Polyolefin Catalyst Market Overview
Technical & Commercial Progress in the Global Catalyti c Process Industries THE CATALYST REVIEW April 2014 A Publicati on of The Catalyst Group Resources, Inc. Volume 27, Issue 4
Polyolefi n Catalyst Market Overview
InsideIndustry Media Rumors: Review: U.S. Carbon Energy Capture...Policy. The Catalyst Review April 2014 1 Jennifer Wilcox CONTENTS
THE CATALYST REVIEW (ISSN 0898-3089) April 2014, Volume 27, Number 4 The Catalyst Review is designed to provide readers with a Published by The Catalyst Group global overview of events impacting the $23 billion catalyst industry, Resources, Inc., 750 Bethlehem Pike, through selected abstracts, company interviews, and original Lower Gwynedd, PA 19002, USA articles. There is also a special "Industry Rumors" column that gives +1-215-628-4447 Fax +1-215-628-2267 a view of what's going on behind the scenes, too. Reader questions [email protected] and comments are welcomed, to provide an additional value to subscribers. This POSTMASTER: Send address changes to: The Catalyst Group Resources, Inc. reinforces the purpose of The Catalyst Review, which is to provide a timely line on 750 Bethlehem Pike key news and research, in an easy-to-digest format. Lower Gwynedd, PA 19002, USA For more information or to request a trial subscription, please call The Catalyst Group Copyright 2014 The Catalyst Group Resources at +1-215-628-4447, or e-mail [email protected]. Resources, Inc. All rights reserved. Legal Disclaimer. Copyright Clearance Center. The Catalyst Group Resources, Inc. is a division of The Catalyst Group, Inc., a worldwide techni- In This Issue cal & commercial consultancy specializing in Commercial News chemical process-driven change. The Catalyst Group Resources, Inc. is dedicated to helping Shale Gas to Drive New Capacity Wave...... 2 clients understand the business impacts of technology change. Enhance Competitiveness of China’s Propylene Oxide Industry through Innovation and Industrial Chain Extension...... 2 CEO Clyde F. Payn JX Nippon Oil & Energy HS-FCC Technology Demonstrated...... 2 PRESIDENT GTL Joint Venture...... 3 John J. Murphy ExxonMobil Chemical Opens World-Scale Production Plant for Synthetic Managing Editor Mark V. Wiley Base Stocks...... 3 Contributors Johnson Matthey Davy Technologies Ltd. and Rennovia, Inc. to Develop and Eugene F. McInerney, PhD Commercialize Production Technology for Bio-based Glucaric Acid and Adipic Salvatore Ali, PhD Robert Rioux, PhD Acid...... 3 Norman Deschamps, MASc Board of advisors Process News Salvatore Ali, PhD Michele Aresta, PhD Siluria Technologies Unveils New Development Unit for Liquid Fuels from Miguel A. Banares, PhD Natural Gas Based on OCM and ETL Technologies...... 4 Carlos A. Cabrera, MBA Arthur Chester, PhD Custom Catalyst Resists Oxidation...... 4 Gabriele Centi, PhD Media Review Avelino Corma, PhD Frits Dautzenberg, PhD Carbon Capture...... 5 Burtron Davis, PhD George Huber, PhD Special Feature Phil Kowalski, MBA Warren S. Letzsch, MS Polyolefin Catalyst Market Overview...... 7 Joseph Porcelli, DEngSci Gadi Rothenberg, PhD Experimental layout & design Meda Spence Effect of CO2 on the DeNOx Activity of a Small Pore Zeolite Copper Catalyst
Advertising for NH3/SCR...... 15 For information about advertising in The Catalyst Review, contact Oligomerization of Ethylene to α-Olefins: Discovery and Development of the +1 215-628-4447 or Shell Higher Olefin Process (SHOP)...... 16 [email protected] Heterogeneous Catalysis of C–O Bond Cleavage for Cellulose Deconstruction: The Catalyst Review provides busy executives, A Potential Pathway for Ethanol Production...... 17 researchers, and production managers with a timely update on catalysis and process advances Movers and Shakers in the petroleum, petrochemical, environmental, and specialty chemical industries. Robert (Rob) M. Rioux, PhD...... 18
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The2 CatalystThe Review Catalyst Review April 2014 Jennifer Wilcox COMMERCIAL NEWS
Synthetic Biology Axens, Total and IFPEN launch Atol™, an Company Launches Innovative Technology for Bio-Ethylene JV to Commercialize Production Through Dehydration of Bio-
Gas-to-Liquids Ethanol... Bioconversion; Atol™ is a technology for the most profitable production of polymer grade bio-ethylene by dehydration of 1G and 2G-renewable ethanol. The bio-ethylene produced can be Isobutanol First integrated in existing downstream polymerization installations such as polyethylene Target... (PE), polystyrene (PS), polyethylene teraphthalate (PET), polyvinylchloride (PVC) and In This Issue acrylonitrile-butadiene-styrene (ABS) without need for modifications. Atol™ is the result of a partnership between Total, IFP Energies Nouvelles (IFPEN) and its affiliate Axens Commercial News Synthetic biology company Intrexon Corporation has formed Intrexon Energy that started in 2011. Within this cooperation, Total developed a high performance Shale Gas to Drive New Capacity Wave...... 2 Partners (IEP), a joint venture with a catalyst formulation at its research Center in Feluy, Belgium, IFPEN scaled up catalyst Enhance Competitiveness of China’s Propylene Oxide Industry through group of external investors, to optimize performance within a heat recovery innovative process while Axens industrialized the Innovation and Industrial Chain Extension...... 2 and to scale-up Intrexon’s gas-to-liquids catalyst formulation and finalized the process scheme with particular focus on energy- efficiency. Total and IFPEN are the co-owners of the technology and Axens is now in JX Nippon Oil & Energy HS-FCC Technology Demonstrated...... 2 (GTL) bioconversion platform. IEP’s first target product is isobutanol for gasoline charge of commercializing Atol™ by providing all process licensing related services and GTL Joint Venture...... 3 blending. Intrexon’s natural gas upgrading catalyst manufacturing. Atol™ is the first of a series of technologies, for the production of other olefinic monomers by processing bio-derived higher alcohols, to be developed ExxonMobil Chemical Opens World-Scale Production Plant for Synthetic program is targeting the development in parallel based on Atol’s technology platform. Source: Axens, Total, IFP Energies Base Stocks...... 3 of an engineered microbial cell line for industrial-scale bioconversion of natural Nouvelles (IFPEN), 3/25/2014. Johnson Matthey Davy Technologies Ltd. and Rennovia, Inc. to Develop and gas to chemicals, lubricants and fuels, as Commercialize Production Technology for Bio-based Glucaric Acid and Adipic opposed to employing standard chemical Acid...... 3 Braskem Seeks Larger U.S. Footprint via routes. Intrexon says it has already achieved initial proof of concept with an Acquisitions... Process News engineered microbial host converting Brazil’s Braskem is setting its sights on further expansion in the Americas – through Siluria Technologies Unveils New Development Unit for Liquid Fuels from methane into isobutanol in a laboratory- organic projects, creative collaborations, and mergers and acquisitions (M&A). The Natural Gas Based on OCM and ETL Technologies...... 4 scale bioreactor. Intrexon says that its Ascent (Appalachian Shale Cracker Enterprise) project in West Virginia, U.S. – planned Custom Catalyst Resists Oxidation...... 4 biocatalyst approach to GTL bioconversion to be built by Brazil’s industrial conglomerate Odebrecht and operated by Braskem reduces energy use, production costs, Media Review which is part of Braskem’s strategy to use more gas-based feedstocks and extend its and waste while producing a single Polyethylene (PE) reach to the U.S. “We are focused on extracting more profits from the Carbon Capture...... 5 high value product. It thus offers assets we have – we are working to create more integrated complexes,” said Braskem's economic advantages over traditional CEO, Carlos Fadigas. “We have attracted BASF onsite, and have also partnered with Special Feature conversion platforms that rely on costly Styrolution of building an ABS [acrylonitrile butadiene styrene] plant.” Meanwhile, Polyolefin Catalyst Market Overview...... 7 thermochemical catalytic processes, Braskem aims to complete its planned acquisition of polyvinyl chloride (PVC) producer such as the FischerTropsch (F−T) method Solvay Indupa which is currently under regulatory review. In Brazil, Braskem faces a Experimental of carbon upgrading, or depend on difficult macroeconomic climate. “The cost of doing business –infrastructure, the cost available plant-based feedstocks. IEP will Effect of CO on the DeNOx Activity of a Small Pore Zeolite Copper Catalyst of energy, and the cost of raw materials in key value chains – is too high," said Fadigas. 2 utilize natural gas as its feedstock—a less for NH /SCR...... 15 “The industry is also impacted by high interest rates, and also the exchange rate [vs. the 3 expensive carbon source than biomass U.S. dollar]. The value of the real is too strong.” Source: ICIS Chemical Business, 3/31- Oligomerization of Ethylene to α-Olefins: Discovery and Development of the or sugar-based technologies. Through 4/6/2014, p. 10. Shell Higher Olefin Process (SHOP)...... 16 an Exclusive Channel Collaboration Heterogeneous Catalysis of C–O Bond Cleavage for Cellulose Deconstruction: (ECC) agreement, IEP will pay Intrexon CB&I Announces Refining Technology Award in A Potential Pathway for Ethanol Production...... 17 a $25-million technology access fee to leverage the company’s synthetic biology China... Movers and Shakers capabilities, including the UltraVector CB&I recently announced its Chevron Lummus Global joint venture (JV) has been Robert (Rob) M. Rioux, PhD...... 18 platform, to further enhance the performance of a target biocatalyst. In awarded a contract valued in excess of $100 million. The scope of work includes the addition, IEP, in which Intrexon owns a license, engineering design package and catalyst supply for three grassroots refinery 50% interest, will invest up to $50 million units to be located in China. One unit will utilize LC-MAX residue hydrocracking in program development costs. Source: technology – the first commercialization for a grassroots unit. Another will utilize Green Car Congress, 3/28/2014. ISOCRACKING distillate hydrocracking technology, and the third will utilize VRDS (vacuum residue desulfurization) technology and UFR (upflow reactor) technology, all from Chevron Lummus Global. Source: CB&I, 4/7/2014.
The Catalyst Review April 2014 1 Jennifer Wilcox COMMERCIAL NEWS
Shale Gas to Drive Enhance Competitiveness of China’s Propylene New Capacity Wave... Oxide Industry through Innovation and
The US is about to see a massive Industrial Chain Extension... increase in petrochemical, polymers and derivatives capacity with a wave of new Currently, there are more than twenty propylene oxide (PO) producers in China, petrochemical projects in the coming including Sinopec, CNOOC and Shell Petrochemicals Co., Ltd., Befar Group Co., Ltd., years, all on the back of the shale gas Jinhua Group Chlor-Alkali Co., Ltd., Tianjin Dagu Chemical Co., Ltd. and Shandong boom. The new capacities will have major Jinling Group. This differs from the rest of the world where PO production is highly implications for the global petrochemical concentrated with Dow Chemical and LyondellBasell being the major producers. It market, including Latin America, as much is expected that in 2015, the domestic capacity of PO will reach 2,965 kt/a. Since PO of the additional US production will be production using the chlorohydrin route has been restricted in China, new PO projects targeted for export. There are plans are considering the co-oxidation and direct oxidation route. The first hydrogen peroxide for a total of at least 10 new ethane to propylene oxide (HPPO) unit in China being built by Jilin Shenhua Group Co. Ltd., crackers in the US – eight on the US Gulf using Evonik technology, is scheduled to start up in the first half of 2014. Although Coast and two in the Northeast US. This other Chinese enterprises are interested in the HPPO processes, requirements from represents around 12.2m tonnes/year of technology licensors make it difficult. Meanwhile, several Chinese institutes and ethylene capacity. In addition to the 10 universities are engaged in developing HPPO processes. It is believed that Chinese planned greenfield projects, there are HPPO technology will see breakthroughs in the near future. Source: China Chemical also 10 expansions planned at existing Reporter, 4/6/2014, p.11; TCGR. crackers amounting to 1.5m tonnes/year of ethylene capacity – equivalent to one large world-scale cracker. If all 10 crackers JX Nippon Oil & Energy HS-FCC Technology are built and the expansions go through as planned, the US is looking at a massive Demonstrated... 51% increase in existing ethylene capacity to over 41m tonnes/year. Source: ICIS JX Nippon Oil & Energy completed the verification test of its high-severity fluid catalytic Chemical Business, 3/24-30/2014, p. 57. cracking unit (HS-FCC) at its Mizushima Refinery (Kurashiki, Okayama Prefecture; Japan). The HS-FCC unit achieved a propylene yield of 27-28% when combined with an olefin conversion unit (OCU), approximately five times the yield of a normal fluid Bayer Sells Patents for catalytic cracking (FCC) unit. Source: The Chemical Daily online, 4/2/2014; TCGR. Carbon Nanotubes and Graphenes... U.S. Chemical Sector Eyes 30% Growth over Bayer MaterialScience (BMS) is divesting itself of fundamental intellectual property Decade... in carbon nanotubes (CNT) and graphenes. The company FutureCarbon GmbH, based Dow Chemical and other U.S. chemical makers will boost output capacity 30% in a in Bayreuth, Germany, will acquire the decade as they invest billions of dollars in factories to take advantage of low-cost bulk of the corresponding patents from shale gas. The producers are adding 105 million metric tons of capacity by 2024, led the past ten years. Researchers from Bayer by ethylene and methanol units on the Gulf Coast. Growth will peak in 2017 with the MaterialScience had conducted substantial addition of 23 million tons of capacity. Gas prices that have dropped by half in a decade research and development work in the in the U.S. are allowing producers to process liquids such as ethane into chemicals field of carbon nanotubes in collaboration at a lower cost than other regions of the world. The cost advantage, combined with with external partners in recent years. This expanded production, will result in a five-fold increase in U.S. earnings from ethylene. included complex issues relating to safe Ethylene earnings will rise to $31.6 billion in 2018 from $6.9 billion a decade earlier. production and methods for scaling up the Lower energy costs are also attracting other industries to invest in the U.S., which will production processes. Next-generation help consume some of the new chemical production. Still, exports will need to increase catalysts and new product grades were to keep U.S. chemical markets balanced. Source: Hydrocarbon Processing, 3/27/2014. also developed. Source: Bayer, 3/31/2014.
2 The Catalyst Review April 2014 Jennifer Wilcox COMMERCIAL NEWS
GTL Joint Venture... ExxonMobil Chemical Opens World-Scale
Velocys plc, the technology innovator Production Plant for Synthetic Base Stocks... for smaller scale gas-to-liquids (GTL), announced that it has entered a joint ExxonMobil Chemical recently announced the opening of its world-scale manufacturing venture (JV) with Waste Management, facility that will enable the company to produce up to 50,000 tons of SpectraSyn NRG Energy (NRG), and Ventech Engineers Elite metallocene polyalphaolefin (mPAO) synthetic lubricant base stocks annually International (Ventech) to develop gas-to- at its integrated refining and chemical complex in Baytown, TX (U.S.). Developed liquids (GTL) plants in the United States using a proprietary metallocene catalyst process, SpectraSyn Elite mPAO base stocks and other select geographies. The JV are scientifically engineered to offer improved performance characteristics versus will pursue the development of multiple conventional PAO base stocks. These attributes include higher viscosity index, improved plants utilizing a combination of renewable shear stability and enhanced low-temperature properties. Source: Businesswire, biogas (including landfill gas) and natural 3/28/2014. gas. Waste Management intends to supply renewable gas and, in certain cases, project sites. All four members will work Rive Technology and Zeolyst International exclusively through the JV to pursue the intended application (GTL using renewable Enter into Joint Development and gas, optionally in conjunction with natural Commercialization Agreement... gas) in the United States, Canada, United Kingdom and China. As its first commercial Rive Technology and Zeolyst International announced that they have entered into a facility, the JV is targeting a plant to be Joint Development Agreement (JDA) to further develop, manufacture, and market located at Waste Management’s East hydrocracking catalysts within the petroleum refining sector. Rive’s proprietary Oak landfill site in Oklahoma, US. The JV Molecular Highway™ technology makes zeolite refining catalysts more accessible intends making a final decision to proceed to hydrocarbon molecules, resulting in increased yields of transportation fuels such on this first plant this year. Development as diesel. Refiners profit from the enhanced catalytic performance by improving activities for additional facilities are refinery-wide operating flexibility, increasing throughput, processing heavier crude expected to commence shortly. Source: oil, and maximizing production of high quality fuels. Molecular Highway technology is Velocys, 3/24/2014. already commercially-proven in fluid catalytic cracking (FCC) applications. Source: Rive Technology, 3/24/2014. Chevron Phillips Chemical and Johnson Matthey Davy Technologies Ltd. and Repsol Anncounce Rennovia, Inc. to Develop and Commercialize Metallocene License Production Technology for Bio-based Glucaric Agreement... Acid and Adipic Acid...
Chevron Phillips Chemical Company LP Johnson Matthey Davy Technologies Ltd. (JM Davy) and Rennovia, Inc. announced that (CPChem) and Repsol’s Chemicals Division they are embarking on a collaboration to develop, demonstrate and commercialize announced that Repsol has entered catalytic process technologies for the production of bio-based glucaric acid and adipic into an agreement to license CPChem’s acid. Under the collaboration, Rennovia and JM Davy will work together to develop and proprietary technology for production demonstrate the processes based on Rennovia’s technology for the catalytic aerobic of metallocene-based polyethylene (PE) oxidation of glucose to glucaric acid, as well as the catalytic hydrogenation of glucaric resins. Repsol will be implementing this acid to adipic acid. The goal of the collaboration is to develop and jointly license a technology in its existing integrated technology package enabling commercial production of these chemical products. site in Tarragona, Spain, which already Source: Johnson Matthey; Rennovia, 3/20/2014. uses CPChem MarTECH™ SL Loop Slurry Technology. Source: Chevron Phillips, 3/24/2014.
The Catalyst Review April 2014 3 Jennifer Wilcox PROCESS NEWS
Siluria Technologies Less Resource-Intensive Way to Make Unveils New Ethanol...
Development Unit Producing ethanol from renewable electricity would reduce the amount of land and for Liquid Fuels from water needed to make biofuels. Today, nearly all ethanol fuel is made from corn or sugarcane, which requires vast tracts of land and huge quantities of water and Natural Gas Based fertilizer. Researchers at Stanford University have now developed an electrochemical on OCM and ETL process that could be far cheaper and better for the environment. The work is still experimental, but it’s significant because the group was able to synthesize ethanol Technologies... and other desired products with so little energy input. “The levels of activity for CO reported here are unprecedented and a large step toward the realization of a practical Siluria Technologies unveiled a first-of- system for converting CO to ethanol,” says Clifford its-kind development unit for producing Kubiak, professor of chemistry and biochemistry liquid fuels from natural gas based on at the University of California, San Diego. The Siluria's proprietary oxidative coupling scientists created a copper-based catalyst that of methane (OCM) and ethylene-to- is very effective at producing ethanol and other liquid (ETL) technologies. Siluria's OCM carbon compounds from carbon monoxide and and ETL technologies form a unique water in a simple chemical reaction. They say the and efficient process for transforming process could be powered by renewable sources methane — the principle ingredient in of electricity, such as solar and wind, and would natural gas and renewable methane — be an alternative to traditional biofuel production. into gasoline, diesel, jet fuel and other Making ethanol is normally remarkably energy- liquid fuels. Unlike the high-temperature, intensive, involving gathering and treating biomass high-pressure cracking processes and then fermenting the sugar found in the plant employed today to produce fuels and matter. The Stanford paper shows it’s feasible to produce ethanol directly from water chemicals, Siluria's process employs and waste gases using an electric current. The researchers envision a two-step process catalytic processes to create longer- in which carbon dioxide is first converted into carbon monoxide using either existing chain, higher-value materials, thereby processes or more energy-efficient ones currently under development. Then the dramatically reducing operating costs carbon monoxide would be converted to ethanol or other carbon-based compounds and capital. At commercial scale, Siluria's electrochemically. The key to the new catalyst is preparing the copper in a novel way process will enable refiners and fuel that changes its molecular structure. Until now, copper catalysts produced a wide range manufacturers to produce transportation of carbon-based compounds, rather than one desired product, and required a lot of fuels that cost considerably less than energy. The Stanford group starts with copper metal and, by heating it in air, grows a today's petroleum-based fuels, while layer of copper oxide on top. Then that surface layer is chemically converted back to reducing overall emissions, NOx, sulfur metallic copper. In the process, the copper takes on a very different surface with more and particulate matter. Earlier this year, active area for it to act as a catalyst. It will take years to know whether a device based Siluria announced that it will build an on this chemistry would be commercially viable. But if perfected, it could provide an OCM demonstration plant at Braskem's economic incentive for removing carbon dioxide from the atmosphere. Source: MIT site in La Porte, Texas. Siluria and Braskem Technology Review, 4/9/2014. have also entered into a relationship to explore commercialization of this technology. The OCM demonstration Custom Catalyst Resists Oxidation... plant will begin operations later this year. Siluria's Hayward, CA ETL facility and the A team led by Jason Hattrick-Simpers and Jochen Lauterbach of the University of La Porte, TX OCM demonstration plant South Carolina, Columbia, report a strategy for avoiding aging in solid-state catalysts. are the last scale-up steps prior to full In a proof-of-concept study, the team shows that cobalt-based catalysts that drive commercialization of Siluria's technology Fischer-Tropsch (FT) chemistry can be tailored to resist oxidation by water vapor, a platform. Source: Siluria, 3/21/2014. common problem. The trick is selectively exposing oxidation-resistant crystal faces by preparing the catalyst as elongated nanorods instead of nanoparticles. Catalysis tests and spectroscopy analysis show that in contrast to cobalt-based nanoparticles, which become oxidized and lose catalytic activity quickly in the presence of steam, nanorods remain largely unaffected. The group attributes the oxidation resistance to the more favorable reduction potential of the nanorod surfaces relative to those of nanoparticles. Source: Chemical & Engineering News, 3/31/2014, p. 25.
4 The Catalyst Review April 2014 Jennifer Wilcox MEDIA REvIEW The views expressed are those of the individual author and may not refl ect those of The Catalyst Review or TCGR. less Resource-Intensive Way to Make Carbon Capture Ethanol... By Jennifer Wilcox, 2012 Springer, New York, NY, $79.95 (eBook $59.95) Producing ethanol from renewable electricity would reduce the amount of land and water needed to make biofuels. Today, nearly all ethanol fuel is made from corn Carbon, and its role in climate change, has become one of the most vivid topics of this generati on. Virtually or sugarcane, which requires vast tracts of land and huge quanti ti es of water and every aspect of modern life creates carbon dioxide (CO2), and we are only now becoming aware of the ferti lizer. Researchers at Stanford University have now developed an electrochemical eff ects on climate caused by the extensive CO2 humanity produces. While there is signifi cant discussion on process that could be far cheaper and bett er for the environment. The work is sti ll reducing emissions through fi ltrati on and improving effi ciencies, there is another opti on; fi nding ways to experimental, but it’s signifi cant because the group was able to synthesize ethanol capture CO2—i.e., separati ng it from other gasses in emissions from industrial plants and power plants— and other desired products with so litt le energy input. “The levels of acti vity for CO so as to lock it away in storage systems or purify it and use it for other chemical processes. However, reported here are unprecedented and a large step toward the realizati on of a practi cal separati ng and capturing the CO2 produced as part of industrial processes is sti ll a new idea, and Carbon system for converti ng CO to ethanol,” says Cliff ord Capture is the fi rst textbook of its kind to provide the necessary engineering background and mathemati cs Kubiak, professor of chemistry and biochemistry to implement such real-world carbon capture projects. at the University of California, San Diego. The scienti sts created a copper-based catalyst that The 335-page book is broken down into nine chapters. The focus of the book is specifi cally on the processes for capturing carbon, is very eff ecti ve at producing ethanol and other and is writt en primarily as a textbook for both the undergraduate and graduate levels, but is also useful as educati onal material for carbon compounds from carbon monoxide and people working with carbon capture technologies and as a reference for scienti sts and engineers either researching or evaluati ng water in a simple chemical reacti on. They say the carbon capture and separati on processes. The three core chapters (Chapters 3-5) deal with the capture topics of carbon absorpti on, process could be powered by renewable sources adsorpti on and membrane separati on processes, respecti vely. However, the book also touches on other aspects that make up a of electricity, such as solar and wind, and would typical carbon capture project, including compression and transport of CO2 (Chapter 2), cryogenic disti llati on and air separati on be an alternati ve to traditi onal biofuel producti on. (Chapter 6), and the roles algae, catalysis and mineral carbonati on (Chapters 7, 8 and 9, respecti vely) play in carbon capture. Most Making ethanol is normally remarkably energy- of these chapters include worked examples to supplement the equati ons provided in the text, with problems for students to solve intensive, involving gathering and treati ng biomass at the end of Chapters 3-5. In additi on, the book also contains an introductory chapter, preface, acknowledgments, table of symbols, and then fermenti ng the sugar found in the plant appendices, glossary, and an index. matt er. The Stanford paper shows it’s feasible to produce ethanol directly from water and waste gases using an electric current. The researchers envision a two-step process The three core chapters are extensive, covering all of the major concepts important for in which carbon dioxide is fi rst converted into carbon monoxide using either existi ng developing diff erent types of carbon capture systems, with extensive treatment of the processes or more energy-effi cient ones currently under development. Then the fundamental chemical and physical processes concerning the mass transfer of CO2 from a carbon monoxide would be converted to ethanol or other carbon-based compounds gas to captured form. Wilcox frames the discussion around each type of process in terms electrochemically. The key to the new catalyst is preparing the copper in a novel way of the operati ng, maintenance and capital costs for each carbon capture process, but the that changes its molecular structure. Unti l now, copper catalysts produced a wide range book only looks at their costs obliquely, if at all. Instead, it focuses on developing methods of carbon-based compounds, rather than one desired product, and required a lot of to calculate the design and operati ng conditi ons for each process relati ve to gas inputs and energy. The Stanford group starts with copper metal and, by heati ng it in air, grows a desired captured quanti ti es. layer of copper oxide on top. Then that surface layer is chemically converted back to metallic copper. In the process, the copper takes on a very diff erent surface with more The chapter on the role of catalysis in carbon capture is brief, spanning just 11 pages. Essenti ally, it consists of two brief primers acti ve area for it to act as a catalyst. It will take years to know whether a device based on electrocatalysis and photocatalysis, with litt le mathemati cal treatment of either topic. The electrocatalysis secti on focuses on producing hydrocarbons from CO using a copper catalyst. The photocatalysis secti on is even briefer, primarily consisti ng of an on this chemistry would be commercially viable. But if perfected, it could provide an 2 example of CO reducti on over TiO (ti tania) to produce methanol. economic incenti ve for removing carbon dioxide from the atmosphere. Source: MIT 2 2 Technology Review, 4/9/2014. The fi rst thing that really stood out about this book for me was the incredibly comprehensive list of the over 250 symbols used in the book, which appears just aft er the table of contents. To some, parti cularly those familiar with this fi eld, this table may seem Custom Catalyst Resists Oxidation... of limited use. For others fi rst learning the topic, however, or even an experienced engineer unfamiliar with the fi eld, the table of symbols is extremely useful, parti cularly as there is a reference to the equati on number in the book where the symbol is fi rst used A team led by Jason Hatt rick-Simpers and Jochen Lauterbach of the University of with each symbol. This additi on makes the table an extremely useful reference for any owner of the book for years to come. South Carolina, Columbia, report a strategy for avoiding aging in solid-state catalysts. Within each chapter, the provided informati on is well presented with topics of increasing complexity added to the discussion as In a proof-of-concept study, the team shows that cobalt-based catalysts that drive each chapter progresses. Each chapter also has a suffi cient number of relevant worked examples within the text, as well as extensive Fischer-Tropsch (FT) chemistry can be tailored to resist oxidati on by water vapor, a references in each chapter that will be useful to engineers using the book as reference for project development. In fact, the enti re common problem. The trick is selecti vely exposing oxidati on-resistant crystal faces by book is laid out in a very well structured way, with suffi cient focus on carbon capture, as the ti tle promises. preparing the catalyst as elongated nanorods instead of nanoparti cles. Catalysis tests and spectroscopy analysis show that in contrast to cobalt-based nanoparti cles, which A small sour note for me is the author’s tendency to place the only reference to necessary equati ons and important Appendix data become oxidized and lose catalyti c acti vity quickly in the presence of steam, nanorods within worked examples rather than presenti ng an initi al descripti on within the main body of the text. Perhaps this is simply a pet remain largely unaff ected. The group att ributes the oxidati on resistance to the more peeve of my own, born from countless hours struggling through textbooks during my own undergraduate years, searching for a favorable reducti on potenti al of the nanorod surfaces relati ve to those of nanoparti cles. necessary equati on or piece of reference data in someti mes confusing layouts. A second minor point is that the resoluti on of the Source: Chemical & Engineering News, 3/31/2014, p. 25. diagrams is lower than the text of the book itself, making the images look slightly blurry and the smaller text within them more diffi cult to read. conti nue on page 6
The Catalyst Review April 2014 5 Jennifer Wilcox MEDIA REvIEW The views expressed are those of the individual author and may not refl ect those of The Catalyst Review or TCGR.
conti nued from page 5
At any rate, these are minor issues against an otherwise well-writt en and well-constructed discussion making up this book. Carbon Capture does precisely what it set out to do—give a concise discussion of the important aspects of capturing carbon, and provide the mathemati cal tools needed to understand the physics and chemistry behind such processes in order to apply them to real-world projects.
About the Reviewer
Norman Deschamps is the owner of Rogue Thought Consulti ng (RTC), a market research fi rm providing in- sightf ul analysis on a variety of global markets since 2007. Based in Moncton, New Brunswick, Canada, RTC’s mission is to provide top quality research, analysis, and writi ng to every single client. As a dedicated analyst, Norman provides market intelligence and forecasti ng to companies within the renewable energy and biore- newables sectors, and has writt en over a dozen market research reports on topics such as biofuels, bio-based chemicals, energy storage technologies, wind, and solar. He holds a Bachelor of Science in Physics from Dal- housie University and a Master of Applied Science from the University of Toronto.
Multi-Client Study Proposal Competitive and Strategic “Shifts” in Polyolefi n Feedstocks, Catalysts and Processes, 2013-2020 The growth of the global polyolefi ns industry will continue to exceed GDP at +4-5% annually through 2020 and there is no debate about whether it pays to continue to invest! But this growth will be uneven regionally, with low growth within the OECD, and higher consumption and growth within Asia/Pacifi c, the Middle East and Africa. Many traditional market fundamentals are changing. As a result, there is a growing uncertainty because in the largest consuming markets like China, there has been both a slowdown in GDP and a softness in polyolefi n demand. Polyolefi n catalyst suppliers, process technology licensors and resin producers will need better clarity on commodity versus advanced resin demand types which are increasing due to application in automotive, packaging and medical markets. Indeed, the industry is in a “period of uncertainty” with complexity, with many factors affecting the strength of resin licensors’ and catalyst producers’ business competitiveness moving forward, for example:
• The U.S. unconventional feedstock advantage (via shale gas) and how this will be integrated into the global marketplace through exports to 2020 • Increasingly infl uential resin producer and regional market defenders like Braskem, Reliance, SABIC, SINOPEC, etc. • Changing catalyst supply relationships and competitive landscapes as witnessed in Dow Chemical’s announced divestiture of its UNIPOL PP catalyst and licensing business • The Middle East and the U.S. drive to export resins and the growing incongruence with China’s drive for domestic self-suffi ciency
These combined shifts in fundamentals have prompted TCGR to propose an updated analysis of key parameters affecting catalyst suppliers, process licensors and resin producers within the polyolefi ns industry.
Subscribers are requested to contact Mr. John J. Murphy at +1.215.628.4447 or [email protected]. Further information, including a complete proposal, preliminary Table of Contents, and order form, are available at: http://www.catalystgrp.com/php/articledetail.php?Polyolefi nShifts-80
6 The Catalyst Review April 2014 Jennifer Wilcox SPECIAL FEATURE
Polyolefin Catalyst Market Overview By Salvatore Ali, PhD
Polyolefins (polypropylene and polyethylene, PP/PE) have grown since their inception to become an industry with global annual revenues of about $300 billion (USD) and an annual installed capacity of about 180 million tons. The current trend suggests that PE and PP’s global installed capacity growth is expected to continue at 4%-5% over GDP over the next few years; with peak growth rates in Asia, the Middle East, North Africa and the Americas, while Europe and Japan will maintain and/or restructure their current capacity.
The Middle East will consolidate its position as the largest export Figure 1. Inter-regional PP/PE movements trend. production pole worldwide while North America will add significant capacity, building upon their advantaged access to cheaper shale gas feedstock. Asia (China, India, etc.) will continue to be the world’s demand engine, requiring additional PE/PP supply from other regions, despite significant regional investments.
Due to the increasing massive investments in automotive, packaging and medical application markets—including those in the developed regions—the ratio of commodity versus advanced polyolefin resin demand is changing in favor of the more sophisticated Source: Author, 2014 types. Innovation in the PO industry is then necessary for more value‐added profitability and materials substitution, which lead to the enhancement of competitive strength. Thus, catalysts/ processes will continue to play a vital role within all markets.
The polyolefin catalyst market—once solidly linked to process technology licensor activities—is becoming increasingly complex and the relationships between the catalyst supplier and process technology licensor are developed more and more beyond the traditional industry leaders. This is illustrated by the new market entrants and the recent market moves—such as Dow’s decision to divest its Unipol PP catalyst & licensing business, and Clariant’s announcement to develop jointly with the licensor Lummus’s Novolen novel PP catalysts and donor components.
In Section 1 of this article, some of the recent development trends in polyolefin and catalyst technologies are presented in addition to the impact of regulatory demands on technology development and the related implications for the industry. In Section 2, the PE & PP catalyst market shares, growth rates and suppliers are examined. In Section 3, various subjects, such as the linkage between the catalyst suppliers and technology licensors, the catalyst captive vs. toll manufacturing, the high competition of the polyolefin catalyst market and possible new entrants, are further discussed.
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Gwynedd Office Park • P.O. Box 680 • Spring, House, PA 19477 • 215-628-4447 • Fax 215-628-2267 E-mail: [email protected] • Web Site: www.catalystgrp.com Jennifer Wilcox SPECIAL FEATURE
1. Polyolefin Technology Development Trends
Within the broad activity areas of polyolefin catalysts and products, industry research efforts cover the full spectrum of traditional ZN and chromium oxide catalysts through to advanced metallocene and single-site catalysts (SSC), and from traditional catalyzed PP homopolymers to unique new elastomeric polyolefins with structures controlled on a nano-scale. In the area of product development, there appears to be a strong trend toward the design of structurally more complex products, although not necessarily more complex in terms of composition: products that are designed to have more complex molecular architectures and crystalline structures. Product innovations in specialty polyolefins now account for about one fourth of all polyolefin innovations, with the remainder split more or less evenly between PE and PP. Such a high focus on specialties is surprising for a maturing industry and is a good indicator of the continuing vitality of the industry and its research activities. As such, polyolefins are not just commodity plastics, but specialty products too. Innovation in the polyolefins industry is alive and well: advances continue to be made on a broad front, led by breakthrough discoveries in catalysis (TCGR 2011). Regarding the research on Ziegler-Natta (ZN) and chromium-based catalysts the two primary development themes are catalysts with higher activity and catalyst systems that enhance control over product properties. Most of the ZN research is directed at stereo specific systems for production of polypropylene. Significant developments include: • A new generation of ZN phthalate-free catalysts that offers higher performance, versatility and improved PP product properties. • External electron donor systems that improve the operability and safety of PP reaction systems. • External donor systems that can control crystal microstructures, melting point and processing behavior. • Systems with extremely high activities, some claiming to yield 200 kg PP per gram of solid catalyst, over five times the yield of current benchmark systems. Beyond ZN, metallocene and other SSC technologies are at a point in their development analogous to that of ZN catalysts in the late 1970s: new foundational technologies, reducing SSC costs and expanding their versatility, are being introduced and will underwrite continual development for some decades to come. Metallocenes and SSC have been a major focus of the industry since their development in the 1980s, but the frantic level of effort in this area, after a peak in the early 2000s, seemed to abate as many companies abandoned their efforts following cost saving programs. However, interest in metallocenes is reviving; the more important metallocene and SSC developments include: • New activators that multiply the yields of metallocene catalysts by factors of 2 to 8 without changing polymer product properties; simple and low cost activator-supports for metallocenes simplify catalyst preparation and use, in addition to reducing costs; • Metallocene catalysts for production of PP that have yields equivalent to the latest generation of ZN catalysts and are directly cost competitive; • Simple multi-site metallocene catalysts that can be prepared in-line and fed directly to the polymerization reactor, providing a simple, cheap and very versatile route to tailor and control polymer properties on a real-time basis; • Unique elastomeric products based on propylene, both isotactic and syndiotactic, having new property profiles that are very desirable in terms of end-use performance; • Catalysts that yield high performance PE for films that are easy to process, providing access to high-performance markets for even the less sophisticated film producers. These could become the largest volume polymer type sold into global film markets. Regulations, specifically REACH, are going to play an important role in polyolefin catalysts, pushing for a more rapid transition to new catalyst generations and spurring more innovation and market competition. REACH is the European Union (EU) regulatory group on chemicals and their safe use, entered into force on 1 June 2007. The aim of REACH is to improve the protection of human health and the environment through the better and earlier identification of the intrinsic properties of chemical substances and, at the same time, to enhance innovation and competitiveness of the EU chemical industry. Manufacturers and importers are required to gather information on the properties of their chemical substances, which will allow their safe handling. The Regulation also calls for the progressive substitution of the most dangerous chemicals that will be implemented when suitable alternatives have been identified.
8 The Catalyst Review April 2014 Jennifer Wilcox SPECIAL FEATURE
The substance components relevant to the polyolefin catalysts under scrutiny by REACH are the phthalates and Cr-VI substances that are respectively the basic components of the 4th generation ZN PP catalysts and chrome-based PE catalysts. Products containing these chemicals are kept under surveillance and active work is performed by the interested companies to find less hazardous alternatives and to implement those (no date for an eventual ban for using such substances in PO catalysts is fixed). The consequence is that not only the European catalyst manufacturers have to comply with REACH but also all the catalyst manufactures from other regions plan to export catalysts to Europe. Most of ZN PP catalyst consumptions for the time being are Figure 2. PP ZN catalyst generations. 4th generation catalysts, while consumptions of 5th generation catalysts, using non-phthalate internal components, are still limited (Figure 2 presents an overview of PP ZN catalyst generation’s evolution). However, due to the threats from REACH and the growing pressure of purchasers, it is expected that the ZN PP catalyst offerings from various suppliers will include in the short-medium term more and more phthalate-free catalysts. Around 2003, Basell first developed and commercialized 4,di- ether (PP with narrow MWD) and succinate (PP with broad MWD) 5th generation, phthalate free, ZN PP catalysts that improved significantly the previous phthalate generation. Whereas phthalate-based systems can be considered as a family of multi- purpose catalysts, with which it is possible to cover a large part of PP properties and applications, both di-ether and succinate based systems until now have been regarded as specialty drop- in catalysts. However the recent move of Basell regarding the commercialization of mixed di-ether/succinate catalysts seems (in perspective) to launch an offering of a multi-purpose high Source: Author, 2014 performance 5th generation, phthalate-free catalyst line. In addition to Basell’s consistent portfolio of phthalate-free PP catalysts, recently most of the other major PP catalyst manufacturers patented and started the industrialization of phthalate free ZN PP catalysts: Dow started the industrialization of CONSISTA C 601 catalyst, Mitsui recently announced having a PP phthalate- free catalyst in addition to its own di-ether PP ZN catalyst already commercialized; while the Chinese Xiang Yang Chemicals Group has patented a highly active di-ether catalyst. Despite some author (Ceustermans R, 2013) thinking that some phthalate type catalyst still has a future in ZN catalysis, it is easy to forecast that other ZN PP catalyst suppliers are making great efforts to develop or have available their own phthalate free ZN PP catalyst. Also the recent announcement by Clariant to develop jointly with the licensor Lummus Novolen novel PP catalysts and donor components seems another move toward this direction.
2. PP & PE catalyst market
PP & PE estimated revenue market shares in 2013 are shown in Figures 3 & 4. In Figure 3 the market shares of major ZN PP catalyst suppliers such as Basell, BASF, Grace (including the Unipol PP catalyst business
Figure 3. PP ZN catalysts 2013: global market shares (%). Figure 4. Linear PE catalysts 2013: global market shares (%)
Source: Author, 2014 Source: Author, 2014
The Catalyst Review April 2014 9 Jennifer Wilcox SPECIAL FEATURE
recently acquired from Dow), Mitsui, Toho and Sinopec are presented in addition to other producers including Xiang Yang, Süd- Chemie (Clariant) and catalyst self-producers for captive use as Sabic and Reliance. In Figure 4 the market shares of major linear PE (HDPE and LLDPE) catalyst (including ZN, chrome based and metallocene while excluding homogeneous Z and metallocene/SSC catalysts) suppliers such as Basell, Univation, Grace, Mitsui and Sinopec, are presented while in the others producers including Xiang Yang, PQ, BASF, Albemarle and other minor ones. From these estimates the major global polyolefin catalyst suppliers rank as: Basell, Univation, Grace, BASF, Mitsui, Sinopec and Toho.
Current PP/PE global demand is expected to continue to grow close to 4%-5% over GDP also in the next years assuring a significant growth in the catalyst industry sector and boosting the competition in this market.
The polyolefin catalyst suppliers generally belong to the following three groups:
• Integrated process technology providers and catalyst suppliers • Independent catalyst suppliers • Catalyst toll producers
The catalyst suppliers of the first group include Basell with manufacturing plants in Europe and the USA, Mitsui Chemicals with plant in Japan, Sinopec with plants in China, and Univation with a plant in the USA and China. The main catalyst suppliers of the second group include BASF with plants in Europe and USA, Toho with production in Japan, Xiang Yang and Süd-Chemie with plants in China, Grace with plants in Europe and the USA and Albemarle with plants in the USA and Korea. BASF, Grace and Albemarle also produce on a toll basis under a manufacturing license, the commercial catalysts suitable for process plants licensed by licensors such as Ineos, Lummus Novolen, Borealis, CP Chem, NOVA Chemicals, Eastman and Polimeri Europa. In August of 2013, Clariant, owner of Süd-Chemie PO catalyst business, signed a long term agreement with the PP licensor Lummus Novolen to jointly develop new PP catalysts and donor components, build a new catalyst manufacturing plant in USA by 2015 and supply the Novolen PP licensees (for the time being, BASF is supplying these licensees as toll producer) and eventually other PP producers.
Each catalyst producer typically makes multiple grades of catalysts to suit the requirements of different polyolefin production processes and different product types. Usually these catalyst providers have their catalyst production plants close to their R&D labs and commercialize their products in drums of standard volumes worldwide, assuring just-in-time supply through a system of stock locations in various regions close to their customers. In case the catalyst supplier has only one catalyst manufacturing facility, it is usual to maintain a strategic catalyst stock sufficiently large to overcome any possible temporary interruption in supply. An expert and efficient technical service delivery system close to the customers is another critical service for the catalyst producers that any catalyst supplier must ensure.
In general, catalysts used by polyolefin producers are not interchangeable. Catalysts often have a strong influence on the characteristics of the PO products they yield, so a PO producer cannot change catalysts without re-qualifying its products. However, all PO producers must continually strive for greater efficiency and lower costs, so they will go through re-qualification procedures if there is more value from improved catalysts. Although there is considerable inertia in the market, PO producers do switch catalyst suppliers, often away from their process licensor’s catalysts. It is now easier for PO producers to find in the open market suitable alternative catalysts to be used in their PO plants when desired or needed.
Integrated PO catalyst suppliers, especially the largest PO producers/licensors, generate large cash flows that allow more R&D and innovation. The many company mergers, which have recently happened, have allowed the access in house by some PO producers to assets of several diverse technologies, where they are able to test the catalysts before offering them to the market. In the past these suppliers were working only with their own licensees. More recently, some of them started to offer catalysts to other technology platforms also in reaction to the loss of market share for the increasing market penetration from the independent suppliers (see Figure 5). In the last decade among the integrated catalyst suppliers, especially Basell (fully exploiting the performances of its PP catalyst grades), implemented successfully the strategy to penetrate producer communities outside its own licensee population giving to the market the availability of a wider range of alternative catalyst products.
10 The Catalyst Review April 2014 Jennifer Wilcox SPECIAL FEATURE
Figure 5. Business model for integrated suppliers.
Source: Author, 2014
Independent PO catalyst suppliers conduct research targeted at improved performance of existing grades as well as at next- generation catalysts with step-out performance. They supplement in-house research through collaborations with PO producers as well as through contract research by external suppliers (for example, those with specialized high through-put experimentation) and/or sponsored research at universities and science institutes. The independent suppliers obviate the lack of industrial PO plants working very close with the customers, substantially developing custom oriented offerings (seeFigure 6). The following sections provide an overview of the major polyolefin catalyst suppliers.
Figure 5. Business model for independent suppliers.
Source: Author, 2014
LyondellBasell (Basell) is the leading polyolefin technology provider and offers the most complete range of commercialized polyolefin catalyst grades under the trade name Avant, including ZN catalysts for PP and PE, chrome-based catalyst for PE and metallocene based catalysts for PP. Basell has been utilizing its strength in PP/PE process technology licensing to push forward its catalyst products. Historically, Basell has been the PP leader technology provider of the most used Spheripol process technology, adding more recently the licensing of the advanced Spherizone process technology. Over the years, Basell has maintained its prominent PP catalyst market share. Despite losing some part of its catalyst supplies to the Spheripol process licensees for the strong competition, mainly by the major independent suppliers, in the last decade Basell was able to recover any loss through the successful commercial penetration by its Avant ZN PP catalysts into other process platforms as Unipol PP, Novolen and Innovene PP.
Univation Technologies (Univation), a joint venture between ExxonMobil Chemical and The Dow Chemical Company, is the leading PE manufacturer and technology provider of Unipol PE process technology and related catalysts. Univation catalysts include ZN catalysts, called UCAT A&J for HDPE, MDPE and LLDPE; chrome-based catalysts, called UCAT B&G for producing broad MWD HDPE and MDPE; metallocene catalysts; and engineered bimodal catalysts called Prodigy. Univation’s strategy has leveraged its position as the PE leading process licensor of the Unipol PE process technology to supply their catalysts, building at the same time a sound technology position to compete effectively in the PE catalyst market.
The Catalyst Review April 2014 11 Jennifer Wilcox SPECIAL FEATURE
Grace Catalyst Technologies (Grace) historically has maintained silica as its core strength. They have been able to effectively utilize this capability in their chrome based PE catalyst business. Building upon its strength in silica, and being in close association with licensors like ChevronPhillips, Grace commercialized successfully the Sylopol PE catalysts. The key strategy of Grace has been to align themselves with key technology licensors and/or grow their catalyst portfolio through acquisitions. This ability has allowed Grace to supply the Novacat PE catalysts, under the Nova license, and the Energx PE catalyst, under the Eastman license, to the Innovene PE process licensees of Ineos. In 2002, Grace diversified into PP catalysts through the acquisition of Borealis PP catalysts manufacturing assets in Europe, offering the Polytrak PP catalysts in the market (Hummel A, 2006). In 2013 Grace acquired also the Unipol PP catalyst and technology licensing business of Dow, commercialized under the names SHAC, SHAC catalysts ADT (Advanced Donor Technology) and the innovative last-generation phthalate-free catalyst CONSISTA C 601, making the company a premier supplier of PP catalysts.
BASF Catalysts LLC (BASF) has a very long heritage in chemical catalysts. It entered the polyolefin catalyst business in 2006 with its acquisition of Engelhard, including its Lynx PP catalyst commercial platform (licensed by Chinese BRICI; Beijing Research Institute of the Chemical Industry). BASF Catalysts have been able to exploit the key strength of their platform, which is high activity with good operability and product breath (O’Reilly N, 2007). The drop-in capability of their catalyst offerings has helped BASF to be successful as a third party supplier despite the barriers to entry. In addition to this catalyst line, BASF has aligned Itself with selected licensors to enhance their catalyst offerings over the years: BASF is licensed to toll produce and supply proprietary catalysts such as Ineos CD PP catalyst to the licensees of the Innovene PP process technology and the PTK PP catalyst to the licensees of the Novolen PP process technology.
Mitsui Chemicals (Mitsui) built its strong global catalyst position on the back of its very successful process technology licensing business: the Mitsui CX slurry CSTR process for HDPE is the benchmark in Asia and is widely used in most regions of the world; and its Hypol bulk loop slurry/gas phase process for PP also is widely used in Asia. Mitsui offers the TK, RK and RH PP catalyst series to its PP process licensees and the PZ, TE and RZ PE catalyst series to their PE process licensees. RK catalysts include a high performance 5th generation di-ether PP phthalate-free catalyst. Following the long industry recession in the 1990s and subsequent industry restructuring, Mitsui radically altered its long-term strategy away from commodity polyolefins and ZN catalysts toward specialties and single-site catalysts. While Mitsui continues to support its ZN catalyst business as one of its fine chemical specialties, it continues to be a major force in the supply of highly specialized polyolefins made with its SSC technologies.
Toho Catalyst Company (Toho) is unique in the industry in being essentially independent of the polyolefins industry. It is part of a mining and metals company and yet has self-developed catalyst technology and a strong global supply position. Toho sells its PP catalysts under the catalyst platform THC; these grades are available for gas phase, bulk and slurry processes (Kataoka T, 2006). Both spherical and granular catalyst morphology are offered with a range of grades suitable for specific applications. Toho is aggressively peddling its catalysts all over the world: their PP catalysts are well known to be abreast with the PP technology and have a range of catalyst offerings. Toho also has custom synthesis capabilities and as a third party supplier it fine tunes its catalysts as per the customer requirements.
Sinopec Catalyst Company (SCC) was founded in Beijing in 2004, resulting in the unification of the Chinese catalyst business spanning the entire range of petrochemical catalysts, including polyolefin catalysts. SCC has developed various PP and PE catalyst technologies and supplies a range of ZN, chrome-based and metallocene catalysts for PP and PE (Wei C, 2006). SCC holds approximately half of the market share in China for polyolefin catalyst with major competitor Xiang Yang Chemicals. The third catalyst producer in China is Süd- Chemie, recently acquired by Clariant, which markets its PP catalysts worldwide through the distribution and service network of its catalyst division (Wyzycki M, 2011). The Chinese PO catalyst producers started with imitative catalyst products to supply the internal PO licensed capacity with homeland produced catalysts but now are equally active and successful in the catalyst R&D and innovation. Chinese PO catalyst producers are fully capable to supply products to the internal polyolefin tumultuous double digit grow; they seem less successful than expected to export these catalysts to the international market. Initially some commercial barriers (such as language, perceived product quality, and technical assistance) have somewhat limited the catalyst business expansion abroad.
A respective summary of the major commercial PP and linear PE catalyst suppliers and products, is given in Table 1 and Table 2. From the notes above we have seen that the polyolefin catalyst market is very competitive with a lot of M&A, cooperation agreements and new entrants into the market along the years. These activities seem to have impacted PP more than PE; this is due to the fact that the complexity of PP and PE catalysts is very different. While with a proper ZN catalyst most of PP commercial grades (e.g., homopolymers, random and impact copolymers) can be produced, for PE it is necessary to cope with many PO process/product clusters where time by time the ZN or chrome or metallocene or homogeneous catalyst is the right choice. Until 10-to-15 years ago, the PP catalyst suppliers were mainly the major process technology licensors producing the catalysts directly or through toll
12 The Catalyst Review April 2014 Jennifer Wilcox SPECIAL FEATURE
manufacturers under a license to supply their licensees with few independent third party suppliers. Currently, the market has completely changed: the majority of catalyst suppliers are independent third party suppliers and the trend indicates that very likely other new entries are very possible into this group of suppliers shortly.
Table 1. Summary of major PP ZN catalyst suppliers and products. Table 2. Summary of major linear PE Z catalyst suppliers and products.
Source: Author, 2014 Source: Author, 2014
3. PE & PP Catalyst Players
The polyolefin catalyst industry traditionally has been based in Europe, Japan and North America where the production of polyolefins began in the 1940s and 1950s and where the first catalyst technologies were discovered. Catalyst producers in these regions supplied the growing global polyolefins industry and developed new and improved catalysts, most often as an integral part of ongoing R&D and process licensing activities of the polymerization process developers.
As the industry matured during the 1980s and 1990s, the dominant process licensors, which made their own catalysts, consolidated their catalyst supply positions based on the demand from process licensees. Many of the smaller process licensors spun-off their catalyst production activities to independent toll catalyst producers, allowing the consolidation of these toll suppliers to achieve the economies of scale to compete with the dominant process licensors. The global polyolefin catalyst industry comprised the dominant licensors such as Basell and Univation, some large independent suppliers that offered a broad range of catalysts based on multiple technologies, such as Grace and Engelhard (now BASF), and smaller, more focused, suppliers, such as Mitsui and Toho, tending to use a limited range of technologies but having well established and strong reputations built over the past decades.
In the meantime, and beginning in the mid-90s, China’s vigorous growth, first with Sinopec and then with Xiang Yang, that in cooperation with university research institutes, develops and manufactures a suitable range of PE and PP catalysts. In China there currently is a vibrant and innovative home-grown polyolefin catalyst industry that will soon become an important independent source of catalysts for the global polyolefin industry. The industry is a strong competitor in the home market, not just because import substitution is encouraged by government, but also because it has fully competitive or superior systems compared to those of traditional suppliers. The strategic response so far of some traditional suppliers has been, firstly, to join them, as exemplified by Süd-Chemie (now Clariant) and BASF, who maintain their global positions with catalyst technologies made in China; and secondly, to compete locally, as exemplified by Univation building a plant in China to make locally its highly active Ucat J system for the Unipol PE process.
The introduction of metallocene and other single-site catalysts during the 1990s and 2000s presented an opportunity for new entrants, initially in supply of metallocene catalyst components, such as ligands, metallocene compounds, catalyst activators, etc. There has been some consolidation in this field as it became clear which chemistries and compounds were most needed. Albemarle is an example of a supplier of components and activators that moved into supported metallocenes. Grace provides an example of a move in the other direction; from a supplier of silica supports and chromium based catalysts, to a supplier of ZN catalysts, and then to metallocenes through an agreement with Eastman and the acquisitions of Single Site Catalysts LLC and Synthetech.
The change in industry structure with its greater participation of independent catalyst suppliers, combined with the evolving shifts in global demand patterns toward the less-developed regions of the world, presents additional opportunities for new companies to enter the polyolefin catalyst supply chain. These new entrants include suppliers of catalyst components and/or co catalysts, independent suppliers of other types of catalysts that can leverage their global distribution networks and/or regional leaders in less-developed markets that leverage advantaged local conditions, combined with rapidly growing local polyolefin production
The Catalyst Review April 2014 13 Jennifer Wilcox SPECIAL FEATURE
capacity. The polyolefin catalyst industry is now based in Europe, Japan, North America and China. Looking to the future, opportunities for new entries are in the Middle East, Asia/Pacific (especially in Korea, but excluding China) and in prospective in Latin America, Eastern Europe/Central Asia and India. These are all areas that already have or are approaching the critical mass for a reasonable starting point of a new catalyst business with the lack of a regional supplier. In these regions some polyolefin leaders, including Sabic, NPC, Braskem, Reliance, etc. (Sabic and Reliance are already polyolefin catalyst producers for supplying their large captive uses), or some new catalyst supplier, could be considering the opportunity to develop and/or improve its own catalyst technology in the next few years to supply a regional captive and/or merchant market and entry the polyolefin catalyst business.
References
Ceustermans R. (2013). Will Phthalate Based Catalysts Still Have a Place in the Future of the Polypropylene Industry? Paper presented at Maack PEPP Global Congress, Zurich 2013 Hummel A. (2006). PP Catalysts from Grace Davison. Paper presented at the Dubai Maack PlastPro Conference, Dubai, April 24-26, 2006 Kataoka T. (2006). Toho Tailored Catalyst Approach for PP Processes. Paper presented at the Dubai Maack PlastPro Conference, Dubai, April 24-26, 2006 O’Reilly N. (2007). BASF Polyolefin Catalysts. Paper presented at the Maack PEPP Global Congress, Zurich March 6-8, 2007 TCGR. (2011). Progress in Technology for Polyolefin Production: Quantifying the Value-Added of Advanced Catalysts, Co-catalysts/ Activators and Stereoregulators. A Multi-Client Report. http://www.catalystgrp.com/php/articledetail.php?num=73 Wei C. (2006). Polyolefin Catalyst Development of Sinopec BRICI. Paper presented at the Dubai Maack PlastPro Conference, Dubai April 24-26, 2006 Wyzycki M. (2011). C-MAX Catalysts: Diversified PP Catalyst Portfolio from Süd-Chemie. Paper presented at the Maack PEPP Conference, Zurich September 22, 2011
About the Author
Salvatore Ali, PhD is an independent consultant whose long-career spanned most aspects of polyolefins industry. He is providing advisory services to the petrochemical industry on polyolefins catalysts, technologies and polymer products with focus on technology markets, technology commercialization, acquisitions and IP and know- how management. Over the past 30 years, Dr. Ali has served as VP Technology Projects and Licensing ME/CA in LyondellBasell (2005–10), VP Catalyst Coordination in Basell Polyolefins (2001–04), VP PP/PE Technology Licensing and Catalyst BU in Montell (1997–2000), VP and GM of Technipol Technology Company of Montedison Group (1995–96), and GM of the Functional Chemicals BU of Himont Inc. Dr. Ali has a doctorate degree in Chemical Engineering from the Polytechnic University of Milan and a Masters in International Business Management at IMD, Lausanne. He has over 40 publications in referred scientific journals and books. He can be reached at [email protected]
visit: http://tinyurl.com/7q9lgvc
14 The Catalyst Review April 2014 Jennifer Wilcox EXPERIMENTAL
Effect of CO2 on the DeNOx Activity of a Small Pore Zeolite Copper Catalyst for NH3/SCR...
Urea-based selective catalytic reduction (urea/ Figure 1. Effect of CO2 on NO conversion over CuSSZ13. Feed conditions: 500 ppm NH , 500 ppm NO, 5% O2, 10% H2O, 0 or 10% CO , and N balance; SCR) of NO is acknowledged to be one of 3 2 2 x gas hourly space velocity (GHSV): 100 000 h-1. the most efficient and reliable technologies to remove NOx from diesel engine exhaust. Prominent among the catalysts employed in this application are ZSM5-based materials, including CuZSM5 and Mn-Fe/ZSM5. However, these catalysts suffer from hydrothermal deactivation during the regeneration of the diesel particulate filter-(>750 °C), which hampers their commercial application to the diesel after-treatment system.
Recently, small-pore zeolite catalysts such as CuSSZ13 and CuSAPO34 have been proposed as commercial urea/SCR catalysts due to their robust hydrothermal stability as well as their excellent low-temperature deNOx activity and—in some cases (CuSSZ13)—a high resistance toward hydrocarbon poisoning. Herein, the authors Figure 2. Profiles of a) NOx TPD and b) NH3 TPD over CUSSZ13 before and present the results of a systematic investigation after CO2 pre-adsorption. into the effect of CO2 on the catalytic activity of CuSSZ13. The rationale for this undertaking is rooted in the fact that CO2 is always abundantly present in the exhaust gas stream at approximately 10%. In addition, they examined the effect of CO2 on the adsorption of NOx and
NH3 on CuSSZ13 in order to better understand the deactivation mechanism of CuSSZ13.
The results of this study indicate that exposure of CuSSZ13 to CO2 at temperatures below 300 °C can deactivate its low-temperature deNOx activity during NH3/SCR, with the severity of deactivation being directly related to reaction temperature (Figure 1). Moreover, they discovered that the 2+ adsorption of NO on Cu ion is inhibited by CO2 due to its competitive adsorption. The adsorption of NH3 on acidic sites of CuSSZ13, however, is largely unaffected by CO2, as evidenced by NO- and NH3-TPD in the presence of CO2 (Figure 2).
Under O2-rich conditions, CO2 forms unidentate carbonates on Cu2+ sites suppressing the formation of nitrates, a key reaction intermediate essential for NOx reduction during the NH3/SCR reaction, as revealed by an in situ FTIR study. Source: Kim Y, Min KM, Lee JK, et al. (2014). ChemCatChem online preview.
The Catalyst Review April 2014 15 Jennifer Wilcox EXPERIMENTAL
Oligomerization of Ethylene to α-Olefins: Discovery and Development of the Shell Higher Olefin Process (SHOP)...
The author, who worked from 1965 to 1973 as a chemist, group leader, department head and manager for Shell Development, USA, herein provides a fascinating Figure 1. Model conception of ethylene oligomerization. retrospective on the origins of the so-called SHOP methodology which continues to supply much of the world’s demand for α-olefins. At the time this technique was in its early stages of development, α-olefins were primarily produced either by cleavage of wax or by the Ziegler polymerization of ethylene—both routes being very expensive pathways leading to lower quality products suited best for the manufacture of detergents. Shell, therefore, decided to investigate transition-metal catalyzed coupling of olefins as a potential pathway to ethylene oligomerization (as shown in Figure 1) whereby a catalytic cycle occurs in which repeated ethylene coordination and insertion form the basis of chain extension. The first breakthrough occurred with the development of a catalyst based on nickel complexes with bidentate chelate ligands possessing heteroatoms P, N, O, S and As. The next challenge was how to solve the problem of product distribution which was ultimately resolved via controlled olefin isomerization. The author provides considerable insight into the market dynamics of the early-mid 1970 leading up to the commissioning of the first SHOP production plant in 1977 (Figure 2). Subsequent academic research led to development of a proposed mechanism for the SHOP Process (Figure 3). “Success has many fathers” and, in words taken from a Shell report echoed by the author, “it was luck, green thumbs and nine years of hard work on the part of hundreds of people. That’s what goes into a project like SHOP.” Source: Keim W. (2013). Angew. Chem. Int. Ed., 52: 12492–12496
Figure 2. Flow diagram of the SHOP production plant. Figure 3. Mechanism of ethylene oligomerization.
* * * * * Nanoelectrocatalysts...
A new class of bimetallic nanocatalysts that are an order of magnitude higher in activity than the 2017 target level set by the U.S. Dept. of Energy (DOE) for fuel cells and electrolyzers has been discovered by researchers at the DOEs Lawrence Berkeley National Laboratory (LBL) and Argonne National Laboratory (ANL). The catalysts feature a hollow nanoframe structure with 3D platinum-rich surfaces that are accessible for catalytic reactions, explains LBL chemist Peidong Yang. When encapsulated in an ionic liquid (IL), the Pt/Ni nanoframes exhibited a 36-fold enhancement in mass activity and 22-fold enhancement in specific activity compared with conventional Pt nanoparticles dispersed on carbon for the O2 reduction reaction. Source: Chemical Engineering, 4/2014, p.14.
16 The Catalyst Review April 2014 Jennifer Wilcox EXPERIMENTAL
Heterogeneous Catalysis of C–O Bond Cleavage for Cellulose Deconstruction: A Potential Pathway for Ethanol Production...
As the United States continues to pursue sustainable energy strategies, a concern has been raised dealing Scheme 1. Pt nanoparticle catalyzed peanut shell decomposition. with the ethics associated with obtaining biofuels from edible food sources. Consequently, efforts are now being directed towards use of other renewable energy supplies—such as cellulose—which can be extracted from natural materials that do not exist within the food chain. With the development of a commercially viable cellulosic process, ethanol can be made from trees, grasses and even crop waste, such as peanut shells. Currently, due to the difficulty in deconstructing the linkages between lignin, hemicellulose and cellulose during the Scheme 2. B-O-4 motif in lignin (left) and ethereal linkage in cellulose. conversion of cellulose to sugar, the commercial production of cellulosic ethanol is limited. However, as the authors herein demonstrate, this problem can be overcome by using a high surface-area metal catalyst. Specifically, by use of high surface-area metal NPs prepared from chloroplatinic acid and cobalt chloride using generation four poly(amido) amine (PAMAM) terminated dendrimer (G4-NH2), Pt+2 and Co+2 ions were reduced to metal zero (via introduction of sodium borohydride). UV-Vis and XRD analyses show the formation of Pt and Co nanoparticles using dendrimer templating Figure 3. Mechanism of ethylene oligomerization. methodology. Both TLC and HPLC show that when peanut shells are treated with platinum nanoparticles without the presence of hydrogen gas, sugars are indeed released (as depicted in Scheme 1).
Making use of this approach, the authors have demonstrated a one-step process in which the lignocelluloses network can be deconstructed into monomeric sugars without an initial harsh acidic or basic pretreatment step. Since lignin is 48–50% -O-4 linkages (Scheme 2) and previous work has shown that a Ru catalyst system is known to depolymerize an analog of lignin, a catalyst that is able to do both hydrogen shuttling and C–O insertion should, in principle, be able to depolymerize lignin and break down cellulose into monomers as well.
Based on their results, the authors suggest that a previously proposed mechanism for ruthenium catalyzed depolymerization can be extrapolated to the conclusion that any metal, with similar capabilities, will follow the same mechanistic pathway (Scheme 3). Source: Crews K, Reeves C, Thomas P, et al. (2014). ISRN Nanotechnology, Article ID 634679.
The Catalyst Review April 2014 17 Jennifer Wilcox MOvERS & SHAKERS
Robert (Rob) M. Rioux, PhD friedrich g. Helfferich Assistant Professor of Chemical Engineering at the Pennsylvania State university
Professor Rob Rioux received his BS and MS degrees in chemical engineering from Worcester Polytechnic Insti tute (1999) and the Pennsylvania State University (2001), respecti vely. He went on to receive his PhD in physical chemistry from the University of California, Berkeley in 2006—working under Professor Gabor Somorjai. Prior to joining the Pennsylvania State University in 2008, Rioux was a NIH Postdoctoral Fellow at Harvard University in the Department of Chemistry and Chemical Biology working with Professor George Whitesides. In 2013 Rob received a Nati onal Science Foundati on (NSF) CAREER Award. His group’s research focuses on heterogeneous catalysis, catalyst design and synthesis, ti me-resolved FTIR spectroscopy of condensed systems, x-ray absorpti on spectroscopy (EXAFS, XANES), reacti on mechanisms in nanoscale systems, and photocatalysis. Current interests include the development of soluti on calorimetric techniques to understand catalyti c processes at the solid-liquid interface, and spati ally- and temporally-resolved spectroscopic techniques for imaging catalyti c chemistry. He can be reached at [email protected].
The Catalyst Review asked Professor Rioux to share the results of his efforts to examine the catalytic solid-liquid interface.
Because of the intense interest in biomass conversion, as well as the synthesis of heterogeneous catalysts, design strategies require a bett er understanding of the chemistry of solid-liquid interface. We have recently discovered that isothermal ti trati on calorimetry (ITC)—a technique typically used by biochemists/biophysicists to characterize ligand-receptor binding—can be uti lized to measure directly the thermodynamics at catalyti c solid-liquid interfaces and solvated organometallic complexes. ITC enables the thermodynamic profi le (K, ∆H, ∆S) to be measured in a single experiment by solving the relevant mass and energy balances. In our initi al work, we demonstrated the infl uence of the solvent and the type of monodentate phosphorous ligands on
their associati on with Pd(II)Cl2 complexes. This study established that for systems in which two equivalents of ligand were able to bind to the Pd(II) center, the binding sites on each Pd center in soluti on showed a diff erent thermodynamic affi nity for the same ligand. Solvent dependent studies verifi ed that although ligand binding was strongly enthalpy-driven, solvent played a non-innocent role and signifi cantly infl uenced the observed thermodynamic profi le. We have additi onally applied ITC to explain the binding of bidentate phosphorus ligands
to Pd(II)Cl2(solv)2 and demonstrated that the chelate eff ect, which is typically considered to be an entropic eff ect, is in fact, enhanced by enthalpic contributi ons that control the stability of chelated complexes and generally are accompanied by large entropic penalti es.
We are now exploring applicati ons of ITC to heterogeneous catalysis, and have focused our initi al eff orts on catalyst synthesis and the hydrophobic modifi cati on of catalysts for biomass conversion. We have, for the fi rst ti me, measured the thermodynamic profi le of solvated metal precursors onto the surface of hydrated metal oxides under ion-exchange conditi ons. The measured thermodynamics agree with a model considering only electrostati cs as the driving force for adsorpti on. This study also demonstrated the strength of this soluti on- phase contact infl uences the fi nal catalyst properti es aft er calcinati on and/or reducti on. Another study from our laboratory has demonstrated that the thermodynamic profi le of small molecule adsorpti on on solvated nanoparti cles can be characterized. Future eff orts employing ITC will focus on determining the adsorpti on thermodynamics of biomass molecules on a variety of heterogeneous catalysts and chiral modifi ers on heterogeneous metal-supported catalyst.
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