Essen, Germany — Bayer's decision to use carbon dioxide as a raw material (Hall 6/Hall A751-3) is based on sustainability, industrial value creation, market acceptance and climate protection, but according to Christoph Gürtle, it is not a fossil resource The replacement comes from Bayer's polyurethane process research department.
Gürtle spoke at the Nova Institute conference in Essen on October 9th on carbon dioxide as a raw material for chemistry and polymers. He said that it is possible to add up to 43% carbon dioxide to aliphatic and cyclic polycarbonates. Bayer positions PU as the "all-rounder among plastics."
Bayer and RWTH Aachen University in Germany established a joint CAT catalytic center laboratory in 2009 to develop CO2-based polyols as a step in the implementation of the "Dream Production" project in 2010. Bayer opened a carbon dioxide-based polyol pilot plant in 2011 and plans to start a production plant in Dormagen, Germany in 2015.
Gürtle said the plant should produce "reasonable industrial output, thousands of metric tons." "This is a new chemical process that involves everything from a small factory to several thousand tons to ensure everything is running properly." Gürtle believes that carbon dioxide-based polyols have great potential in flexible PU foams because they account for 2.8 million metric tons of PU blocks. 36% of the material market.
He described the development of CO2 polyols as a stage of continuous innovation of PU flexible foam. Gürtle said it took 40 years for Bayer scientists to find a sufficiently efficient catalyst to produce polyols from carbon dioxide.
The RWE AG power station near Cologne supplies scrubbed CO2 flue gas to Bayer Technical Service Co., Ltd. in Leverkusen, Germany, which is responsible for the development and conversion of CO2. The gas from RWE “is not suitable for direct use in carbon dioxide-based polyols used in mattresses because of the need to remove sulfur and nitrogen,” Gürtle said. Bayer MaterialScience AG uses purified CO2 to manufacture CO2 polyols and has switched from batches to continuous processes in early 2013. The produced polyols were evaluated in a foam mattress test on Bayer's PU block trial production line.
Gürtle says that the carbonate groups in CO2 polyols help increase viscosity. It depends on function and CO2 content. PU foam based on CO2 polyols "looks as good as today's materials, or even better," Gürtle said. "It has an interesting point: the heat of combustion is lower."
PU slab foams produced from CO2-based polyols show thermal stability that matches that of PU from traditional polyols. The starting temperature and mass loss are the same, and there is no difference in thermal sensitivity. Gürtle concluded that CO2 is fixed in the PU skeleton.
"As the CO2 content in flexible foams made with CO2-based polyols increases, thermal combustion is systematically reduced," Gürtle said.
Niklas van der Assen of RWTH Aachen University continued to introduce and showed the results of life cycle analysis based on the CO2 capture from the flue gas of lignite power stations to the production of polyols from epoxides, and the reaction of CO2 polyols with isocyanates to generate PU foams .
The production of 1 kg of CO2 in traditional polyols involves 3.59 kg equivalent CO2 emissions; the carbon dioxide polyol with 20% CO2 input is only 2.99 kg. For the 0.6 kg reduction, the raw material replacement accounted for 0.49 kg, and the captured CO2 was 0.14 kg, which partially offset the 0.03 kg emission increase due to CO2 transmission and the reaction initiator used to react to generate polyols. A polyol containing 30% CO2 has an equivalent CO2 emission of 2.64 kg.
Van der Assen said that using captured carbon dioxide and replacing epoxides would bring climate benefits. "The more carbon dioxide used, the better," he said. There are also resource efficiency and other environmental benefits. "It is effective and achieves very good foam characteristics while reducing carbon dioxide emissions," Van der Asen said.
Van der Assen said that major chemical plants produce their own ammonia and ethylene oxide to produce CO2, and CO2 polyols can be supplied through pipelines. Gürtle added that steam methane reforming used to produce hydrogen also produces CO2 as a by-product.
Zhang Xiaoqing, Department of Polymer Engineering, Commonwealth Scientific and Industrial Research Organization, CSIRO, Melbourne, Australia, introduced the opportunity for CO2-based biodegradable polymer materials, focusing on polypropylene carbonate with a CO2 content of up to 48% as a copolymer of carbon dioxide and propylene.物oxides.
Zhang mentioned rare earth tertiary complexes and double metal cyanide complex catalysts, saying that the catalyst is the key to polymerization efficiency and is also at a competitive price.
PPC compounds are usually biodegradable by 63.3% within 95 days, which meets Australia's six-month biodegradation standards, but there are no more stringent requirements. Zhang said: "It depends on additives, chain length, degree of cross-linking, etc.. A Chinese PPC manufacturer mixed PPC with other biopolymers for shopping bags and passed the US 95% biodegradability requirement within six months. ."
Zhang said that industrial PPC products from China, Germany and the United States are dimensionally stable between minus 5°C and 50°C, have the same 85% transparency as PE, and provide better moisture resistance than polylactic acid and PVC. However, the glass transition temperature and mechanical strength of these amorphous PPCs are lower than PLA.
He said that PLA usually costs US$3,000 per ton, and PPC made in China is also available at the same price. At some point in the future, Zhang expects that the price of PLA will fall to US$1,400-1,500, but PPC will fall to US$950-1,100 per metric ton.
In order to increase the PPC molecular weight of 40°C Tg PPC (compared to 55-60°C for PLA), Zhang recommends end-capping, using 1-2% bifunctional epoxide and a large amount of multifunctional epoxide. Promote cross-linking. CSIRO has made this high molecular weight PPC into a fine wood powder reinforced PPC compound, mixed it at 170°C, and then compressed it.
PPC compounds have ductile failure, and PLA has brittle failure. Zhang said that PPC can be foamed, extruded and compression molded. Further work will focus on the blending and grafting of high molecular weight PPC, the use of chain extenders and the crosslinking of low molecular weight PPC.
In a paper on the sustainability of carbon dioxide sources, Dietmar Wexler of the Wuppertal Institute advocates the production of polymers from hydrogen produced by electrolysis, which are operated by renewable energy sources, and from fossil power plants, Carbon dioxide is captured in blast furnace steel furnaces and cement kilns. However, Wexler warned, "You won't always have coal-fired power plants in the future." Wexler said that traditional energy costs for electrolysis are still too high, so politicians should seek renewable energy storage solutions.
Maria Barbosa of Wageningen University and its AlgaeParc Algae Production and Research Center in the Netherlands described the 13 million euro SPLASH project, which represents sustainable polymers from algae and hydrocarbons. The 2012-16 project has 20 partners, including Fraunhofer UMSICHT (Hall 6/E68), the exhibitor of K 2013.
Barbosa said that algae contains 20-60% oil and can produce 20,000-50,000 liters of oil per hectare per year, while the annual output of palm oil is 6,000 liters per hectare. Algae grow in fresh water and sea water and use residual nutrients to produce valuable by-products such as starch and protein.
She said that the global microalgae market is less than 10,000 tons per year. In the SPLASH project, algae can extract and separate sugars and hydrocarbons in situ for further processing into polymers. These include innovative polyesters and copolyesters derived from sugar, as well as polyolefins.
The algae production in the factory uses blue transparent UV-resistant PVC pipes. The Georg Fischer piping system won the SolVin Innovation Award at K 2010 for the algae processing plant equipped with such piping. In 2011, the company acquired Harvel Enviroking in the United States, which also produces blue, UV-resistant, transparent pipes for algae production, and now operates as Georg Fischer Harvel LLC in Easton, Pennsylvania.
In her presentation, Barbosa referred to the development of polyvinyl furan ester bottles as a bio-based alternative to PET. Although Barbosa did not mention it, Avantium Chemicals BV announced in May that it intends-with Alpla Werke Alwin Lehner GmbH & Co KG, The Coca-Cola Company and Danone-to launch PEF bio-based PET bottles by 2016, using YXY catalyst technology through the The ethylene glycol reaction converts furandicarboxylic acid to PEF.
Avantium stated that it is providing PEF produced in a pilot plant in Geleen, the Netherlands, to its development partners, and plans to build a commercial plant with an annual output of 50,000 tons, which is planned to be launched in 2016 to achieve the full commercial launch of PEF bottles.
In a paper on carbon dioxide as a substrate for the sustainable biotechnology industry, Klaas Hellingwert of the University of Amsterdam in the Netherlands mentioned various ways of photosynthesis, including the use of cyanobacteria. He recommended photosynthesis based on three-dimensional lighting of light-emitting diode lamps. Based on 70% LED efficiency and 50% photovoltaic efficiency, 700 nanometer photons can be converted into fuel with 35% efficiency. The overall efficiency of 0.1 MW per acre is 10%, which means that “solar panels on non-fertile soil will drive natural photosynthesis more effectively than the photosynthesis of the plants themselves.”
Hellingwert says this solution does not compete with the food supply or cause mineral problems, and it requires almost no water. But "design organisms" should be developed for maximum efficiency.
Mathias Reckers of LIKAT Leibniz Institute of Catalysis in Rostock, Germany and I. Peckermann of Bayer Technical Services GmbH advocate carbon capture and utilization instead of carbon capture and storage. He said that carbon dioxide should be regarded as an economical and abundant raw material rather than waste.
Jeanette Hilf of the Johannes-Gutenberg University of Mainz, Germany, said that by using a suitable catalyst to copolymerize CO2 with epoxides, using CO2 as a direct building block for aliphatic PC "may eventually eliminate toxic reactions such as phosgene." Things". Randomly distributed functions on the polymer backbone can provide customized hydrophilic and hydrophobic properties, as well as biodegradability.
Do you have any thoughts on this story? Do you have any thoughts you would like to share with our readers? Plastic News is pleased to hear from you. Send your letter to the editor via e-mail [email protection]
Please enter a valid email address.
Please enter your email address.
Please select at least one newsletter to subscribe.
Plastic news is sent directly to your inbox for free, allowing you to easily grasp the latest information.
Plastic News covers the business of the global plastics industry. We report news, collect data and provide timely information to provide our readers with a competitive advantage.
1155 Gratiot Avenue Detroit MI 48207-2997