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Bio-based aniline: a new route to an “old” intermediate
FOCUS ON C A T A L Y S T S AN INTERNATIONAL NEWSLETTER MONITORING TECHNICAL AND COMMERCIAL DEVELOPMENTS IN THE MANUFACTURE AND USE OF CATALYSTS ISSN 1351–4180
A MONTHLY REPORT FROM TOM DEGNAN JULY 2017 IN THIS ISSUE MARKETS AND BUSINESS
2
Asia's next big shift Low oil prices hit Coal-to-Olefins and ethane imports Another wave of US crackers? Speciality chemicals market to reach $1.79 trillion by 2025 Pollution concerns drive market for air-cleaning coatings Speciality enzymes market to reach $3726.4 M by 2025 Agricultural enzymes market worth $474.7 M by 2022 EUR Industry Consortium receives funds for polyethylenfuranoate Making bioplastics fit for purpose
COMPANY NEWS
4
Wison Engineering to collaborate with Honeywell UOP on MTO Demeta designs catalytic breakthrough solutions for asset production Global Bioenergies, Ineos & Clariant get funding for bio-isobutene Venture to produce algae-based renewable inks Fusion between Clariant and Huntsman Jacobs signs with BASF in Germany Yeast maker opens new tech branch Switching paper for chemicals Rennovia and Johnson Matthey enter into license agreement
NEW PLANTS
5
Oriental Energy Co. Ltd starts propylene production China's Yantai Wanhua to use Honeywell UOP's technology for PDH Novozymes to expand Nebraska enzymes unit ICM releases new details about showcase biorefinery Next investment for Chevron Phillips Convion SOFC for DEMOSOFC project uses renewable biogas
NEW TECHNOLOGY
6
Covestro pursues bio-based aniline New enzyme blends save costs and enable better detergents Activated carbon non-woven fabric Pt-based catalyst Cerium modified HZSM-5 catalysts on methanol-togasoline reaction Advanced treatment of refinery wastewater by ozone catalytic oxidation
PATENTS
7
Nanoparticles, nanosponges, methods of synthesis, and methods of use Selective olefin metathesis with cyclometalated ruthenium complexes Molecular diffusion measurement in a porous powder
BOOKSHELF
7
Encapsulated catalysts Nanotechnology Commercialization: Processes and Products Essentials of Chemical Reaction Engineering
EVENTS
8
BIO-BASED ANILINE: A NEW ROUTE TO AN "OLD'' INTERMEDIATE Aniline is one of the "top 50'' largest volume petrochemicals in the world. It is also one of the oldest intermediates used in the synthesis of other petrochemicals. First produced in 1826 by the destructive distillation of indigo, aniline production grew dramatically following the discovery by Frenchman Antoine Beauchamp of a catalytic process for reducing nitrobenzene using iron and HCl. The demand for aniline was driven by the William Henry Perkin's discovery of the first synthetic organic dye, aniline purple (also known as mauveine). Aniline became the staple for the development of Germany's dye business in the 1860's. Globally, approximately five million metric tonnes of aniline are produced each year. Its total demand has been increasing by an average of about five percent annually. Today, about 75% of aniline is used as an intermediate in the production of isocyanates. The most commonly practiced industrial process for producing aniline involves nitration of benzene followed by selective catalytic dehydrogenation of the nitrobenzene typically over a copper/silica catalyst in a fluidized bed reactor. Aniline is also produced by a newer process involving ammonolysis of phenol. In the nitration – selective hydrogenation route, the nitration step requires about 50% of the capital investment. Direct amination of benzene with ammonia has been a long sought after goal. Although a significant amount of research has been directed to the catalytic amination of benzene, particularly by DuPont, the process has never been commercialized. In late May, Leverkusen, Germanybased Covestro AG announced a potential "breakthrough'' in the production of aniline in a catalytic process that uses plantbased raw materials instead of benzene (p. 6). The new route is reportedly based on the microbial conversion of sugars into an aniline precursor. According to the
company, the aniline is then ". . .derived by means of chemical catalysis in a second step.'' [1] Neither the microorganism nor the chemical catalyst has been disclosed. Covestro claims that the sugars used in the ultimate production of aniline can be derived from corn, straw or wood. The development is the result of a collaboration between Covestro and the University of Stuttgart, the CAT Catalytic Center at RWTH Aachen University and Bayer AG. Covestro plans to scale-up the process with its research and industrial partners from the laboratory to a pilot plant with the objective of moving quickly to the first commercial scale bio-based aniline process. Covestro is a major producer of aniline, which it uses in the production of rigid polyurethane foam, mainly for use as insulation in buildings and refrigeration systems. Covestro's aniline manufacturing capacity is one million metric tonnes per year. The company has experience in developing new products from renewables and has incorporated renewables in several of its products. A coating hardener, developed by the company has approximately 70% of its carbon content derived from plants. Covestro is researching and developing other products based on the use of CO2. Last December, Covestro extended its catalysis research partnership with RWTH Aachen University by agreeing to contribute 12 million Euros over seven years to fund Aachen's CAT Catalytic Center. [2] The company and Aachen launched the CAT Center in 2007. Aachen University's CAT Center has 25 employees devoted to basic research in catalysis. Professor Walter Leitner has been the scientific director of the Center since its inception. Professor Leitner is the Chair of Technical Chemistry and Petrochemistry at RWTH. A major focus of the CAT Catalytic Center has been the
CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS
FOCUS development of catalytic processes that use CO2 in plastics manufacture. Tom Degnan [1] K. Laird, "Covestro develops bio-based route to aniline,’’ Plastics News, 30 May 2017, (Website: http://www.plasticsnewseurope.com/ article/20170530/) © Plastics News 2016. [2] "Covestro to invest additional €12 million in CAT catalytic center operated jointly with RWTH Aachen University,’’ China Plastics & Rubber Journal (CPRJ), 23 Dec 2016, (Website: https://www.adsalecprj.com/ Publicity/MarketNews/lang-eng/ article-67025221/NewsArticle.aspx) © Adsale Publishing Limited 2017.
MARKETS AND BUSINESS Asia’s next big shift Major structural changes are happening in Asia's petrochemical industry. Chinese naphtha cracking is expected to lead the capacity expansions in Asia, while India is also seen to have increased petrochemical capacity. While Chinese coal-to-olefins (CTO) capacity expansions are slowing down with less than 1 M tonnes/y of expected additional downstream polyethylene (PE) capacity in 2017, Chinese naphtha is seen to grow with around 10 new naphtha crackers by 20212022. Zhejian Petroleum and Chemical (ZPC) will construct a petrochemical and refining complex in two phases, with the initial phase set to be launched in late 2018 and the final in late 2021. The project comprises 2.8 M tonnes/y of ethylene (two crackers), 10.4 M tonnes/y of aromatics and 1.2 M tonnes/y of propylene (two propane dehydrogenation plants). The Chinese government will also develop seven refining and petrochemical plants from Dalian to Guangdong along the coast of China. Sinopec intends to spend Yuan 200 bn ($29 bn) through 2020 to construct four refining and petrochemical bases in Maoming-Zhanjiang, Zenhai, Nanjing and Shanghai. The Chinese ethylene capacity is forecast to increase to 28 M tonnes/y in 2020 from 23 M tonnes/y in 2016. It is seen to grow further to 37 M tonnes/y by 2025, with naphtha cracking representing 73-75% of the overall supply. Chinese propylene capacity is expected to grow to 35 M tonnes/y in 2020 and to 45 M tonnes/ y in 2025 from 25 M tonnes/y in 2016. PDH production is seen to account 20% of the total supply. This uptick in naphtha cracking and PDH could do well in China's self-sufficiency in downstream polypropylene (PP), which is predicted to rise from 82% in 2016 to 92% in 2020. China's PE self-sufficiency meanwhile is expected to be flat from 66% in 2016 to 65% in 2020. India is also expected to be a great contributor in the expansion of
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capacities in Asia with Reliance Industries' Jamnagar petrochemical complex. The project can produce 800,000 tonnes/y of monoethylene glycol (MEG), 550,000 tonnes/y of linear low density PE (LLDPE) and 400,000 tonnes/y of low density PE (LDPE). Original Source: ICIS Chemical Business, 2-8 Jun 2017, 291 (22), 5 (Website: http://www. icis.com) © Reed Business Information Limited 2017.
Low oil prices hit Coal-to-Olefins and ethane imports Lower oil price is adversely impacting the cost advantage of coal-to-olefins (CTO). At the Asia Petrochemical Industry Conference (APIC) in Sapporo, Japan, an ICIS analyst said that the decline in crude oil values has significantly flattened the ethylene cost curve. This has also resulted in weakening the competitiveness of ethane crackers in the Middle East or North America. Much weaker naphtha values and moderately good co-product demand have contributed to reducing naphtha-cracking costs while polyolefins demand remains high. Globally, steam cracking is still the primary method for petrochemical production, although non-conventional processes like CTO, methanol-to-olefins (MTO) and propane dehydrogenation (PDH) are set to take a vital share in the future. Approximately 94% of the world's petrochemicals in 2015 are produced via steam cracking or refinery gas, and this figure would decline to about 87% in 2025 as adoption of non-conventional methods rises. In China, nearly 7 M tonnes/y of ethylene are anticipated to be produced through MTO/CTO by 2020. A graph shows the costs ($/tonne) of ethylene from NEA naphtha and imported ethane, and the price of ethylene on a CFR NEA basis from 2000 to 2020. Original Source: ICIS Chemical Business, 2-8 Jun 2017, 291 (22), 15 (Website: http://www. icis.com) © Reed Business Information Limited 2017.
Market outlook: another wave of US crackers? Outlook for the US Gulf Coast petrochemicals growth is currently bullish on another prospective series of new crackers being constructed in the country. The recovery of oil production could secure sufficient feedstock for the new facilities. On 11 May 2017, Dow Chemical announced $4 bn of additional capital investment over the succeeding five years mainly due to shale gas and oil-based economics. Projects included in the investment programme is constructing a new 600,000 tonnes/y polyethylene (PE) facility on the US Gulf Coast, and increasing the capacity of its new cracker in Freeport, TX
to 2 M tonnes/y, making it the world's largest ethylene plant. The firm will also debottleneck current PE units to raise polymer capability by another 350,000 tonnes/y and build a global-scale polyolefins facility in Europe. Enterprise Products also announced new cracker capacity plans that would translate to 250,000-300,000 barrels/d of ethane demand. LyondellBasell stated a possible wave of projects of two to three crackers, which is still below the worldwide demand growth of four to five crackers. The company started the construction of a new high-density polyethylene (HDPE) facility employing its Hyperzone platform in May 2017. SABIC and ExxonMobil have selected a plot in Corpus Christi, TX for a potential cracker and downstream units. NOVA Chemicals is also partnering with Total and Borealis for a 1 M tonnes/y cracker in Port Arthur, TX. Nearly all of the new crackers are being developed along the US Gulf Coast, prompting concerns over adequate ethane supply when all of the ethylene facilities begin operations. This new wave of crackers would entail additional ethane imports from sources outside of the US that could increase feedstock costs and reduce margin. Feedstock costs would also separately cover costs for delivering ethylene derivatives overseas. Despite this, companies stay committed to add ethylene crackers due to the resilience of US crude production even with prices under $55/ barrel. By 2022, the US oil and condensate output is projected to be around 12 M barrels/d. In the coming years, oil production under the $55/barrel forecast in Jan 2017 surpasses the $85/barrel forecast in Apr 2014. This is positive news for new crackers as oil wells also produce associated gas, which also contains rich amounts of ethane and other natural gas liquids (NGLs). The increase in oil production is concentrated in basins near the Gulf Coast. In the Permian basin, Enterprise Products is increasing its naturalgas processing capacity through the 300 M cu ft/d Orla processing facility slated for launch in 2Q 2018. The company also intends to lay out the Shin Oak pipeline that will deliver NGLs from the Permian basin to the hub in Mont Belvieu, TX. Natural gas production is also expected to increase to 94 bn cu ft/d in 2022, higher than the current estimate of 72 bn cu ft/d. In general, Enterprise predicts US ethane output to rise by 46% to 2.76 M barrels/d from its current estimate of 1.89 M barrels/d. Original Source: ICIS Chemical Business, 1925 May 2017, 291 (20), 22-23 (Website: http://www.icis.com) © Reed Business Information Limited 2017.
Speciality chemicals market to reach $1.79 trillion by 2025 The global speciality chemicals market is expected to reach $1.79 trillion by 2025,
July 2017
A MONTHLY REPORT FROM TOM DEGNAN JULY 2017 IN THIS ISSUE MARKETS AND BUSINESS
2
Asia's next big shift Low oil prices hit Coal-to-Olefins and ethane imports Another wave of US crackers? Speciality chemicals market to reach $1.79 trillion by 2025 Pollution concerns drive market for air-cleaning coatings Speciality enzymes market to reach $3726.4 M by 2025 Agricultural enzymes market worth $474.7 M by 2022 EUR Industry Consortium receives funds for polyethylenfuranoate Making bioplastics fit for purpose
COMPANY NEWS
4
Wison Engineering to collaborate with Honeywell UOP on MTO Demeta designs catalytic breakthrough solutions for asset production Global Bioenergies, Ineos & Clariant get funding for bio-isobutene Venture to produce algae-based renewable inks Fusion between Clariant and Huntsman Jacobs signs with BASF in Germany Yeast maker opens new tech branch Switching paper for chemicals Rennovia and Johnson Matthey enter into license agreement
NEW PLANTS
5
Oriental Energy Co. Ltd starts propylene production China's Yantai Wanhua to use Honeywell UOP's technology for PDH Novozymes to expand Nebraska enzymes unit ICM releases new details about showcase biorefinery Next investment for Chevron Phillips Convion SOFC for DEMOSOFC project uses renewable biogas
NEW TECHNOLOGY
6
Covestro pursues bio-based aniline New enzyme blends save costs and enable better detergents Activated carbon non-woven fabric Pt-based catalyst Cerium modified HZSM-5 catalysts on methanol-togasoline reaction Advanced treatment of refinery wastewater by ozone catalytic oxidation
PATENTS
7
Nanoparticles, nanosponges, methods of synthesis, and methods of use Selective olefin metathesis with cyclometalated ruthenium complexes Molecular diffusion measurement in a porous powder
BOOKSHELF
7
Encapsulated catalysts Nanotechnology Commercialization: Processes and Products Essentials of Chemical Reaction Engineering
EVENTS
8
BIO-BASED ANILINE: A NEW ROUTE TO AN "OLD'' INTERMEDIATE Aniline is one of the "top 50'' largest volume petrochemicals in the world. It is also one of the oldest intermediates used in the synthesis of other petrochemicals. First produced in 1826 by the destructive distillation of indigo, aniline production grew dramatically following the discovery by Frenchman Antoine Beauchamp of a catalytic process for reducing nitrobenzene using iron and HCl. The demand for aniline was driven by the William Henry Perkin's discovery of the first synthetic organic dye, aniline purple (also known as mauveine). Aniline became the staple for the development of Germany's dye business in the 1860's. Globally, approximately five million metric tonnes of aniline are produced each year. Its total demand has been increasing by an average of about five percent annually. Today, about 75% of aniline is used as an intermediate in the production of isocyanates. The most commonly practiced industrial process for producing aniline involves nitration of benzene followed by selective catalytic dehydrogenation of the nitrobenzene typically over a copper/silica catalyst in a fluidized bed reactor. Aniline is also produced by a newer process involving ammonolysis of phenol. In the nitration – selective hydrogenation route, the nitration step requires about 50% of the capital investment. Direct amination of benzene with ammonia has been a long sought after goal. Although a significant amount of research has been directed to the catalytic amination of benzene, particularly by DuPont, the process has never been commercialized. In late May, Leverkusen, Germanybased Covestro AG announced a potential "breakthrough'' in the production of aniline in a catalytic process that uses plantbased raw materials instead of benzene (p. 6). The new route is reportedly based on the microbial conversion of sugars into an aniline precursor. According to the
company, the aniline is then ". . .derived by means of chemical catalysis in a second step.'' [1] Neither the microorganism nor the chemical catalyst has been disclosed. Covestro claims that the sugars used in the ultimate production of aniline can be derived from corn, straw or wood. The development is the result of a collaboration between Covestro and the University of Stuttgart, the CAT Catalytic Center at RWTH Aachen University and Bayer AG. Covestro plans to scale-up the process with its research and industrial partners from the laboratory to a pilot plant with the objective of moving quickly to the first commercial scale bio-based aniline process. Covestro is a major producer of aniline, which it uses in the production of rigid polyurethane foam, mainly for use as insulation in buildings and refrigeration systems. Covestro's aniline manufacturing capacity is one million metric tonnes per year. The company has experience in developing new products from renewables and has incorporated renewables in several of its products. A coating hardener, developed by the company has approximately 70% of its carbon content derived from plants. Covestro is researching and developing other products based on the use of CO2. Last December, Covestro extended its catalysis research partnership with RWTH Aachen University by agreeing to contribute 12 million Euros over seven years to fund Aachen's CAT Catalytic Center. [2] The company and Aachen launched the CAT Center in 2007. Aachen University's CAT Center has 25 employees devoted to basic research in catalysis. Professor Walter Leitner has been the scientific director of the Center since its inception. Professor Leitner is the Chair of Technical Chemistry and Petrochemistry at RWTH. A major focus of the CAT Catalytic Center has been the
CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS CATALYSTS
FOCUS development of catalytic processes that use CO2 in plastics manufacture. Tom Degnan [1] K. Laird, "Covestro develops bio-based route to aniline,’’ Plastics News, 30 May 2017, (Website: http://www.plasticsnewseurope.com/ article/20170530/) © Plastics News 2016. [2] "Covestro to invest additional €12 million in CAT catalytic center operated jointly with RWTH Aachen University,’’ China Plastics & Rubber Journal (CPRJ), 23 Dec 2016, (Website: https://www.adsalecprj.com/ Publicity/MarketNews/lang-eng/ article-67025221/NewsArticle.aspx) © Adsale Publishing Limited 2017.
MARKETS AND BUSINESS Asia’s next big shift Major structural changes are happening in Asia's petrochemical industry. Chinese naphtha cracking is expected to lead the capacity expansions in Asia, while India is also seen to have increased petrochemical capacity. While Chinese coal-to-olefins (CTO) capacity expansions are slowing down with less than 1 M tonnes/y of expected additional downstream polyethylene (PE) capacity in 2017, Chinese naphtha is seen to grow with around 10 new naphtha crackers by 20212022. Zhejian Petroleum and Chemical (ZPC) will construct a petrochemical and refining complex in two phases, with the initial phase set to be launched in late 2018 and the final in late 2021. The project comprises 2.8 M tonnes/y of ethylene (two crackers), 10.4 M tonnes/y of aromatics and 1.2 M tonnes/y of propylene (two propane dehydrogenation plants). The Chinese government will also develop seven refining and petrochemical plants from Dalian to Guangdong along the coast of China. Sinopec intends to spend Yuan 200 bn ($29 bn) through 2020 to construct four refining and petrochemical bases in Maoming-Zhanjiang, Zenhai, Nanjing and Shanghai. The Chinese ethylene capacity is forecast to increase to 28 M tonnes/y in 2020 from 23 M tonnes/y in 2016. It is seen to grow further to 37 M tonnes/y by 2025, with naphtha cracking representing 73-75% of the overall supply. Chinese propylene capacity is expected to grow to 35 M tonnes/y in 2020 and to 45 M tonnes/ y in 2025 from 25 M tonnes/y in 2016. PDH production is seen to account 20% of the total supply. This uptick in naphtha cracking and PDH could do well in China's self-sufficiency in downstream polypropylene (PP), which is predicted to rise from 82% in 2016 to 92% in 2020. China's PE self-sufficiency meanwhile is expected to be flat from 66% in 2016 to 65% in 2020. India is also expected to be a great contributor in the expansion of
2
ON
C ATA LY S T S
capacities in Asia with Reliance Industries' Jamnagar petrochemical complex. The project can produce 800,000 tonnes/y of monoethylene glycol (MEG), 550,000 tonnes/y of linear low density PE (LLDPE) and 400,000 tonnes/y of low density PE (LDPE). Original Source: ICIS Chemical Business, 2-8 Jun 2017, 291 (22), 5 (Website: http://www. icis.com) © Reed Business Information Limited 2017.
Low oil prices hit Coal-to-Olefins and ethane imports Lower oil price is adversely impacting the cost advantage of coal-to-olefins (CTO). At the Asia Petrochemical Industry Conference (APIC) in Sapporo, Japan, an ICIS analyst said that the decline in crude oil values has significantly flattened the ethylene cost curve. This has also resulted in weakening the competitiveness of ethane crackers in the Middle East or North America. Much weaker naphtha values and moderately good co-product demand have contributed to reducing naphtha-cracking costs while polyolefins demand remains high. Globally, steam cracking is still the primary method for petrochemical production, although non-conventional processes like CTO, methanol-to-olefins (MTO) and propane dehydrogenation (PDH) are set to take a vital share in the future. Approximately 94% of the world's petrochemicals in 2015 are produced via steam cracking or refinery gas, and this figure would decline to about 87% in 2025 as adoption of non-conventional methods rises. In China, nearly 7 M tonnes/y of ethylene are anticipated to be produced through MTO/CTO by 2020. A graph shows the costs ($/tonne) of ethylene from NEA naphtha and imported ethane, and the price of ethylene on a CFR NEA basis from 2000 to 2020. Original Source: ICIS Chemical Business, 2-8 Jun 2017, 291 (22), 15 (Website: http://www. icis.com) © Reed Business Information Limited 2017.
Market outlook: another wave of US crackers? Outlook for the US Gulf Coast petrochemicals growth is currently bullish on another prospective series of new crackers being constructed in the country. The recovery of oil production could secure sufficient feedstock for the new facilities. On 11 May 2017, Dow Chemical announced $4 bn of additional capital investment over the succeeding five years mainly due to shale gas and oil-based economics. Projects included in the investment programme is constructing a new 600,000 tonnes/y polyethylene (PE) facility on the US Gulf Coast, and increasing the capacity of its new cracker in Freeport, TX
to 2 M tonnes/y, making it the world's largest ethylene plant. The firm will also debottleneck current PE units to raise polymer capability by another 350,000 tonnes/y and build a global-scale polyolefins facility in Europe. Enterprise Products also announced new cracker capacity plans that would translate to 250,000-300,000 barrels/d of ethane demand. LyondellBasell stated a possible wave of projects of two to three crackers, which is still below the worldwide demand growth of four to five crackers. The company started the construction of a new high-density polyethylene (HDPE) facility employing its Hyperzone platform in May 2017. SABIC and ExxonMobil have selected a plot in Corpus Christi, TX for a potential cracker and downstream units. NOVA Chemicals is also partnering with Total and Borealis for a 1 M tonnes/y cracker in Port Arthur, TX. Nearly all of the new crackers are being developed along the US Gulf Coast, prompting concerns over adequate ethane supply when all of the ethylene facilities begin operations. This new wave of crackers would entail additional ethane imports from sources outside of the US that could increase feedstock costs and reduce margin. Feedstock costs would also separately cover costs for delivering ethylene derivatives overseas. Despite this, companies stay committed to add ethylene crackers due to the resilience of US crude production even with prices under $55/ barrel. By 2022, the US oil and condensate output is projected to be around 12 M barrels/d. In the coming years, oil production under the $55/barrel forecast in Jan 2017 surpasses the $85/barrel forecast in Apr 2014. This is positive news for new crackers as oil wells also produce associated gas, which also contains rich amounts of ethane and other natural gas liquids (NGLs). The increase in oil production is concentrated in basins near the Gulf Coast. In the Permian basin, Enterprise Products is increasing its naturalgas processing capacity through the 300 M cu ft/d Orla processing facility slated for launch in 2Q 2018. The company also intends to lay out the Shin Oak pipeline that will deliver NGLs from the Permian basin to the hub in Mont Belvieu, TX. Natural gas production is also expected to increase to 94 bn cu ft/d in 2022, higher than the current estimate of 72 bn cu ft/d. In general, Enterprise predicts US ethane output to rise by 46% to 2.76 M barrels/d from its current estimate of 1.89 M barrels/d. Original Source: ICIS Chemical Business, 1925 May 2017, 291 (20), 22-23 (Website: http://www.icis.com) © Reed Business Information Limited 2017.
Speciality chemicals market to reach $1.79 trillion by 2025 The global speciality chemicals market is expected to reach $1.79 trillion by 2025,
July 2017