Industrial biotechnology: Chemical building blocks from renewable resources

22:54 PM | August 12, 2013 | —Michael Ravenscroft

Holmgren: Having a positive impact.

Chemical majors are collaborating with biotechnology companies to develop chemicals derived from renewable feedstocks. Most activity is still at the development stage with only a small number of chemicals, such as 1,3-propanediol and lactic acid, being produced at industrial scale. Biobased succinic acid is the latest chemical from renewable feedstocks that is being produced on a larger scale.

The global market for renewable chemicals is anticipated to grow from $3.6 billion today to over $12 billion by 2020, according to Rennovia (Menlo Park, CA), which is targeting production of a suite of chemical products from renewable feedstocks.

There continues to be demand for products derived from renewable raw materials, such as biobased polyethylene from consumer products companies such as Coca-Cola, Danone, and Procter & Gamble. There is a lot of activity in developing new routes to conventional chemicals using renewable materials such as biomass, agricultural, and forest waste. Nevertheless, with a few exceptions, biobased chemicals have not yet made it into the big time to compete with petrochemical counterparts. Some of the exceptions are specialty fine chemicals, such as citric acid and amino acids. The most prominent biobased chemicals include 1,3-propanediol and lactic acid, which are 100% and 99% biobased, respectively, according to IHS Chemical data. In contrast, about 12% of global epichlorohydrin and about 8% of propylene glycol productions are biobased. Both substances are derived from glycerin, a by-product of biodiesel production.

Commercial prospects for biobased chemicals depends on a number of factors, including feedstock costs, scale, available technology, voluntary corporate environmental initiatives, and greehouse gas (GHG) emission regulations, says Marifaith Hackett, senior manager at IHS Chemical. Cradle-to-gate analyses show biobased chemicals have lower GHG emissions—and in some cases are GHG negative—resulting in removal or permanent storage of GHG. Such analyses are, however, feedstock- and process-specific, and other environmental impacts, such as land use, water demand, and eutrophication, may be significant, Hackett adds.

There are no clear-cut advantages or disadvantages to using fossil-based or renewable raw materials per se, BASF says. It is best to decide on a case-by-case basis, taking environmental concerns, cost effectiveness, and social impact over the entire product life cycle into account. BASF’s ecoefficiency analysis has shown that biobased plastics are not always more ecoefficient than their petrochemical-based counterparts. If relatively little water and fertilizer are required and transportation routes are short, using plant-based raw materials can be best. But if a large amount of energy is needed to process the materials, beneficial effects can be reversed. BASF used about 3% renewable raw materials for its production in 2012. “Customers in the electronic and automotive industries will not pay a premium for biobased products unless there is a technical advantage,” says Matthias Scheibitz, specialist R&D/product development at BASF automotive.

Factory of the future: BASF and Purac eye Basfi succiniproucens to make biobased succinic acid.

A product will be sustainable if it meets economic, environmental, and social drivers, “the three pillars of sustainability,” says Jennifer Holmgren, CEO at LanzaTech (Roselle, IL). “Our drivers are to reduce the carbon footprint; to make low-carbon fuels, but do it from feedstocks that don’t negatively impact society or are perhaps [even] beneficial for society; not negatively impacting food, land, water, but positively impacting [them],” she says.

DSM says its investments in the biobased economy are viewed as a medium-to-long-term opportunity, created by the necessary transition from the current fossil-based system toward one that is biobased.

“This development is seen as a combination of DSM’s ambitions in innovation and sustainability while laying the foundation for a sound future business,” says Joost Dubois, DSM director/branding and communication. “DSM’s aim is to have technology solutions in time to be able to respond to [expected] customer demand whilst using DSM’s established competencies in biotechnology and materials science,” Dubois says. “This will depend on rising prices making petro-based raw materials unwanted by the industry or when customers demand a preference for sustainable or renewable solutions.”

Food versus fuels

Using agricultural products as a renewable resource poses a dilemma between their use as food versus their use in chemicals production. The biofuel industry faced the same question. “On the chemical side, a lot of people say that the chemical market is so much smaller, the impact is going to be very small, so there’s nothing wrong with using sugars as feedstocks. I would beg to differ,” says LanzaTech’s Holmgren. Second- and third-generation processes use nonfood agricultural material, such as lignocellulosics.

The surface required to grow sufficient feedstock for today’s bioplastic production is less than 0.006% of the global agricultural area of 5 billion hectares, according to European Bioplastics and based on figures from the Food and Agriculture Organization of the United Nations and calculations by the Institute for Bioplastics and Biocomposites at the University of Hannover, in Germany.

Senator Debbie Stabenow (D., MI) has introduced legislation in the United States aimed at reducing taxes for US producers of renewable chemicals. “These tax cuts for our domestic, biobased manufacturing companies will help spur innovation, grow the economy, and create jobs across the country,” Stabenow says. Creating a level playing field in tax policy will help US industrial biotech companies innovate and develop new products, says Jim Greenwood, president and CEO at Biotechnology Industry Organization (Washington).

Germany’s biotechnology trade association, DIB (Frankfurt), meanwhile, has called for state support to help maintain the competitiveness of biotech in the country and in Europe. “Germany and Europe need biotech, because it can contribute to solving some of society’s greatest challenges,” says Matthias Braun, chairman of DIB. The organization is calling for the introduction of tax subsidies, in addition to previous financial support, to encourage innovation. “Tax support for research is an effective means of supporting economic growth. Germany is currently at a disadvantage compared with other countries,” Braun says.

“Research-based companies should be able to deduct 10% of their self-financed R&D spending from their tax liabilit[ies],” says Ricardo Gent, executive director at DIB. “A tax credit of at least 10% seems reasonable for Germany, as a tax credit of 8–20% is usually granted in the major industrial countries,” he says. “On the whole, we think that there is a statistical undervaluation of biotech in Germany,” he adds.

The European Commission, EU member states, and European industry are investing €3.8 billion ($5.0 billion) in a biobased industries initiative, Biobased and Renewable Industries for Development and Growth (Bridge). The initiative is slated to start in January 2014 and run to 2020. “The emerging biobased industry sector is set be the game changer for stimulating smart, sustainable, and inclusive growth in Europe. By finding commercially viable ways of generating fuel and other products from plants and waste, it will significantly reduce our dependency on oil, help us meet climate change targets, and lead to greener and more environmentally friendly growth,” says Máire Geoghegan-Quinn, European commissioner for research, innovation, and science. “Europe must develop technology leadership in this sector, which is why the EU and industry are backing this new joint technology initiative.”

Product pipeline

One product drawing attention from several producers is biobased succinic acid (BSA). Capacity for succinic acid is about 25,000–30,000 m.t./year, says DSM, which produces it from petrochemical feedstocks. Demand for BSA, driven by applications such as intermediates, solvents, polyurethanes (PUs), and plasticizers, is anticipated to grow strongly. The addressable market for BSA could be worth up to $7.5 billion, according to Myriant. BSA production capacity is growing rapidly, leaping from 3,000 m.t. in 2011 to 50,000 m.t./year in 2013 (chart).

BASF and Purac, a subsidiary of CSM (now Corbion), have been working together since 2009 to make BSA using Basfi succiniproducens using glycerin or glucose as feedstock. The companies formed a 50-50 joint venture, Succinicity (Düsseldorf), which started business this year. Succinicity is building a plant near Barcelona with a capacity of 10,000 m.t./year of BSA, scheduled to be onstream late this year or early in 2014. BASF says that it is planning a second plant with a capacity of 50,000 m.t./year, following a successful market introduction. CW was unable to obtain further details.

Reverdia (Geelen, Netherlands), a jv of DSM with Roquette Freres (Lestreme, France), started up a 10,000-m.t./year BSA plant at Spinola, Italy, at the end of 2012. Reverdia is considering a second plant for BSA, the company says.

ThyssenKrupp commissioned Europe’s first multipurpose fermentation plant at Leuna, Germany, for the continuous production of biobased chemicals earlier this year. The plant has capacity to make 1,000 m.t./year of biobased chemicals such as lactic acid and succinic acid. ThyssenKrupp has been working with Myriant since 2009 to develop a commercial process for BSA. Industrial biotechnology is part of ThyssenKrupp’s growth strategy, the company says.

Myriant started a 13,500-m.t./year BSA plant at Lake Providence, LA, this year. A second plant, with BSA capacity of 64,000 m.t./year, is being planned for start-up in 2015, Myriant says.

BioAmber supplies its BSA from a 3,000-m.t./year plant in France. The company is building a plant at Sarnia, ON, with capacity of 30,000 m.t./year, slated to be onstream in 2014.

LanzaTech is using waste carbon monoxide from steel mills and other sources to make chemicals such as 2,3-butanediol (2,3-BDO). The company uses a native organism that is able to produce 2,3-BDO, which can be dehydrated to butadiene or converted into other chemicals, such as methyl ethyl ketone or butanol. The company is working to pilot that now, CEO Holmgren tells CW. The second route, which is longer term, is to genetically modify the organism to be able to produce butadiene directly. “This is quite exciting, to genetically modify an organism to make something like butadiene,” Holmgren says. “This changes the rules. Now, you’ve totally decoupled the production of a commodity chemical because you’re not using a commodity feedstock.” Invista is collaborating with LanzaTech to develop biobased butadiene as feedstock for adiponitrile, used for nylon-6,6.

LanzaTech is also working on using carbon dioxide directly as a carbon source for petrochemicals’ production, using hydrogen from synthetic gas as the energy source to make acetic acid. The company is working towards a pilot demonstration scale of tens of hundreds of kilograms per year, scheduled for end-2013 or early 2014, Holmgren tells CW.

Meanwhile, several chemical companies are working with Genomatica’s (San Diego) process for biobased 1,4-butanediol (bioBDO). Novamont (Novara, Italy) is building a bioBDO plant with a capacity of 18,000 m.t./year, based on Genomatica technology. Toray Industries and Lanxess have produced polybutylene terephthalate (PBT) using bioBDO from Genomatica. Toray plans to build a commercial-scale plant “once bioBDO availability allows,” the company says. Lanxess intends to market biobased PBT as a drop-in replacement for petrochemical-based material. Global PBT capacity is about 700,000 m.t./year and consumes about 29% of all BDO consumed globally. BASF has a petrochemical-based BDO capacity of 530,000 m.t./year and intends to build a new plant in China with a petrochemical-based capacity of 100,000 m.t./year. The company plans to offer bioBDO in the plastics, textile, and automotive industries, BASF says.

Lanxess is producing 10,000 m.t./year of biobased ethylene propylene diene monomer (EPDM) rubber in Brazil. The EPDM contains 50–70% renewable ethylene derived from sugarcane, Lanxess says.

DSM has developed a proprietary pathway for the production of renewable adipic acid, “but commercialization within five years cannot be confirmed at this stage,” DSM’s Dubois tells CW. About 60% of the global adipic acid market of 2.5 million m.t./year, worth $5 billion, is used for nylon-6,6, DSM says.

Rennovia is running a kilogram-scale pilot plant for adipic acid using glucose as feedstock and is aiming at 2015 for commercial production. Earlier this year, the company produced hexamethylene diamine (HMDA) from renewable feedstocks, enabling production of 100% biobased nylon-6,6 for the first time. The next stage will be production of HMDA on a demonstration scale, Rennovia says. About 1.36 million m.t. of HMDA is produced each year, worth about $4 billion, according to Rennovia.

Verdezyne has developed yeast that can produce adipic acid using sugar or plant oil as feed. The company operates a 300-liter fermenter, which is capable of producing 1,000 kilograms/year if run continuously, Verdezyne tells CW. The pilot plant has been used to make kilogram samples for market testing of adipic acid, sebacic acid, and dodecanedioic acid (DDDA). These samples have been successfully used as drop-ins for nylon and PUs, Verzedyne says. Demonstration trials at up to 1,000 m.t./year are planned for first-half 2014, the company says. Verdezyne claims a 30–50% cost advantage based on current feedstock cost over diacids produced from petrochemicals, depending on specific feedstock composition, the company says.

Sebacic acid is used in production of nylon-6,10 for toothbrush bristles, coatings, and polyesters, a market worth $600 million, according to Verdezyne. DSM’s biobased nylon-4,10 is used in the engine cover of the Mercedes Benz A-Class automobile. The acid is produced from castor oil—the supply of which is limited, so more demand for products based on it could lead to shortages, says DSM.

DDDA, produced from butadiene, is used to make nylon-6,12. Verdezyne’s yeast-based platform can produce DDDA from low-cost plant-based feedstocks. The DDDA market is worth $250 million/year, according to Verdezyne.

Evonik has started a pilot plant for omega-amino lauric acid (ALS) in Slovakia. The biobased ALS, derived from palm oil, is an alternative to petroleum-based laurin lactam (LL). Evonik says that ALS can potentially replace LL as a monomer in high-performance plastics, such as nylon-12. The process is seen as complementing the butadiene-based production of nylon-12. Evonik claims that the biobased material makes the company less dependent on fossil fuel resources and provides a second pillar for its back-integrated production to stand on. Evonik has a conventional, hydrocarbon-based nylon-12 plant with a capacity of 20,000 m.t./year in the planning stage in Singapore.

Toray is working with Gevo (Englewood, CO) to convert biobased para-xylene (bio p-xylene) into purified terephthalic acid, to make polyethylene terephthalate (PET) or PBT. Virent (Madison, WI) is converting sugars into aromatics such as bio p-xylene, which has been converted into PET and PET bottles, the company tells CW.

The prospect of sustained high propylene prices is driving companies to pursue biobased acrylic acid. BASF, with partners Cargill and Novozymes, has announced a successful pilot plant trial earlier this year on a “larger kilogram scale” to make 3-hydroxypropionic acid, a precursor for acrylic acid. BASF is looking to use 100% biobased acrylic acid for the manufacture of superabsorbent polymers.

Myriant (Quincy, MA) is using low-cost sugars as feedstocks for a biobased route to acrylic acid. The global acrylic acid market is worth more than $14 billion, according to Myriant.

Avantium (Amsterdam) is developing biobased routes to 2,5-furandicarboxylic acid (FDCA), initially using commercially available carbohydrates (first-generation sugar and starch crops), but later using second- and third-generation, nonfood feedstocks. The company aims to use FDCA to replace purified phthalic acid in petroleum-based polyesters, such as PET.

Avantium is partnering with Solvay to develop FDCA-based polyamides for engineering plastics and with Coca-Cola, Danone, and Alpla for the development of 100% biobased polyester polyethylene-furanoate (PEF) bottles. PEF could replace PET in typical applications such as films, fibers, and particularly bottles for the packaging of soft drinks, water, and beverages.

“Products won’t sell themselves just because they are based on renewable resources,” says Jan Ravenstijn, a bioplastics consultant. “Companies need to understand how to bring new biopolymers to market.”

The success of biobased chemicals will rest on competitive economics or premium end uses, says IHS Chemicals’ Hackett.

“[We need] to address long-term procurement exposure to price volatility and security of supply of critical raw materials,” says Lee Edwards, CEO at Virent.

Scorecard: Chemical building blocks from renewables
(biofuels not included—not an exhaustive fuel)
Biobased Chemical Laboratory, Pilot, Demonstration Unit Commercial-Scale Production
C2 Ethylene Dow Chemical/Mitsui1 Braskem: from sugarcane ethanol, 200,000 m.t./year PE; Lanxess has capacity of 10,000 m.t./year of EPDM rubber, Brazil
C2 Ethylene glycol Greencol Taiwan: 100,000-m.t./year bioMEG plant, 2012 India Glycols: from sugarcane ethanol, 175,000 m.t./year
C2 Glycolic acid (hydroxyacetic acid) Metabolic Explorer/ Roquette
C2 Acetic acid Wacker, 500-m.t./year pilot plant
C3 Propylene Braskem, Dow, Global Bioenergies Braskem, considering a 30,000–50,000-m.t./year PP plant
C3 Propylene glycol Senergy Chemical, from glycerin Archer Daniels Midland, 100,000 m.t./year
C3 1,3-Propanediol Metabolic Explorer, 8,000 m.t./year DuPont Tate & Lyle Bio Products, 45,000 m.t./year
C3 Epichlorohydrin Dow Solvay: 10,000-m.t./year plant, France; 100,000-m.t./year plant, Thailand; plant announced for China, 2014, with 100,000-m.t./year capacity, Spolchemie, 15,000-m.t./year plant
C3 Lactic acid Cargill: increasing polylactic acid capacity to over 150,000 m.t./year, Galactic, Purac
C3 Acetone TetraVitae Bioscience: acquired by Eastman Renewable Materials, Nov 2011 Cathay Industrial Biotech; Jiangsu Lianhai Biological Technology Co.
C3 Acrylic acid Arkema: glycerin-based; BASF, Cargill, Metabolix, Myriant, OPX Biotechnologies/Dow: fermentation-based; SGA Polymers: from lactic acid
C3 3-Hydroxy acrylic acid BASF/Cargill/Novozymes jv, kilogram scale
C4 Isobutene Gevo/Lanxess; Global Bioenergies Lanxess has 10,000 m.t./year of biobased EPDM rubber, Brazil
C4 Butadiene Global Bioenergies; Genomatica
C4 Succinic acid BASF/Purac jv (Purac belongs to CSM, now Corbion), BioAmber, Myriant, and Reverdia (DSM, Roquette Freres jv) BASF/Purac, Succinity: Barcelona plant, 10,000 m.t./year, late 2013; plans for a 50,000-m.t./year plant, BioAmber: 350,000-liter fermenter; demo plant, 2,000 m.t. in France; building a 30,000-m.t./year plant, Sarnia, ON (due 2014), with plans to add 20,000 m.t./year; planning plant in Thailand with capacity about 100,000 m.t./year BDO and biosuccinic acid; Reverdia: Dec 2012, 10,000 m.t./y commercial plant
C4 1,4-Butanediol BioAmber, Genomatica/Chemtex, Genomatica/Tate & Lyle, Metabolix (from poly-3-hydroxybutyrate (PHB), 8,000 m.t./y SE Asia, Myriant/DPT Lanxess, Genomatica: trial run June 2013 of 20 m.t. PBT using Genomatica’s bioBDO. Genomatica did five-week BDO run, 2,000 m.t., Toray Apr 2013, BASF and Geonomatica, May 2013, Novamont (Genomatica), 2013
C5 Isoprene Amyris, Genencor/Goodyear, Glycos Biotechnologies due to start BioSIM (biobased Synthetic Isoprene Monomer) production 2014
C6 2,5-Furandicarboxylic acid (FDCA) Avantium, 20-m.t./year pilot plant; partnership with Solvay for nylon, engineering thermoplastics Avantium at engineering stage for a 50,000-m.t./year plant
C6 Glucaric acid Rivertop Renewables
C6 Adipic acid and other nylon precursors BioAmber/Celexion, Draths (now Amyris), Genomatica, Rennovia, and Verdezyne
C6 Hexamethylenediamine (HMDA) Rennovia, Draths (now Amyris)
C6 Aromatics Virent (BTX); 10,000-gal/year pilot plant, Annellotech
C8 para-Xylene (PX) Gevo2: from bioisobutanol, Virent Energy Systems, Toray: from biobutanol, Anellotech
C10, C12 Sebacic acid (decanoic acid), dodecanoic acid Verdezyne Cathay Industrial Biotech
1) Agreement for 350,000-m.t./year ethanol plant, set onstream 2015. 2) Working with Toray and Coca-Cola to make bio p-xylene, for purified PTA, to make PET.