DOE’s 12 Top Biobased Molecules – what became of them?

Although this subject is a bit larger than the focus of Bioplastics News, I find it useful to cast light on the precursor molecules of bioplastics as their commercial development and availability at affordable cost is paramount to the availability of downstream bioplastics. Many of the articles of Bioplastics News present the bioplastics paired with its precursors. This time, let’s have a view on where we stand with all the precursors that are the pillars of plant based chemistry.

I re-edit below an excellent article published by Jim Lane in BiofuelsDigest on April 30,2015,  which gives a comprehensive update on the development of 12 bio-based molecules highlighted in the strategy paper of the DOE as key for the development of bio-based chemistry .

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With the news that Cargill has acquired OPX Bio’s fermentation-based technology, which featured a hot route to biobased paints, adhesives, diapers, and detergents — we take a look back at a DOE paper that sparked so much interest in these biobased molecules.

If they handed out Platinum and Gold certification to scientific papers as we do with recorded music, “Top Value Added Chemicals from Biomass” would be a multi-platinum chart-busting monster. This 2004 survey, completed by staff led by Gene Petersen (now a DOE Project officer) and Todd Werpy, at the Pacific Northwest National Laboratory and NREL, is the Dark Side of the Moon of biobased, a perennial classic that has recorded 172,314 downloads to date via the Digest SuperData, alone, and gives the down-low on why 12 bio-based chemicals matter more than others.

But what has become of the 12 molecules? Which ones are hits, which ones are languishing, unloved, in labs or in scholarly journals that trumpet their potential.

 

RED HOT

Four Carbon 1,4-Diacids (Succinic, Fumaric, and Malic)

Succinic is hot, hot, hot. Four companies have been chasing the target – Myriant, BioAmber, BASF-Purac (Succinity), and Reverdia (DSM-Roquette).

Bio-succinic acid, according to our friends at Myriant USA, forms the basis for many high-value replacement products,including phthalic anhydride, adipic acid, and maleic anhydride.

Fumaric acid is commonly used as a preservative in food and beverages, in the production of paints and coatings, as well as in the production of paper. It is the chemical equivalent of maleic anhydride (MAN) and water, and therefore can be used as a replacement for MAN.

The hot company these days is, without question, BioAmber. In December, the company announced it has signed an exclusive supply agreement for bio-based succinic acid with Oleon France. Under the terms of the 5-year contract,which runs from 2014 to the end of 2018, BioAmber Sarnia, a joint venture with Mitsui & Co., will supply Oleon with bio-based succinic acid for the development and production of succinate lubricants. Meanwhile, last July,BioAmber signed a 210,000 ton per year take-or-pay contract for bio-based succinic acid with Vinmar International. Under the terms of the 15-year agreement, Vinmar has committed to purchase and BioAmber Sarnia has committed to sell 10,000 tons of succinic acid per year from the 30,000 ton per year capacity plant that is currently under construction in Sarnia, Canada.

Meanwhile, Myriant’s high purity bio-succinic acid is a drop-in replacement for petroleum-based succinic acid . Customer analysis of Myriant’s bio-succinic acid validates that our renewable chemical is chemically identical to petroleum-based succinic acid, while also being more environmentally friendly and cost-advantaged without government subsidies. But the company, after attracting major support from PTT, has gone into stealth mode.

In 2012, Reverdia, the joint venture between DSM ( The Hetherlands) and Roquette Frères (France) commenced operations in Cassano Spinola, Italy, at a commercial-scale plant producing Biosuccinium sustainable succinic acid. The plant has a capacity of 10,000 tonnes/yr. Key applications for Biosuccinium include polybutylene succinate (PBS), polyester polyols for polyurethanes, coating and composite resins, phthalate-free plasticizers, and 1,4 butanediol. End products include footwear, packaging and paints.

In 2012, BASF (Germany)  and Purac (The Netherlands) , a subsidiary of CSM, established a joint venture for the production and sale of biobased succinic acid. The company was named Succinity GmbH and aimed for an annual capacity of 10,000 metric tons.

Over in the world of malic acid, Industrial Microbes has jumped into the fray. Founded by a trio of former LS9ers – Derek Greenfield, Elizabeth Clarke and Noah Helman, they picked up $500,000 in the latest round of Alberta’s CCEMC Grand Challenge, an Alberta-based $35M grant program that funds important emerging technologies to capture and utilize carbon dioxide. As a Grand Challenge finalist, Industrial Microbes will receive its award over the next two years to fund development of its fermentation technology to create products from CO2, and an opportunity to compete for $3M and $10M CCEMC grant awards in 2015 and 2017.The team’s target molecule? Malic acid — one of the stars of the DOE’s Top 12 Biobased Molecules list. Malate has many direct uses and can be used in the manufacture of materials such as biodegradable plastics, fiberglass,and fabrics. But it’s been relatively overlooked — compared, say, to the interest shown on biosuccinic acid.

Malic acid is used as a flavor enhancer in the food industry and can be converted into other chemical derivatives used for a variety of plastic, polymer and resin products. Along with succinic acid and fumaric acid it belongs to the group of C4 dicarboxylic acids. C4 acids can be converted into 1.4-butanediol (BDO) that can be further converted into numerous chemicals, including plastics, polymers and resins for use in everything from golf balls and skateboard wheels to printing inks and cleaning agents. The global market for malic acid is around 60,000 tons per year with a value of $130 million and a growth rate of 4% per year. The market for BDO and derivatives is around 1.4 million tons with a value of $2.8 billion and a growth rate of 3%.

2,5-Furan dicarboxylic acid (FDCA)

Avantium’s YXY technology converts plant-based sugars into Furanics building blocks . YXY enables the cost competitive production of 100% biobased plastic materials and chemicals via chemical catalytic processes.

Its main building block, 2,5-Furandicarboxylic acid FDCA, can be used as a replacement for terephthalic acid (TA),a petroleum-based monomer that is primarily used for to produce PET.

In a public-private partnership with Dutch industry, Wageningen UR Food & Biobased Research works at eliminating this crucial hurdle, by developing a process that will allow the production of sufficient quantities of pure FDCA for application tests. Research conducted at Food & Biobased Research is directed at converting renewable biomass feedstock, such as,  agricultural biomass, into 5-hydroxymethylfurfural (HMF). This chemical compound can be converted into FDCA by bacteria through fermentation, and is therefore an important precursor to FDCA.

 

3-Hydroxypropionic acid (3-HPA)

The big news here, just out this week, is that Cargill that the agricultural giant has acquired OPX Biotechnologies’ proprietary fermentation-based processes and systems. While OPX’s secret sauce is its EDGE technology (Efficiency Directed Genome Engineering), which is up to 5,000 times faster than conventional bioengineering methods for redesigning the genetic code of microbes), the company has been focused in developing applications to produce 3-HP (3-hydroxypropionic acid) via fermentation, which is then converted in one step to bio-based acrylic acid. And therein, a gateway to an existing $10 billion global market opportunity in acrylic acid, which is used in paints, adhesives, diapers, and detergents.

Back in 2008, Cargill and Novozymes announced a joint agreement to develop technology enabling the production of acrylic acid via 3-hydroxypropionic acid (3HP) from renewable raw materials. The project was supported by a $1.5 million matching cooperative agreement from the U.S. Department of Energy. The collaboration aimed at enabling fermentation of sugar into 3HP using a bioengineered microorganism.

Glucaric acid

What is glucaric, anyway? It’s an organic acid and an emerging platform chemical with wide applications in detergent, de-icing, cement, and anti-corrosion markets. Last April, Rivertop Renewables , a Montana-based producer of novel chemicals derived from natural plant sugars, announced that it has raised $26 million in its Series B investment round from Cargill, First Green Partners and existing investors. Rivertop will leverage these funds and an existing manufacturing relationship to produce market development quantities of salts of glucaric acid for select customers. In addition, it will complete construction and begin operations at a semi-works facility at its headquarters in Missoula, where it will optimize its process for world-scale deployment. Rivertop plans to hire more than 20 employees in the next 12 months to support commercial development, effectively doubling the size of its workforce.

But that’s not the first $25M+ cap raise for biobased glucaric. In March 2014, ADM committed to a $25 million equity investment in Rennovia, which develops catalysts and processes for the cost-advantaged production of chemical products from renewable feedstocks. Rennovia’s initial focus is on the development of catalytic process technologies for the production of bio-based adipic acid (AA) and glucaric acid (GA). The company has demonstrated the capability to convert glucose to glucaric acid to adipic acid, using Rennovia’s catalyst technologies. And is developing the capaity to make hexamethylenediamine (HMD), which can be combined with adipic acid to make 100% renewable nylon-6,6. You might as well have found a way to convert sugar into the Hope Diamond.

 

WARM

Glycerol

Glycerol is in widespread supply owing to the amount produced as a by-product of biodiesel — accordingly, ventures have focused less on how to make it than how to use it. Case in point. In Switzerland, . To meet the rising demand for polylactic acid as a degradable plastic used mostly for packaging , ETH researchers have developed an eco-friendly process to make large amounts of lactic acid from glycerol, a waste by-product in the production of biodiesel.

And last December, Iowa State University of Science and Technology received $1 million for the development of new paint, coating, and adhesive products that are derived from acrylated glycerol, which is a co-product of the biodiesel industry.

And last May, a new fuel-cell concept, developed by an Michigan State University researcher , is using microbes to glean ethanol from glycerol and has the added benefit of cleaning up the wastewater, will allow producers to reincorporate the ethanol and the water into the fuel-making process.

Aspartic acid

Not much action since 2011, when Flexible Solutions announced that their aspartic acid from sugar had reached commercial operating status at their Taber Alberta facility. Flexible stated that the next step is to increase production at the new plant. Production ramp up is expected to take several months given this process is a biochemical process as well as a first of its kind in the world. The company also stated that for competitive reasons, they will not disclose details concerning production or production volumes, and when the decision is made to expand production beyond the name-plate 5,000 metric tons per year, they will then announce the decision.

Back in 2010, Flexible Solutions International, a developer and manufacturer of biodegradable and environmentally safe water and energy conservation technologies, announced a production delay at its aspartic acid facility in Taber, Alberta.

But, interestingly, Joule Unlimited recently cited aspartic as a molecule of interest for their novel low carbon process which makes target fuels and chemicals from modified cyano-bacteria using sunlight, CO2 and water —are they developing an aspartogen that secretes aspartic acid? Probably not at the moment, but they appear to have the capabilities and the interest.

Itaconic acid

Itaconic acid is used to produce rubber, resins for coatings, lubricants, thickeners, and some herbicides — and it is also used in medical applications.

Recently, there’s been some activity on Itaconic. In 2013, Weastra produced a report which cited: “DSM is most active in the area of production of UPR. The company is currently focused on the task of using itaconic acid in the most effective way for the production of UPR. The company is already planning to start with the commercialization of their itaconic-based UPR. DSM is developing a route for 100% bio-based polyester composites and in May 2012 it published its patent for the production of bio-based polyester composites from itaconic acid.

“In 2009, Itaconix received a $2 million grant from the USDA to research and develop the use of wood biomass as a feedstock for fermenting itaconic acid. The company worked with the University of Maine and the University of Massachusetts at Lowell to establish its ability to ferment itaconic acid from a variety of carbohydrate sources. In 2011, the company received an SBIR research grant from NSF for the enzymatic production of itaconic acid. In 2012, the company received an SBIR research grant from NSF to produce novel latex polymers.

COLD

3-Hydroxybutyrolactone

No action outside of academic labs. One group at MIT described “A Platform Pathway for Production of 3-hydroxyacids [that] Provides a Biosynthetic Route to 3-hydroxy–butyrolactone” in 2013.

http://dx.doi.org/10.1038/ncomms2418

Sorbitol (Alcohol Sugar of Glucose)

Not much action here. In general, sorbitol has been found primarily as a feedstock. The algal pioneer Solzayme ferments heterotrophic algae, grown in the dark using supplements of inexpensive cellulosic sugars and sorbitol, to produce renewable oil for fuels, chemicals, for ingredients and nutraceuticals. And Joule, which declared an interest in aspartic acid, also has sorbitol on their wide-ranging target list.

Xylitol/arabinitol (Sugar alcohols from xylose and arabinose)

In 2013, Xylitol Canada announced they had completed pilot demonstration of its cellulosic xylose process. The successful three month campaign proved out critical process and economic metrics needed to advance into commercial scale detailed engineering. The recently completed trial builds on previously completed pilot scale work by integrating the Xylitol Canada process from end-to-end in a single facility. Representative aspen hardwood was used as feedstock. Trial results were consistent with laboratory experiments, supporting the technical feasibility of process scale-up. A commercial facility is being designed to produce up to 10,000 tonnes of xylose per year from sustainably harvested North American hardwood.

Back in 2010, before being acquired by DuPont, Danisco announced the launch of XIVIA – its new brand name for sustainable xylitol, based on the Life Cycle Assessment results of its unique wood based integration concept.

Based on an LCA using 1000 kg of crystalline  xylitol manufactured using the Danisco Wood Based Concept and the equivalent using the biomass hydrolysis concept (BHP) and corn cob as the raw material and found that their DWB integrated concept (DWB) produced as little as 1% to 16% of the environmental impact associated with the competitive biomass hydrolysis process based production method using corn cobs as raw material.

Glutamic acid

PNNL has done some work on Gluatmic acid. Their technology for Hydrogenation of Glutamic Acid to Pyroglutaminol and Prolinol is lab demonstrated and available for license. PNNL says, “biomass feedstocks are increasingly in higher demand across the petrochemical industry as manufacturers research ways to make chemical products from something more environmentally friendly than petroleum. Glutamic acid is a ready platform for conversion to value added products. Among those are pyroglutaminol and prolinol, which may benefit a number of applications.”

Levulinic acid

Incitor was producing it before they morphed into xF technologies and went chasing furans, and Segetis is using it as a feedstock. There’s been a steady amount of work at DOE labs. Here’s an example.

Last year, we reported that gasoline-like fuels can be made from cellulosic materials such as farm and forestry waste using a new process invented by chemists at the University of California, Davis. The process could open up new markets for plant-based fuels, beyond existing diesel substitutes. The feedstock for the new process is levulinic acid.

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