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Record values for Japanese catalyst shipments may not be cause for celebration
FOCUS ON C A T A L Y S T S A MONTHLY REPORT FROM ALAN E COMYNS AUGUST 2008
PLENTY OF ROOM AT THE BOTTOM – FOR CATALYSTS
In this issue
MARKETS AND BUSINESS
1-3
Japanese catalyst market still robust Biofuels from cellulosics US enzyme market growing at 6%
COMPANY NEWS
3-5
INEOS Silicas and PQ to combine Oxonica and Neuftec settle patent dispute UOP and Rentech in jv for clean fuels
NEW PLANTS
5-6
Süd-Chemie making catalysts in Qatar Shell’s OMEGA plant started up
NEW TECHNOLOGY
6-7
Osaka has catalyst for visible light Mitsui trimerises ethylene Algal diesel meets ASTM specs
ENVIRONMENT
7
World’s first municipal waste-toethanol plant for Canada
PATENTS
AN INTERNATIONAL NEWSLETTER MONITORING TECHNICAL AND COMMERCIAL DEVELOPMENTS IN THE MANUFACTURE AND USE OF CATALYSTS ISSN 1351–4180
7-8
BOOKSHELF
8
EVENTS
8
As a former member of the Colloid Science Panel of the former Science Research Council I view nanotechnology with a degree of déjà vue. I used to think that nanotechnology was just a buzz-word for Applied Colloid Chemistry, until I read Feynman’s seminal 1959 lecture (www.zyvex.com/ nanotech/feynman.html) which opened my eyes to the nano-world. Of course, catalytic chemists want smaller particle sizes for their catalysts because of their increased surface areas and thus increased productivities. But other subtle effects can come into play at very small sizes which can have larger effects. The best current example is gold, which is usually a poor catalyst for anything but becomes capable of catalysing the oxidation of CO to CO2 under ambient conditions when it is very finely divided. This is sure to find application in fuel cells where CO poisoning of the catalysts can be a major problem. In general, it would be a good idea to make samples of all the common heterogeneous catalysts in nanoparticulate form and test them – not only in reactions where they are usually used, but also in more speculative ones. Unexpected results are certain to come. I would test them all for that holy grail of industrial chemistry – the efficient functionalisation of methane. Nano-catalysts could be used in suspension (as they are usually made) but they would be hard to remove from the products. This might not matter – metallocene catalysts for making poly-olefins are always left in
the polymers – but this could cause environmental problems and waste money. Ideally they would be supported on larger particles which would be easier to recover; a patent abstracted below addresses this problem. All nano-particles could, in principle, have toxicological properties different from their macro counterparts and should therefore be tested for toxicity before use. National and international bodies are starting to address this problem. Catalysts are a special case in that they are mostly used in industry, in controlled situations, there is no public exposure, so they present a much smaller problem. Photochemical titania is an exception: it has been widely used for about 50 years and is starting to be used in domestic products, but no adverse medical effects have ever been reported from its use. Nano-catalysts have a great future and I commend them to all my readers. Alan E. Comyns
MARKETS AND BUSINESS Record values for Japanese catalyst shipments may not be cause for celebration Catalyst shipments in Japan are hitting record values, but a closer inspection shows it may not be a
CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS
F O C U S reason to rejoice. Japan’s Ministry of Economy, Trade, and Industry statistics showed that the country’s domestic shipments of catalysts amounted to an all-time value of over Yen 500 bn ($4.85 bn) in 2007, after surpassing the Yen 300 mark in 2005 and Yen 400 bn mark in 2006. In volume terms, Japan’s domestic catalyst shipments declined by 1% in 2006 and grew 4% in 2007, after enjoying historic volume levels for seven successive years through 2005. The sharp disparity of the shipment value and volume levels in 2006 and 2007 was due to the surging prices of rare metals in several catalysts that producers had passed on to the finished products’ costs. In 2007, shipments of automotive-exhaust catalysts with rare earth metals increased 2% in volume terms and 27% in value terms over 2006. The catalysts represented 16% of the total shipment volume, and 72% of total value in 2007. In comparison, oil refining catalysts and petrochemical catalysts, which accounted for 44% and 15%, respectively, of total shipment volume, represented just 6% and 13% of the total shipment value, respectively. Catalysts, under the fine and speciality chemicals category, have surpassed the printing inks and agrochemicals catalysts since 2006 to rank behind cosmetics and paints in terms of shipment value. Meanwhile, synthetic dyes and agrochemicals are experiencing rapid slumps. Japan Chemical Week, 5 Jun 2008, 49 (2468), 2
Japanese catalyst market still robust The catalyst market remains robust, particularly for eco-friendly formulations, as stricter environmental regulations are implemented in Japan and overseas. Demand for petrochemical catalysts is also growing steadily, driven by increasing production of petrochemicals in Asia and the Middle East. Novel applications, such as those suitable for new energy systems including fuel cells, are expected to advance. Data from Japan’s Ministry of Economy, Trade and Industry indicated that the country’s catalyst output in Jan-Oct 2007 grew 6.6% to 92,714 tonnes, year-on-year. Volume of shipments
2
ON
C ATA LY S T S
climbed 4.3% to 91,995 tonnes, while deliveries value surged 25% to Yen 412.2 bn, nearly at par with the shipment value of the full 2006 period. The market for automotive-exhaust catalysts is expanding rapidly and anticipated to grow further with the imminent adoption of Japan’s 2009 Post-New Long-term Emission regulations. For oil-refining catalysts, which represent the biggest sector of the catalyst market, demand is solid for fluid catalytic cracking and hydrogenation used in the manufacture of sulfur-free diesel oil and gasoline. Japan Chemical Week, 12 Jun 2008, 49 (2469), 8
Ethanol from wood waste an opportunity for refiners The Energy Independence and Security Act of 2007, Renewable Fuels Standards, requires 36 bn gallon/y of renewable fuels output by 2022. To help meet this objective, wood waste is seen as a potential second-generation feedstock for making cellulosic ethanol. A study found that if all forestry wastes, mill wastes, and cellulosic wastes were recycled, there would be adequate additional wood waste in the US Southeast to feed 172 new 20 M gallon/y ethanol facilities. These units could yield an aggregate of 3.432 bn gallon/y of cellulosic ethanol. Cellulosic ethanol will be essential in the next few years as corn ethanol will not be able to keep up with the projected US biofuels needs. Corn ethanol currently meets 99% of current demand, but it will only be able to satisfy 65% of demand by 2018 and 42% of demand by 2023. The US DOE projects cellulosic ethanol requirement will reach 16 bn gallon/y by 2023. Oil and Gas Journal, 2 Jun 2008, 106 (21), 54-59
Dash for cellulosics: flurry of research investment into second-generation biofuels Companies are rushing to invest in research involving second-generation fuels derived from cellulosic materials. DuPont and Genencor will make an initial investment of $140 M for three years to establish a pilot plant in the
US to make cheap cellulosic fuels. Construction is pencilled to begin in 2009 and be operational by 2012. DuPont Danisco Cellulosic Ethanol, the resulting jv, will combine Genencor’s enzyme technology and DuPont’s pre-treatment and ethanologen technologies. SüdChemie, a German catalyst firm, and Linde, a gas company, also announced their plans to come up with inexpensive cellulosic fuels. Their demo plant for cellulosic ethanol will probably be located in Munich, Germany, and be operational in 2010. In early Apr 2008, Venernium, a USbased enzymes and biofuels firm, opened a cellulosics demo facility. Meanwhile, investors in firstgeneration biofuels had to defend their investment against claims that they are competing for food supplies. BP plans to invest $60 M for a 50% share in the jv with Tropical BioEnergia and spend 50% of the $1 bn needed to build two ethanol refineries with Grupo Maeda, a Brazilian agribusiness group, and Santelisa Vale, an ethanol producer. TCE (formerly The Chemical Engineer), Jun 2008, (804), 5
Time to bring in plan B for biofuel Problems associated with current methods of producing biofuels are discussed in terms of developments towards the commercialization of cellulosic ethanol, the cost of which is currently 50% higher than producing bioethanol from starch. In the US there are 30 cellulosic ethanol projects, six of which are financed by a $385 M government development fund. In May 2008, Verenium commissioned a demonstration unit at Jennings, LA, for the production of ethanol from sugar bagasse. However, the first commercial unit to use corn husks and bagasse as feedstock is likely to be that being planned by Genencor, a producer of industrial enzymes, and DuPont. At Rome, NY, Boston-based Mascoma and General Motors are building a pilot plant that will use microorganisms to process switchgrass into ethanol in a single step, thus lowering the cost of the biological process. The development by Iogen, a Canadian biotechnology
AUGUST 2008
PLENTY OF ROOM AT THE BOTTOM – FOR CATALYSTS
In this issue
MARKETS AND BUSINESS
1-3
Japanese catalyst market still robust Biofuels from cellulosics US enzyme market growing at 6%
COMPANY NEWS
3-5
INEOS Silicas and PQ to combine Oxonica and Neuftec settle patent dispute UOP and Rentech in jv for clean fuels
NEW PLANTS
5-6
Süd-Chemie making catalysts in Qatar Shell’s OMEGA plant started up
NEW TECHNOLOGY
6-7
Osaka has catalyst for visible light Mitsui trimerises ethylene Algal diesel meets ASTM specs
ENVIRONMENT
7
World’s first municipal waste-toethanol plant for Canada
PATENTS
AN INTERNATIONAL NEWSLETTER MONITORING TECHNICAL AND COMMERCIAL DEVELOPMENTS IN THE MANUFACTURE AND USE OF CATALYSTS ISSN 1351–4180
7-8
BOOKSHELF
8
EVENTS
8
As a former member of the Colloid Science Panel of the former Science Research Council I view nanotechnology with a degree of déjà vue. I used to think that nanotechnology was just a buzz-word for Applied Colloid Chemistry, until I read Feynman’s seminal 1959 lecture (www.zyvex.com/ nanotech/feynman.html) which opened my eyes to the nano-world. Of course, catalytic chemists want smaller particle sizes for their catalysts because of their increased surface areas and thus increased productivities. But other subtle effects can come into play at very small sizes which can have larger effects. The best current example is gold, which is usually a poor catalyst for anything but becomes capable of catalysing the oxidation of CO to CO2 under ambient conditions when it is very finely divided. This is sure to find application in fuel cells where CO poisoning of the catalysts can be a major problem. In general, it would be a good idea to make samples of all the common heterogeneous catalysts in nanoparticulate form and test them – not only in reactions where they are usually used, but also in more speculative ones. Unexpected results are certain to come. I would test them all for that holy grail of industrial chemistry – the efficient functionalisation of methane. Nano-catalysts could be used in suspension (as they are usually made) but they would be hard to remove from the products. This might not matter – metallocene catalysts for making poly-olefins are always left in
the polymers – but this could cause environmental problems and waste money. Ideally they would be supported on larger particles which would be easier to recover; a patent abstracted below addresses this problem. All nano-particles could, in principle, have toxicological properties different from their macro counterparts and should therefore be tested for toxicity before use. National and international bodies are starting to address this problem. Catalysts are a special case in that they are mostly used in industry, in controlled situations, there is no public exposure, so they present a much smaller problem. Photochemical titania is an exception: it has been widely used for about 50 years and is starting to be used in domestic products, but no adverse medical effects have ever been reported from its use. Nano-catalysts have a great future and I commend them to all my readers. Alan E. Comyns
MARKETS AND BUSINESS Record values for Japanese catalyst shipments may not be cause for celebration Catalyst shipments in Japan are hitting record values, but a closer inspection shows it may not be a
CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS
F O C U S reason to rejoice. Japan’s Ministry of Economy, Trade, and Industry statistics showed that the country’s domestic shipments of catalysts amounted to an all-time value of over Yen 500 bn ($4.85 bn) in 2007, after surpassing the Yen 300 mark in 2005 and Yen 400 bn mark in 2006. In volume terms, Japan’s domestic catalyst shipments declined by 1% in 2006 and grew 4% in 2007, after enjoying historic volume levels for seven successive years through 2005. The sharp disparity of the shipment value and volume levels in 2006 and 2007 was due to the surging prices of rare metals in several catalysts that producers had passed on to the finished products’ costs. In 2007, shipments of automotive-exhaust catalysts with rare earth metals increased 2% in volume terms and 27% in value terms over 2006. The catalysts represented 16% of the total shipment volume, and 72% of total value in 2007. In comparison, oil refining catalysts and petrochemical catalysts, which accounted for 44% and 15%, respectively, of total shipment volume, represented just 6% and 13% of the total shipment value, respectively. Catalysts, under the fine and speciality chemicals category, have surpassed the printing inks and agrochemicals catalysts since 2006 to rank behind cosmetics and paints in terms of shipment value. Meanwhile, synthetic dyes and agrochemicals are experiencing rapid slumps. Japan Chemical Week, 5 Jun 2008, 49 (2468), 2
Japanese catalyst market still robust The catalyst market remains robust, particularly for eco-friendly formulations, as stricter environmental regulations are implemented in Japan and overseas. Demand for petrochemical catalysts is also growing steadily, driven by increasing production of petrochemicals in Asia and the Middle East. Novel applications, such as those suitable for new energy systems including fuel cells, are expected to advance. Data from Japan’s Ministry of Economy, Trade and Industry indicated that the country’s catalyst output in Jan-Oct 2007 grew 6.6% to 92,714 tonnes, year-on-year. Volume of shipments
2
ON
C ATA LY S T S
climbed 4.3% to 91,995 tonnes, while deliveries value surged 25% to Yen 412.2 bn, nearly at par with the shipment value of the full 2006 period. The market for automotive-exhaust catalysts is expanding rapidly and anticipated to grow further with the imminent adoption of Japan’s 2009 Post-New Long-term Emission regulations. For oil-refining catalysts, which represent the biggest sector of the catalyst market, demand is solid for fluid catalytic cracking and hydrogenation used in the manufacture of sulfur-free diesel oil and gasoline. Japan Chemical Week, 12 Jun 2008, 49 (2469), 8
Ethanol from wood waste an opportunity for refiners The Energy Independence and Security Act of 2007, Renewable Fuels Standards, requires 36 bn gallon/y of renewable fuels output by 2022. To help meet this objective, wood waste is seen as a potential second-generation feedstock for making cellulosic ethanol. A study found that if all forestry wastes, mill wastes, and cellulosic wastes were recycled, there would be adequate additional wood waste in the US Southeast to feed 172 new 20 M gallon/y ethanol facilities. These units could yield an aggregate of 3.432 bn gallon/y of cellulosic ethanol. Cellulosic ethanol will be essential in the next few years as corn ethanol will not be able to keep up with the projected US biofuels needs. Corn ethanol currently meets 99% of current demand, but it will only be able to satisfy 65% of demand by 2018 and 42% of demand by 2023. The US DOE projects cellulosic ethanol requirement will reach 16 bn gallon/y by 2023. Oil and Gas Journal, 2 Jun 2008, 106 (21), 54-59
Dash for cellulosics: flurry of research investment into second-generation biofuels Companies are rushing to invest in research involving second-generation fuels derived from cellulosic materials. DuPont and Genencor will make an initial investment of $140 M for three years to establish a pilot plant in the
US to make cheap cellulosic fuels. Construction is pencilled to begin in 2009 and be operational by 2012. DuPont Danisco Cellulosic Ethanol, the resulting jv, will combine Genencor’s enzyme technology and DuPont’s pre-treatment and ethanologen technologies. SüdChemie, a German catalyst firm, and Linde, a gas company, also announced their plans to come up with inexpensive cellulosic fuels. Their demo plant for cellulosic ethanol will probably be located in Munich, Germany, and be operational in 2010. In early Apr 2008, Venernium, a USbased enzymes and biofuels firm, opened a cellulosics demo facility. Meanwhile, investors in firstgeneration biofuels had to defend their investment against claims that they are competing for food supplies. BP plans to invest $60 M for a 50% share in the jv with Tropical BioEnergia and spend 50% of the $1 bn needed to build two ethanol refineries with Grupo Maeda, a Brazilian agribusiness group, and Santelisa Vale, an ethanol producer. TCE (formerly The Chemical Engineer), Jun 2008, (804), 5
Time to bring in plan B for biofuel Problems associated with current methods of producing biofuels are discussed in terms of developments towards the commercialization of cellulosic ethanol, the cost of which is currently 50% higher than producing bioethanol from starch. In the US there are 30 cellulosic ethanol projects, six of which are financed by a $385 M government development fund. In May 2008, Verenium commissioned a demonstration unit at Jennings, LA, for the production of ethanol from sugar bagasse. However, the first commercial unit to use corn husks and bagasse as feedstock is likely to be that being planned by Genencor, a producer of industrial enzymes, and DuPont. At Rome, NY, Boston-based Mascoma and General Motors are building a pilot plant that will use microorganisms to process switchgrass into ethanol in a single step, thus lowering the cost of the biological process. The development by Iogen, a Canadian biotechnology
AUGUST 2008