Resources, Conservation and Recycling 44 (2005) 237–243

Promoting sustainability through green chemistry

Mary M. Kirchhoff ∗
American Chemical Society, 1155 Sixteenth Street, NW, Washington, DC 20036, USA

Accepted 18 January 2005

Available online 7 March 2005

Abstract

Green chemistry is an important tool in achieving sustainability. The implementation of green chem-
istry, the design of chemical products and processes that reduce or eliminate the use and generation of
hazardous substances, is essential if the expanding global population is to enjoy an increased standard
of living without having a negative impact on the health of the planet. Cleaner technologies will allow
the chemical enterprise to provide society with the goods and services on which it depends in an
environmentally responsible manner. Green chemistry provides solutions to such global challenges
as climate change, sustainable agriculture, energy, toxics in the environment, and the depletion of
natural resources. A collaborative effort by industry, academia, and government is needed to promote
the adoption of the green chemistry technologies necessary to achieve a sustainable society.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Sustainability; Green chemistry; Pollution prevention

1. Introduction

The Brundtland Commission (1987) defined sustainable development as “development

that meets the needs of the present without compromising the ability of future generations
to meet their own needs.” Current practices by society are not sustainable, however. Natural
resources are being consumed faster than they are being replenished, global population
continues to rise, and hazardous materials are being released into the environment in large
quantities. In 2001, for example, more than six billion pounds of the 522 chemicals listed
on the Toxics Release Inventory (2001) were released both on- and off-site in the U.S.
∗ Tel.: +1 202 872 4562; fax: +1 202 872 6206.
E-mail address: m kirchhoff@acs.org.

0921-3449/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.resconrec.2005.01.003
238 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243

How can science address the challenge of sustainability, especially as an increasing global
population and an increased standard of living exert pressure on the resources of the planet?
Scientific innovations must play a major role in meeting this challenge. While technolog-
ical advances have created a number of unanticipated environmental concerns, scientific
breakthroughs offer solutions to many of these problems. Green chemistry provides one
such opportunity.
Green chemistry is the design of chemical products and processes that reduce or eliminate
the use and generation of hazardous substances (Anastas et al., 2000). Green chemistry
prevents pollution at the source by using innovative chemical processes to provide society
with the products on which it depends. The implementation of green chemistry technologies
minimizes the use of materials that are hazardous to human health and the environment,
decreases energy and water usage, and maximizes efficiency. The collaborative efforts
of academia, industry, and government are needed to advance sustainability through the
adoption of green chemistry. The following sections highlight green chemistry approaches
to sustainability within these sectors.

2. Academia

Academic research in green chemistry serves several key functions. First, it provides
fundamental knowledge related to new chemical products and processes, data that are nec-
essary to develop cleaner technologies. Second, new products and processes developed in an
academic setting can, in some cases, have direct applications to industry. Third, academia
serves as the primary means to educate students about the need to design green chem-
istry technologies, and provides them with the tools to do so. It is important to connect
green chemistry with the broader issue of sustainability so that students can clearly see the
applications of their work within a global context.
A major concern with regard to sustainability is the release of hazardous substances into
the environment. Green chemistry can have a significant impact in this area. Solvents, for
example, are ubiquitous in academic, industrial, and government laboratories. Many of the
commonly used solvents are volatile organic compounds (VOCs), hazardous air pollutants
(HAPs), flammable, and/or toxic. Alternatives to organic solvents are needed to decrease
the negative environmental impact of these substances.
One solvent finding new applications is supercritical carbon dioxide, which is widely
used to decaffeinate coffee. sc-CO2 has an easily accessible critical point and is nontoxic,
nonflammable, and inexpensive. Poliakoff (Licence et al., 2003) and coworkers at the Uni-
versity of Nottingham investigated a variety of organic reactions in sc-CO2 , laying the
foundation for the first commercial chemical plant using carbon dioxide. This facility, op-
erated by Thomas Swan & Company, opened in 2001 and employs supercritical carbon
dioxide to carry out a variety of reactions, including hydrogenations (Fig. 1), Friedel Crafts
alkylations, and etherifications. The partnership between the University of Nottingham and
Thomas Swan demonstrates the value of academic-industry collaboration in moving sus-
tainable technologies from the bench top to commercialization.
Further applications of CO2 as a commercial solvent depend upon the development of
inexpensive surfactants to facilitate reactions in carbon dioxide, which is a rather poor
 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243 239

Fig. 1. Hydrogenation of isophorone in sc-CO2.

Fig. 2. Synthesis of adipic acid from cyclohexene.

solvent on its own. Beckman and coworkers (Sarbu et al., 2000) have designed a series
of functionalized polyethers and copolymers of cyclic ethers and carbon dioxide, such as
propylene oxide and CO2 , which represent a new class of surfactants. These polymers are
less persistent and 10–100 times less expensive than the currently available fluorinated
compounds.
Catalysts play a significant role in green chemistry by decreasing energy requirements,
increasing selectivity, and permitting the use of less hazardous reaction conditions. Consider
the commercial manufacture of adipic acid, one of the monomers in the production of nylon-
6,6. High temperature and pressure are needed to reduce benzene to cyclohexane, which
is subsequently oxidized to a mixture of cyclohexanone and cyclohexanol. The mixture
is oxidatively cleaved, yielding the desired adipic acid and nitrous oxide, a greenhouse
gas and ozone depleting substance. Noyori et al. (1998) synthesized adipic acid directly
from cyclohexene using an aqueous 30% hydrogen peroxide solution, a catalytic amount
of Na2 WO4 , and a phase-transfer catalyst (Fig. 2). Adipic acid is produced in high yield
without the use of organic solvents and without the generation of nitrous oxide.

3. Industry

Significant environmental and economic benefits are realized when industry implements
technologies that eliminate hazardous substances from their products and processes. Com-
panies adopt cleaner technologies because of favorable economics: material, compliance,
and clean-up costs are lowered. Improvements are being made at both the process and
consumer level.
A number of pharmaceutical companies are dramatically reducing the quantity of haz-
ardous waste produced in the manufacture of best-selling drugs. Pfizer, for example, has
redesigned the synthesis of several pharmaceuticals with green chemistry in mind. Changes
in the synthetic route to sildenafil citrate, the active ingredient in ViagraTM (Dunn et al.,
2004), resulted in a more efficient synthesis requiring no extractive work-up steps and en-
hanced solvent recovery (Fig. 3). The E-factor (Sheldon, 1992) for the process dropped
to 6 kg waste/kg product, substantially lower than an E-factor of 25–100 typical for many
240 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243
Fig. 3. Synthesis of sildenafil citrate.
 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243 241

Fig. 4. Sorona, PDO-terephthalic acid copolymer.

pharmaceutical processes. Furthermore, all chlorinated solvents have been eliminated from
the commercial process.
The polymer industry is another sector that is adopting more sustainable practices. Asahi
Kasei Corporation has developed a new manufacturing process for a polycarbonate used in
cars, appliances, CDs, and DVDs (Fukuoka et al., 2003). Currently, this polycarbonate is
manufactured from bisphenol-A using large quantities of highly toxic phosgene and methy-
lene chloride, a suspected carcinogen, as solvent. The new process combines bisphenol-A,
ethylene oxide, and by-product carbon dioxide, obtained from Asahi’s ethylene oxide plant.
A melt polymerization process eliminates the use of methylene chloride as the polymer-
ization solvent. This new technology reduces CO2 emissions by 173 tonnes per thousand
tonnes of polycarbonate produced.
DuPont has turned to biotechnology to produce 1,3-propanediol (PDO), a monomer in its
Sorona line of polymers (Ritter, 2003). The process starts with renewable resources: genet-
ically engineered Escherichia coli converts corn-derived glucose to PDO. The fermentation
process does not require an organic solvent or metal catalyst and runs near room temper-
ature, thereby saving energy. Commercial routes to PDO typically use petroleum-based
feedstocks, elevated temperatures and pressures, and heavy metal catalysts. Combining
PDO with terephthalic acid yields Sorona, a polymer with fiber and fabric applications
(Fig. 4).
Disposing of waste in landfills or by incineration is an unsustainable practice that is
being addressed through the design of consumer products that can be reused or recycled.
For example, new materials used in carpet tiles offer improved recyclability. Most carpet tiles
contain a polyvinyl chloride (PVC) based backing material. PVC is a concern because of
disposal issues; burning a PVC-containing product in an incinerator, for example, releases
toxic dioxins. To avoid this problem, Shaw Industries (Ritter, 2003) developed a carpet
backing using polyolefin resins and waste fly ash. The backing is PVC-free. Carpeting will
be collected and recycled into new carpet and backing, thereby eliminating the need to
landfill or incinerate the used carpet.
Agriculture is another area that can benefit from green chemistry. We are able to feed far
more people using far less land thanks to the use of fertilizers and pesticides. Environmental
problems exist for both these agricultural products, however. Agricultural runoff has led to
eutrophication of bodies of water, while the use of broad-spectrum pesticides may harm
beneficial organisms along with target pests. Dow AgroSciences has developed a number of
pesticides that are more selective and less persistent. Instead of creating a chemical barrier
around a structure to keep out termites, Dow’s SentriconTM Termite Colony Elimination
System (2002) employs traps baited with hexaflumuron, a substance that disrupts the molting
cycle of termites. Unable to molt, the colony dies. The SentriconTM System is a targeted
approach to pest management that reduces reliance on conventional pesticides.
242 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243

Cargill Dow addresses resource depletion by using renewable resources, such as corn
and sugar beets, to manufacture its NatureWorksTM polylactic acid (PLA) (Ritter, 2002).
No organic solvents are used in the production of PLA, and the product itself is recyclable,
biodegradable, and compostable. A number of consumer products are made from PLA,
including clothing and food packaging. Crops replace petroleum as the feedstock for this
versatile polymer.

4. Government

Government organizations can promote sustainability through mechanisms such as fund-

ing for research and education, and regulatory relief for the adoption of cleaner technologies.
In the U.S., H.R. 3970, The Green Chemistry Research and Development Act of 2004, seeks
to coordinate green chemistry activities across Federal agencies. The European Union has
supported a Green Chemistry Summer School in Venice, Italy since 1998, and the Green
and Sustainable Chemistry Network supports green chemistry research and development in
Japan. Government entities around the world recognize the importance of green chemistry
in advancing sustainability.
Government laboratories conduct their own green chemistry research directed toward
sustainable processes. Argonne National Laboratory (2004) has done extensive work on
ethyl lactate, a nontoxic, biodegradable solvent derived from renewable carbohydrates.
Increased use of ethyl lactate depends upon economics; ethyl lactate needs to be competi-
tively priced if it is to replace traditional organic solvents, such as methylene chloride and
chloroform. Argonne’s process cuts the selling price of lactate esters in half. Argonne’s
breakthrough was the development of a selective membrane technology for synthesizing
ethyl lactate. Eliminating the production of an equimolar amount of salt waste was a critical
synthetic challenge. Argonne addressed this challenge using pervaporation membranes and
catalysts to directly convert the salts to esters, thereby eliminating the problem of salt waste.
At Los Alamos National Laboratory, researchers have discovered new applications for
supercritical carbon dioxide in the semiconductor industry (Frazer, 2001). The manufacture
of integrated circuits typically consumes enormous quantities of organic solvents and ultra-
pure water, along with large amounts of energy. Photoresist removal during this process
employs acids or bases, organic solvents, or radio-frequency plasmas. Research at Los
Alamos identified sc-CO2 as a better solvent for photoresist removal. The supercritical
CO2 resist removal (SCORR) process replaces water with sc-CO2 in the final rinse step.
Lowering the pressure at the end of the process returns the carbon dioxide to the vapor
phase, leaving the chip dry and eliminating the use of isopropyl alcohol as a drying agent.
The low surface tension of sc-CO2 enables it to clean the fine features on the integrated
circuit better than conventional solvents.
In addition to long-term research, government agencies adopt more sustainable tech-
nologies to address immediate needs. The U.S. Bureau of Engraving (1999), for example,
developed an alternative solvent for cleaning postage stamp and overprinting presses when
the solvent mixture used for this purpose no longer met environmental regulations in the
District of Columbia. The Bureau replaced Typewash, a mixture of methylene chloride,
toluene, and acetone, with Isomet, a combination of isoparaffinic hydrocarbon, propylene
 M.M. Kirchhoff / Resources, Conservation and Recycling 44 (2005) 237–243 243

glycol monomethyl ether, and isopropyl alcohol. Isomet, currently used to clean all postage
stamp and overprinting presses in the Bureau, is less toxic and less polluting than Typewash.

5. Conclusion

Establishing a sustainable society is a monumental task, one that will clearly require a
collaborative effort. Green chemistry is an essential component of the sustainability agenda
because it applies scientific innovations to global challenges; it addresses environmental
concerns at the most fundamental level, the atomic and molecular level. Partnerships among
academia, industry, and government will maximize the use of available resources, minimize
duplication of effort, and accelerate the adoption of sustainable products and processes by
the chemical enterprise.

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