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THE CATALYST REVIEW - The Catalyst Group

Technical & Commercial Progress in the Global Catalytic Process Industries

THE CATALYST REVIEW

March 2010 A Publication of The Catalyst Group Resources, Inc. Volume 23, Issue 3

DIRECT COAL LIQUEFACTION:

INSIGHTS FROM PATENT ANALYTICS

by:

Dr. Madan Bhasin

Industry Rumors: Europe's Mood in Chemicals Darkening ...

Source: West Virginia University

The Catalyst Review March 2010

1


THE CATALYST REVIEW (ISSN 0898-3089)

March 2010, Volume 23, Number 3

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On Our Calendar - Industry Conferences & Events

May 2010

World GTL 10 Summit (GTL, BTL,CTL)

May 10-12, 2010

London, UK

www.cwcxtl.com

9th Annual Carbon Capture &

Sequestration Conference

May 10-13, 2010

Pittsburgh, PA, USA

www.carbonsq.com

2nd Carbon Capture and Storage Summit

May 19-20, 2010, Berlin, Germany

www.acius.net

June 2010

Gordon Research Conference–Catalysis

June 22 - July 2, 2010

New London, NH, US

www.grc.org/programs.aspxyear=2010&program=catalysis

July 2010

16th International Zeolite Conference

(joint with 7th International

Mesostructured Materials Symposium)

July 4-9, 2010, Sorrento, Italy

http://izc-imms2010.unime.it/

6th Tokyo Conference on Advanced

Catalytic Science and Technology & 5th

Asia Pacific Congress on Catalysis

July 18-23, 2010, Sapporo, Japan

www.shokubai.org

October 2010

Gasification Technologies Conference

October 31 – November 3, 2010

Washington, DC, USA

www.gasification.org/conferences/

annual_conferences.aspx

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2

The Catalyst Review March 2010


In This Issue

INDUSTRY RUMORS

Europe's Mood in

Chemicals Darkening...

By Clyde Payn

There are a

number of

convoluted

reports that

are stirring

the general

rumor mill in

Europe that

have executives

becoming

increasingly concerned. These are:

(1) the financial stability and debt

Clyde Payn, CEO

The Catalyst Group, Inc.

structures of weakened existing EU

member countries, most notably the

recent financial bailout of Greece, but

with the knowledge that others like

Spain are not that much better off.

This has fueled the general concern

that broader economic recovery in

the Eurozone will at best be delayed.

There is a growing worry that the

recovery is stagnating, with a flat but

potentially negative outcome; (2) the

pending surge of polyolefin capacity

coming on stream in the Middle

East and the nearest export market,

Europe (with its antiquated capacity),

becoming uncompetitive. There is a

report by KPMG that 14 of the 45

crackers in Europe are under threat of

being uneconomic and uncompetitive

based on the higher cost of feedstocks

in Europe. Moreover, other export

markets such as N. America are more

isolated and advantaged by lower cost

natural gas, meaning an increased

pressure on Europe’s locality; and

(3) that China is in a better position

to take advantage of any recovery in

the commodity chemicals segment

globally.

The convergence of these factors

is the reason that more executives

are sanguine about Europe’s

competitiveness in the commodity

chemicals sector. There has been a

general call for more innovation in

the specialty chemicals segment as a

solution to help stave off considerable

consolidation. There is no doubt that

plant closures and rationalization

must come from both Europe and N.

America, but how this will play out has

yet to be seen.

SPOTLIGHT: Peak Performance in

China and India ............................ 2

Mitsui Seeks Partners for

CO 2

-Based Methanol Plant .......... 2

Evonik Acquires Catalyst Business

from H.C. Starck ........................... 2

Refining Industry Grapples with

Downshift as Structural Change

Looms .......................................... 3

Sasol to Apply for Chinese Mine,

Catalyst Plants this Year ............... 3

Danish Enzyme Maker Claims

Biofuel Breakthrough .................. 3

Dual-bed Catalyst System for

C-C Coupling of Biomass-derived

Oxygenated Hydrocarbons to

Fuel-grade Compounds ............... 4

Scientists Figure Out Way to

Convert CO 2

Into Carbon

Monoxide Using Visible Light ...... 5

Special Feature:

Direct Coal Liquefaction:

Learnings from Patent Analytics .. 6

Exceptionally Active Single-Site

Nanocluster Multifunctional

Catalysts for Cascade Reactions .. 11

Light-Driven Hydrogen Generation:

Efficient Iron-Based Water

Reduction Catalysts ..................... 12

Next-Generation Catalysis for

Renewables: Combining Enzymatic

with Inorganic Heterogeneous

Catalysis for Bulk Chemical

Production ................................... 15

Transition Metal–Tungsten

Bimetallic Catalysts for the

Conversion of Cellulose into

Ethylene Glycol ............................ 16

Movers and Shakers ................... 18

The Catalyst Review March 2010

1


COMMERCIAL NEWS

SPOTLIGHT: Peak Performance in China and

India…

China and India are preparing

themselves for an epoch of

success and unadulterated growth,

provided that neither of them find

themselves in a bursting economic

bubble. China is taking big steps

towards cutting the huge amounts

of easy credit flowing around its

economy. India, meanwhile, has a

fairly conservative banking sector

and did not suffer greatly from

financial instability. Both of these

developing nations have adopted

a very different stance for their

expansion and success. Compared

with other emerging markets,

India has a lower dependence on

product exports and, as a result,

has been somewhat insulated

from the downturn. China is more

macroeconomic-driven, India is

more micro-economic. In China,

self-sufficiency and secure and

competitive access to feedstocks are

a major driver, but in India, the stance

is to retain maximum intellectual

capital and achieve the best returns.

Chinese companies are more driven by

cash flow. "It's very hard to compare

India and China - both have their own

strengths and internal challenges.

However, they do face many of the

same issues," says Jennifer Kao,

Accenture outsourcing lead for

chemicals in Greater China. "The

countries are growing very fast, there

are concerns over pollution and water

treatment, and then there is REACH

[the EU chemical legislation]. They

need to start addressing these issues.

Huge markets are opening up because

of this - but it will also increase costs

for investors." Source: ICIS Chemical

Business, 2/22-28/2010, p. 19.

Mitsui Seeks Partners for CO 2

-Based

Methanol Plant…

Mitsui Chemicals says it is seeking partners who would be interested in

participating in a first commercial-scale methanol plant based on Mitsui’s Green

House Gases-to-Chemical Resources (GTR) technology. The process is currently

being tested at a pilot plant at Mitsui’s Osaka manufacturing complex and it

will take another two years to develop, said Korehiro Odate, deputy general

manager/new business development at Mitsui. Potential partners would become

offtakers of methanol from the commercial GTR-process plant “because Mitsui is

not active in the methanol business,” Odate says. Mitsui is looking at a number

of locations for the commercial plant, which is likely to be designed to produce

600,000 mt/yr of methanol. China, Japan, and Singapore are being considered

as possible locations. Mitsui’s GTR pilot plant at Osaka has capacity to produce

100 mt/yr of methanol and it has been onstream since March 2009. The plant

was built at a cost of $16 million and uses an oxidized copper, zinc, aluminum,

zirconium, and silicon catalyst developed through a joint research project with the

Research Institute of Innovative Technology for the Earth (Kyoto, Japan). Carbon

dioxide (CO 2

) and hydrogen are the two main feedstocks used by the plant. Mitsui

supplies hydrogen to the plant from an adjacent ethylene oxide (EO) unit. The

GTR process could play an important role in helping to reduce CO 2

emissions.

Chemical Week online, 3/1/2010.

Evonik Acquires

Catalyst Business from

H.C. Starck…

Evonik Industries has acquired the

catalyst business of H.C. Starck GmbH

based in Goslar (Germany). Following a

transition phase, Evonik will produce the

Amperkat® catalysts in Hanau (Germany).

The Amperkat® brand comprises activated

metal catalysts—known as skeletal

catalysts and customized supported

catalysts. The Amperkat® business focuses

principally on activated nickel catalysts,

which are used in the pharmaceuticals

and food industries and in fine and

industrial chemicals. The newly acquired

business also makes it possible for Evonik

to manufacture activated metal catalysts

based on spray alloys and in tablet form,

two highly specialized processes that offer

additional freedom when designing highperformance

catalysts. Source: Evonik,

3/2/2010; TCGR.

Hitachi SCR Catalyst

Tech Will Help AEP

Meet Emission

Reduction Goals…

Hitachi Power Systems America, Ltd.,

a subsidiary of Hitachi America, Ltd.,

announced that it has been awarded

a blanket contract to supply Selective

Catalytic Reduction (SCR) DeNOx catalyst

for American Electric Power (AEP)’s SCR

Fleet. Financial terms were not disclosed.

Hitachi will design, engineer, and supply

catalyst for up to eight of AEP’s coal-fired

electric generating stations for deliveries

starting in 2012 through 2014, similar

to the current blanket contract between

Hitachi and AEP which runs through

2011. The blanket contract could result

in 9,000m 3 of catalyst being installed in

over 10,050MW of power generation at

AEP’s facilities during this time period.

Hitachi’s proven plate-type catalyst

technology has been operating in over

750 units worldwide, with over 300 coalfired

applications. Source: Hitachi Power

Systems America, Ltd., 3/1/2010.

2

The Catalyst Review March 2010


COMMERCIAL NEWS

Refining Industry Grapples with Downshift as

Structural Change Looms…

Consultants Ensys Energy, in a study co-authored with OPEC for its World Oil Outlook

last year, found that a reduction of 7 MMbpd to 10 MMbpd of refining capacity through

closures would be necessary to bring global utilization rates back to an average of

85%. Energy Market Consultants is also predicting 7 MMbpd of closures by 2015, with

a further 4 MMbpd reduction possibly by 2020. Since last year, the storm clouds have

stubbornly parked themselves over the European and US refining industries. They are

now set to stay until a great swath of distillation capacity is washed away. As suggested

before, this is an OECD storm, with a nasty eye swirling over the Atlantic. BP executives

disclosed in an earnings call in February that it recorded refining margins of less than

$1.59/bbl in 4Q of 2009. That $1.59 number is the level reached by BP’s Global Refining

Indicator, which itself is at a 15-year low. According to Martin Tallett of EnSys Energy,

this is not the first time that a reduction in refining capacity has happened. He says that

in the 1980s, global refining capacity fell by 9 MMbpd, from 82 MMbpd to 73 MMbpd.

Source: Hydrocarbon Processing, 3/2010, p. 11; TCGR.

Sasol to Apply for Chinese Mine, Catalyst

Plants this Year…

Sasol Ltd. will this year submit applications for mines and catalyst plants as a part

of a bid to build a coal-to-liquids plant in China. A project application report was

submitted to the Chinese government for approval in December, the Johannesburgbased

company said. However, according to a government document, the review of

the joint venture project is being delayed while Chinese regulators wait for a rival plan

based on Chinese-developed technology. The document, prepared by the local-level

economic planning agency of the Ningxia Autonomous Region where Sasol’s planned

project will be built, outlined a case against the joint venture project and quoted a

senior government official recommending against cooperating with Sasol. According

to the document, Sasol’s Chinese partner in the proposed CTL plant, Shenhua Ningxia

Coal, has asked a unit of China Petrochemical Corp. to put together a research report on

the feasibility of CTL technology based on China’s own technology. Source: Dow Jones

Newswires, 3/8/2010.

Danish Enzyme Maker Claims Biofuel

Breakthrough…

Novozymes has claimed a breakthrough in efforts to produce biofuels from agricultural

waste a day after rival Danisco made its own push for leadership of what could become

a multi-billion dollar industry. The two Danish enzyme makers have each poured

tens of millions of dollars into development of technology to enable production of

ethanol from non-edible plant leftovers, such as straw, corn cobs and sugar cane offcuts.

Both are aiming to show that the investments are close to paying off as they

unveil new enzymes designed to make so-called cellulosic ethanol commercially

viable after years of unfulfilled promises. Novozymes, spun off from Novo Nordisk,

the Danish pharmaceutical group a decade ago, has created an enzyme capable of

producing cellulosic ethanol at a cost of $2.25 a gallon - close to the price of petrol and

conventional ethanol. Martin Sikorski, an analyst at Cheuvreux in Stockholm, says that,

if met, the US target would imply annual enzyme sales of about $5 BIL, with Novozymes

and Danisco in pole position to benefit. Steen Riisgaard, Novozymes chief executive,

said full-scale production would start in 2011 when Poet, the big US biofuel producer, is

scheduled to open the world’s first commercial cellulosic ethanol facility. Several other

plants are also planned, including two in the US by BP. Source: Financial Times online,

2/16/2010.

Chemical Sector Must

Reduce Overcapacity…

The global chemical industry remains in a

state of oversupply and 15-20% of capacity

- or around 50m tonnes/year - needs

to be shut down to restore sustainable

profitability by 2015. While the industry

can say that it has put the demand side

of its problems behind it, "we still have

the supply side to go through," said Gary

Adams, president of Houston-based

advisory firm Chemical Market Associates

Inc. (CMAI). For North America, the good

news is that the overcapacity issue is less

severe than it is in Europe and Northeast

Asia, Adams told a luncheon hosted by

the Southwest Chemical Association.

The problem of excess capacity is being

exacerbated by a worst-case scenario in

which a wave of new plants, notably in the

Middle East, are coming on stream at a

time when demand is at a cyclical bottom,

he said. Source: ICIS Chemical Business,

2/22-28/2010, p. 12.

Development of Coalto-Gas

and Coal-to-

Hydrogen Facilities

Pursued…

Peabody Energy and GreatPoint Energy

have signed an agreement to pursue

development of coal-to-gas and coal-tohydrogen

projects in the United States and

around the world. The projects would be

developed using GreatPoint's proprietary

Bluegas technology, which utilizes

catalytic hydromethanation to create

pure hydrogen and substitute natural

gas (SNG). This process is more efficient

and cost effective than conventional

gasification. The hydrogen will be used

for industrial applications or combusted

to generate near-zero carbon electricity.

The SNG can be transported in the existing

pipeline infrastructure and used as fuel in

home heating, power plants or industrial

processes. Source: Peabody Energy,

2/18/2010.

The Catalyst Review March 2010

3


PROCESS NEWS

Dual-bed Catalyst System for C-C Coupling of Biomass-derived

Oxygenated Hydrocarbons to Fuel-grade Compounds…

Mono-functional intermediates produced by catalytic

conversion of sugars and polyols over Pt–Re/C catalysts

(consisting of alcohols, ketones, carboxylic acids, and

heterocyclic compounds) can be upgraded to fuelgrade

compounds using two catalytic reactors operated

in a cascade mode. The first reactor achieves C–C

coupling of mono-functional intermediates using a

dual-bed catalyst system, where the upstream catalyst

bed (Ce 1

Zr 1

Ox) is employed to carry out ketonization

of carboxylic acids, and the downstream catalyst

bed (Pd/ZrO 2

) is used to achieve aldol condensation/

hydrogenation of alcohols and ketones. This second bed

is not significantly inhibited by CO 2

and H 2

O produced

during ketonization. The high molecular weight ketones

produced by C–C coupling reactions in the dual-bed

catalyst system are subsequently converted to alkanes

by hydrodeoxygenation (i.e., dehydration/hydrogenation) over a Pt/SiO 2

–Al 2

O 3

catalyst. Using the aforementioned approach, an

aqueous feed containing 60 wt% sorbitol was converted to a liquid stream of alkanes, 53% of which consisted of C 7+

alkanes with

minimal branching, desirable for diesel fuel. Source: Green Chemistry 2010, Volume 12.

New Applied Catalysis Research Findings from C. Neyertz and

Co-researchers Published…

The reactive properties of Pd-Cu and Pd-In catalysts over weak anionic exchange resin as support was investigated in catalytic nitrate

reduction. Pd-Cu/resin catalysts were prepared using different copper fixation procedures (ion exchange method and controlled

surface reaction). The samples were tested in a batch reactor with H 2

bubbling and constant pH. The fresh and reacted catalysts were

characterized by TEM, EPMA, XRD and XPS. The results demonstrated a higher activity of the Pd-Cu/resin catalyst prepared upon

controlled surface reaction due to a high concentration of binary sites in the external surface. On the other hand, the XRD and TEM

analyses indicated that sinterization occurs during reaction, leading to an increase in the average particle size. In the same way, a Pd-

In/resin was investigated showing more activity and less selectivity than the Pd-Cu/resin sample. Source: Science Letter, 2/23/2010,

p. 143.

Researchers Develop Single-Step, Solid Acid-Catalyzed Process for

Production of Biodiesel from Feedstocks with High Free Fatty Acid

Content…

Researchers at the University of Waterloo (Canada) have demonstrated a single-step solid acid-catalyzed process with the potential

for industrial-scale production of biodiesel from high free fatty acid (FFA) feedstocks. Aijaz Baig and Flora Ng developed a single-step

solid acid-catalyzed process for the production of biodiesel from high FFA feedstocks. The solid acid catalyst based on a supported

heteropolyacid catalyst (PSA) was evaluated for the production of biodiesel from soybean oil (SBO) containing up to 25 wt% palmitic

acid (PA). This solid acid catalyst catalyzed simultaneously esterification (the reaction of fatty acids with methanol in the presence of

an acid catalyst and water to produce biodiesel) and transesterification (the reaction of triglycerides with methanol in the presence

of a catalyst to produce biodiesel). The palmitic acid was converted to biodiesel with 95% conversion using the solid acid catalyst

(PSA), and the soybean oil was successfully transesterified with 99% CBG (chemically bound glycerin) conversion. Source: Green Car

Congress online, 2/21/2010.

4

The Catalyst Review March 2010


PROCESS NEWS

Scientists Figure Out Way to Convert CO 2

Into

Carbon Monoxide Using Visible Light…

A team of scientists has figured out a way to efficiently turn carbon dioxide (CO 2

)

into carbon monoxide using visible light, like sunlight. The method was developed by

University of Michigan biological chemist Steve Ragsdale, along with research assistant

Elizabeth Pierce and scientists led by Fraser Armstrong from the University of Oxford in

the UK. Ragsdale and his associates succeeded in using an enzyme-modified titanium

oxide to get carbon dioxide's electrons excited and willing to jump to the enzyme, which

then catalyzes the reduction of carbon dioxide to carbon monoxide. A photosensitizer

that binds to the titanium allows the use of visible light for the process. The enzyme is

more robust than other catalysts, willing to facilitate the conversion again and again.

The trick is that it can't come near oxygen. "By using this enzyme, you put it into a

solution that contains titanium dioxide in the presence of a photosensitizer," Ragsdale

said. The direct product - carbon monoxide - is a desirable chemical that can be used

in other processes to produce electricity or hydrogen. Carbon monoxide also has

significant fuel value and readily can be converted by known catalysts into hydrocarbons

or into methanol for use as a liquid fuel. Not only is it a demonstration that an abundant

compound can be converted into a commercially useful compound with considerably

less energy input than current methods, it also is a method not so different from what

organisms regularly do. Source: newKerala online, 3/9/2010.

Refined Path from Biomass to Biofuel…

The challenge of economically converting lignocelluosic biomass into transportation

fuels is to develop efficient chemistry that minimizes processing. In a bid to meet

that challenge, Jesse Q. Bond, James A. Dumesic, and coworkers at the University of

Wisconsin, Madison, have devised an integrated flow-reactor system for converting the

versatile biomass-derived feedstock γ-valerolactone into ready-to-use gasoline and jet

fuel. The Wisconsin team’s method improves downstream processing of γ-valerolactone

by first using a silica-alumina catalyst to open the ring and decarboxylate aqueous

γ-valerolactone to a mixture of butenes and CO 2

. The butenes are subsequently strung

together by using an amberlyst catalyst to form octenes and higher alkene oligomers

with molecular weights and branching that can be selectively formulated as gasoline

or jet fuel. The new approach provides several bonuses. It avoids costly preciousmetal

catalysts and doesn’t require an external source of H 2

. And although the process

generates CO 2

as a by-product, the reactor design allows the CO 2

to be trapped as a

relatively pure, pressurized stream that could be readily sequestered or used to make

methanol or polycarbonates. Source: Chemical & Engineering News, 3/1/2010, p. 34.

Thin Sheets of ZSM-5 Constitute Zeolite

Membrane…

Researchers from Osaka Prefecture University, Stockholm University and the Korea

Advanced Institute of Science and Technology (KAIST) have synthesized sheets of

ZSM-5 (MFI type) zeolites that are only 2 nm thick, which corresponds to the b-axis

dimension of a single MFI unity cell. The sheet structure is said to improve the surfaceto-volume

ratio compared to conventional zeolite catalysts: the larger number of acid

sites on the external surface of the zeolite sheets have been demonstrated to impart

a higher catalytic activity for the cracking of large organic molecules. The reduced

crystal thickness also facilitates diffusion, thereby dramatically suppressing catalyst

deactivation through coke deposition during methanol-to-gasoline conversion, says

Osaka’s Yasuhiro Sakamoto. The scientists believe the synthesis approach – which

involves crystallization in bifunctional surfactants – could be applied to make other

zeolites with improved catalytic performance. Source: Chemical Engineering, 2/2010.

Co-Catalyst Tag

Team…

Adding a chiral urea’s embrace to a

ring-forming reaction catalyzed by an

achiral Brønsted acid renders the process

highly enantioselective, chemists at

Harvard University have found. The

work could inspire a general strategy

for using organocatalysts to perform

enantioselective transformations on

cations. Several teams have already

used “cooperative catalysis” that pairs

a metal catalyst or organocatalyst

with a cocatalyst to achieve selective

bond formations. Eric N. Jacobsen and

colleagues have now applied that school

of thought to a strong acid-catalyzed

cycloaddition that forms a heterocyclic

motif common in bioactive compounds.

On its own, the Brønsted acid reacts with

an imine substrate to form a reactive

cationic intermediate, leading to a fast

but nonselective reaction. But add the

chiral urea, and things change, according

to the team’s kinetic, spectroscopic, and

computational data. The urea interacts

with the cation via a network of hydrogen

bonds and a π-π interaction. Effectively,

this enzyme-like strategy slows the

reaction and blocks one face of the

cation, permitting formation of only one

enantiomer, Jacobsen says. The team

plans to extend this controlled reactivity

to other classes of cations. Source:

Chemical & Engineering News, 2/22/2010,

p. 35.

In a computer model, a chiral urea (blue)

binds the anion of a Brønsted acid (yellow)

and blocks one face of the cation (red) in a

cycloaddition, allowing a reaction partner

(green) to approach from only one side.

The Catalyst Review March 2010

5


ENVIRONMENTAL

Special Feature

Direct Coal Liquefaction:

Insights from Patent Analytics

Introduction:

With the ever growing demand for petroleum based fuels, scientists and

researchers worldwide are working on alternative transportation fuels. The

liquefaction of coal, both Direct(DCL) and Indirect(ICL) routes had been

commercialized prior to the Second World War in 1930s-40s in Germany and UK.

Following the War, all the DCL plants were shut down due to the low cost and availability of petroleum feedstocks. Extensive research

had been conducted by industry as well as governments through funded projects. During the last five decades, only the ICL route

developed by SASOL in South Africa through the Fischer-Tropsch process (patented in 1925) has been commercially practiced. The

development of direct coal liquefaction has been stimulated in the past whenever there were shortfalls in supply of petroleum/crude

oil and sharp increases in prices. Indeed, interest in DCL has picked up and a first train of a commercial plant is now in operation at

Shenhua, China. However, this DCL plant is the only one of seven total coal-based demonstration plants being developed in Western

China. There are several plants in the planning stages in India and USA, but none are being developed, as yet. This inspired us to

take a critical look into the recent patent filing activities in the DCL area in order to analyze the key patent filers, their associated

technology, trends in technology, etc.

This Special Feature highlights the patent activity of the last decade and the current state-of-the art in direct coal liquefaction

technology. Recent advancements in the technology are identified through an analysis of patents for the period of the last ten years

(1999-June, 2009). These patent analytics based findings are consistent with the above-mentioned commercial activities in the DCL

technology.

Methodology:

A patent search has been conducted on Patweb in Micropat. Patweb covers patents filed in US, Japan, European Union, Germany,

France and Great Britain, for the designated period. The patents which are filed in other countries and have equivalent filings in the

above countries are also considered for the study.

The search was conducted for the period January 1999 to June 2009 using a combination of keywords related to direct coal

liquefaction and International Patent Classification (IPC) codes.

The search results were screened manually to identify relevant patents. The relevant patents thus obtained were analyzed using

several technical parameters. The resultant patent analyses are used to draw different patent maps which in turn are used to identify

filing activity of key players, different schemes of direct coal processes, catalysts, technology trends, research collaborators, etc.

State-of-the-art:

The synonyms of coal used for the patent search on Micropat are anthracite, lignite and peat. The IPC codes used for searching are

all sub-groups used under C10G 1/00. This classification code indicates production of liquid hydrocarbon mixtures from non-melting

solid carbonaceous materials such as coal, wood etc. The total number of relevant patents in this area after manual screening was

found to be 31 over the last 10 years.

The leading companies from patent filing activity (See Figure 1) are Zhaoqing Shunxin Coal Chemical Industries, Agency of Industrial

Science and Technology, Kobe Steel, Mitsui Engineering and Shipbuilding, Accelergy Corp and Max-Planck Institute. All these

companies have two or more patents globally. The intent of companies is watched based on their unique technologies and the

number of new patents filed. Multiple patents filed across different countries, for a given invention, are treated as one entity/patent.

It is quite clear that the DCL technology is dominated by Chinese and Japanese companies as most of the above companies belong to

these two countries except Accelergy which is US-based and Max Planck, which is based in Germany.

Source: West Virginia University

6

The Catalyst Review March 2010


ENVIRONMENTAL

Four patents by China-based Zhaoqing

Shunxin disclose hydrogenation catalysts

which are used for liquefaction of coal and

for supplying the necessary hydrogen. The

catalysts used in the process are sulfides

of Group VIB or VIII on an alumina carrier.

Agency of Industrial Science and

Technology (AIST), in Japan, has filed

two patents in collaboration with Mitsui

Sekitan Ekika, Nippon Steel Corp, Asahi

Chemical Industrial Co Ltd and Catalysts

& Chemical Industries Co Ltd. The two

patents disclose prevention of catalyst

aggregation and preparation of iron hydroxide catalyst for liquefaction. Another patent by AIST alone discloses novel hydrogenation

catalyst composition.

Two patents by Kobe Steel describe improving cetane number of light oil produced from liquefied coal. Another patent by the same

company discloses the use of iron ore in hydrogenation process for improving yield of coal liquefaction.

Two patents by Mitsui Engineering and Shipbuilding disclose a novel method for hydrogenolysis of coal and organoborane-halogen

compounds/ halogenohydroboranes as catalysts.

US based Accelergy’s patents are based on integration of direct and indirect coal liquefaction. Indirect liquefaction of coal is through

gasification and the Fischer–Tropsch process.

Germany-based Max-Planck Institute’s patents focus on borane based catalysts for hydrogenation/ hydrogenolysis of coal.

Patents by Zhaoqing Shenxin, Kobe Steel

and Accelergy Corp are very recent

with priority dates during 2006-2007.

The patent filing activity is found to be

increasing with nearly 45% of the number

of patents filed during 2006-2007.

Along with these major active players,

there are new entrants such as Hanergy

Tech, Combustion Resources and a few

independent inventors. It is noteworthy

that even the independent inventors

and collaborators are mostly from Japan,

China, Germany and only one from US

(a full list of independent inventors is

included in the references and can be

provided upon request).

Patent filing activity is high in the

countries Japan, China, US and Australia.

Also, significant number of applications

has been filed through the PCT 1 route (vs.

other, traditional or more likely route).

All of the four patents by Zhaoqing are

Figure 1: Leading Companies in Direct Coal Liquefaction

5

0

5

Independent

Inventors

Zhaoqing

Shunxin Coal

Chemical

4 4

3 3 3

Source: Dr. Madan M. Bhasin, Innovative Patent Solutions

2 2

through PCT route and it has entered national phase in China. None of the major players listed in Figure 3 have filings in US indicating

stronger interest in patenting DCL away from USA and primarily in Asia and Europe. This is reasonable given the strong interest in

developing/commercializing in Asia and Europe. Eni technologies seems to be the only company interested in South Africa.

Collaborations

1

1

Mitsui

Shipbuilding

Eng

2

1

2

Kobe Steel Ltd

Agency Ind

Science Techn

2

1

1

Max-Planck

Institute

Figure 2: Patent Filings by Year of Companies, Collaborators and Independent

Inventors

6

4

2

0

1999

2000

1

2001

2002

2003

1 1 1

2

1

1 1 1

2

1 1

1

1

1

1

1

1

2004

2005

2006

2007

Mitsui Shipbuilding Eng

Accelergy Corp

Max-Planck Institute

Combustion resources

Hydrocarbon Technologies Inc

Motoyama Eng Works Ltd

Hanergy Tech Co Ltd

Toshiba Corp

Enitechnologie S P A

Hitachi Medical Corp

Accelergy Corp

2

Independent Inventors

Collaborations

Zhaoqing Shunxin Coal Chemical

Agency Ind Science Techn

Kobe Steel Ltd

The Catalyst Review March 2010

7


ENVIRONMENTAL

The liquid fuels obtained from direct coal

liquefaction are hydrocarbon oils such as

gas oil, light oil, kerosene, motor spirit

etc.—directed towards the respective,

localized interests/needs and/or the novel

features of the patent applications.

Iron based catalysts such as iron hydroxide

and iron disulfide are widely used catalysts

for coal liquefaction. Zhaoqing Shunxin

broadly discloses hydrogenation catalysts

used for coal liquefaction. Metal sulfides

of Group VIB or Group VIII supported

on alumina are used by Zhaoqing for

hydrogenation. Max-Planck Institute uses

boranes and iodine based catalysts for

coal liquefaction.

Patent assignees and process steps

are plotted on x and y axes and the

number of patents is taken on the

z-axis in Figure 5. The process steps are

retrieved from a brief manual analysis

of patent documents. Liquefaction

and hydrogenation are the widely

used techniques for converting coal to

liquid. Kobe Steel’s patents deal with

hydrogenation which is followed by

distillation. Two patents by Max-Planck

Institute deal with hydrogenation followed

by liquefaction.

Combining Information from different

sources:

Knowledge generated from patent

analytics can be useful for making a range

of business decisions. But, combining

patent information with commercial

information generated from market

research reports, news items etc. will

provide more authentication for making

decisions.

A search conducted on recent news items

revealed following details on direct coal

liquefaction:

• Axens (Paris), a petrochemicals

technology provider, and Headwaters

(South Jordan, UT), a materials

technology firm, say they have

created a joint venture company

Alliance DCL, to provide solutions for

producing clean transport fuels via

direct coal liquefaction (DCL). ----

Chemical Week Business Daily | 20

January 2010

Figure 3: Patent Filings by Countries and Companies

6

4

2

0

1 2 2 1 1 1 1 1 1

2

4

1

1 2

1 1

2

2 1 1

2 2

1 1

2

1 1 1

1 1

1

1 1

1

1 1 1 1 1 1 1

1 1 1 1 1 1 1

US

JP

CN

DE

EP

AU

CA

RU

LT

PL

ZA

PC

Combustion resources

Hydrocarbon Technologies Inc

Motoyama Eng Works Ltd

Hanergy Tech Co Ltd

Toshiba Corp

Enitechnologie S P A

Hitachi Medical Corp

Accelergy Corp

Max-Planck Institute

Source: Dr. Madan M. Bhasin, Innovative Patent Solutions

Figure 4: Use of Various Catalyst Types by Companies

6

4

2

0

2

3

1

1

1 1 1

2 2

2

1

Source: Dr. Madan M. Bhasin, Innovative Patent Solutions

Independent Inventors

Collaborations

Zhaoqing Shunxin Coal Chemical

Agency Ind Science Techn

Kobe Steel Ltd

Mitsui Shipbuilding Eng

1 1 1 Independent Inventors

1 1

Collaborations

1

Enitechnologie S P A

Iron based

Iodine based

Borane

Metal sulfide of Group VIII

Metal sulfide of Group VIB

Group VIII metals

Group VIA metals

Nickel-Mo and nickel-W

Molybdenum

Co-Mo oxide

Co

Without catalyst

Hanergy Tech Co Ltd

Hitachi Medical Corp

Studiengesellschaft Kohle Mbh

Kobe Steel Ltd

Mitsui Shipbuilding Eng

Agency Ind Science Techn

Zhaoqing Shunxin Coal Chemical

Figure 5: Patent Assignees as a Function of Various Processing Steps

6

4

2

0

1

1 3

Zhaoqing Shunxin Coal Chemical

Kobe Steel Ltd

Max-Planck Institute

Accelergy Corp

Agency Ind Science Techn

Toshiba Corp

Hydrocarbon Technologies Inc

Hitachi Medical Corp

Hanergy Tech Co Ltd

Enitechnologie S P A

Combustion resources

Collaboration

Independent Inventors

1

2

Source: Dr. Madan M. Bhasin, Innovative Patent Solutions

2

1

1 1 1 1

1

1

1

1

1

1

1

1

Adding Tetralin to coal

Biological treatment

Hydrog.

Hydrog., Distill.

Hydrog., Liquef.

Hydrogen generation, Hydrog. & Distill.

Liquef.

Liquef., Distill. & extraction & Hydrog.

Liquef., Distill. & Hydrog.

Liquef. with supercritical/ subcritical

water

Radiation-irradiated coal Liquef.

Thermal Dissolution Catalysis

Thermomechanical cracking, Hydrog.

8

The Catalyst Review March 2010


ENVIRONMENTAL

• Accelergy Corporation, a leading alternative energy technology company, announced a global licensing agreement with

ExxonMobil Research and Engineering Company (EMRE), for Accelergy to produce liquid fuels and chemicals from abundant coal

resources using EMRE technology. --- Energy Business Journal | 30 December 2009

• China's largest coal producer Shenhua Group will start the second trial of its direct coal liquefaction project in July 2009, in a bid

to collect data and economic indicators from 1,000-hour operation. --- SinoCast | 25 June 2009

• According to Axens researcher John Duddy at the World CTL 2009 conference in Washington, D.C., last month, Axens prepared

basic engineering design and provided start-up support for the Shenhua DCL plant. --- Gasification News | 29 April 2009

• Quantex Energy Inc. announced that it has entered into a Letter of Intent with CES Environmental Services, Inc. and Port Arthur

Chemical & Environmental Services, LLC for the construction of a Commercial Demonstration Unit (“CDU”) in Port Arthur,

Texas (the "Project Site"). The CDU will allow the Company the opportunity to demonstrate its bio-hydrogenated, direct coal

liquefaction technology, capable of converting coal to heavy oil for refineries and other high value carbon products such as green

coke for the metals and aluminum industries. The CDU will use the patent pending direct liquefaction process (the "Quantex

Process") developed by West Virginia University and licensed exclusively to Quantex. --- Canada Newswire | 08 April 2009

• Indonesia's PT Tambang Batubara Bukit Asam (PTBA) said it has asked South Africa Synthetic Oil Ltd (SASOL) to involve other coal

miners in a US$10 billion venture to build a coal-liquefaction plant in the country. --- Asia In Focus | 19 February 2010

From the above analysis of news items, it is understood that there were companies which have technical know-how in direct coal

liquefaction technology which do not appear among patenting companies.

Conclusions:

1. The representative patent analyses conducted, for the last decade (1999-June, 2009) gives a good picture of the companies,

research institutes and independent inventors conducting research and development in the area of direct coal liquefaction (DCL).

2. It is quite evident that Japan and China, followed by Germany and USA, are the key players in patent filings. This is consistent with

the immediate and urgent interests of these countries for a coal-based, alternate feedstock to produce liquid fuels for vehicular

applications, particularly since these countries do not have sufficient abundance of crude oil for their respective growing internal

needs. Furthermore, it is also important to reduce dependence on imported crude oil.

3. Though a large variety of catalysts are described and claimed in these patent filings, iron and iron-based catalysts are dominant

followed by Co, Ni, and Mo based catalysts. Though the costly, noble metal catalysts are described, the emphasis is definitely more

on non-noble metal catalysts.

4. Most of the patent filings from China are from 2006 onwards and significantly, all have been filed as PCT applications but entered

into China only.

5. All, except one, collaborators and independent inventors are from Japan and China—emphasizing again the intense activity on

DCL in these regions.

6. Finally, the insights derived from such patent analytics (along with more detailed drill-down of technology), when combined

with market research information, provide valuable competitive intelligence information and can be helpful in making strategic

decisions in areas such as licensing, mergers/acquisitions and other patent/IP related issues.

References:

1. Patent references are available by contacting thecatalystreveiw@catalystgrp.com

2. http://www.ifp.com/information-publications/notes-de-synthese-panorama/panorama-2008/la-liquefaction-du-charbon-ou-enest-on-aujourd-hui

3. http://www.indiatogether.org/2008/jul/eco-ctlpolicy.htm

4. Information on news items: Onesource

1

The PCT (Patent Co-operation Treaty) system enables an applicant to file a single patent application. The application, called an international application, can, at a

later date, lead to the grant of a patent in any of the states contracting to the PCT.

The Catalyst Review March 2010

9


ENVIRONMENTAL

Author Bios:

Dr. Madan Bhasin is CEO of Innovative Catalytic Solutions, LLC (www.inocatsol.com), which provides novel consulting services

to industrial, academic, and governmental organizations. The company helps accelerate or catalyze the research, development,

and commercialization of new concepts/ideas, or concept to commercialization (c2C©TM). The company specializes in chemical,

petrochemical, catalyst, and materials including all related analytical/surface characterization techniques and the planning of

experiments. Innovative Catalytic Solutions has developed alliances with three leading industry research, patenting, and consulting

companies in the world! These include: The Mid-Atlantic Technology, Research & Innovation Center, Inc. (MATRIC), West Virginia,

U.S.A., a non-profit research, development, engineering, and technical commercialization organization currently employing over

100 world-class scientists and engineers; SciTech Patent Art, of Hyderabad, India which provides high value-added patent and intellectual property

services to global clients; and The Catalyst Group (TCG) headquartered in Pennsylvania, U.S.A., with offices worldwide. He founded a joint venture,

Innovative Patent Solutions, with SciTech Patent Art. Dr. Bhasin holds a Ph.D from the University of Notre Dame, masters work from Indiana

University (US) and Atomic Energy Establishment (India), as well as a B.S.c (Honors) from the University of New Delhi (India).

Madan has also been a major contributor to research in the areas of Hydrocarbons and Energy, specifically in alternative feedstocks and methane

activation. He published landmark papers and patents in the area of methane coupling, holds more than 21 United States patents, and authored

numerous papers in the areas of catalysis and industrial chemistry. In building an impressive career, Madan received several national and

international awards for his work, including the Industrial Research Institute Achievement Award in 2002, the AIChE Award in Chemical Engineering

Practice in 2001, the American Chemical Society Award in Industrial Chemistry in 1999, and The Eugene Houdry Award of the North American

Catalysis Society in 1995. In 2006, Madan was elected into the National Academy of Engineering. He was also elected a fellow of the Industrial &

Engineering Chemistry Division of the American Chemical Society in 2008. He was elected a Fellow of the American Chemical Society, in the First

class of Fellows, in August 2009.

Mr. Balakrishna Uppala holds an M.Tech (Chemical Engg.) from National Institute of Technology, Warangal (India) and currently

works for SciTech Patent Art Services Pvt. Ltd., as an Assistant Manager of Client Relations. SciTech Patent Art Services is a

leading Intellectual Property technology services firm with offices in India and the US.

The “Intelligence Report 2010”

An Opportune Time to Reset Expectations and Implement Changes

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pragmatically implement changes for 2010-11 and beyond. For this reason, a subscription to this year’s “Intelligence Report,”

TCGR’s market assessment and technology evaluation of the catalytic process industries is worthwhile. The opportunities in

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these expectations. Our 2010 “Intelligence Report” will be a vital reference for all of your business segments, as it has been for

the last 26 years!

The Intelligence Report 2010 will address key topics such as:

• Maximizing feedstock value by optimizing technology choices

• Downward pressure on refi nery margins

• A predicted return to volume growth in the medium-term promises gains in alternative routes to olefi ns

The overhang of capacity additions in petrochemicals, nonetheless, is expected to impact returns for an extended period.

• Regional factors will continue to impact how and where technology development takes place.

The 2010 edition will also include a "Special Feature" section on the role of catalytic and membrane technologies in

addressing the challenges of CO 2

and greenhouse gases (GHG).

Key Benefi ts of The Intelligence Report 2010 include:

• Comprehensive, concise industry statistics on adjusted catalyst volumes and values including forecasts

• Producer-and user-specifi c developments in production and technology, including alliances, ventures and acquisitions/

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http://www.catalystgrp.com/intelreport2010.html or contact John J. Murphy at John.J.Murphy@catalystgrp.com.

10

The Catalyst Review March 2010


EXPERIMENTAL

Exceptionally Active Single-Site Nanocluster Multifunctional Catalysts

for Cascade Reactions...

Recently there has been discussion of the merits of nanoparticle metals and bimetallic nanoparticles supported on silica or alumina

describing metals, such as Pt, Pd, Ru, Au, and bimetals, such as Pt-Pd, Pt-Rh, that fall in the size range from about 3 nm to 10 nm.

However, in this size range there are some 103-106 atoms present in each particle, which means that a continuous band of electronic

energy levels exists within such nanocatalysts and notwithstanding their minuteness, they are quite different electronically from

nanoclusters composed of aggregates of approximately 3-20 atoms.

Herein the authors discuss the remarkable catalytic performance of such nanoclusters, both in selective hydrogenations and in

selective ammoxidation-involving cascade processes that are of considerable industrial importance. Specifically, the structurally welldefined

nanocluster, {Cu 4

Ru 12

C 2

}, serves as a multifunctional catalyst, well-suited to effect cascade (consecutive) reactions of value in

the preparation of a number of desirable organic products.

Turnover frequencies and conversions are high for the supported {Cu 4

Ru 12

C 2

} nanocluster-catalyzed hydrogenation of 1,5,9-

cyclododecatriene, and the desirable product cyclododecene, which is much used as a builder molecule in the polymer industry, is

produced in high yield. The same nanocluster also gave good turnover and conversion in the selective ammoxidation of 3-picoline

to nicotinonitrile (vitamin B precursor). In addition, the authors show the supreme advantages of this catalyst in producing the

important polymer linker molecule 1,4-cyclohexanedimethanol (CHDM) from its parent dimethylterephthalate (DMT) via the

intermediate dimethyl hexahydroterephthalate (DMHT) (Figure 1).

Finally, based upon micrographic analysis, the authors suggest that isolated atoms or a mere few atoms anchored onto an

appropriate support could alter our thinking regarding heterogeneous catalysts. Future work will address dynamic, real time, in situ

studies of supported catalysts at operating temperatures typical of many catalytic reactions using recently developed instruments

such as AC-TEM and AC-STEM (aberration-corrected scanning transmission electron microscopy). Source: ChemCatChem early

preview, 1 – 5; Thomas et al.

Figure 1: Two examples of the exceptional catalytic performance of the

anchored {Cu 4

Ru 12

C 2

} nanocluster: The cascade hydrogenation of 1,5,9-

cyclododecatriene (353 K; 2 MPa H 2

) and the selective ammoxidation of

3-picoline (403 K; 2 MPa NH 3

; 4 MPa air) to yield vitamin B3 (niacin).

The Catalyst Review March 2010

11


EXPERIMENTAL

Light-Driven Hydrogen Generation: Efficient Iron-Based Water

Reduction Catalysts...

Hydrogen is considered to be an attractive

energy source, since it can be used in a

clean and highly efficient manner in fuel

cells. A current drawback for the wider

use of hydrogen is the dependence of

hydrogen production on fossil resources

by reforming processes. A more benign

objective is the conversion of the almost

unlimitedly available energy of sunlight

into non-fossil-based energy carriers such

as hydrogen using water as the hydrogen

source.

In the late 1970s, the first homogeneous

multicomponent systems for water

reduction employing photosensitizers

(PS) and noble-metal water reduction

catalysts (WRC) were established.

The general principle of these water

reduction cascades was adapted from

nature, where reduction equivalents are

generated by light in combination with

coupled redox cycles in photosystems II

and I. In such a cascade an iridium PS, for

example, is excited by light irradiation

and subsequently reductively quenched

by the SR to give the reduced species Ir

PS. This compound immediately transfers

an electron onto the Fe WRC, which then

reduces aqueous protons to hydrogen.

Thus both the WRC and the PS are

required for a catalytic cycle (Scheme 1).

Scheme 1: Principle of light-driven water reduction cascade with

iridium photosensitizer (Ir PS), sacrificial reagent (SR), and an iron

water reduction catalyst (WRC).

Scheme 2: Proposed mechanism for the reduction of aqueous

protons by iron carbonyls and PS.

The authors have developed a novel,

convenient, bimetallic system for water

reduction cascades consisting of simple,

cheap, and readily available iron(0)

carbonyls; TEA as a sacrificial reagent;

and an iridium photosensitizer. The

activity for the iron water reduction

catalyst is the highest for any iron water

reduction system known to date and can

compete with the known cobaloxime

water reduction catalysts. The proposed

mechanism is given in Scheme 2. Source:

Angew. Chem. Int. Ed. 2009, 48, 9962-

9965; Gärtner et al.

12

The Catalyst Review March 2010


EXPERIMENTAL

Lipase-Catalyzed Polycondensation in Water: A New Approach for

Polyester Synthesis...

Reaction engineering is a valuable tool to overcome bottlenecks in (bio)chemical reactions. In particular, biphasic reaction systems

promise to have a great potential to optimize reactions concerning space-time yield and selectivity. In biphasic media the second

phase can either be used to increase the substrate concentration in the whole reaction system, or it allows an integrated product

removal (IPR). Apart from this, the benefits of biphasic reaction media can help to suppress side and consecutive reactions.

Herein, the authors demonstrated that the lipase-catalyzed polycondensation of sebacic aid and 1,4-butanediol can be performed in

a biphasic reaction system composed of an aqueous reaction phase and an organic extraction phase.

Figure 1: Calculated and experimentally

determined partition coefficients of 1,4-butanediol

and 1,6-hexanediol in n-heptane (a)

and MTBE (b) at 50 °C.

In this biphasic reaction system the product yield, molecular

weight and polydispersity are dependent on the partitioning of

the substrates and the product between the phases (Scheme

1). By determining and optimizing the influence of temperature,

pH, monomer structure, and nature of the extraction phase,

the polyester concentration was increased up to 98% yielding a

product with a very narrow molecular weight distribution (PDI

between 1.02-1.05). Such products are of significant interest as

additives.

In addition to conversion data, the partition coefficients were

investigated either experimentally and/or via calculation by the

quantum chemical program COSMO-RS. The tendencies of the

calculated partition coefficients veer towards the experimental

data and can indicate the efficiency of phase transfer (Figure

1). Source: Organic Process Research & Development 2010, 14,

48–57; Duwensee et al.

Scheme 1: Schematic illustration of the

polycondensation of sebacic acid and 1,4-

butanediol in the biphasic reaction system.

The Catalyst Review March 2010

13


EXPERIMENTAL

Remote Control of Regio- and Diastereoselectivity in the Hydroformylation

of Bishomoallylic Alcohols with Catalytic Amounts of a Reversibly

Bound Directing Group...

The hydroformylation of olefins is the largest volume application of homogeneous catalysis in industry with about 9 million tons

of oxo-products produced worldwide annually. Despite the obvious advantages associated with this approach, hydroformylation

of olefins is still not commonly employed in the course of a complex synthesis, because of the difficulty in controlling regio- and

stereoselectivity simultaneously.

Although a number of catalysts exist today that allow the hydroformylation of terminal aliphatic alkenes to give linear products

selectively, no catalyst is known for a general hydroformylation of terminal and internal alkenes to give branched products selectively.

One approach to this problem has been the use of removable catalyst-directing groups covalently bound to the substrate which

facilitate both regiocontrol and acyclic stereocontrol in reactions of allylic and homoallylic alcohols. However, such an approach

requires additional steps for introduction and removal of the directing group as well as the need for stoichiometric amounts.

Previously the authors identified

diphenylphosphinites as ideal systems

for the reversible transesterification

of alcohols under hydroformylation

conditions, suggesting that a highly

regioselective hydroformlyation of

homoallylic alcohols could be realized

using this catalyst system to furnish

γ-lactols in excellent yields (Scheme

1,a). The basis for the observed high

regioselectivity is believed to be due

transition state effects in which the

functional hydroxy group to which the

directing group is bound has a 1,3-relation

to the reacting functional group.

Now they report that it is possible to

shift the hydroxyl function to which the

directing group becomes bound yet one

more atom further away from the reacting

functional alkene group into a remote

1,4-relation (Scheme 1,b) and still get

excellent levels of both regioselectivity

and diastereoselectivity in the course

of the hydroformylation of terminal and

internal bishomoallylic alcohols in which

only a catalytic amount of a catalystdirecting

group is employed. The new

method allows for atom-economical

preparation of a wide range of δ-lactols

and lactones and even structural units

of polypropionate natural products—all

of which are important building blocks

in organic synthesis (Table 1). Source:

Angew. Chem. Int. Ed. 2010, 49, 967 –970;

Grünanger and Breit

Scheme 1: Remote control of regioselectivity in the hydroformylation of

homoallylic and bishomoallylic alcohols.

Table 1: Results of the phosphinite-directed branched-regioselective

hydroformylation of bishomoallylic alcohols.

14

The Catalyst Review March 2010


EXPERIMENTAL

Next-Generation Catalysis for Renewables: Combining Enzymatic with

Inorganic Heterogeneous Catalysis for Bulk Chemical Production...

The conversion of biomass necessitates the development of a new generation of catalysts that enable new kinds of reactions,

processes, and conditions than those conventionally employed. Both enzymatic catalysis (biocatalysis) and heterogeneous inorganic

catalysis are likely to play a major role and, potentially, be combined. One type of combination involves one-pot cascade catalysis

with active sites from bio and inorganic catalysts as key components in the development of a biorefinery - a facility that integrates a

number of processes in biomass conversion to produce fuels, power, and chemicals.

Currently, three phases can be

distinguished in the development of

biorefineries (Figure 1, top). Limiting

the discussion to the feedstock and

available conversions, the three phases

in biorefinery development can briefly be

described as follows. A phase 1 biorefinery

holds limited and fixed processing

possibilities with feedstocks limited to

simple sugars. A phase 2 biorefinery

operates with more sophisticated process

options, focusing on different integrated

and flexible product solutions that can

be adjusted to meet market demands.

In a phase 3 biorefinery, the focus is

not fixed upon the product range but

rather on flexibility in the use of various

feedstocks for adaptability towards supply

and demand in animal feed, food, and

industrial commodities.

Figure 1. Overview of different biorefinery scenarios depending on the

overall feedstock.

Transportation, availability and demand

for the feedstock are all important factors

when it comes to what type of biorefinery

is best suited for a specific location

and whether the production should

be centralized or decentralized. In this

respect, three different approaches for

the production of chemicals and fuels are

debated (Figure 1, bottom).

The authors discuss new routes and combinations which can be envisioned when considering these combined systems that would

otherwise be difficult or impossible with conventional conversion methods. However, these new systems do have some limitations.

Combinations are only possible within a limited and defined set of reaction conditions and catalyst kinetics must be matched. For

the same reason, deactivation issues become more critical. Furthermore, regeneration and separation of used catalysts must be

developed for commercial purposes. A new generation of catalysts able to withstand aqueous conditions and match the conditions

of biocatalysis is needed in a chemicals industry that will be increasingly reliant on renewable feedstocks. The authors therefore

propose that more emphasis be placed on systems integrating enzymatic and heterogeneous catalysts in one-pot cascade reactions

because such conversions offer a new approach to a chemical industry in need of new catalyst designs. Source: ChemCatChem 2010,

2, 249 – 258; Vennestrøm et al.

The Catalyst Review March 2010

15


EXPERIMENTAL

Transition Metal–Tungsten Bimetallic Catalysts for the Conversion of

Cellulose into Ethylene Glycol...

Cellulose is the most abundant source of biomass and generally accounts for 30–60 wt% of dried plants - which explains why so much

effort has been devoted to the development of a green and effective process for cellulose conversion (fermentation with enzymes to

produce ethanol, thermo-pyrolysis to biooils and syngas, and hydrolysis with dilute acids in ionic liquids to yield oligomers).

Recently it was reported that the direct conversion of cellulose into ethylene glycol (EG) could be achieved via a heterogeneous

catalytic reaction under hydrogen atmosphere and hydrothermal conditions. Using an active-carbon-supported tungsten carbide

catalyst (W 2

C/AC), cellulose was completely depolymerized and EG was produced with a yield of 27% which could be increased to

61% by the addition of nickel to the catalyst.

Herein, the same workers developed a series of bimetallic catalysts for the cellulose conversion, including Ni–W, Pd–W, Pt– W,

Ru–W, and Ir–W, supported on different carriers. A remarkable synergy was observed between tungsten and metals of groups 8, 9,

and 10 [M(8,9,10)] leading to a 74.5% maximum yield of EG using a Ni–W/SBA-15 catalyst. Moreover, it was found that the product

selectivity can be tuned effectively by changing the weight ratio of W to M(8,9,10). The reaction results for the conversion of

cellulose into polyols over monometallic and tungsten-based bimetallic catalysts are summarized in Table 1.

Table 1. Results of cellulose conversion and yields of main products.[a]

Because the cellulose transformation

under these conditions involves

many reactions, including hydrolysis,

hydrogenation, and C-C cracking, a good

balance between hydrogenation and C-C

cracking will determine the final product

distribution. Therefore, by changing

the weight ratio of M(8,9,10) to W, one

can effectively tune the competition

between hydrogenation and C-C cracking

capabilities, and accordingly the selectivity

towards ethylene glycol. This rule will

guide the design of more-efficient

catalysts for the catalytic conversion of

cellulose into a desired polyol. Source:

ChemSusChem 2010, 3, 63–66; Ming-Yuan

Zheng et al.

PET Project: Using Organic Catalysts to Make More Biodegradable

Plastics...

A team of IBM and Stanford University researchers report they have created a new family of organic catalysts that could be used to

make plastics that are free of metal and fully recyclable. "The idea is to make a class of polymers that's fully biodegradable," says

Spike Narayan, manager for science and technology at IBM's Almaden Research Center in San Jose, Calif. Organic catalysts are those

made from carbon, hydrogen, sulfur and other nonmetallic elements. IBM and Stanford report having demonstrated that organic

catalysts can rival even highly active metal-based catalysts while being environmentally benign. They also think their research could

lead to a new recycling process that can break polymers back down into reusable monomers.

IBM's next step is to launch a pilot PET recycling project with scientists from King Abdulaziz City for Science and Technology (KACST)

in Saudi Arabia. This additional research will help determine whether the new organic catalysts can help develop plastic products that

are cheaper and more easily recycled. In an interesting twist for Saudi Arabia, greater use of recycled plastics means there will be less

demand for petroleum to make new plastics. Source: Scientific American online, 3/9/2010.

16

The Catalyst Review March 2010


EXPERIMENTAL

A Comparative In Situ HP-FTIR Spectroscopic Study of Bi- and

Monodentate Phosphite-Modified Hydroformylation...

The hydroformylation of olefins by homogeneous transition metal catalysis represents one of the most important C-C coupling

reactions in industry. Rhodium complexes are known to form highly active catalysts that allow for the use of mild reaction conditions.

Extensive research has been performed in the field – with detailed mechanistic insight gained using a combination of kinetic methods

with modern spectroscopic analysis carried out under reaction conditions. In situ high-pressure (HP) FTIR and NMR spectroscopic

techniques are appropriate diagnostic tools applied in hydroformylation.

The generally accepted mechanism for ligand-modified rhodiumcatalyzed

hydroformylation is depicted in Scheme 1 and a

detailed explanation is provided- giving impetus to the author’s

efforts to conduct an in situ FTIR spectroscopic study of the

phosphite-modified rhodium-catalyzed hydroformylation of

3,3-dimethyl-1-butene accompanied by gas chromatographic

analysis. As ligands, the bidentate O-acyl phosphite A and the

bulky monophosphite tris(2,4-di-tert-butylphenyl)phosphite B,

olefins were chosen (Scheme 2). Ligand A is known to behave

differently from known diphosphites, but forms a powerful

rhodium catalyst for the isomerizing hydro-formylation of

internal olefins. One remarkable detail of the structure of A

is the sterically demanding substituted 2,2’-dioxydiphenyl

backbone, characteristic for a prominent family of ligands

that induce high regioselectivity in rhodium-catalyzed

hydroformylation and which have been reported for the first

time in the patent literature. Contrasting results concerning the

catalyst preformation in the presence of B and similar ligands

have been reported, and encouraged these workers to focus on

the Rh–B catalytic system in a more comprehensive and timeresolved

manner, covering the full olefin conversion range.

3,3-Dimethyl-1-butene was selected as a substrate not capable

of double-bond isomerization, which would otherwise alter the

kinetics and qualify this olefin for kinetic in situ investigations. To

exclude ligand decomposition, especially that by acid-catalyzed

ligand hydrolysis with water (formed subsequently from

product aldol condensation), all investigations were performed

in the presence of a noncoordinating strongly basic 2,2,6,6-

tetramethylpiperidine-4-ol carboxylic acid ester derivative known

to act as a phosphite stabilizer.

The comparative study of a mono- and a diphosphite in the

ligand modified rhodium-catalyzed hydroformylation of 3,3-

dimethyl-1-butene leads to the conclusion that the change of

the reaction order with respect to the terminal olefin during

hydroformylation is a phenomenon not generally restricted

to monodentate ligands. Additionally, the view that catalysts

formed with bulky monophosphites are characterized by a

predominant acyl complex intermediate until complete terminal

olefin conversion has to be corrected. The concentration of

acyl complex decreases immediately from the onset of reaction,

with hydrogenolysis remaining the rate-limiting step over the

full conversion range. Source: ChemCatChem 2010, 2, 287 – 295;

Kubis et al.

Scheme 1: Mechanism of modified rhodium-catalyzed

hydroformylation.

Scheme 2: Hydroformylation of 3,3-dimethyl-1-butene

and ligands used in this study.

The Catalyst Review March 2010

17


Prof. Melanie Sanford, Ph.D.

MOVERS & SHAKERS

Professor Melanie Sanford received her B.S. and M.S. degrees at Yale University. She pursued graduate studies at the California Institute

of Technology working with Professor Robert Grubbs, where she investigated the mechanism of ruthenium-catalyzed olefin metathesis

reactions. Following postdoctoral work at Princeton University, she joined the faculty at the University of Michigan in the summer of

2003 as an Assistant Professor of chemistry. In spring 2007 she was promoted to her current position of Associate Professor of chemistry.

Professor Sanford has been recognized with a number of awards, including a Camille and Henry Dreyfus New Faculty Award, a Beckman

Young Investigator Award, a Research Corporation Cottrell Scholar Award, and a Presidential Early Career Award in Sciences and

Engineering, and has also been named an Alfred P. Sloan Foundation Research Fellow. In addition, she has received young investigator

awards from a number of companies, including Boehringer Ingelheim, Amgen, Eli Lilly, Bristol Myers Squibb, AstraZeneca, Abbott,

GlaxoSmithKline, Roche, and Dupont. In 2008 she received an Arthur Cope Scholar Award from the American Chemical Society, and in

2009 she was the recipient of the BASF catalysis award. Research in the Sanford group focuses broadly on the development and mechanistic study of new transition

metal catalyzed reactions for applications in organic synthesis. More specifically, the group is working to develop a diverse set of transformations for the direct

conversion of unactivated carbon-hydrogen bonds into new functional groups with high levels of chemo-, regio-, and stereoselectivity. Professor Sanford can be

reached at mssanfor@umich.edu or at (734) 615-0451.

The Catalyst Review asked “In your view, what are the prospects for catalytic

C-H functionalization in commercial processes”

In the field of Pharmaceuticals/Agrochemicals: The past 10 years has seen significant progress in the development of single

site catalysts for the direct conversion of C–H bonds into C–X bonds (X = O, N, F, Cl, Br, I C, S, B) in the context of complex

organic substrates. 1,2,3 With appropriate catalyst design and substrate selection, these reactions can proceed with high

selectivity, high TONs, and high TOFs. Such reactions have already been applied to the synthesis of numerous complex

biologically active molecules, including incarvillateine, 2 lithospermic acid, 2 6-deoxyerythronolide B, 4 and celogentin C. 5 In

addition, transformations of this type have been utilized for elaboration of several commercial pharmaceuticals, including

gemfibrozil, ibuprofen, and flurbiprofen. 6 Thus, these catalytic methods are poised to be employed in a commercial

pharmaceutical and/or agrochemical process in the context of an appropriate molecule. Such applications are likely to start to

start emerge very soon.

In the field of Fuels/Commodity Chemicals: The development of new commercial processes based on single-site catalysts for

direct C–H bond functionalization in the context of commodity chemical/fuel applications likely has a somewhat longer horizon.

Nonetheless, significant fundamental efforts and breakthroughs are in progress in this area. The vast majority of recent work

has focused on the direct catalytic oxygenation of methane to form methanol or derivatives. The Catalytica system (a Pt-based

homogeneous catalyst that converts CH 4

to CH 3

OSO 3

H) 7 shows significant promise, and second generation catalysts designed

to address limitations of sub-optimal TOF’s and product inhibition are currently in progress. 8,9,10 Other relevant processes

being targeted include catalysts for directly converting methane to higher alkanes, benzene to phenol, and benzene to aniline.

In the US, two federally-funded research centers have been formed to address these types of big challenges for C–H

functionalization catalysis: the National Science Foundation-funded Center for Enabling New Technologies through Catalysis

(CENTC) and the Department of Energy-funded Center for Catalytic Hydrocarbon Functionalization. Both of these centers

involve collaborative teams of some of the top academics in the field. Their work is likely to make great strides to address some

of these grand challenges and to develop and conduct fundamental investigations on technologies that could be pursed for

commercialization.

References:

1

F Lyons, T. L.; Sanford, M. S. Chem. Rev. 2010, 110, 1147

2

Colby, D. A.; Bergman, R. G.; Ellman, J. A. Chem. Rev. 2010, 110, 624.

3

Mkhalid, I. A. I.; Barnard, J. H.; Marder, T. B.; Murphy, J. M.; Hartwig, J. F. Chem. Rev. 2010, 110, 890.

4

Stang, E. M.; White, M. C. Nat. Chem. 2009, 1, 547.

5

Feng, Y.; Chen, G. Angew. Chem., Int. Ed. 2010, 49, 958.

6

Wasa, M.; Engle, K. M.; Yu, J. Q. J. Am. Chem. Soc. 2009, 131, 9886.

7

Periana, R. A.; Taube, D. J.; Gamble, S.; Taube, H.; Sath, T.; Fujii, H. Science 1998, 280, 560.

8

Villalobos, J. A.; Hickman, A. J.; Sanford, M. S. Organometallics 2010, 29, 257.

9

Ahlquist, M.; Nielsen, R. J.; Periana, R. A.; Goddard, W. A. J. Am. Chem. Soc. 2009, 131, 17110.

10

Palkovits, R.; Antonietti, M.; Kuhn, P.; Thomas, A.; Schüth, F. Angew. Chem., Int. Ed. 2009, 48, 6909.

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The Catalyst Review March 2010

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