Green chemistry, also called sustainable chemistry, is an area of chemistry and chemical engineering focused on the designing of products and processes that minimize the use and generation of hazardous substances. Whereas environmental chemistry focuses on the effects of polluting chemicals on nature, green chemistry focuses on the environmental impact of chemistry, including technological approaches to preventing pollution and reducing consumption of nonrenewable resources.
The overarching goals of green chemistry—namely, more resource-efficient and inherently safer design of molecules, materials, products, and processes—can be pursued in a wide range of contexts.
IUPAC definition
Green chemistry (sustainable chemistry): Design of chemical products and processes that reduce or eliminate the
use or generation of substances hazardous to humans, animals, plants,
and the environment.
History
Green chemistry emerged from a variety of existing ideas and research efforts (such as atom economy and catalysis) in the period leading up to the 1990s, in the context of increasing attention to problems of chemical pollution and resource depletion.
The development of green chemistry in Europe and the United States was
linked to a shift in environmental problem-solving strategies: a
movement from command and control regulation
and mandated reduction of industrial emissions at the "end of the
pipe," toward the active prevention of pollution through the innovative
design of production technologies themselves. The set of concepts now
recognized as green chemistry coalesced in the mid- to late-1990s, along
with broader adoption of the term (which prevailed over competing terms
such as "clean" and "sustainable" chemistry).
In the United States, the Environmental Protection Agency
played a significant early role in fostering green chemistry through
its pollution prevention programs, funding, and professional
coordination. At the same time in the United Kingdom, researchers at the
University of York contributed to the establishment of the Green Chemistry Network within the Royal Society of Chemistry, and the launch of the journal Green Chemistry.
Principles
In 1998, Paul Anastas (who then directed the Green Chemistry Program at the US EPA) and John C. Warner (then of Polaroid Corporation) published a set of principles to guide the practice of green chemistry.
The twelve principles address a range of ways to reduce the
environmental and health impacts of chemical production, and also
indicate research priorities for the development of green chemistry
technologies.
The principles cover such concepts as:
- the design of processes to maximize the amount of raw material that ends up in the product;
- the use of renewable material feedstocks and energy sources;
- the use of safe, environmentally benign substances, including solvents, whenever possible;
- the design of energy efficient processes;
- avoiding the production of waste, which is viewed as the ideal form of waste management.
The twelve principles of green chemistry are:
- Prevention. Preventing waste is better than treating or cleaning up waste after it is created.
- Atom economy. Synthetic methods should try to maximize the incorporation of all materials used in the process into the final product.
- Less hazardous chemical syntheses. Synthetic methods should avoid using or generating substances toxic to humans and/or the environment.
- Designing safer chemicals. Chemical products should be designed to achieve their desired function while being as non-toxic as possible.
- Safer solvents and auxiliaries. Auxiliary substances should be avoided wherever possible, and as non-hazardous as possible when they must be used.
- Design for energy efficiency. Energy requirements should be minimized, and processes should be conducted at ambient temperature and pressure whenever possible.
- Use of renewable feedstocks. Whenever it is practical to do so, renewable feedstocks or raw materials are preferable to non-renewable ones.
- Reduce derivatives. Unnecessary generation of derivatives—such as the use of protecting groups—should be minimized or avoided if possible; such steps require additional reagents and may generate additional waste.
- Catalysis. Catalytic reagents that can be used in small quantities to repeat a reaction are superior to stoichiometric reagents (ones that are consumed in a reaction).
- Design for degradation. Chemical products should be designed so that they do not pollute the environment; when their function is complete, they should break down into non-harmful products.
- Real-time analysis for pollution prevention. Analytical methodologies need to be further developed to permit real-time, in-process monitoring and control before hazardous substances form.
- Inherently safer chemistry for accident prevention. Whenever possible, the substances in a process, and the forms of those substances, should be chosen to minimize risks such as explosions, fires, and accidental releases.
Trends
Attempts are being made not only to quantify the greenness of a chemical process but also to factor in other variables such as chemical yield,
the price of reaction components, safety in handling chemicals,
hardware demands, energy profile and ease of product workup and
purification. In one quantitative study, the reduction of nitrobenzene to aniline receives 64 points out of 100 marking it as an acceptable synthesis overall whereas a synthesis of an amide using HMDS is only described as adequate with a combined 32 points.
Green chemistry is increasingly seen as a powerful tool that
researchers must use to evaluate the environmental impact of
nanotechnology. As nanomaterials
are developed, the environmental and human health impacts of both the
products themselves and the processes to make them must be considered to
ensure their long-term economic viability.
Examples
Green solvents
Solvents
are consumed in large quantities in many chemical syntheses as well as
for cleaning and degreasing. Traditional solvents are often toxic or
are chlorinated. Green solvents, on the other hand, are generally
derived from renewable resources and biodegrade to innocuous, often a
naturally occurring product.
Synthetic techniques
Novel
or enhanced synthetic techniques can often provide improved
environmental performance or enable better adherence to the principles
of green chemistry. For example, the 2005 Nobel Prize for Chemistry was awarded, to Yves Chauvin, Robert H. Grubbs and Richard R. Schrock, for the development of the metathesis method in organic synthesis, with explicit reference to its contribution to green chemistry and "smarter production." A 2005 review identified three key developments in green chemistry in the field of organic synthesis: use of supercritical carbon dioxide as green solvent, aqueous hydrogen peroxide for clean oxidations and the use of hydrogen in asymmetric synthesis. Some further examples of applied green chemistry are supercritical water oxidation, on water reactions, and dry media reactions.
Bioengineering
is also seen as a promising technique for achieving green chemistry
goals. A number of important process chemicals can be synthesized in
engineered organisms, such as shikimate, a Tamiflu precursor which is fermented by Roche in bacteria. Click chemistry is often cited
as a style of chemical synthesis that is consistent with the goals of
green chemistry. The concept of 'green pharmacy' has recently been
articulated based on similar principles.
Carbon dioxide as blowing agent
In 1996, Dow Chemical won the 1996 Greener Reaction Conditions award for their 100% carbon dioxide blowing agent for polystyrene
foam production. Polystyrene foam is a common material used in packing
and food transportation. Seven hundred million pounds are produced each
year in the United States alone. Traditionally, CFC and other ozone-depleting chemicals were used in the production process of the foam sheets, presenting a serious environmental hazard.
Flammable, explosive, and, in some cases toxic hydrocarbons have also
been used as CFC replacements, but they present their own problems. Dow
Chemical discovered that supercritical carbon dioxide
works equally as well as a blowing agent, without the need for
hazardous substances, allowing the polystyrene to be more easily
recycled. The CO2 used in the process is reused from other industries, so the net carbon released from the process is zero.
Hydrazine
Addressing principle #2 is the Peroxide Process for producing hydrazine without cogenerating salt. Hydrazine is traditionally produced by the Olin Raschig process from sodium hypochlorite (the active ingredient in many bleaches) and ammonia. The net reaction produces one equivalent of sodium chloride for every equivalent of the targeted product hydrazine:
- NaOCl + 2 NH3 → H2N-NH2 + NaCl + H2O
In the greener Peroxide process hydrogen peroxide is employed as the oxidant and the side product is water. The net conversion follows:
- 2 NH3 + H2O2 → H2N-NH2 + 2 H2O
Addressing principle #4, this process does not require auxiliary extracting solvents. Methyl ethyl ketone
is used as a carrier for the hydrazine, the intermediate ketazine phase
separates from the reaction mixture, facilitating workup without the
need of an extracting solvent.
1,3-Propanediol
Addressing principle #7 is a green route to 1,3-propanediol, which is traditionally generated from petrochemical precursors. It can be produced from renewable precursors via the bioseparation of 1,3-propanediol using a genetically modified strain of E. coli. This diol is used to make new polyesters for the manufacture of carpets.
Lactide
Lactide
In 2002, Cargill Dow (now NatureWorks) won the Greener Reaction Conditions Award for their improved method for polymerization of polylactic acid . Unfortunately, lactide-base polymers do not perform well and the project was discontinued by Dow soon after the award. Lactic acid is produced by fermenting corn and converted to lactide,
the cyclic dimer ester of lactic acid using an efficient, tin-catalyzed
cyclization. The L,L-lactide enantiomer is isolated by distillation and
polymerized in the melt to make a crystallizable polymer, which has some applications including textiles and apparel, cutlery, and food packaging. Wal-Mart
has announced that it is using/will use PLA for its produce packaging.
The NatureWorks PLA process substitutes renewable materials for
petroleum feedstocks, doesn't require the use of hazardous organic
solvents typical in other PLA processes, and results in a high-quality
polymer that is recyclable and compostable.
Carpet tile backings
In 2003 Shaw Industries
selected a combination of polyolefin resins as the base polymer of
choice for EcoWorx due to the low toxicity of its feedstocks, superior
adhesion properties, dimensional stability, and its ability to be
recycled. The EcoWorx compound also had to be designed to be compatible
with nylon carpet fiber. Although EcoWorx may be recovered from any
fiber type, nylon-6 provides a significant advantage. Polyolefins are
compatible with known nylon-6 depolymerization methods. PVC interferes
with those processes. Nylon-6 chemistry is well-known and not addressed
in first-generation production. From its inception, EcoWorx met all of
the design criteria necessary to satisfy the needs of the marketplace
from a performance, health, and environmental standpoint. Research
indicated that separation of the fiber and backing through elutriation,
grinding, and air separation proved to be the best way to recover the
face and backing components, but an infrastructure for returning
postconsumer EcoWorx to the elutriation process was necessary. Research
also indicated that the postconsumer carpet tile had a positive economic
value at the end of its useful life. EcoWorx is recognized by MBDC as a
certified cradle-to-cradle design.
Trans and cis fatty acids
Transesterification of fats
In 2005, Archer Daniels Midland (ADM) and Novozymes won the Greener Synthetic Pathways Award for their enzyme interesterification process. In response to the U.S. Food and Drug Administration (FDA) mandated labeling of trans-fats on nutritional information by January 1, 2006, Novozymes and ADM worked together to develop a clean, enzymatic process for the interesterification of oils and fats by interchanging saturated and unsaturated fatty acids. The result is commercially viable products without trans-fats. In addition to the human health benefits of eliminating trans-fats,
the process has reduced the use of toxic chemicals and water, prevents
vast amounts of byproducts, and reduces the amount of fats and oils
wasted.
Bio-succinic acid
In 2011, the Outstanding Green Chemistry Accomplishments by a Small Business Award went to BioAmber Inc. for integrated production and downstream applications of bio-based succinic acid.
Succinic acid is a platform chemical that is an important starting
material in the formulations of everyday products. Traditionally,
succinic acid is produced from petroleum-based feedstocks. BioAmber has
developed process and technology that produces succinic acid from the
fermentation of renewable feedstocks at a lower cost and lower energy
expenditure than the petroleum equivalent while sequestering CO2 rather than emitting it.
Laboratory chemicals
Several laboratory chemicals are controversial from the perspective of Green chemistry. The Massachusetts Institute of Technology created a "Green" Alternatives Wizard to help identify alternatives. Ethidium bromide, xylene, mercury, and formaldehyde have been identified as "worst offenders" which have alternatives.
Solvents in particular make a large contribution to the environmental
impact of chemical manufacturing and there is a growing focus on
introducing Greener solvents into the earliest stage of development of
these processes: laboratory-scale reaction and purification methods. In the Pharmaceutical Industry, both GSK and Pfizer have published Solvent Selection Guides for their Drug Discovery chemists.
Legislation
The EU
In 2007, The EU put into place the Registration, Evaluation, Authorisation and Restriction of Chemicals
(REACH) program, which requires companies to provide data showing that
their products are safe. This regulation (1907/2006) ensures not only
the assessment of the chemicals' hazards as well as risks during their
uses but also includes measures for banning or restricting/authorising
uses of specific substances. ECHA, the EU Chemicals Agency in Helsinki,
is implementing the regulation whereas the enforcement lies with the EU
member states.
United States
The U.S. law that governs the majority of industrial chemicals (excluding pesticides, foods, and pharmaceuticals) is the Toxic Substances Control Act
(TSCA) of 1976. Examining the role of regulatory programs in shaping
the development of green chemistry in the United States, analysts have
revealed structural flaws and long-standing weaknesses in TSCA; for
example, a 2006 report to the California Legislature concludes that TSCA
has produced a domestic chemicals market that discounts the hazardous
properties of chemicals relative to their function, price, and
performance.
Scholars have argued that such market conditions represent a key
barrier to the scientific, technical, and commercial success of green
chemistry in the U.S., and fundamental policy changes are needed to
correct these weaknesses.
Passed in 1990, the Pollution Prevention Act helped foster new approaches for dealing with pollution by preventing environmental problems before they happen.
In 2008, the State of California approved two laws aiming to encourage green chemistry, launching the California Green Chemistry Initiative. One of these statutes required California's Department of Toxic Substances Control
(DTSC) to develop new regulations to prioritize "chemicals of concern"
and promote the substitution of hazardous chemicals with safer
alternatives. The resulting regulations took effect in 2013, initiating
DTSC's Safer Consumer Products Program.
Education
Many institutions offer courses and degrees on Green Chemistry. Examples from across the globe are Denmark's Technical University, and several in the US, e.g. at the Universities of Massachusetts-Boston, Michigan, and Oregon. A masters level course in Green Technology, has been introduced by the Institute of Chemical Technology, India. In the UK at the University of York
University of Leicester, Department of Chemistry and MRes in Green
Chemistry at Imperial College London. In Spain different universities
like the Universidad de Jaume I or the Universidad de Navarra,
offer Green Chemistry master courses. There are also websites focusing
on green chemistry, such as the Michigan Green Chemistry Clearinghouse
at www.migreenchemistry.org.
Apart from its Green Chemistry Master courses the Zurich University of
Applied Sciences ZHAW presents an exposition and web page "Making
chemistry green" for a broader public, illustrating the 12 principles.
Scientific journals specialized in green chemistry
- Green Chemistry (RSC)
- Green Chemistry Letters and Reviews (Open Access) (Taylor & Francis)
- ChemSusChem (Wiley)
- ACS Sustainable Chemistry & Engineering (ACS)
Contested definition
There
are ambiguities in the definition of green chemistry, and in how it is
understood among broader science, policy, and business communities. Even
within chemistry, researchers have used the term "green chemistry" to
describe a range of work independently of the framework put forward by
Anastas and Warner (i.e., the 12 principles). While not all uses of the term are legitimate,
many are, and the authoritative status of any single definition is
uncertain. More broadly, the idea of green chemistry can easily be
linked (or confused) with related concepts like green engineering, environmental design, or sustainability in general. The complexity and multifaceted nature of green chemistry makes it difficult to devise clear and simple metrics. As a result, "what is green" is often open to debate.
Awards
Several scientific societies have created awards to encourage research in green chemistry.
- Australia's Green Chemistry Challenge Awards overseen by The Royal Australian Chemical Institute (RACI).
- The Canadian Green Chemistry Medal.
- In Italy, Green Chemistry activities center around an inter-university consortium known as INCA.
- In Japan, The Green & Sustainable Chemistry Network oversees the GSC awards program.
- In the United Kingdom, the Green Chemical Technology Awards are given by Crystal Faraday.
- In the US, the Presidential Green Chemistry Challenge Awards recognize individuals and businesses.
