Eco-friendly Developments Blossom

The partners have identified four key technology areas: amine synthesis, polymers from renewable resources, glycoscience, and wider oxidase applications.

BASF, which is investing €1.3 million ($1.7 million) of its own money alongside €600,000 ($791,000) of EU funds from the European Research FP7 program, is particularly focused on projects that involve the biocatalytic synthesis of amines and the use of enzymes in the manufacturing of functional polymers (Figure 1).

Commenting on the overall project, Dr. Kai Baldenius, head of biocatalysis research at BASF and the man with responsibility for BIONEXGEN, says, "It is a general target of BASF to make processes more efficient. In this EU project, we engage in early phase research, searching for new, highly selective biocatalysts."

Amines are among the most important family of compounds produced by chemical makers — and used in bulk for manufacture of pharmaceuticals, agrochemicals, polymers and speciality chemicals. Traditional routes to amines often rely on toxic metal reagents and catalysts that mandate costly protective measures and produce wasteful byproducts. Biocatalytics offer great potential to reduce cost and the amount of waste products. Research here will focus on three enzyme classes: monoamine oxidases, ammonia lyases and transaminases.

BASF's amine synthesis goals within BIONEXGEN will build on existing experience, notes Baldenius: "BASF has successfully commercialized the biocatalytic production of enantiomerically pure chiral amines for the pharma and agro industry. We now strive to extend the scope of biocatalytic amine production to a broader range of amines. How far this scope can be extended remains unknown at this very early stage."

Glycoscience and oligosaccharide synthesis is one of the most challenging disciplines in organic synthesis, often requiring complex protection and reaction strategies. Currently biotechnology can serve in a few glycosynthetic and oligosaccharide transformation methods. However, these methods aren't yet routinely applied industrially, although it's acknowledged that enzymatic systems offer great potential for selective synthesis.

This part of the project is developing methods that will prove valuable for simplifying the synthesis of molecules of pharmaceutical, nutraceutical and household chemical interest. Researchers at the University of Manchester, Manchester, U.K., and BASF are combining biology, chemistry and molecular biology to synthesize a variety of glycoproteins, glycolipids and polysaccharides, all of which are important molecules in medicine and nutrition.

BASF also is using BIONEXGEN to build on its existing knowledge on the applications of enzymes to glycoscience and oligosaccharide synthesis. Baldenius explains: "Polysaccharides such as starch are a masterpiece of nature's synthetic power. We believe that clever derivatization can provide them with properties usually found in petro-derived polymers, so that the biopolymers can be used, for example, as dispersants. The framework of BIONEXGEN is to identify new enzymes and basic fields of application. Following proof-of-concept, the actual product development would then be carried out at BASF, or one of the other industrial partners."

FRANCO-CHINESE INITIATIVE
In early November 2011, the French National Center for Scientific Research, Rhodia, the Ecole Normale Supérieure of Lyon and the East China Normal University officially opened the Laboratory of Eco-efficient Products and Processes (E2P2), an international joint research unit in Shanghai, China.

Based at Rhodia's research center in Shanghai, the new laboratory is dedicated to developing eco-efficient chemical processes. It will house research jointly carried out by scientists from academic institutes in China and Europe working together with industrial partners.

"All our research projects are assessed by a methodology based on the principles of lifecycle analysis. At a very early stage in designing a product or process, this analysis validates the pursuit of a research project if the results reveal a clear benefit with respect to human health and environment," explains E2P2 laboratory director Floryan Decampo, who comes to the lab from Rhodia. "Our E2P2 lab is another step further in this effort by targeting specifically new technologies capable of reducing significantly the use of fossil raw materials in specialty chemicals and hence reducing the carbon footprint of both our products and processes."

Decampo says that partnering with top academic institutions is key because the projects being carried out in Shanghai typically pose significant scientific challenges and may require breakthrough innovations. "The unique feature of this lab is that it assembles within the same team experts in different key competencies — including chemistry, polymers, catalysis, industrial, theoretical and eco-efficiency — allowing them to quickly tackle key challenges and deliver faster solutions."

Although Rhodia has other research centers around the world, Decampo says China was chosen for this latest investment — none of the financial details have been revealed — for three main reasons: Rhodia has a long presence in China, which is a key area for chemical industry growth; the country is facing some major environmental challenges, in part from the fast development of its chemical industry; and, with the rise of Chinese academic research to world-class stature, being in China presents a unique opportunity to develop strong partnerships with some of the best laboratories in their respective fields.

The center will help Rhodia with its "Rhodia Way" set of sustainability commitments, which include cutting water use by 10% between 2010 and 2015, decreasing energy consumption by 8% in the same period, and developing products that contribute to a reduced carbon footprint — for example, eco-friendly solvents, and plant-based products for body and hair applications.

"E2P2 is another strong initiative and a long-term commitment to sustainable development by ensuring that the new chemistries that will be developed in the future are eco-friendly and deliver significant environmental benefits. Thus, even upstream research is now focused and committed to sustainable development," notes Decampo.

The first projects will focus largely on carbon-based products, mainly surfactants or plastics — with the hope that the associated technologies will also deliver new businesses for the Rhodia group as a whole.

"Most of the projects have two firm targets, one environmental and another one economical. For example, for the projects aiming at replacing oil-based raw materials by bio-sourced raw materials, the target is to reduce by 30–50% the overall carbon footprint of products compared to existing industrial benchmarks. Of course, to achieve a full benefit and to replace the existing technologies, there must also be an economical target that is realistic."

Decampo anticipates that moving new technologies from the laboratory to industrial scale will take between two and ten years, depending on the particular project.

JAPANESE DRIVE
Meanwhile, Mitsubishi Rayon Company and subsidiary group Lucite International, both part of the Mitsubishi Chemical Holdings Corporation, Tokyo, are continuing their drive for innovation by developing sustainable feedstock sources for producing methyl methacrylate (MMA). They plan to use sustainable feedstocks for commercial MMA production by 2016, and to get at least 50% of their MMA output from these sources as soon after that as possible.

To achieve this, the companies are investing in two approaches: using renewable feedstock sources as raw materials in existing processes, and developing novel routes for producing methacrylate monomers directly from renewable sources.

Simultaneously, the companies will continue to innovate in catalysis and process technology to reduce resources consumed per unit of output in all of their activities.

"In terms of alternative feedstocks, in the short term, there are some potential bio-based feedstocks for Mitsubishi Rayon Group's existing MMA plant, including acetone, ethylene (from ethanol) and isobutylene (from isobutanol). In the long term, carbohydrates are the most promising feedstocks," says spokesman Hiro Naitou.

A number of new processes are being advanced in parallel, with one, which he declines to identify, already at the scale-up stage.

Naitou and others from Mitsubishi Rayon are named in U.S. Patent 7,557,061, which outlines a method for producing a catalyst containing molybdenum and phosphorus for use in synthesizing MMA through gas-phase catalytic oxidation of methacrolein with molecular oxygen. According to Naitou, this latest initiative takes a different direction: "The technology of sustainable MMA is altogether different from previous catalysts and processes. Mitsubishi Rayon Group is doing the R&D at corporate research laboratories in Japan and U.K."

In December, Toray Industries, Tokyo, announced it had produced laboratory-scale samples of the world's first fully renewable polyethylene terephthalate (PET) fiber by using PET derived from bio-based paraxylene supplied by Gevo, Eaglewood, Colo.

Gevo converts isobutanol produced from biomass into paraxylene via a production method that uses synthetic biology in a conventional commercial chemical process.

Toray made PET from terephthalic acid synthesized from Gevo's paraxylene and commercially available renewable monoethylene glycol by applying a new technology and polymerization. This bio-based PET exhibits properties equivalent to petro-based PET in laboratory conditions.

"The success of this trial, albeit under laboratory conditions, is proof that polyester fiber can be industrially produced from fully renewable biomass feedstock alone. This is a significant step that would contribute to the realization of a sustainable, low-carbon society," says the company.

In a separate development, in early December 2011, Gevo received U.S. Patent 8,017,358 on another aspect of its yeast technology that enables low-cost, high-yield production of bio-based isobutanol. The patent covers additional "Methods of Increasing Dihydroxy Acid Dehydratase (DHAD) Activity to Improve Production of Fuels, Chemicals, and Amino Acids."

"This invention further details and protects the innovations contained in the Gevo yeast organism to turn an industrial yeast strain into a highly efficient cell factory to produce isobutanol," notes Brett Lund, executive vice president and general counsel.

OTHER DEVELOPMENTS
Verdezyne, Carlsbad, Calif., has started up a pilot plant there to make bio-based adipic acid, a key component of nylon 6,6, via a yeast fermentation process that uses non-food plant-based feedstocks (Figure 2). Because of the demand for nylon, the global adipic acid market today is said to amount to more than $6 billion/yr.

"We are excited to achieve this key milestone," says Dr. E. William Radany, president and CEO. "This is the first demonstration of the production of bio-based adipic acid at scale from a non-petroleum source. Our novel yeast platform enables production of adipic acid at a lower cost than current petrochemical manufacturing processes."

Verdezyne's approach reportedly offers a number of other advantages over petroleum-based methods, including less generation of carbon dioxide and other pollutants.

"This plant will allow us to demonstrate the scalability of our process, validate our cost projections and generate sufficient quantities of material for commercial market development," notes Dr. Stephen Picataggio, chief scientific officer.

Meanwhile, P2 Science, New Haven, Ct., a Yale University spin-off, is using patent-pending technology from the Yale Center for Green Chemistry and Green Engineering to develop and manufacture a new class of high-performance surfactants, C-glycosides (CGs).

CGs can be used in a range of consumer and industrial products such as detergents, personal care products, cosmetics, lubricants, hard-surface cleaners and emulsion polymers as well as in mining and oilfield chemicals.

The new surfactants are mild in use, stable, customizable and manufactured in low-energy-intensive conditions, says the firm.

Carbohydrate-based surfactants have long been of interest because of their desirable performance properties and potential to be derived from renewable feedstocks. Although most carbohydrate-based surfactants utilize an O-glycoside linkage, recent advances in carbohydrate C–C bond formation have allowed for the synthesis of new classes of carbohydrate-based surfactants using a C-glycoside linkage.

Seán Ottewell is Chemical Processing's Editor at Large. You can e-mail him at [email protected].