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Issue 06/2015

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  • Bioplastics
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Basics epoxides, for

Basics epoxides, for example propylene oxide and ethylene oxide. Up to 30 – 43 % of petrochemical feedstock can be replaced by CO 2 from industrial waste streams such as chemical or power plants. Econic Technologies started operations in 2012 after initial investment from Imperial Innovations and Norner Verdandi to develop the technology further towards commercial applications. The current technology is covered by a number of worldwide patents and patent applications. A further £ 5.1 million (€ 7.1 million) investment in 2013 by Jestream Capital and Imperial Innovations will be used to scale up and commercialise the technology. Definitions: CO 2 -plastic? – Bioplastic? – recycled CO 2 ? It must be pointed out that it is not easy to give an unambiguous classification to PPC, because its definition falls into a grey area. As discussed above, it can be produced from CO 2 recovered from flue gases and conventional propylene oxide, and in this case it cannot be defined as biobased. It may still be attractive due to its 43 % of recycled CO 2 and its full biodegradability. The production of PPC from CO 2 , which is produced during the combustion of biomass, can be classified as 43 % biobased and complies with the official ASTM D6866 definition. Additionally, if propylene oxide could be produced through the oxidation of biobased propylene, it could be then declared 57 % biobased, or even 100 % biobased if CO 2 and propylene oxide are both biobased. Since more and more plastics and chemicals will be derived from recycled CO 2 in the future, a new classification and definition such as recycled CO 2 will be needed to avoid confusing consumers. Polyurethanes (PUR) Worldwide, more than 13 million tonnes of polyurethanes are produced every year for a wide variety of applications. Since researchers have found a way to incorporate CO 2 into the molecular structure of polyurethanes, this polymer is also particularly sustainable. The Dream Production and the intensive research in CO 2 of Covestro (formerly Bayer MaterialScience) is the bestknown example at the present time. After four decades of research, the group of German scientists from Covestro, RWE Power, RWTH Aachen University and CAT Catalytic Center, found a suitable catalyst to produce polyurethane blocks made from CO 2 -derived polyols (where CO 2 replaces some of the mineral oils). The zinc-based catalyst allows for the conversion of propylene oxide with carbon dioxide from the flue gas, produced by coal-fired power plant of RWE Power, into a light-coloured viscous polyol, one of the two building blocks needed to produce polyurethane (figure 3). In February 2011, Covestro started up a pilot plant in Leverkusen, in which CO 2 was combined with propylene oxide on a large scale. Carbon dioxide comes from a RWE power plant near Cologne and is first separated from flue gas, liquefied, filled up in cylinders and in the end transported to Covestro. Tests disclosed good properties of the new polyol with the result that CO 2 -based polyurethanes can be used for many applications. The new polyol has the same level of quality as conventionally manufactured materials, it has an equal stability to existing products and a more sustainable impact. Other noteworthy facts are the lower heat of combustion and the reduction of costs by replacing a certain amount of petro-based propylene oxide by carbon dioxide. Not to be forgotten is the lower greenhouse gas emission, since CO 2 is chemically bound. Taken as a whole the CO 2 balance of the new process is far better than that of the conventional production method. High-quality polyols based on CO 2 are currently not available on a commercial scale. However, after a successful pilot phase, a commercial production line with an annual capacity of 5,000 tonnes is under construction in Dormagen, Germany, as part of the Dream Production project, totalling an investment of € 15 million. Commercial production of these CO 2 -based polyols is expected to start early 2016. Polyols are initially planed for the production of flexible foam for mattresses. While the proportion of petroleum in this chemical is 80 %, Covestro aims at reducing the petro-based content to 60 % in a next step. In the new process, CO 2 is used twice. First, the greenhouse gas is incorporated directly into a new kind of precursor (polyoxymethylene polycarbonate polyol, POM PET), replacing 20 % of the petroleum. Second, it is also indirectly used for the production of a chemical that is also incorporated into the precursor for a further 20 % saving in petroleum. As a result, the proportion of alternative raw materials is 40 %. In addition, the number of plastics that can be produced using carbon dioxide is increasing: among thermoplastic polyurethanes Figure 3: Production of polyurethane (Covestro, 2014) O R O O x y O O N C R˙ OH + R O O O O x y O O N R˙ Polyol Isocyanate (Poly)urethane H 48 bioplastics MAGAZINE [06/15] Vol. 10

Basics (TPU), films and casting elastomers, it is also possible to use the new polyol in all kinds of applications, including automotive interiors, cable sheathing and sporting goods such as ski boots. This part of the Dream Polymers project is still at lab scale. It is being supported by the German Federal Ministry of Education and Research. External institutions in Germany such as the CAT Catalytic Center, the Leibniz Institute for Catalysis and the Fraunhofer Institute for Chemical Technology are also involved. Polymers and chemicals derived from biotechnology and other processes Beside these polymers produced by a chemical synthesis to a polyol via a metallic catalyst, some biotechnology routes for the production of well-known biobased polymers are also on their way. This is especially true for the technology to produce polyhydroxyalkanoates (PHA) and polylactic acid (PLA) based on the biotechnological production of lactic acid. These technologies using acetogenic bacteria to produce this kind of product are not on the market yet but several companies and research bodies are working on it. Examples are among others: LanzaTech (AU/USA), they are using patented, whollyowned microbes to convert carbon rich waste resources from industries or biogenic sources into valuable fuels and chemicals (platform chemicals and building blocks) through a process of gas fermentation. Another example but with a strong focus on fuel production is JOULE Unlimited (USA). They pioneered a unique CO 2 -to-liquids conversion technology that also offers an entirely new alternative for the production of CO 2 -based chemicals. Last but not least is Phytonix Corporation, based in the United States. This company is manufacturing sustainable chemicals directly from carbon dioxide, sunlight, and water via patented photobiological and genomics technology. In this manner, Phytonix produces n-butanol which can be used for the production of biobased plastics. Without doubt, Liquid Light (USA) is one of the key players in producing major chemicals from low-cost, globally-abundant carbon dioxide. The core technology, developed initially on the basis of licensed processes from Princeton and substantially enhanced since then, is centered on low-energy catalytic electrochemistry to convert CO 2 to chemicals, combined with hydrogenation and purification operations. Liquid Light’s first process via oxalic acid is for the production of ethylene glycol (MEG), which is used to make a wide range of consumer products such as PET plastic bottles, antifreeze and polyester clothing. Liquid Light’s technology can be used to produce more than 60 chemicals with large existing markets, including propylene, isopropanol, methyl-methacrylate and acetic acid. The first commercial production plant is planned for the year 2017. © Resysta Furniture and Decking (2), Faurecia, Tecnaro Sixth WPC & NFC Conference, Cologne Wood and Natural Fibre Composites 16 – 17 December 2015, Maritim Hotel, Germany World’s Largest WPC & NFC Conference in 2015! Market opportunities through intersectoral innovation in Wood-Plastic Composites and Natural Fibre Composites New applications – huge replacement potential in plastics and composites! ■ The international two-day programme, taking place in English ■ The world’s most comprehensive WPC exhibition ■ Vote for „The Wood and Natural Fibre Composite Award 2015“ ■ Gala dinner and other excellent networking opportunities Programme, Sponsors: Dr. Asta Eder Organisation, Communication, Exhibition: Dominik Vogt Organiser: nova-Institut GmbH Chemiepark Knapsack Industriestraße 300 50354 Hürth Germany bioplastics MAGAZINE [06/15] Vol. 10 49

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