Recently in R&D Category

In the new technology session, presenters will include Solazyme, LS9, Elevance Renewable Sciences, Codexis, P2 Science and Amyris as well as viewpoints from cleaning products manufacturers P&G Chemicals and Seventh Generation.

I will tweet from that conference (hopefully there's wifi available) via @ICISChemicalBiz. In the meantime, here are two interesting developments on biobased surfactants that the blog has been keeping in its draft for months now.

One is this company called AGAE Technologies LLC, which has shipped its first laboratory research-grade biosurfactant called rhamnolipid that is used in environmental remediation, pharmaceuticals, cosmetics, etc. AGAE started in May 2011 and has licensed this biosurfactant technology from the Oregon State University.

Rhamnolipids can be produced by fermenting a C18 fatty acid source using a certain bacteria, and mannosylerythritol lipids, which can be produced via microbial conversion of glycerin. I first wrote about this biosurfactant (and saphorolipids) in 2010 on ICIS Chemical Business, where Germany-based Henkel and Belgium-based Ecover were also looking into it.

The US Department of Agriculture (USDA) has also been working on rhamnolipids (and saphorolipids) while US-based Janeil Biosurfactant has already been selling laboratory research-grade rhamnolipids as well.

According to AGAE, the company is currently developing commercial-grade rhamnolipid products of various purity specifications for pharmaceuticals, bioremediation, personal care and several other application.

"The real bottleneck to replacing synthetic chemicals with biosurfactants like rhamnolipids is the high cost of production. We are applying the latest genome sequencing technologies to strain improvement for NY3 and creating a nonpathogenic, high-yield rhamnolipid producer. Using renewable low-cost sources of ingredients, we are optimistic about further increasing the yields, reducing costs by scaling up production and promoting the global applications of these very eco-friendly biosurfactant molecules."

Henkel, by the way, is already using saphorolipids, on some of its commercial cleaning products. The quest is to now lower the cost of these biosurfactants.

Aside from surfactant developments that Amyris, Elevance, LS9, Codexis, Solazyme and P2 Science are working on, other products I've been monitoring (lots of interesting discussions on this Surfactant Linked In group) include a coconut oil-based surfactant with a sugar-based glycol backbone, and a product called sucroglycerides based on vegetable oils and sugar.

The blog received this news from BioBased Technologies (a US biobased polyol producer) about their partnership with Palmer International, a US company working with Cashew Nut Shell Liquid (CNSL) for over 50 years. The firms is developing a new bio-based polyols from CNSL in rigid foam systems.

The blog was immediately intrigued about CNSL given the unfamiliarity of this material. After a bit of googling, the blog came across this document submitted to the US EPA (dated June 2002) from New Jersey, US-based Cardolite Corporation about CNSL. Cardolite is another company working on CNSL for decades.

According to Cardolite, CNSL, a source of naturally occuring phenols, is composed of 70% anacardic acid, 18% cardol and 5% cardanol, with the rest made of other phenols via cold, solvent extraction. In technical CNSL (such as heat extracted), the composition is 52% cardanol, 10% cardol, 30% polymeric material and the rest are other substances.

Here are some of the industrial uses of CNSL:

• CNSL resins have typically been used in the manufacture of friction-resistant components in applications such as brake and clutch linings. CNSL-aldehyde condensation products and CNSL-based phenolic resins are used in applications such as surface coatings, adhesives, varnishes and paints. Various polyamines synthesised from CNSL or cardanol are used as curing agents for epoxy resins.


• CNSL and its derivatives have been used as antioxidants, plasticisers and processing aids for rubbercompounds and modifiers for plastic materials. Resins based on the reaction products of cardanol phenol and formaldehyde are used to improve the resistance of rubber articles to cracking and ozone. 


•  CNSL, cardanol and cardol are all used to provide oxidative resistance to sulfur-cured natural rubber products. Cardanol, CNSL or sulfurated CNSL is added to rubber gum stock or nitrile rubber to improve the processability, mechanical properties and resistance to crack and cut properties of the vulcanisates.


• A number of products based on CNSL are used as antioxidants, stabilisers and demulsifiers for petroleum products. Metal xanthates of partially hydrogenated, sulfurised cardanol is used to lower the pour point of lubricating oils as well as acting as antioxidant and anticorrosive properties. Soluble metal derivatives of CNSL are used to improve the resistance to oxidation and sludge formation of lubricating oils. 


•  Oxidised CNSL and its derivatives are used as demulsifying agents for water in oil type petroleum emulsions.

BioBased Technologies will be responsible for R&D of the new polyol in rigid foam systems, marketing and sales of the final product. Palmer will be responsible for scale-up and manufacturing. The partners will use both companies' existing research and manufacturing facilities.

By the way, a 2004 study by the United Nation's Food and Agricultural Organization (UN FAO) reported main markets for CNSL back then were the United States, the European Union (mainly the United Kingdom), Japan and the Republic of Korea. Together these account for over 90% of world trade, most of which is supplied by India and Brazil.

Just to remind readers how furanics are made:

Now while Avantium's polyamides are made from sugars, most of the bio-based polyamides today are from oilseed particularly castor oil. Rhodia itself is already selling products developed from polyamide 6,10 partly made from castor oil. Solvay has also been working with Mitsubishi Gas Chemical since 2010 on developing high-temperature castor oil-based polyamides for high-performance durable applications.

The key ingredient in castor oil for polyamides use is sebacic acid also known as decanedioic acid. I covered this market since I started in ICIS Chemical Business (which was Chemical Market Reporter back then), and believe me, it was difficult to get information on sebacic acid market given that there are very few chemical players in the US using this and most are based either in India or China.

More than 70% of global sebacic acid demand is for polyamide 10,10 and 6.10, according to an industry source. In 2010, global demand for sebacic acid was 58,700 tonnes and more than 90% are produced in China.

Cathay Industrial Biotech, meanwhile, produces fermentation-based dodecanedioic acid (DDDA) where polyamide 6,12 is its largest market (applications incude monofilaments for toothbrushes, paint brushes, cosmetic brushes and in automobile use). Other producers of DDDA, which is mostly petroleum-based with butadiene as feedstock, include Evonik, Ube, and Invista.

Evonik, however, has already been marketing castor oil-based polyamide 6,10, polyamide 10,10 and polyamide 10,12 under the trademark Vestamid Terra.

I've mentioned Arkema who is a big producer and developer of castor oil-based polyamides and who claimed to be the only producer of castor-based polyamide 11 marketed under the tradename Rilsan. Arkema just acquired late last year China-based Hipro Polymers, a producer of castor-based polyamide 10,10; and China-based Casda Biomaterials, a producer of sebacic acid. Arkema also noted that specialty bio-sourced polyamides has a growth rate of 15-20%/year.

Hipro polymers is expected to triple its production capacity this year.

Another company working on castor-based polyamide 4,10 is DSM under the tradename EcoPaXX. The high-performance engineering plastic is being marketed in automotive and electrical markets application.

One interesting development is that DSM is also working with Elevance on bio-based high performance specialty thermoplastics. As you probably know by now, Elevance's portfolio also focuses on 9-decenoic acid which can be a building block for producing specialty polyamides. Elevance's bio-polyamide target includes homopolymers such as polyamide 11 and polyamide 12.

Methionine is an essential amino acid mainly used in animal feeds. According to METEX, the amino acid is currently made from propylene via a synthetic chemical process. The global methionine market for animal feed is around $2.85bn for 850,000 tonnes last year, METEX reported.

The blog did a little research on this market and it seems major global methionine manufacturers include China National Bluestar, Evonik, Jinzhou Jirong Amino Acid Co., Mitsubishi Tanabe Pharma, Nippon Soda, Novus, Sumitomo Chemical, Zheijiang Chemicals. For the feed market, Evonik, Nippon, Novus and Sumitomo are the major producers.

According to the press release, Roquette is preparing an analytical and toxicological file for the product to obtain European approval that they hope will be finalized in mid-2012.

By the way, do you know who else is working on bio-methionine?

CJ CheilJedang and Arkema are actually planning to build a bio-methionine plant in Southeast Asia (Malaysia or Thailand). CJ said it has developed a bio-fermentation process to produce L-methionine from plant-based materials. Now whether it's 100% bio-based, the blog is not sure. Arkema said their bio-methionine will use methyl mercaptan, a sulfur-based intermediate which is a key to the manufacture of methionine. Is methyl mercaptan a bio-based material?

Anyway, Arkema and CJ will the bio-methionine plant will have a capacity of 80,000 ton/year and would come onstream at the end of 2013.