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Green Chemistry and Engineering: Towards a Sustainable Future

A white paper reporting on the green chemistry philosophy of reducing waste, toxicity and hazards, and its application on an industrial scale.

Green Chemistry and Engineering: Towards a Sustainable Future 1


Table of ConTenTs

I. Executive Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

II. What Does It Mean to be Green? . . . . . . . . . . . . . . . . . . . . . . 3

III. Designing Safer Syntheses . . . . . . . . . . . . . . . . . . . . . . . . 7

IV. Reducing Toxicity by Design . . . . . . . . . . . . . . . . . . . . . . . 11

V. Renewable Feedstocks . . . . . . . . . . . . . . . . . . . . . . . . . 13

VI. Green Chemistry in Industry . . . . . . . . . . . . . . . . . . . . . . . 15

VII. Education . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

VIII. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19

IX. Works Cited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21

X. Appendix A: The 12 Principles of Green Chemistry . . . . . . . . . . . . . . 26

XI. Appendix B: The 12 Principles of Green Engineering . . . . . . . . . . . . . 27

abouT This RepoRTThis special report is for exclusive use by members of the American Chemical Society . It is not

intended for sale or distribution by any persons or entities . Nor is it intended to endorse any

product, process, organization, or course of action . This report is for information purposes only .

© 2013 American Chemical Society

abouT The auThoRMelissae Fellet has written about chemistry for New Scientist, Chemical & Engineering News

and Chemistry World . She graduated from the Science Communication program at the

University of California, Santa Cruz and holds a Ph .D . in chemistry from Washington

University in St . Louis .

Green Chemistry and Engineering: Towards a Sustainable Future2 Green Chemistry and Engineering: Towards a Sustainable Future

I . Executive Summary

The slogan “benign by design” summarizes the ethos of green chemistry, and 12 principles

guide its implementation . In short, the main goals and applications of green chemistry are

to reduce environmental, human health and safety risks of chemicals by redesigning toxic

molecules, synthetic routes, and industrial processes .

Green chemistry is an interdisciplinary field, drawing on knowledge from chemistry,

chemical engineering, toxicology, and ecology . Chemists can design new catalysts that

reduce the amount of reagents used and thus reduce the amount of waste generated in

reactions . Chemical engineers can design a production line to recycle certain reagents and

minimize energy consumption . Toxicologists and ecologists provide information about the

toxic characteristics and effects of molecules so that chemists can then work to design new

molecules that avoid structures linked to toxicity .

Green chemistry researchers develop new catalysts, test new solvents, and experiment

with microscale flow processes . Some of this research is adopted by the chemical industry,

particularly in pharmaceuticals . Through annual green chemistry awards, the American

Chemical Society and the U .S . Environmental Protection Agency reward successful applications

of green chemistry in industry . The Royal Society of Chemistry in the United Kingdom offers a

green chemistry award every two years .

Educating future chemists is also an important part of the philosophy of green chemistry .

Green chemistry experiments, with their low-risk ingredients and connection to sustainability,

can be used as demonstrations for school groups . Green chemistry experiments are working

their way into undergraduate teaching laboratories as well . And as the next generation of

chemists learns these principles, perhaps one day green chemistry will not be an additional

consideration when designing a synthetic route or industrial process . It might just be how

things are done .

Green Chemistry and Engineering: Towards a Sustainable Future 3Green Chemistry and Engineering: Towards a Sustainable Future

II . What Does It Mean To Be Green?

The 12 principles of green chemistry (see Appendix A), outlined in 1998, ask chemists to

prevent waste, minimize energy use, use renewable raw materials, design biodegradable

products, and choose chemicals to minimize potential accidents .(1) But putting those

principles into practice often requires trade-offs, especially when you’re trying to determine the

“greenness” of an entire process .

For example, a reaction with a hazardous reagent is not attractive for a process scale because of

the inherent safety risks . But sometimes using such a reagent can shorten a reaction sequence,

reducing costs, waste and solvent use . Jeffrey V . Mitten of Novasep, a company that specializes

in chemical process development, described how the company handled this situation when

converting a hydroxyester to an aminoalcohol using diborane gas, which can ignite in humid

air .(2) Novasep’s chemists and engineers created a way to generate diborane on site and

meter it into the reaction . With the hazards contained, this route eliminated protection and

deprotection steps, shortening a five-step sequence to two steps . By using this new route, costs

were reduced by 60%, and the product yield was improved from 59% to 81% .(2)

Hazardous, But Greener

Novasep’s route to aminoalcohols defies green chemistry principles by using

hazardous diborane gas as a reagent . The process makes up for the transgression by

reducing the reaction to two steps, generating less waste, and reducing costs .

Z ORHO

O

PGZ ORPGO

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Initial process:

Z OHPGO

Z OMs PGOMsCl – PG

Z NH

PGOR NH2 R

Z NH

HOR

Z ORHO

O O

Greener process:

B2H6R NH2

Z = CH2, NH, O, or S; PG = protecting group; Ms = methanesulfonyl

Z NH

HOR

Z NH

HOR


Green metrics seek to quantify the abstract concept of sustainability .(3) These measurements

can help scientists compare processes for their overall “greenness,” although trade-offs exist

here as well . Optimizing a process for environmental effect might reduce its safety, for

example . One easily calculated metric is the E-factor, which is the mass of waste per mass of

product . This ratio, typically up to 100 for pharmaceuticals(4), reflects the amount of waste

generated in a process . In contrast, petrochemicals have an E-factor around 0 .1, near the ideal

waste-free value of zero .(2)

There’s also a need for qualitative metrics too . “You could have an E-factor of 20, which would

be low by pharmaceutical standards, but if the solvent in every single step in the process

is benzene, it’s not a green process,” Berkeley W . Cue Jr ., chair of the ACS Green Chemistry

Institute Governing Board, told Chemical & Engineering News in 2012 .(4) Many pharmaceutical

companies use a different green metric: process mass intensity (PMI) . This value reflects the

total mass of material in a process per mass of product . The ideal PMI is 1, indicating that all

reagents are converted into product . It provides a broader indication of process efficiency than

just tracking waste using the E-factor .

However, any single metric cannot describe the range of factors — from sources of raw

materials to energy use and water consumption — that affect sustainability of a particular

process . Thus, the ACS Green Chemistry Institute spearheaded the Greener Chemical Products

& Processes Standard to develop common measurements that chemists, consumers, and

policymakers can use to evaluate the environmental aspects of a particular product .(5)

“Ecolabels” on cleaners also attempt to describe sustainability . But these labels, or ingredient

lists ranked by toxicity, are not as comprehensive as the proposed standards . Industry trade

groups or environmental groups often develop the current ecolabels and product guides .

Though the rankings may reflect products with reduced toxicity, they may not account for

other sources of environmental damage, like using water and energy when washing clothes or

dishes .(6)


Environmental life cycle assessment (LCA) tracks the environmental impact of a product from

the origin of its raw materials through its production, distribution, use, and disposal . Such

an analysis allows scientists to identify destructive points in the life cycle and make changes

to stem the damage . Early LCAs in the 1970s looked at ingredients, emissions, and waste

produced by different beverage containers .(7) Now a variety of analyses allows scientists

to estimate a range of potential ecological consequences, like global warming, nutrient

overloading, or environmental toxicity . Other analyses track product resource use and human

toxicity of a particular process .

These analyses provide a view of the environmental impacts and trade-offs of a particular

process that is more accurate than just looking at a single metric, such as waste . That’s because

an LCA inherently accounts for the connections between different steps of production,

distribution, and utilization . Collecting enough data about a particular process can be time-

consuming and expensive . And the methods of data collection, any models used, and any

assumptions employed in an LCA need to be known before an organization changes its policies

based on information in the analysis .(8)

There are several ways to analyze a product over its life cycle without doing a full LCA . Process

mass intensity (PMI), a common green metric, can be used to quickly estimate life cycle

impacts, as it correlates with global warming potential for compounds under development

at the pharmaceutical company GlaxoSmithKline(GSK) .(9) Chemists at GSK have also

developed several specific LCA tools . One allows for quick comparisons of synthetic routes

from experimental stages through to manufacturing .(11) Another combines this streamlined

LCA tool with a PMI calculator developed by Merck to be a standard quick LCA for the

pharmaceutical industry .(12)

An online resource, iSustain .com, helps scientists and students quickly estimate how a product

fits with the 12 principles of green chemistry .(10) Users input information about the materials

that enter a process and the waste that comes out . The site generates a Green Chemistry Index

rating that reflects a quick snapshot of process efficiency, without doing a full LCA .

CRadle-To-CRadle design The cradle-to-cradle engineering philosophy involves considering the life cycle of a product,

from raw material to disposal .(13) Industrial and academic labs that add this framework to the

12 principles of green engineering (see Appendix B) build biodegradable, renewable products

that require less energy for production . Recyclable carpet tiles are one practical application

resulting from this union .(14) Carpet fibers are often made of recyclable nylon 6, while the

backing is commonly made from rigid polyvinylchloride plastics . In 1996, Shaw Industries

started to redesign the backing to be made from a recyclable polymer as well, primarily a

low-density polyethylene . The new backing composition also created carpet tiles with better

flame-retardant characteristics than traditional carpet treated with arsenic or aluminum oxides .

The new tiles are fully recyclable, once the fibers are separated from the backing, and building


blocks of each polymer can be used to make new carpet

tiles . The product won a U .S . Environmental Protection

Agency (EPA) Presidential Green Chemistry Challenge

Award for Designing Greener Chemicals in 2003 . To

encourage their customers to recycle the tile, the company

also provides free collection and recycling of used tiles .

Along with carpet, plastics are another major component

of landfills . Polylactic acid (PLA) plastics made from corn

are the leading biorenewable plastics, but breaking

them down requires high temperatures and agitation at

commercial composting sites . Plastic that isn’t recycled or

deposited in a landfill washes out to sea and disintegrates

into tiny pieces that harm wildlife . The X Prize Foundation

is developing a project challenging researchers to create

plastics that degrade in the ocean .

A researcher at the University of Florida is already working

on building plastics that break down in water . He has

designed a new way to make plastic that installs an

acid-sensitive functional group, an acetal, throughout

a polydecylene plastic made from a fatty acid in castor

seeds .(15) Plastics made with this method degrade faster

than PLA plastics in acidic tetrahydrofuran solution, a

preliminary test for water degradability . However, these

materials are still too soft to replace current PLA plastics .

five easy Things you Can do To Make youR lab MoRe susTainable

A certification program at the University of Michigan recognizes laboratory efforts to become more sustainable . At the request of the manager or head of the lab, a staff member from the university’s Office of Campus Sustainability visits the lab and provides recommendations for sustainable practices based on green chemistry principles, waste reduction, and pollution prevention . Sudhakar Reddy, the program’s coordinator, says 45 labs have participated in the program as of March 2013 . He shares a few recommendations encouraged by the program:

1 . Close fume hoods when not in use to reduce energy use .

2 . Run experiments on the microscale to reduce waste .

3 . Switch to green solvents: Use 2-methyl tetrahydrofuran in place of methylene chloride, and use cyclopentylmethyl ether in place of tetrahydrofuran, 1,4-dioxane and ether .

4 . Neutralize basic phosphate-buffered HPLC waste or acidic HCl waste to pH 7 and pour down the drain .

5 . Recycle electronics, ice packs, packaging materials, toner cartridges, pipette tip boxes, and water purification cartridges .

For more information on the program, check out the ACS GCI Nexus blog:

https://communities .acs .org/community/science/sustainability/green-chemistry-nexus-blog/blog/2013/01/10/university-of-michigan-sustainable-laboratories-recognition-program


III . Designing Safer Syntheses

Chemists design safer syntheses by looking for ways to reduce waste from solvents and added

reagents . Minimizing reagent hazards and toxicity by running reactions on a small, continuous

process is also another way to reduce risk . One classic green synthesis is a route to ibuprofen

developed by the BHC Company (now BASF) in 1991 and put into industrial production the

next year .(15) This new route condensed a six-step stoichiometric synthesis to a three-step

catalytic sequence . This revamped synthesis won the EPA Presidential Green Chemistry

Challenge Award for Greener Synthetic Pathways in 1997 . This synthesis reduces waste in

several ways . About 80% of the atoms in all the reactants end up in the final product, compared

to less than 40% in the original synthesis . This increased atom economy inherently reduces

reactant waste, as more of the reagents are converted to product . Additionally, all the catalysts

in the synthesis — hydrofluoric acid and palladium — are recovered and recycled . No other

solvent besides HF is needed .

This section will discuss concepts in four areas of green chemistry research — catalysis,

solvents, alternative energy sources for reactions, and continuous processing — and show how

these ideas are reaching industry .

CaTalysisCatalysis dominates the literature on green synthesis (17), even though it’s an important

research area in its own right . The goals of catalyst development dovetail with the principles

of green chemistry: Chemists want to build a fast, long-lived, and highly selective catalyst that

works under mild conditions . Since a catalyst regenerates itself after a reaction, one molecule

of catalyst can perform several transformations . That allows scientists to get high yields from a

reaction that uses only a relatively small amount of catalyst .

Traditionally, transition metals like palladium, platinum, and ruthenium are used to build catalysts

for carbon-carbon bond-forming reactions . However, these metals are expensive and in low

abundances in the Earth’s crust . In some cases, the catalysts require large ligands to control the

selectivity of a reaction, which can be considered wasteful according to the 12 principles .

Therefore, researchers look to get the same functionality of these catalysts with a more

available and sustainable metal: iron . Iron catalysts can carry out a wide range of cross-

coupling reactions, but many of those reactions require flammable Grignard reagents .(18)

Currently, that requirement may prompt researchers to avoid using these catalysts on larger

scales until more is understood about how they work . Another iron catalyst can make an

alkylsilane used in shampoo and to soften denim with greater activity and selectivity than

industrial platinum catalysts .(19)


Another independent area of research, nanoscience,

might provide insights into building green metal catalysts

too . Gold-palladium nanocatalysts can generate hydrogen

peroxide, an acceptable oxidant for green chemistry, from

hydrogen and oxygen .(20) Attaching catalysts to magnetic

nanoparticles makes it easy for chemists to separate and

recycle the catalyst after a reaction .

Other types of catalysts can reduce safety risks . Acid

catalysts attached to silica, for example, reduce

the aqueous waste generated by quenching and

neutralizing a reaction .(21) Phase transfer catalysts (often

ammonium salts) carry an insoluble reactant between

the organic and aqueous phases in a mixture . Chemists

used tetrabutylammonium bromide to catalyze the

displacement of a chloride by a cyanide ion on a process

scale . The reaction releases heat, but the researchers could

control the exotherm and prevent a temperature spike just

by controlling the stirring speed .(22)

Enzymes are commonly used as catalysts in industry,

particularly pharmaceuticals, because they work at

ambient temperatures and pressures in water .(2) That

makes them safe to handle on a process scale . One

example is the three-step enzymatic route to the key

chiral building block used to make the active ingredient

in the cholesterol-lowering drug Lipitor . The process won

enzyme company Codexis an EPA Presidential Green

Chemistry Challenge Award in 2006 . Previous routes to

the key intermediate involved separating enantiomers

in the first step (at 50% maximum yield) and a final step

plagued with byproducts . The enzymatic process gives the

desired intermediate in a greater than 90% isolated yield .

(23) The overall process has an E-factor about five times

smaller than a typical pharmaceutical designed with green

chemistry principles .

But in practice, biocatalysts are not necessarily “greener”

than chemical catalysts . A streamlined LCA comparing a

metal catalyst to an enzymatic reduction of a ketoester

revealed that some of the processes and reaction

ReCyCling and ReplaCing RaRe eaRTh eleMenTs

Much of modern technology contains rare earth elements . Magnets in wind turbines, medical imagers and hard disk drives contain terbium, neodymium, and praseodymium . So do the nickel metal hydride batteries of hybrid cars . Light emitting diodes and energy efficient fluorescent light bulbs contain europium and ytterbium .

The big issue with rare earth elements is not their suggested scarcity . These 17 elements are moderately abundant in the Earth’s crust, though they are too dispersed for extraction to be economically efficient .(1) Most of the easily-extracted metal is found in China . Mines in the country provide 97% of the world’s supply of rare earth elements, and that supply can be cut off if and when China sets export restrictions .(2) Restricting supply means prices for the metals climb .(3)

New mines in the United States and Australia, along with ones planned in Brazil, Canada and Vietnam, could stabilize the supply of rare earths . But new mines bring radioactive mining waste and potentially more fossil fuel energy needed to recover metal buried in poor ore .

So companies that make products using rare earth elements are looking for ways to recycle and reuse the metals . In 2010, Hitachi developed a method to recycle rare earth metals from hard drives and compressors . In March 2013, Honda announced a process to reuse the metals from batteries in hybrid cars .

University researchers are also creating new materials that can replace those in common products that rely on rare earth elements . An experimental electrode material for lithium ion batteries contains an organic molecule from plants called purpurin .(4) Quantum dots LEDs, made from silicon(5) or other metals, could replace LEDs colored using rare earth elements . Nanostructured films of manganese and gallium can exert magnetic fields of strength similar to rare-earth containing magnets .(6)

1 . Humphries, M . Rare Earth Elements: The Global Supply Chain . R41347, Congressional Research Service: 2012 .

2 . Cho, R . “Rare Earth Metals: Will We Have Enough?” Columbia University Earth Institute blog, Sept . 9, 2012 . http://blogs .ei .columbia .edu/2012/09/19/rare-earth-metals-will-we-have-enough/

3 . Trembley, J .-F . “Managing a Dearth of Rare Earths .” Chemical & Engineering News 2012, 90(14): 14-15 .

4 . Reddy, A . L . M ., Nagarajan, S ., Chumyim, P ., Gowda, S . R ., Pradhan, P . Jadhav, S . R ., Dubey, M ., John, G ., Ajayan, P . M . “Lithium storage mechanisms in purpurin based organic lithium ion battery electrodes .” Scientific Reports, 2012, 2, 960 .

5 . Patel, P . “LEDs Made From Silicon Quantum Dots Shine In New Colors .” Chemical & Engineering News, January 28, 2013 . http://cen .acs .org/articles/91/web/2013/01/LEDs-Made-Silicon-Quantum-Dots .html

6 . Nummy, T . J ., Bennett, S . P ., Cardinal, T ., Heiman, D . “Large Coercivity in Nanostructured Rare-earth free MnxGa films .” Applied Physics Letters, 2011, 99, 252506 .


conditions most impacted the analysis .(24) Including bioprocesses in LCA would help the

pharmaceutical industry evaluate these catalysts .

Applications for enzymes can be found outside of the pharmaceutical industry, too . In 2012,

a chemical company, Buckman International, won an EPA Presidential Green Chemistry

Challenge Award for using enzymes to create stronger paper without added wood pulp or

chemical additives . The enzymes connect the fibers of cellulose within the paper, resulting in a

stronger end product . The enzymes also allow for increased production . Combined with energy

reductions, the new process saves the company an estimated $1 million per year .(25)

gReen solvenTsGreen solvent research in academic labs is targeted at finding new solvents . Scientists also

develop applications for interesting liquids like water, supercritical carbon dioxide (CO2), and

ionic liquids . Water is often not thought of as a potential solvent for organic reactions, because

many reagents are water-sensitive or insoluble in water . But some reactions, like an aqueous

Diels-Alder reaction between cyclopentadiene and butanone, run faster in water than in

organic solvents like methanol .(26, 27) Often the rate enhancement is due to hydrophobic

effects and hydrogen bonds that stabilize transition states . Running a reaction in water makes it

possible to use enzyme catalysts as well .

A 2007 analysis of green solvents that includes life cycle impacts ranks water and supercritical

CO2 as promising green alternatives to traditional organic solvents .(28) Many chemicals

do not dissolve in these solvents, but the researchers write that that fact is “more than

counterbalanced” by the ease of handling and separating these solvents, as well as their low

environmental impact .

Supercritical CO2 has properties between that of a gas and a liquid . It’s commonly used as

a dry cleaning solvent or to extract caffeine from coffee beans . Scientists can control what

compounds dissolve in the supercritical fluid by adjusting its density to tune its polarity . The

volatility of CO2 means that the supercritical fluid is easily removed after a reaction .

Ionic liquids are mentioned in almost half of the green solvent research published in Green

Chemistry in 2010 .(29) The structure of positive and negative ions in these liquid salts control

solubility and guide a reaction . Ionic liquids work as solvents for a variety of reactions (30), and

they can be designed to catalyze reactions too .(31) While ionic liquids might be interesting

substances from the perspective of basic research, their potential utility in industry is unclear

due to as-yet-to-be-determined disposal protocols on a large scale .(32)

The amount of research into various green solvents doesn’t match predicted needs for solvents

to reduce environmental damage, writes Philip Jessop of Queen’s University in Canada, in a

2011 perspective in Green Chemistry .(29) While Jessop supports basic research into solvents,

he asks his colleagues to consider their research topics carefully if they wish to reduce solvent-

caused environmental damage .


Of course, the best way to reduce solvent use is to not use solvents in the first place .

It’s often thought that a solvent is needed to increase catalyst efficiency or improve the

enantioselectivity of a catalyzed reaction . Some asymmetric reactions, however, can be run just

by mixing the reagents together .(33)

alTeRnaTive eneRgy souRCes foR ReaCTionsRunning reactions can be energy intensive . When chemists boil a reaction, they simultaneously

cool the solvent vapors . The resulting droplets fall into the reaction so that the reaction never

runs dry . But this standard process requires energy to both heat and cool the reaction, in

addition to the water being constantly run through a condenser .

Therefore, some green chemists look to new energy sources to drive reactions . Microwave-

assisted reactions can be run in water at a small scale, often with accelerated rates due to

temperature and pressure effects . Reactions to build oxygen-, nitrogen- or sulfur-containing

rings common in medicinal chemistry can also be driven using microwaves, though these

reactions aren’t running on a process scale yet .(34) Alternatively, the energy from grinding

reagents together using a mortar and pestle or a ball grinder can be enough to trigger a

reaction .(35)

Ultrasound sonication is another energy source with useful applications such as deprotecting

an amine, protecting hydroxyls on sugars, or reducing an α,β-unsaturated ketone in a steroid .

The sound waves create areas of high and low pressure, much like ripples in a pond, as they

travel through liquid . Bubbles form in the low-pressure areas, collapse when they reach

high-pressure regions, and send shockwaves through the reaction . Surprisingly, ultrasound

sonication can influence the products of a reaction . When chemists stirred a suspension of

benzyl bromide and alumina-supported potassium cyanide, they retrieved diphenylmethane,

which contains two connected benzene rings, as the product of a Friedel-Crafts reaction . But

when they sonicated the reaction, the cyanide ion replaced the bromine atom, giving benzyl

cyanide as the product . The researchers suspect that the bubbles generated during sonication

masked the metallic catalytic sites on the solid support .(35)

ConTinuous pRoCessingTypical syntheses, whether in academic labs or batch processes, proceed through a series of

discrete steps and reactors . This creates large amounts of solvent and water waste . Continuous

processing, however, carries production in a steady flow by adding reagents to a stream of

liquid . Such reactions can address nine of the 12 principles of green chemistry .(36)

These experiments are often performed on the microscale by pumping reactants through

small channels . This scale has inherent safety benefits . Chemists can use smaller amounts of

potentially hazardous reagents, and the flow system gives them better control over conditions

that might otherwise lead to runaway reactions . Continuous processes can even be designed to

run short, multistep syntheses .(37)


Microscale reactions can be scaled up by running one reactor for a long time, or by running

multiple reactors in parallel . It’s also possible to scale up flow reactions by increasing the width

of the tubes, and thus the volume of liquid traveling through them . A pilot-plant project made

more than 100 kilograms of 6-hydroxybuspirone over three runs of the flow process .(38)

Continuous production can be hampered by clogs in the lines or mechanical problems, like

leaking or valve failures . Thus, monitoring the reactions in the stream for blockages, as well as

product formation, helps to keep the flow processing moving . Chemists in Denmark built an

industrial-scale inline monitoring system for the production of allylcarbinol using a Grignard

reaction .(39) A Grignard reaction as the first step in a pharmaceutical synthesis, for example,

needs precise stoichiometric control of the Grignard reagent and ketone substrate to prevent

byproducts and yield loss . The monitoring system measures the amount of ketone left in the

product, and then controls the flow rate of the Grignard reagent into the reaction to maintain

the proper stoichiometry .

In a recent survey, eight of nine pharmaceutical companies reported using continuous

processing in pilot plants or on the production scale .(40) However, most companies in the

survey responded that they hesitate to build continuous-process plants when existing batch-

plant infrastructure meets demands .

IV . Reducing Toxicity By Design

Toxicologists track how chemicals harm the body, by studying their effects on biochemical

pathways, cells, and tissues . They also uncover relationships between the dose of a chemical

and its physical effect . These dose-response relationships are part of risk assessment and

hazard management plans . But one principle of green chemistry aims to do more than manage

risks; it challenges chemists to reduce a molecule’s toxicity during the design process, rather

than managing the effects after a molecule has been synthesized .

Currently, it’s not possible to fully predict the toxicity of any new molecule . But principles of

toxicology can help chemists identify characteristics of a molecule that might impart toxicity .

(41) Certain molecular structures bind to metabolic enzymes . Other electron-poor molecules

are carcinogenic because they bind to DNA . And fat-soluble molecules can accumulate in fat

cells and not be cleared from the body .

Medicinal chemists can exploit some of these structures to help develop killer drugs specific

for diseased cells . Green molecular designers, however, want to avoid those structures, as they

want to prevent a molecule from causing biological harm .


ReduCing endoCRine disRupTionEndocrine disruptors are harmful molecules that behave like hormones in humans and alter

the body’s natural signaling system . Endocrine disruptors are thought to be linked to health

conditions such as obesity, cancer, diabetes, and infertility . Now a new protocol helps chemists

design molecules to reduce their endocrine-disrupting effects .

Bisphenol-A (BPA), a phthalate used as a plasticizer in polycarbonate plastics, is an example

of a potentially endocrine-disrupting chemical . It’s also found in the linings of canned food

and cash register receipts . Many products advertise that they are BPA-free, due to consumer

concerns about ingesting BPA . Chemical companies are searching for molecules to replace BPA

for food and beverage applications, but they’re struggling to find something that’s an equally

effective replacement .(42)

A new tiered system of tests, developed by a team of 23 scientists, might help chemical

companies determine if a new molecule is a potential endocrine disruptor .(43) The first tier

involves computer modeling based on physical properties, chemical reactivity, and estimates of

biological reactivity using structural similarities . The second tier involves biochemical pathway

screening . Then a molecule is tested in tissues of increasing complexity — from cells to whole

amphibians to mammals .

The study of endocrine disruption is still a growing field, so protocols will evolve to include

assays that incorporate knowledge as it is discovered .(44) For example, a growing body of

evidence suggests that chronic, low doses of endocrine disruptors like BPA may cause physical

harm .(45) That means a typical interpretation of toxicology — reducing risk by preventing

exposure to harmful doses — may not apply to this class of chemicals .


V . Renewable Feedstocks

The ingredients for many chemicals and materials come from petroleum and natural gas

processing . One principle of green chemistry calls for using renewable feedstocks when

technically and economically possible, instead of drawing on materials that deplete

natural resources .

Plants are seen as a source of sugars for biofuel production . Starch from corn is an easily

accessible sugar source, but it’s impractical to scale up biofuel production using corn .

Every acre of corn destined for biofuel production is one less acre that’s not in agricultural

production . However, there are other fast-growing plants like switchgrass and a species of

poplar tree that could make attractive sugar sources, while avoiding a “food versus fuel” debate .

However, it’s difficult to break apart these woody plants into sugars needed for fuel production .

Tough fibrils of lignocellulose reinforce plant cell walls .(46) Releasing the sugars in that

lignocellulose is key to getting the maximum amount of fuel from a plant .

Chemical catalysts can convert plant matter to oxygenated fuels like ethanol, furfural, and

levulinic acid .(47) Virent, a biofuel company in Wisconsin, converts sugars to hydrocarbons

— essentially the same blend as gasoline — using an aqueous process and chemical catalyst .

Alternatively, engineered microbes can consume sugars and produce a fatty acid methyl ester

or farnesane for biodiesel .

Multiple Highways

Many starting points lead to many end points for biofuels .

STARCHES/SUGARS Corn grainSugarcane

Aqueous sugarsFermentation

Aqueous-phase processing

Ethanol or butanolDiesel fuel or jet fuel

GasolineDiesel fuelJet fuel

LIPIDSSoybeansOther oilseedsAnimal fatAlgae

Vegetable oil/animal fat EsterificationHydrotreating

Diesel fuelJet fuel

LIGNOCELLULOSECrop residuesForest wasteMunicipal wasteEnergy crops

Hydrolysis/enzymes

Gasification

Pyrolysis

Aqueous sugars

Synthesis gas

Biocrude oil

Aqueous-phase processing

Fischer-Tropsch chemistry Fermentation

Catalytic cracking Hydrotreating

GasolineDiesel fuelJet fuelEthanol


Currently the economics of biofuel production still lie in favor of petroleum-based fuel . But

a biofuel plant can offset its production of low-value fuel by also producing high-value bulk

chemicals .(48) In 2004, the U .S . Department of Energy listed 15 chemicals as top targets to

make in a biorefinery . Included on the list were glycerol, succinic acid, aspartic acid, and

furandicarboxylic acid . An experimental small scale biorefinery from researchers at the

City University of Hong Kong transforms wasted pastries from Starbucks into succinic acid .

Companies like BioAmber, an industrial biotechnology firm in Minneapolis, are looking to use

more traditional sugar sources, and won a 2011 EPA Presidential Green Chemistry Challenge

Award for its microbial production of succinic acid from glucose, corn sugar, and corn stover .

(49) BioAmber operates a plant in France that produces 3,000 metric tons of succinic acid a year .

It plans to open a larger factory in 2013, capable of producing 11,000 additional metric tons

at full capacity . A wave of upcoming factory openings for other biobased chemicals, including

isobutyl alcohol, glucaric acid, acetic acid, and farnesene, carves out a place for biobased

chemical production in the industry, although the bottom-line profitability of these companies

is still unknown .(50) What is known is that the chemicals being produced are destined for

solvents, detergents, and coatings .

Companies large and small are working on developing ingredients for rubber(51),

fragrances(52), and plastics(53) as well . Polylactic acid (PLA) made from corn sugar is a

common biobased plastic used in compostable cups, plates, and utensils . A material that

mimics the structure and properties of polyethylene terephthalate (PET) can be made from

lignin-derived vanillin and methanol-derived acetic acid .(54)

It’s also possible to make traditional plastics, like polystyrene and PET, at least partially from

renewable feedstocks . Again, these traditional plastics from renewable feedstocks cannot yet

compete economically with their petroleum-derived relatives . However, interest from large

companies like Coca-Cola and Heinz might increase demand for these biobased plastics and

might help give the market some momentum .(53)

But a recent LCA of plastics shows that switching to a biobased feedstock doesn’t improve the

“greenness” of the process overall .(55) PLA and polyhydroxyalkanoate plastic from corn grain

or stover get high marks compared to the petroleum-derived plastics when analyzing their

adherence to green design principles . But production of 10 different traditional plastics, like

polystyrene, propylene, and polycarbonate, has less environmental impact in terms of nutrient

overloading, ecotoxicity, ozone depletion, and carcinogenicity than bioplastic production .

That’s because the biobased plastics the researchers analyzed come from corn that requires

fertilizer, pesticides, and farmland . Microbial fermentation and other chemical processing

steps also contribute to the negative environmental impact from biobased plastic feedstocks .

This bioplastics LCA did not include recycling or biodegradation in the analysis; negative

environmental impacts might be found to be reduced if recycling and biodegradation were

considered in the analysis .


VI . Green Chemistry in Industry

Three roundtables, convened by the ACS Green

Chemistry Institute, unite companies in various

chemical industries to spread green chemistry

principles through their industries .(56) There’s

a roundtable for manufacturers and one for

formulators, companies that mix chemicals to

make shampoos, cleaners, and/or cosmetics . The

third, and oldest, is the Pharmaceutical Roundtable,

started in 2005 as a partnership between Eli Lilly

& Co ., Merck & Co ., and Pfizer . Today the group has

grown to 16 members, including enzyme company

Codexis and supplier DSM .

Of the different kinds of chemical industries,

pharmaceutical companies produce the smallest

amount of product and the largest amount of

waste . Refining petroleum produces 106 to 108

tons of chemicals each year, compared to tens

to thousands of tons of pharmaceuticals . But

pharmaceutical production generates up to 1,000

times more waste, as measured by E-factor, than

petrochemical production .(57)

Due in part to the efforts of the ACS

Pharmaceutical Roundtable, a group of

process chemists in the pharmaceutical and

fine chemical industry that was convened by

ACS Green Chemistry Institute, the principles

of green chemistry are spreading through the

industry . The roundtable produces biannual

reviews of green chemistry literature of interest

to the pharmaceutical industry .(58–62) The

group also develops tools like solvent selection

guides to help chemists make greener choices

during product design . It also funds academic

green chemistry research applicable to industry

and brainstorms new directions for that

research .(24, 63)

biogas and beeR WasTe poWeR food faCToRies

Companies in the food industry, large and small, turn waste into energy for their factories . Straus Family Creamery, a family-owned dairy just north of San Francisco, converts manure to energy that powers the dairy . (1) Workers flush manure and wastewater from rinsing the barns into a holding pond that separates the solids from the liquids . The liquid manure runs into a second pond covered with a tarp, called an anaerobic digester . Bacteria in the pond convert the manure to biogas, which is mostly methane . They collect that methane and use it to run a generator that powers the dairy . Heat from the generator warms water used to clean barns and excess energy is returned to the area’s electrical grid .

Anaerobic digesters can also be used on a larger scale . This summer, one will open in Wisconsin to process liquid waste from cheesemaking, called whey, from five cheese factories and a soy food ingredient factory .(2) Thick Greek yogurt gets its consistency due to extra straining, so these yogurt factories also have to dispose of whey . The Fage factory in New York funnels some of its whey waste to an anaerobic digester, which was able to completely power the factory when Hurricane Sandy hit the area last October .(3) The Chobani factory, about 50 miles east of the Fage factory, trucks its sugar-filled liquid waste to farmers who use it as fertilizer .

Dairy waste isn’t the only thing that can be fed to microbes for biogas . The Campbell Soup Company is building an anaerobic digester in Ohio to process waste from soup, sauce and drink production .(4) Switching to this source of renewable energy, the company expects to cut its greenhouse gas emissions due to electricity by the equivalent of 3,000 cars .

Sometimes waste from the food industry can be burned to create power for a plant . The Alaskan Beer company in Juneau is the first craft brewery to use spent grain as the sole fuel source for their steam boiler .(5) Spent grain must first be dried before it can be burned as fuel . But spent grain is not an efficient fuel source if it takes more energy to dry the grain than comes from burning it . The brewery found a way to create drier grain by improving the efficiency of how they remove the mash from the liquid beer . Then they combined their 20-year experience running a grain dryer to help design an efficient grain-powered steam boiler . The company estimates this new process will cut their fuel consumption in half .

1 . Straus Family Creamery . Methane Digester . http://strausfamilycreamery .com/values-in-action/methane-digester

2 . Content, W . “GreenWhey to open $28 million food waste-to-energy project .” Milwaukee-Wisconsin Journal Sentinel, Feb . 19, 2013 . Available at: http://www .jsonline .com/business/greenwhey-to-open-28-million-food-wastetoenergy-project-gi8qo71-191938931 .html

3 . Charles, D . “Why Greek Yogurt Makers Want Whey To Go Away .” National Public Radio, November 21, 2012 . Available at: http://www .npr .org/blogs/thesalt/2012/11/21/165478127/why-greek-yogurt-makers-want-whey-to-go-away

4 . Campbell Soup Company . “Campbell Soup Company and CH4 Biogas, L .L .C . Create Ohio’s First Commercial Biogas Power Plant .” November 5, 2012 . Available at: http://investor .campbellsoupcompany .com/phoenix .zhtml?c=88650&p=irol-newsArticle&ID=1754130&highlight=

5 . Alaskan Beer Company . “Alaskan now serving beer-powered beer .” January 15, 2013 . Available at: www .alaskanbeer .com/press-room-2/312-alaskan-now-serving-beer-powered-beer-press-release .html


A recent survey of

21 pharmaceutical

and fine chemical

companies showed

that about 88% of them

had policies regarding

green chemistry .

(4) Green solvents

are a priority for all

companies surveyed . Process design, energy use, green metrics, and sustainable raw materials

were also issues of high importance to the companies . Some of the basic principles of process

design — waste minimization, reducing energy use, increasing safety — dovetail with the 12

principles of green engineering . But other green chemistry technologies and approaches need

more research to be used in industry . Continuous processing and LCA of bioprocesses are two

important green engineering research areas important to the pharmaceutical industry .(24)

solvenT useAt GlaxoSmithKline (GSK), solvents contributed 85-90% of the total mass of non-aqueous

materials used to make a drug in 2005 .(32) A growing awareness in green chemistry has

influenced solvent use among companies in the Pharmaceutical Roundtable . In 2012, about

54% of the mass of a product came from solvents .(4) Many common organic solvents carry

inherent environmental, health, and safety risks . Emissions from volatile solvents can destroy

the atmospheric ozone layer . Other solvents, like benzene, are classified as carcinogens .

Flammable solvents also pose storage risks . In 1998, chemists at GSK developed a solvent

selection guide to help their chemists pick solvents to maximize yield and minimize risk . The

first version of the chart ranked solvents in terms of their risks to the environment, health,

and safety . Now the amount of information involved in the rankings has expanded, while

the presentation is still simple and easy to read . The latest edition of the guide ranks 110

solvents by preferred use based on their physical properties, flammability, and waste handling .

(65) A quick reference guide explains the rankings . Solvents with a high boiling point are

disfavored because they require energy to remove them by distillation . For other solvents,

the environmental damage caused during production and transport is greater than that from

their emissions alone . The chart also includes an LCA ranking for each solvent to help chemists

consider solvent production in their selection . A more detailed version of these rankings is

available for process chemists who need more information when choosing solvents compared

to medicinal chemists running smaller-scale experiments . Other companies have their own

solvent selection guides, too . However, any chemist can access the solvent selection guide

created by the ACS GCI Pharmaceutical Roundtable .

Solvent use is declining in industry, particularly for the most harmful chlorinated solvents .

Of 21 pharmaceutical and fine chemical companies surveyed in 2011, none use chloroform

or carbon tetrachloride .(4) Dichloromethane is used only when necessary as well . Academic


journals are encouraging the use of “greener” solvents too . Editors at Organic Process Research

and Development will not publish papers using solvents like benzene, carbon disulfide, or

chloroform unless the authors have analyzed alternative solvents or justified the use of those

solvents .(66)

Quantitative metrics of solvent selection charts can help chemists improve the “greenness”

of processes . But sometimes qualitative determinations of sustainability are a matter

of perspective . In the ibuprofen synthesis mentioned at the beginning of this chapter,

hydrofluoric acid used in the first step usually would not be considered a low-risk solvent . Its

fumes are irritants, and liquid HF can seep through skin and pull calcium out of bones . But in

this synthesis, anhydrous HF serves both as reagent and solvent, reducing waste . The liquid is

also recycled, thus reducing solvent consumption .(67)

VII . Education

Chemical accidents, like the release of methyl isocyanate in 1984 at a factory in Bhopal, India

that killed more than 3,800 people, help foster a negative public perception of chemistry . Green

chemistry seeks to prevent such tragedies by reducing hazards and toxicity . Environmentally

aware students who may be wary of chemicals can connect to chemistry through the

sustainable values of green chemistry .

Beyond Benign, a foundation based in Massachusetts, brings green chemistry concepts to

kindergarten through high school students .(68) The foundation also sponsors a fellowship

program for undergraduate and graduate students to be green chemistry ambassadors around

Boston . The fellows do outreach with local groups and schools and develop their own green

chemistry experiment .

The ACS Summer School on Green Chemistry and Sustainable Energy is a week-long program

aimed at educating graduate students and postdoctoral scholars from the U .S ., Canada, and

Latin America on the basic concepts of sustainability, green chemistry and engineering, and

sustainable energy technologies . Many students who have participated in the program return

to their labs eager to apply the knowledge they’ve gained about green chemistry to their

research .

lab expeRiMenTsIntegrating green chemistry into an already packed undergraduate curriculum is possible,

but it can be challenging . The University of Oregon, for example, has had green chemistry

laboratory courses for more than a decade .(69) To further this integration more broadly, Beyond

Benign proposed last year that colleges and universities sign a Green Chemistry Commitment,

pledging to absorb green chemistry into their curricula .(70)


For introductory general laboratory courses,

at least, there are advantages to incorporating

experiments from green chemistry . These

experiments have less waste, lower liability, and

lower energy costs, with the added benefit of

increased safety . Green chemistry is especially

advantageous for old labs that do not have proper

ventilation because the experiments can be

performed on bench tops .(71)

There are several resources for people interested in

learning more about green chemistry experiments .

The Greener Educational Materials (GEMs) database,

run by the University of Oregon, is an interactive,

online collection of chemistry education materials

and experiments focused on green chemistry .(69)

Users can search the database by a specific chemical

concept they want to teach, like enzymes, boiling

point, or molecular reactivity . They can also search

by lab technique, or identify experiments that

demonstrate particular principles of green chemistry .

Some experiments teach “greener” lab techniques, like performing a multi-step, small-scale

synthesis without metal catalysts . Undergraduates at Harvey Mudd College in California

developed a green synthesis of warfarin, a drug that reduces blood’s ability to form clots .

(72) The students used an organocatalyst, rather than transition metals, to introduce the

stereochemistry needed in the product .

There’s even an

opportunity to

learn about green

chemistry beyond

the 15 college

programs currently

offered in the United

States . The University

of California, Berkeley

Extension offers

continuing education

for professionals from

materials science

to environmental


management to sharpen their knowledge of green

chemistry .(73) Eventually all of the courses for the

certificate will be available online .

VIII . Conclusions

Green chemistry is spreading from academic labs

into industry as a way to reduce costs, as well as

environmental, health and safety risks . Applications of the

12 guiding principles are found on scales small and large,

from choosing ingredients for reactions that minimize

waste and risk to metrics that quantify waste and process

efficiency . And principles of engineering and process

design lead green chemists to track energy use during

production, search for sustainable raw materials, and build

biodegradable or recyclable products to prevent waste .

But green chemistry is still not widely implemented .

Current estimates put green chemistry products at only

1% of the products from the chemical sector . Several

barriers hinder implementation of green chemistry

in the United States .(74) The challenge of developing

sustainability metrics keeps companies from evaluating

their processes and incorporating green chemistry into

business decisions . Regulations around drug production

and the investment tied up in existing chemical plants

hinder the development and implementation of new

technologies . The interdisciplinary nature of green

chemistry also challenges the specialized knowledge

gained in current training and industrial work experience .

In the U .S ., government policies that forward knowledge

sharing or provide economic incentives can help spur

green chemistry innovation .

The prospects and barriers for green chemistry are

different in a developing country like China . The current

growth of the Chinese chemical industry offers great

potential for incorporating green chemistry practices as

a way to combine the goals of environmental protection

and economic growth .(75) Some of the barriers to

suMMeR sChool on gReen CheMisTRy and susTainable eneRgy

The ACS Summer School on Green Chemistry and Sustainable Energy has educated almost 600 graduate students and postdoctoral scholars since it launched in 2003 . Participants engage in lectures, case studies, discussions, and poster sessions as they assess the greenness and sustainability of specific technologies . World-class researchers—including Joan Brennecke of the University of Notre Dame, Philip Jessop of Queen’s University, and Eric Beckman of the University of Pittsburgh—share their expertise in green chemistry and sustainable energy throughout the week-long program .

The Summer School has a significant impact on the participants, and a number of former students who are now faculty members have sent their own students to the program . A survey of 274 students who participated in the Summer School from 2003-2007 garnered a 64 percent response rate . Eighty-six percent of the respondents indicated they have used green chemistry in their careers since participating in the Summer School, and 90 percent reported that the Summer School had a positive influence on their career paths . Connections made during the Summer School are remarkably strong, with 80 percent of the survey respondents still in contact with at least one other participant .

Feedback from participants is uniformly positive on post-Summer School surveys . One student who attended the 2010 Summer School commented, “I got more great ideas for my research at this course than I ever have before at any other class or conference . The social aspect was also extremely awesome and I made tons of friends and contacts .” A 2012 Summer School participant observed that the best thing about the course was the “diversity of backgrounds of participants and speakers! I had no idea that students from so many areas of chemistry could all be green chemists!” The 2013 Summer School will once again be held at the Colorado School of Mines with support from the ACS Petroleum Research Fund .


adopting green chemistry widely in the country overlap

with general barriers to innovation, like markets,

economics, regulations, and culture . Nevertheless,

implementing green chemistry in new factories as the

chemical industry grows in China could impact the

trajectory of the industry for decades .

Further adoption of green chemistry could improve the

public’s perception of the field of chemistry as a whole .

(76) Proponents of green chemistry say the field combines

environmental, health, and safety benefits with the

traditional goals of economic gains in industrial chemistry

and knowledge gains through academic research .

Economics and knowledge, while important reasons to

pursue chemistry, can conflict with the public’s perception

of chemistry as a toxic undertaking, particularly when

safety, sustainability, and protection of the environment

are on their minds . Promoting green chemistry research,

and its adoption into industry, through federal policies

and education might help the field of chemistry bridge the

divide between its values and those of the public . Thus, the

growth of green chemistry can lead to gains in other areas:

profits, public perceptions, and protecting our planet .

inspiRing fuTuRe CheMisTs ThRough gReen CheMisTRy k-12 ouTReaCh

A common perception of a chemist is a wild-haired person dressed in a lab coat who sets things on fire . Amy Cannon and John Warner, co-founders of the green chemistry education non-profit Beyond Benign, argue that chemists themselves help create this misperception . “When we perform demonstrations to a group of school children to get them excited about science we do exactly what we would hope never happens in the “real world”: explode things and set them on fire,” they write .(1) Green chemistry experiments offer a way to perform demonstrations showing that chemistry does not have to be hazardous or environmentally damaging . Beyond Benign works to bring green chemistry to K-12 classrooms, through demonstrations, teacher training and curriculum development . Another project brings green chemistry to the broader public by connecting artists and scientists to develop community exhibits . One classroom project has students build dye-sensitized solar cells using a titanium dioxide semiconductor, blackberries as the dye, and pencil lead as the counter electrode . The experiment is an opportunity to talk about alternative energy and chemical concepts like oxidation and reduction of the electrolyte . Students test their solar cells to see how much energy they can harvest from the sun . Another program aims to specifically help school-age girls get excited about chemistry . In 2011, Aisling M . O’Connor, at Fitchburg State University in Massachusetts, worked to expand the chemistry activities performed by the nonprofit Science Club for Girls . The students meet for four days during vacation to do experiments related to personal care products . The girls learn about acids, bases and chemical bonding as they make fizzy bath balls from baking soda and citric acid . The final project is to make soap using lye, vegetable oil and lavender oil . Then the girls compare the safety of their ingredients to those used in a few commercially available soaps . By exposing school-age children to chemistry early in their education, these outreach efforts hope to increase students’ understanding of science by engaging them in activities that connect science to their daily lives . 1 . Cannon, A . S . and Warner, J . C . “K-12 Outreach and Science Literacy Through Green Chemistry .” In Green Chemistry Education: Changing the Course of Chemistry; Anastas, P .T ., Levy, I . J ., Parent, K . E ., Eds .; ACS Symposium Series 1011; American Chemical Society: Washington, DC, 2009 .

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Appendix A: 12 Principles of Green Chemistry

1. Prevention It is better to prevent waste than to treat or clean up waste after it has been created .

2. Atom Economy Synthetic methods should be designed to maximize the incorporation of all materials used in the process into the final product .

3. Less Hazardous Chemical Syntheses Wherever practicable, synthetic methods should be designed to use and generate substances that possess little or no toxicity to human health and the environment .

4. Designing Safer Chemicals Chemical products should be designed to effect their desired function while minimizing their toxicity .

5. Safer Solvents and Auxiliaries The use of auxiliary substances (e .g ., solvents, separation agents, etc .) should be made unnecessary wherever possible and innocuous when used .

6. Design for Energy Efficiency Energy requirements of chemical processes should be recognized for their environmental and economic impacts and should be minimized . If possible, synthetic methods should be conducted at ambient temperature and pressure .

7. Use of Renewable Feedstocks A raw material or feedstock should be renewable rather than depleting whenever technically and economically practicable .

8. Reduce Derivatives Unnecessary derivatization (use of blocking groups, protection/deprotection, temporary modification of physical/chemical processes) should be minimized or avoided if possible, because such steps require additional reagents and can generate waste .

9. Catalysis Catalytic reagents (as selective as possible) are superior to stoichiometric reagents .

10. Design for Degradation Chemical products should be designed so that at the end of their function they break down into innocuous degradation products and do not persist in the environment .

11. Real-time analysis for Pollution Prevention 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. Inherently Safer Chemistry for Accident Prevention Substances and the form of a substance used in a chemical process should be chosen to minimize the potential for chemical accidents, including releases, explosions, and fires .

*Anastas, P . T .; Warner, J . C . Green Chemistry: Theory and Practice, Oxford University Press: New York, 1998, p . 30 .


Appendix B: 12 Principles of Green Engineering

1. Inherent Rather than Circumstantial Designers need to strive to ensure that all materials and energy inputs and outputs are as inherently nonhazardous as possible .

2. Prevention Instead of Treatment It is better to prevent waste than to treat or clean up waste after it is formed .

3. Design for Separation Separation and purification operations should be designed to minimize energy consumption and materials use .

4. Maximize Efficiency Products, processes, and systems should be designed to maximize mass, energy, space, and time efficiency .

5. Output-Pulled Versus Input-Pushed Products, process and systems should be “output pulled” rather than “input pushed” through the use of energy and materials .

6. Conserve Complexity Embedded entropy and complexity must be viewed as an investment when making design choices on recycle, reuse, or beneficial disposition .

7. Durability Rather than Immortality Targeted durability, not immortality, should be a design goal .

8. Meet Need, Minimize Excess Design for unnecessary capacity or capability (e .g ., “one size fits all” solutions) should be considered a design flaw .

9. Minimize Material Diversity Material diversity in multicomponent products should be minimized to promote disassembly and value retention .

10. Integrate Material and Energy Flows Design of products, processes, and systems must include integration and interconnectivity with available energy and material flows .

11. Design for Commercial “Afterlife” Products, processes, and systems should be designed for performance in a commercial “afterlife .”

12. Renewable Rather Than Depleting Material and energy inputs should be renewable rather than depleting .

*Anastas, P .T ., and Zimmerman, J .B ., “Design through the Twelve Principles of Green Engineering”,

Environmental Science & Technology 2003, 37, 94A-101A .

28 Green Chemistry and Engineering: Towards a Sustainable Future

NOTES


A white paper reporting on the green chemistry philosophy of reducing waste, toxicity and hazards, and its application on an industrial scale.

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