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Early Industrial Roots of Green Chemistry
International “Pollution Prevention” Efforts During the 1970s and 1980s*
* This article was solicited as a result of a joint project between Chemistry International and Substantia. Substantia is an open access peer-reviewed international journal dedicated to traditional perspectives as well as innovative and synergetic implications in all fields of Chemistry, from current research to historical studies. It is meant to be a crucible for discussions on science, on making science and its outcomes. This joint project is simply to seed interest across communities and bring to CI readers contents of historical relevance; reader are encouraged to review full articles in Substantia. https://fupress.com/substantia
by Mark A. Murphy
Many literature articles, conventional histories, and narratives about the origins of “Green Chemistry” describe it as being a result of concepts and actions at the US Environmental Protection Agency (EPA) and/or research in Academia during the 1990s and later. But many examples of increasingly environmentally friendly real-world chemical processes were invented, developed, and commercialized in the oil refining, commodity chemical, and consumer product industries in many countries decades before the 1990s. The earliest efforts evolved and accelerated into many environmentally-oriented and commercialized industrial examples of “Pollution Prevention” during the 1970s and 1980s. The “Green Chemistry” terminology and “Principles” adopted by the EPA and Academia in the 1990s evolved from and re-named the mostly industrial “Pollution Prevention” approaches and inventions.
In 1984, this author conceived one of the earliest and currently well-known industrial examples of Green Chemistry, the BHC Ibuprofen Process, commercialized in 1992. That invention won a Kirkpatrick Award from Chemical Engineering magazine in 1993, and one of the first US Presidential Green Chemistry Challenge Awards. This author recently argued in three published historical / philosophical articles [1-3] that the complex technical and/or human/cultural evolutionary origins of Green Chemistry began long before the 1990s, and identified many examples from chemically related industries that traced their origins to shortly after World War II. Many references that support and document these assertions can be found in this author’s original articles.
This author’s 2018 article [2] recounted, from an inventor’s perspective, the genuine story of the conception, development, and commercialization of the BHC Ibuprofen process, a story that had been badly mis-told many times in the academic literature and industry press. That article told the BHC Ibuprofen story in a broad context of many prior and relevant technical developments and inventions, as well as many scientific / economic / engineering, historical, cultural and economic/business influences, all of which contributed to the invention, development, and commercialization of the BHC Ibuprofen process. Those predecessors included the long prior commercialization of increasingly environmentally friendly and atom economical processes for making commodity organic chemicals such as methanol, ethanol, formaldehyde, acetic acid, and many higher organic commodity aldehydes, alcohols, and carboxylic acids, via the use of catalytic methods and reactions. The article also documented the influence of the “Quality” principles and methods of W. Edwards Deming that were widely taught in industry in the 1980s, and Deming’s emphasis on waste reduction in all the multi-disciplinary aspects of a real-world commercial product or process.
This author’s most recent article [1], published in September 2020 in Substantia, applies a yet broader historical perspective to produce a major re-write of the early history of Green Chemistry. The evolutionary pathway that led toward Green Chemistry had its origins in the oil refining industry boom that began at about the time of World War II. Prior to WWII, oil refining was carried out primarily by distillation processes that produced relatively low octane gasolines, and also produced large quantities of light and heavy waste residues that were often dumped, burned, or evaporated into the atmosphere. Leaded compounds were added to those early gasolines to increase the octane ratings, but the environmental problems caused by the lead additives were ignored for many years.
The oil industry was innovating catalytic process beginning in the 1950s, leading to less pollution.
Starting just before WWII, oil refineries began to chemically modify the organic compounds found in oil, via catalytic processes, to decrease the waste residues and increase the amount and quality of the salable products, which also had a favorable impact on the environment. In 1936 Eugene Houdry introduced a fixed bed catalytic cracking process into a commercial refinery that doubled the gasoline produced from the heavy residues. Esso introduced a much-improved fluidized bed catalytic cracker into its Baton Rouge refinery in 1942. Later (in the 1970s and later) the natural clay catalysts initially used were replaced with synthetic zeolite catalysts that were more selective for producing products in the desired size ranges. The cracking processes also increased the availability and lowered the price of ethylene and propylene, which spawned the invention, development, and commercialization of a wide variety of downstream commodity products, monomers, and polymers; including polyethylene and polypropylene which were not biodegradable. But the inexpensive availability of ethylene and propylene also stimulated the commercial development of other derivative compounds, such ethylene oxide and acetic acid, which were used to produce downstream biodegradable products such as surfactants, polyvinyl acetate, polyvinyl alcohol, and others.
New catalytic “alkylation” processes entered refinery service in about 1940. Alkylation reactions condense volatile alkenes (such as propylene or butene) with branched alkanes (often isobutane) in the presence of strong acids (initially and typically HF or sulfuric acid) to produce higher branched alkanes (typically iso-heptane and iso-octane) having high octane numbers. The HF catalyst was more easily recycled than the sulfuric acid catalyst, but because of HF’s volatility, corrosive properties, and toxicity it represents a significant safety risk at the plant site. As the decades passed, refineries began to replace HF with H2SO4 for safety reasons. The oil refining industry then conducted a decades-long R&D “Grail Quest” for even safer alkylation catalysts. Recently two new alkylation catalysts have been commercialized (based on new zeolite or ionic liquid catalysts), inventions which have won recent major awards, including Presidential Green Chemistry Awards.
During the 1950s through 1970s the oil refining industry continued to invent, develop, and commercialize other new catalytic processes to chemically manipulate the organic compounds of oil in ways that were both economically and environmentally beneficial. Catalytic reforming processes convert low octane normal alkanes and napthenes into branched alkanes and aromatics with higher octane numbers. Hydrogen produced by the catalytic reforming processes is used in catalytic hydrocracking processes that break up the heavy aromatics and heteroaromatics in oil, remove polluting sulfur and nitrogen heteroatoms, and produce higher value hydrocarbon components for gasolines. Olefin metathesis was serendipitously discovered by Eleuterio at DuPont in the late 1950s and is sometimes used in commercial refineries. Later olefin metathesis chemistry developed into new “Green” applications by academics such as Chauvin, Grubs, and Schrock, who later won the Nobel Prize in 2005. In the 1970s Mobil developed a zeolite-based catalytic process for making synthetic gasolines from methanol, which can itself be manufactured very cleanly and efficiently from either methane or coal.
By the early 1990s, it was credibly estimated that the oil refining industry produced only about 0.1 kg of waste product per kg of useful salable products, in comparison to the several orders of magnitude higher ratios of waste product production in the fine chemical and pharmaceutical industry segments, where use of traditional synthetic organic chemistry methods were prevalent.
A narrative has been often repeated in the academic literature and popular press over the last 20 years, to the effect that Green Chemistry originated in the 1990s at the EPA and/or in Academia. Those narratives are highly incomplete and misleading. Green Chemistry was actually a subset of and/or a re-naming of much earlier “Non-Waste Technology and Production” and/or “Pollution Prevention” concepts and actual commercialized environmentally oriented industrial processes, which evolved and emerged from the efforts of many people from many backgrounds in many countries during and even before the 1970s and 1980s. Strong supporting evidence for these assertions can be found in 712-page book published in 1978 by the United Nations and/or its Economic Commission for Europe (ECE) [4].
After many years of ECE activity in environmental fields, a committee of Senior Advisers was established in 1971, and in 1973 the Senior Advisers “decided to include, among other subjects, the principles and creation of non-waste production systems in their work programme.” In Geneva in 1974, the Senior Advisers defined “Non-Waste Technology” as “the practical application of knowledge, methods and means so as, within the needs of man, to provide the most rational use of natural resources and energy and to protect the environment.”
The subsequent 1978 “Non-Waste Technology and Production” book [4] contains two addresses and seventy-six papers from a November 1976 UN/ECE Seminar held in Paris. More than 150 representatives of thirty countries and nine international inter-governmental and non-governmental organizations took part. The addresses and papers covered a very wide variety of interdisciplinary technical, economic, and policy questions, issues, topics, and documented many examples of already commercialized environmentally friendly products and processes. Many details can be found in that book, and many edifying and inspiring passages from the book are quoted in this author’s recent paper. The “Conclusions and Recommendations” section stated:
“The question today is whether technology can solve the environmental problems which technology has helped to cause. There is widespread belief that this question can be answered positively….”
M.G. Royston, an economist from Geneva (who later became a leader in the economic/social/legal aspects of Non-Waste Technologies and Pollution Prevention), contributed an important paper entitled “Eco-Productivity: A Positive Approach to Non-Waste Technology”. Mr. Royston’s commented:
“Pollution is waste. Waste today leads to shortages tomorrow, “Waste not want not” is a motto as true now as it was for all those generations before the brief flowering and decaying of the affluent/effluent society. The very sustainability of dignified life on this planet Earth must depend on re-establishment of a non-waste society, a non-waste economy, a non-waste technology, and above all a non-waste value system.”
3M’s Pollution Prevention Pays program was an early example of green Chemistry in industry
Royston then commented on many highly relevant economic, political, and legal issues, as well as examples of already commercialized non-waste processes in many countries, and on possible future waste-savings approaches for the energy, organic chemicals, inorganic chemicals, non-metallic minerals, metallic minerals, paper, coatings, and packaging industries, efforts that could be economically and even profitably undertaken to reduce pollution of the air, land, and water. Royston subsequently published a 1979 book entitled “Pollution Prevention Pays” [5] and began (together with 3M personnel as mentioned below) a sustained international campaign of writing and speaking to advocate Pollution Prevention approaches.
Another major paper was contributed by Joseph T. Ling, the Vice-President for Environmental Engineering and Pollution Control at 3M Corporation. In 1975 Dr. Ling had initiated 3M’s “Pollution Prevention Pays” program that moved 3M away from pollution control (“end-of-the pipeline,” treatment methods) that had been legally mandated by “command and control” statutes in many countries. Ling instead moved 3M toward “Pollution Prevention” and/or natural resource conservation approaches that could simultaneously improve efficiency, production yields, and profits. Dr. Ling was elected to the National Academy of Engineering in 1976. If this author were to nominate any one person as “The Father of Pollution Prevention,” I would certainly nominate Dr. Joseph T. Ling.
Portrait from Ling' Memorial Tribute by National Academy of Engineering.
- Dr. Joseph T. Ling. Quote reproduced from “A Century of Innovation – The 3M Story", 2002, 3M Company. (ISBN 0-9722302-1-1 ), p. 188; https://multimedia.3m.com/mws/media/171240O/3m-century-of-innovation-book.pdf
Literally thousands of “Pollution Prevention” projects were subsequently commercialized at 3M over the following decades. A National Academy Memorial Tribute to Dr. Ling (in 2008) remarked that “After 30 years, the 3P program is still a key strategy in 3M’s Environmental Management Plan. From 1975 to 2005, with some 8,500 pollution prevention activities and programs in 23 countries, the company was able to keep from producing an estimated 2.2 billion pounds of pollutants while saving nearly $1 billion.” 3M’s 3P global pollution prevention achievements from 1975 to 2018 is graphed in 3M’s 2019 Sustainable Report [6] and shown at right.
In the 1980s, many companies in many countries emulated and evolved the 3M strategies and inter-disciplinary approaches to invent, develop, and commercialize many real-world industrial processes that simultaneously reduced pollution and saved the companies large amounts of money. Supporting efforts began to appear in many national governments and their agencies, especially in Europe, Canada, and the United States. Relevant news stories began to appear in many trade journals and even in the mainstream consumer press, including the Harvard Business Review, Washington Post, New York Times, and the Journal of Commerce. Many details and quotations from those articles are included in this author’s paper [1].
As noted in the National Academy’s tribute to Joe Ling, “by 1988, 34 states had established pollution prevention programs, and EPA had published a national policy and established the Office of Pollution Prevention. In 1990, the United State Congress passed the Pollution Prevention Act, requiring that pollution prevention be considered the first phase of any environmental enhancement program.”
There was relatively little interest in such interdisciplinary work in academia until the 1990s however until the “Green Chemistry” terminology was coined at the EPA in 1991. After the Clinton Administration assumed power in January 1993, a program for grants for academic research was initiated. The “Green Chemistry” terminology was first used at Academic Conferences in 1993 and was officially endorsed by the EPA with the announcement of the new Presidential Green Chemistry Challenge Awards in 1995, which generated large amounts of publicity and interest in Green Chemistry.The “12 Principles of Green Chemistry” were only published in 1998, decades after many companies had already commercialized many examples of “Pollution Prevention” technologies. Not one of the 12 Principles was new at the time however, and every one of them had been previously used and commercialized in industry long before, as had combinations of those 12 Principles. This author’s article strongly challenges the narrative that has been repeated in many subsequent academic articles, and taught to many students that Green Chemistry originated at the EPA and in academia in the 1990s. The article offers a very different historical account and perspective on the origins of Green Chemistry. Green Chemistry actually emerged as a holistic product of a very complex and multi-disciplinary evolutionary process that arose from many semi-independent evolutionary sub-processes, which had their origins in the efforts of many industrial inventors from many places over decades. Green Chemistry actually had many, many, fathers and mothers. A 2007 article in Chemistry International [7] has also argued that Green Chemistry emerged from a complex mixture of interdisciplinary influences and efforts.
This author’s third article, in [3] offers a more philosophical perspective on the infinite and/or vast possibilities and/or uncertainties faced by Green Chemists but offers suggestions on how to apply “Quality” principles and techniques to solve “Green” problems in real-world industrial settings.
References
1. Murphy, M.A., “Early Industrial Roots of Green Chemistry - II : International “Pollution Prevention” Efforts During the 1970’s and 1980’s” Substantia, 4(2), 2020; https://doi.org/10.13128/Substantia-894
2. Murphy, M.A., “Early Industrial Roots of Green Chemistry and the History of the BHC Ibuprofen Process Invention and Its Quality Connection”, Foundations of Chemistry, 2018, 20: 121-165m; https:// doi.org/10.1007/s10698-017-9300-9
3. Murphy, M.A., “Exploring the Vastness of Design Space for Greener Solutions Using a Quality Approach”, Physical Sciences Reviews 2020; https://doi.org/10.1515/psr-2020-0001 AOP 2 June 2020 (also to be published as a chapter in “Green Chemical Processing, Volume 6: Green Chemistry and Technology”; Mark Benvenuto, Editor, to be published in 2021 by De Gruyter, Berlin)
4. “Non-Waste Technology and Production” published in 1978 by Permagon Press on behalf of the United Nations; https://doi.org/10.1016/C2013-0-02935-0
5. Royston, M.G., “Pollution Prevention Pays”, Permagon Press, 1979; https://doi.org/10.1016/C2013-0-03101-56
6. 3M’s 2019 Sustainable Report, https://multimedia.3m. com/mws/media/1691941O/2019-sustainability-report.pdf
7. Pietro Tundo and Fabio Aricò, 2007, Chem Int 29(5), 4-7 ; see http://publications.iupac.org/ci/2007/2905/1_ tundo.html or https://doi.org/10.1515/ci.2007.29.5.4
Mark Alan Murphy obtained a B.S. in Chemistry from Tulane University and a Ph.D. in Chemistry from the University of Wisconsin – Madison in January 1983. Mark worked as a Research Chemist at Celanese Corporation (later Hoechst Celanese Corporation) in Corpus Christi Texas until mid-1993. He obtained a J.D. from the University of Texas School of Law in 1998 and became a partner at two Atlanta IP law-firms. Founder of UVLAW Patents LLC in 2009, he practiced patent and business law until he recently retired. He lives near Atlanta Georgia, continuing his career leading by example, somewhere at the interfaces of science, business, and law.
Cite: Murphy, M. A. (2021). Early Industrial Roots of Green Chemistry, Chemistry International, 43(1), 21-25; https://doi.org/10.1515/ci-2021-0105
