Defining Moment for Bioplastic Feedstock Developments

saving-earth
The recent decline of crude oil prices during 2015 forward has hampered the growth of bioplastics, yet the remarkable technology achievements in biochemical building blocks of the past two decades will continue strong during this transition period.  (Image: omnexus.specialchem.com).

With declining oil prices bioplastics will experience increased competition from fossil fuel based, volume plastics, particularly in the packaging market. Yet bioplastic companies will continue to demonstrate the same technical marketing business ingenuity they have exhibited over the past 25+ years by specialty feedstock/resin niche market development, by holding in place their existing technology, further focusing on added production efficiencies, and in some limited cases withdrawing from the bioplastic market segment as a result of non-competitiveness. This first Bioplastic Feedstocks article will be followed by a Bioplastic Materials and Bioplastic Applications reviews.

Editor’s Note:
This omnexus.specialchem.com articles provides an impressive overview of new conversion technologies for the manufacture of bio-based plastics. Some biomass-based products have been made since the 1920’s (e.g. Furfural). Furfural is one of the top 30 building blocks for bio-based chemicals and plastics.

Advances in Bioplastic Feedstock

Let’s now start by taking a current, broad ranging, summary look at recent bioplastic feedstock advances.

  • Braskem is the only global supplier of bio-polyethylene based on sugarcane, with 200 kilotons per year plant in Rio do Sul, Brazil. Sugar feedstock has exhibited a low but stable price, despite lower ethanol prices as a result of low crude oil and in turn gasoline prices. Bio-polyethylene market prices average 40% higher than standard fossil fuel based polyethylene. Braskem has put on hold its sugar cane based bio-polypropylene program until crude oil to ethanol pricing improves. Elsewhere in Europe, Sabic is planning to enter the bio-polyethylene and bio-polypropylene market segments using bio-naphtha from Neste Oil based on hydrocracked waste oils and fats feedstocks.
  • In the bio-polyester segment, bio-PolyButylene Succinate (PBS), bio-PolyTrimethylene Terephthalate (PTT), and bio-PolyEthylene Terephthalate (PET) are based on a range of renewable content feedstocks such as bio-diacids (succinic acid) and bio-diols (ethylene glycol, 1,3 propanediol).
  • BioAmber has brought on line 30 kilotons per year plant in Sarnia (Ontario) Canada, the largest in the world. Other succinic acid producers include US based Myriant (14 kilotons), Italy based Riverdia (10 kilotons), and Spain based Succinity (10 kilotons). Thailand based PTTMCC Biochem will take 15 kilotons per year of succinic acid from BioAmber and react it with 1,4 butanediol at its 20 kilotons per year bio-PolyButylene Succinate (PBS) plant.
  • DuPont’s Sorona PTT is manufactured from 1,3 PropaneDiOl (PDO) and Terephthalic Acid (TA). Its PDO is built off its Susterra molecule that establishes it as an alternative to fossil fuel based glycols. Further, the well-established DuPont Tate & Lyle alliance manufactures their glucose variety PDO at their 64 kilotons per year plant in Loudon, Tennessee, United States. Elsewhere. China’s Zhangjiagang Glory Industrial at its 65 kilotons per year glycerol type PDO and 2,3 ButaneDiOl (BDO) plant to captively manufacture its own PTT. Finally, China based Suzhou Shenghong Group is in the early planning stages of PDO (glycerol based) and PTT project.
  • Coca-Cola’s renewable content bottle program continues to grow slowly due mainly to low crude oil prices and high priced Mono Ethylene Glycol (MEG) monomer and bio-PET polymer materials. Sugar cane derived MEG are produced by only two global suppliers namely, Greencol Taiwan Corporation and India Glycols. Italy’s M&G Chemicals is developing a China based bio-MEG and bio-ethanol facility. India’s JBF Industries is considering a bio-MEG plant in South Carolina, potentially working with Coca-Cola.

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Coca-Cola’s Bio-Based PET PlantBottle

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PlantBottle Manufacturing Process (Green; 30% Bio-MEG, or Component B)

  • Bio-based systems such as 1,5 FuranDicCarboxylic Acid (FDCA) and Purified Terephthalic Acid (PTA)/paraxylene are opening new feedstock pathways to bio-PET. Furthermore, FDCA is a PTA feedstock replacement option. New York based Anellotech is pilot manufacturing development of bio-toluenes and bio-xylenes by thermal catalytic converting of biomass. Other companies namely Vertimass and Virent are pioneering similar bio-aromatics feedstock routes to bio-PET. Soon to be publicly announced will be The Netherlands based Avantium’s European FDCA commercial scale plant, with Japan’s Mitsui & Company being a major customer. Avantium has been providing FDCA development samples from a Geleen, The Netherlands 40 tons per year pilot facility. Their FDCA two step catalytic process converts sugars via proprietary “YXY” technology.
  • Mitsui & Company and Avantium are cooperating on PolyEthylene Furanoate (PEF) joint development based on FDCA and MEG to replace PET, targeting end use applications such as PEF bottles in Japan and thin films starting from Japan to across Asia.
  • In an adjunct area, Gevo (US) is converting bio-isobutanol into bio-paraxylene and producing sample quantities for Toray Industries (Japan) for bio-PET fiber development.
  • Princeton University spinoff company, Liquid Light Inc. (US) has advanced a laboratory scale photosynthesis process that transforms ethanol processed waste CO2 into bio-MEG.
  • In the bio-acrylic field due to competitive pricing pressures strong feedstock development transitions have occurred at a rapid rate. For example, Germany’s BASF and the US’ OPX Biotechnologies have pulled out of bio-acrylic acid development with US based Cargill and Novozymes respectively. Archer Daniels Midland (ADM, US), Arkema (France), and Nippon Shokubai (Japan) are developing bio-acrylic acid from glycerine, with only ADM having a pilot plant thus far.
  • Technology innovator Novomer (US) is developing their acrylic acid via specialized catalysts to make propiolactone from carbon monoxide and ethylene oxide. Then they take their polypropiolactone and with pyrolysis it becomes glacial acrylic acid. Depending on economics, the ethylene oxide can be renewably or fossil fuel based. No commercialization evident at present.
  • With regard to bio-MMA (Methyl MethAcrylate (MMA), state of the art French technology took the lead here. Arkema (France) in concert with Global Bioenergies (France) jointly developed bio-MMA with isobutene feedstock derived from glucose. Elsewhere at a very early development stage, Evonik’s Creavis Division (Germany) plus LanzaTech (Germany) is focused on fermentation processing to change syngas into a purified 2-HydroxyIsoButyric Acid (2-HIBA) to arrive at bio-MMA.
  • Lucite International (US, division of Japan’s Mitsubishi Rayon)) is exploring multiple biochemical feedstock routes to bio-MMA primarily including bio-methanol, bio-acetone, and bio-ethylene, with the goal of fitting them into currently used acrylic manufacturing schemes. Additionally, serious R&D efforts are investigating unique single step fermentation process methods to bio-MMA.
  • Itaconix (US) and Leaf Technologies (France) are pursuing maleic acid like, naturally occurring itaconic acid (or methylene succinic acid) as a feedstock for acrylic resins.

renewablefeedstocksRenewable Feedstocks (L) in Relation to Conventional Petrochemical Routes (R)— Plastics Institute of America

Commercializing Renewable Feedstocks : Projects

Global chemical industry companies are continually seeking new feedstocks and products derived from renewable sources to reduce dependence on petroleum longer term. Numerous strategic partnerships, investments and construction projects are making inroads in this drive to convert to biobased feedstocks and products. Let’s take a technology snapshot of some recent noteworthy development projects to commercialize renewable feedstocks as follows:

Methane to Lactic Acid Fermentation Technology

Let’s begin with milestone methane to lactic acid fermentation technology in development. Methane is a greenhouse gas that is approximately 20 times more harmful than carbon dioxide (CO2). Generated by the natural decomposition of plant materials and a component of natural gas, methane is also produced from society’s organic wastes such as waste-water treatment, decomposition within landfills, and anaerobic digestion. If successful, the technology could directly access carbon from any of these sources. NatureWorks and Calysta Energy, a company specialized in the development of industrial products from sustainable sources, are collaborating to develop a process for fermenting methane into lactic acid. Last year, Calysta announced it had successfully fermented methane into lactic acid, the building block for NatureWorks Ingeo lactide intermediates and polymers that are used in consumer and industrial products. Currently, Ingeo relies on carbon from CO2 feedstock fixed or sequestered through photosynthesis into simple plant sugars, known as ‘first generation materials.’ The US DOE (Department of Energy) has awarded $2.5 million to NatureWorks to transform biogas into the lactic acid building block in support of the NatureWorks/Calysta development program.

methanetolactic-acidfermentationtechnology

NatureWorks/Calysta Energy’s Methane to Lactic Acid Fermentation Technology

Key goals are to provide a simplified, lower cost Ingeo production platform and diversify NatureWorks’ feedstock portfolio. While the critical lab scale first stage of the project has confirmed methane conversion to lactic acid, much additional development work remains. A full demonstration of commercial feasibility may require up to five years of development effort. The companies will share commercialization rights for select products developed under the agreement.

Disruptive Carbon Capture Process Scheme

Next, let’s review plastic from disruptive carbon capture technology. Newlight Technologies is using its patented GHG (GreenHouse Gas) to-plastic bioconversion technology to harness methane-containing GHG that would otherwise become part of the air. Disruptive carbon capture technology that is patented by Newlight Technologies uses air and green-house gas to produce AirCarbon, a PHA (PolyHydroxyAlkanoate) based bioplastic material.

disruptivecarboncaptureprocess

Newlight Technologies Disruptive Carbon Capture Process Scheme

First, GHG carbon is captured, diluted with air, and directed into a conversion reactor. The air/GHG stream is then contacted with a micro-organism-based biocatalyst. The biocatalyst works by separating carbon and O2 from an air stream containing GHG, and then re-assembling the molecules into a long chain PHA-based bioplastic. Once synthesized, AirCarbon is then removed from the reactor system and processed into pellets.
Newlight’s biocatalyst is said to generate a polymer conversion yield over nine times higher than previous greenhouse gas-to-PHA conversion technologies and fundamentally shifts the cost structure of the greenhouse gas to a plastic conversion process. Newlight says its AirCarbon plastic can significantly out-compete oil-based plastics, such as polypropylene and polyethylene, on price. Newlight has signed a 20 year take-or-pay contract with Vinmar International for a total of up to 19 billion pounds of AirCarbon PHA over the 20 year period. Vinmar International Ltd is a privately held plastics and chemicals marketing, distribution and project development company headquartered in Houston, Texas. The contract launches AirCarbon to world-scale volume.

Hemicellulose Xylan Feedstock

Continuing, let’s evaluate a biobased, non-conventional building-block namely, Xylan complex polysaccharides. The main hemicelluloses in angiosperms (flowering plants), xylans make up 25-35% of the lignified tissues in grasses and cereals. This highly complex polysaccharide, made from units of xylose (a pentose sugar) is present in large quantities in agricultural and forestry by-products. Biobased and biodegradable Xylan is both sustainable and economical. Xylan is being extracted from cereal husks by Chalmers University spin-out company Xylophane AB using technology developed at the Chalmers University of Technology in Sweden. Isolated by an extraction process from an agricultural by-product, the material is not based on feedstock competing with food production. Xylan in powder form is blended with additives to form a barrier material that can be used in food packaging. The barrier product named Skalax is dissolved in water and coated onto food packaging substrates using reverse roll, rod or curtain coating processes.

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Xylophane AB’s Hemicellulose Xylan Feedstock

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Xylan Manufacturing Process

Tomato Waste Feedstock for Automotive Applications

Finally, let’s examine a tomato waste fiber source that is bioplastic feedstock filler mechanically blended for potential use in plastic composites. Ford Motor Company with H. J. Heinz, the food processor, are investigating the use of tomato fibers to develop sustainable composites for auto applications. Heinz researchers were looking for innovative ways to repurpose the peel, stem, and seed by-product from more than 2 million tons of tomatoes used annually to produce Heinz ketchup. Tomato by-products are shipped to Ford facilities where they are processed into small, dry pellets that can be used in manufacturing. Ford is testing the fiber in a polypropylene composite.

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Ford/Heinz’s Raw Form Tomato Waste Fiber (L), Tomato By-Product Pellets (R)

The goal is to develop a strong lightweight material that meets Ford vehicle requirements while also reducing overall environmental impact. Odor is a key concern that is being carefully monitored. Still in the very early stages of research, Ford is testing the tomato fiber composites’ durability for potential use in wiring brackets and car console storage bins.

ford-focus-electric-vehicle

Ford Focus Electric Vehicle—Tomato Waste Feedstock to Renewable Content Car Parts

Ford has been working with plant fibers for more than a decade, and last year introduced cellulose fiber-reinforced console components and rice hull-filled electrical cowl brackets. The company is also working with coconut-based composite materials and recycled cotton material for carpeting and seat fabrics. The company’s commitment to reduce, reuse and recycle is part of its global sustainability strategy to lessen its environmental footprint while accelerating development of fuel-efficient vehicle technology worldwide.

Conclusion

In conclusion, the road ahead looks bright for bioplastic feedstock development. The biobased economy is holding promise as rapid development of biochemicals based on biomass offers customers alternate supply chains compared with the traditional petroleum routes. The ‘Plastics Industry’ is undergoing dramatic transformation as bioplastics primarily derived from renewable feedstocks continue to gain recognition in a market dominated by petroleum-based products. Biobased raw materials will shift to non-food sources, for example, lignocellulosic biomass, algae, drought resistant plants, waste products and greenhouse gases. Collaborations between companies from agricultural, forestry and the chemical sectors will become increasingly important. Just as it is common for a petrochemical company to have interests in oil extraction, it will also become normal for chemical companies to look to ensure renewable feedstock availability.

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Today (L) versus Tomorrow (R) in Bioplastic Feedstock Development— Plastics Institute of America


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