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Green Chemistry

Green Chemistry: Environment,

Economics, and Competitiveness
Dennis L. Hjeresen*, Mary M. Kirchhoff and Rebecca L. Lankey

The concept of sustainability has generated much discussion and has been incrementally
induced in corporate thinking. However, implementation of changes in industrial processes,
products, and practices has progressed at a slow pace. One reason for this is the enduring
myth that economic profitability must always be sacrificed to achieve environmental goals.
However, innovative technologies have been developed that contribute to improving both the
environmental and economic corporate bottom line. This paper highlights examples of the
successful implementation of such technologies and the benefits that these strategies have
provided. 䊚 2002 Elsevier Science Inc. All rights reserved.

Dennis Hjeresen is Director of the Green Chem- *Corresponding Author: Director, Green Chemistry In-
istry Institute. Dr. Hjeresen also serves as Senior stitute, American Chemical Society, 1155 Sixteenth St.
Program Manager for the Risk Reduction and N.W., Washington, DC 20036, USA.
Environmental Stewardship Division at Los Ala- Tel.: q1-202-872-4078; Fax: q1-202-872-6206;
E-mail: d [email protected].
mos National Laboratory. He also serves on the
advisory boards of the journal Green Chemistry
and the Environmental Science and Technology
magazine.

Mary Kirchhoff is Assistant Director of the Green Sustainability is an attractive idea that has
Chemistry Institute. Prior to joining the Green been embraced by a growing number of
Chemistry Institute, Dr. Kirchhoff was a AAAS companies. Yet, a decade after the Rio de
Fellow and Visiting Scientist with the U.S. Envi- Janeiro Earth Summit, the concept still en-
ronmental Protection Agency’s Green Chemistry genders more discussion than concrete ac-
Program and an Associate Professor of Chemistry tion. While there is no shortage of interest
at Trinity College in Washington, DC. groups pointing out what is happening envi-
ronmentally on a global level and why it is
Rebecca Lankey is an American Society of Me- important to do something about it, there is
chanical Engineers (ASME) Federal Government a paucity of information on how to proceed.
Fellow at the White House Office of Science and
Technology Policy (OSTP). Dr. Lankey has previ-
ously worked for the Green Chemistry Institute Advances in science and technology can
and the Environmental Protection Agency’s (EPA) address the challenges of global environmen-
Green Chemistry Program. Views expressed are tal sustainability, which include the release of
the authors’ and are not necessarily those of persistent organic pollutants, climate change,
ASME, OSTP, or EPA. bioaccumulation of contaminants, atmos-

D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002) 259
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Green Chemistry

pheric distillation, endocrine disruption, and To address the issue of implementing sus-
ozone depletion. Achieving sustainability re- tainability, green chemistry seeks to integrate
quires an intricate balance between resource a new generation of scientific and engineer-
use, economic growth, and environmental ing technologies with economic behavior by
impact. Green chemistry is a growing field of analyzing the processes and the materials
research that addresses many of these con- used in production and development to en-
cerns by combining the critical elements of hance resource use and foster environmental
environmental improvement, economic com- improvement. The global chemical enterprise
petitiveness, and social responsibility. Green provides compelling examples of this rela-
chemistry began as a program of the U.S. tionship.
Environmental Protection Agency in the early
1990s with the goal of achieving pollution Chemicals underpin many of the processes
prevention through a science-based, non- and products that define modern standards
regulatory, and economically driven ap- of living: life-saving pharmaceuticals, agricul-
proach.1–6 Green chemistry is defined as the tural chemicals, sanitation systems, energy
design, development, and implementation of production, semiconductors, and paper
chemical products or processes to reduce or products. Indeed, few modern consumer
eliminate the use and generation of hazard- products would exist without the use of
ous and toxic substances. The Twelve Prin- chemicals. The demand for chemical goods
ciples of Green Chemistry that have guided and services is expected to parallel the pro-
development in the field1 are shown in Table jected increase in world population, from 6.1
1. billion in mid-2000 to between 7.9 and 10.9

Table 1 The Twelve Principles of Green Chemistry

1. It is better to prevent waste than to treat or clean up waste after it is formed.

2. Synthetic methodologies should be designed to maximize the incorporation
of all materials used in the process into the final product.
3. Wherever practicable, synthetic methodologies should be designed to use and
generate substances that possess little or no toxicity to human health and the
environment.
4. Chemical products should be designed to achieve efficacy of function while
reducing toxicity.
5. The use of auxiliary substances (e.g., solvents, separation agents, etc.) should
be made unnecessary wherever possible and, innocuous when used.
6. Energy requirements should be recognized for their environmental and
economic impacts and should be minimized. Synthetic methods should be
conducted at ambient temperature and pressure.
7. A raw material or feedstock should be renewable rather than depleting
wherever technically and economically practicable.
8. Unnecessary derivatization (e.g., blocking group, protectionydeprotection,
temporary modification of physicalychemical properties) should be avoided
whenever possible.
9. Catalytic reagents (as selective as possible) are superior to stoichiometric
reagents.
10. Chemical products should be designed so that at the end of their function
they do not persist in the environment and break down into innocuous
degradation products.
11. Analytical methodologies need to be further developed to allow for real-
time, in-process monitoring and control prior to the formation of hazardous
substances.
12. Substances and the form of a substance used in a chemical process should
be chosen so as to minimize the potential for chemical accidents, including
releases, explosions, and fires.

260 D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002)
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 Green Chemistry

billion by 2050.7 Demands for an increased mental level – the molecular level. It attempts
standard of living throughout the developing to reduce hazards that have a negative im-
world will also drive an increased demand pact on human health and the environment.
for consumer goods and increased chemical Adoption of green chemistry will improve the
use. Yet, many of the most serious global future of industrial science and technology in
ecosystem issues have direct ties to chemi- several important ways.
cals in industry and their consumption.8 Many
industries, especially in developing countries,
use technologies that are outmoded in terms Chemical goods and services are
of their environmental performance, ineffi- expected to parallel the projected
cient in resource and energy use, and ulti-
mately, economically unsound when the so-
increase in world population«
cial costs of pollution are accurately w1x
accounted for. Green chemistry offers a path- Environmental benefits: The environmental
way by which the increased production of benefits of green chemistry are significant.
needed chemical goods and services can be When Eli Lilly redesigned its synthesis of an
achieved in a more materials-efficient, eco- anticonvulsant drug candidate, it eliminated
nomically competitive, and environmentally 300 kg of chromium waste and 34,000 liters
benign manner. of solvent for every 100 kg of product pro-
duced. At the same time, yield increased
It is true that more environmentally sound, threefold. Dow Chemical replaced 3.5 million
scientifically viable chemical alternatives to lbsyyear of CFCs and HCFCs by switching
current technologies are being researched to carbon dioxide as the blowing agent for
and developed, but to be effective, the eco- polystyrene foam. Mobil Technology Com-
nomic viability of these alternatives must also pany eliminated the use of corrosive phos-
be demonstrated. Scientists, engineers, pol- phoric acid and aluminum chloride in its
icy makers, and especially industry leaders synthesis of cumene by employing a zeolite
will need to be educated about the availability catalyst. The new process gives high yields,
of alternative technologies, and it must be fewer byproducts and waste streams, and
proven that they are both environmentally reduced consumption of raw materials. Fur-
sustainable and economically sound. This will thermore, these companies enjoy additional
require an effective system of information savings by reducing or eliminating the
dissemination. amount of waste produced, which often re-
quires expensive treatment and disposal.
Green Chemistry Applied to
Environmental Challenges Economic performance: Second, the adop-
Green chemistry provides options for ad- tion of green chemistry by industry uses
dressing the world’s most pressing challeng- basic science and engineering to redesign
es to sustainability, which include population chemical processes and products in a man-
growth, energy production and use, food ner that enhances both environmental and
production, global climate change, toxics in economic performance. It is this connection
the environment, and non-renewable re- that motivates the implementation of green
source depletion. Green chemistry research chemistry technologies.
has focused on technologies that reduce or
eliminate the use or generation of toxic and The application of tools such as life cycle
hazardous materials, as well as on replacing assessment to studying material and energy
non-renewable feedstocks with renewable flows in products and processes can help
materials. Green chemistry tries to reduce chemical companies more easily identify the
the toxicity of a product at the most funda- sources of hidden costs associated with pro-

D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002) 261
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Green Chemistry

duction. When factoring in costs such as ed. Some have been highlighted in the
waste treatment and disposal, site remedia- Presidential Green Chemistry Challenge
tion, regulatory compliance, public relations, Awards, established by the U.S. EPA in 1995.
and legal consultation, the net impact of Summaries of the winning projects are avail-
able at the EPA program website.9 Other
examples have been published in a volume
Many examples of the economic of case studies.10 Advances in green chem-
and environmental advantages of istry provide specific methods and tech-
niques to improve life-cycle environmental
using green chemistry in impacts and to achieve the goals of sustain-
manufacturing have been ability. Some specific examples illustrate both
documented. the environmental and economic benefits
provided by green chemistry.

ineffective resource use rises. Companies

New Feedstocks for Industrial
seeking to increase profits recognize that
new processes that eliminate problem waste Processes
streams are in their economic interest. How- One of the principles of green chemistry is
ever, because of the competitive nature of that a raw material or feedstock should be
business, the capital costs of new technical renewable, rather than depleting, wherever
solutions may slow the dissemination of technically and economically practical. Such
technologies, even if the long-term economic a principle is critical in the chemical industry,
benefits would provide significant return. To where the selection of raw materials dictates
encourage such economically and environ- much of the environmental impact of future
mentally preferable processes, the Green products derived from that feedstock. One
Chemistry Institute is working to collect and example is the production of plastic consum-
disseminate quantifiable data on the eco- er products using renewable feedstocks rath-
nomic and environmental benefits realized er than petrochemicals. Cargill Dow has be-
through the implementation of green chem- gun operation of a full-scale production plant
istry technologies. Such data is crucial to for polylactic acid, initially using corn sugar
furthering the widespread application of to make polymers for fibers or plastic pack-
green chemistry science and technology. aging. The intent is to replace corn sugar
w2x with agricultural byproducts over time.
Collaborative initiatives: A third important
point is that green chemistry technologies The plant can produce 140,000 metric tons
are multidisciplinary and encourage collabo- per year and was designed to recycle by-
rative partnerships. These technologies rep- product streams internally. The product is
resent the state-of-the-art in several fields in marketed as Nature Works娃 PLA and has
addition to chemistry: agricultural science, several advantages over petrochemical feed-
biotechnology and biological sciences, eco- stocks. By starting with a fermentation proc-
nomics, engineering, and public policy, ess, traditional solvent-based processes are
among others. avoided along with the disposal problems
associated with them. Overall fossil fuel re-
quirements can be reduced as much as fifty
Green Chemistry as a percent. However, capital investments of this
Successful Business Strategy: scale are also driven by the performance of
Case Studies the polymer. Fibers made from Nature
Many examples of the economic and envi- Works娃 PLA are reported to have excellent
ronmental advantages of using green chem- wear characteristics. A key advance in the
istry in manufacturing have been document- Cargill Dow process is the relative ease of

262 D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002)
1066-7938/02/$ - see front matter. 䊚 2002 Elsevier Science Inc. All rights reserved.
 Green Chemistry

product recycling. With typical plastic prod- This is particularly important in the pharma-
ucts, the blending of different polymer ma- ceutical industry where the long research and
terials allows recycling only into lower value licensing process and the limited patent life
products. Nature Works娃 PLA is composta- of drugs frequently result in suboptimal first
ble11 and will degrade in landfills. More im- generation processes. Two examples illus-
portantly, PLA products can be hydrolyzed trate the benefits of this trend.
to return to lactic acid and then reprocessed
to make feedstock-grade polymer, demon-
strating polymer recycling at the highest lev- The use of green chemistry
el. While Cargill Dow also reports significant technologies has proven to be a
CO2 emissions benefits of this process over
traditional polymer synthesis,12 these benefits
smart business strategy.
do not readily translate into short-term finan- w3x
cial gains, but conceivably could. Roche Colorado Corporation, an affiliate of
the Roche Group, was awarded the 2000
Presidential Green Chemistry Challenge
Pharmaceutical Manufacturing
Award for its redesigned synthesis of Cytov-
Since all materials are some form of a chem-
ene䉸, a drug used to treat cytomegalovirus
ical substance, they lend themselves to the
retinitis infections in patients with compro-
advances and advantages that have accom-
mised immune systems, such as transplant
panied developments in the field of green
patients and those with HIVyAIDS. Imple-
chemistry. One of the most important advan-
mentation of the new process decreased air
tages is versatility in starting materials. The
emissions by sixty six percent, liquidysolid
more complex the target product, the more
waste generation by eighty nine percent, and
alternative starting materials and chemical
solvent usage by ninety four percent. Further
pathways will be available.13 In the case of
environmental enhancements came from in-
some complex pharmaceuticals, there are
creased efficiency in the use of raw materials
literally thousands of theoretical routes to
and solvents. The company has used this
manufacture the products. This versatility in
approach to eliminate over 450 tons in annual
chemical manufacturing provides enormous
VOC emissions since 1989, and these chang-
potential for positive impact on the materials
es also resulted in a twenty-five percent
requirements for product manufacture.
increase in production.
Knowing that it is possible to manufacture a
product from a variety of materials allows for
selection and decision criteria in the choice Similarly, Pfizer has begun to systematically
of material input. Therefore, instead of use green chemistry principles to redesign
changing the final product and perhaps af- different drug processes. A good example is
fecting product performance, one can man- the redesign of the process used to manu-
ufacture the identical product while dramati- facture the antidepression drug Zoloft䉸.14 The
cally improving the environmental profile of required changes were made at several dif-
the product life cycle. ferent points in the manufacturing process.
The net result was the elimination of 140
Pharmaceutical manufacturing requires com- tonsyyear of hazardous titanium tetrachlo-
plex and multi-step processing chemistry. A ride, 440 metric tons of solid titanium dioxide
key trend in the industry is the development wastes, 150 metric tons of thirty five percent
of second- and third-generation processes HCl, and 100 metric tons of fifty percent
for the production of pharmaceutical com- NaOH. Additives and washing steps were
pounds. This approach looks for environmen- eliminated, which reduced solvent and water
tal, regulatory, process-efficiency, and cost use. Since discovery in 1985, the process
benefits by redesigning existing processes. has been through three design changes with

D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002) 263
1066-7938/02/$ - see front matter. 䊚 2002 Elsevier Science Inc. All rights reserved.
Green Chemistry

yield increases of twenty, thirty and thirty- Anticipating Regulatory Changes

seven percent respectively, while costs de-
– Wood Treatment
creased.
The protection of wood products from pests
is an important economic issue. However,
ninety-five percent of pressure-treated wood
Semiconductor Manufacturing in the U.S. uses chromated copper arsenate
Much of the water consumed and many of (CCA) as a preservative. In 2000, the North
the hazardous chemicals used in the manu- American wood preservation industry’s use
facturing of semiconductors are used for of CCA was estimated to be between 140
cleaning at multiple stages of the photoli- and 170 million lbs to treat 6 to 7 billion
thography process. The water is typically board feet (about 15 million m3) of lumber.15
deionized and therefore requires a significant Because arsenic and hexavalent chromium
energy investment. The industry is particular- are known carcinogens, the U.S. EPA is con-
ly focused on the removal of hard-baked, cerned about human exposure and the fate
ion-implanted photoresists. Organic solvents of disposed wood.16,17 New regulations are
and aqueous cleaners have been used suc- pending,18 but without an effective alternative
cessfully, but the surface tension of the to CCA, the impacts on the building industry
cleaners prevents penetration into the in- could be devastating.
creasingly finer architectures of a new gen-
eration of chips. New surfactants required for Chemical Specialties, Inc. decided to act in
finer chip structure necessitate subsequent advance of anticipated restrictions to devel-
rinsing and drying steps. This has presented op an alkaline copper quaternary preserva-
the industry with a barrier to decreased chip tive. The preservative eliminates the use of
size, increased production speed, and de- carcinogens and obtains its copper from re-
creased energy consumption. cycled scrap copper. In an alkaline form,
copper has proven effective against decay
fungi. The other active ingredient, quaternary
An approach developed by Los Alamos Na- ammonium compounds, inhibits fungal and
tional Laboratory (LANL), in conjunction with insect growth and demonstrates low toxicity.
semiconductor and equipment manufactur- The net result is that by preparing for regu-
ers, has been the replacement of convention- latory changes, Chemical Specialties has
al cleaning techniques with supercritical CO2 used greener chemistry to position itself to
(scCO2). Supercritical CO2 offers a variety of take advantage of changing market condi-
advantages compared to traditional solvents. tions.
Gas-like properties, high diffusivity, and low
viscosity allow scCO2 to effectively reach the Lessons on Sustainable Futures
smaller features of the new wafer designs. The use of green chemistry technologies has
The ability to adjust the solvent properties of proven to be a smart business strategy that
scCO2 enhances the cleaning capability for can provide both environmental and eco-
both organic and inorganic material. The sol- nomic benefits and can motivate further tech-
ubility can be further adjusted by using co- nology dissemination. Teaching industrial sci-
solvents tailored to address specific removal entists and business managers about these
processes, and LANL has used non-hazard- successful green chemistry technologies will
ous chemical co-solvents to achieve this. be the next important step towards achieving
This technology demonstrates that green implementation of the next generation of en-
chemistry can offer process improvements vironmentally friendly technologies. These
that enhance productivity and corporate technologies can help us to address our most
competitiveness while also addressing envi- pressing global challenges. Sustainability will
ronmental and resource consumption issues. not be facilitated by inefficient technologies.

264 D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002)
1066-7938/02/$ - see front matter. 䊚 2002 Elsevier Science Inc. All rights reserved.
 Green Chemistry

The use of environmentally beneficial tech- ing Composting, in: Science and Engineering
nologies, such as those provided by green of Composting: Design, Environmental, Mi-
chemistry, will be realized only when those crobiological and Utilization Aspects, H.A.
technologies also contribute to overall cor- Hoitink, H.N. Keener (Eds.), Renaissance
porate competitiveness. Publications, Worthington, Ohio, 1993, p.
339.
12. Cargill Dow reports that PLA has a green-
house gas emission rate of about 1600 kg
CO2 ymetric ton compared to rates for poly-
Endnotes propylene, polystyrene, PET, and Nylon of
1850, 2740, 4140, and 7150 kg CO2 y metric
1. P.T. Anastas, J.C. Warner, Green Chemistry: ton, respectively (Patrick Gruber, Keynote
Theory and Practice, Oxford University Address, Massachusetts Green Chemistry
Press, New York, 1998. Symposium, Amherst, MA, October 30,
2. P.T. Anastas, C.A. Farris (Eds.), Benign by 2001; co-sponsored by the University of
Design: Alternative Synthetic Design for Pol- Massachusetts Amherst, the National Envi-
lution Prevention, Oxford University Press, ronmental Technology Institute at the Univer-
New York, 1994. sity of Massachusetts Amherst; the Massa-
3. P.T. Anastas, P. Tundo (Eds.), Green Chem- chusetts Executive Office of Environmental
istry: Challenging Perspectives, Oxford Uni- Affairs; and the Toxic Use Reduction Insti-
versity Press, New York, NY, 2000. tute at the University of Massachusetts Low-
4. P.T. Anastas, T.C. Williamson (Eds.), Green ell.)
Chemistry: Designing Chemistry for the Envi- 13. P.T. Anastas, R.L. Lankey, Life Cycle Assess-
ronment, ACS Symposium Series No. 626, ment and Green Chemistry: The Yin and
American Chemical Society, Washington, Yang of Industrial Ecology, Green Chemistry
DC, 1996. 2 (2000) 289–295.
5. P.T. Anastas, L.G. Heine, T.C. Williamson 14. J.L. Tucker, Chemistry the Color of Money,
(Eds.), Green Chemical Syntheses and 223rd ACS National Meeting (Orlando, April
Processes, ACS Symposium Series No. 767, 7–11, 2002), Paper No. 253, Industrial and
Oxford University Press, New York, NY, Engineering Chemistry Division Symposium
2000. on Applications of Chemistry in the Pharma-
6. P.T. Anastas, T.C. Williamson (Eds.), Green
ceutical Industry.
Chemistry: Frontiers in Benign Chemical
15. A.F. Preston, Wood Preservation: Trends of
Synthesis and Processes, Oxford University
Today That Will Influence the Industry To-
Press, New York, NY, 1998.
morrow, Forest Products Journal, 50 (9)
7. World Population Prospects: The 2000 Revi-
(2000), 11–19. Available on the web at http:
sion, Population Division, Department of Ec-
y ywww.treatedwood.com y newsyfp journal
onomic and Social Affairs, United Nations,
New York, NY, 10017. sept 00.pdf (accessed May 21, 2002).
8. B.C. O’Neill, F.L. MacKellar, W. Lutz, Popula- 16. Environmental Protection Agency web page,
tion and Climate Change, Cambridge Uni- Manufacturers to Use New Wood Preserva-
versity Press, Cambridge, UK, 2001. tives, Replacing Most Residential Uses of
9. Environmental Protection Agency web site, CCA, Office of Pesticide Programs, February
EPA’s Green Chemistry Program, http:y y 12, 2002, http:y ywww.epa.govy pesticidesy
www.epa.govygreenchemistryypast.htm (ac- citizensy cca transition.htm噛bkmrk3 (ac-
cessed May 13, 2002). cessed May 20, 2002).
10. M.C. Cann, M.E. Connelly. Real World Cases 17. Environmental Protection Agency web page,
in Green Chemistry; American Chemical So- Inorganic Chromium Report of the Hazard
ciety; Washington, DC, 2000, available on- Identification Assessment Review Commit-
line at: www.acs.orgyeducation ygreenchemy tee, Office of Science Coordination and Poli-
cases.html cy, August 28, 2001, http:y ywww.epa.gov y
11. R. Narayan, Degradation of Polymeric Mate- scipolyy sap y2001 yoctober yarsenicgraphda-
rials (Anthropogenic Macromolecules) Dur- ta.pdf (accessed May 20, 2002).

D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002) 265
1066-7938/02/$ - see front matter. 䊚 2002 Elsevier Science Inc. All rights reserved.
Green Chemistry

18. Environmental Protection Agency, Federal

Register Environmental Documents web
page, ‘‘Notice of Receipt of Requests to
Cancel Certain Chromated Copper Arsenate
(CCA) Wood Preservative Products and
Amend to Terminate Certain Uses of CCA
Products’’, Federal Register, 67 (36), Febru-
ary 22, 2002, 8244–8246, http: y y
www.epa.govyfedrgstry EPA-PESTy2002 y
Februaryy Day-22yp4306.htm (accessed
May 20, 2002).

266 D.L. Hjeresen et al., Corporate Environmental Strategy, Vol. 9, No. 3 (2002)
1066-7938/02/$ - see front matter. 䊚 2002 Elsevier Science Inc. All rights reserved.