Syngas Production and Conversion to Products - The Catalyst Group

The Catalyst Group Resources, Inc.Syngas Production and Conversion to Products -A Strategic Assessment of the Technologies,Markets and Competitive LandscapeVolume 1: Syngas Production Assessment(completed March 2007)A MULTI-CLIENT STUDY IN TWO VOLUMESCONTENTSSECTION I - EXECUTIVE SUMMARY..................................................................1A. THE CURRENT ENVIRONMENT ..................................................................1B. VOLUME 1 : “SYNGAS PRODUCTION ASSESSMENT” -APPROACH ......................................................................................................2C. SYNGAS SOURCES –TECHNICAL PROGRESS..........................................31. Natural Gas – the Benchmark ......................................................................32. Other Sources – Including Coal, Petcoke, Resid/Heavy Oil,Biomass and UCG.......................................................................................5D. CATALYST MARKETS/PLAYERS AND TECHNOLOGYLICENSING.......................................................................................................9E. COMPETITIVE IMPLICATIONS OF TECHNOLOGY CHANGE..............101. GE...............................................................................................................112. Shell............................................................................................................113. Sasol – Lurgi (focused on low rank coals and CTL)..................................114. ConocoPhillips ...........................................................................................115. Others .........................................................................................................12F. CONCLUSIONS AND RECOMMENDATIONS ..........................................181. Industry Issues............................................................................................192. CO 2 Capture and Separation/Sequestration................................................19The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

3. “Out of Box” Developments ......................................................................234. Moving Forward.........................................................................................24SECTION II - INTRODUCTION/BACKGROUND..............................................25A. Introduction ......................................................................................................25B. Background ......................................................................................................26C. The Need for the Study ....................................................................................26D. Scope and Methodology...................................................................................27E. The Study Team ...............................................................................................29F. Glossary of Terms and Abbreviations..............................................................31SECTION III - TECHNICAL PROGRESS IN NATURAL GAS AND LIGHTHYDROCARBON CONVERSION TO SYNGAS .................................................35A. COMMERCIAL STATUS OF NATURAL GAS CONVERSIONTO SYNGAS....................................................................................................351. Methane Steam Reforming – The Gasification Benchmark ......................352. State-Of-The-Art Steam Reforming...........................................................353. Natural Gas Steam Reforming Economics.................................................374. Economic Comparison of Natural Gas Reforming Processes....................40B. EMERGING TECHNOLOGIES .....................................................................421. Non-Conventional Approaches to Syngas Production...............................422. Syngas Production Using Ion Transport Membrane Technology..............42a) ITM Syngas Team................................................................................42b) OTM Syngas Alliance..........................................................................47c) Is Commercialization Near?.................................................................483. Advanced Gas Heated Reforming (AGHR)...............................................484. Catalytic Partial Oxidation (CPO)..............................................................51C. REFERENCES.................................................................................................51SECTION IV - TECHNICAL PROGRESS IN GASIFICATION OF OTHERSOURCES TO SYNGAS...........................................................................................55A. TECHNICAL AND COMMERCIAL STATUS .............................................551. Introduction ................................................................................................552. Coal ............................................................................................................58a) GE Energy, GE.....................................................................................59The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

) Shell, SCGP..........................................................................................61c) Uhde (Krupp-Koppers), Prenflo...........................................................64d) Sasol-Lurgi, FBDB...............................................................................65e) ConocoPhillips, E-Gas .........................................................................67f) Siemens, SFG.......................................................................................69g) Others ...................................................................................................703. Petroleum coke...........................................................................................73a) GE Energy, GE.....................................................................................74b) Shell, SCGP..........................................................................................74c) ConocoPhillips, E-gas ..........................................................................754. Heavy oil ....................................................................................................79a) GE Energy, GE.....................................................................................80b) Shell, SGP ............................................................................................82c) Lurgi, MPG ..........................................................................................84B. EMERGING TECHNOLOGIES .....................................................................881. Membrane Technology ..............................................................................88a) ANL / Mixed-Conduction Ceramic Membranes..................................89b) Eltron Research / H 2 Transport Membranes ........................................92c) Los Alamos & Idaho Composite Polymeric-Metallic Membranes......97d) Oak Ridge / Porous Inorganic Membranes for H 2 Separation .............992. Solvent Absorption...................................................................................103a) Morphysorb Acid Gas Removal Process ...........................................1033. Sulfur Removal ........................................................................................109a) RTI / Eastman Hot Gas Desulfurization System (HGDS) Process....109b) RTI & Eastman -- Direct Sulfur Recovery Process (DSRP)..............114c) UCSRP-HP Gas Cleaning Sulfur Recovery Process .........................119d) NETL & ORNL / Selective Catalytic Oxidation of H 2 S....................1234. Multi-Component Removal......................................................................132a) RTI / Eastman Multi-Contaminant Control (MCC) Process..............132b) Siemens Westinghouse Filter-Reactor Gas Cleaning.........................1365. CO 2 Separation and Sequestration ...........................................................141The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

a) Introduction ........................................................................................141b) Advantages and Concerns ..................................................................142c) Path Forward & Conclusions .............................................................1426. New Gasifier Designs...............................................................................143a) GE Global / Unmixed Fuel Processor (UFP).....................................143b) U- GAS® Fluidized Bed Gasification Process ..................................152c) KBR Transport Gasifier (TRIG TM ) ....................................................158d) Catalytic Coal Gasification - Bluegas ............................................161e) New Gasifiers - Summary..................................................................164C. TECHNICAL PROGRESS - SUMMARY....................................................165D. REFERENCES...............................................................................................168SECTION V - SIZE AND GROWTH OF CATALYST MARKETSFOR SYNGAS PRODUCTION AND THE TECHNOLOGYLICENSING BUSINESS .........................................................................................179A. CATALYST MARKET SIZE AND GROWTH ...........................................1791. Ammonia and Methanol...........................................................................1792. Hydrogen, Power and GTL/CTL .............................................................181B. CATALYST SUPPLY, SUPPLIERS AND COMPETITION.......................184C. PROCESS TECHNOLOGY LICENSING ....................................................1861. Technology Licensors and General Interests .......................................... 186a) Established leaders .............................................................................186b) Other technologies offered for license ...............................................1892. Feedstocks and Flexibilities .....................................................................189a) Fossil Fuels.........................................................................................189b) Biomass ..............................................................................................190c) Underground Coal Gasification (UCG) .............................................1993. Target Markets and Products....................................................................202D. REFERENCES...............................................................................................205SECTION VI - COMPETITIVE/COMMERCIAL IMPLICATIONS OFTECHNOLOGY CHANGE ....................................................................................207A. TECHNOLOGY HOLDERS AND DEVELOPERS.....................................2071. Leaders .....................................................................................................207The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

a) GE.......................................................................................................207b) Shell....................................................................................................208c) Sasol – Lurgi (focused on low rank coals and CTL)..........................208d) ConocoPhillips ...................................................................................2082. Others .......................................................................................................209a) Commercial ........................................................................................209b) Near-commercial................................................................................2093. Alliances/Partnerships..............................................................................209a) The CoalFleet Project.........................................................................209b) GE and Bechtel (for IGCC)................................................................210c) GE and BP (Coke to H 2 and power with CO 2 recovery)....................210d) Shell and Anglo American .................................................................210e) Shell and Uhde (SGP for liquid and gaseous feeds) ..........................211f) Siemens and Sustec-Group (coal gasification)...................................211g) The FutureGen Alliance.....................................................................211h) Sasol and Lurgi (for coal feeds) .........................................................211i) ConocoPhillips and Fluor...................................................................211j) NRG Energy and New York Power Authority...................................211k) URS Corporation and Energy Resources ConsultancyInternational (ERC)............................................................................212B. RELATIVE COMMERCIAL SUCCESS TO DATE AND FUTURE PROMISE........................................................................................................................2121. Feedstocks, Technologies and Plant Scale...............................................212a) Feedstocks ..........................................................................................212b) Technologies ......................................................................................213c) Plant Scale and Scale-up Issues .........................................................2132. Likely Next Steps (i.e. development needed) ..........................................214a) Technology.........................................................................................214b) Commercialization .............................................................................223C. RELATIVE ECONOMICS OF SYNGAS PRODUCTION..........................2261. Coal, Petcoke and Resid/Heavy Oil to Produce Syngas forUse in Power, Chemicals and Liquid Fuels .............................................228The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

2. Biomass to Produce Syngas for Use in Power, Chemicalsand Liquid Fuels.......................................................................................2343. Underground Coal Gasification (UCG) – based CTL..............................235D. IMPLICATIONS OF RELATIVE COSTS....................................................238E. REFERENCES...............................................................................................239SECTION VII - CONCLUSIONS AND RECOMMENDATIONS.....................247A. THE AUTOTHERMAL REFORMING (ATR) BENCHMARK..................247B. EMERGING TECHNOLOGIES WITH POTENTIAL IMPACTS...............2491. RTI / Eastman - Hot Gas Desulfurization System (HGDS) Process........2502. RTI & Eastman - Direct Sulfur Recovery Process (DSRP).....................2513. RTI / Eastman Multi-Contaminant Control (MCC) Process....................2524. GE Global / Unmixed Fuel Processor (UFP)...........................................2555. Catalytic Coal Gasification - Bluegas ..................................................260C. ISSUES AND DEVELOPMENTS DEFINING THE OUTLOOK FORGASIFICATION............................................................................................2621. Industry Issues..........................................................................................2632. CO 2 Issues ................................................................................................264a) CO 2 Capture .......................................................................................264b) CO 2 Separation and Sequestration .....................................................2653. “Out of Box” Developments ....................................................................267D. REFERENCES...............................................................................................269FIGURESI-F-1 CPS IGCC Comparative Study............................................................20I-F-2 Low Rank Coal Study – EPRI .............................................................20III-A-1 Configuration of Steam Reformer........................................................36III-A-2 Effect of Scale on Syngas Investment Cost .........................................41III-B-1 ITM Syngas Membrane Reactor ..........................................................43III-B-2 ITM Syngas Process Concept ..............................................................44III-B-3 One Version Of Ion Transport Membrane Module and VesselSystem ..................................................................................................46The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

III-B-4 AGHR + Secondary Reformer .............................................................49IV-A-1 NOx emission Buggenum IGCC..........................................................56IV-A-2 Sox, NOx and dust emissions from coal fired plants ...........................57IV-A-3 Gasification integrated in Shell Pernis refinery ...................................57IV-A- 4 GE Energy coal gasification process with water quench .....................59IV-A- 5 GE Energy Coal gasification process with effluent cooler ..................60IV-A- 6 Effect of water slurry type feed on efficiency of gasifier ....................61IV-A- 7 Shell Coal Gasification Process ..........................................................62IV-A- 8 The Sasol-Lurgi Gasification system ...................................................66IV-A-9 The E-Gas Gasifier system...................................................................68IV-A-10 Siemens SFG reactor for coal application............................................69IV-A-11 BGL Gasifier........................................................................................71IV-A-12 KBR Transport Gasifier .......................................................................72IV-A-13 Configuring the PHTW gasifier ...........................................................73IV-A-14 Values of Liquid Hydrocarbons ...........................................................79IV-A-15 GE Reactor with water quench and with boiler. ..................................80IV-A-16 GE Soot water processing ...................................................................81IV-A-17 Shell Gasification Process, SGP...........................................................83IV-A-18 Lurgi MPG Process with Water Quench..............................................85IV-B-1IV-B-2IV-B-3IV-B-4IV-B-5IV-B-6IV-B-7IV-B-8Hydrogen flux through ≈15 µm-thick cement membrane on aporous substrate at 500 and 900°C using 100% H 2 at ambientpressure as the feed gas. .......................................................................90Time dependence of hydrogen flux ≈0.20 mm-thick cermetmembrane at 900°C with feed gas of ≈400 ppm H 2 S/73%H 2 /balance He.......................................................................................91Schematic of H 2 Transport Across Membrane.....................................94Tubular HTM Configuration................................................................94Simplified Flowsheet of CO-Shift / HTM Process StagedIntegration ............................................................................................95SEM Image of PBI-coated Pall AccuSep Tube used for moduledevelopment .........................................................................................97PBI-coated Pall AccuSep Tube with ~67cm2 of activemembrane area .....................................................................................98Schematic of molecular sieving separation via micro-porous membranes............................................................................................................100The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

IV-B-9 Separation Module for Gas Separation .............................................100IV-B-10 Separation Factor for gas pairs of different moleculardiameters ............................................................................................100IV-B-11 DEGT “Kwoen” Morphysorb Plant near Chetwynd,BC Canada..........................................................................................105IV-B-12 DEGT Kwoen Morphysorb Bulk Removal Plant PFD ......................105IV-B-13 Solubility of CO 2 in Morphysorb compared to DMPEG ...................106IV-B-14 Solubility of H 2 S in Morphysorb compared to DMPEG ...................106IV-B-15 Morphysorb Pilot Plant at GTI...........................................................108IV-B-16 HGDS Flowscheme............................................................................110IV-B-17 Pilot Plant Facility at Eastman’s Kingsport, TN Plant.......................111IV-B-18 DSRP Pilot Plant at Eastman Gasification Plant...............................111IV-B-19 Simplified Process Flow Diagram of Integration ofHGDS & DSRP Processes .................................................................115IV-B-20 Eastman Plant Main Gasifier & Field Test Units...............................117IV-B-21 DSRP Pilot Plant Skid at Eastman Gasification Plant .......................117IV-B-22 PFD for UCSRP for syngas with contaminant removal feature.........121IV-B-23 Simplified Schematic of SCOHS Process..........................................124IV-B-24 Process Flow Diagram of SCOHS with Thermal Regeneration ........126IV-B-25 Process Flow Diagram of Monolithic SCOHS Concept ....................126IV-B-26 SCOHS Single-Stage Process Schematic for IGCC ..........................129IV-B-27 SCOHS Single-Stage Desulfurization Process Schematic.................130IV-B-28 MCC Process Schematic of Proposed Approach ...............................134IV-B-29 Eastman Plant Ammonia and Trace Metal Removal Skid.................134IV-B-30 RTI Ultra Gas Cleaning Process ........................................................135IV-B-31 RTI / Eastman Development Programs Status...................................135IV-B-32 Ultra Clean general arrangement at GTI Flex Fuel Facility...............137IV-B-33 Candle Filter Battery ..........................................................................138IV-B-34 Conceptual Basics of the UFP Technology........................................145IV-B-35 Conceptual Flowscheme of UFP Process...........................................145IV-B-36 Schematic Comparison of Gasification versus UFP ..........................146IV-B-37 UFP Process Flowscheme with highlighted features .........................147IV-B-38 Example of Integrated UFP Power Plant ...........................................147The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

IV-B-39 UFP Program Development Plan .......................................................151IV-B-40 U-GAS-based Wu Jing Gas Plant No. 2, Shanghai, China................153IV-B-41 U-GAS ® Gasifier Schematic ..............................................................153IV-B-42 RENUGAS CHP Plant, Skive Denmark............................................156IV-B-43 KBR/Southern Company Transport Gasifier .....................................160V-C-1 Solid Fuel Gasification Experience...................................................190V-C-2 Underground Coal Gasification (UCG) ............................................200V-C-3 Cost of Fossil Fuels to the U.S. Electric Power Industry..................203VI-A-1 ConocoPhillips Technology Development in Gasification................208VI-B-1 Current (2006) Gasification Projects with Identified Feeds...............212VI-B-2 Changes in Market Share; Shell vs. GE .............................................213VI-B-3 Escalation of Plant Construction Costs ..............................................220VI-C-1 Schematic of a Polygeneration Facility..............................................230VI-C-2 Syngas Production from Coal – Gasification Routes to Products......233VI-C-3 Capital Cost of New Fossil Fuel Power Plants, Alberta, Canada ......236VI-C-4 Cost of Electricity (New Fossil Fuel Plants, Alberta, Canada)..........237VI-C-5 Scoping Economics: UCG for CTL (Coal-to-Liquids) and for ElectricPower Generation...............................................................................238VII-A-1 Effect of Scale on Syngas Investment Cost .......................................247VII-B-1 Simplified Process Flow Diagram of Integration ofHGDS & DSRP Processes .................................................................251VII-B-2 Process Schematic of Proposed Approach in Multi-Contaminant Control(MCC) ................................................................................................254VII-B-3 Eastman Plant Ammonia and Trace Metal Removal Skid.................254VII-B-4 RTI Ultra Gas Cleaning Process ........................................................255VII-B-5 Conceptual Basics of the UFP Technology........................................257VII-B-6 Conceptual Flowscheme of UFP Process...........................................258VII-B-7 Schematic Comparison of Gasification versus UFP ..........................259VII-B-8 UFP Process Flowscheme with highlighted features .........................259VII-B-9 Example of Integrated UFP Power Plant ...........................................260VII-C-1 Plant Construction Cost Escalation....................................................262VII-C-2 CPS IGCC Comparative Study ..........................................................264VII-C-3 Low Rank Coal Study – EPRI ...........................................................265The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

TABLESI-C-1 List of Technologies Reviewed but Not Reported in Detail ..................8I-D-1 Syngas Catalyst Volume and Growth 2006-2010 by Application(MIL mt/yr and $ MIL) ..........................................................................9III-A-1 Prototypical Syngas Economics...........................................................38III-A-2 Prototypical Syngas Economics (Low Natural Gas PriceScenario)...............................................................................................39III-B-1 Benefits of AGHR for GTL Plant ........................................................50IV-A-1 Solids Gasification Technologies: Summary of Highlights.................76IV-A-2 Liquids Gasification Technologies: Summary of Highlights...............86IV-B-1 Progress towards DOE FutureGen Targets ..........................................93IV-B-2 Comparison of Relative Solubility of Components inMorphysorb ........................................................................................107IV-B-3 Desulfurization Capital Cost Evaluation............................................112IV-B-4 Development History of DSRP technology .......................................116IV-B-5 IGCC Capital Cost w Conventional and SCOHS SulfurSystems...............................................................................................127IV-B-6 IGCC Cost-of-Electricity w Conventional and SCOHSSulfur Systems....................................................................................127IV-B-7 Conventional Gas Cleanup Approach vs. Filter-Reactor GasCleanup Concept Applied to IGGC ...................................................139IV-B-8 Conventional Gas Cleanup Approach vs. Filter-Reactor GasCleanup Concept for Combined Power (IGCC)/Methanol................139IV-B-9 Comparison of features of UFP and IGCC ........................................148IV-B-10 Comparison of Cost of Electricity for UFP (AGC) and IGCC ..........150IV-B-11 Feedstocks Processed in the U-GAS Gasification Process ................155IV-C-1 List of Technologies Reviewed but Not Reported in Detail ..............167V-A-1 Catalysts and Corresponding Poisons in Stream Reforming,Shift Conversion, Methanation, Ammonia and MethanolSynthesis.............................................................................................180V-A-2 Market Size and Growth of Syngas Catalysts for Ammonia and MethanolProduction 2006 to 2010 (Mmt/yr = 000’s mt/yr) ............................181The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com

V-A-3 Market Size and Growth of Ammonia and Methanol Production Catalysts2006 to 2010 (Mmt/yr = 000’s mt/yr) ................................................181V-A-4 Syngas-Production Capacities (MMTons/Year) ................................182V-A-5 Market Size and Growth for Hydrogen, Power and GTL/CTLApplications of Syngas Catalysts 2006 to 2010 (MIL mt/yrand $ MIL) .........................................................................................183V-A-6 Market Size and Growth for Oxochemicals and AcetylsApplications of Syngas Catalysts 2006 to 2010 (MIL mt/yr and$ MIL) ................................................................................................183V-A-7 Syngas Catalyst Volume and Growth 2006-2010 byApplication (MIL mt/yr and $ MIL) ..................................................184V-B-1 Syngas Catalyst Supply/Process Licenses: Strengths/Weaknesses ........................................................................................185V-C-1 Overview of Biomass Gasification Technologies..............................191V-C-2 Potential Number of IGCC Plants Added by 2025 ............................203VII-A-1 Benefits of AGHR for GTL Plants.....................................................248The Catalyst Group Resources, Inc., P.O. Box 680, Spring House, PA 19477, Phone: (215) 628-4447,Fax: (215) 628-2267, E-mail: tcg@catalystgrp.com, Website: www.catalystgrp.com