New Bio Monomers Are Growing Fast

By Jan H. Schut

Keep an eye on two new bio feed stocks–bio-paraxylene and bio-succinic acid. Both could alter the biopolymer commercial landscape fairly rapidly because both can produce new 100% biopolymers. They have been under intense development for the past five years, so they are well known to bio chemistry companies, but plastics processors so far have heard little about them.

Why should plastics processors care? Because reportedly these bio-based chemical feed stocks could actually be considerably less expensive than their petro-based equivalents. That’s a first. So for the first time they could challenge conventional commodity plastics like PET, PE and PP head on. They are also designed to drop into existing equipment for petro-based chemicals, so they could be commercialized fast.

Bio paraxylene was on the program at the Society of Plastics Engineers’ first Bioplastic Materials Topical Conference, co-sponsored by the Pacific Northwest Section and Bioplastics Special Interest Group in Seattle, Wash. (www.4spe.org) May 16-18 and also at the 6th Bioplastics Markets conference in Bangkok, organized by the Centre for Management Technology in Singapore (www.cmtevents.com) on May 23-24. Bio succinic acid was the big topic at the Bioplastics Markets conference in Bangkok as well.

WHY BIO-PARAXYLENE?

Bio-paraxylene will enable production of 100% bio-based PET for the first time. Bio PET was widely announced by Coca Cola Co. (www.coca-cola.com) in 2009 and H.J. Heinz Co. (www.heinz.com) in 2011 as the “plant bottle” with roll outs of up to 30% bio-based PET. Up to 30% bio content is achievable by using mono-ethylene glycol made from plant-based ethylene. But paraxylene, which is used to make purified terephthalic acid, makes up about 70 wt% of PET, and is based on naptha from oil.

At the SPE’s Bioplastics TopCon Robert Kriegel, senior scientist at Coca Cola Co. in Atlanta (www.coca-cola.com), outlined Coke’s partnerships with Virent Inc., Madison, Wis. (www.virent.com), and Gevo Inc., Englewood, Colo. (www.gevo.com). Virent and Gevo have different biochemistry routes to paraxylene, but both add up to 100% bio PET. Bio PET also has the advantage that it won’t disturb existing PET bottle recycling the way any clear non-PET bottle would, like the biopolymers PLA or polyethylene furanoate (PEF), a new high barrier polyester.

Virent’s plant-based chemistry makes paraxylene from sugar or non-food bio mass like corn stover or even pine tree waste. The technology has been under development for over a decade based on R&D by Randy Cortwright, founder and chief technology officer of Virent. The company was spun off from the University of Wisconsin, Madison in 2002 with investment from Cargill Inc. (www.cargill.com), Royal Dutch Shell (www.shell.com), and Honda Motor Co. (world.honda.com). Virent claims over 160 patents and patent applications in 25 technology families, based on a catalytic “reforming” technology that can convert biomaterial in an aqueous solution into conventional hydrocarbons. These hydrocarbons can then be used in conventional fuel or chemical production, such as bio-paraxylene. Virent currently makes bio-paraxylene in a 10,000 gal/yr pilot plant in Madison. Virent first announced production of bio-paraxylene at the BioPlastek conference in 2011, organized by Schotland Business Research in Skillman, N.J. (www.plastek.com), but no expansion or scale-up plans have been announced. Virent has claimed in the past that its aqueous conversion technology can be cost competitive with petro paraxylene  when crude oil is over $60/bbl.

Virent Inc., a spin off from the University of Wis., Madison, makes bio paraxylene in this 10,000 gal/year demo plant. Bio paraxylene is needed to make 100% bio-based PET.

Gevo was founded in 2005 by NatureWorks’ co-founder, Patrick Gruber, who is Gevo’s CEO. President and COO Christopher Ryan and executive v.p. technology David Glassner also formerly worked at NatureWorks. Gevo uses proprietary yeast fermentation, a patented bio-catalyst (seven patents, including U.S. Pat. # 8017375), and patented separation technology (U.S. Pat. # 8101808) to make bio-based isobutanol from sugar-based feedstock like cornstarch and sugar cane or cellulosic biomass like corn stover or forest byproducts. Gevo just started up the world’s first commercial bio-isobutanol plant on May 24 in Luverne, Minn., with capacity to make 110 million lb/year. Gevo’s bio isobutanol technology could spread fast because it’s designed to retrofit into existing ethanol plants. Toray Industries Inc. (www.toray.com) has an agreement with Gevo to make PET from bio paraxylene made from Gevo’s bio isobutanol.

Coke also partners with Avantium in Amsterdam, the Netherlands (www.avantium.com), to develop bio PEF, a new polyester also for 100% bio-based bottles.  Avantium was spun off in 2000 from Shell into a consortium of Shell, Eastman Chemical, Akzo-Nobel and Pfizer set up to speed development of new catalysts. Avantium began to work with bio mass conversion in 2005, focusing on producing furanes economically from carbohydrates based on lignocellulosics like waste paper or agricultural residues. In 2008, Avantium raised venture capital to develop its own bio-based furane technologies and in 2010 won the SPE GPEC Clean Technologies Award for bio PEF. In December 2011 it started up an 80,000 lb/year pilot plant in Geleen, the Netherlands, to make 2,5 furandicarboxylic acid monomer, the precursor for bio PEF, and to make PEF polymer, which it expects to make commercially in three to four years. Avantium CTO Gert-Jan Gruter claims 43 patents. (The furanics patents and applications are under Gerardus Johannes Gruter and assigned to Furanix Technologies B.V., not to Avantium directly.) Avantium says that limited amounts of PEF can be recycled with PET without degrading PET properties.

WHY BIO-SUCCINIC ACID?

Conventional petro-based succinic acid (1.4 butanedioic acid) monomer is used as a flavoring and preservative in foods and as a chemical in personal care products. It’s also used to make biodegradable polyesters such as polybutylene succinate (PBS) polymer and polybutylene succinate adipate (PBSA). PBS was first commercialized by Showa Denko Co. in Japan in the early 1990s as Bionolle. Other makers of PBS include Hexing Chemical Anhui in China; Mitsubishi Chemical in Japan; and IRE Chemicals in Korea, recently bought by Samsung. Petro-based PBS can be similar to polyolefins like PE and PP or to PET, and can be blended with PLA to raise HDT, reduce brittleness, and increase flexibility, but only a few million lb/year of PBS are made because it’s so expensive.

Five production partnerships have been announced to produce new bio-based succinic acid and/or bio butanediol (BDO), based on sugar, starch or cassava, or on non-food bio mass like corn stover or pine tree waste—BioAmber Inc. (formerly Diversified Natural Products) in Minneapolis (www.bio-amber.com); Myriant Corp. in Quincy, Mass. (www.myriant.com); Reverdia VOF in Geleen, the Netherlands (www.reverdia.com); Purac (a unit of CSM) in Gorinchem, the Netherlands (www.purac.com); and Genomatica Inc., San Diego, Calif. (www.genomatica.com). Each has close connections to a polymer company to open markets for new bio materials like bio succinic acid, bio BDO, and bio PBS. Bio BDO can be combined with bio succinic acid to make bio PBS. Several other chemical companies have patents on bio succinic acid technology, but haven’t announced projects. What will all that new bio succinic acid and bio BDO be used for? New commodity plastics.

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Myriant’s 30 million lb/year bio succinic acid plant in Lake Providence, La., starts up in early 2013 to produce the new bio monomer, which will be used to make both bio PBS and bio BDO.

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Reverdia’s 22 million lb/year bio succinic acid plant in Italy starts up later this year using yeast fermentation, which reportedly creates fewer waste products than bacterial fermentation.

BioAmber is the early leader. It operates a 350,000 liter fermenter for bio succinic acid in Pomacle, France, and has a joint venture with Mitsui & Co. in Japan (www.mitsui.com) to build three more plants—in Sarnia, Ont.; Bangkok, Thailand; and either Brazil or the U.S. The Thai plant will supply bio succinic acid exclusively to PTT-MCC Biochem, a joint venture between PTT PLC, a chemical company in Thailand, and Mitsubishi Chemical. PTT Global Chemical, part of the PTT Group, recently bought 50% of NatureWorks. The PTT-MCC bio PBS plant in Bangkok is expected to be operating by 2014. BioAmber currently uses bacterial fermentation, but also licenses yeast technology from Cargill. BioAmber also recently announced production and sampling of bio BDO.

Myriant is building a 30 million lb/year fermenting plant for bio succinic acid in Lake Providence, La., which is expected to be operational in 1Q 2013. Investment comes from a $50 million U.S. government grant plus $60 million from PTT Chem in Thailand. Myriant also announced plans to build a full scale 140 million lb/year plant in the U.S., which could be the first such full scale plant in the world. Myriant is expected to supply bio succinic acid to PTT-MCC’s future bio PBS plant in Thailand and to Showa Denko’s PBS. Myriant partnered with Davy Process Technology in London, U.K. (www.davyprotech.com) to ensure that its succinic acid would also drop into Davy’s single-reactor process to make BDO. Myriant has an understanding with China National BlueStar (Group) Co. (www.china-bluestar.com) to plan a bio succinic acid plant in China to supply Davy Process BDO.  Myriant says its bio BDO will be cost competitive if oil is over $45 bbl. The Lake Providence plant will use sugar as feedstock or grain sorghum, a non-food grain byproduct, and bacterial fermentation.

Reverdia is a joint/venture between French starch producer Roquette Group in Lestrem, France (www.roquette.com) and DSM in Heerlen, the Netherlands (www.dsm.com) since 2008. The venture is starting up a 22 million lb/year semi works plant in a Roquette site in Cassano Spinola, Italy, in 3Q 2012 to make bio succinic acid. Reverdia claims 15 patents for its process, which uses a low-PH yeast and reportedly creates less salt by product. Reverdia is the only known bio succinic acid venture that isn’t tied to a producer of PBS. DSM doesn’t make PBS, but makes PBT.

Purac announced a partnership last year with BASF in Ludwigshaven, Germany (www.basf.com), to build a 55 million lb/year bio succinic acid plant in Spain by 2013. Purac and BASF have partnered since 2009, using bacteria developed by BASF. Purac has demonstrated its succinic acid technology in a test fermenter near Barcelona, Spain. The joint venture says it will sell succinic acid to any maker of PBS or modified PBS.

Genomatica, founded in 2000, has biochemistry to produce BDO and butadiene, based on sugar.  Its patented bio BDO process (multiple patents including U.S. Pat. # 8067214) was demonstrated on a 3000-liter pilot scale in 2010 and scaled up at Tate & Lyle’s 13,000-liter demo plant in Decatur, Ill., in 2011. Genomatica is partnering with Mitsubishi Chemical since 2011 to plan a bio BDO plant in Asia and has a joint venture with Novamont SpA in Novara, Italy (www.novamont.com). Novamont will invest $50 million and convert a 40 million lb/year plant in Adria, Italy, to Genomatica’s bio BDO process. The Adria plant is expected to start up in 2013 and supply BDO to Novamont.

The first data sheets for bio succinic acid-based polymers recently became available. In February BioAmber  announced a joint venture with NatureWorks called AmberWorks, which will add compounded grades based on combining poly lactic acid and succinic acid polymers. The first two AmberWorks grades are AW 240D and AW 300D for thermoformed and injection molded food service ware respectively. These initial grades are bio PBS based, but NatureWorks could also use copolymers like bio PBSA (an adipic acid, succinic acid copolymer with BDO) in future blends. FKuR Kunststoffe GmbH in Willich, Germany (www.fkur.com) also recently introduced two grades based on PLA and PBS, BioFlex S5630 for thermoforming and injection molding, and BioFlex S6540 for injection molding.

Properties of first biodegradable polymers made with bio PBS and PLA

Supplier                                AmberWorks                                     FKuR Kunststoffe

Ingeo                      Ingeo                   Bio-Flex              Bio-Flex

Grade                          AW 240D               AW 300D            S 5630                 S 6540

PLA content (%)         <10                         40-50

PBS content (%)          60-70                     40-50

Talc (%)                       20-30                     <10

Density. g/cc               1.48                        1.34                      1.55                    1.62

MFR, g/10 min.

(190 C, 2.16 kg)        6                             27                        10-12                   8-10

Clarity                         Opaque                  Opaque                Opaque                Opaque

Flex. Modulus, MPa   1650                       2450                     2400                    2890

Vicat Softening

Point, F                      220                         225                      192                      192

Notched Izod Impact,

ft-lb/in.                      —                            0.62                       —                        —

Notched Impact Str.,

Charpy, kJ/m2          —                             —                           3                        3

HDT @ 66 psi, F        185*                       122*                      154**                N/A

Flex. Strain @

Break, %                    —                             —                          No break           6

* Using ASTM D648; ** Using ISO 75

Bio succinic acid is also used in new bio-based plasticizers and other additives for 100% bio plastic formulations. A new 100% bio ester, for example, introduced by HallStar Co. in Chicago (www.hallstar.com), is based on bio succinic acid. Hallstar’s patented (U.S. Pat. # 8158731) HallGreen R8010 plasticizer can be used at loadings of 5% up to 30% depending on desired material properties.

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3 Responses to New Bio Monomers Are Growing Fast

  1. Bio-Based Chemicals Analyst says:

    Gevo was not founded by Pat Gruber. Gevo was founded by Matt Peters, Peter Meinhold (both CalTech scholars), and Francis Arnold, CalTech professor. Gruber came in as CEO only after the company had narrowed its focus to bio-butanol technologies.

  2. Our group of scientists are making tailor made biomonomers from triglycerids according to the expectations of the bioplastic producers. Special feature: nearly limitless variations of molecular structures. You tell what plastic you want, we tell you how to reach the biomonomers molecular structure. Regards – Dr. Laszlo Kondor – KEMIA GmbH, Vienna, Austria

  3. Pingback: Avantium raises $50M from Coca-Cola, Danone, Swire and more: renewable PEF plastic bottles take the spotlight | Buys Fan

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