURE – 2:
MEMBRANES AND SOLID SORBENTS
30-1
Experimental Investigation of a Molecular Gate Membrane for
Separation of Carbon Dioxide for Flue Gas
James Hoffman, Henry W. Pennline, DOE/NETL, USA
Shingo Kazama, Teruhiko Kai, Takayuki Kouketsu, Shigetoshi Matsui, Koichi
Yamada, RITE, JAPAN
Commercial-sized modules of the PAMAM dendrimer composite membrane with high
CO 2 /N 2 selectivity and CO 2 permeance were developed according to the In-situ Modification
(IM) method. This method utilizes the interfacial precipitation of membrane materials on the
surface of porous, commercially available polysulfone (PSF) ultrafiltration hollow fiber
membrane substrates. A thin layer of amphiphilic chitosan, which has a potential affinity for
both hydrophobic PSF substrates and hydrophilic PAMAM dendrimers, was employed as a
gutter layer directly beneath the inner surface of the substrate by the IM method. PAMAM
dendrimers were then impregnated into the chitosan gutter layer to form a hybrid active layer
for CO 2 separation. Permeation experiments of the PAMAM dendrimer composite
membrane were carried out using a humidified mixed CO 2 / N 2 feed gas at a pressure

difference up to 97 kPa at ambient temperature. When conducted with CO 2 (5%) / N 2 (95%)
feed gas at a pressure difference of 97 kPa, the PAMAM composite membrane exhibited an
excellent CO 2 /N 2 selectivity of 150 and a CO 2 permeance of 1.7×10 -7 m 3 (STP) m -2 s -1 kPa -1 .
The impact of various process parameters on the permeability and selectivity was also
examined.
30-2
An Analysis of Dense Hydrogen Membranes as a Means of Producing a CO 2 Rich
Stream Consistent with the CO 2 Capture Requirements of a Futuregen Plant
Paul J. Grimmer, Carl R. Evenson IV, Xiaobing Xie, Harold A. Wright, Clive
Brereton, Warren Wolfs, Eltron Research Inc., USA
Several methods have been proposed for capturing CO 2 from coal combustion. Most
involve scrubbing CO 2 from the low-pressure combustion gases. Eltron, NORAM and
their partners are developing a system built around Eltron’s hydrogen separation
membrane in which the synthesis gas from a coal gasifier is converted to CO 2 and H 2
prior to combustion and the CO 2 and H 2 are separated, leaving the H 2 for fuel and the
CO 2 “captured” at high pressure, ready for sequestration. This work is partially funded
by the DOE as part of the FutureGen clean coal initiative. The system produces
essentially 100% pure H 2 which can readily be used in gas turbines, various types of
fuel cells, used in various crude oil refining and petrochemicals or even as a starting
point for the “Hydrogen Economy”. Although the membrane and its accompanying
“no-carb” fuel system have wide application, this paper focuses on use of the system in
coal gasification. Comparisons are made for capital and operating costs and
performance of the “no-carb” system versus both currently available systems and those
still in development. There have been a number of recent advances in the development
of these membranes. Experiments have shown that no sweep gas is needed in current
operation; they have also shown that the H 2 permeate pressure can now be up to H 2
pipeline pressures for ease of downstream use, and that staged systems with >90%
hydrogen recovery with lower hydrogen compression costs are possible. These recent
advances will be examined from an economic perspective.
30-3
CO 2 Adsorption by Dendrimers Bound to Mesoporous Substrates
Alan Chaffee, Zhijian Liang, Bandar Fadhel, Caspar J. Schneider, Monash University,
AUSTRALIA
Chemical absorption, by amine solvents has long been used by industry for acid gas
removal. Amine-based chemical solvents absorb CO 2 very selectively. However,
regeneration of the solvent is energy-intensive and is also plagued by the generation of
corrosive byproducts. Recently, solid adsorbents based on amine functionalized substrates
have been proposed as a possible means of overcoming these limitations via the Pressure
Swing Adsorption (PSA) process. This paper will report our investigation of CO 2 adsorption
efficiencies for a stepwise growth series of amine terminated melamine dendrimers that have
been iteratively grown (generations 0 to 4) within the channels of SBA-15 and related
mesoporous silica substrates. The CO 2 adsorption efficiencies of the materials were
determined from thermogravimetric analysis (TGA) and adsorption isotherm measurements.
The adsorption efficiencies were found to be dependent upon both temperature and structure
(support material and dendrimer generation). Heats of CO 2 adsorption, measured by
differential thermal analysis (DTA), in the range of 40 - 60 kJmol -1 , suggest that strong
interactions form during adsorption. Nevertheless, these heats of adsorption are less than
those reported for amine solvents, suggesting that, with these materials, the energy
requirement for sorbent regeneration will be lower.
30-4
CO 2 Release Property of Lithium Silicate under Reduced Atmosphere
Masahiro Kato, Toshihiro Imada, Kenji Essaki, Yasuhiro Kato, Toshiba Corporation,
JAPAN
A novel CO 2 separation technique that employs the chemical reaction of lithium-containing
oxide with CO 2 has been developed. Because this method is effective in the temperature
range from 450°C to 700°C, it has the advantage of enabling CO 2 separation in power plants
without lowering the temperature. As a result, the energy needed for CO 2 capture is expected
to be much lower than with conventional methods such as the amine method. Among all
absorbents, lithium orthosilicate (Li 4 SiO 4 ) shows immediate CO 2 absorption and release,
which results in an obvious weight change of up to 36%. However, in order to remove and
capture high-purity CO 2 , CO 2 release should be conducted in a 100% pure CO 2 atmosphere.
Under such conditions, the temperature must be more than 800°C, and degradation of
absorption properties tends to occur. This study focused on reducing the pressure to lower
the CO 2 release temperature, and cyclic testing was performed for up to 500 cycles. The
results showed that the release temperature was lowered to 700°C under 0.7 atm of pure
CO 2 , and the absorption ratio was found to be maintained at about 90% of the initial value.
30-5
CO 2 Capture Utilizing Solid Sorbents
Abbie Layne, Ranjani Siriwardane, DOE/NETL, USA
Clark Robinson, Research Development Solutions, USA
26
Combustion of fossil fuels is one of the major sources of the greenhouse gas CO 2 . Pressure
swing adsorption/sorption (PSA/PSS) and temperature swing adsorption/sorption
(TSA/TSS) are some of the potential techniques that could be utilized for removal of CO 2
from fuel gas streams. It is very important to develop sorbents to remove CO 2 from fuel gas
streams that are applicable for a wide range of temperatures. NETL researchers have
developed novel CO 2 capture sorbents for both low temperature and moderate temperature
applications.
Novel liquid impregnated solid sorbent was developed for CO 2 removal in the temperature
range of ambient to 60°C. The sorbent is regenerable at 60-80°C. Multi cycle tests conducted
in an atmospheric bench scale reactor with simulated flue gas indicated that the sorbent
retains its CO 2 sorption capacity (~ 2 moles of CO 2 /liter of the sorbent) with CO 2 removal
efficiency of about 99%. Presence of water vapor did not affect the performance of the
sorbent. The sorbent was also tested in a high pressure (20 atm.) bench scale flow reactor
with simulated coal gas. The CO 2 sorption capacity (~ 6 to 9 moles of CO 2 /liter of the
sorbent) at high pressure was significantly higher than that at atmospheric pressure. The CO 2
absorption capacity was higher at higher concentrations of CO 2 . It was possible to regenerate
the sorbent at 20 atm in the presence of water vapor. The sorbent retained the CO 2 sorption
capacity during a 30 cycle test conducted at 20 atm. Results of the bench scale multi cycle
flow reactor tests and results of the system analysis will be discussed in the paper.
A novel solid sorbent containing mixture of alkali earth and alkali compounds was
developed for CO 2 removal at 200-250°C from high pressure gas streams suitable for IGCC
systems. The sorbent showed very high capacity (4 moles of CO 2 /kg of sorbent) for CO 2
removal from a gas streams containing 28% CO 2 at 200°C and at 20 atm during a lab scale
reactor test. This sorbent can be regenerated at 20 atm and at 375°C utilizing a gas stream
containing steam. High pressure and high CO 2 concentration enhanced the CO 2 sorption
process. Results of the ten-cycle test with the sorbent and potential applications will also be
discussed in the paper.
31-1
SESSION 31
GASIFICATION TECHNOLOGIES:
ADVANCED TECHNOLOGY DEVELOPMENT – 1
“CoalFleet for Tomorrow” IGCC Research, Development and
Demonstration Augmentation Plan
John Wheeldon, Neville Holt, Jeffrey Phillips, John Parkes, EPRI, USA
The industry initiative “CoalFleet for Tomorrow” was launched in November 2004 to
accelerate the deployment and commercialization of clean, efficient, advanced coal power
systems, thereby preserving coal as a vital component in the electric generation mix. The
“CoalFleet” initiative has participation by over 50 organizations including power generators
of various types, suppliers, engineering firms, Department of Energy, and other US and
international organizations. CoalFleet is tackling the technical and economic/institutional
challenges of making advanced coal power plants a prudent investment option both in the
short term and in the long term, while taking into account the potential for future CO 2
emissions regulations.
As part of the CoalFleet for Tomorrow initiative in 2005, the Electric Power Research
Institute (EPRI) created research, development & demonstration (RD&D) augmentation
plans for IGCC and combustion technologies. The purpose of the plans was to identify
RD&D needs, over and above the activity already underway or planned, which is needed to
foster the early deployment of these advanced coal-based generation technologies.
This paper focuses on the long-term roadmap portion of the CoalFleet IGCC RD&D
augmentation plan and identifies the important technology improvements which could be
implemented to improve the economics of IGCCs incorporating CO 2 capture. The roadmap
indicates that IGCCs with CO 2 capture could potentially be built at lower $/kW cost and
with higher thermal efficiency than today’s IGCCs without CO 2 capture.
This paper will describe the motivation for creating the plan and provide brief descriptions of
the key steps in the long term roadmap. The steps where additional RD&D effort is needed
are identified, and the most appropriate entities (e.g., government, technology suppliers, or
power industry collaborative) for carrying the various elements of the roadmap are
discussed.
31-2
Current and Future IGCC Technologies: Bituminous Coal to Electric Power
David Gray, Charles White, John Plunkett, Sal Salerno, Mitretek Systems, USA
Glen Tomlinson, Consultant, USA
The United States Department of Energy through the National Energy Technology
Laboratory (NETL) is funding research & development (R&D) whose objective is to
improve the efficiency and reduce the costs of advanced Integrated Gasification
Combined Cycle (IGCC) technologies for generation of clean electric power. In order
to evaluate the benefits of the ongoing R&D, NETL contracted Mitretek Systems to
utilize their Energy Systems Analysis capabilities and conceptual computer simulation
models to quantify the potential impact of successful R&D on the IGCC system.
Mitretek Systems has developed detailed computer simulation models of IGCC
configurations. These spreadsheet based models simulate the gasification of coal to
clean synthesis gas and the subsequent utilization of this gas in gas turbine and steam

turbine cycles. The models provide complete material and energy balances of the
system and are flexible with respect to technology and configuration. They also
estimate capital and operating costs and calculate the required selling price (RSP) of
the electric power based upon standard discounted cash flow (DCF) analysis.
Emerging advanced gasification, advanced gas cleaning, and novel gas and steam
turbine technologies can be incorporated into the baseline (based on current
technologies) IGCC configuration. Also, advanced air separation technology and fuel
cell technologies can be integrated into the IGCC configuration. Incorporation of these
advanced technologies into the baseline IGCC plant allows a quantitative estimate of
the potential benefits of these technologies. These benefits are measured ultimately in
terms of improved thermal efficiency (reduced heat rate) and in reduction of the cost of
electric power. In this paper, a baseline IGCC configuration that is representative of
the current state of the art is first established. Sequential improvements have then been
assumed for this base plant. These improvements include changing the gasifier feed
system from a water slurry to a dry feed pump, greater on-stream time or capacity
factor, advanced warm gas cleaning, advanced gas turbine systems, ceramic membrane
technology for air separation, and finally integration of solid oxide fuel cells as a
topping cycle before the gas turbine. The order of introduction corresponds with the
timeline in which R&D for these improvements is expected to be completed. To the
extent possible, the same plant size was used for all configurations analyzed. However,
because the gas turbine input determines to a great extent the plant size, when
advanced turbines were used the overall plant size was adjusted to be compatible with
the gas turbine input.
31-3
Field Trial Results of an Improved Refractory Material for Slagging Gasifiers
James Bennett, Kyei-Sing Kwong, Cynthia Powell, Hugh Thomas, Art Petty,
DOE/NETL, USA
H. David Prior, ANH Refractries Corp., USA
Mark Schnake, Harbison-Walker Refractories Company, USA
Gasifiers are used commercially to react a carbon feedstock with water and oxygen
under reducing conditions; producing chemicals used as feedstock for other processes,
fuel for power plants, and/or steam used in other processes. A gasifier acts as a high
temperature, high pressure reaction chamber, typically operating between 1250-
1575°C, and with pressures between 300-1000 psi. Ash that originates from mineral
impurities in the carbon feedstock becomes a by-product of gasification. In a slagging
gasifier it melts, forming a liquid which flows down the gasifier sidewall; penetrating
and wearing away the refractory liner by corrosive dissolution, abrasive wear, or by
other processes such as spalling. The refractory liner must withstand the severe service
environment, protecting the steel shell against corrosive gases, temperature, and
material wear. Users have identified refractory service life as the most important
limitation to sustained on-line availability of gasifiers, limiting gasifier acceptance and
use by industry. The National Energy Technology Laboratory in Albany, OR, has
developed and patented (US Patent # 6,815,386) a phosphate containing high chrome
oxide refractory for use in slagging gasifiers. In cooperation with ANH Refractories
Company, this refractory material has been commercially produced and is undergoing
field tests in commercial gasifiers. An analysis of data from these field tests indicates
that the phosphate containing refractory results in an improved service life over other
refractory materials currently used as gasifier liners. Results from the post-mortem
analysis of the field trial in relation to the failure mechanisms in a slagging gasifier
will be presented.
31-4
ITM Oxygen: Enabling Technology for Clean Coal
Phillip A. Armstrong, ITM Oxygen, USA
Douglas L. Benette, EP (Ted) Foster, VanEric E. Stein, Air Products and Chemicals,
Inc., USA
Presently over 10% of methane natural gas produced in the United States is from coal
seams. Average gas content of coal seams is 50-500 scf per ton of coal in the
Appalachian, Raton, San Juan, and Powder River coal seams. The lowest gas content is
in the Powder River Basin. During the past 20 years of increased commercial activities
in these areas, the gas production is steadily declining in many of the wells. However,
with increasing energy prices, the demand for natural gas has substantially increased.
Today the existing reserves of coal exceed 400 billion tons and almost 5.6 trillion tons
of coal resources are estimated by the USGS at an unmineable depth. An in situ
bioconversion of these vast resources of coal can become a source of large domestic
supply of natural gas.
Methane formation is an end product of anaerobic degradation of organic matters
including coal in the natural environment. To date biological techniques for production
of methane from coal have not been demonstrated on a large scale. The objective of
this research is to establish the feasibility of ARCTECH MicGASTM technology for in
situ enhancement of methane generation in deep coal seams.
The feasibility of this approach has been established by utilizing anaerobic microbial
consortia (Mic1) derived from the hind guts and soil eating termites to convert coals
into methane and CO 2 . Laboratory tests were conducted with Powder River Basin subbituminous
core coal samples under simulated subsurface conditions (saturation at
66% coal loading) by growing Mic1 culture (lysed or live) mixed with media or
laboratory simulated groundwater under anaerobic conditions at ambient temperature
or 37°C. Bacterial count with Epifluorescence methods, pH measurements, volatile
fatty acid content, gas composition and gas volume measurements were conducted
periodically to evaluate methane generation from coal samples over 6 months.
At ambient temperature, results indicated that gas was generated at an estimated rate of
350 scf/ton of coal/year. However, at 37°C, gas was produced at a higher rate of 900
scf/ton/year as compared to the positive and negative controls.
The microscopic observation confirmed the aforementioned results. Mic1 culture
grown in medium with core coal showed higher bacterial count with predominantly
filamentous and rod shapes compared to Mic1 grown in groundwater and medium in
the absence of coal. Validation tests were also conducted at simulated high pressure
(300 psi) which also resulted in methane production. An anaerobic fermentation kinetic
model based on the laboratory results predicted a production potential of 3-7 million
scf/day from thick Powder River Basin coal seams. This paper will provide a rigorous
test protocol for this feasibility study, laboratory tests, procedures, and approach for
commercial scale production.
31-5
Nuclear-Coal Cycle
Vladimir Popov, Krzhizhanovsky Power Engineering Institute, RUSSIA
The logic of the present-day power engineering evolution dictates that coal shall be
considered not only as a conventional fuel for heat and electric energy (e.e.)
generation, but also as a material, which can potentially become a source for producing
some chemical products, motor fuel inclusive. The geography of the coal fields is such
that in many regions they are the only (or prevailing) source of raw materials (currently
used as fuel). Force majeur situations, that compelled some countries (not without
success) to address coal as a source material for production of motor fuel on industrial
scale, are known in the history of the past century.
Nonetheless, in the post-war period the relevant technologies did not find extensive
use, which was explained by economic reasons, i.e. opening of oil and gas fields. Since
resources of coal in the medium- and long run are incomparable to those of any other
organic energy resource, the today s oil and gas euphoria cannot last long and it will
pass earlier than one can envision. It will be followed by the coal-nuclear era, that will
take up hundreds of years, even if no breeder reactors are used. Incremental growth of
e.e. consumption in time will aggravate the situation still more. Up to the present day
the use of nuclear and coal energy sources used to be (and still is) absolutely separated
from each other, conforming to the difference in the nature of nuclear and chemical
forces. The difference is very explicitly pronounced in the emerging terminology
nuclear and coal cycle. The cycles mentioned have their own intrinsic drawbacks and
advantages. The technical disadvantage of the first cycle consists in compliance with
the most stringent safety requirements (the requirements being followed deliberately
and uncompromisingly) and low efficiency of nuclear energy conversion to e.e., the
problem, which is comprehended, but cannot be solved, at least until high-temperature
gas reactor is constructed. The problems inherent of the coal cycle are well-known and
they cannot be solved either, owing to the lack of industrial methods of carbon dioxide
capture. In this context, not quite new, though modernized, approach, i.e. integration of
the cycles for enhancing the relevant positive and mitigating the relevant negative
features, can suggest an alternative way out. The approach is based on setup of an
integrated energy-technological complex, comprising: (1) a pyrolyzer for partial
catalytic oxidation of the initial brown coal to semi-coke; (2) a modular nuclear
reactor, generating e.e. and heat (its thermal power 200 MW, its electric power 50
MW, helium temperature (°C) at the core inlet and outlet 300/750-950, helium pressure
5 MPa, making use of spherical fuel elements); (3) a catalytic gasifier of the semi-coke
with steam superheated (~800°C;) in the nuclear reactor, producing syngas (H 2 /CO ≈
45/45); and (4) the Fischer- Tropsch synthesizer. Its catalyst is a cheap product. Partial
replacement of coal energy with nuclear energy during generation of e.e., heat and
chemical products, motor fuel inclusive, can be mentioned among the main specific
features of the process. The use of an energy-technological facility of this type will be
especially advantageous in hard to reach places with no transport infrastructure. The
process is based solely on published domestic developments (both design and
experimental ones).
The author is deeply appreciative and grateful to the John D. and Catherine T.
MacArthurs Foundation for awarding a grant (No. 04-81306-000-GSS) in support of
program of individual research projects.
SESSION 32
GASIFICATION TECHNOLOGIES:
FUNDAMENTALS AND SIMULATIONS – 3
32-1
Impact of Coal Quality and Gasifier Technology on IGCC Performance
Ola Maurstad, Olav Bolland, Norwegian University of Science and Technology,
NORWAY
Howard Herzog, Janos Beer, MIT, USA
27

Integrated coal gasification combined cycle (IGCC) plants with pre-combustion
capture of CO 2 represent one of the most promising near-term options for power
generation with carbon capture and storage. This work investigates to what extent
IGCC performance (with and without CO 2 capture) is affected by coal quality for two
different entrained flow slagging gasifiers. Based on an IGCC model developed in
Aspen Plus and combined with GTPRO, mass and energy balances were computed.
Two gasification technologies were considered: A dry feed gasifier with syngas heat
recovery which represents the Shell technology, and a slurry feed gasifier with full
water quench which represents the GE technology. For each gasifier, five different
coals were used and alternatives with and without CO 2 capture calculated. It was found
that the efficiency, CO 2 emissions and net power output of the slurry feed IGCC was
strongly dependent on coal type, and had lowest performance for low rank coals. On
the other hand, the dry feed IGCC was little affected by coal type. The slurry feed
IGCC performed closest to the dry feed IGCC when CO 2 was captured and the two
highest rank bituminous coals were used.
32-2
Gasification of Lignite in a Transport Reactor
Michael Swanson, Douglas R. Hajicek, Michael E. Collings, Ann K. Henderson,
University of North Dakota, USA
Ronald Breault, DOE/NETL, USA
The U.S. Department of Energy (DOE) National Energy Technology Laboratory
(NETL) Office of Coal and Environmental Systems has as its mission to develop
advanced gasification-based technologies for affordable, efficient, zero-emission
power generation. These advanced power systems, which are expected to produce
near-zero pollutants, are an integral part of DOE’s Vision 21 Program. DOE has also
been developing advanced gasification systems that lower the capital and operating
costs of producing syngas for chemical production. A transport reactor has shown
potential to be a low-cost syngas producer compared to other gasification systems
since its high-throughput-per-unit cross-sectional area reduces capital costs. This work
directly supports the Power Systems Development Facility utilizing the Kellogg,
Brown, and Root transport reactor located at the Southern Company Services
Wilsonville, Alabama, site. Over 2700 hours of operation on 16 different coals ranging
from bituminous to lignite along with a petroleum coke has been completed to date in
the pilot-scale transport reactor development unit (TRDU) at the Energy &
Environmental Research Center (EERC). The EERC has established an extensive
database on the operation of these various fuels in both air-blown and oxygen-blown
modes utilizing a pilot-scale transport reactor gasifier. This database has been useful in
determining the effectiveness of design changes on an advanced transport reactor
gasifier and for determining the performance of various feedstocks in a transport
reactor. The effects of different fuel types on both gasifier performance and the
operation of the hot-gas filter system have been determined. It has been demonstrated
that corrected fuel gas heating values ranging from 90 to 130 Btu/scf have been
achieved in air-blown mode, while heating values up to 230 Btu/scf on a dry basis have
been achieved in oxygen-blown mode. Carbon conversions up to 95% have also been
obtained and are highly dependent on the oxygen– coal ratio. Higher-reactivity (lowrank)
coals appear to perform better in a transport reactor than the less reactive
bituminous coals. Factors that affect TRDU product gas quality appear to be coal type,
temperature, and air–coal ratios. Testing with a higher-ash, high-moisture, low-rank
coal from the Red Hills Mine of the Mississippi Lignite Mining Company have
recently been completed. Testing with the lignite coal generated a fuel gas with
acceptable heating value with a high carbon conversion, although some drying of the
high-moisture lignite was required before coal-feeding problems were resolved. No ash
deposition or bed material agglomeration issues were encountered with this fuel.
32-3
Manipulation of Gasification Coal Feed in Order to Increase the Ash Flow
Temperature of the Coal, Enabling the Gasifiers to Operate at Higher
Temperatures
Johan van Dyk, Sasol Technology, SOUTH AFRICA
Coal is a crucial feedstock for South Africa’s unique synfuels and petrochemicals
industry and used by Sasol as a feedstock to produce synthesis gas via the Sasol-Lurgi
Fixed Bed Dry Bottom (FBDB) gasification process. The ash flow temperature (AFT)
gives detail information on the suitability of a coal source for gasification purposes,
and specifically to which extent ash agglomeration or clinkering is likely to occur
within the gasifier. Ash clinkering inside the gasifier can cause channel burning and
unstable operation.
Sasol-Lurgi FBDB gasifiers are currently operated with the philosophy of adding an
excess of steam to the process to control the H 2 /CO ratio of the syngas produced, but
indirectly also to control the maximum gasifier temperature below the AFT of the coal.
An opportunity exists to increase the AFT of the coal fed to the gasifiers by adding
AFT increasing minerals to the coal blend before it is fed into the gasification process.
For the aim of this study a South African coal source was investigated, as being used
by the gasification operations in Secunda.
With the specific aim of this study, to increase the AFT, the determination of the AFT
of the coal blends where some acidic components such as silica (SiO 2 ), alumina
(Al 2 O 3 ) and titania (TiO 2 ) were added was conducted. The oxide Al 2 O 3 had the biggest
and most significant effect on the AFT with the least addition to the coal blend. The
effect of SiO 2 and TiO 2 were very similar with regards to the effect on the AFT. Less
Al 2 O 3 was needed to increase the AFT to a similar AFT level in comparison to the
SiO 2 used and the question still remains why Al 2 O 3 (as pure oxide component) did
react different and increased the AFT to a certain temperature with less addition, in
comparison to that of TiO 2 and SiO 2 . The Al 2 O 3 keeps the oxygen molecules stronger
bound to the molecule than to the other components, and when the element becomes
“free”, with free electrons, a different mineral phase can form with a different flow
property. Another observation from the AFT results was that the AFT was definitely
non-additive (not a linear weighted calculated average) and not the weighted average
AFT as was expected for the other coal properties such as the ash content, for example.
The ash slagging characteristics is a non-additive property of individual coal sources in
the blend and therefore difficult to predict.
In general it can be concluded that the unique opportunity exists to increase the AFT,
was tested, proven and mechanistically outlined in this study on the coal source fed to
the Sasol-Lurgi FBDB gasifiers. The AFT can be increased to >1350°C by adding
AFT increasing minerals or species, for example Al 2 O 3 or kaolinite, to the coal blend
before it is fed into the gasification process. By increasing the AFT, the direct effect
will be that steam consumption can be decreased, which in turn will improve carbon
utilization. It can be recommended that roof and floor sections, containing mainly
siltstone layers, have high AFT properties which might be suitable for use as dilution
agent to the current coal in order to increase the AFT of the feed. From a
thermodynamic point of view in the gasification environment, it might be worth to
mention that FactSage is able to handle organic and inorganic components and might
be a first decision for further work and development in this area.
32-4
Gasification of Lignites to Produce Liquid Fuels, Hydrogen and Power
Michael Swanson, Steven Benson, Michael Jones, Jason Laumb, Michael Holmes,
University of North Dakota, USA
Edward Klunder, DOE, USA
DOE is investigating various options for removing mercury from warm fuel gas
conditions at temperatures above the dew point of the moisture in the fuel gas in order
to obtain higher system efficiencies (3). DOE and others have significant investments
in other hot-/warm-gas cleanup technologies that are going to require at least warm-gas
(300 to 700°F [150 to 370°C]) Hg control systems to be developed if these other gas
cleanup technologies are going to be effective. This project will combine demonstrated
mercury removal technology from Corning Inc. and the University of North Dakota
Energy and Environmental Research Center. This project team will combine Corning s
high-surface-area impregnated carbon monoliths with the EERC s experience with
pretreating activated carbon to generate a treated carbon capable of removing greater
than 95% of the mercury from a warm fuel gas at 500°F. This pretreatment should be
able to be readily applied to Corning s impregnated carbon monolith. Depending on the
final loading capacity, these monoliths could potentially be utilized as hot-gas filter
fail-safe devices while also capturing Hg, As, Se, and Cd on those devices. Control of
these contaminants to 5 ppbw Hg, 5 ppb As, 0.2 ppm Se, and 30 ppb Cd is desired
under the project. The project benefit would be to potentially combine multicontaminant
trace metal control with backup particulate control for the protection of a
gas turbine in the event of a candle filter failure. This technology would also provide
the carbon sorbent in a form that could easily be regenerated in place or removed and
regenerated in a separate process without creating a lot of fines that could adversely
affect a gas turbine located farther downstream. This has the potential to provide a
sorbent in a form that is both compact with a much smaller pressure drop than a packed
bed, and could be regenerable to last numerous cycles. If the contaminant loading is
not high enough or an in-situ regeneration process is not successfully developed, these
monoliths could still be utilized in separate multitrain vessels that could be taken offline
and regenerated or replaced depending on the process economics. These monoliths
could be utilized in either a cross-flow configuration (as a third level of dust protection
for the turbine) or in a straight-through flow configuration in order to minimize
pressure drop. This project will start with monolith production and laboratory testing
utilizing a synthesized bottled syngas followed by bench-scale testing with an actual
coal-derived syngas will be completed. The actual bench-scale gasification testing is
important because it will allow the generation of actual trace constituents from coal,
and at this scale, spiking of the coal to achieve desired metal constituents is possible.
32-5
Experimenting and Operating Coal Gasification in a 2 ton/day Entrained Bed
Gasifier
Cheng-Hsien Shen, Heng-Wen Hsu, Min-Chain Lo, Ching-Lin Shieh, Wei-Chung
Chen, Mei-Yen Chen, Industrial Technology Research Institute, P.R. CHINA
Coal is one widely used energy source, which provides 32.5% of energy in Taiwan.
Clean coal technology is one of the major discussion topics during National Science
meetings from 2000 in Taiwan. The main purpose of this thesis is to develop coal
gasification technology. The pressurized gasification testing facility is located in
Kaohsiung in Southern Taiwan. Gasifier is a single-stage, refractory-lined, and
entrained bed slagging research reactor designed for the gasification of coal or
petroleum coke in oxygen-blown gasification modes. The gasifier designs at pressures
28

up to 290 psia and temperatures up to 3000 degree F at a nominal coal feed rate of 2
metric tons per day. This paper focuses on illustrating some experiences in operating
gasifier procedures. It includes preheating gasifier process with air cooling the LPG
burner header, keeping the pressure difference between coal vessels and gasifier and
setting up oxygen detector at the syngas outlet, which could experiment stably on
operating the gasifier. This study investigates the results of gasifying three imported
coal and petroleum coke. One finding is that carbon conversion efficiency at the high
gasifying pressure is higher than the low gasifying pressure. This is due to high
pressure in gasifier enable coal to react with other reactants. Adding steam is helpful to
increase the flammable components in syngas, carbon conversion efficiency and cold
gas efficiency in gasifying procedure. Future research objectives include improving
carbon conversion and cold gas efficiencies and increasing operating pressure to 235
psia.
SESSION 33
COMBUSTION TECHNOLOGIES – 6: COMBUSTION STUDIES
33-1
The Development of Tangential Coal-Fired Burner to Reduce
Unburned Carbon and Enhance Flame Stability
Hyeok-Pill Kim, Si-Hong Song, Sang-Hyeun Kim, Hyuk-Je Kim, Doosan Heavy
Industries & Construction Co., Ltd., REPUBLIC OF KOREA
This report presents a study of the development of an advanced coal nozzle used in
burners to reduce unburned carbon (UBC) in a tangential coal-fired boiler. To
understand the mechanism of UBC reduction, experiments using conventional burners
were carried out to evaluate the effects of air injection velocity, coal fineness and over
fired air (OFA) on combustion efficiency. It was confirmed that ignition of pulverized
coal particles close to the burner is helpful toward the complete burn of residual carbon
in fly ash. These efforts indicated the additional results that UBC was strongly
dependent on the primary air velocity and coal fineness; especially that UBC
dramatically decreased when the weight fraction of pulverized coal under 75μm was
over 85%. New coal nozzles, modified from conventional nozzles, were prepared and
tested to improve the combustion efficiency. Some of these nozzles offered relatively
lower unburned carbon than those of conventional burners and are referred to as HPFS
(High Performance Flame Stability) coal nozzles.
33-2
Engineered-Flow Chutes Improve Coal Handling at
AmerenUE's Rush Island Plant
Michel Schimmelpfenning, AMEREN, USA
Greg Bierie, Martin Engineering Services Group LLC, USA
This presentation will look at an advanced conveyor technology that offer the
opportunities for significant improvement in the handling of coal in power plants, and
in prep plants, bulk transportation facilities, and other coal-handling operations. This
technology is flow-engineered chutes. Based on material testing and flow studies, these
chutes allow the development of transfer chute systems that provide better control,
continuous coal flow at higher capacities, and dramatic reductions in material spillage
and the release of airborne dust. By regulating the coal flow path of movement, these
engineered chutes improve the load placement on the belt, eliminate chute blockages,
reduce safety hazards, and minimize maintenance costs. In this presentation, the
authors will feature discussions of recent installations of these technologies separately
and in combination in coal handling facilities. In particular, Mr. Schimmelpfennig will
discuss the engineering and installations of flow- engineered chute systems at Ameren
s Rush Island Electric Generating Plant, to reduce fugitive material and improve
system performance in the operation s barge unloading and stack-out areas.
33-3
Influence of Coal Composition on the Release of Na-,K-,Cl- and
S-species during the Combustion of Brown Coal
Holger Oleschko, Annette Schimrosczyk, Michael Muller, Forschungszentrum Julich
GmbH, GERMANY
The use of brown coal can cause severe problems in combustion systems as far as
fouling and slagging are concerned. Especially alkali metals that are released during
combustion are responsible for the formation of sticky deposits in the boiler. In order
to tackle this problem, an increased understanding of the combustion chemistry of
brown coal is necessary. For this reason, laboratory combustion experiments with 7
different German brown coals from the Rheinland area were conducted at temperatures
of 800 and 1200°C. High pressure mass spectrometry (HPMS) was used for the on-line
analysis of the combustion products such as HCl, NaCl, KCl, SO 2 and Na2SO4. The
results show that the release of HCl, NaCl and KCl is strongly dependent on the Clcontent
of the coals. Furthermore, at temperatures of 1200°C, NaCl and SO 2 were
released in two steps, whereas at 800°C these species were released in one step only.
33-4
Refurbishment of an Old PC Boiler Confronted with Coal Quality
Degradation by a CFBC Boiler - A Case Study
D. N. Reddy, Osmania University, INDIA
V.K. Sethi, Rajiv Gandhi Technological University, INDIA
The Global concern for reduction in emission of green house gases (GHG) especially
CO 2 emissions are likely to put pressure on Indian Power Sector for adoption of
improved power generation technologies. Although India does not have GHG
reduction targets, it has actively taken steps to address the climate change issues.
Various options for India for CO 2 reduction which have been taken up vigorously
include, GHG emission reduction in power sector through adoption of Co-generation,
Combined Cycle, Clean Coal Technologies (CCTs) and coal beneficiation and
Renewable Energy Technologies particularly for Rural Sector. The CO 2 emissions per
unit of electricity generated are significantly high in India as large proportion of power
generated comes from low sized, old and relatively inefficient generating units which
constitute over 45% of our total installed capacity of about 1,18,000 MW. Growing
environmental regulations would force many utilities within the country to go in for
revamping of these polluting old power plants using environmentally benign
technology. CFBC offers a promising technology on this front. This technology has
shown high operational availability even while firing washery rejects and middilings of
high ash content up to 60%.
33-5
Experimental Study of Heat Transfer in a Horizontal Swirling Fluidized Bed
Wei-Ping Pan, Ping Lu, Andy Wu, Yan Cao, Western Kentucky University, USA
In this paper, a horizontal swirling fluidized bed was designed through a specially
designed gas distributor and varied secondary air allocation to generate bed material
swirling in dense zone. The heat transfer coefficients between submerged tube and bed
material in horizontal fluidized bed were measured with the help of a fast response heat
transfer probe. The influences of fluidization velocity, bed material particle size, bed
height, probe orientation and secondary air injection, etc. on heat transfer were
intensively investigated. Test results indicated that the heat transfer coefficients
increase with fluidization velocity, however reach their maximum value at the certain
fluidized velocity. The heat transfer coefficient in the backward orientation is higher
than that in the upward orientation. The heat transfer coefficients decrease with
increasing of bed height. The bed material size is inversely proportional to heat
transfer. The secondary air injection generates the preferred hydrodynamics in dense
zone and enhanced heat transfer.
34-1
SESSION 34
ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY – 1
Practical Applications of Innovative Mercury Control Technologies
Brian W. Armet, John E. Batorski, The Mattabassett District, USA
The Mattabassett District operates a 20 mgd Regional Wastewater Treatment Facility
located in Cromwell, Connecticut with a 1.55 dry ton/hour biosolids fluidized bed
incinerator that runs 24 hours/day, seven days/week. In response to Connecticut
Department of Environmental Protection (CTDEP) administrative orders and
judgments, The District embarked on an ambitious program to evaluate new and
emerging mercury removal technologies to address stricter mercury emissions limits
planned by CTDEP for municipal sewage sludge (biosolids) incinerators. These
administrative orders and judgments imposed targets of 180 and 150 micro-grams per
cubic meter (μg/m³): CTDEP’s goal is 100 μg/m³.
The District evaluated a number of technologies including: Sodium tetra sulfide
injection into the incinerator emissions’ air stream, which has been used in several
power generation plants with success; the introduction of foul air containing hydrogen
sulfide, which is believed to oxidize some of the mercury in the incinerator emissions
into a more stable form, enhancing overall removal rates; a static carbon bed; and, the
most novel and leading edge technology, a Ultra High Efficiency traveling filter cloth
system.
The Carbon Bed and Ultra High Efficiency filter manufacturer’s experience were with
other industries, and the Ultra High Efficiency filter manufacturer’s experience was not
even related to power generation or sewage sludge incinerators, let alone as an add on
following a wet scrubber system.
This evaluation demonstrated that the Ultra High Efficiency traveling filter cloth
system will remove sub-micron particles as well as mercury, and the carbon canister
will remove mercury.
This study has value to the industry: Jeffery Holmstead, EPA assistant administrator
for air and radiation, has been quoted stating, “Mercury control technology is not
available on a commercial scale, so the agency was unable to set a MACT standard.”
Scott Segal, director of the Electric Reliability Coordinating Council, has been quoted
as stating, “There is no mercury control technology that exists today that can achieve
29

the reduction levels finalized in the Clean Air Mercury rule, let alone the 90 percent
reductions advocated by some activists.”
34-2
Mercury Vapor Capture From Coal Derived Fuel Gas in the
Presence of Hydrogen Chloride Over Iron Based Sorbents
Shengji Wu, Masaki Ozaki, Md. Azhar Uddin, Eiji Sasaoka, Okayama University,
JAPAN
Laboratory studies were conducted to develop an elemental mercury (Hg 0 ) removal
process based on the reaction of H 2 S and Hg 0 using iron oxide sorbents for coal
derived fuel gas. It is well known that hydrogen chloride (HCl) is present in the fuel
gases of some types of coal, but the effect of HCl on the Hg 0 removal performance of
iron based sorbents in coal derived fuel gases is not yet understood. In this study, the
effects of HCl on the removal of Hg 0 from coal derived fuel gases over iron based
sorbents such as iron oxides, iron oxide-Ca(OH) 2 , and iron sulfides were investigated.
The iron oxides were prepared by precipitation and conventional impregnation
methods. The iron oxide-Ca(OH) 2 sample was prepared by mixing iron oxide with
Ca(OH) 2 mechanically. Iron disulfide (FeS 2 ) used in this study was a reagent grade
chemical. The Hg 0 removal experiments were carried out in a laboratory-scale fixedbed
reactor in a temperature range of 60-100°C using simulated fuel gases having the
composition of Hg 0 (4.8 ppb), H 2 S (400 ppm), HCl (0-10ppm), CO (30%), H 2 (20%),
H 2 O (8%), and N 2 (balance gas). In the case of iron oxides, the presence of HCl
suppressed the Hg 0 removal rate. However, the Hg 0 removal rate of iron oxide-
Ca(OH) 2 was not affected by the presence of HCl, because Ca(OH) 2 reacted with HCl.
The Hg 0 removal performance of FeS 2 was not suppressed by the presence of HCl in
the coal derived fuel gas.
34-3
Nanocrystalline Sorbents for Mercury Removal from Warm Fuel Gas
Raja Jadhav, Howard Meyer, Gas Technology Institute, USA
Slawomir Winecki, NanoScale Materials, Inc., USA
Ronald Breault, National Energy Technology Laboratory, USA
Coal-fired utilities are the single largest source of anthropogenic mercury emissions in
the U.S. The mercury regulations currently proposed for coal-combustion systems will
most likely be extended to the next-generation gasification-based systems. Therefore, a
significant amount of research work is currently being carried out to address the
concern of mercury release from coal-fired power plants. A majority of this research is
focused on development of sorbents for mercury capture from “warm” fuel gas.
Sorbents currently proposed for flue gas application, such as activated carbon, have
limited application in fuel gas because of their lower sorption capacity at elevated
temperatures. The presence of reducing components provides additional challenge for
development of high capacity mercury sorbents for fuel gas applications. In this paper,
development and evaluation of novel nanocrystalline sorbents for mercury removal
from warm fuel gas are discussed. Nanocrystalline materials exhibit a wide array of
remarkable chemical and physical properties, and can be considered as new materials
that bridge molecular and condensed matter. One of their remarkable properties is
enhanced surface chemical reactivity (normalized for surface area) toward incoming
adsorbates, which is attributed to extremely large surface areas, unique morphology
and porous nature of the nanomaterials. Gas Technology Institute (GTI), in
collaboration with NanoScale Materials, Inc., is evaluating highly reactive
nanocrystalline metal oxides/sulfides for capture of mercury from high-pressure (300–
1000 psi) and high-temperature (300–700°F) fuel gas. The sorbents are evaluated in a
lab-scale, fixed bed reactor with the outlet mercury concentration monitored by a semicontinuous
mercury analyzer. This paper discusses unique properties of nanoscale
sorbents and gives preliminary results of mercury capture by these sorbents in
simulated fuel gas conditions. The project is sponsored by DOE’s National Energy
Technology Laboratory.
34-4
Advanced Mercury/Trace Metal Control with Monolith Traps
Michael Swanson, Edward Olson, Ramesh Sharma, Grant Dunham, Mark Musich,
University of North Dakota, USA
Jenny Tennant, DOE/NETL, USA
Youchun Shi, Benedict Johnson, Lisa Hogue, Corning, INC., USA
The U.S. Department of Energy (DOE) is investigating warm-gas (300° to 700°F [150°
to 370°C]) cleanup technologies to remove all coal contaminants at temperature
conditions above the dew point in the fuel gas to obtain higher system efficiencies.
Mercury is especially difficult to remove at these target warm-temperature conditions,
but if mercury cannot be removed at warm temperature, the whole warm-gas cleanup
scenario will fail. This project is to develop a warm-gas, multicontaminant (including
mercury) cleanup system. Furthermore, this technology is expected to be compact,
regenerable, and result in a much smaller pressure drop than possible with a packed
bed. This project combines high-surface-area impregnated carbon monoliths from
Corning, Inc., with demonstrated mercury removal technology from the University of
North Dakota Energy & Environmental Research Center (EERC). The EERC has
pretreated activated carbon to generate a treated carbon capable of removing greater
than 95% of the mercury from a warm fuel gas at 500°F (260°C). The EERC and
Corning are working together to apply this pretreatment to Corning’s impregnated
carbon monoliths and to develop materials to also remove arsenic, selenium and
cadmium using the monolith system. Target contaminant removal levels are 5 ppbw
Hg, 5 ppb As, 0.2 ppm Se, and 30 ppb Cd. Another goal for this technology is to
provide a process for regeneration in place, or to remove and regenerate the monolith
system in a separate process without creating a lot of fines that could adversely affect a
gas turbine located farther downstream. Depending on the final loading capacity, these
monoliths could potentially be utilized not only to capture Hg, As, Se, and Cd, but also
as hot-gas filter fail–safe devices– backup particulate control for the protection of a gas
turbine in the event of a candle filter failure.
In this mode, the monoliths would be utilized in a cross-flow configuration. This
project has begun with monolith production and laboratory testing of the monolith
system to remove mercury utilizing a simulated syngas. This will be followed by
bench-scale testing with an actual coal-derived syngas, which will allow the generation
of actual trace constituents from coal to determine their impact on the process early in
the technology’s development. To date, the lab-scale work has successfully
demonstrated that treated monoliths can remove mercury at the target temperatures.
34-5
Removing Trace Metals From Coal-Derived Syngas at Elevated
Temperatures: A Progress Report on Sorbent Development
John R. Albritton, Brian S. Turk, Santosh Gangwal, Raghubir Gupta, RTI
International, USA
The sustained elevated prices for crude oil and natural gas have generated renewed
interest in gasification technologies as a means to convert cheaper carbonaceous fuels,
primarily coal, into electricity, hydrogen, chemicals and transportation fuels. One of
the most significant challenges of realizing the potential of gasification for this
conversion is effectively capturing the variety of contaminants present in these cheaper
carbonaceous fuels. For the more prominent contaminants like sulfur, chlorine and
nitrogen, commercial technologies are readily available and ongoing R&D efforts are
spawning new and better technologies. However, control technologies for the trace
contaminants have received much less attention. RTI International (RTI) is actively
developing sorbent-based technologies for removing mercury, arsenic, selenium and
cadmium that are specifically designed and optimized for syngas applications. The
specific objective is to develop sorbents to remove these trace contaminants, from coal
derived syngas at high pressures between 300 and 700ºF. With RTI’s specialized
testing systems for arsenic and mercury, a sorbent screening program has been
completed and capacity testing and process optimization has begun. Because more
materials interact with the arsenic in the syngas compared to mercury, the R&D for
arsenic has focused on sorbents capable of capturing arsenic in the presence of sulfur
for optimal system integration. Similar specialized testing systems have been set up for
selenium and cadmium and sorbent screening has begun. The results from these
different testing programs will be presented in this paper.
SESSION 35
GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND
HYDROGEN APPLICATIONS – 2
35-1
A Study of the Transport of Coal Syngas Species through a
Solid Oxide Fuel Cell Anode
Jason Trembly, Randall S. Gemmen, National Energy Technology Laboratory, USA
David J. Bayless, Ohio University, USA
High temperature fuel cells, especially solid oxide fuel cells (SOFCs), represent a
technology that may be used to more efficiently and cleanly produce both power and
heat using fossil fuels such as coal. Although technical investigations have shown that
SOFCs may be readily coupled with hydrogen and natural gas to produce power, few
investigations (experimental or theoretical) have focused on the feasibility of operating
SOFCs with gasified coal as fuel. Porous media models provide valuable insight into
the transport of gas species through the anode of a PSOFC and may be adapted to
investigate the transport behavior of coal syngas species throughout the anode of the
PSOFC. Two models, the Mean Transport Pore Model (MTPM) and the Dusty Gas
Model (DGM), have been widely used to study steady state and transient transport of
gaseous species through porous materials. While both models have previously been
applied to SOFC applications using both hydrogen and natural gas as fuels, only
recently has NETL applied the DGM to SOFC anode systems using coal derived
syngas as fuel. The following paper presents modeling results from a study of coal
syngas transport under such conditions using the MTPM model. Also a comparison
between the MTPM and DGM applied to SOFCs using coal derived syngas as fuel is
presented.
30

35-2
Development of Iron-Based Perovskite Materials as Carbon and
Sulfur Tolerant SOFC Anodes
John Kuhn, Umit Ozkan, The Ohio State University, USA
Current Ni-based solid oxide fuel cells (SOFC) anodes deactivate in the presence of
coal-derived gas because they are easily poisoned by low levels of sulfur and catalyze
coke formation. Their use requires a large steam to carbon ratio to limit coking. In
addition to these problems, the Ni-based anodes also lose activity through sintering.
All of these processes deactivate the anodic reaction rates, cause low power densities,
and increase operation costs due to large steam requirements. Thus, the development of
highly active and carbon and sulfur tolerant materials suitable for use as anodes is
necessary to bring coal-gas fed SOFC systems closer to commercialization. Ongoing
SOFC cathode research shows iron-based perovskite materials are developed as
promising materials for use as SOFC cathodes between 500°C and 700°C. The
electrochemical activity and oxide ion mobility that make it such a great cathode
material can also be harnessed for the oxidation reactions at the anode. The current
research demonstrates the iron-based perovskite materials are stable in highly reducing
conditions and possess catalytic activity for the direct oxidation of hydrogen and
carbon monoxide in the desired temperature range. The effect of the increased lattice
oxygen mobility on the water requirements and the influence of hydrogen sulfide
concentration on the oxidation activity are discussed. Characterization using X-ray
diffraction, X-ray photoelectron spectroscopy, simultaneous thermogravimetric and
differential scanning calorimetric analyses, and temperature-programmed techniques is
performed to compliment the anodic oxidation results and correlate the bulk and
surface structure-activity relationships.
35-3
Coal-Based Solid Oxide Fuel Cell Power Plant Development
Hossein Ghezel-Ayagh, Fuel Cell Energy, USA
Jody Doyon, FuelCell Energy Inc., USA
FuelCell Energy (FCE) has recently been selected by the Department of Energy (DOE)
to initiate a multi-phase program for development of near zero-emission power plants
that are very efficient in converting coal to electricity. The primary goal of the program
is the development of an affordable fuel cell based technology for utilization of
synthesis gas (syngas) from a coal gasifier. One of the key objectives is development
of fuel cell technologies, fabrication processes, and manufacturing infrastructure and
capabilities for scale-up of Solid Oxide Fuel Cell (SOFC) stacks for large multimegawatt
base-load power generation plants. The other key objective is
implementation of an innovative system concept in design of a 100+ MW power plant
with anticipated efficiencies approaching 60% of higher heating value (HHV) of coal.
Combined with existing carbon dioxide separation technologies, the power plant is
expected to achieve greater than 50% overall efficiency while emitting near-zero levels
of emissions of SO x , NO x , and greenhouse gases to the environment.
FCE is a world leader in development and manufacture of high temperature fuel cell
power plants. The Company has developed carbonate fuel cell technology that involves
large fuel cell areas and 250 kW to MW power plant products. FCE has focused on
commercialization of its technologies for distributed generation markets by offering
products of up to 2-MW in capacity. Over 40 commercial units have been installed
worldwide. FCE also heads a project team under the Department of Energy s Solid
State Energy Conversion Alliance (SECA) initiative for development of 3-10 kW
SOFC power plants. FCE and its partner, Versa Power Systems (VPS), have developed
a highly efficient, high power density and cost effective anode-supported planar SOFC
technology that would form a basis for design of the large-scale hybrid SOFC/Turbine
power plants. VPS, a world-class developer of the solid oxide fuel cells, is developing
high power density and reliable SOFC cells and stacks.
FCE s experience with operation of its fuel cells on coal gas dates back to 1992 with
operation of a subscale fuel cell power module for over 4000 hours at the Louisiana
Gasification Technology Inc. site in Plaquemine, LA. Recently, a 2 MW power plant
was designed and fabricated for operation with coal gas. The path forward for
development of coal-based multi-MW power plants includes a multi-faceted approach
for both SOFC stack module design as well as development of a hybrid fuel cell/gas
turbine system. The technical approach consists of an innovative fuel cell stack
configuration, fabrication of scaled-up cells, newly developed fuel cell seals, novel
implementation of a fuel cell clustering concept, and integration of SOFC clusters with
a gas turbine. The future development plans include investigation of both fabrication
and operational issues related to scale-up of the fuel cell active area to 900 cm 2 . A
unique cell arrangement, C-plate, will extend the planar cell area further to 3600 cm 2 .
An innovative and patented power cycle will be utilized to achieve very high
efficiencies by integration of the fuel cell with an indirectly heated gas turbine. The
proposed system has the flexibility of using both the atmospheric as well as
pressurized fuel cells. The eventual driver for the selection will be the cost and
efficiency of the system.
The power plant design is projected to have a factory cost of $400/kW, based on a
production capacity of about 1.4 GW/year or twelve 120 MW power plants per year.
This cost is very competitive with today s cost of combined cycle technologies. The
basis for the factory cost estimate is a detailed material inventory and the results of a
recent cost breakdown analysis for a 40MW hybrid Direct FuelCell®/Turbine power
31
plant which was performed under a co-operative agreement with DOE. As a result, fuel
cells are one of the most attractive power generating technologies for the future.
Advances made under the Fuel Cell Coal-Based Systems program are expected to
become key enabling technologies for FutureGen, a planned DOE demonstration of
advanced power systems that emit near-zero emissions, have double today s electric
generating efficiency, co-produce hydrogen, and sequester carbon dioxide. This project
will take a major step toward enabling the nation to use its ample coal resources more
cleanly and efficiently and to significantly reduce the amount of carbon dioxide
released to the atmosphere.
35-4
Coal-Based, Ultra-Clean, High Efficient Fuel Cell Hybrid Power Generation
Kevin Litzinger, Siemens Power Generation, USA
Brian Attwood, Ravi Srivastava, US Environmental Protection Agency, USA
Carl Singer, Arcadis, USA
Siemens Power Generation heads one of three teams engaged in development of ultraclean,
highly efficient, fuel cell/gas turbine hybrid power systems in coal-fired power
plants. Under the sponsorship of the U. S. Department of Energy s National Energy
Technology Laboratory, the Fuel Cell Coal-Based Systems initiative targets systems
with a minimum plant thermal efficiency of 50% on a high heating value basis, greater
than 90% carbon dioxide capture, and zero emissions of criteria pollutants.
The program extends work already underway in the Department of Energy s Solid
State Energy Conversion Alliance (SECA) to hybrid fuel cell/turbine plants of greater
than 100 MWe scale and operating on coal-based synthesized fuel. The program
further extends the SECA product cost goal of $400/kWe for the power island in an
Integrated Gasified Fuel Cell (IGFC) power plant. The program culminates in system
demonstrations, at multi megawatt scale, in the FutureGen or other host generating
plant. This paper discusses alternative hybrid cycles under consideration, methods for
carbon dioxide separation, and development steps necessary for fuel cell operation on
synthesized fuels. The paper also discusses test facilities and methodologies for
preliminary bench scale verification of Solid Oxide Fuel Cell (SOFC) operation under
pressurized conditions typical of the hybrid cycles.
35-5
The Effect of a Current Collection Layer Containing a Sulfur Tolerant
Material on the Operation of a PSOFC Utilizing Coal Derived
Syngas Containing H 2 S as Fuel
Jason Trembly, David J. Bayless, Ohio University, USA
Randall S. Gemmen, NETL, USA
High temperature fuel cells, especially solid oxide fuel cells (SOFCs), represent a
technology that may be used to more efficiently and cleanly produce both power and
heat using fossil fuels such as coal. The primary problem with the use of coal syngas as
a fuel source for the PSOFC is the degradation effect of H 2 S on the anode of the cell.
Traditional PSOFC anodes containing materials such as Ni and Cu sustain large
performance losses when the fuel being used contains H 2 S. Although plans for future
IGCC power plants use gas clean up systems that will remove H 2 S below 1ppm,
system disturbances may still take place allowing higher concentration of the
contaminant to reach the electrochemical module thereby causing costly damage to the
fuel cell. As a result, there exists an opportunity to investigate ways to introduce
reliable passive methods for dealing with such real-world operational risks. To pursue
this opportunity, we consider in this paper PSOFC anodes that are sulfur tolerant. A
promising sulfur tolerant material that has recently been demonstrated is the perovskite
LSV (La 0.7 Sr 0.3 VO 3 ). This material demonstrated the ability to oxidize H 2 S without
incurring any significant cell performance degradation. Unfortunately the material can
not readily oxidize H 2 at the anode and has a low electrical conductivity when
compared to traditional anode materials. Since coal syngas contains 30-50vol% H 2 ,
LSV may not be used alone in an anode for efficient utilization of coal syngas. Since
H 2 S strongly adsorbs onto LSV and the material shows the ability to oxidize the sulfur
contaminant, it may be beneficial to use the material in the current collection layer of
the PSOFC anode and use a standard Ni-GDC interlayer to efficiently oxidize the fuel
species of the syngas. This paper will present the preliminary results from research
investigating the effect of PSOFC anode containing an LSV current collection layer on
the performance of the PSOFC utilizing a coal syngas mixture containing up to
160ppm H 2 S.
36-1
SESSION 36
COAL PRODUCTION AND PREPARATION – 1
The Efficacy of Dry Coal Cleaning for High-Density Separations
R. Q. Honaker, D. Patil, University of Kentucky, USA
G.H. Luttrell, R. Bratton, Virginia Tech, USA
Maximizing the recovery of coal reserves and optimizing coal operations have been a
focus of recent attention. Past practices in the western U.S. discarded the coal near the

top and floor of large surface mining operations rather than cleaning the material
through a preparation plant. In many situations in the eastern U.S., coal and associated
rock are hauled over long distances to the preparation plant where the rock is separated
from the coal, hauled and disposed into a refuse area. In an effort to improve coal
mining economics, an evaluation has been performed to determine the feasibility of
removing high-density rock from the coal using a dry, density-based technology at the
mine site. Using a 5 tph mobile unit, approximately 70% of the rock comprised in a
run-of-mine coal was removed while recovering nearly 100% of the coal. The ash
content of the tailings stream was greater than 80% in many tests. The results obtained
from on-site tests at western and eastern U.S. coal operations will be presented and
discussed in the publication.
36-2
How Vibratory Machines Can Improve Coal Handling & Processing
George D. Dumbaugh, Kinergy Corporation, USA
Reliably discharging and completely emptying Storage Bins that contain non-flowable
coals, prompting large stock piles to flow even when drenched with rain or happen to
freeze, and unloading Unitrains in 4 hours by means of a large vibrator that becomes
an integral part of the car, are significant improvements in Coal Handling.
For the coal being processed, the Vibrating Feeders, Conveyors, Screens for Scalping,
Washing, Desliming, Dewatering, and Grade Sizing, plus the fluidized beds for Drying
can be provided with a vibratory drive that has a high degree of “energy efficiency”
that reduces the power consumed, are ecologically friendly because of integrally “dusttight”
enclosures, are electrically adjustable over a broad range to enable added
operating versatility, are no longer limited in width and length because the driving
forces are better “distributed”, are started and stopped frequently without detriment to
the drive, and are Dynamically Counterbalanced for easier installation.
To help make it a more viable fuel for firing a Boiler, a Vibrating Grate that burns
ROM Coal has been developed for this purpose.
The design engineering of these vibratory machines is very important. However, the
installed “interface”, particularly at the inlet, and how the vibratory machine is being
operated must also be taken into consideration.
When the engineering design factor is combined with the proper “interfacing” and the
best method of operation, any one of these vibratory machines will inherently have the
following attributes:
1. The moisture content can markedly vary over a wide range. The wet, “sticky”
coal caused by the particles becoming very adhesive and cohesive have been
uniquely overcome.
2. All the different kinds of coal can be handled. For example, the hard surfaced
bituminous coals, the soft texture of low sulfur coals such as PRB, and even the
partially developed coals such as lignite.
3. Abrasive wear can be minimized to where it appears to be practically eliminated.
Particularly, by preventing impact abrasion.
4. The reported productive availability is usually 98% or better.
5. The initial cost is very competitive, plus the operating costs are reduced and so is
the maintenance expense.
Much of this improved vibratory technology is already in productive use handling or
processing coal in the areas surrounding western Pennsylvania, such as West Virginia,
western Maryland, Virginia, and eastern Kentucky.
The purpose of this paper is to explain why the chosen design of the vibratory machine
must be combined with the appropriate “interface” and the proper “method of
operation” to effectively achieve some or all of these beneficial improvements.
36-3
Picobubble Enhanced Column Flotation of Fine Coal
S. Yu, R. Honaker, D. Tao, B.K. Parekh, University of Kentucky, USA
Froth flotation is widely used in the coal industry to clean -28 mesh or -100 mesh fine
coal. A successful recovery of particles by flotation depends on efficient particlebubble
collision and attachment with minimal subsequent particle detachment from
bubble. A fundamental analysis has shown that use of picobubbles can significantly
improve the flotation recovery of particles by increasing the probability of collision
and attachment and reducing the probability of detachment. An experimental study of
column and mechanical flotation of fine coal has been conducted to study the effects of
picobubbles on flotation recovery, clean coal ash, and reagent consumption.
Picobubbles were produced based on the hydrodynamic cavitation principle.
Experimental results have shown that the use of picobubbles in flotation increased fine
coal recovery by 10-30%, depending on the feed rate, collector dosage, and other
flotation conditions. Picobubbles also acted as a secondary collector and reduced the
collector dosage by one third to one half.
36-4
Impact of CBM Development on Environment in Jharia Coal Field, India
P. Verma, H.V. Singh, S.R. Wate, S. Devotta, R.N. Singh, National Environmental
Engineering Research Institute, INDIA
Coal Bed Methane (CBM) has emerged as a valuable energy source. Recently in India,
exploration studies have been initiated to commercially exploit the methane trapped in
32
coal beds. Despite being an environmentally friendly source of energy, several issues
need to be addressed in order to understand environment impacts during its
exploitation. The present work was carried out to study the impact of developmental
drilling in Jharia coalfields for extracting methane gas in coal beds. Baseline data on
different environmental components have been collected and analyzed. Based on the
site specific conditions and technology used for developmental drilling, environmental
impacts arising out of this activity have been predicted and an suitable environmental
management plan is drawn in order to mitigate the adverse impacts arising out of this
proposed activity.
36-5
Optimization of the Distribution and Blending of Coal-Petroleum
Coke in a Thermal Power Stations Park
Carmen Clemente, Carlos Funez, Universidad Politecnica de Madrid, SPAIN
The blending of imported coal of different origin with national Spanish coal and
petroleum coke is very common in thermal power stations, being the optimum
determination of these blends the main objective of this research. Besides, the
determination of the best blend takes implicit the distribution of imported coal among
the power stations in study. This provides an important way of saving, because it
allows to diminish the generation costs and to gain flexibility in the fuel, representing a
main objective to be considered in the investigation of the use of coal as a significant
power source of future. The applied optimization tool uses the method "Simplex",
creating a matrix of possible results and selecting the optimum solution. When the
restrictions prevail, the matrix of possible results diminishes. Several series of data is
necessary to be introduced in the optimization tool: national coal, imported coal, fuel
and coke prices (€/te); transport price of the imported coal to the generation groups
(€/t); fuels characterization; available amount (t) of each fuel used in the optimization;
premiums to the national coal consumption and plant operative restrictions (for
example the number of mills in which imported coal can be introduced).
Besides other data have been useful for the determination of the optimum mixture as
net specific consumption of the group (kcal/kWh), coal consumption in the period (kt),
energy generated in the period (GWh) and the differential cost respect to the national
coal (M€). If an electrical company applied this methodology of calculation for the
determination of the optimum blend (smaller cost of generation) during a year, taking a
conservative hypothesis for the improvement of the generation cost (1% for
improvement), the differential of costs awaited is approximately of 2 million euros.
The research has been carried out for the distribution of a ship of imported coal
(Australian) of 150000 tons in three thermal power stations fed with national coal,
imported coal and petroleum coke. The imported coal consumption in the evaluated
power stations, has supposed an improvement in the net specific consumption,
reduction of the maintenance costs and improvement of the availability. Also the
limitations in the capacity of equipment (primary air ventilators and mills) are reduced
with the increase of the imported consumption of coal. There are differences for the
petroleum coke blended with national coal respect to the mixture of coke and imported
coal. When f the coke is blended with national coal, the rate of shutdowns improves
and the cost of maintenance of mills is reduced, in comparison with the feeding of the
100% national coal. Nevertheless, when the coke is blended with imported coal, these
parameters get worse, and also the availability, the boiler yield and the emissions.
It has been verified that the proposed methodology works correctly, supposing its use
an improvement in the management of the fuel, giving trustworthy results and
observing some differences among the fuel mixtures used in the power stations park
superior to the 5 % of the total cost of generation.
37-1
SESSION 37
GASIFICATION TECHNOLOGIES:
ADVANCED TECHNOLOGY DEVELOPMENT – 2
Industrial Size Gasification for Syngas, SNG, Hydrogen and Small
Power Production Using the BGL 1000 Gasifier Module
Victor Shellhorse, Allied Syngas Corporation, USA
Jeffrey Hoffmann, US Department of Energy, USA
Industry is the largest and most diverse energy-consuming sector in the United States,
using over one-third of all the energy consumed. Most of the energy industry uses is
supplied by natural gas and petroleum products, with electricity a distant third. Based
on the 2002 EIA Manufacturing Energy Consumption Survey, industry consumed over
5.7 quads of natural gas and over 964,000 GW-hrs (3.3 quads) of electricity. About
134,000 GW-hrs of electricity was generated on-site by industry. With the current high
price of natural gas and the projected volatility in natural gas prices in years to come,
industry benefits from an abundant, stable cost, reliable energy source. Coal has the
potential of meeting this need through the use of efficient, industrial size gasification
technologies. This paper explores the potential of the British Gas Lurgi (BGL) 1000
fixed bed gasification technology to supply industry with clean fuel gas from coal
economically and with virtually no increase in industrial plant air emissions. The

features of the BGL 1000 technology that make it particularly attractive for industrial
application include: A single module producing about 1000 million Btu/hr of a clean
synthetic fuel gas, a size applicable to a large number of industrial plants. Modular in
design for small and medium size power applications in the 80 MWe to 250 MWe
range. Capability of processing essentially all U.S. coals and many opportunity fuels
including Eastern bituminous, Western sub-bituminous, and lignite coals; petcoke,
biomass, TDF, and other potential fuels whether non-caking or strongly caking, with
low or high ash fusion temperature, or having high sulfur, moisture, or mercury
content. Utilization of solid fuels in the ¼ to 2 size range, typical of as-received coals,
with minimal preparation (i.e. no drying, pulverizing or slurrying). Demonstrated high
cold gas efficiency (88 to 92%) among the best of commercial gasification
technologies, with low specific consumption of oxygen and steam. Designed for very
low environmental emissions practically no SO x or particulate emissions; greater than
90% mercury removal; non-leachable slag; and environmental performance unaffected
by input quality.
37-2
Recent Developments in Modularized Air-Blown Coal Gasification
Systems for Industrial Applications
F. Denis d’Ambrosi, Robert G. Jackson, Econo-Power International Corporation, USA
Coal gasification is receiving a significant amount of interest as the Energy Policy Act
of 2005 takes effect. Most of the publicized attention is focused on relatively large
scale applications for either power generation or for the production of syngas for use as
a feedstock in the production of either liquid fuels or other chemical products. These
applications typically are oxygen blown gasification with the attendant requirement to
include an air separation system in the overall plant design. Recent developments in
two stage, fixed bed, air blown gasification systems make this approach very attractive
for smaller, industrial scale applications where the inclusion of an air separator plant
would drive operating costs to uneconomic levels. Two stage, fixed bed, air blown
gasifier plants can reliably and economically support fuel gas production requirements
as low as 120 million BTU per hour. These plants typically include modularized
systems for removal and recovery of particulates, tars and oils and for the removal of
hydrogen sulfide (H2S). Additional equipment for removal of mercury (Hg) and for
H 2 S polishing can be included. Projects using this technology are currently under
development for a variety of industrial applications including mining and cement kilns,
industrial steam boilers, various types of dryers, glass furnaces and IGCC plants.
This paper will discuss the design features of a modularized two stage, air blown
gasification plant. The paper will also summarize the development status of the
industrial applications mentioned above.
37-3
Chemical Looping Reforming Process for the Production of Hydrogen from Coal
L.S. Fan, Puneet Gupta, Luis G. Velazquez-Vargas, Fanxing Li, The Ohio State
University, USA
The Chemical Looping Reforming (CLR) process is described. It utilizes direct
reduction of iron oxide particles with coal to form metallic iron liberating CO 2 and
H 2 O. After condensing the H 2 O, a sequestrable CO 2 stream is obtained. The reduced
iron is oxidized with steam in a second reactor producing hydrogen and regenerating
the iron oxide. The paper describes the technology in more detail including ASPEN
simulations for heat integration and efficiency calculations. The CLR process is
capable of transforming close to 86% of the thermal energy of coal into hydrogen.
Economic evaluation of the technology shows a production cost of $0.83/kg H 2 which
is very competitive with respect to the $1.1/kg H 2 as obtained from SMR of natural
gas. The environmental benefits, the high hydrogen production efficiency and
significantly lowered production costs put CLR technology at the forefront of
emerging clean coal technologies.
37-4
ALSTOM's Hybrid Combustion-Gasification Chemical
Looping Technology Development - Phase II
Herbert E. Andrus, Jr., Paul R. Thibeault, ALSTOM Power, Inc., USA
Suresh C. Jain, DOE, USA
ALSTOM Power Inc. (ALSTOM) has just completed Phase 2 of a multiphase program
to developed entirely new, ultra-clean, low cost, high efficiency power plant for the
global power market. This new power plant concept is based on a hybrid combustiongasification
process utilizing high temperature chemical and thermal looping
technology.
The chemical and thermal looping technology can be alternatively configured as 1) a
combustion-based steam power plant with CO 2 capture, 2) a hybrid combustiongasification
process producing a syngas for gas turbines or fuel cells or 3) an integrated
hybrid combustion-gasification process producing hydrogen for gas turbines, fuel cells
or other hydrogen based applications while also producing a separate stream of CO 2 for
use or sequestration. In its most advanced configuration this new concept offers the
promise to become the technology link from today’s Rankine cycle steam power plants
to tomorrow’s energy plants. This paper covers the progress of recently completed
Phase II Work with the US DOE. The objective for Phase 2 was to develop the
33
carbonate loop – lime (CaO) / calcium carbonate (CaCO 3 ) loop, integrate it with the
gasification loop from Phase I, and ultimately demonstrate the feasibility of hydrogen
production from the combined loops.
The main conclusion from Phase 1 and Phase 2 is that the PDU chemistry required for
the chemical looping process has been validated. The following processes were
demonstrated and significant data was generated for each:
• CaS – CaSO 4 looping
• CaCO 3 – CaO looping
• Water gas shift: CO + H 2 O to H 2 +CO 2
• Hydrogen production
• Sorbent reactivation on line
• CO 2 removal
• Char gasification
• Coal devolitilization
Economics were reevaluated based on the results of Phase II testing and were found to
still be valid.
37-5
Advanced Unmixed Combustion/Gasification: Potential Long Term Technology
for Production of H 2 and Electricity from Coal with CO 2 Capture
Parag Kulkarni, Wei Wei, Raul Subia, Vladimir Zamansky, George Rizeq, Greg
Gillette, Zhe Cui, Roger Shisler, Tom McNulty, GE Global Research, USA
With its abundant domestic supply, coal is one of the most secure, reliable, and
affordable energy supplies for the U.S. Today, gasification of coal to produce
electricity is being commercially introduced as Integrated Gasification Combined
Cycle (IGCC) power plants. The IGCC technology is well suited to better meet the
needs for power generation from coal more cleanly than other conventional
technologies. It is also compatible with tomorrow s need for carbon sequestration and
production of hydrogen fuel. Looking further into the future, GE along with
Department of Energy (DOE), is evaluating the feasibility of a novel gasification
technology called Unmixed Fuel Processing (UFP) of coal to achieve efficiency
advances in meeting the long-range hydrogen and electrical production needs from
coal with CO 2 capture. The evaluation is continuing. The presentation will include
fundamentals of UFP technology and a brief overview of research activities
undergoing at GE Global Research including economic and experimental (bench and
pilot-scale) feasibility evaluation.
In the UFP technology, coal, steam and air are simultaneously converted into separate
streams of (1) hydrogen-rich gas that can be utilized in fuel cells or turbines, (2) CO 2 -
rich gas that can be sent for sequestration and (3) high temperature/pressure vitiated air
to generate electricity in a gas turbine expander. While the technology challenges are
significant, UFP technology has the potential to eliminate the need for the air
separation unit (ASU) using oxygen transfer material (OTM). The UFP technology
captures CO 2 inherently at higher temperature and pressure using CO 2 adsorbing
material (CAM) as compared to the conventional energy intensive low-temperature
CO 2 capture processes. Further, as fuel and air are not mixed together and also because
of the lower gas turbine inlet temperature, the UFP process can potentially produce
lower amounts of pollutants such as NO x as compared to conventional combustion
process. Thus the UFP technology offers the potential for reduced cost, increased
process efficiency and lower emissions relative to conventional gasification and
combustion systems.
GE was awarded a contract from U.S. DOE NETL to evaluate the UFP technology
and address its technical risks. Work on the Phase I program started in October 2000
and work on the Phase II effort started in April 2005. The Phase I R&D program
established the chemical feasibility of the individual processes of the UFP technology
through modeling, lab- and bench- scale testing. The Phase II effort focuses on three
high-risk areas: economics, sorbent attrition and lifetime, and product gas quality for
turbines. The economic analysis includes estimating the capital cost as well as the costs
of hydrogen and electricity for a full-scale UFP plant. These costs will be benchmarked
with IGCC polygen costs for plants of similar size. Sorbent attrition and lifetime are
being addressed via bench-scale experiments that monitor sorbent performance over
time and by assessing materials interactions at operating conditions. The product gas
from the third reactor (high-temperature vitiated air) will be evaluated experimentally
in a pilot-scale unit to assess the concentration of particulates, pollutants and other
impurities relative to the specifications required for the gas turbine expander.
"This abstract was prepared with the support of the U.S. Department of Energy, under
award No. DE-FC26-00FT40974. However, any opinions, findings, conclusions, or
recommendations expressed herein are those of the authors and do not necessarily
reflect the views of the DOE".
SESSION 38
COAL CHEMISTRY, GEOSCIENCES AND RESOURCES: GEOSCIENCES
38-1
A Review-Geology and Coal Resources of Mand Raigarh
Coalfield, District Raigarh, Chhattisgarh
D. R. Patel, Geology & Mining Regional Office Bilaqspur (C.G.), INDIA

The Mand-Raigarh coalfield (21° 45’ to 22° 42’ N and 83° 01’ to 83° 44’ E) is part of
the Ib River-Mand-Korba master basin lying within the Mahanadi grabens in
Chhattisgarh state. It shows a typical half-Grabens configuration with the southern
boundary marked by major NW-SE trending faults coinciding with the trend of the
Mahanadi graben whereas the northern boundary is not faulted.
In Mand-Raigarh coalfield, Gondwana sediments comprising of Talchir, Barakar,
Barren Measure, Raniganj and Kamthi Formations, rest unconformable over the Pre-
Cambrian crystalline basement in the northeastern parts. The coal basin has a faulted
contact with Proterozoic Chhattisgarh rocks in the south and southwestern part. Inliers
of crystalline rocks are seen at several places. Total thickness of Barakar sediment in
the northern part of Mand-Raigarh coalfield as reported by Kamara Guru et. al. (1980)
is 706m to 840m while that in the Southern part of Chhal is estimated to be around
950m.
The rocks of Barakar Formation comprises of sandstone and shale interbanded with
carbonaceous shale and coal seams. Mand-Raigarh coalfield is mainly divided into
four major coal sectors viz Chhal, Dharamjaygarh, Kudumkela-Palma and Trans-mand
sector. The coal measures lying between Kharsia and Dharamjaygarh exhibit a broad
synclinal structure. The northern limb of the Mand River basin is exposed to the north
in the Sithra-Dharamjaygarh area where the Barakar beds are found to strike broadly in
a NW-SE direction from the Talchir contact. In the south Limb, the strike is
approximately NW-SE with minor variations and the beds dip towards northwest.
In all XII coal seems have been identified. The grade of coal seams is characterized by
non-cocking coal. The ultimate heat value of different coal seams ranges from 1186
kcal/kg to around 6237 kcal/kg (dominantly power grade i.e. E to G).
Geological Survey of India has estimated 19106.04 million tonnes of reserves in this
coalfield as on 01-01-2006 in coal seams over 0.90 m thickness and up to a depth of
1200m from surface. This includes 1409.87 million tonnes proved, 15161.84 million
tonnes of indicated and 2534.33 million tonnes of inferred reserves.
38-2
Genesis of Natural Coke and Its Industrial Utilisation
Ashok K. Singh, N.K Shukla, Mamta Sharma, S.K. Choudhury, B.N Roy, G. Ghose, S.
K. Srivastava, CFRI, INDIA
Some Indian coalfields were intensely affected due to igneous intrusion in the
geological past. Dykes and sills of lamprophyre and dolerite have intruded the coal
seams of different rank and type and have caused colossal wastage of the coal
resources by converting it into natural coke and other products, rendering very meagre
marketability. There were series of episodes of volcanic activity during post
depositional phase of Gondwana period. As a result there were magmatic intrusions,
both concordant and discordant, in the coalfields of this period. Damodar valley
coalfields expanding from Raniganj coalfield in the east to Daltanganj coalfield in the
west, witnessed two major volcanic episodes (Mid Jurassic & Cretaceous) and
transformed huge amount of coking and non-coking coals into natural coke and char.
Coking coal during metaplast phase (300-500ºC) due to its viscous nature got
intermixed with adjoining shale, sandstone and other rock fragments and produced
natural coke, while non coking coal, being non viscous, produced the chars of varying
properties.
Natural cokes are characterised by high ash content (heterogeneous), high inert
materials, strongly anisotropic, less reactive macerals and more electrically conductive
(less resistive). The studies carried out on different samples have indicated that the
natural coke or jhama is characterised by moisture (as received)

Heat-exchangers, particle filters, turbines, and other components in integrated coal
gasification combined cycle system must withstand the highly sulfiding conditions of the
high-temperature coal gas over an extended period of time. The performance of components
degrades significantly with time unless expensive high alloy materials are used. Deposition
of a suitable coating on a low-cost alloy may improve its resistance to such sulfidation
attack, and decrease capital and operating costs. The alloys used in the gasifier service
include austenitic and ferritic stainless steels, nickel-chromium-iron alloys, and expensive
nickel-cobalt alloys such as Inconel, Hastelloy and Haynes alloys. Not only are these
materials expensive, their machining is also difficult, which makes fabrication of
components particularly costly.
SG Solution's coal gasification power plant in Terre Haute, IN, uses ConocoPhillips' E-Gas
technology. The need for corrosion-resistant coatings exists in two areas: (1) the tube sheet
of a heat exchanger at ~1000°C that is immediately downstream of the gasifier, and (2)
porous metal particulate filter at 370°C, which is downstream of the heat exchanger. These
components operate at gas streams containing as much as 2% H 2 S. This corrosion is the
leading cause of the unscheduled downtime at the plant and hence success in this project will
directly impact the plant availability and its operating costs. Coatings that are successfully
developed for this application will find use in similar situation in other coal-fired power
plants. A protective metal or ceramic coating that can resist sulfidation corrosion will extend
the life-time of these components and reduce maintenance.
SRI has developed a low-cost fluidized-bed-reactor chemical vapor deposition (FBR-CVD)
technology to deposit coatings of various metals including Cr, Si, Ti, Al, B, Ni, W, and Mo
on metals and ceramics. SRI s method for depositing corrosion-resistant coatings also has
advantages over the commonly used techniques such as thermal or plasma spraying, which
produce coatings with internal porosity and microcracks, so that they must be thick to
prevent gas penetration to the substrate. The FBR-CVD technology allows (1) both internal
and external surfaces to be coated, (2) diffusion bonding to the substrate, and (3) formation
of a dense layer on the surface and increased corrosion protection of the substrate.
We have successfully deposited coatings of Cr, Cr-Al, Ti, Ti-Al nitrides, and Si-Al nitrides
on various steel samples, and tested them in simulated gasifier environments. Coatings on
low carbon steels in the 400 series was most effective as these samples showed minimal
corrosion under conditions where Inconel and other coated samples were badly corroded.
Ferritic steels appear to be more suitable for diffusion barrier coatings than steels containing
Ni. Some of the coated samples have been placed in the SG Solutions gasifier plant in Terre
Haute, IN, and we await their retrieval at the next scheduled maintenance.
39-2
Oxidation of Alloys for Advanced Steam Turbines
Gordon Holcomb, Malgorzata Ziomek-Moroz, David E. Alman, NETL, USA
Ultra supercritical (USC) power plants offer the promise of higher efficiencies and
lower emissions. Current goals of the U.S. Department of Energy s Advanced Power
Systems Initiatives include power generation from coal at 60% efficiency, which
requires steam temperatures of up to 760°C. This research examines the steam
oxidation of alloys for use in USC systems, with emphasis placed on applications in
high- and intermediate-pressure turbines.
39-3
Experimental Evaluation for Fireside Corrosion Resistance of Advanced
Materials for Ultra-Supercritical Coal-Fired Power Plants
Horst Hack, Greg Stanko, Foster Wheeler North America Corp, USA
The U.S. Department of Energy (DOE) and the Ohio Coal Development Office (OCDO) are
co-sponsoring a project, managed by Energy Industries of Ohio (EIO), to evaluate candidate
materials for coal-fired boilers operating under ultra-supercritical (USC) steam conditions.
Power plants incorporating USC technology will deliver higher cycle efficiency, and lower
emissions of carbon dioxide (CO 2 ) and other pollutants than current coal-fired plants.
Turbine throttle steam conditions for USC boilers approach 732°C (1350°F), at 35 MPa
(5000 psi). The materials used in current boilers typically operate at temperatures below
600°C (1112°F) and do not have the high-temperature strength and corrosion properties
required for USC operation. Materials that can meet the high temperature strength and
corrosion requirements for the waterwalls and superheater/reheater sections of USC boilers
need to be tested and evaluated.
The focus of the current work is experimental evaluation of fireside corrosion resistance of
candidate materials for use in USC boilers. These materials include high-strength ferritic
steels (SAVE12, P92, HCM12A), austenitic stainless steels (Super304H, 347HFG, HR3C),
and high-nickel alloys (Haynes® 230, CCA617, INCONEL® 740, HR6W). Protective
coatings (weld overlays, diffusion coatings, laser claddings) that may be required to mitigate
corrosion were also evaluated. Corrosion resistance was evaluated under synthesized coalash
and flue gas conditions typical of three North American coals, representing Eastern
(mid-sulfur bituminous), Mid-western (high-sulfur bituminous), and Western (low-sulfur
sub-bituminous) coal types. Laboratory testing for waterwall materials was performed at
455°C (850°F), 525°C (975°F), and 595°C (1100°F). The superheat/reheat materials were
exposed to 650°C (1200°F), 705°C (1300°F), 760°C (1400°F), 815°C (1500°F), and 870°C
(1600°F). Samples were exposed for 1000 hours, with ash being replenished every 100
hours to maintain aggressive conditions. Samples were evaluated for thickness loss and
subsurface penetration of the corrosive species. The laboratory testing was useful for
screening different alloys in controlled environments, where the different variables of alloy
content, temperature, fuel/ash and sulfur in the flue gas could be evaluated.
35
Promising materials from the laboratory tests were assembled on corrosion probes for testing
in three utility boilers. Air-cooled, retractable corrosion probes were designed to maintain
metal temperatures using multiple zones, representing USC superheat/reheat temperatures,
ranging from 650°C (1200°F) to 870°C (1600°F). The probes were installed in utility
boilers, equipped with low NO x burners, representing each of the three coal types. This paper
presents an update on the current status of this ongoing fireside corrosion advanced materials
research program.
39-4
Carbon Molecular Sieve Membrane/Module and its Use for
Hydrogen Production for Coal
Paul Liu, Richard Ciora, Media & Process Technology, Inc., USA
Theodore Tsotsis, University of Southern California, USA
Carbon, due to its inertness, is considered an ideal material candidate for handling
coal-related process streams. Although carbon molecular sieve (CMS) materials have
been used extensively in industry as adsorbents, they have not moved beyond the
academic novelty stage as a membrane material. Two major application-related
barriers have prevented industrial acceptance of a CMS membrane, specifically, (i)
poisoning and/or aging by a wide range of contaminants/impurities present in the
atmosphere either during storage or in the stream to be treated and (ii) the lack of a
module that is both cost and commercially/industrially acceptable, particularly for a
high temperature and high pressure applications. Media and Process Technology Inc.
has overcome these two barriers by choosing appropriate operating conditions and
developing a CMS/ceramic composite membrane/module. One of the major
application focuses for this CMS membrane/module is hydrogen/electricity coproduction
from coal. By operating at an intermediate temperatures, i.e., 150 to 300°C,
our unique CMS membrane/module can function as a simple hydrogen separator or as
a membrane reactor for water gas shift reaction. Hydrogen permeances of 1 to
>3 m 3 /m 2 /hr/bar and H 2 /CO selectivities of 50 to >100 are typical in this operating
temperature range. Based upon the performance of the membrane and the features of
the module, we have developed several process scenarios for hydrogen production
from coal. Process intensification as a result of the use of our membrane/module will
be presented.
39-5
FT-IR and XRD Study of Tirap Coal
Binoy K. Saikia, R. K. Boruah, P K Gogoi, Tezpur University, INDIA
Coal sample from Tirap colliery of Assam, India was studied using FTIR and XRD
methods. FTIR study shows the presence of aliphatic -CH, -CH 2 and -CH 3 groups,
aliphatic C-O-C stretching associated with -OH and -NH stretching vibrations and
HCC rocking (single and condensed rings). XRD pattern of the coal shows that it is
amorphous in nature. Function of Radial Distribution Analysis (FRDA) indicates that
coal is lignite in type and there is no evidence of graphite like structure. The first
maximum in the FRDA at R = 0.133 nm relates to the C = C bond (Type C – CH = CH
– C), the second maximum at R = 0.25 nm relates to the distance between carbon
atoms of aliphatic chains that are located across one carbon atom. The curve intensity
profiles obtained from FRDA show quite regular molecular packets for this coal.
SESSION 40
ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY – 2
40-1
Recent Advances in Trace Metal Capture Using Micro and Nano-Scale Sorbents
Jason D. Monnell, Radisav D. Vidic, University of Pittsburgh, USA
Dianchen Gang, West Virginia University Institute of Technology, USA
Andrew Karash, Evan J. Granite, DOE/NETL, USA
The adsorption of mercury, arsenic, and selenium on micro and nano-scale sorbents is
reviewed. In particular, efforts on trace metal capture from coal-derived gas streams
using nano-scale sorbents are summarized. A collaborative effort between the
University of Pittsburgh, WVU Tech, and NETL on the development of novel micro
and nano-scale sorbents has been initiated with the preliminary results presented
herein. Future research directions are suggested and an extensive list of references is
provided.
40-2
Aqueous Mercury and Lead Removal with Activated Carbons
Derived from High Sulfur Carbonaceous Materials
Shitang Tong, Shuqing Zhang, Xiaoqing Wu, Wuhan University of Science and
Technology, CHINA
Jenny Cai, Loraine Laiyin Chiu, Donald W. Kirk, Charles Q. Jia, University of
Toronto, CANADA
Hg and Pb are of environmental concerns due to their toxic and bioaccumulative
nature. Developing cost effective adsorbents for controlling their emissions to the

environment is of practical value. In this work, the adsorption of aqueous Hg 2+ (200-
400 ppm) and Pb 2+ (570 ppm) onto a series of activated carbons was investigated. The
activated carbons used were prepared from high sulfur coal or petroleum coke via
chemical activation processes using alkaline materials such as KOH and its mixture
with other reagents. Activated carbons were analyzed for specific surface area, porous
size distribution, total sulfur, as well as sulfur functional groups. The adsorption
capacity was determined at controlled pH (5.0~6.0) and temperature (20-60°C) using
ICP and AAS. The activated carbons had total sulfur contents from 0.16 to 20.14 wt%,
and their specific surface areas varied from 47 to 2232 m 2 /g. A pseudo first order
model was applied to describe the adsorption kinetics. Experimental data indicated that
the increase in sulfur content and specific surface area enlarged the adsorption rate and
capacity for both Hg(II) and Pb(II). The type of sulfur in activated carbons was found
to be the most important factor in determining the effectiveness of adsorbing Hg(II)
and Pb(II).
40-3
Novel Sorbents for Removal of Mercury from Flue Gas
Evan Granite, Albert A. Presto, DOE/NETL, USA
Numerous materials have been examined as sorbents for the capture of mercury in a
lab-scale packed-bed reactor located at NETL. The sorbents examined include
activated carbons, Thief carbons, precious metals, fly ash, metal oxides, and metal
sulfides. Simulated flue gases containing sulfur dioxide, nitrogen oxide, oxygen,
carbon dioxide, elemental mercury, and nitrogen were contacted with the sorbents in
the lab-scale packed-bed reactor. Several promising sorbent candidates have been
identified. The mechanisms of mercury capture are discussed. Future research on
sorbents will be conducted in a bench-scale packed-bed reactor employing both
simulated and real flue gas streams generated on-site at NETL.
40-4
Impacts on Trace Metal Leaching from Fly Ash Due to the
Co-Combustion of Switchgrass with Coal
Wayne Seames, Mandar Gadgil, Chunmei Wang, Joshua Fetsch, University of North
Dakota, USA
Biomass/coal blended fuel combustion is gaining popularity as a means to reduce
greenhouse gas emissions. The impact of co-combustion upon the solubility of trace
metals contained in the various fly ash regimes has yet to be addressed. In this study,
Blacksville coal/switch grass blended fuel is combusted in a 19kW laboratory
combustor and sampled using a low pressure impactor. Leaching tests of the three
particle regimes – submicron, fine fragmentation, and bulk ash – were performed. A
modified TCLP-type leaching method was utilized with acidic, neutral, and basic
solvents and the relative solubility of arsenic, selenium, and antimony were determined
as a function of solvent and particle regime. The results were then compared to
comparable results obtained from the combustion of Blacksville coal alone. The results
suggest that co-combustion may have beneficial effects by lowering the solubility of
arsenic, antimony, and to a lesser extent selenium, contained on the surface of
submicron and fine fragmentation particles into acid and basic solutions. By contrast,
the potential to leach these trace elements from bulk ash collected in disposal piles
increases.
40-5
Effect of Hydrogen Chloride in Coal Combustion Flue Gas on the Mercury
Removal Performance of Activated Carbon from Coal Combustion Flue Gas
Toru Yamada, Yuki Yamaji, Eiji Sasaoka, Md. Azhar Uddin, Shengji Wu, Okayama
University, JAPAN
In this study, the effect of HCl on the Hg 0 removal performance for coal combustion
flue gas system using activated carbons prepared from fly ash and pitch and activated
carbon derived from coconut shell (a commercial sample) was investigated. Mercury
(Hg 0 ) removal capacity of fly ash-pitch activated carbon was higher than that of
coconut shell activated carbon in the absence of HCl, however fly ash-pitch activated
carbon showed lower mercury adsorption performance compared to the coconut shell
activated carbon in the presence of HCl. It is suggest that in the absence of HCl,
surface H 2 SO4 was produced by the adsorption of SO 2 , O 2 and H 2 O on the activated
carbon which then reacted with Hg 0 to produce HgSO 4 and enhanced the mercury
adsorption capacity of the activated carbons. The presence of HCl in the feed gas
increased the Hg 0 removal performance of the activated carbon sorbents many fold.
However, the presence of SO 2 has an adverse effect on the adsorption capacity of the
activated carbons in the presence of HCl.
SESSION 41
COAL UTILIZATION BY-PRODUCTS – 1
41-1
Overview of C2P2, the Industrial Resources Council, and
the Green Highways Initiative
David Goss, American Coal Ash Association, USA; Mark Bryant, AmerenEnergy,
USA
The use of coal combustion products (CCPs) in a wide variety of applications allows
for the use, reuse and recycling of nearly 50 million tons annually of these materials.
As new emission control systems are added to coal fueled power plants, there are new
challenges facing producers and markets of CCPs. The formation of private and public
sector partnerships is having a positive impact on developing new markets for CCPs
and in increasing the awareness of the value of these products to potential end-users
and specifiers. The Coal Combustion Products Partnership (C2P2), the Industrial
Resources Council and the Green Highways Initiative all are providing information
and outreach to those whose decisions could increase the beneficial use of these
materials. This paper will provide an overview of these partnerships and the results of
their efforts.
41-2
Beneficial Land Application Uses of FGD Products
Warren Dick, David A. Kost, Liming Chen, The Ohio State University, USA
Combustion of fossil fuels for energy production releases sulfur dioxide (SO 2 ) at a rate
proportional to the S concentration in the fuel. Industrialized nations have adopted flue
gas desulfurization (FGD) technologies to reduce SO 2 emissions. FGD technologies
will generate increased amounts of product in the future as more utilities install
scrubbers for SO 2 control. These FGD products raise economic and environmental
issues for which satisfactory solutions still need to be found. The type of coal and
desulfurization process used influences the chemical composition and properties of an
FGD product. The properties of the FGD material have a direct impact on potential
land application uses. FGD properties most commonly captured for beneficial purposes
are (1) ability to neutralize acid, (2) high amounts of soluble calcium and sulfate, (3)
source of plant nutrients, and (4) uniform particle size. Land application uses of FGD
materials are identified by matching the properties of the FGD material with
improvement in some ecosystem function (or functions). For beneficial use, the change
in ecosystem function is assumed to be positive. FGD use must be considered in terms
of recommended application rates, environmental impact and economic return.
Beneficial land application implies the applied FGD material will improve the soil
(primarily) and also the total environment. Often, the intended benefit relates to plant
growth, but there may be other benefits to soil or water such as reduction of erosion,
improved quality of runoff and/or leachate water, or improved internal drainage. The
application rate must be sufficient to cause soil improvement, but not so great as to
constitute disposal of the FGD material. Although there is recognition of the potential
of using FGD materials in agriculture, there is also uncertainty whether this use is
sustainable. Currently, there is a general lack of acceptance in the agricultural
community for using FGD materials. This barrier can only be overcome by research
and sound knowledge that sometimes already exists in the scientific and technical
literature. To promote use of FGD products, especially FGD gypsum, a national
network of agricultural demonstration and research sites has been established. Network
sites, strategically located in the United States, are available to producers, users and
marketers of FGD products to provide places where observations can be made as to the
benefits of FGD product use under regional agricultural conditions. In addition, data on
crop yields, environmental impacts and economic benefits will aid in the marketing of
the FGD products.
41-3
On the Behavior of Coal Combustion By-Products (CCP) under
Different Geotechnical and Geoenvironmental Stress Conditions
Vincent (Tobi) Ogunro, Mutiu Ayoola, Hilary Inyang, Brian Anderson, John Daniels,
University of North Carolina, USA
Environmental and economic concerns regarding management of coal combustion
products (referred to as Recycled Granular waste Media, RGWMs, in this study) have
led to several investigations into potential contaminant releases from RGWMs used as
substitute materials in construction of geotechnical and geoenvironmental
infrastructures. Most of these studies understandably have been focus on assessing the
leaching potential of RGWMs. The results of these studies have provided only limited
data on the behavior of RGWMs compared with conventional construction materials.
In order to provide further insight into the engineering behavior and leaching potentials
of RGWMs especially under unusual stress conditions, series of drained and undrained
triaxial compression tests are performed. It was observed that RGWMs exhibit
significantly different behavior compared with sand subjected to the same stress
condition. This include significant volumetric contraction of specimen compacted at
95% maximum unit weight, deviation from Rowe’s dilatancy theory and steady state
concept, static liquefaction of medium dense specimen at low confining stresses,
significant loading rate sensitivity and pseudo-viscoelastoplastic behavior within some
strain rate regimes. Also, stress-dependent contaminant releases from fresh and aged
RGWM are being investigated.
36

41-4
Using Fly Ash-Based Foundry Composition for Molds and
Cores (FASAND) to Pour Iron Castings
Robert Purgert, Energy Industries of Ohio, USA; Andrzej Baliski, Pawel Darlak, Jerzy
Sobczak, Foundry Research Institute, POLAND
The study discusses the results of experiments and trials concerning application of fly
ash as a base material of foundry sands (FASAND mixture) to produce iron castings
for automotive industry. Two types of fly ashes were examined: the fly ash from
Eastlake Plant (USA) and, for comparison, the fly ash from Skawina Power Plant. For
these fly ashes detailed investigation was made as regards chemical composition, phase
constitution, density distribution of individual fractions, toxicity, and thermal
characteristics. After initial selection of binding systems, the technological properties
of the FASAND type mixtures were tested. Using the three selected chemical
compositions and fabrication methods, under the local conditions of Energy Industries
of Ohio and Foundry Research Institute - Krakow, some trials were conducted on
casting the grey and ductile irons, using cores assigned for production of castings for
the automotive industry and the conventional sand casting technology. The ready
castings were subjected to macroscopic examinations to check the surface condition
and gas content. It has been stated that further work on practical application of
FASAND mixtures in pouring iron castings should focus on searching for other types
of fly ash, characterized by higher thermal characteristics, and on search for other
means to improve the permeability of the ready mixtures by raising their open porosity.
41-5
Legal, Ecological and Technological Aspects of the Mass Production of
Lightweight Concretes Based on High Volume of Coal Ashes
Mark Nisnevich, Gregory Sirotin, Tuvia Schlesinger, The College of Judea and
Samaria, ISRAEL
In an earlier publication in the framework of the 22 nd Annual International Pittsburgh
Coal Conference we reported the preliminary results of a R&D program related to the
development of a technology for the combined utilization of bottom ash, fly ash and a
by-product of stone quarries (unprocessed crushed sand) for the manufacture of
ecologically friendly lightweight concrete with desirable building characteristics.
In the recent months we made progress in the further development of this technology.
Our efforts are concentrated on the solution of problems related the mass production of
the ternary lightweight concrete. Special attention has been given to the study of
radiological characteristics of coal ashes from different sources and lowering the
activity concentrations of radionuclides in the lightweight concrete based on coal
ashes. The results of our theoretical and experimental studies will be reported.
SESSION 42
COAL PRODUCTION AND PREPARATION – 2
42-1
Efficiency and Productivity Analysis of Coal Mines
Subhash C. Sharma, M.K. Mohanty, J. Hirschi, P. Melvin, H. Patil, Southern Illinois
University, USA
The technical efficiency of twelve underground coal mines in Illinois is estimated for
the period 1989 to 2003 and some factors contributing to inefficiencies at these mines
have been identified in this study by using the stochastic production frontier model.
Next, the output growth is decomposed into its three components: growth due to
change in technical efficiency, growth due to technological progress, and growth due
to change in inputs. The overall average technical/productive efficiency of all the
mines considered in this study is 69%. There is a clear distinction among the mines.
Three mines are around 80% technically efficient. Four mines are in the 69% to 76%
efficiency range. The other five mines are in the 50% to 65% range. Besides the
amount of labor and capital used in production, other factors which have contributed to
inefficiency are depth to the coal seam, injury frequency rate and age of the mine. The
output growth of these twelve mines was negative between 1991/1992; 1996/1997;
2000/2001; 2001/2002 and 2002/2003 and positive the remainder of the time. Negative
growth periods were due to negative growth in inputs and negative changes in
technical efficiencies. Our results reveal that the rate of technological progress has
been decreasing throughout the period of study.
42-2
A Unified Model to Characterize the Performance of Density Separators
Manoj K. Mohanty, Pramod K. Sahu, Vishal Gupta, Southern Illinois University, USA
Coal preparation plants clean nearly 90% of the run-of-mine coal using some form of
density based separators, which are characterized by their partition models. A variety
of these models are available, some of which are more suitable for heavy medium
based separators, whereas some others are better suited for water-based gravity
separators. After evaluating many of these available models, a modified log-logistic
model has been developed in this study that is equally suitable for characterizing the
37
performance of all different types of density based separators, including heavy medium
vessel, jig, heavy medium cyclone, water only cyclone, spiral etc. This model will be
discussed in comparison to the actual data collected from the aforementioned density
separators operating in three different coal preparation plants.
42-3
Development of Chemical Inhibitors Using Differential Scanning Calorimeter
Equipment for Controlling Spontaneous Heating/Fire in Coal Mines
R.V.K. Singh, G. Sural, V.K. Singh, Central Mining Research Institute, INDIA
The problem of spontaneous heating/fire is very much serious in Indian coal mines.
Due to fire in coal mines, huse quantity of national property like coal is being lost and
environment is badly affected due to release of noxious gases. Under this
circumstances, chemical inhibitors has played very important role in controlling fire.
After carrying out literature survey work, different chemical inhibitors have been
identified and analysed in Differential Scanning Calorimeter (DSC) equipment.
Different proportions of the inhibitors have been analysed in DSC equipment to
determine their endothermicity (heat absorbing capacity) at different temperature.
Chemicals like boric acid, di-ammonium phosphate, urea, sodium silicate, sodium
chloride has mixed in different proportion and analysed in the DSC equipment. After
that some of the suitable composition has been applied in coal mines to control the
surface as well as overburden dump fire. The objective of this paper is to describe
about the application of chemical inhibitors for controlling spontaneous heating/fire in
coal mines.
42-4
Analysis of the Migrating Laws of Methane in the Mining-
Induced Fracture Zones in Overburden Strata
Li Shugang, Lin Haifei, Cheng Lianhua, Li Xiaobin, Xi’an University of Science &
Technology, P.R. CHINA
In most Chinese coal mines, the inherent permeability coefficient and methane
pressure in coal seams are so low that the degasification is more inefficient compare
with other countries. So, first of all, the released methane in the mining induced
fractures should be degassed. It is necessary to study the methane migrating laws in
mining-induced fracture zones through research on the storage characteristic of coal
bed methane in China. Based on the results of physical modeling and field monitoring,
the shape of the mining induced fracture zone over the long wall gob can be
represented by a 3-D elliptic paraboloid function, called the Elliptic Paraboloid Zone.
The coupling mathematical model of the methane delivery law is applied in the mining
fissure Elliptic Paraboloid Zone and the migrating laws of methane is obtained. The
mining fissure Elliptic Paraboloid Zone is the delivery and collection zone of relieved
methane, which is verified by the results of a long wall gob degasification tests at a
coal mine of Yangquan in China. This study provides a reasonably basis for designing
the gob-well degasification system for long wall mining operations.
42-5
Simulation Material Experiment Research on the Coupling of
Seepage Field and Stress Field in Underground Mining
Zhang Jie, Hou Zhong Jie, Xi’an University of Science & Technology, P.R. CHINA
It is important to take solid-liquid coupling simulation material experiment in the
research on the coupling of seepage field and stress field in the underground mining. It
is difficult to find the suitable coupling simulation material. So the great progress has
not been made for a long-term. Based on large number of tests, paraffin wax is chosen
as the cementing material of coupling simulation material model. At the same time, the
change law of model physics mechanics parameters has been drawn with different
simulation material’s rate. Shen-Fu mining area coal is in the north of china which is
covered with rock and water. The mining model is made on the base of the research of
solid-liquid coupling simulation material. Through the simulation material experiment,
the law of water seepage in destructed rock and the law of rock destructed in seepage
field are drawn. The reasonable face advancing distance in water resources
preservation mining is gained. It proved that the result of simulation material
experiment is consistency with the field through observation. So the research is
important to guide reasonable planning-exploitation of the water resources
preservation mining. The success of this experiment provides a new way to research on
the coupling of seepage field and stress field.
SESSION 43
GASIFICATION TECHNOLOGIES:
ADVANCED TECHNOLOGY DEVELOPMENT – 3
43-1
Oxygen Carrier Development for Chemical Looping Combustion of
Coal Derived Synthesis Gas
Ranjani Siriwardane, James Poston, DOE/NETL, USA
Karuna Chaudhari, Anthony Zinn, Thomas Simonyi, Clark Robinson, Research
Development Solutions, USA

In the present work, NETL researchers have studied chemical looping combustion
(CLC) with an oxygen carrier NiO/bentonite (60 wt.% NiO) for the IGCC systems
utilizing simulated synthesis gas. Multi cycle CLC was conducted with NiO/Bentonite
in TGA at atmospheric pressure and in a high pressure reactor in a temperature range
between 700- 900°C. Global reaction rates of reduction and oxidation as a function of
conversion were calculated for all oxidation-reduction cycles utilizing the TGA data.
The effect of particle size of the oxygen carrier on CLC was studied for the size
between 20-200 mesh. The multi cycle CLC tests conducted in a high pressure packed
bed flow reactor indicated constant total production of CO 2 from fuel gas at 800°C and
900°C and full consumption of hydrogen during the reaction.
43-2
Substitute Natural Gas from Coal Co-Production Project - A Status Report
John Ruby, Sheldon Kramer, Nexant, Inc., USA
Raymond Hobbs, Arizona Public Services, USA
Bruce Bryan, Gas Technology Institute, USA
The US DOE National Energy Technology Laboratory awarded four co-production
projects in December 2005. This paper presents the status and early results from the
project sponsored by Arizona Public Service Company (APS). The 3-year project will
research and develop a hydrogasification process to co-produce substitute natural gas
(SNG) and electricity from western coals. The proposed system uses hydrogen instead
of air or oxygen in the gasification process, an approach that offers higher operating
efficiencies, lower water consumption, and a gas product that is richer in methane than
other gasification processes. The concept has the potential to produce SNG below the
projected market price for natural gas. It will separate a carbon dioxide stream ready
for sequestration. In the first year the project will focus on concept design and
laboratory tests; the overall objective will be to field test the hydrogasification SNG
concept at one of the APS power stations.
43-3
Co-Production of Substitute Natural Gas and Electricity via
Catalytic Coal Gasification
Brian S. Turk, Raghubir Gupta, RTI International, USA
Although coal is well known to be the most abundant fossil fuel available on this
planet, its reputation as a fuel is tarnished by its inconvenient solid form, complexity
for converting into useful energy and work, pollution, and a negative public image that
discourages coal use. In a recently funded DOE project, RTI plans to develop key
technologies to convert coal into two more desirable energy forms, namely substitute
natural gas and electricity. RTI’s technology platform is based on extensive research
performed by Exxon in the 1970’s for substitute natural gas (SNG) production via
catalytic gasification. Unfortunately, this process was not economically viable because
an extensive recovery process was necessary to recover the active catalyst from the ash
to mix with the coal feed, the active catalyst and ash reacted at the operating conditions
inhibiting effective catalyst recovery, and cryogenic separation was used to separate an
SNG product and a hydrogen and carbon monoxide recycle stream. RTI has adapted a
number of newer and novel technologies to overcome these problems and
simultaneously achieve near zero emissions, produce a high pressure CO 2 product and
co-produce electricity. In the proposed process, the active catalyst material is loaded on
a support material and remains fixed in a catalytic reactor. The coal is initially
preprocessed to convert the coal into a mixture of gas phase carbon species, H 2 and
solid char fines prior to the catalytic reactor. In the catalytic reactor, the catalyst
promotes the conversion of the gas phase carbon species and H 2 into CH 4 . Because the
ash is trapped in the solid char fines and the catalyst on a support, physical contact
between the ash and catalyst is impossible eliminating the potential for reaction. The
product gas mixture from the catalytic reactor is cleaned using the hot gas
desulfurization and CO 2 capture technologies that have been developed at RTI. The
product from the CO 2 capture process is a high pressure sequestration ready CO 2
byproduct. More conventional ammonia and methanation processes will be used to
polish the final SNG to meet pipeline specifications. Finally, the carbon trapped in the
char fines is combusted in a pressurized fluid-bed combustor to generate steam and
electricity. This presentation will describe the available results from the bench-scale
testing program for evaluating the technical and economic feasibility of the proposed
process.
43-4
Fundamentals of an Optimized Catalyst Gasification System
Edwin Hippo, Raman Mahato, James May, Narcrisha Norman, Even Odell, Southern
Illinois University, USA
Aarron Mandell, GreatPoint Energy, USA
GreatPoint Energy has begun the development of a catalytic gasification process. This
process is aimed at operating at lower gasification temperatures than processes
previously developed. In conjunction with GreatPoint Energy, The Department of
Mechanical Engineering and Energy Processes at Southern Illinois University at
Carbondale has initiate fundamental studies to determine the feasibility of converting
coal into methane while keeping processing temperatures below 700°C. These studies
have included basic thermodynamics, laboratory scale gasification tests and laboratory
38
catalyst recovery tests. Three types of laboratory gasifiers have been developed. These
gasifiers were used to screen catalysts systems, and process variables. Catalyst
recovery screening was conducted in a Soxhlet extractor. The results demonstrate that
coal can be converted to methane at temperatures as low as 500°C within reasonable
reaction times of less than 1 hour and as short as 15 minutes. The optimum catalyst
system utilized thus far, consists of two catalyst. One catalyst apparently activates a
second catalyst to accomplish very rapid low temperature conversion of the coal. There
are many advantageous to the low temperature operation, They include lower steam
requirements, decrease gas separation costs, less catalyst tie-up with mineral
constituents, higher catalyst recovery, smaller boiler requirements, higher methane
concentration in the product gases, and less gas recycle. Basic thermodynamics will be
discussed. The paper will report results from batch, high pressure mini-gasifiers, semi
continuous, high pressure, mini fluid bed gasifier, and a differential bed gasifier.
Future development plans will be discussed.
43-5
A Novel Catalytic Coal Gasification Process to Produce SNG
Francis Lau, GreatPoint Energy, USA
GreatPoint Energy is commercializing a novel catalytic process for converting coal
(and other carbon-based feedstocks) into high value clean substitute natural gas (SNG).
Coal is available in abundance in the United States and will ensure a secure and an
affordable fuel for many generations. GreatPoint converts this low cost, but dirty
feedstock into the cleanest of all commercially viable fuels. GreatPoint s substitute
natural gas product, called bluegas TM , meets pipeline quality gas requirements, and is
transported by standard natural gas pipeline. Production can be centralized in close
proximity to the coal mine, where over half of the carbon (in the form of CO 2 ) can be
sequestered. GreatPoint Energy intends to build, own, and operate bluegasTM
production facilities and sell bluegasTM to regional distributors and customers in the
power generation, industrial, heating and chemical sectors. The company s technology
is based on the discovery that coal mixed with mixtures of alkali metal catalysts
promotes coal gasification reactions including methanation at mild conditions, around
500 to 700°C. Research into this finding has a led to a one-reactor system which offers
an efficient and cost-effective route to produce low cost methane from coal. The
objective of this paper is to describe the bluegasTM process, the status of the
technology, and areas of new process development.
44-1
SESSION 44
COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES:
MINERAL MATTER, COAL ASH, COAL COMBUSTION
Characterization of Source Rocks Producing Respirable Quartz and
Aluminosilicate Dust in Underground US Coal Mines
Steven Schatzel, NIOSH, PRL, USA
A research effort has been undertaken at the Pittsburgh Research Laboratory (PRL) of
the National Institute of Occupational Safety and Health (NIOSH) to characterize the
source material producing respirable quartz and aluminosilicate dust in coal mines.
Mine regulatory personnel suggested that problematic silicate mineral dust
concentrations were known in some coal mines operating in southern West Virginia,
Virginia and eastern Kentucky. Six mines were selected in this region for rock and dust
sampling by PRL researchers based on elevated quartz concentrations in historical dust
samples. Four of the coal mines sampled produced elevated respirable quartz dust
concentrations on active production sections during sampling, the other two mines
produced about 5% quartz, the regulatory reduced standard limit for quartz. Prior
research has suggested that the source of respirable silicate dust in underground coal
mines is typically immediate roof or floor lithology, not mineral matter bound within
the mined coalbed. At some of the sites included in this research there were only
potential quartz source rocks in either the floor or the roof units. At other sites sampled
during the study, potential quartz sources existed in both the roof and floor lithologies.
In the later cases, elemental data have suggested the enrichment of certain cations in
the roof lithologies compared to floor rock may have the potential to distinguish
potential quartz and aluminosilicate sources produced in respirable dust samples.
Research results from Pennsylvanian-age coalbeds in western Pennsylvania surface
mine sites has suggested the clastically derived mineral matter in the immediate roof
rock, coal-bound mineral matter and the immediate floor lithology are derived from a
common source material. Some of the enrichment of certain cation species in the roof
units (i.e., Ca, Fe, Mg, Na) compared to immediate floor rock may be related to the
percolation of fluids through the overburden and diminished probability for fluids to
migrate effectively through the coal or coal precursor and into the floor units.
Comparisons of the elemental composition of dust cassette mineral matter and possible
source rocks have shown that the dust composition is not identical to any of the
sampled potential sources rocks. It is considered likely that the mining process,
including rock breakage and the entrainment of dust particles in the ventilation air
stream have modified the dust composition from the starting parent materials.
However, normalizing the data has shown promise in distinguishing potential source

ocks using elemental ratios. Data from the single quartz rock sources sites have been
used to assess the viability of the methodology. The elemental data suggests roof strata
as the primary source of mineral-generated respirable dust produced during mining and
captured by the dust samplers on the cassettes. This finding is contrast to the quartz
dust sources identified in the field and by x ray diffraction analysis of roof and floor
rock where at least one site showed the primary silicate dust source to be in the floor.
The suite of x ray fluorescence sample data suggests a strong relationship between the
overall amount of Si and the quantity of quartz in the samples. A similar relationship
was not found in the parent source rocks. These findings may be significant since the
potential severity of the silicosis risk to miners is strongly influenced by both the
quantity of quartz and the clay minerals in the respirable dust fraction.
44-2
Studies on Abrasive Propensity of Thermal Coals of India: Effect
of Ash and Quartz Contents
Anup Kumar Bandopadhyay, Rajatmay Chatterjee, Central Fuel Research Institute,
INDIA
A suite of 50 thermal coals from various coalfields of India, viz. Eastern Coalfield Ltd,
Western Coalfield Ltd, Northern Coalfields Ltd and Talcher Coalfields Ltd, used as fuel in
major thermal power stations,Viz. Farakka Super Thermal Power Project (STPP), Talcher
STPP, Talcher TPP, Kahalgaon TPP, Unchahar TPP, Vindyachal STPP, Singarauli STPP,
Rihand STPP, Dadri STPP. Rihand STPP, Majia TPP, Tanda TPP and NSTCL PP, in recent
times has been systemically characterized for the first time for the purpose of assessing
abrasive propensity in terms of their ash and quartz contents. Abrasive propensity of all the
coals has been determined according to the procedure given in IS: 9949-1986, while the
quartz content in each coal has been determine using Fourier Transform Infra for
quantitative analysis of quartz in minerals. Thermal coal in India is of drift origin and as
such, the mineral contents are high in them. Coals fed to thermal power stations have been
found to contain 30-60% ash and quartz in them varies between 5 and 20% graph plotted
between quartz and ash contents of the coals shows, statistically, % quartz = 0.25x % Ash,
i.e., quartz makes one-fourth of the ash. There are poor correlations between abrasion index
and ash content and between abrasion index and quartz content as suggested by the large
scatter in respective graph with correlation coefficient of 0,56 and 0.31 respectively.
The commonly occurring minerals found in thermal coal are: kolinite, illite, montmorrilonite
and quartz with smaller amounts of carbonate species, pyrite and feldspar. Quartz and pyrite
are the harder materials present in coal with hardness of 7.0 and 6.5 on Mohs’ scale
respectively, but as pyrite is present in small amounts, only about 1% of the weight of the
coal, its contribution towards abrasive propensity is insignificant compared to that of quartz.
Quartz is found to occur as rounded and angularly shaped particles of various sizes in coal.
Although both size and shape contribute to wear, angular particles are more abrading than
the rounded ones. Poor correlations between abrasion index and quartz to the factors not
being given due consideration.
The correlation between abrasion index and ash content is, however, found to improve when
thermal coals are bifurcated into two groups: one with quartz/ash ratio less 0.25 and the other
greater than 0.25. For the two groups respectively abrasion index (AI) is given by the
following empirical relations:
AI = 1.12* Ash + 0.71 (R 2 = 0.85)
and AI = 1.28* Ash + 6.90 ( R 2 = 0.64)
The factor of 0.25 chosen for bifurcation has been taken from scatter diagram between the
variables. This seems to be plausible as for most of thermal coals the ratio is 0.25, the chances for getting
adventitious quartz from mining operations are higher. Quartz particles from extraneous
sources are characterized by their higher angularity and as such, abrasion of coal containing
these particles over and above the inherent ones is higher.
The study also shows that there is very poor correlation between AI and HGI. Although HGI
is a technical design parameter and has assumed commercial importance because of its use
in coal contract specification, presence of quartz in coal dictates the performance and life
time of a mill. Notwithstanding the limitations, the equations proposed are instrumental in
preliminary assessment of abrasive propensity of Indian coals required for maintenance
schedules of power plant machinery.
44-3
Sulfur and Carbon Isotope Geochemistry of Coal and Derived Coal Combustion
By-Products: An Example From an Eastern Kentucky Mine and Power Plant
James C. Hower, Ana M. Carmo, Tao Sun, Sarah M. Mardon, University of Kentucky,
USA
Erika R. Elswick, Indiana University, USA
The isotopic compositions of sulfur (* 34 S) and carbon (* 13 C) were determined for the
coal utilized by a power plant and for the fly ash produced as a by-product of the coal
combustion in a 220-MW utility boiler. The coal samples analyzed represent different
lithologies within a single mine, the coal supplied to the power plant, the pulverized
feed coal, and the coal rejected by the pulverizer. The ash was collected at various
stages of the ash-collection system in the plant. There is a notable enrichment in 34 S
from the base to the top of the coal seam in the mine, with much of the variation due to
an upwards enrichment in the 34 S values of pyrite. Variations in 34 S and in the amount
of pyritic S in the coal delivered to the plant show that there was a change of source of
coal supplied to the plant, between week one and week two of monitoring, supporting a
39
previous study based on metal and sulfide geochemistry for the same plant. The fly ash
has a more enriched * 34 S than the pulverized coal and, in general, the 34 S is more
enriched in fly ashes collected at cooler points in the ash-collection system. This
pattern of 34 S suggests an increased isotopic fractionation due to temperature, with the
fly ash becoming progressively depleted in 34 S and the flue gas sulfur-containing
components becoming progressively enriched in 34 S with increasing temperatures.
Substantially less variation is seen in the C isotopes compared to S isotopes. There is
little vertical variation in 13 C in the coal bed, with 13 C becoming slightly heavier
towards the top of the coal seam. An 83 to 93% loss of solid phase carbon occurs
during coal combustion in the transition from coal to ash owing to loss of CO 2 . Despite
the significant difference in total carbon content only a small enrichment of 0.44 to
0.67 in 13 C in the ash relative to the coal is observed, demonstrating that redistribution
of C isotopes in the boiler and convective passes prior to the arrival of the fly ash in the
ash-collection system is minor.
44-4
A Measurement technique for Coal Ash Emissivity in
High Temperature Atmospheres
Miki Shimogori, Hidehisa Yoshizako, Yoshio Shimogori, Babcock-Hitachi.K.Kure
Laboratory, JAPAN
The purpose of our work is to examine the characteristics of coal ash emissivitiy to
better understand the heat transfer mechanism through ash deposits on tubes in coalfired
boilers. This paper presents a method for determining coal ash emissivity in high
temperature atmospheres and the influence of the ash surface temperature on its
emissivity. Emissivity was determined by comparing theoretical radiation intensities
with measurements obtained by a shield tube emissometer. An ash sample was heated
in an electric furnace during the measurement and the radiation intensity from the
sample was measured with a digital pyrometer. Emissivity characteristics of Powder
River Basin (PRB) coal ash and bituminous coal ash were examined. The main results
are as follows: (1) Emissivity of deposited ash increases with an increase in deposit
surface temperature. (2) The emissivity of a sample having fused surface exceeds 0.9.
(3) PRB deposits have lower emissivities compared with bituminous deposits in the
range of the surface temperature from 600°C to 1100°C.
44-5
A Theoretical Study of the Kinetics of Selected Arsenic and Selenium
Reactions in Coal Combustion Flue Gases
Jennifer Wilcox, David Urban, Worcester Polytechnic Institute, USA
As environmental regulations pertaining to mercury are becoming much stricter, other
trace metals, particularly arsenic and selenium, are beginning to be examined as well.
A noted source of compounds containing these elements is coal combustion flue gases
and, as such, the mechanism(s) of their removal is a topic of much attention. Given that
any removal strategy will be dependent upon the speciation, and the speciation in turn
will be dependent upon the reaction kinetics of the flue gas, determination of the
kinetic parameters of reactions involving these metals is key to developing effective
removal techniques. Previous experimental work has been performed to determine the
speciation for a variety of conditions, however the nature of many of the compounds
created as a result of the combustion process makes them undetectable to current
experimental techniques. To develop a more complete understanding of the overall
speciation it is thus necessary to determine the importance of these compounds. To
accomplish this, computational chemistry techniques are employed to determine the
kinetic parameters of the elementary reactions taking place within the combustion flue
gas environment. The initial phases of the overall project will be presented; namely,
the theoretical computations and the development of kinetic rate expressions for a
selection of arsenic and selenium reactions. Additionally, the methodology used for the
calculations will also be discussed.
SESSION 45
MATERIALS, INSTRUMENTATION, AND CONTROLS – 2
45-1
Co-Coking of Hydrotreated Decant Oil/Coal Blends in a Laboratory Scale
Coking Unit: Product Distribution of Distillates
Omer Gul, Leslie R. Rudnick, Amy Scalise, Harold H. Schobert, Caroline Burgess
Clifford, The Pennsylvania State University, USA
Delayed coking, used in petroleum refineries throughout the world, is a process that
converts heavy petroleum residua (vacuum residua and decant oil) into light distillate
fraction and coke. This is achieved by the pyrolysis and thermal degradation of the
feedstock in a semi-continuous process, at temperatures between 450-500°C, in an
inert atmosphere, and at pressures around 10 psig. A pilot-scale delayed coker at The
Energy Institute at The Pennsylvania State University is used to provide reliable
continuous delayed coking for 4-6 hours to provide acceptable quantities of liquids and
cokes for the further evaluation. The unit is capable of operating under most delayed
coking process conditions. The system pressure, temperature and flow rates are

monitored by a number of computer-controlled devices, and data from these devices is
recorded throughout the run. In the present paper, we describe the coking and cocoking
of decant oil and decant oil/coal blends using a pilot-scale delayed coker.
Decant oil was hydrotreated at several levels of severity for use in the coking/cocoking
work. The feedstock of the first control experiment contained only decant oil.
The subsequent co-coking experiments used feedstocks in an 80:20 ratio of
hydrotreated decant oil to coal. A typical product distribution for a delayed coking
operation is 70% liquids, 20% coke and 10% gas. The boiling point distribution of the
liquid products was determined using vacuum distillation and simulated distillation.
ASTM 2887 method was used for the simulated distillation analyses. The results from
vacuum distillation and simulated distillation reveal that the percentage of the liquid
products corresponding to jet fuel increases with increasing hydrotreatment. The
percentage of liquid products boiling in the jet fuel range, 180-270°C, ranges from 4.5-
11.3%. The overall yields of jet fuel and diesel in the co-coking run increases with
degree of hydrotreating level. The percentage that corresponds to gasoline is
approximately 0.5-2.5% and that of diesel is 6.5-15%, whereas the percentage
corresponding to fuel oil ranges from approximately 78-48% for low to high degrees of
hydrotreatment, respectively. Additionally, the total liquid product yield decreases
when coal is present. While this information provides a good basis for determining the
relationship between severity of hydrotreating and product yield, further process
optimization is needed to determine the best co-coking conditions to produce jet fuel
range material. The chemical compositions of different fractions, e.g., gasoline, jet
fuel, will be discussed.
45-2
High Temperature Corrosion Probes: How Well Do They Work
Sophie Bullard, Albany Research Center, USA
Bernard Covino, Gordon Holcomb, Margaret Ziomek-Moroz, NETL-Albany, USA
The ability to monitor the corrosion degradation of key metallic components in fossil
fuel power plants will become increasingly important for FutureGen and ultrasupercritical
power plants. A number of factors (ash deposition, coal composition
changes, thermal gradients, and low NO x conditions, among others) which occur in the
high temperature sections of energy production facilities will contribute to corrosion.
Several years of research have shown that high temperature corrosion rate probes need
to be better understood before corrosion rate can be used as a process variable by
power plant operators. Our recent research has shown that electrochemical corrosion
probes typically measure lower corrosion rates than those measured by standard mass
loss techniques. While still useful for monitoring changes in corrosion rates, absolute
probe corrosion rates will need a calibration factor to be useful. Continuing research is
targeted to help resolve this situation. This paper will present the results of this
research.
45-3
Application of a Diode-laser-based Ultraviolet Absorption Sensor for In Situ
Measurements of Atomic Mercury in Coal Combustion Exhaust
Jesse K. Magnuson, Robert P. Lucht, Thomas N. Anderson, Purdue University, USA
Udayasarathy A. Vijayasarathy, Kalyan Annamalai, Hyukjin Oh, Texas A&M
University, USA
A diode-laser-based ultraviolet absorption sensor was successfully demonstrated for
both in situ and extractive sampling atomic mercury measurements in a laboratory
scale 30 kWt coal combustor at Texas A&M University. Laser sensor measurements
were compared to measurements from a commercial mercury analyzer. A 375-nm
single-mode laser and a 784-nm distributed feedback (DFB) laser are sum-frequency
mixed in a nonlinear beta-barium borate crystal to generate a 254-nm beam. By tuning
the frequency of the DFB laser, the ultraviolet beam is tuned across the transition
frequency of mercury at 253.7-nm, leaving an off-resonant baseline on either side. No
pretreatment is required for either the in situ or extractive sampling configurations; the
effects of broadband absorption can be effectively eliminated during data analysis.
Extractive sampling was demonstrated to improve the detection limit of the sensor and
to demonstrate the feasibility of total mercury concentration measurements in the
future through extractive sampling. Significant variation in the atomic mercury
concentration of coal-combustion exhaust was observed over short time periods during
our in situ measurements. The sensor detection limits for in situ and extractive
sampling are 0.3 and 0.1 parts per billion over a one meter path length, respectively.
45-4
Detection of Mercuric Chloride Using a Fiber Laser
Thomas Reichardt, Alexandra A. Hoops, Dahv A. V. Kliner, Jeffrey P. Koplow, Sean
W. Moore, Sandia National Laboratories, USA
We demonstrate photofragment emission with a compact fiber-laser source to measure
gaseous HgCl 2 concentration with the goal of developing a real-time stand-off
speciating mercury emissions monitor. Assuming typical flue gas concentrations (74%
N 2 , 12% CO 2 , 8% H 2 O, and 6% O 2 ) at 200°C, we calculate a stand-off detection limit
of 0.7 ppb for a fieldable monitoring instrument.
40
45-5
Thermal Stability of Mercury Adsorbed on Sulphur-Containing
Activated Carbon Prepared from Petroleum Coke
Irina Bylina, Charles Q. Jia, University of Toronto, CANADA
Shitang Tong, Wuhan University Department of Science and Technology, CHINA
The hazards associated with mercury exposure have prompted a tightening of
regulations governing mercury emissions from utility coal boilers. Accordingly,
advancements are needed not only in clean-up and control technologies, but also in the
monitoring of mercury emissions. To meet the need for a real-time, speciating mercury
analyzer, we are developing laser-based techniques for stand-off, sensitive detection of
the two forms of vapor-phase mercury emitted by coal-fired power plants, Hg 0 and
HgCl 2 . The approach for measuring HgCl 2 concentration in combustion flue gas is to
detect emission at 254 nm from Hg (6 3 P 1 ) fragments produced by the
photodissociation of HgCl 2 at 210 nm. Selection of a laser wavelength that is not
resonant with ground state transitions of Hg 0 ensures that the laser photofragment
emission (PFE) technique is selective for HgCl 2 , even in the presence of large
quantities of Hg 0 . The PFE method was characterized and quantified by evaluating the
potential impact of interference gases, determining the dependence of the HgCl 2 PFE
signal on laser irradiance, and examining the effects of collisional quenching by flue
gas constituents N 2 , O 2 , and CO 2 . In addition, time-resolved measurements of the
atomic emission provide insight into both the preparation and decay of the Hg (6 3 P 1 )
state. Extension of the PFE technique to a fieldable instrument requires a UV laser
source that is not subject to the physical limitations of conventional laboratory laser
systems. In addition to producing high average and peak powers with excellent beam
quality, the laser source must be compact, rugged, and light weight. Frequency
conversion of pulsed, rare-earth-doped fiber lasers has the potential to meet these
requirements for a practical laser source. Recent experiments in our laboratory using
the frequency-quintupled output of a Sandia-built fiber laser at 213 nm have
demonstrated the ability to detect trace amounts of HgCl 2 in an environment
characteristic of flue gas. Using this source, we achieved a detection limit of 0.5 ppb
for a signal acquisition time of 5 minutes. While this detection sensitivity meets the
requirements for real-time monitoring of the HgCl 2 concentration in a flue gas
environment, ongoing efforts to increase the output power of fiber lasers will enable
the realization of equivalent detection limits with decreased signal acquisition times
and/or greater stand-off distances.
SESSION 46
ENVIRONMENTAL CONTROL TECHNOLOGIES: MERCURY/OTHERS
46-1
Semi-Continuous Detection of Mercury in Flue Gas by Photo-Deposition
Evan J. Granite, DOE/NETL, USA
The United States Environmental Protection Agency issued a regulation in March of
2005 for the emission of mercury from coal-burning power plants. In addition, several
states have also enacted legislation requiring control of mercury emissions from coalburning
plants. Methods for the detection of mercury in flue gas are needed in order to
determine compliance with state and federal regulations. Photo-deposition of mercury
upon a quartz substrate is shown to be a simple and inexpensive method for the semicontinuous
determination of total mercury in coal-derived flue gases.
A small particulate-free slipstream of flue gas is heated to temperatures above 950 o F,
converting all of the mercury to the elemental form. A small stream of oxygen or air is
blended into the slipstream, which is cooled to temperatures below 280 o F. Short-wave
254-nm ultraviolet (UV) light is applied to the resulting gas mixture, yielding
quantitative deposition of mercuric oxide upon a quartz substrate, and forming the
basis for a SCEM. The quartz substrate can be a surface acoustic wave (SAW) mass
sensor, allowing for near instant detection of total mercury in the flue gas.
The UV-SAW combination results in a simple SCEM for total mercury in flue gas. It
has the advantages of being a dry environmentally friendly system which is reliable,
inexpensive, and has the potential for being fully automated.
46-2
Sulphur Transformation during Chemical Activation of
High Sulphur Petroleum Coke
Jenny Cai, Charles Q. Jia, University of Toronto, CANADA
Shitang Tong, Wuhan University of Science and Technology, P.R. CHINA
High sulphur petroleum coke was used to produce sulphur-impregnated activated
carbon (SIAC) which had been proven to be more effective than virgin activated
carbon for Hg adsorption. The purpose of this work was to study the behaviour of
sulphur compounds in high sulphur petroleum coke during chemical activation and to
determine how sulphur was retained in the activated coke and what types of sulphur
reaction were involved. This is needed for producing SIACs that contain certain
sulphur functional groups particularly active in mercury adsorption. Two types of
petroleum cokes containing 5-7 wt% of sulphur were used to produce SIAC by
potassium hydroxide (KOH) activation in the presence of sulphur dioxide (SO 2 ) at

600-900°C. Changes in the amount of different sulphur types were determined by wet
chemical analysis. The sulphur functional groups in the raw coke and activated coke
were quantitatively analyzed using X-ray Photoelectron Spectroscopy (XPS). The
results showed that more sulphur formed on coke surface at the temperature around
700°C. The main sulphur functional groups and their fractions changed after
activation. Sulphur transformation under various activation conditions was observed
and the role of sulphur in coke activation was discussed.
46-3
Preparation of High-Performance Activated Carbon from Shenfu Coal
for Absorptive Desulfurization of Liquid Hydrocarbon Fuels
Anning Zhou, Xiaoliang Ma, Chunshan Song, The Pennsylvania State University,
USA
A novel method for preparing an ultra-high-surface-area activated carbon from Shenfu
coal by chemical activation with NaOH and KOH as activating agents was explored in
this study. The preparation method was optimized based on examination of diverse
experimental variables such as impregnation time, activating-agent/coal ratio,
KOH/NaOH ratio, activating temperature. The adsorptive performance of the prepared
activated carbons was evaluated for removal of sulfur compounds from a liquid
hydrocarbon fuel. The results indicate that effects of the activating-agent/coal ratio,
KOH/NaOH ratio, activating temperature and time are significant for improvement of
the adsorptive desulfurization performance of the activated carbons.
The chemical activation with two activating agents (NaOH-KOH mixture) might be a
more efficient method to develop an activated carbon with high desulfurization
capacity in comparison with the chemical activation with KOH or NaOH alone. The
specific surface of the activated carbon prepared by using the two activating agents can
be up to 3000 m 2 /g.
46-4
Catalytic Direct Oxidation of Coal-Gasification Syngas: Conversion of Hydrogen
Sulfide to Elemental Sulfur with Concomitant Capture of Mercury
James Aderhold, Raj Palla, Dennis Leppin, Gas Technology Institute, USA
This paper presents the results of an experimental study on the use of catalytic direct
oxidation (DO) for the upgrading of syngas generated from the gasification of coal in
an IGCC system. This work was sponsored by the Illinois Clean Coal Institute (ICCI)
and conducted by the Gas Technology Institute (GTI). The DO approach would be
expected to have significant cost savings for syngas versus the current technology for
removing sulfur from coal gasifier syngas, which involves an amine or physicalsolvent
treating system, followed by Claus and Tail Gas Treating of the off-gas.
The overall objectives of these studies were (1) to define processing conditions for
bulk removal of sulfur compounds as elemental sulfur from the syngas and (2) to
accomplish simultaneous removal of other contaminants, such as mercury from the
syngas. A bench-scale testing system has been constructed at GTI to measure the
performance of full-particle-size catalysts at elevated pressures and temperatures. A
blended gas stream, which contains the primary components of syngas, is combined
with oxygen (in the form of air), and passes over hot catalyst. From measured changes
in composition of the syngas stream, the activity and selectivity of the catalyst are
evaluated. Processing conditions were found where the added oxygen reacted
selectively with the hydrogen sulfide in the syngas, with minimal oxidation of the
valuable syngas components of carbon monoxide and hydrogen. Considerable testing
was done at temperatures below the estimated dew-point of the elemental sulfur in the
product gas. There was evidence of considerable yield of elemental sulfur, but
significant levels of the undesirable side reaction to carbonyl sulfide (COS) were also
noted in the initial studies. A diffusion-tube system was incorporated into the catalysttesting
system to add mercury vapor into the blended feed to the catalyst. With a
considerable effort, procedures were developed so that ppb levels of mercury could be
added consistently to the blended syngas feed, at the relatively-high pressures utilized
for catalyst testing. However, in "blank" testing, the mercury in the feed was
completely removed before reaching the product sampling system. Therefore, the
catalyst testing system was modified in respects: first, the hold-up volume (and thus
also the internal surface area) was greatly reduced, and second, an inert coating was
applied the piping and vessels in the reactor and product recovery sections of the
experimental system. In "blank" testing subsequent to these modifications, mercury
capture by the catalyst testing system was greatly reduced. In testing with a
commercially-available catalyst in the upgraded experimental system, process
conditions were found where high conversion of hydrogen sulfide selectively to
elemental sulfur was measured, with concomitant removal of mercury. Data from the
laboratory catalyst test unit experiments, as well as the GTI experience in introducing
and measuring Hg at high-pressure and high temperatures, will be presented and
discussed.
46-5
Promotion of Sulfur-fixing Capability in Coal Water Mixture
Combustion by Alkali Metal Salt
Huang Bo, China University of Mining & Technology, P.R. CHINA
41
Coals with Middle and high sulfur content have been prepared into coal water mixture
(CWM) to reduce the sulfur dioxide emission. In order to increase the sulfur-fixing
efficiency, the role of promotion to sulfur-fixing capability with alkali metal salt in
CWM combustion has been investigated. In this experiment, three coal samples were
from Xinjiang, Gaoyang and Shuiyu. Xinjiang coal with the sulfur content of 1.32%
was low sulfur content coal, and contain 76.52% of inorganic sulfur; Gaoyang coal
was middle sulfur content coal, with the sulfur content of 1.85%, and contain 60.37%
of organic sulfur; Shuiyu coal was high sulfur content coal, with the sulfur content of
3.28%, and contain 59.46% of organic sulfur. Experimental results showed that the
sulfur-fixing efficiency could be increased obviously by alkali metal salt. The sulfurfixing
capability could be increased by 6%~9% when alkali metal dosage was one
percent of calcium carbonate dosage. With the increase of alkali metal salt dosage, the
aperture of calcium oxide increased too, when the aperture increased excessively, the
surface area of calcium oxide would reduced notably, which would be unfavorable to
the sulfur-fixation reaction. The reason for alkali metals could improve the sulfurfixing
efficiency of CWM was: Alkali metal can improve the aperture of calcium
oxide, helped sulfur dioxide and oxygen through calcium sulphate surface layer to
diffuse into calcium oxide inside, enhanced the sulfur-fixing efficiency.
47-1
SESSION 47
COAL UTILIZATION BY-PRODUCTS – 2
A Technical Review of the Final Report of the National Academy of
Sciences "Managing Coal Combustion Residues in Mines"
Kemery C. Vories, U.S. DOI Office of Surface Mining, USA
On March 1, 2006, the National Research Council released to the public its final report
by the National Academy of Sciences “Managing Coal Combustion Residues (CCRs)
in Mines.” Based on the news release of the National Academy of Sciences (NAS),
putting coal ash back into mines for reclamation is a viable option for disposal, as long
as precautions are taken to protect the environment and public health. The report also
acknowledged that CCRs could serve a useful purpose in mine reclamation, lessen the
need for new landfills, and potentially neutralize acid mine drainage. The report
recommends development of enforceable Federal standards that give the States
authority to permit the use of CCRs at mines but allows them to adopt requirements for
local conditions. The report lists 40 findings or recommendations under 12 categories.
This paper addresses these findings on a case by case basis to evaluate their merits
against the extensive record of data and scientific studies on the subject. The NAS has
chosen to use the term “Coal Combustion Residues” where OSM has historically used
the term “Coal Combustion By-Products.” The terms are interchangeable. The author
is in agreement with the NAS findings that support: (1) the use of these materials in
mine reclamation; (2) the need for specific Federal regulations under the Surface
Mining Control and Reclamation Act of 1977 (SMCRA) that spells out the minimum
permitting, bonding, and environmental performance standard requirements when they
are placed on active coal mines; (3) the research priorities to specifically address the
hydrogeologic fate of CCBs and any leachate generated by those CCBs in relation to
public health and environmental quality; and (4) to develop mining appropriate
leachate tests. A limitation of the report is in its inability to: (1) acknowledge the
profound differences between regulatory environments that control placement of CCBs
at mines; (2) evaluate available ground water monitoring data and scientific research
within the context of the applicable regulatory environments; and (3) acknowledge the
volumes of scientific studies and State regulatory data that shows no degradation of
water quality due to placement of CCBs at SMCRA mines for the last 29 years. The
following review is strictly the opinion of the author and carries no institutional
endorsement.
47-2
Evaluation of the Effects of Treating Waynesburg Surface Mine Spoil with
Fluidized Bed Combustion Ash to ControlAcid Mine Drainage
Paul Ziemkiewicz, West Virginia University, USA
Surface mining of the Waynesburg Coal seam in northern West Virginia has typically
resulted in acid mine drainage (AMD) generation. The Office of Surface Mining s
Acid Mine Drainage Policy of 1998, proscribed permitting of mines with the prospect
of indefinite generation of AMD. In 2002 Patriot Mining Co. began to develop
Waynesburg reserves and sought a means of controlling AMD in compliance with the
policy. The reserves were to serve a newly constructed fluidized bed combustion
(FBC) plant in nearby Morgantown WV. The selected control method included
complete mining of all coal and immediately adjacent carbonaceous shales for
shipment to the FBC unit. This accounted for the bulk of pyritic material on site. FBC
ash was then to be used as a compacted, cementitious barrier applied to the mined pit
floor, against the highwall and as a compacted cap over the regraded spoil. The
objective was to direct most water flow away from the regraded spoil to minimize
AMD formation. Monitoring data are shown indicating that since treatment with the
FBC cap, AMD has been controlled to the extent that the site s NPDES permit is in
compliance without treatment. The NPDES permit contaminants include Al, Fe, Mn

and pH. Additional elemental monitoring required by the WV Department of
Environmental Protection indicates that levels of As, Se, Ba, Cu, Pb, Ni and Hg are
below drinking water or aquatic life standards as appropriate indicating that the
benefits with respect to AMD remediation are not offset by the introduction of other
contaminants.
47-3
Environmental Concerns Related to the Use of Coal
Combustion By-products in Mine Placement
Tamara Vandivort, Paul F. Ziemkiewicz, WV Water Research Institute, USA
Earlier this year, the National Academy of Sciences Committee on Mine Placement of
Coal Combustion Wastes, released a report on Managing Coal Combustion Residues in
Mines. The Committee found placing coal combustion residues in mines to be a viable
way of disposing these materials as long as placement avoids adverse impacts to
human health and the environment. The Committee indicated advantages of doing so
including assisting with mine reclamation, lessening the need for new landfills, and
neutralizing acid mine drainage. The Committee recommended that minefills be
designed in such a way that water movement through the residues is minimized. This is
not based on any actual damage cases associated with minefilling, but on data on
environmental effects from surface impoundment and landfill sites which indicate that
adverse environmental impacts can occur when coal combustion residues have contact
with water or when the residues are not properly covered.
A U.S. Department of Energy - National Energy Technology Laboratory-funded
program, the Combustion Byproducts Recycling Consortium (CBRC), seeks to
promote and support the commercially viable and environmentally sound recycling of
CCBs for productive and sustainable uses of resources, through scientific research,
development, and field testing. Since its inception in 1998, the CBRC has funded 52
CCB research projects nationwide. Several of those projects include using CCBs in
mine filling, surface mine reclamation, and the mobility and control of metals in CCB
leachate. This paper will focus specifically on the projects related to using CCBs in
mining operations.
47-4
Influence of Residence Time on Fly Ash Leachability: Long-Term Implications
Gautham Das, Mark E. Hill, John L. Daniels, Vincent O. Ogunro, University of North
Carolina at Charlotte, USA
A considerable body of research has been conducted regarding the use of coal
combustion byproducts (CCBs) in general and leachability in particular. There are
many leach tests available as recommended by various agencies and described in the
open literature. Many of these have been used to characterize the leaching potential of
CCBs when considered for highvolume use in civil and highway engineering
applications. The majority of this work suggests that CCBs tend to leach various
constituents, often metals, boron, sulfates and chlorides, at concentrations above
applicable regulatory standards. However, in typical leaching tests, the leaching
solution composition, solid:liquid (L/S) ratio, residence time, temperature and level of
effective stress often has little in common with the field condition. As such, there is a
level of uncertainty regarding the true behavior of CCBs used as embankment or fill
material. This uncertainty tends to encourage disposal, even when all other technical
and financial constraints for reuse are met. As part of a broader research program to
better predict in situ performance of CCBs in construction, this paper reports on the
influence of pH and flowrate on fly ash leachate data. In particular, column
experiments were conducted at three levels of pH (4.3, 6.9 and 9.0) and at three
different flowrates (500, 1000 and 2000 mL/day). The results show differences in
conductivity, pH and Eh as the flowrate is increased. In general, these results suggest
that laboratory testing to determine field leachability should use flowrates similar to
that expected in situ. Such an approach has the added advantage of accounting for
time-dependent changes in mineralogy, which in turn dictate the chemical and physical
performance of CCBs.
47-5
A Business Opportunity in the Mid-Atlantic Highlands: An Environmentally
Sound and Cost Effective Solution for Filling Underground
Voids to Mitigate Hazards
John Jenkins, iLF Engineers, USA
Joseph F. Giacinto, Lenny G. Rafalko, Environmental Resources Management, Inc.,
USA
Paul Petzrick, Maryland Deparmtent of Natural Resources, USA
This paper outlines the sources and problems associated with abandoned mines, the
proximity of these mines to power plants producing CCPs and the beneficial utilization
of the CCPs to mitigate problems with abandoned underground mine lands. Coal
Combustion by-Products (CCPs), a waste product of coal fired power plants, have been
used for several years as material for subsurface void stabilization projects. CCP
material exhibits chemical reactions similar to commercially available Portland cement
when mixed with water and lime with dry strength properties more than sufficient to
support overlying rock strata and man made structures. Approximately 30 million tons
of CCPs are produced in close proximity to the 6,000 abandoned underground mines in
42
the Mid-Atlantic Highlands. Lime sources required for pozzolan stabilized CCP
cement grout are plentiful throughout the Mid-Atlantic Highlands. CCP use in
subsurface void stabilization provides stowage for the continuous and voluminous CCP
waste stream in a beneficial, safe and environmentally benign manner to mitigate
hazards from abandoned underground mines common to the Mid-Atlantic Highlands.
Hazards from abandoned mines include subsidence, acidic water production, and
drastically disturbed hydrogeology. Abandoned mine hazards include subsidence (sink
holes) in addition to the release of radon gas and increased likelihood of groundwater
pollution. As a waste product, CCP material can be obtained for little to no cost. Using
CCP material presents an economic as well as an environmental incentive for large
volume grouting projects required of abandoned underground mine lands.
Through a cooperative effort of public and private sectors, the Maryland Power Plant
Research Project (PPRP) has developed a program to beneficially use CCPs in an
environmentally safe and effective manner. As a part of this program, PPRP developed
a cost optimization study to examine and minimize costs associated with CCP grouting
projects. This cost optimization evaluates the use of CCPs as subsurface void
stabilization and identifies the optimal means, methods, and associated budget costs to
transport, manage, mix, and inject CCP grout. Given the resources available in the
Mid-Atlantic Highlands, existing technology, the success of PPRP mine grouting
projects, and clearly demonstrated economical feasibility of using CCPs, a new
business opportunity exists in the Mid-Atlantic Highlands to restore thousands of
square miles of potentially hazardous real estate to productive use through subsurface
void stabilization.
SESSION 48
COAL PRODUCTION AND PREPARATION – 3
48-1
New Coals Collections. The First Results and Prospects
Svetlana A. Aiphtein, D.L. Shirochin, V.I. Minaev, Moscow State University of
Mining, RUSSIA
The new coals collection made of representative seems probes from Kuznetsk and
Donetsk basins are submitted. The collection consists of vitrinite coals with the
reflection index from 0.5 up to 1.5 %. Within the framework of similar rank, the coals
differing on facial conditions of primary coalification, chemical composition,
thermoplastic and physical properties are submitted. According to the Russian
classification these coals concern to different genetic types on a reducing degree. The
similar coals are allocated in the countries of Europe and the USA name «perhydrous
coals». The coal collection constantly replenishes and at the moment includes 22
samples. The coals have the full characteristic on technical, maceral and element
structure, on caking ability, on sorption and strength properties.
48-2
Application of Bacteria Thiobacillus Ferrooxidans by Desulphurization of Coal
Peter Fecko, Zuzana Sitavancova, Lukas Cvesper, Lukas Koval, VSB-TU Ostrava,
CZECH REPUBLIC
The aim of this paper is the suitability of bacterial leaching applied on the coal sample
from mine Most. The results of this work show that using clean cultures of
Thiobacillus ferroxidans is in the case very good if we evaluate desulphurisation from
point of view of pyrite sulphur, which, after one month of leaching is almost gone from
sample contains much organic sulphur which is produced by bacteria Thiobaicllus
ferrooxidans degraded only a little. Applying bacterial leaching it is possible to remove
approximately 36% of total sulphur and 32% of pyritic sulphur from the coal; better
results are obtained eliminating sulphate sulphur, i.e. up to 63% desulphurization and
desulphurization of organic sulphur is complicated; it fluctuates around 10%.
48-3
Clean Coal Technology for the Future - NEDO's Challenge
Shunichi Yanai, New Energy and Industrial Technology Development Organization,
JAPAN
Kyoichi Kohgami, Yusuke Tadakuma, Ichiro Fujiwara, Sadao Wasaka, NEDO,
JAPAN
In the paper, the activities of clean coal technology development by New Energy and
Industrial Technology Development Organization (NEDO), Japan are introduced.
We have three main projects as follows; 1) a high efficiency coal gasification
technology development (EAGLE), 2) ash-free coal production technology
development (Hyper-coal), and 3) clean fuel production technology development from
asphalt (ATL). In the EAGLE project, a gasifier, that can produce multi-purpose coal
derived synthesis gas efficiently, has been developed. The features of the gasifier are
that it has high efficiency and wide variety of coals is acceptable in the gasifier. The
progress of the development is explained in the paper. Hyper-coal is a challenging
technology development project, that produces completely ash-free coal (less than
200ppm) by the solvent de-ashing technology. In the paper, the progress of its
technology and its applications are introduced. ATL stands for Asphalt To Liquids.

ATL process has three stages, namely gasification stage, FT synthesis stage, and
hydrocracking stage. In the project, high activity FT catalyst and hydrocracking
catalyst are developed.
48-4
Behavior of the Solid-Liquid Removal to Make the Ash-Free Coal
Noriyuki Okuyama, Atsushi Furuya, Nobuyuki Komatsu, Takuo Shigehisa, KOBE
Steel, Ltd., JAPAN
Hyper-coal is an ash-free coal produced by applying the solvent de-ashing technology.
Coal is thermally extracted in the coal-derived solvent, which consists with 2-ring
aromatics at 360-380°C. The coal-extracted slurry, which consists with the coal
solution and the insoluble solid including ash, is introduced into the settler. The solid is
settled down by gravity and concentrated in the bottom. Inversely, the solution is
clarified in the top of the settler. After solvent removal, the ash-free coal, which is
named Hyper-coal (HPC), and the ash condensed residue coal (RC) are produced.
This paper concerns with the settling behavior of RC and the clarification behavior
using the batch-type and the continuous settler. The influences of the settling time, the
solid concentration were examined. We understood that the one to two hours of settling
time was needed for converging the solid-liquid separation under the conditions of 310
~ 380°C, 10 ~ 25 wt.% of the initial coal concentration. The ash concentration in HPC
converged around one to three thousand PPM by remaining of the microscopic
particles. The maximum RC concentration in underflow was 35 ~ 40 wt.%, regardless
of the initial ash concentration in raw coal and coal extraction rate.
The operations using the continuous system (0.1t/d bench scale unit, BSU) were
carried out. The clarification grade of the overflow was almost same as the batch
system. The connecting filtration unit further clarified the overflow. The continuous
operations successfully demonstrated the targets, negligible small amount of ash (300
~ 600 PPM in HPC), high yield of HPC (60wt.% on daf) and stable operation.
48-5
Advanced Efficient Equipment for Coal Concentration in China
Xianguo Li, Keping Chen, Mingxu Zhang, Anhui University of Science and
Technology, CHINA
China is a big coal producer in the world, with a total output amounting to about 2100
Mt/a, of which 40% is prepared now. This paper gives a detailed description of
different types of modern high-efficient coal preparation equipment including a jigging
machine, dense medium cyclone, flotation machine, flotation column, and dry
separation equipment. These equipments have been used in China in recent years in
order to raise the qualities of various kinds of coal.
SESSION 49
GASIFICATION TECHNOLOGIES:
ADVANCED TECHNOLOGY DEVELOPMENT – 4
49-1
High Efficiency Coal Plant that Meets the DOE 2020 Goals - One Decade Early
William S. Rollins, NovelEdge Technologies, LLC, USA
The DOE has set goals in its Clean Coal Power Initiative (CCPI) for a clean, efficient,
and cost effective coal facility that can separate and sequester CO 2 by 2020. This plant
is intended to demonstrate high efficiency, ultra-low emissions, and moderate cost. In
addition, it is to have the ability to produce hydrogen for external use, and separate
CO 2 for sequestration. To meet this objective, the DOE has funded development
programs for numerous technologies that are intended to help power plant constructors
attain the 2020 CCPI objective. However, by employing only a select few of these new
technologies, along with technology that has been developed independently by
industry, it is possible to meet the essence of the 2020 CCPI objective almost 10 years
early. Not only does this new plant have the ability to meet the CCPI objectives at an
early date, but it also demonstrates a new system for separation of CO 2 that is
significantly less energy and cost intensive than other CO 2 separation methods. The
potential exists for this technology package to provide a coal-fueled power plant,
which includes CO 2 removal at pipeline pressure, that is 20% more efficient, yet less
costly than a conventional supercritical pulverized coal plant of today that includes no
CO 2 removal whatsoever.
49-2
Development of a Coal Feeder for Continuous Injection into Gasification
Operating Pressures of 1000 psi - DOE Funded Phase III Program Review
Tim Saunders, Derek Aaldred, Stamet Inc., USA
43
The DOE, working through the National Energy Technology Laboratory, has funded a
research project to develop the unique Stamet “Posimetric Solids Pump” to a level able
to feed coal into current and planned gasification system operating pressures. The
program’s research objective is a mechanical rotary device for continuously feeding
coal into pressurized environments up to 1000 pounds per square inch. The DOEfunded
research project comprises three phases, Phase I for design and testing of a
device to feed coal into 300 psi, Phase II for feeding into 500 PSI and Phase III with a
1000 PSI injection target. The first phase target was achieved in December 2003 with
results reported at this conference in 2004. In January 2005, the Phase II feeder
achieved a new record pressure for continuous injection of coal, 560 psi, exceeding the
Phase II target. Following success in reaching the Phase II pressure target, the program
addressed fuel flexibility of the machine. Testing was carried out on a range of
carbonaceous fuels from bituminous to lignite, as well as renewable fuel samples, all
of which were successfully fed into pressure. To assess long-term reliability of the
Stamet pump, the Phase II unit has been installed at the DOE-funded Power Systems
Development Facility (PSDF) in Wilsonville AL for extended testing. This is currently
ongoing. Stamet is now undertaking design and assembly of the Phase III feeder.
Additionally, in order to accommodate the latest pressure target and allow flexibility in
future developments, a new and up-rated test rig with a 1500 psi pressure rating is
being fabricated. This paper will present selected results of Phase II, including the
1000-hour testing being undertaken at PSDF, along with a review and evaluation of the
phase III program to the date of the conference and extended semi-scale commercial
testing which should have concluded by the date of the conference.
49-3
The PWR/DOE High-Pressure Ultra-Dense Phase Feed System and
Rapid-Mix Multi-Element Injector for Gasification,
Kenneth Sprouse, David R. Matthews, Pratt & Whitney Rocketdyne Inc., USA
Greg F. Weber, University of North Dakota, USA
This paper provides the status of a high pressure ultra-dense phase feed system and
rapidmix multi-element injector currently being developed by Pratt & Whitney
Rocketdyne Inc. (PWR) and the U.S. Department of Energy (DOE) under a
cooperative agreement. The high pressure feed system is part of PWR’s advanced
gasification program to improve overall performance and reduce capital and operating
costs. This effort scalesup work initiated by PWR in the 1970’s (at nominal coal flow
rates of 6 to 24 tons/day) -- see, e.g., Oberg and Hood (1980) and Sprouse and
Schuman (1983, 1986) – to near commercial sizes of 400 to 1200 tons/day.
Construction of a new high pressure (> 1200 psia) test facility at the University of
North Dakota Energy and Environmental Research Center (UNDEERC – Grand Forks,
ND) is in progress with testing expected to commence in January 2007. The dry feed
system minimizes the amount of carrier gas to only that residing within the interstices
of a static coal pile (void fractions nominally 55 vol%). This carrier gas minimization
allows the use of rocket engine style rapid-mix multi-element injectors having coal
flow non-uniformities among the elements below 2 %RSD (relative standard
deviation). The program will test both a 6-element and 18- element injector design
using multiple short-duration (4 minute long) batch mode tests. A continuous highpressure
discharge solids pump at 400 tons/day is also being developed for future longduration
feed system testing in 2008. Uniform flow splitting in dry ultra-dense phase is
an enabling technology for rapid-mix compact gasifier operation. This technology
produces flame temperatures in excess of 5,500°F within a few inches of the injector
face for fast reactions.
49-4
The Exergy Optimization of the Reverse Combustion
Linking in Underground Coal Gasification
Michael Blinderman, Ergo Exergy Technologies Inc., CANADA
Dmitry Saulov, Alexander Klimenko, The University of Queensland, AUSTRALIA
Underground Coal Gasification (UCG) is a gasification process carried on in nonmined
coal seams using injection and production wells drilled from the surface, which
enables the coal to be converted into product gas. A key operation of the UCG is
linking the injection and production wells. Reverse combustion linking (RCL) is a
method of linking the process wells within a coal seam, which includes injection of an
oxidant into one well and ignition of coal in the other so that combustion propagates
towards the source of oxidant thereby establishing a low hydraulic resistance path
between the two wells. The new theory of the RCL in typical UCG conditions has been
recently suggested. The key parameters of the RCL process are determined using the
technique of Intrinsic Disturbed Flame Equations (IDFE). This study is concerned with
extending the results of the RCL theory to incorporate hydro- dynamics of air injection
and flow during RCL operation to derive mass flow rate of air to the combustion front
as a function of the injection pressure. The results enabled an optimization procedure
maximizing the exergy efficiency of the RCL process. The optimization has been
performed on a model case using a quasi-two-dimensional air flow model in the coal
seam. The results have been compared to the industrial operational data of RCL in the
conditions of the Chinchilla UCG project in Australia. The comparison has indicated a
reasonable conformity of the modeling with the operational results. The preliminary
outcomes of the study will be further refined to incorporate more realistic air flow
models in the coal seams.
49-5
Process Analysis and Performance Evaluation of Updraft Coal Gasifiers
Vittorio Tola, Giorgio Cau, University of Cagliari, ITALY

Coal gasification is becoming commercially even more important due to its potential
application in hydrogen, ammonia, methanol and other chemicals and clean fuels
production, other than power generation, together with carbon dioxide capture and
sequestration. In this framework the technological development is also addressed, with
a renewed interest, to simplified processes and plant solutions based, for example, on
gasification with air (or air enriched with oxygen) and on moving or fluidised bed
gasifiers, of interest for small and medium scale plants. The design, analysis and
performance evaluation of the overall system (gasification, gas clean-up,
desulphurisation, CO-shift conversion, CO 2 and hydrogen separation, etc.) require a
preliminary estimation of gasifier mass and energy balances and raw gas composition,
which influence the whole downstream gas clean-up and treatment systems. The
present study reports a process analysis and performance evaluation of updraft moving
bed gasifiers, which have been carried out by a computer simulation model developed
using the Aspen Plus 12.1 software, The model schematises the gasifier in several
different zones: coal preheating and drying, devolatilization, gasification, combustion
and oxidant preheating, under the hypothesis of char gasification at thermodynamic
equilibrium. The model allows to appraise the mass and energy balance of the gasifier
and the main characteristics of the syngas produced by the gasification process
(composition, mass flow, temperature, lower heat value, etc.), being assigned coal
composition and coal, steam and oxidant (air eventually enriched with oxygen) mass
flows. In this paper the model is applied to predict the performance of two updraft
moving bed gasifiers (sized respectively for 35 kg/h and 700 kg/h of low sulphur coal
and high sulphur coal (Sulcis). The gasifiers are part of a small pilot gasification and
gas treatment plant for hydrogen production under construction at the Sotacarbo
Research Centre in Sardinia.
SESSION 50
COAL CHEMISTRY, GEOSCIENCES, AND RESOURCES:
COAL CHEMISTRY
50-1
The Pore Structure of Coals Dewatered by Mechanical
Thermal Expression (MTE)
Alan L. Chaffee, Janine Hulston, Yuli Artano, Monash University, AUSTRALIA
Christian Bergins, Christian Vogt, Karl Strauss, University of Dortmund, GERMANY
The mechanical thermal dewatering (MTE) process has been shown to effectively
dewater high moisture low rank coals via the application of mechanical force at
elevated temperatures. The MTE process produces a low porosity product coal, which
undergoes further shrinkage upon drying. In this study, the porosity and its
development within MTE products has been probed through a combination of
geometric measurements, helium pycnometry and mercury intrusion porosimetry
(MIP). An advantage of MIP is that it allows pore size distributions to be determined
over a broad pore size range, spanning several orders of magnitude. The technique
however has its limitations, in that samples need to be completely dry. Thus porosity
and pore size distribution data can only be obtained for dried MTE products, which
have undergone shrinkage. Moreover, care must be taken when interpreting the
mesopore diameter range (2-50 nm), as the high intrusion pressures required to
measure pore sizes in this region may also lead to sample compression. This can be
compensated if the inherent compressibility, κ, of the sample is known and the raw
data is adjusted accordingly. Most prior work in the literature has taken no account of
the coal’s compressibility, κ; or, if κ has been considered, it has been determined by
extrapolation of the intrusion portion of the MIP curve in the high pressure region
(>100MPa, at least) where there (sometimes) appears to be a linear relationship
between the cumulative intrusion volume and pressure. However, if mesopore filling is
still occurring in this region the compressibility, κi, determined by this method will
clearly be compromised. Consistent with this understanding, the values of κ
determined in this study from the intrusion portion of the curve varied from sample to
sample and were observed to increase as the proportion of pores in the mesopore size
domain increased. In contrast, the compressibilities determined from the extrusion
portion of the curve, κe, were relatively constant for all MTE products prepared from
the same coal. Thus, it is inferred that the extrusion data provide a better measure of
the true compressibility of a coal and more correctly account for elastic deformations
in the coal’s macromolecular network (consisting of not only coal, but also closed or
inaccessible pores and unfilled micropores) that occur under the influence of high fluid
pressures. Moreover, the skeletal densities determined from MIP, after correcting for
the compressibility (using κe), are lower than the He densities determined by
pycnometry, in accord with physical reality (and unlike the skeletal densities
determined using κi). Elimination of the compressibility effects then facilitates the
calculation of micropore (pores < 2nm diameter) volumes which are physically
sensible and appear consistent with values determined by other approaches.
50-2
Direct Sourcing of Coal: Part-I -Solubilization of Coal
from North Eastern Region of India
Debapriya Choudhury, Raja Sen, Gora Shosh, Sunil K. Srivastava, Central Fuel
Research, INDIA
44
High Performance Engineering plastics are being touted as materials of the future.
Already quite a few such polymers are already in the market e.g. Kevlar from Dupont,
Xydar from Amoco, Vectra from Hoechst Celanese. Polyethylene Napthalate (PEN)
from Teijen and Amoco. Most of the high performance polymers are aromatic
polymers or liquid crystal polymers, both of which are derived from aromatic
monomers. However mass use of such polymers are inhibited by their much higher
cost. However with rapidly growing market demand of such polymers the demand of
aromatic monomers are also increasing rapidly and will continue to so in the near
future. However contrary to this increasing demand this availability of aromatics
particulars, 2-4 ring compounds has declined significantly due to world wide decline in
production of coal tar which continues to be major source of 2-4 aromatic ring
compounds. The main reason for the decline in coal tar production is linked with the
worldwide decline in steel production, which concomitantly reduces coke production,
and this in effect reduces coal tar production. Furthermore development of newer steel
technologies like direct coal injection etc. have decreased this demand of coke and
with adoption of these technologies coke product and as a result tar product is likely to
fall rapidly in the coming decades. Moreover by product coke oven opera is now
sensed to be an extremely environment unfriendly operations and with enforcement of
more stringent environmental standards blast furnace steel technologies which is
directly related with coke making is expected to be replaced by these newer
technologies.
Although coal tar still continues to be the major source (about 95% of the world
production) for 2-4 ring aromatics, the total process is not very efficient vis a vis
production of chemicals considering that good quality bituminous coal produces only
around 30 liters of tar which then consists only of about around 25% of two to four
ring aromatics of which are present in very small quantities. Furthermore coal tar is an
extremely complex mixture and separation of various components particularly those
present in lower concentration make it a rather costly operation However as such
technological trends which is leading to reduction in tar production are an anti thesis of
the trend of increasing demand of 2-4 aromatics and therefore there is urgent need for
development of newer technologies for their production in on sustainable if not on
mass scale. Two broad strategies have been proposed in this regard, one being the
indirect route and the other direct. The indirect route consists of coal conversion route
and coal liquefaction, which involves basically separation of the coal liquids obtained,
followed by further conversion if necessary to produce the chemicals of interest. Short
contact time coal liquefaction followed by catalytic de-alkylation to obtain aromatic
monomers as suggested by some authors (1,2) is a good example of such a concept.
However coal liquefaction products are again complicated mixtures which will require
complicated and time consuming separation techniques which will add to the cost of
the chemicals produced, an inhibiting factor in mass production as discussed before.
However direct sourcing of coal for production of value added products particularly for
production of monomers for high performance engineering plastics is a much bolder
and challenging strategy, although definite technologies have yet to be fully developed.
Coal is predominantly an aromatic material, the structure of which contains crosslinked
polyaromatic units of three or more rings having hydroaromatic and aliphatic
structures as peripheral groups. Unfortunately for the chemical industry the aromatic
part contributes solely to coke formation and is not therefore available for preparation
of aromatics. The direct sourcing route proposes to use these aromatic units in coal
macromolecule available as aromatic monomers (of three or more rings) or precursor
of such monomers. The methods proposed envisage processes for scission of certain
target bonds (mainly bridging bonds) between the polyaromatic units. A similar
method suggested by Song and Schobert (3) for generating high yields of benzene
carboxylic acids from selective oxidation of low rank coals is a good example.
In NorthEastern region of India about 900 million tones of high sulfur coal is available
but that has to be judiciously utilized. About 75-90% of the total sulfur is in the
organic form that also mostly in thiophenic & thio-ketonic form, which is very difficult
to remove. The pyretic sulfur is highly disseminated in the organic matrix of coal
hence can not be separated by physical processes. Therefore use of high sulfur NE
region coal in any industry possess a limitation. Hence its gainful utilization in an
environment friendly way is the need of the day.
This paper explores the method of coal oxidation with dilute nitric acid as a possible
method for oxidative degradation of coal to produce benzene carboxylic acids as
precursors for such monomers. The coals used for these studies are coals from NE
region of India which have limited application in conventional coal based industries, in
spite of substantial reserves (about 900 MT), considering it high organic sulfur content
combined with highly disseminated pyrite which is difficult to remove physically.
50-3
Transformation of the Fe-Mineral Associations in Coal during Gasification
Frans Waanders, North-West University, SOUTH AFRICA
John Bunt, Sasol Technology, SOUTH AFRICA
The mineral matter associated with coal undergoes various transformations during the
coal gasification process. Optimisation of the gasification process is necessary in the
coal to liquids technology. The principle aim of this investigation was to determine the
changes that the Fe-containing minerals and mineral associations undergo during
gasification of coal. Due to the complexity of the counter-current coal-gas process
used, a gasifier dissection was undertaken on one of the Sasol gasifiers. Detailed
characterisation profiles of various properties of the coal were undertaken after a

commercial-scale gasifier was shutdown for routine maintenance of which the
Mössbauer spectroscopy technique will be described here. Representative samples
from the gasifier were extracted after sufficient cooling was done to allow the safe
turn-out of the gasifier. In the coal samples that entered the gasifier, pyrite was the
abundant Fe-containing mineral, whilst the pyrite changed gradually to form, in
conjunction with the SiO 2 and Al 2 O 3 present in the coal, a Fe-containing glass and
hematite at the bottom, or ash grate of the gasifier.
50-4
Uneven Distribution of Sulfurs and Their Transformation during Coal Pyrolysis
Baoqing Li, Fenrong Liu, Wen Li, Haokan Chen, Chinese Academy of Sciences, P.R.
CHINA
Two Chinese coals, Liuzhi high pyrite coal with high ash content (LZ) and Zunyi high
organic sulfur coal (ZY), were pyrolyzed in a fixed-bed reactor under nitrogen and
hydrogen at temperature ranging from 400 to 700ºC. The effects of heat rate,
temperature and gas atmosphere on sulfur transformation and sulfur uneven
distribution were examined by XPS combined with traditional sulfur analysis method.
The ratio of surface S to bulk S is used to describe the uneven distribution of sulfurs. It
is found that oxygen is rich on the surface, while S in the bulk. The increasing ratio of
surface S to bulk S with increasing temperature clearly indicates the sulfur transfer
from the bulk to the char surface during pyrolysis. The ratios are higher at all
temperatures studied for ZY coal than for LZ coal, which may be related to the higher
ash content in LZ coal. The ratio of surface S to bulk S increases with increasing
heating rate for LZ coal, while it decreases for ZY coal. In the presence of H 2 , the S on
the surface is much lower than that under N 2 and surface S in sulphidic, thiophenic and
sulfoxide forms is totally disappeared for LZ coal at various temperatures and heating
rates, while the surface S in thiophenic and sulfoxide forms is not totally disappeared
for ZY coal, which may be related to the high rank of ZY coal. The ratio of surface S
to bulk S decreases before 600ºC with increasing temperature for both coals in the
presence of H 2 , showing that gaseous H 2 can easily react with the surface S to form
H 2 S, while above 600ºC it increases because the supply of H 2 cannot match the rate of
formation of HS· free radicals at high temperature.
50-5
Advanced Carbon Foams from Coal
Drew Spradling, Touchstone Research Laboratory, USA
Carbon foams manufactured from bituminous coal feedstocks have seen increasing
application in composites manufacturing and in naval shipbuilding, due to the unique
properties of these lightweight materials. In the unique manufacturing process,
pulverized coal is converted into a lightweight, high strength, open cell carbon foam
with highly uniform pore size distribution, and tailorable electrical and mechanical
properties. A state-of-the-art manufacturing facility is being commissioned and large
cross-sections of carbon foam are being consistently produced on a limited commercial
volume scale. Many advanced applications ranging from aerospace composites to
naval shipbuilding have been demonstrated through subscale component qualification
testing. As an example, carbon foam is being tested as a potential material for the new
Navy DDX class warship. Prototype testing in the deckhouse composite structure is
underway, with the carbon foam providing low radar cross-section, corrosionresistance,
excellent electromagnetic shielding effectiveness, and the ability to meet
fire, toxicity, and smoke requirements. The material has been demonstrated that it can
be integrated into the ship s planned composite and steel structures. In the development
of the carbon foam materials, extensive coal chemistry studies were performed, leading
to a comprehensive understanding of the controlled coking nature of the manufacturing
process. During manufacturing, the fluid and devolatilization properties of the coals
are manipulated with precise control of the heating, pressure, and atmosphere variables
necessary to produce large quantities of highly uniform foam. High pressure autoclaves
and atmosphere furnaces have been custom designed for this unique manufacturing
process. Extensive characterization of the different carbon foam grades produced,
allows for advanced material application such as those found in the aerospace and
defense industries. Mechanical, electrical, and acoustical properties of the foam were
extensively characterized, leading to the selection of appropriate application in areas
where conventional materials are inferior. A brief overview of the carbon foam
production process, as well as some of the unique applications of this advanced carbon
material will be presented.
SESSION 51
MATERIALS, INSTRUMENTATION, AND CONTROLS – 3
51-1
Studies on the Preparation of Mesophase Pitchs by Thermal
Conversion of a FCC Slurry
Xiaolong Zhou, Jing Chen, Guoxian Yu, Cheng-lie Li, East China University of
Science and Technology, P.R. CHINA
Minglin Jing, Zuo Zhang, Shanghai Institute of Technology, P.R. CHINA
Ordered mesophase pitch was prepared by thermal polymerization of a fluid catalytic
cracking (FCC) slurry stock. Thermal conversion experiments were performed on a
multi-tube well-shape crucible programmed heated furnace. Optical microscope
observation and solvent extraction separation were used to elucidate formation
behaviors of ordered mesophase. It has been indicated from our work that there are
three steps, i.e., containing the formation of the mesophase micro-crystal, the growth
of mesophase micro-crystals and the coalescence of mesophase spherules. The former
two steps are slow, whilst the last is a fast one. In addition, a novel tubular reactor
reducing in the central section was designed to guide the ordered growth of mesophase
spherules under the oriented flowing gas stream by thermal cracking. The optical
structure observation showed that anisotropic mesophase fibrous structures were first
formed radial-in-ward around the reaction tube wall. At prolonged time on stream
(TOS), such structures further developed from the wall toward the centre of the tube
and thus form a ring-shape structure.
51-2
Effect of KOH in Preparation of Activated Carbon with Low Ash Content and
High Specific Surface Area from Law Rank Bituminous Coal
Jin Lei, Qiang Xie, China University of Mining and Technology, P.R. CHINA
An experimental study on the effect of K-containing compounds in preparation of coalbased
activated carbon was conducted in this paper. KOH was used in the cocarbonization
with coal, changes in graphitic crystallites in chars derived from
carbonization of coal with and without KOH were analyzed by X-ray diffraction
(XRD) technique, activation rates of chars with different contents of K-containing
compounds were deduced, and resulting activated carbons were characterized by
nitrogen adsorption isotherms at 77 K and iodine numbers. The results showed that the
introduction of KOH into the coal feedstock before carbonization can realize the
intensive removal of inorganic matters from chars under mild conditions, especially for
the efficient removal of dispersive quartz, an extremely difficult separated mineral
component in other processes else. Apart from this, KOH demonstrates a favorable
effect in control over coal carbonization with the goal to form nongraphitizable
isotropic carbon precursor, which is a necessary prerequisite for the formation and
development of micro pores. However, the K-containing compounds such as K 2 CO 3
and K 2 O remaining in chars after carbonization catalyze the reaction between carbon
and steam, which leads to the formation of macro pores. In the end an innovative
method, in the light of which KOH is added in coal feedstock before carbonization and
K-containing compounds are removed by acid washing after carbonization, was
proposed for the synthesis of coal-based activated carbon with ash content less than
10% and specific surface area more than 1600 m 2 /g.
51-3
Effect of the Coking-Coal Property Change on Blend
Quality and Coke Microstructure
Gaifeng Xue, Peng Chen, Shangchao Liu, Wuhan Iron and Steel
Corporation, P.R. CHINA
By studying the vitrinite reflectance and its distribution, technical indexes of the single
coal and blended coal for coking in WISCO in recent years, it was discovered that the
single coal quality changed obviously, especially the metamorphism, its changes
obviously affected blended-coal qualities and coke microstructure.
51-4
Experimental Research on Coke Braise as a Cokemaking Additive
Shizhuang Shi, Wuhan University of Science and Technology, CHINA
Xueying Zhou, Wuhan Iron and Steel Corporation, P.R. CHINA
The experiment of suitability of coke braise with coking coal was carried out firstly
and then cokemaking experiment, coke braise as an additives and petroleum coke for a
comparison, was carried out in a semi-commercial scale. The influence of particle size
and its distribution, proportion of coke braise and property of coke-oven charge on
coke quality was researched. The experimental results show that there is a good
suitability between coking coal and coke braise; For high quality of coke, the particle
size of coke braise should be less than 0.45mm. The addition of 3% coke braise is
feasible under the condition of routine production in Coking plant of WISCO. The
effect of addition of 3% coke braise is superior to the effect of addition of 3%
petroleum coke.
51-5
Study of CH 4 -H 2 O In Coke-Oven Reforming to Produce
Syngas Catalyzed by Carbon Catalyst
Yongfa Zhang, Wei Zhao, Huawei Zhang, Xiling Miao, Yan Liang, Guojie Zhang,
Yaling Sun, Kechang Xie, Taiyan University of Technology, P.R. CHINA
Coke-oven gas that contains mainly 57~62% H 2 , 25~28% CH 4 , and ~6% CO is a high
quality hydrogen resource. However, coke-oven gas that contains more organic sulfur
such as COS, thiophene S, and more tar can not be converted into syngas easily by Nicatalyst
process. Based on this limitation a new kind of catalyst, carbon catalyst for
reforming CH 4 .in coke-oven gas to syngas was studied. The research of CH 4 -H 2 O (in
45

coke-oven gas) reforming was taken in a Plug Flow Reactor (PFR). The research
indicated that: 1) in the uncatalyzed CH 4 -H 2 O reforming, the conversion rate of CH 4 is
lower. At the reaction temperature of 1100°C the conversion rate is about a half.
However, in the carbon catalyzed CH 4 -H 2 O reforming, the conversion rate of CH 4 at
1100°C is 97.4%. The carbon catalyst can accelerate the reaction of CH 4 -H 2 O
reforming; 2) In the process of CH 4 -H 2 O reforming, the reaction of water gas shift
happened because of the existence of H 2 O and the component contents of the product
gas have been changed. At lower temperatures, the water gas shift reaction has the
trend of reduce the content of CO and increase the content of H 2 in the product gas; 3)
Because of the existence of water gas shift reaction, in the CH 4 -H 2 O reforming
reaction, as the ratio of H 2 O/CH 4 was towards 1, the content of methane in coke-oven
gas appeared towards highest; At 1200°C, with the staying time 0.5 seconds, the
methane conversion rate in carbon catalyzed reaction is 85.5%. When the resident time
lengthens to 1 second, the conversion rate of methane in coke-oven gas can reach
above 95.0%. 4) At the temperature about 1000°C carbon catalyst shows the catalytic
activity on water gas shift reaction. When the reaction temperature reaches above
1050°C, the amount of CO 2 will rapidly decrease to below 0.5%. This could be due to
that at the temperature, the reaction between C and CO 2 could rapidly increase, i.e. the
CO 2 from shifting reaction reacts with the C in catalyst, rapidly decreasing CO 2
contents. 5) The result of element analysis and specific surface area analysis of the
carbon catalyst indicated that the contents of S and N in the carbon catalyst decreased
sharply and the pore specific volume and the surface area increased after the reaction
of CH 4 -H 2 O reforming.
SESSION 52
ENVIRONMENTAL CONTROL TECHNOLOGIES: GENERAL TOPICS
52-1
Polycyclic Aromatic Hydrocarbon in Soil from Beijing, China
Xiaobai Xu, Ma Ling-Ling, Xu Xiao-bail, Li Xing-Hong, Chinese Academy of
Sciences, CHINA
Cheng Hang-Xin, Institute of Geophysical & Geochemical Exploration, CHINA
The rapid urbanization and industrialization of Beijing has resulted in significant stress
to Beijing environments. In the present study, 16 priority polycyclic aromatic
hydrocarbons (EPA-PAHs) in the surface soils from Beijing were determined using
gas chromatography and mass spectrometry (GC–MS). The total concentration of 16
EPA-PAH varied from 0.016 to 5.470 μg g -1 in soil of Beijing. The spatial distribution
of PAHs was displayed by the contour plot, which clearly showed that the sites with
higher content of PAHs are located in the urban areas and northwest outskirts and
those with lower content are distributed in the south and northeast outskirts.
Compounds profiles presented that the 4-, 5- and 6-ring PAHs were major
compositions and represented about 76%. It was worth noticing that the level of BaP,
the most potent carcinogenic PAHs, was from less than limits of detection to 0.402 μg
g -1 in soils. The correlation analysis showed that PAHs have the similar source in most
sampling sites and BaP might be considered as the indicator of total PAHs.
Characteristic ratios of PAHs indicated that the PAHs pollutants probably mainly came
from the pyrogenic origins, especially coal combustion and vehicular emission. The
level of PAHs in our study area was also compared with other studies. The information
from this study is significantly for understanding PAHs pollution in the environment of
integrated Beijing city.
52-2
Eco-Friendly Reclamation of Mine Spoil for Agro-Forestry
through Fly Ash and Biological Amendments
Lal Chand Ram, Nishant Srivastava, S.K. Jha, A.K. Sinha, Central Fuel Research
Institute, INDIA
The generation of huge quantities of mine spoil comprising unwanted shaly matter,
stones, etc. in the ratio (1:4, coal:mine spoil) produced from open cast coal mining
contributing about 70% of total coal extraction is a big challenge for environmental
managers apart from utilization of huge amount of fly ash (110 million tones/annum)
being generated from 85 thermal power plants (TPPs) in our country. Such problems of
management/disposal and utilization of mine spoil and fly ash will continue to
compound in near future in view of ever increasing demand of energy. As such the
development of an eco-friendly technology for reclamation of mine spoil through
amendment of fly ash will be of much significance. Fly ash being alkaline and
endowed with an excellent pozzolanic nature, silt loam texture, and plant nutrients, has
the potential to improve the texture, fertility and crop productivity of mine spoil.
Extensive field demonstration trials on the reclamation of mine spoils of Neyveli
Lignite Corporation (NLC), Tamil Nadu and Bharat Coking Coal Ltd., Dhanbad was
carried out for three years using fly ash from NLC and Santhaldih TPPs. For
agricultural purpose fly ash from NLC was applied at varying doses (@ 0, 5, 10, 20,
50, 100, 200 t/ha) alone and in combination with press mud and other amendments,
where repeat application was made up to 50 t/ha. For forestry plantations Santhaldih
TPP ash was applied at selective dose of fly ash with other amendments.
For agricultural application, the mine spoil area (6000 m 2 ) having a randomized block
design and 18 treatments (T1-T18), crop rotation (rice-green gram-rice-sun hemp-ricerice)
was selected. Biometric observation of the growth and development stages of rice
crops revealed that overall growth condition of rice plants was luxuriant, with less
incidence of pest, uniform and early maturity, intense colour of green leaves and
bigger size of panicle in the plots amended with fly ash alone and in combination with
press mud in one time and repeat applications. The crop yield (grain and straw) was
found to be increased in the range from 3.0 to 42.0% over corresponding control from
5 to 20 t/ha, however repeat applications of fly ash at lower dosages (up to 20 t/ha)
were more effective in increasing the yield apart from improvement in the texture and
fertility of mine spoil and the nutrient content of crop produce than the corresponding
one-time applications and repeat applications up to 50 t/ha. Some increase in the
content of trace and heavy metals and the level of g emitters in mine spoil and crop
produce was observed, but well within the permissible limits. The residual effect of fly
ash on succeeding crops was also encouraging in an eco-friendly manner. For forestry
plantations, about 6000 plants consisting 17 different species were planted on the mine
spoil/over burden dump (BCCL) along with fly ash and other amendments (cow dung,
coco peat, humic acid, biofertilizer, etc.) which evinced that the physico-chemical and
biological characteristics of mine spoil was significantly (p

52-5
Pilot-Scale Demonstration of Upgrading Waste Sulfuric Acid From Acid
Washing Process for Crude Benzol Production in a Coke Plant
Shitang Tong, Cui Zhengwei, Wuhan University of Science and Technology, P.R.
CHINA
Zhanghua Zhen, Hua Qi, Jinan Iron and Steel Corperation, CHINA
Charles Q. Jia, University of Toronto, CANADA
To process crude benzol from coke oven gas, the acid washing process is widely used
in coke manufacturers in China. Although the hydrogenation process was known to be
a superior process due to its better quality control of the final benzene products and the
avoidance of the generation of waste sulfuric acid containing coal tar, many coke
manufacturers still hesitate to adapt the technology due to its high cost. Containing
acidic tar, the waste sulfuric acid generated from the acid washing process is a pinkish
black liquid that has an odious smell and a rather high COD value. With nearly 50 wt%
of sulfuric acid, it contains sulfonic surfactant, saturated and unsaturated hydrocarbons.
Despite its troublesome nature and potential impacts on the environment, nothing was
practically done to deal with this waste stream. Recently, we have developed an
environment-friendly process for upgrading the waste sulfuric acid. A 30 L installation
was built and successfully demonstrated in Jinan Iron and Steel Co., China, where 3.5
million tons of coke are produced each year. The process consists of two major
operation units: polymerization and extraction. In the first unit, a specific catalyst is
used for inducing the polymerization of unsaturated organic species and the
precipitation of a coke-like solid material. In the second unit, the filtrate from the first
unit is extracted with an organic solvent obtained from coal tar distillation to clear off
most of the remaining organic compounds in the sulfuric acid. To reduce the amount of
the solvent used in the primary extraction step, a secondary extraction with another
solvent obtained from the crude benzol processing may be used. Upon the treatment
using the two-stage process, the COD value was reduced from 200 g/l to 20g/l, a
removal of over 80 %. Color index was reduced by up to 96%. The yield of the cokelike
solid sludge was 15-25 % of the mass of the waste acid. The purified acid was then
used to produce ammonia sulfate crystals of a satisfactory quality, without
encountering any engineering problem. The coke-like material was used as a precursor
for activated carbon production.
SESSION 53
COAL UTILIZATION BY-PRODUCTS – 3
53-1
Investigation of the Relationship between Particulate Bound Mercury and
Properties of Fly Ash in a Full-scale 100 MWe Pulverized
Coal Combustion Boiler
Wei-Ping Pan, Chin-Min Cheng, Yan Cao, Western Kentucky University, USA
Sen Li, Purdue University, USA
The properties of fly ash in coal-fired boilers influence the emission of mercury
pollutant from power plants into the environment. In this study, fly ash samples were
collected from mechanical hopper (MHP) and electrostatic precipitator hopper (ESP)
of a full-scale 100-MWe, pulverized coal combustion boiler. The mercury content,
specific surface area (SSA), unburned carbon, and elemental composition of the fly ash
samples were analyzed to evaluate the correlation between the concentration of
particulate bound mercury and the properties of fly ash in coal combustion boilers. For
a given coal, it was found that the mercury content in the fly ash collected from ESP
was greater than in the fly ash samples collected from MHP. This phenomenon may be
due to higher sulfur, unburned carbon, and manganese contents, as well as SSA, of
ESP fly ash than of MHP fly ash. Comparison of the fly ash samples generated from
seven different coals by using the statistical Pearson Correlations indicates that the
mercury adsorbed on both MHP and ESP fly ashes has a highly positive correlation
with the unburned carbon and manganese contents of those fly ashes, respectively.
Moreover, no significant correlations were found between particulate bound mercury
and other elemental compositions of fly ash. The high SSA and unburned carbon
contents are beneficial for fly ash to catch gaseous mercury by physical adsorption,
while sulfur will aggregate with gaseous mercury. Manganese in fly ash is believed
participating in oxidizing volatile elemental mercury (Hg 0 ) to mercury (Hg 2+ ). The
oxidized mercury in flue gas can form a complex with the fly ash and then get removed
before the flue gas get out from the stack of the boiler.
53-2
Distinguishing Free Crystalline Quartz in Coal Fly Ash using
Electron Microscopy Techniques
Gerald Huffman, Nick Cprek, Naresh Shah, Frank Huggins, University of Kentucky,
USA
Determination of the amounts and classification of the types of silica contained in coal
fly ash is a subject of interest because of the adverse health effects caused by
inhalation of crystalline quartz. Workers with prolonged exposure to this carcinogen
can develop respiratory diseases over time. Here we examine crystalline quartz in coal
fly ash by computer controlled scanning electron microscopy (CCSEM).
Both the size and shape of the quartz particles are related to their toxicity. In the
present study, energy-dispersive x-ray (EDX) spectra identify quartz particles as those
that contain > 90% Si. CCSEM size distributions are then used to classify respirable
quartz particles as those having a mean particle diameter of < 4μm. Shape is also very
important since crystalline quartz particles will generally be more angular and
elongated than glassy SiO 2 particles. Such angular and/or elongated particles will more
readily penetrate cell walls to cause biological damage. In order to classify particle
shape quantitatively by CCSEM, we define another parameter called circularity.
Glassy ash particles are very often in the form of spheres, near-spheres, or at least
smooth equant particles. The parameter circularity is therefore defined as the ratio of
the radius determined from the particle perimeter to that obtained from the particle area
subtended by the electron beam. A perfect sphere would have a circularity of 1.
CCSEM data for these parameters for ~2,000 3,000 fly ash particles are then combined
into plots that display volume percentages of Si-rich particles as a function of size and
circularity. Regions of interest can be highlighted based on parameter definitions. On
the basis of a CCSEM examination of NIST K-411 Glass Microspheres standard
reference material, we conclude that SiO 2 glass particles have a circularity < 2. The
SiO 2 particles that are then classified as respirable quartz are those with mean
diameters < 4 µm and circularity >2. Based on our investigation of four power plant
ashes using this method, the percentage of the total SiO 2 particles that would be
classified as respirable quartz is relatively small and constitutes a very small fraction of
the total ash.
53-3
A Study on the Ash from Coal Gangue Fired Power
Plant-Characteristics and Application
Jianglong Yu, Hui Song, Shenyang Institute of Aeronauctical Engineering
Liping Chang, Wei Xie, Kechang Xie, Taiyuan University of Technology, P.R.
CHINA
Coal will continue to dominate China s energy supply in the future. The mining of coal
creates large amount of gangue which not only occupies a large area of land but also
generate environmental problems. On the other hand, coal gangue is a low calorific
fuel which should be utilized properly. A few small power plants are current running
or under construction in China. However, due to its high ash content, coal gangue
generates a large amount of ash when it is combusted in power plants. The ash from
power stations not only contributes to emissions of fine particulates in the air but also
results in the contamination of soil. The utilization of coal gangue ash is therefore
important to reduce China s environmental pollution. In this paper, current status of the
research and development of gangue ash utilization in China is reviewed. The gangue
ash has found its application in a wide range of areas, such as road construction,
chemicals, agriculture fertilizers, etc. Some ash samples were collected by the authors
from a coal gangue fired power plant in Fuxin, northeast China. Characteristics of the
ash were analyzed by using XRD, SEM, Laser sizer and other techniques. Because of
its physical structure (e.g., large surface area and porosity) and its composition (i.e.,
containing mainly SiO 2 , Al 2 O 3 and CaO) the gangue ash has a potential in the
application of iron-based sorbents for high temperature removal of hydrogen sulfide
from coal gas. A desulphurization sorbent was prepared by using the mixture of iron
oxide and the gangue ash collected from the power plant. The structure and property of
the surbent were examined using XRD, SEM and other techniques.
53-4
Flotoreagent on Base of the Products of the By-Product Coke Plant
Viktor Saranchuk, The Litvinenko L.M. Institute of Physical-Organic Chemistry and
Coal Chemistry, UKRAINE
Igor Arovin, Pilot-line Production, UKRAINE
Flotation method is used for enrichment of ordinary coal having small part less 0,5
mm. In connection with deficit of flotoreagent has got up the question about creation
flotoreagent on the base own non-deficit products and waste-products by-product coke
production. Such work was done in laboratory condition on flotomachine 240-FL-À.
As complex flotoreagent were trieded usual and formilin straw oil, polymers of
benzene department, formilin polymers, non-phenol butter, stillage bottoms and their
mixture. The best results are received when use formilin straw oil, on base which is
created flotoreagent UR-410. Efficiency of the work flotoreagent was explored on
charge of Avdeevka by-product coke plant.
53-5
Geology and Mineralogy of Coal and Combustible Shale World Deposits as a
Resources Forecast Basement of Energy-Chemical and Mineral Raw Materials in
View of Valuable and Potentiality Toxic Rare Elements it Contains
Mikhail Povarennykh, Russian Academy of Sciences, RUSSIA
Mikhail Shpirt, Institute of Fossil Fuels, Ministry of Natural Resources, RUSSIA
Inevitable in the nearest future exhausting of oil and gas deposits in view of the
modern constantly increasing industrial consumption forces us to pay maximum
attention to significantly more huge world resources of hard fossil fuels (HFF) (coals
47

and combustible shales, C&CS) much more evenly distributed along the Earth’s
territory. In contrast to oil and gas, the production and usage of HFF is significantly
connected with prospects of a by-product obtaining of huge resources of mineral raw
materials for production of building materials, commercial aluminium compounds as
well as compounds and concentrates of rare and trace elements (R&TE)(Ge, Ga, Re,
TR) and valuable metals (VM)(Au, Ag, PGE). At the same time, realization of
energetical potential of HFF is connected with environmental pollution in several
regions of the world by significant amounts of sulphur compounds and potentially
toxic R&TE (As, Be, Cr, Zn, Pb, Sr, Mn a.o.). In view of the above mentioned
problems, it seems very important to make a world C&CS reserves and resources
distribution analysis as well as to create databese on their compositions and
technological properties based on detailed geological and geochemical-mineralogical
knowledge of C&CS basins and estimation of potentially toxic R&TE compounds'
outburst volumes. As it is planned by the international team of specialists of C&CS
geology, during nearest three years it is expected to achieve the following results:
- Creation of GIS and databases of different categories resources, organic and
mineral components compositions, parameters of quality and concentrations of
valuable and potentially toxic R&TE for the world main C&CS deposits;
- Choice of promising utilization directions of each C&CS deposit under detailed
analysis;
- GIS and set of maps of the world C&CS deposit distribution;
- Expert auto express analysis of C&CS deposits for revealing of economically
promising reserves and resources of by-product valuable R&TE, environmental
outburst volumes of toxic sulphur compounds and trace elements during their
mining and utilization as well as volumes and compositions of ash&slag wastes
produced as a result of combustion and gasification of HFF.
Hyper-Coals can be produced by thermal extraction from various coals with organic
solvent, and by the gravity settling the soluble. HPC is an ash-less coal, and has an
excellent thermal plasticity, and has high total dilatation by Audibert-Arnu dilatometer.
These characters of HPC are advantages in coke manufacturing. So, effective
utilization of the HPC as a coke making material was investigated. Adding a small
amount of the HPC to blended coals could be improved the strength (I-type drum
index: IDI) of the coke manufactured with the coal blends. Possibility of substituting
the HPC for coking coals in coke manufacturing process was investigated in this study.
We confirmed that HPC could be substituted for high fluidity coal, and blending of
HPC into coal blend increased blending ratio of poorly-coking coal in coal blend
without change of the IDI. The quality of industrial coke is usually evaluated as DI
(Drum Index). Preparation of 10 kg of coke sample is needed to obtain the DI. When
the amount of HPC is too small to manufacture coke for DI test, another evaluating
method is necessary to get the strength of cokes manufactured with coal blend
containing HPC. Therefore we tried to evaluate the coke strength as tensile strength
(St) of small cylindrical coke sample in the case of the smallest test in our study.
Correlations between St and IDI, DI and IDI, St and DI were investigated for same
coke samples manufactured with coal blend containing HPC. We confirmed high
correlation coefficient in these correlations. By using of these correlations, it becomes
possible to estimate DI when we are not able to get enough amount of HPC sample for
DI test. In this study, estimated St of small cylindrical coke sample carbonized in test
tube (φ15mm) was 5.5-6.0 MPa corresponding to DI of industrial coke.
54-4
Surface Modification of Fe 3 O 4 Nanoparticles
Yongjian Liu, Hong Zhuang, University of Science & Tech of Suzhou, P.R. CHINA
Hongyi Jia, CUMT, P.R. CHINA
54-1
SESSION 54
COAL PRODUCTION AND PREPARATION – 4
Low Rank Coal Upgrading with Syncrude Oil Production using
"SynCrude-SynCoal" Medium Temperature Pyrolysis Processing
Ebbe Skov, Hetagon Energy Systems, Inc., USA
Franklin G. Rinker, Keith A. Moore, ConvertCoal, Inc., USA
This article discusses the surface modification process of Fe 3 O 4 nanoparticles in details
through a series of experiments. And on the basis of the surface modification coating
mechanism, the theoretical analysis is done to the experimental phenomena and the
effects on the variation of size, magnetism and stability of Fe 3 O 4 nanoparticles
produced by the different of pH value, temperature and added dosage of surfactant.
54-5
The Strategic Thinking of the Coal Resources for Wuhan Steel Group
Shangguo Liang, Wuhan Steel Group, P.R. CHINA
The coal-to-liquid (CTL) conversion of low-sulfur Western Low Rank Coals by
medium-temperature processing called SynCrude-SynCoal (SC2) produces both a
syncrude for oil refining and a low-emissions coal-char fuel for power-boiler electrical
generation. A 10,000-ton/day SC2 CTL project will produce 8000-barrels/day oil and
5500-tons/day coal-char sufficient for a 600-MW electric power plant. Conceptually,
ten SC2 projects could provide the US a new secure domestic oilfield resource of
80,000 barrels/day. The SC2 processing significantly upgrades the quality of the coalchar
fuel by removing moisture, fuel sulfur, nitrogen and mercury. This product can
potentially meet EPA’s stringent new Clean Air Interstate Rules (CAIR) for SO 2
compliance and increase the power plant’s boiler efficiency and capacity. The yield
and quality of coaltar oil produced by SC2 mild pyrolysis of LRC differs substantially
from high temperature coal-tars produced by other processes. Conventional petroleum
refining and hydro-treatment will convert the SC2 coal-oil into syncrude and provide
feedstock for added-value chemical intermediates products. The SC2 CTL technology
is based on earlier mild pyrolysis demonstration projects and requires only
commercially mature equipment. The SynCrude-SynCoal process, its products and
applicability to the energy supply industries are described herein.
54-2
Characteristics of Hyper-Coal (Ash Free Coal) for Coke Production
Nobuyuki Komatsu, Noriyuki Okuyama, Atsushi Furuya, Takuo Shigehisa, Kobe
Steel, Ltd., JAPAN
Hyper-coal means ash free coal that is produced by coal extraction and solid-liquid
separation treatment. The autoclave (AC) for batch test and the small-scale continuous
process of Hyper-coal (BSU : Bench Scale Unit, capacity : 0.1 t/d) were developed and
operated in Kobe Steel, Japan. Using this AC and BSU, several kinds of coal, from
lignite to bituminous coal, were tested and evaluated for Hyper-coal process and lots of
samples were produced to investigate the utilization for power generation, coke for
blast furnace iron production and others materials. Especially, Hyper-coal has some
merits to strengthen the coke materials and has possibility to reduce the production
cost of coke. This paper discusses the characteristics of Hyper-coal suitable for the
coke production.
Wuhan Steel Group (Wusteel for short) is a large iron and steel corporation with steel
capacity of 14 million of tons now and 18 million of tons in near future. In the last few
years, as a result of fast development of national economy, the need of domestic
market for the coal, electricity, oil, transportation has significant growth. Along with
the metallurgy productivity fierce extend, the metallurgy industry is sturdy to pull the
metallurgy coal demand. The market price of coal increases continuously. The coal
supply is gradually tense up. At the same time, be subjected to influence of the rapid
increase of the goods, the shortage of conveyance capacity and the circuit direction
restrict etc, the national railroad carry ability was serious hard up. It is anticipated that
within the short period, the situation could not alleviate. Under the restrict of both coal
resources and the railroad conveyance, how do the work well to supply the coal at
present and in a period of aftertime, to insure the energy and materials supplies for
Wusteel’s productivity growth need is a strategic topic that the company needs solve
urgently. Firstly the paper introduces the coal yield of the world mainly producers,
main coal consumers and their consumption in the world, coal import and export
circumstance in China, the Coking coal resources distribution in China and the yield
growth circumstance of coke from 1994 to 2004, and the yields of iron, steel & coke in
China within 1994-2004. Secondly the paper predict the coal demand in China,
including electric power industry, iron & steel making industry, architectural material
industry, chemical industry and other industries; as well as the trend about average
selling price of merchandise coal for state- owned pivot coal mine. Then the paper
introduces the coal resource species constitute of Wusteel, the strategic supply chains
of the medium and long-term agreement and cooperate relations and the predict of coal
supply structure when steel yield reaches 18 million. Lastly the paper introduces the
new technology used in Wusteel for coke quality improvement including coke dry
quenching technique, the hriquette coking process, the coal expert system etc; and
compare Wusteel’s coke quality with baosteel’s and the advanced level in the world;
and points out the difficulties and measures of coal strategic supply of Wusteel.
54-3
Evaluation of Strength for Metallurgical Coke Manufactured with Hyper-Coal
Kanji Matsudaira, Yuko Nishibata, Masaru Nishimura, The Kansai Coke & Chemicals
Co, Ltd., JAPAN
Noriyuki Okuyama, Takuo Shigehisa, Kobe Steel, Ltd., JAPAN
48

POSTER SESSION 1
COMBUSTION TECHNOLOGIES
P1-1
Importance of the Lignite for Energy in Turkey
Ilker Senguler, Mineral Research Institute (MTA), TURKEY
Hayrullah Dagistan, General Directorate of Mineral Research and Exploration,
TURKEY
Energy is the main input for industrialization and development. In electrical power
generation, the share of thermal plants is 64%. Because of their low capacity and high
initial investment cost renewable energy sources are not preferred.
Since the coal resources comprise 27% of all the energy sources, it will continue to
take a role in the 21 st Century. 1.75% of these resources are located in Turkey and most
of the electrical power generation is based on thermal power stations.
Most of the known lignite deposits in Turkey are of low calorific value, high
percentage of ash, volatile matter, moisture and sulphur. Almost 75% of the total
reserves are with a calorific value of below 2500 kcal/kg. 17% are between 2500 and
3000 kcal/kg. While only the 8% are over 3000 kcal/kg. Therefore, it is inevitable that
the majority of such lignites which are feasible technically and economically for
exploitation must be enriched by washing before marketing.
Total installed capacity of based on lignite thermal power plants is 6390 MW in
Turkey. In addition to 1760 MW (Can and Elbistan) is under testing. It is planned to
have thermal power plants with capacities of power 13810 MW in 2010 and 16060 in
2020.
Coal exploration studies will be accelerated to correspond the energy deficiency of
Turkey. General Directorate of Mineral Research and Exploration of Turkey (MTA)
will carry out a series of coal exploration projects in different regions of Turkey. As a
result of these studies including drilling activities, the coal reserves will have been
increased importantly.
United Nations Framework Convention on Climate Change (UNFCCC) regulations
stipulates that the green gas emissions should be dropped to 1990’s level. Therefore
new combustion technologies are required for energy resources. The thermal power
plant in Can, Canakkale, capacity of power 2x160 MW with fluidized bed combustion
technology will be a good example for the future use of this application.
Turkey possesses a large lignite potential with 8.3 billion tons. New combustion
technologies and coal mining applications will make this potential more attractive in
the near future. The sensibility to the environmental problems in Turkey can be taken
as a guarantee that we will not face the environmental problems industrialized
countries had faced before. We should not forget that “a living society is one that
obtains its current needs without destroying the belongings of the next generations”.
P1-2
The Char-CO 2 Reaction at High Temperatures and Pressures
Elizabeth Hodge, Daniel Roberts, David Harris, CSIRO Energy Technology – QCAT,
AUSTRALIA
John Stubington, UNSW, AUSTRALIA
The rate of coal conversion in an entrained flow gasifier is limited by the rate of
reaction of char with steam and CO 2 . Under these conditions, rates of carbon
conversion depend on the chemical reaction rate on the char surface and the rate of gas
diffusion to the surface of, and within the pores of, the particle. For pulverised coal
particles, at low temperatures (below about 900–1000°C) the conversion rate depends
only on the chemical reaction rate. As temperatures increase, the influence of gas
diffusion becomes significant and the conversion process becomes more complicated.
Whilst the rate of the char–CO 2 reaction at high pressures has been investigated at low
temperatures, few data exist that allow quantification of this reaction at high
temperatures and pressures relevant to full-scale entrained flow gasifiers. This paper
presents new data from measurements of the rate of the char–CO 2 reaction at
temperatures up to 1400°C and pressures up to 20 bar in a pressurised entrained flow
reactor. The data have been compared to reaction rates obtained at lower temperatures
in order to begin to develop the link between low and high temperature reaction rates.
P1-3
Utilization of Energy Grasses for Combustion
Dagmar Juchelkova, Helena Raclavska, Bohumir Cech, Jan Frydrych, David Andert,
VSB-Technical University of Ostrava, CZECH REPUBLIC
The highest degree utilization of domestic energetic sources and supply the
information important for energetic conception of individual country and regions is the
main request of EU government on research. Utilization of energy grasses is very
important because of various reasons - social benefit, environmental benefit, country
benefit, etc. The energy utilization of the energy grasses is one of the main topics for
future developments of recoverable sources in the European Union and in the Czech
Republic. The aim of research is combustion tests in the boilers of various producers
located in the Czech Republic. The experiments are carried out for Czech grasses and
wastes including analyses and recommendations for optimal thermal utilization and
49
minimizing harmful emissions. From the results of experiments and thermal modeling
it is clear that near 38 % of energy grasses can be used in the large fluidized-bed
boilers located in the Czech Republic. From energetic point of view has a growing
importance the grass and permanent grass covers for biogas production. According to
research projects the grass is the most suitable material for biogas generation because
its high biological activity, high content of nutrients and easy cells degradability in all
stages of moisture. The origin of solution is based on determination of grass mixtures
suitable for combined combustion, determination of technological processes of
growing, harvest and fuel preparation and further determination of grass mixture
suitable for biogas production. This paper presents only the results from the
experiments of combustion of energy grasses.
P1-4
CO 2 Reduction Potential on the Czech Condition
Dagmar Juchelkova, Helena Raclavska, Vaclav Roubicek, Pavel Kolat, Jiri Bilik,
Darja Noskievicova, Pavlina Pustejovska, Jarmila DolezalovaVSB-Technical
University of Ostrava, CZECH REPUBLIC
At present the task of minimizing carbon dioxide emissions in relation to its influence
on environment belongs to the priorities of EU research activities. For achieving the
best possible results it is necessary to focus attention on information concerning input
materials character study of production as well as manufacturing processes and
subsequent returning the products back to environment (anthroposphere). The highest
degree utilization of domestic energetic sources and supply the information important
for energetic conception of individual country and regions is the main request of EU
government on research. Reduction of CO 2 production can begin if following
information will be known:
- Character of input materials (content of C, H, N, S and TOC - total organic carbon),
pollutants, physical-chemical properties, determination of phase occurrence, amount of
input materials etc.).
- Production and technological processes (energy demand technological limits for
realization of IPPC and LAC etc.).
- The utilization and character of by-products (evaluation of properties → processing
for other kind of utilization or alternative technology for disposal).
P1-5
The Rheology of Coal-Oil Mixtures (COM)
Gunduz Atesok, Mustafa Ozer, Feridun Boylu, Istanbul Technical University,
TURKEY
Today 90% of electricity in the world is produced from fossil fuels such as coal, oil
and natural gas. Oil equivalent of fossil in the world is calculated to be 68% coal, 18%
oil and 14% natural gas. According to these figures the lifetime of oil, natural gas and
coal is 40, 60 and 220 years respectively. Coal water slurries (CWS) and coal oil
mixtures (COM) may be an alternative energy source to fuel-oil. In COM or CWS
technology, the coal loading rate is an important factor and it depends on the rheology
of mixtures.
In this study, the COM was prepared using fuel-oil(#6) and high rank bituminous coal
at a temperature range 20 to 90°C and coal loading rate were examined. The results of
the study showed that the rheology of COMs loaded with high amount of coal as much
as 60% could be advanced by increasing the mixture temperature to 90°C. However,
for slurries with suitable viscosity, the mixture temperature at 60°C is found to be
enough with lower coal loading rates such as 50%.
In conclusion, it was found that fuel-oil can be loaded with high amount of solids using
high rank coals. Thus, the consumption rate of fuel-oil could be decreased without
sacrificing on the heating value of the new fuel, COM.
POSTER SESSION 2
GASIFICATION TECHNOLOGIES / HYDROGEN FROM COAL
P2-1
Carbon Dioxide Capture and Separation Techniques for Advanced Power
Generation Point Sources
Henry Pennline, David Luebke, Badie Morsi, Yannick J. Heintz, Kenneth L. Jones,
Jeffery B. Ilconich, DOE/NETL, USA
The capture/separation step for carbon dioxide (CO 2 ) from large-point sources is a
critical one with respect to the technical feasibility and cost of the overall carbon
sequestration scenario. For large-point sources, such as those found in power
generation, the carbon dioxide capture techniques being investigated by the in-house
research area of the National Energy Technology Laboratory possess the potential for
improved efficiency and costs as compared to more conventional technologies. The
investigated techniques can have wide applications, but the research has focused on
capture/separation of carbon dioxide from flue gas (postcombustion from fossil fuelfired
combustors) and from fuel gas (precombustion, such as integrated gasification
combined cycle – IGCC). With respect to fuel gas applications, novel concepts are
being developed in wet scrubbing with physical absorption; chemical absorption with

solid sorbents; and separation by membranes. In one concept, a wet scrubbing
technique is being investigated that uses a physical solvent process to remove CO 2
from fuel gas of an IGCC system at elevated temperature and pressure. The need to
define an ideal solvent has led to the study of the solubility and mass transfer
properties of various solvents. Fabrication techniques and mechanistic studies for
hybrid membranes separating CO 2 from the fuel gas produced by coal gasification are
also being performed. Membranes that consist of CO 2 -philic silanes incorporated into
an alumina support or ionic liquids encapsulated into a polymeric substrate have been
investigated for permeability and selectivity. An overview of two novel techniques is
presented along with a research progress status of each technology.
P2-2
Selective Catalytic Oxidation of Hydrogen Sulfide -
Systems Analysis for IGCC Application
Richard A. Newby, Dale L. Keairns, Science Applications International Corporation,
USA
Maryanne Alvin, DOE/NETL, USA
Selective catalytic oxidation of hydrogen sulfide (SCOHS) has been evaluated
conceptually for IGCC applications, and the theoretical limits of reaction performance,
process performance, and economic potential in IGCC have been estimated. Syngas
conditions that have high partial pressures of total sulfur result in substantial liquid
sulfur retention within the catalyst bed, with relatively complex processing being
required. Applications that have much lower total sulfur partial pressure in the process
gas might permit SCOHS operation under conditions where little liquid sulfur is
retained in the catalyst, reducing the processing complexity and possibly improving the
desulfurization performance. The results from our recent IGCC process evaluations
using the SCOHS technology and conventional syngas cleaning are presented, and
alternative SCOHS process configurations and applications that provide greater
performance and cost potential are identified.
P2-3
Optimization of Heat Recovery Steam Generators for IGCC Power Plants
D. N. Reddy, Osmania University, INDIA
Basic human needs can be met only through industrial growth, which depends to a
great extent on energy supply. The large increase in population during the last few
decades and the spun in industrial growth have placed tremendous burden on the
electrical utility industry and process plants producing chemicals, fertilizers,
petrochemicals, and other essential commodities, resulting in the need for additional
capacity in the areas of power and steam generation throughout the world. Steam is
used in nearly every industry; and it is well known fact that steam generators and heat
recovery boilers are vital to power and process plants. It is no wonder that with rising
fuel and energy costs engineers in these, fields are working on innovative methods to
generate electricity, improve energy utilization in these plants, recover energy
efficiently, from various waste gas sources, and simultaneously minimize the impact
these processes have on environmental pollution and the emission of harmful gases to
the atmosphere. Heat recovery boilers, also known as waste heat recovery boilers or
heat recovery steam generators (HRSGs), form an inevitable part of chemical plants,
refineries, power plants, and process systems. They are classified in several ways,
according to the application, the type of boiler used, whether the line gas is used for
process or mainly for energy recovery, cleanliness of the gas, and boiler configuration,
to mention a few. The main clarification is based on whether the boiler is used for
process purposes or for energy recovery. Process waste heat boilers are used to cool
waste gas streams from a given inlet temperature to a desired exit temperature for
further processing purposes. An example can be found in the chemical industry in a
sulfuric acid or hydrogen plant- where the gas steam is cooled to a particular gas
temperature and then taken to a reactor for further processing. The exit gas temperature
from the boiler is an important parameter affecting the downstream process reactions
and hence is controlled by using a gas bypass system. Steam generation is of secondary
importance in such plants. In energy recovery applications, on the other hand, the gas
is cooled as much as possible while avoiding low temperature corrosion and steam
generation throughout the world. Steam is used in nearly every industry; and it is well
known that steam generators and heat recovery boilers are vital to power and process
plants. It is no wonder that with rising fuel and energy cost engineers in these, fields
are working on innovative methods to generate electricity, improve energy utilization
in these plants, recover energy efficiently, from various waste gas sources, and
simultaneously minimize the impact these processes have on environmental pollution
and the emission of harmful gases to the atmosphere.
P2-4
Thermogravimetric characteristics and kinetic of coal/plastic blends co-pyrolysis
Limin Zhou, Yipin Wang, Qunwu Huang, Junqing Cai, Tianjin University, CHINA
Co-pyrolytic behaviours of different plastics(high density polyethylene, low density
polyethylene and polypropylene) and low volatile coal (LVC) were investigated using
TGA. The results indicated that coal was decomposed at in the temperature range 174-
710°C, while the thermal degradation temperature of plastic is 438-521°C. Plastics
showed similar pyrolysis behaviors due to similar chemical bonds in their molecular
structures. The overlapping degradation temperature interval between coal and plastic
is beneficial to hydrogen transfer from plastic to coal. The difference of weight loss
(ΔW) between experimental and theoretical ones, calculated as a algebraic sums of
those from each separated component, is about 5-6% at 550-650°C. These
experimental results indicate on significant synergistic effect during plastic and
biomass co-pyrolysis at the high temperature region. In addition, a kinetic analysis was
performed to fit thermogavimetric data, the global processes being considered as one
to three consecutive first order reactions. A reasonable fit to the experimental data was
obtained for all materials and their blends.
P2-5
Solvent Extraction of South African Coal-A Review
Johan van Dyk, TJ van de Walt, Sasol Technology, SOUTH AFRICA
Sasol’s Secunda plants in South Africa are very conveniently placed with respect to the
vast coal reserves of the Mpumulanga region. Sasol converts these coal reserves, via its
indirect liquefaction process, into liquid fuels and various chemicals. This process is
operated under severe process conditions, and the concomitant release of big volumes
of CO 2 presents environmental problems. In addition to this, these plants consume
utilities other than coal (such as water) and need the support of a well developed
infrastructure (like e.g. a good roads network). Other, more remote (with respect to the
Secunda plants) coal reserves may be in need of a different kind of coal conversion
technology before these can be monetised. Such is the case for the Waterberg coal
reserves – coal that is high in vitrinite content and may be eminently suitable for
conversion via coal solvent extraction. The coal solvent extraction process is mild
(with respect to process conditions) and CO 2 release is low; coal is the major utility
consumed in light of the process being self-sustainable in terms of the solvent that is
required. The product from solvent extraction (mild coal dissolution) is a lowash and
low-sulphur solid or pitch and is suitable for use as a fuel in new technology power
generation plants, or as a reductant in the metallurgical industry, and even as a
precursor for several carbon products. Coal solvent extraction is a well known
technology and the majority of literature is based on vitrinite rich coal. Little work is
reported on the mild solvent extraction of inertinite rich coals, or the role of other
reactive macerals (besides vitrinite). Thus, work on South African coal, also rich in
other reactive macerals, is reviewed.
P2-6
Regenerable Sorbent Development for Sulfur and Chloride
Removal From Coal-Derived Synthesis Gas
Ranjani Siriwardane, DOE/NETL, USA
Thomas Webster, Research Development Solutions, USA
A large number of components in coal form corrosive and toxic compounds during
gasification processes. According to the U.S. Department of Energy, National Energy
Technology Laboratory (DOE NETL) goals, contaminants have to be reduced to parts
per billion in order to utilize gasification gas streams in fuel cell applications. Even
more stringent requirements are expected if the fuel is to be utilized in chemical
production applications. Regenerable hydrogen sulfide removal sorbents have been
developed at DOE NETL. These sorbents can remove the hydrogen sulfide to parts per
billion range at 316°C and at 20 atmospheres. The sorbent can be regenerated with
oxygen. Reactivity and physical durability of the sorbent did not change during the
multi-cycle tests. Results of the multi-cycle, benchscale tests utilizing simulated coal
gas and results of the tests with real coal gas will be discussed in the paper.
Regenerable hydrogen chloride removal sorbents have also been developed at DOE
NETL. These sorbents can remove HCl to parts per billion range at 300°C to 500°C.
The sorbent can be regenerated with oxygen. Results of thermogravimetric analysis
and bench-scale flow reactor tests with both regenerable and non-regenerable HCl
removal sorbents will be discussed in the paper.
P2-7
Assessment and Environmental Performance of Coal and Biomass
Based Combined Heat and Power Plants (CHP)
D.N. Reddy, K. Basu, Osmania University, INDIA
Shortage and quality of grid power prompted Indian Industries to go for captive power
plants. For process industries, uninterrupted steam supply becomes a necessity.
Generally, coal based captive power plants are employed for these duties. These plants
have efficiency range between 5% to 10%. Biomass based Combined Heat and Power
plant (CHP) could improve both generation efficiency and environmental performance.
Biomass based power generation using reciprocating engine is well established
technology. However, low life expectancy and higher cost of generation slowed down
the wider adaptation of this technology. Gas turbine manufacturers are pursuing
development of burning Low Btu gas in combustor. Biomass gasifier integrated to gas
turbine as topping cycle and steam Turbine as bottoming cycle could provide power
cycle efficiency of 2% to 4% higher than that of conventional power plant. Centre for
Energy Technology carried out designs of a CHP plant utilizing the existing
equipment. In spite of limitation on component efficiency, power block can attain a net
thermal efficiency of 9.9 and CHP efficiency of 49.79 for a plant capacity of 51.72
kWe. The validation of the mathematical models was carried out by using
50

experimental data available in literature and data from the equipment available at CET.
The report presents the considerations for equipment selection and sensivity analysis of
down-draft Gasifier and design of HRB.
P2-8
Removal of H 2 S in Gas from Coal Gasification Using a Polymer
Sorbent Supported on Mesoporous Molecular Sieves
Xiaoxing Wang, Xiaoliang Ma, Chunshan Song, The Pennslyvania State University,
USA
The deep removal of H 2 S from natural gas, coal/biomass gasification gas and the
reformate is one of the major challenges in the hydrogen production process and
utilization of these fuel gases. In order to develop a more efficient sorbent with high
capacity, selectivity and regenerability, a series of polyethylenimine (PEI) sorbents
supported on mesoporous molecular sieves, including SBA-15, MCM-41 and MCM-
48, have been prepared and characterized by XRD and N 2 physisorption. The sorption
performance of the prepared sorbents for removing H 2 S from a simulated coal
gasification gas, which contains 4000 ppmv H 2 S and 20 vol% H 2 in nitrogen, has been
tested in a fix-bed system at a temperature range from 22 to 75°C. The effects of
operating conditions, including temperature, gas hourly space velocity (GHSV), on the
sorption performance have been examined in detail. It is found that the increase in
temperature and GHSV resulted in the decrease of the breakthrough capacity. The
breakthrough capacity and the saturation capacity of the supported PEI sorbents
change with the PEI loading. A positive synergetic effect between SBA-15 support and
loading PEI on H 2 S sorption was observed. The maximum breakthrough capacity of
1.97 mmol/g-PEI was obtained at a PEI loading of 50 wt %, while the maximum
saturation capacity of 4.65 mmol/g-PEI was obtained at a PEI loading of 65 wt %. The
comparison of the supports indicates that the higher porous volume and the threedimension
channel structure favor improving the sorption performance. The desorption
and regeneration of the spent sorbents have also been conduced in the fix-bed system
at 22 and 75°C, respectively. It indicates that desorption of the saturated sorbents can
be conducted easily at 75°C and the sorbent is stable during the adsorption-desorption
cycles. The results imply that the developed sorbent is a promising sorbent for
removing H 2 S from gas streams at more environmentally friendly and energetically
efficient conditions. In addition, the mechanism for the sorption of H 2 S on the
supported PEI is also discussed on the basis of the experimental and computational
results.
P2-9
Investigating Reactive Ball Milling of Anthracite Coal
Apurba Sakti, Caroline E. Burgess Clifford, Angela D. Lueking, The Pennsylvania
State University, USA
Development of alternative energy technologies is the key to address future energy
concerns of depleting fossil fuel reserves and the hydrogen economy is one of the
forerunners amongst the various options being considered. A combined hydrogen
production and storage process using coal as a precursor and ball milling it in the
presence of a hydrogen donating solvent is investigated here. Tests of our current
hypotheses that ball milling induces cross links in the coal structure facilitated by the
evolution of hydrogen will be presented. The effect of mineral matter present in the
coals has been investigated as well and will be presented along with the possible
commercial applications.
P2-10
The Impact of Trace Impurities in Coal Gasification Products on the
Performance of Solid Acid Catalysts for Phenolics Transformations
Jack C. Q. Fletcher, Walter Bohringer, University of Cape Town, SOUTH AFRICA
Cathy L. Dwyer, Sasol Technology Research and Development, SOUTH AFRICA
The effect of impurities as potential catalyst poisons in the raw phenolics stream from
a Lurgi coal gasifier was investigated for the transformation of phenolic compounds
over zeolite H-MFI as a solid Brønsted acid catalyst. A model mixture of light
phenolics, representing the major constituents of such a stream, was converted at
350ºC and 60 bar in the liquid phase. A series of potential catalyst poisons were added,
individually, each representing the ‘parent compound’ of one of the families of typical
impurities in such a stream. Conversion of p-cresol was monitored vs. time-on-stream
as a catalyst activity indicator. After the introduction of poison, the response in catalyst
activity, i.e. the conversion of p-cresol, ranged from a steeply declining behaviour to
showing no effect at all. Upon re-introduction of poison-free feed, catalyst activity
recovered, completely or in part, and was more or less rapid. Potential poisons that
were evaluated, their applied concentrations (in wt -ppm) and the results obtained are
as follows:
- Pyridine (200), strong poisoning effect, partially reversible
- Benzonitrile (3700), strong poisoning effect, presumably by the decomposition
co-product NH 3 from hydrolysis with moisture, reversible
- Aniline (200), weak poisoning effect, improved activity after removal
- Indole (200), very weak poisoning effect, improved activity after removal
- Thiophenol (850), no poisoning effect, no effect after removal
51
- Benzothiophene (850), very weak poisoning effect, slightly improved activity
after removal.
The strength of the poisoning effects reflects the basicity of the respective poison
compounds and their adsorptive strength on the acid sites of the catalyst. From these
findings it is apparent which gasifier impurities are problematic, and require removal,
and which may be adequately managed during solid acid processing.
POSTER SESSION 3
GAS TURBINES AND FUEL CELLS FOR SYNTHESIS GAS AND
HYDROGEN APPLICATIONS
P3-1
Syngas Fuel Composition Sensitivities of Combustor Flashback and Blowout
David Noble, Quingguo Zhang, Tim Lieuwen, Georgia Institute of Technology, USA
This paper reports experimental data detailing the fuel composition sensitivities of
flashback and lean blowout limits of syngas (H 2 /CO/CH 4 mixtures). Data were
obtained over a range of fuel compositions at fixed approach flow velocity, reactant
temperature, and combustor pressure at several conditions up to 7.1 atm and 500 K
inlet reactants temperature. Consistent with prior studies, these results indicate that the
percentage of H 2 in the fuel dominates the mixture blowout characteristics. These
blowout characteristics can be captured with classical Damköhler number scalings to
predict blowoff equivalence ratios to within 10%. Counter-intuitively, the percentage
of hydrogen had far less effect on flashback characteristics, at least for fuels with
hydrogen mole fractions less than 60%. This is due to the fact that two mechanisms of
“flashback” were noted: rapid flashback into the premixer, presumably through the
boundary layer, and movement of the static flame position upstream along the
centerbody. The former and latter mechanisms were observed at high and low
hydrogen concentrations. In the latter mechanism, flame temperature, not flame speed,
appears to be the key parameter describing flashback tendencies.
P3-2
Effect of Syngas Composition on Emissions from an
Idealized Gas Turbine Combustor
Timothy C. Williams, Christopher R. Shaddix, Robert W. Schefer, Sandia National
Laboratories, USA
Future energy systems based on gasification of coal or biomass for co-production of
electrical power and gaseous or liquid fuels may require gas turbine operation on
unusual fuel mixtures. In addition, global climate change concerns may dictate the
production of a CO 2 product stream for end-use or sequestration, with potential
impacts on the oxidizer used in the gas turbine. In this study the operation at
atmospheric pressure of a small, optically accessible swirl-stabilized premixed
combustor, burning fuels ranging from pure methane to conventional and H 2 -rich and
H 2 -lean syngas mixtures is investigated. Both air and CO 2 -diluted oxygen are used as
the oxidizers. CO and NO x emissions for these flames have been determined over the
full range of stoichiometries from the lean blow-off limit to slightly rich conditions (φ
~ 1.03). The presence of hydrogen in the syngas fuel mixtures results in more compact,
higher temperature flames, resulting in increased flame stability and higher NO x
emissions. The lean blowoff limit and the lean stoichiometry at which CO emissions
become significant both decrease with increasing H 2 content in the syngas. For the
investigated mixtures, CO emissions near the stoichiometric point do not become
significant until φ > 0.95. At this stoichiometric limit, where dilute-oxygen power
systems would preferably operate, CO emissions rise more rapidly for combustion in
O 2 -CO 2 mixtures than for combustion in air.
P3-3
Low Temperature Oxygen Activation and Transport over Doped
Lanthanum Ferrites for Use as SOFC Cathodes
John Kuhn, Umit Ozkan, The Ohio State University, USA
Current Ni-based solid oxide fuel cells (SOFC) anodes deactivate in the presence of
coal-derived gas because they are easily poisoned by low levels of sulfur and catalyze
coke formation. Their use requires a large steam to carbon ratio to limit coking. In
addition to these problems, the Ni-based anodes also lose activity through sintering.
All of these processes deactivate the anodic reaction rates, cause low power densities,
and increase operation costs due to large steam requirements. Thus, the development of
highly active and carbon and sulfur tolerant materials suitable for use as anodes is
necessary to bring coal-gas fed SOFC systems closer to commercialization. Ongoing
SOFC cathode research shows iron-based perovskite materials are developed as
promising materials for use as SOFC cathodes between 500°C and 700°C. The
electrochemical activity and oxide ion mobility that make it such a great cathode
material can also be harnessed for the oxidation reactions at the anode. The current
research demonstrates the iron-based perovskite materials are stable in highly reducing
conditions and possess catalytic activity for the direct oxidation of hydrogen and
carbon monoxide in the desired temperature range. The effect of the increased lattice
oxygen mobility on the water requirements and the influence of hydrogen sulfide

concentration on the oxidation activity are discussed. Characterization using X-ray
diffraction, X-ray photoelectron spectroscopy, simultaneous thermogravimetric and
differential scanning calorimetric analyses, and temperature-programmed techniques is
performed to compliment the anodic oxidation results and correlate the bulk and
surface structure-activity relationships.
P3-4
SOFC Reaction Process Suitable for Use with Sulfur-Containing Fuels
Matthew Cooper, David Bayless, Ohio University, USA
Growing concerns over the environment as well as political instability in oil-producing
regions of the world have ignited a large degree of interest in converting the
electrochemical energy from coal-derived fuel streams using fuel cells. One specific
type of fuel cell, known as the solid oxide fuel cell (SOFC), has the ability to produce
energy from hydrocarbon fuels at efficiencies far greater than traditional combustion
engines. However, hydrogen sulfide (H 2 S), a common component of hydrocarbon
fuels, poisons conventional SOFCs and necessitates costly fuel treatment, preventing
the utilization of SOFCs for distributed power from being financially feasible. The aim
of this research is to develop a SOFC reaction process which will allow the use of a
H 2 S-containing fuel derived from coal reserves known as coal syngas. In the proposed
process, a two-stage SOFC reaction system will be used. In the first stage, SOFCs will
utilize an electrode material known as lanthanum strontium vanadate (LSV), which has
shown high activity toward consuming H 2 S; it is hypothesized that these LSV SOFCs
will scrub any H 2 S present in the syngas stream via electrochemical oxidation while
leaving behind non-H 2 S species such as hydrogen (H 2 ) and carbon monoxide (CO).
The outlet gases from this LSV SOFC will then be fed to another SOFC utilizing
conventional Ni anodes; these conventional anodes have been shown to readily oxidize
H 2 and CO, leading to the hypothesis that the combined process will efficiently
produce electricity even when using a H 2 S-contaminated fuel stream. It should be
noted that this research is still in preliminary stages; feedback from the scientific
community on the merit of the effort is desired.
P3-5
Development of a Fuel Flexible Catalytic Combustor for IGCC Applications
Walter R. Laster, Pratyush Nag, Elvira Anaoshkina, Siemens Power Generation, Inc.,
USA
Bruce C. Folkedahl, University of North Dakota, USA
Siemens has been working on the development of an ultra low NO x catalytic
combustor for the SGT6-5000F gas turbine using the Rich Catalytic Lean (RCLTM)
design. By operating the catalyst section fuel rich, this design shows considerable
promise for robust operation over a wide range of fuel compositions including syngas.
Under the sponsorship of the U. S. Department of Energy’s National Energy
Technology Laboratory (DE-FC26-03NT41891), Siemens is conducting a three year
program to develop an ultra low NO x , fuel flexible catalytic combustor for gas turbine
application to Integrated Gasification Combined Cycle (IGCC) plants. The goal of this
program is to significantly reduce the emissions levels for the current diffusion flame
based IGCC combustion systems down to 2 ppm NO x without the requirement for
dilution flow. This paper addresses the current status of the fuel flexible catalytic
combustor development program. Performance of the catalytic coating materials have
been verified for natural gas, typical syngas fuels and hydrogen. The initial verification
testing of the subscale SGT6-5000F combustion module on syngas was performed and
the design changes necessary for the full basket design have been identified. The
program is on track for full scale basket verification next year.
POSTER SESSION 4
MATERIALS, INSTRUMENTATION AND CONTROLS
P4-1
Study on the Orderly Growth of High-Content Mesophase Pitch
Minglin Jin, Haiqi Zhang, Zhuo Zhang, Jing Chen, Shanghai Institute of Technology,
CHINA
Hexing Li, Shanghai Normal University, CHINA
The preparation of high content mesophase pitch was one of key techniques to develop
the needle coke, carbon fibre as well as new carbon materials. High content mesophase
pitch has been previously synthesized from coal tar pitch in more tubes well-crucible
stove. It was found that changes of TI-QS content were as parabola during nonisothermal
polymerization of coal tar pitch. Meanwhile the microstructure changes of
mesophase pitch was observed by microscope with the changes of TI-QS content, such
as the nuclear appearance of mesophase micro-crystal, the growth of mesophase microcrystal
as well as the coalescence in different reaction time. As a result, the key factor
of preparation of high content mesophase was the reaction time and temperature and
comparatively low reaction temperature as well as prolonged reaction time were
propitious to preparation of high-content mesophase. As the growth of mesophase was
a spontaneous process the another one of key techniques was how to make orderly
growth of high content mesophase. The special tube reactor was designed with single
52
flow of pyrolysis gas, the order growth of mesophase was achieved by leading gas
flow. The influences of reactor structure and process conditions on orderly growth of
mesophase were studied by microscope.
P4-2
Performance Difference of Coke from CDQ and CWQ
Shizhuang Shi, Wei Xu, Wuhan University of Science and Technology, CHINA
In order to make clear the performance difference between cokes from CDQ and
CWQ, the contrastive study was carried out on normal analysis, granularity analysis,
strength analysis, thermal performance, catalytic analysis and optical texture analysis
of cokes from CDQ and CWQ from WISCO. The experimental results show that,
compared with coke from CWQ, the performance of coke from CDQ was improved
obviously such as mean granularity, granularity coefficient, mechanical strength,
thermal performance etc.; the ash component catalytic index (MCI), optical texture
index (OTI) etc. are unchanged basically; its alkali absorptance is strong, and its alkali
resistance is weak, but its thermal performance is still superior to coke from CWQ
after alkali absorption; and its boron absorptance is weak, and its passivation effect is
bad, and its thermal performance is even somewhat inferior to coke from CWQ after
boron absorption.
P4-3
Sulfur Transfer Law From Coking Coal to Coke
Shizhuang Shi, Wuhan University of Science and Technology, CHINA
Zhiping Liu, Wuhan Iron and Steel Corporation, CHINA
Sulfur is a harmful ingredient in coke and coke sulfur is from coal sulfur. In order to
reduce sulfur content of coke, the sulfur transfer law from coal to coke must be
understood fully. For that, the sulfur content of various forms in coal and total sulfur
transfer law from coal to coke are researched. The experimental results show that the
sulfur in coal principally organic sulfur, secondly sulfide sulfur and least sulfate sulfur,
and the organic sulfur content increases with the volatile content of coal; and that
sulfur conversion ΔS from coking to coke and the ratio of coke sulfur content to coal
sulfur content ΔS/K all decrease with the increase of the volatile content of coking
coal, for both single coking coals and their blends.
P4-4
Effect of Coking Coal Ash Composition on the Coke Thermal Performance
Shizhuang Shi, Wuhan University of Science and Technology, CHINA
Meicheng Jin, Wuhan Iron and Steel Corporation, CHINA
The coke thermal performance, including the coke reactivity index CRI and the coke
strength after reaction CSR, is an important quality index of metallurgical coke. They
are affected by the property of coking coal and the ash composition. In order to
research the influence of ash composition on the coke thermal performance, firstly the
catalytic index MCI is defined; then cokemaking experiments in laboratory and
industrial coke experiments are carried out successively. According to experimental
results, the mathematical models are established. The experimental results show that
the influence of ash catalytic index MCI on the thermal performance of coke, CRI and
CSR, is very obvious; there is a positive relativity between the ash catalytic index MCI
and the coke reactivity CRI; there is a negative relativity between the ash catalytic
index MCI and the coke strength after reaction; and that the mathematical models
(regression equations) established from the experiment reveal the essence of the effect
of various factors on the thermal performance of coke. They can be used to predict the
thermal performance of coke, CRI and CSR, and to guide the production of coke.
POSTER SESSION 5
ENVIRONMENTAL CONTROL TECHNOLOGIES
P5-1
A New Approach for Semi-Dry Flue Gas Desulphurization
Fan Wang, Hongmei Wang, Fan Zhang, Junfang Wang, Yongli Hao, Jun Lin, Di Jin,
Chinese Research Academy of Environmental Sciences, CHINA
A new semi-dry flue gas desulphurization (FGD) system was established to a 35t/h
coal-fired boiler, in which SO 2 sorbents were activated by steam during conveyance,
the steam temperature was about 200-350°C, with the pressure of about 0.4 MPa.
To investigate behavior of steam activation, experiments were also conducted to
examine changes of surface structure, size distribution, and chemical components of
SO 2 sorbents before and after steam preparation. BET surface area analysis results
show that the sum of specific surface area increases from 7.8688m 2 /g to 10.0715m 2 /g
during SO 2 sorbent activation by steam conveyance. The porous structure gives rise to
specific surface area, which enhances desulphurization process. It is obvious that not
only changes of external and internal structures of fly ash occur, but also the chemical
compositions. Mixture of lime and fly ash (lime to fly ash ratio was 1:8) was used for
SO 2 sorbent, and analysis results were obtained that the content of Ca(OH) 2 was 9.1 %
of initial SO 2 sorbent, while 16.9 % of Ca(OH) 2 content was attained after steam

activation. It was concluded that Ca(OH) 2 content increased after SO 2 sorbent
activation by means of steam conveyance. Experiments were conducted regarding the
factors that closely related with operating performance, which were reacting
temperature, CaO/SO 2 molar ratio, and SO 2 sorbents, where SO 2 sorbents using lime
only and other two different compounds of lime to fly ash ratio were considered.
Testing results show that when CaO/SO 2 molar ratio is 1.2, and SO 2 removal efficiency
is attained as high as 85.1%, and an efficiency of 88.3% is achieved when CaO/SO 2
molar ratio is 1.4. Adding fly ash to lime for SO 2 sorbent can improve desulphurization
process. Experimental results SO 2 removal efficiency increase from 67.43 % to 76.24
% is achieved when the ratio of fly ash to lime increases from 0 to 3:1. A
desulphurization efficiency of 81.07 % was attained when fly ash to lime ratio is 8:1.
P5-2
Metal Compounds of Benzene-1,3-diamidoethanethiol (BDETH2),
a thiol based ligand
David Atwood, Kamruz Zaman, University of Kentucky, USA
Heavy metal pollution is a serious threat to natural ecosystems. Various methods and
technologies are in use to remove heavy metals from the environment. They include
phytoremediation, bioremediation, activated carbon adsorption, extractions, and others.
More recently the use of chemical reagents to combat heavy metal pollution has come
into play. Some of them, the thiol-based ligands in particular, have proven effective in
precipitation heavy metals from aqueous systems. The latest and most versatile
chemical precipitation reagent is known as Benzene-1,3-diamidoethanethiol
(abbreviated as BDETH2). Marketed with the common name MetX this ligand has
been found effective in binding heavy metals in a variety of settings. Synthesis, and
characterization of this relatively inexpensive an dnon-toxic multidentate ligand and its
bonding arrangement to the metals Cd, Hg, and Pb along with the full characterization
data of the BDET-M compounds will be presented here.
P5-3
Conceptual Design of a Supersonic CO 2 Compressor
Robert Steele, Shawn Lawlor, Peter Baldwin, Ramgen Power Systems, USA
Ramgen Power Systems, Inc. is developing a family of high performance supersonic
compressors (Rampressor TM ) that combine many of the aspects of shock compression
systems commonly used in supersonic flight inlets with turbo-machinery design
practices employed in conventional axial and centrifugal compressor design. The result
is a high efficiency compressor that is capable of single stage pressure ratios in excess
of those available in existing axial or centrifugal compressors. A variety of design
configurations for land-based compressors utilizing this system have been explored.
A proof-of-concept system has been designed to demonstrate the basic operational
characteristics of this family of compressors when operating on air. Based on the
results from that effort a compressor specifically designed for the high pressure ratios
required to support CO 2 Capture and Storage has been proposed. The basic theory of
operation of this new family of compressors will be reviewed along with the
performance characteristics and conceptual design features of the proposed CO 2
compressor systems.
P5-4
Dynamics of Gas Isolation at Pyrolysis
Victor Saranchuk, Olga Chernova, Evgeniy Zbykovskiy, Donetsk National Technical
University, UKRAINE
Need of the reception alongside with coke of the coke gas as marketable products has
puted the question about study dynamics of the gas emission of the pyrolysis of the
separate coals and charge of them. For study was an applying installation with mass of
the loading 1400 g. Were received correlation amount stood out separate gas during
undertaking the experience. Exists the certain dependency of the mass stood out gas
from coal metamorphism degree. Is it also built curves of the separation separate
component pyrolysis gas of coals of the different marks and charge, formed from these
coals. The Curves of the separation individual pyrolysis gas of coal of the mark DG
and OS have one maximum. On crooked separations coal gas marks G, ZH, K exists
two maximums. The Observed phenomena of the origin one or two maximums of the
gas emission possible with two affecting factor. The First - a process of the emoving
moisture from coal loading. The First maximum of the gas emission of coals G, ZH
and K appears exactly at moment, when in the centre of the coal loading else lasts the
process of the drying and the temperature continues to remain constant. After
completion of the process of the drying temperature coal loading continues to increase,
but intensity of the gas emission falls. The Second factor is an origin, existence and
consolidation plastic layer since arising the second maximum of the gas emission
complies with the temperature of the existence or origin plastic layer in the centre to
coal loading. I.e. mutual or separate influence of the separation and existence plastic
layer causes origin one or two maximums.
P5-5
MSTLFLO Process for Waste Coal Beneficiation
J.F. Zhong, A. Antoine, L. Hong, B. I. Morsi, M. H. Cooper, S. H. Chiang,
University of Pittsburgh, USA
53
The vast quantities of waste coal in this country present us an opportunity to recover
them as an alternative energy source. This paper describes a newly developed multistage
loop-flow flotation column (the MSTLFLO Process) as an effective means for
recovering waste coal from disposal sites and to produce a clean coal product for
electricity generation. Experimental tests under different column operation conditions
were carried out with three different waste coal samples. The results have
demonstrated that the MSTLFLO process is capable of producing low ash (

is only slightly affected with increased paraffin formation, which is believed to be due
to a slight shift of primary product selectivity as well as effects of secondary
hydrogenation. It is further shown that these effects are not due to uneven potassium
promotion and that the iron and copper need to be co-precipitated in order to achieve
maximum oxygenate promotion.
P6-4
A Gaming Framework for Analyzing Market Potentials and Risks of CTL
A. Tuzuner, Zuwel Yu, Purdue University, USA
Coal-to-liquids (CTL) has been attracting a lot of attention due to persisting high crude
oil prices, energy security concerns, large reserves of coal in many oil importing
countries etc. Both the direct coal liquefaction (DCL) and indirect coal liquefaction
(ICL) processes are proven technologies. However, whether the CTL business will
survive in an open global market depends on many factors, which can be mapped to
risks. The most determining factor of the viability of the CTL business is future oil
price movement. According to many studies, oil prices will have to be above $35-
40/bbl for the CTL business to survive, depending on the location and coal use of the
CTL business. An immediate question is: Do oil exporting countries have the incentive
to reduce oil prices The answer is: If there is no threat of entry to snatch the market
shares of these oil exporting countries, they may not have the incentive to reduce oil
prices by increasing their production. Hence, CTL can be regarded as a threat of entry
into oil market to force the oil exporting countries to reduce prices through production
expansion. Therefore, building the CTL capacity can be used as a gaming approach to
reducing crude oil prices, which may benefit the oil importing countries in many
aspects, including reduced oil prices, increased energy security, plus many other
benefits such as job creation, balancing trade, cash flows improvement etc.
The paper proposes a gaming model to find the equilibrium solution to the CTL
capacity building. A stochastic mean-reversion price model is used, and the Nashequilibrium
can be found using a stochastic root finding approach. In the equilibrium,
the “best” CTL capacity will be calculated based on the “long-run” marginal cost of
the total CTL capacity in the world.
P6-5
Novel Magnetic Method for Separation of Iron Catalysts
from Fischer-Tropsch Wax
R.R. Oder, EXPORTech Company, USA
We describe a novel continuous magnetic method for separation of nano-meter size
iron catalysts from Fischer-Tropsch wax (patent pending). The method has been scaled
up from the bench scale to prepare clean wax containing 0.1 to 0.5 wt.% catalyst from
slurries containing 20- 25 wt.% catalyst at the rate of 50 barrels per day (BPD) feed
wax at 500oF.1 We will discuss the operating mechanism of the separator which is
housed between the poles of an electromagnet producing magnetic fields in the range
of 0.2 to 0.5 Tesla throughout the working volume. The method achieves high levels of
catalyst separation from the wax by promoting magnetic agglomeration throughout the
volume of the vertically oriented elongate cylindrical separation vessel. Downwardlydirected
high velocity jet flows located adjacent to the inside walls of the separation
vessel nearest the magnet poles are used to sweep the catalyst agglomerates from the
magnetized volume of the separator. The jets are controlled to promote movement of
the agglomerates without causing turbulent mixing. Clean wax with a low
concentration of catalyst is continuously issued from the top of the separator while wax
slurry with a high concentration of catalyst is issued from the bottom of the vessel. Use
of a supplemental separation method such as batch operated high gradient magnetic
separation to treat the product of the first stage continuous magnetic separator has
produced clean wax containing 0.01 wt.% catalyst.
POSTER SESSION 7
COAL CHEMISTRY, GEOSCIENCES AND RESOURCES
P7-1
Cleaning Potentality of natural Coke (jhama) through washability
Investigation and Its Suitability for Different End Uses
Ashok K. Singh, N.K. Shukla, Amrita Mukherjee, Mamta Sharma, N. Choudhury, T.
Gauricharan, D.D. Haldar, Central Fuel Research Institute, INDIA
Substantial reserves of natural coke (jhama) are available in Indian coalfields, but due
to its peculiar physical and chemical properties, its suitability for different end uses has
not been established. Earlier workers have attempted to find out new avenues for
utilization of this material by producing coke from different blends of jhama with
coking coal fines, obtained from coal washeries. In the present study, authors have
attempted to study the washability characteristics of a typical natural coke from seam
XIV A of Jharia coalfield. Results of conventional float and sink tests have been used
to determine the yield of cleans at 10% and 15% ash content. The washability data
reveals that a theoretical yield of ~20% and >80% is achievable at 10% and 15% ash
levels. Different gravity fractions were further characterized (chemically and
microscopically) to find out their suitability for carbon artefact industries. These
studies on some of the gravity fractions having medium to high volatile matter and less
to moderate ash content lead to the conclusion that the natural coke may be used for
blending with power coal. Lower VM fractions may be recommended for cement
industry.
P7-2
X-Ray diffraction analysis on the macerals of coals with different type-reductivity
Haizhou Chang, Chuange Wang, Jun Li, Wenying Li, Kechang Xie, Fangui Zeng,
Taiyuan University of Technology, CHINA
In this article, X-ray diffraction (XRD) was carried out to study the crystallite
characteristics of the vitrinite and inertinite from Pingshuo and Shendong coals with
similar coal rank and petrographical composition but with different reductivity
revealing the influence of the reductivity on macerals crystallite. Pingshuo (PR) coal
was with stronger reductivity. Compared with vitrinite (PV) there was bigger
crystallite size, higher regularity and aromaticity (ƒ a ) in inertinite (PI). Shendong (SR)
coal was with weaker reductivity, its inertinite’s crystallite size and regularity were
more obvious than vitrinite (SV), but almost same ƒ a value. The crystallite parameters
of PV and SV are alike, which shows a good relationship with the petrographical
likeness of PV and SV. Compared with PI, there is fewer aromatic layers and lower ƒ a
in Shendong inertinite (SI). The content of highly disordered material called
amorphous carbon was investigated. Results showed that PV was obviously higher
than PI, SV is slightly higher than SI and PV, SI is obviously higher than PI. The
characteristic that there were relatively lower ƒ a as well as more amorphous carbon in
SI with weaker reductivity indicated that SI contains more active components, which
might be related to the fact that SI contained plentiful semifusinite.
P7-3
Comparison of Microwave-Assisted Extraction and Soxhlet extraction
Chen Hong, Lu Junqing, Ge Lingmei, Li Jianwei, Zhou Anning, Xi'an University of
Science and Technology, CHINA
In order to compare extraction yields and the extracts, extraction with several single
organic solvents under microwave-assisted and Soxhlet extraction were conducted for
5 typical Chinese coals –Shenfu, Tongchuan, Huating, Yitai, Panzhihua coal. Above
50% extraction yield was acquired for ethylenediamine under microwave-assisted
extraction, conversely only 40% extraction yield were the highest for Soxhlet
extraction. Extracts were analyzed by GC/MS. Influence of temperature, solvent, coal
type on microwave-assisted extraction are also studied. The cause of different
extraction yield on different coals was discussed.
P7-4
R&D of a New Technology of Conversion of Coke Oven Gas
from Bituminous Coal into Syngas
Yongfa Zhang, Kechang Xie, Taiyuan University of Technology, CHINA
Ping Wan, Changchun Technology College, CHINA
Guangliang Liu, Xiaofei Chen, Yan Liang, Jia Zhang, Li Yang, Shanxi Sunrise Coal
Technology Ltd., CHINA
A kind of new technology with an integrated apparatus (IA) for producing syngas from
bituminous coal is developed. In the integrated apparatus three processes: coal
pyrolysis, partial coal gasification and conversion of coke oven gas (COG) into syngas
are completed and three products: syngas, ferro-alloy coke (semi-coke) and tar are
produced in an environmental friendly manner. In this paper, the status of China’s
semi-coke industry and coke oven gas utilization are introduced; the principle of
conversing CH 4 -rich gas such as COG into syngas with the assistance of H 2 O-O 2 in a
high temperature carbon catalytic system are analyzed; and other technological issues,
such as the process, main technical specifications of the integrated apparatus, product
quality, energy consumption, financial estimation, and environmental protection etc.
are discussed. It has been shown by research that the main technical specifications of
the integrated apparatus are as following: coal processing capability 23 T/d, coke yield
14.7 T/d, tar yield 1.15 T/d, syngas yield 11960 Nm 3 /d. The syngas quality shows CH 4
content 86.5%. The semi-coke is favored product used
for Si-Fe alloy and carbide production. Its volatile rate is lower than 4.00% and
electrical resistance is higher than 1506Ω.mm 2 .m -1 at 1300°C. The content of phenol in
the tar is 16.25%. The integrated apparatus, a clean technology is energy and resource
efficient.
P7-5
Niobium and tantalum content at Kuzbass coals
Boris F. Nifantov, Vadim P. Potapov, Anatoliy N. Zaostorvskiy, Olga P. Zanina, The
Institute of the Coal and Coal Chemistry SB RAS, RUSSIA
At all deposits of the world coals contain niobium and tantalum which maintenance as
a rule do not exceed clark levels. Last years the data of high contents of these metals at
various coal-mining regions were published. In the present message are considered
metal logenic and the geochemical data of niobium and tantalum contents
accompanied by Sc, Ti, Fe, Y, Zn, Ce, Hf, Th, U at III - XVII layers of Tom-Usa
Kuzbass region.
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