Green chemistry gains momentum

Moving on up

19 January 2009 00:00  [Source: ICB]

The principles of sustainable chemistry are finding acceptance throughout the wider industry

Cynthia Challener/Vermont

NUMEROUS cost-saving implementations of green chemistry have shown that reducing the environmental footprint of production processes goes hand in hand with improving the bottom line.

Environmentally friendly chemistry has moved to the mainstream of chemical manufacturing, and companies, both large and small, are developing ways to increase efficiency and productivity with high-performing products by following one or more of Paul Anastas and John Warner's 12 Principles of Green Chemistry (see below).

"In recent years, interest in green chemistry has expanded beyond the initial focus on organic synthesis," states John Warner, president and chief technology officer at the US-based Warner Babcock Institute for Green Chemistry.

"Today, research in [green] chemistry, biochemistry and materials science is taking place in all industry sectors that employ chemistry and in locations around the world."

The Pharmaceutical Roundtable of the American Chemistry Society Green Chemistry Institute (GCI), for example, is funding research to identify greener approaches to the 12 most commonly used transformations. The group has likewise characterized the most-used solvents and begun a search for alternatives to those that are not ecologically sound.

Success with these efforts has led GCI to establish a Formulator's Roundtable focused on cleaning and cleansing products. The Institute is also assembling training materials for students through the post-doctoral level and it hopes to develop standards for green chemistry processes.

"One of our goals is to craft ANSI [American National Standards Institute]-based multiattribute green process technology standards against which companies may be certified by an independent third party," says GCI director Robert Peoples.

In the meantime, companies still face the challenge to prove that the potential return on investment can justify upfront costs. But changes are taking place to address this issue.

"Firms are taking a more global approach to cost determination and are now considering hazardous material handling, energy and water consumption, waste processing and other operational costs," says Richard Engler, program manager for the Environmental Protection Agency (EPA)'s Green Chemistry Program.


Green chemistry is also attractive because it relies on innovation to develop solutions. Advances in technology, combined with cost and regulatory pressures and a growing public awareness, have made implementation of green chemistry initiatives more feasible.

"New solvent systems, process controls and catalysts are just some technologies that are being taken advantage of," notes Warner.

Innovation at the molecular level has been most notable. Topics that seem to be of great interest include C-H activation, polymer degradation, catalytic coupling, supercritical fluids, ionic liquids, nanotechnology, biomimicry and renewable feedstocks.

"Considering green chemistry issues as part of the R&D [research and development] process and tying the Principles to performance and cost is becoming ingrained in the business cycle," Engler says.

The variety of green chemistry initiatives nominated for the EPA's Presidential Green Chemistry Challenge Award (PGCCA), which seeks to discover, highlight and honor environmentally friendly chemistry programs, reflects this shift in emphasis. Judging for this prestigious award is administered by the GCI, and Peoples says the number of applications is growing rapidly.

SiGNa Chemistry, based in New York, won the 2008 Small Business Award for its silica-based, nanoscale encapsulation of reactive alkali metals and their derivatives. Sodium is "solvated" within structured silicas, resulting in a safe, free-flowing powder that retains the desired reactivity but can be used without the need for cryogenic liquid ammonia, and the process produces only sodium silicate as the byproduct of an aqueous work-up.

The company is currently working with replacements for organolithium reagents, which typically require large volumes of ether solvents. Allyl and homoallyl lithium species, as well as all of the common organolithiums, can be stabilized at room temperature for an indefinite period of time with SiGNa's technology.

"We are very excited about these materials because they open up many new possibilities for conducting new chemistry on a commercial scale that previously wasn't practical," says Michael Lefenfeld, president and CEO of SiGNa Chemistry.

Entries for 2008 included improved alcohol oxidation processes based on 2,2,6,6-tetramethylpiperidinyloxy (TEMPO) catalysts being developed at the Center for Applied Catalysis at Seton Hall University in New Jersey. TEMPO and its derivatives are manufactured by German specialty chemical producer Evonik Industries. One process uses bleach as the oxidant, requires much less catalyst, eliminates the methylene chloride solvent and replaces potassium bromide with borax. The level of oxidation can be controlled by varying the temperature and amount of oxidant. Setrak Tanielyan, the center's technology director, has also developed a TEMPO-based oxidation method with air as the oxidant and acetic acid as the solvent.

Minnesota-based Cortec entered corrosion control agents based on renewable materials such as vegetable oils, gluconates and soy proteins. The company's most successful product uses gluconic acid derivatives from sugar beets as components of migratory corrosion inhibitors to protect the reinforcing steel in concrete. Carboxylated amino acid products are used in water treatment systems and offer both antiscalant and anticorrosion properties, unlike traditional polyacrylates or polyphosphates, which are not multifunctional, according to Cortec's lab director Margarita Kharshan. The company is currently developing products based on fatty acids derived from lard oils.

Altogether, winners of the PGCCA have saved trillions of kilowatt hours of energy, tens of billions of gallons of water and avoided the production of millions of tonnes of waste while improving efficiency, reducing air and water emissions and saving costs, according to Peoples.

Many companies developing green technologies have not participated in the EPA's award program yet. Massachusetts-based Novomer's founders developed cobalt and zinc catalysts that react strained cyclic compounds such as ethylene oxide (EO) and propylene oxide (PO) with carbon dioxide (CO2) or carbon monoxide to form polyols or polymers at room temperature and modest pressure. Novomer's first commercial product for the electronics industry, NB-180, is a polypropylene carbonate sacrificial binder that burns cleaner, more uniformly and at lower temperatures than traditional products. The company is currently developing polyols for polyurethane (PU) coatings.

"The catalyst system and nature of the polymerization reaction provide us with tremendous control, and therefore we are able to produce products with excellent performance characteristics," says Novomer president Charles Hamilton. "The value we are providing is a combination of performance, lower cost and green chemistry." In the longer term, the company hopes to develop alternative routes to small molecule products such as succinic anhydride.

Instead of designing a new substance for a new commercial market, California-based Genomatica is developing metabolic pathways to known substances not normally produced by microorganisms. Its first target is 1,4-butanediol. The company has found success at the lab scale and expects to have a commercial process developed by the third quarter of 2009.

Genomatica has eight other products in its pipeline, all of which are large-volume intermediates that require significant capital and energy inputs. Its lower-cost processes, which involve the fermentation of carbohydrates, require less energy and less capital, produce less waste and have a smaller physical footprint than traditional routes. For the future, it is looking at using (CO2) and methane as sources of carbon and hydrogen.

"We see our technology as having green impacts well beyond the chemistry," says Genomatica CEO Christopher Gann.

"These plants can be built anywhere and feedstock can be grown near the facility, eliminating various transport issues. Also, fermentation plants are scalable and can be added in much smaller increments to match market growth. Therefore, we are able to create value in numerous ways that touch on many different aspects of business activities."

If these examples are any indication, the future of green chemistry is bright. "There is a sustainability tsunami sweeping the globe," asserts Peoples. "Chemistry and chemical engineering are supporting that wave. Our willingness to make significant investments and collaborate across many disciplines will make it possible to solve the big sustainability issues we are facing."


Doris de Guzman/New York

This year could be a big one for green chemistry. US president-elect Barack Obama promises to boost the green energy market, while industry talk of chemical restrictions from Congress will bolster alternative development. California has introduced its Green Chemistry Initiative and has already jump-started its rule-making process to restrict certain chemicals and increase development for green chemicals. The state has also adopted the first statewide ecologically sound building standards in the US, which will become mandatory in 2010.

Some of my 2008 predictions have come to fruition: phthalates in certain children's products will soon be banned under the Consumer Products Safety Improvement Act in the US Norway banned the flame retardant deca-BDE in April, while Canada has banned polycarbonate (PC) baby bottles with bisphenol A (BPA).

Another prediction was the record clean technology investment that took place in 2008, despite the start of the global recession. For 2009, clean tech investments are predicted to remain strong, though not at the same level as 2008. Solar and biofuel investments are expected to slow down. Bans on plastic shopping bags and water bottles will continue to plague the industry, while polyvinyl chloride (PVC), BPA and phthalates will remain a big issue for consumer advocates. California is also proposing to ban polystyrene (PS) food containers. Despite the slump, I don't think research and development on green chemicals/product innovation will slow. In fact, it might speed up as it is one way to boost demand from customers. Company sustainability management, however, might have a tough job convincing shareholders this is the way to go.

Finally, climate change will still be at the center of debate and regulatory policies worldwide. The world might be in recession, but if another natural calamity struck, you can bet environmental groups and some scientists will blame it on global warming.

Read the latest commentary on our green chemicals blog


1. Prevent waste

2. Design safer chemicals and products

3. Design less hazardous chemical syntheses

4. Use renewable feedstocks

5. Use catalysts, not stoichiometric reagents

6. Avoid chemical derivatives

7. Maximize atom economy

8. Use safer solvents and reaction conditions

9. Increase energy efficiency

10. Design chemicals and products to degrade after use

11. Analyze in real time to prevent pollution

12. Minimize the potential for accidents


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