Chemicals from Biomass? A major theme of 21st Century industrial development will be replacement of fossil resources by renewable resources in the production of fuels and chemicals. Due to their massive scale and cost, the rate of displacing fossil facilities will necessarily be evolutionary rather than precipitous. The most likely scenario is that the biorefinery will follow from an established platform process that produces a conventional chemical(s) from biomass.
Predicting which biomass chemicals process will spark the era of biorefining is not trivial. Foremost among the challenges is the wide dispersion of biomass resources. Unlike oil and gas that are found as huge reservoirs at a single site, biomass is distributed widely, with variable compositions, requires the handling of solids, and contains high water content. This limits the amount of biomass that can be readily collected in one place, which limits the economies of scale.
Biomass encompasses everything including algae, maize, wood waste etc. and each presents a different composition, and availability. Bio-based chemical processes must compete with existing, finely tuned petroleum based processes and will require more extensive testing at every step of production and utilization. Few end users will pay a premium for a bio-based material without functional advantages with the new material.
Herein, we will identify chemical target molecules that seem to be good candidates to become the cornerstone of a future biorefinery. To fit our criteria the chemical must have 1) large market, and 2) value much greater than raw biomass. In addition, the group developing the process must have the technical and financial capabilities to carry the development through to commercialization. We will describe two strong candidate molecules and suggest two candidates that will emerge as strong contenders.
Two strong candidates for Chemicals from Biomass
Furan dicarboxylic acid (FDCA) has emerged as a leading candidate to be the cornerstone of a future biorefinery. BASF, Corbion, and Coca-Cola have invested in the development, scaleup, and commercialization of FDCA. Polymerization of FDCA with bio-derived ethylene glycol produces polyester, polyethylene-furanoate (PEF), a 100% biobased material that could replace polyethylene-terephthalate (PET) in large markets such as bottles, fiber and film.
Avantium has been a front-runner in the technical development with its ‘YXY’ process that converts sugars to FDCA using a 2-step catalytic process. The Avantium team includes BASF, Danone, Coca-Cola,and Tereos, the world’s 3rd largest sugar producer.
Corbion is leveraging its long history of commercial production of lactic acid, lactic acid derivatives, and lactides, by developing a fermentation process to make FDCA. The Corbion process claims nearly quantitative yield for the biocatalytic conversion of raw hydroxymethylfurfural (HMF) to FDCA. PEF produced via the Corbion route offers a very high polymer yield per kg of feedstock.
Amongst others, Glucan Bio’s TriVersa Process™ technology uses bio-derived gamma-valerolactone (GVL) solvent to greatly accelerate the rate of deconstruction of biomass into its components. The process simultaneously transforms the components into building blocks that can be used to launch other products such as HMF, DMF, THF, and FDCA.
Ava Biochem began commercial production of HMF in 2014 with an initial capacity of about 20 tpa in Switzerland. The company claims to be the first worldwide to produce high-purity biomass-based HMF at commercial scale.
GFBiochemicals is producing commercial quantities of levulinic acid directly from biomass at its 10 ktpa plant in Italy. GFBiochemicals has recently diversified into levulinic acid derivatives with its acquisition of Segetis.
Succinic acid is another chemical precursor that has been projected by industry analysts to undergo almost explosive growth. Thus, several groups have assembled to exploit this nascent opportunity. Conventionally, succinic acid is produced from maleic anhydride, utilizing the C4-fraction of naphtha in quantities greater than 15,000 tpa.
Reverdia, a joint venture of DSM and Roquette, employs a low pH yeast fermentation process and is currently producing bio-based succinic acid (Biosuccinium™) at their first commercial 10 kta plant in Italy. Among the succinic acid markets in their sites are thermoplastics, solvents, 1,4 butanediol/THF, and pharmaceuticals. Swiss group Mader will launch its new range of bio-based alkyl paints with Reverdia’s Biosuccinium and Roquette’s POLYSORB® isosorbide. The new CADELI paint range reportedly has attractive physical properties such as hardness and scratch resistance, and some variants are anti-microbial or depolluting (anti-formaldehyde).
BioAmber uses cellulose based high-purity dextrose to produce 30,000 tpa bio-succinic acid by fermentation in Canada, that will be the basis of future products bio-BDO and bio-THF. The BioAmber team includes private bio-research firm ARD for scale-up, Cargill for yeast, and Johnson Matthey for the production of BDO and THF. The Flokser Grouphas developed an artificial leather fabric with better scratch resistance, and softer touch using bio-based materials supplied by DuPont Tate & Lyle Bio Products and BioAmberThe global addressable market opportunity for bio-based polyester polyols in artificial leather is 330 million pounds/year, half each for succinic acid and -1,3 propanediol.
Amongst others, Corbion and BASF joint venture Succinity is developing a succinic acid technology based on bacterial fermentation. A 10,000 tpa plant was started up in 2014 in Spain. Myriant with partners UPC and Sojitz is focussed on promoting bio-succinic acid based plasticizers. UPC Group plans to utilize Myriant’s bio-succinic acid in the manufacture of phthalate-free plasticizers while Sojitz will handle sales and marketing.
Two challengers for Chemicals from Biomass
Adipic acid is a 6-carbon acid used as a precursor in the manufacture of nylon 6,6, thermoplastic polyurethane resins, plasticizers, adhesives, and synthetic lubricants, with an estimated market of $6.3 billion. Nylon 6,6 accounts for about 85% of the total adipic acid demand.
Start-up companies Rennovia, Verdezyne, and Genomatica are developing bio-based routes to adipic acid, aimed at creating 100% bio-based nylon, with some having reached advanced pilot or demonstration scales. Adipic acid has traditionally been produced from the petroleum-based feedstocks, with a two step cyclohexane-based oxidation process accounting for 93% of global capacity.
Verdezyne uses genetically modified enzymes to ferment glucose to adipic acid, while Rennovia utilizes catalytic air oxidation to convert glucose to glucaric acid, followed by hydro-deoxygenation to adipic acid. The advantage of both bio-routes is their use of $300/mt glucose feedstock, compared to the conventional process using cyclohexane having a market price of $1,250/mt. Both alternative processes face significant challenges in their ability to achieve high feedstock selectivity and catalyst productivity (Rennovia), and high enzyme turnover rates and kinetics for the enzyme fermentation route (Verdezyne). Genomatica uses genetically modified microorganisms that feed on glucose to make adipic acid.
Para-xylene (pX), currently produced by the catalytic reforming of naphtha, contributes 80% of the carbon in PET. The global market for PET is about 50 million tpa ($30 billion) and growing at 6% CAGR. Coca Cola introduced PlantBottle™ in 2009 that contains 30% renewable content from sugar-derived monomethyl ethylene glycol (MEG) along with 70% petro-sourced terephthalic acid. Since Coke reported a sales boost from eco-conscious buyers of bottled water and soft drinks due to PlantBottle, and bio-MEG is reported to command a 30-50% price bump, this is one market where a green premium is being realized for the bio-based materials.
The Coca-Cola development team includes Gevo, Virent, and Avantium, who are each developing a different technology to produce pX. Gevo aims to produce pX from isobutanol via fermentation. Virent’s process hydrogenates and condenses sugars in a high pressure aqueous process called BioForming to produce oxygenates that are catalytically converted to a mixture including pX. Paraxylene from Virent was used to produce Coca-Cola’s first 100% bio-based PET bottles. Avantium is exploring routes to pX involving a multi-step reaction of furan derivatives and olefins.
Another alliance working to develop and commercialize bio-based aromatics is Anellotech and partners Japanese beverage giant Suntory, French process developer IFPEN, licensing and engineering firm AXENS, and catalyst provider Johnson Matthey. A 25-meter tall development and testing plant is under construction in Texas. The Anellotech one reactor process – Bio-TCat™ (one step from biomass to aromatics including pX) provides significant capital and operating cost savings compared to the multi-step processes.
The Bottom Line on Chemicals from Biomass
There are other chemicals that potentially could be the seeds from which biorefineries grow. At a recent USDOE sponsored event the list included methoxyphenols, olefins, paraffins, methane, ethylene, HMF, isoprenoids, higher alcohols, and fatty acids. In 2012 IEA Bioenergy identified an additional 30 products that could be of interest. The seed or seeds have not yet been identified, and how soon they will bloom is uncertain. What is not in doubt is that the biorefinery will emerge. See also: Biomass to Chemicals, Renewable Chemicals, and the Role of Chemical Recycling in a Circular Economy.