May 2022

100th Anniversary

History of the HPI: The 1960s: Synthetic oils, zeolite catalysts, LLDPE, OPEC and and creation of the PLC

During the 1960s, the global refining and petrochemical industries witnessed new processes and products that enhanced the daily lives of millions of people around the world.

Nichols, Lee, Hydrocarbon Processing Staff

During the 1960s, the global refining and petrochemical industries witnessed new processes and products that enhanced the daily lives of millions of people around the world. The decade was responsible for the creation of new petrochemical products to provide better and more durable goods within many industrial sectors and consumer goods applications. Other innovations, such as the creation of synthetic oils and synthetic zeolite catalyst, enhanced processing operations and engine/fuel performance in the automobile and aviation sectors. The 1960s was also a prominent decade for LNG trade [the first transatlantic LNG cargo was carried on the Methane Pioneer in early 1959 from Constock’s LNG production facility in Louisiana (U.S.) to the UK; the UK also received the world’s first commercial LNG cargo from Shell’s Methane Pioneer vessel in October 1964 from Algeria; LNG exports from Alaska (U.S.) to Japan commenced in the late 1960s],96 the creation of the programmable logic controller (PLC)—a significant evolution in automation—and the creation of the Organization of Petroleum Exporting Countries (OPEC), which was, and still is, a major force in setting global oil prices.

Creation and widespread adoption of synthetic oils

Although the first synthetic hydrocarbon oils were produced in 1877 by French chemist Charles Friedel and American chemist James Mason Crafts (i.e., Friedel-Crafts alkylation and acylation reactions), synthetic oils did not see widespread adoption until post-World War 2 (WW2).

Prior to WW2, several individuals developed new reactions to produce synthetic oils. These included German scientists Friedrich Bergius, Franz Fischer and Hans Tropsch (the Bergius and Fischer-Tropsch processes were detailed in the History of the HPI segments published in the January and March issues of Hydrocarbon Processing), as well as American researcher F. W. Sullivan while working at Standard Oil of Indiana (U.S.). Sullivan’s team tried to commercialize synthetic oils in 1929; however, this attempt was challenged due to lack of demand. Regardless, Sullivan published a paper in 1931 titled “Synthetic lubricating oils relation between chemical constitution and physical properties,” which, along with research from the German chemist Hermann Zorn, provided a foundation for the future widespread use of synthetic oils in the aviation and the automobile sectors—Zorn and his team researched more than 3,500 synthetic esters during the early 1940s to find an alternative to petroleum oil to help fuel Germany’s war machine.97,98

The need for synthetic oils did not materialize until Germany’s invasion of the Soviet Union during WW2. During the Battle of Stalingrad, the harsh Russian winter demobilized German tanks, fighter planes and other military vehicles. The main culprit: temperature. Conventional petroleum oil could not stand up to the frigid temperatures during the harsh Russian winter. These oils were produced through conventional distillation, which has several drawbacks, including solidifying in low temperatures, rendering its use extremely ineffective in extremely cold environments—conventional distillation could not completely remove impurities such as waxes, which would solidify in cold temperatures, leading to the inability of engines to start.98 This event demonstrated that a new form of lubricating oil was needed.

The use of synthetic oils found its demand within aircraft engines during and post-WW2. While Zorn was conducting widescale tests on different synthetic esters in Germany, American chemist William Albert Zisman was researching synthetics at the Naval Research Laboratory in Washington D. C. (U.S.). His work (1942–1945)—detailed in the technical article “Synthetic lubricant fluids from branched-chain diesters physical and chemical properties of pure diesters,”99—led to the development of the first diester synthetic base oils, a precursor to the development of modern synthetic lubricants.98,100 With the creation of the jet engine in the 1940s (the history of the jet engine was detailed in the History of the HPI segment published in the February issue of Hydrocarbon Processing), synthetic oils were able to protect engine components against extreme temperatures during flight, a challenge that conventional oils could not accomplish. As a result, synthetic oils were used for military and commercial air travel.

It was not until the 1960s that the idea of using synthetic oils in the automobile industry could provide significant benefits to engine performance. American pilot and inventor Albert Amatuzio conducted research in the 1960s on the use of synthetic lubricants in automobile engines. As a squadron commander in the Minnesota Air National Guard and WW2 fighter pilot (he flew America’s first operational fighter jet, the F80 Shooting Star),101 Amatuzio was aware of the benefits synthetic lubricants provided aircraft engines. His goal was to find a way for automobile engines to gain the same lubricating benefits.

In 1966, Amatuzio formulated his first synthetic motor oil, testing it in his colleague’s new 1966 Ford station wagon.98 After the successful test, he continued to develop new synthetic oils and sell them throughout the late 1960s under the name AMSOIL. However, the public was slow to adopt Amatuzio’s new synthetic motor oil despite the many benefits it provided vs. conventional lubricating oils. The primary challenge was price, as synthetic motor oil costs several times more than conventional motor oil.98

Seeking additional validation of performance standards established by the American Petroleum Institute (API) and the Society of Automotive Engineers, Amatuzio had his motor oil tested by a third-party laboratory in 1972. After rigorous tests, AMSOIL Synthetic Motor Oil became the world’s first synthetic motor oil to meet API service requirements.98 This validation, along with major oil companies producing their own synthetic lubricating oils for the auto industry, would eventually lead to widespread adoption of synthetic motor oils for automobiles.

After Amatuzio’s accreditation and continued sales of his novel product, Mobil followed suit, creating the first Mobil 1 fully synthetic motor oil in 1971—the company first introduced Mobilgrease 28 (still in use) in the early 1960s to prevent military plane wheel bearings from failing during landings in cold temperatures, followed by the Mobil-brand synthetic oil technology for big diesel engines powering oil drilling rigs on Alaska’s North Slope (U.S.) in temperatures as low as –40°C in the late 1960s.102

FIG. 1. Albert Amatuzio developed the world’s first synthetic motor oil to meet API service requirements. For this, he is known as a pioneer in synthetic lubrication. Photo courtesy of AMSOIL.
FIG. 1. Albert Amatuzio developed the world’s first synthetic motor oil to meet API service requirements. For this, he is known as a pioneer in synthetic lubrication. Photo courtesy of AMSOIL.

The formation of OPEC

Following WW2, global oil consumption began to expand significantly. During this timeframe, the U.S. was simultaneously the world’s largest consumer and producer of oil, and global oil supplies were dominated by the Seven Sisters (five were headquartered in the U.S.)—Anglo-Iranian Oil Co. (now bp), Royal Dutch Shell, Standard Oil Co. of California (now Chevron), Gulf Oil and Texaco (both merged into Chevron), Standard Oil Co. of New Jersey and Standard Oil Co. of New York (both are now ExxonMobil). Up until the early 1970s, these multinational organizations controlled approximately 85% of the world’s petroleum reserves—this included large oil reserves in the Middle East.103

Wanting to control more of its domestic reserves, several oil exporting countries—Iran, Iraq, Kuwait, Saudi Arabia and Venezuela—convened in Baghdad, Iraq in September 1960 (FIG. 2). This historic meeting’s (the Baghdad Conference) goal was to discuss ways to increase crude oil pricing produced by these countries, as well as ways to respond to unilateral actions by the Seven Sisters and other multinational organizations.103 This meeting led to the creation of the Organization of Petroleum Exporting Countries (OPEC), which witnessed its member countries increase over the next 15 yr.

FIG. 2. The delegation of Saudi Arabia at the historic Baghdad Conference in mid-September 1960. Photo courtesy of OPEC.
FIG. 2. The delegation of Saudi Arabia at the historic Baghdad Conference in mid-September 1960. Photo courtesy of OPEC.

OPEC grew in prominence during the 1970s, as its member countries gained greater control of their domestic production and began to play a greater role in world oil markets.104 The organization still plays a decisive role in crude oil production, with the ability to significantly affect crude oil pricing globally.

During the 1960s, the Middle East also witnessed the expansion of regional refining and petrochemical capacity. For example, the Ras Tanura refinery in Saudi Arabia expanded its capacity from 50,000 bpd to 210,000 bpd.69 Kuwait National Petroleum Co. expanded the Mina Abdullah refinery’s capacity from 30,000 bpd to 145,000 bpd in 1963, as well as commissioned the 95,000-bpd Shuabia refinery in April 1968—the Shuabia refinery increased processing capacity to 195,000 bpd in 1975. The Shuabia refinery eventually closed in 2017; however, its infrastructure was incorporated into the country’s capital-intensive Clean Fuels Project.105 The Shuaiba Industrial Zone also housed Kuwait’s first chemical fertilizer complex. Petrochemicals Industries Co.—established in 1963—commissioned the facility in 1967, which was the first of its kind in the Middle East. Saudi Arabia and Qatar followed suit, establishing the Saudi Arabian Fertilizer Co. in 1965 and the Qatar Fertilizer Co. in 1969.106

Synthetic zeolite catalysts are patented and commercialized

The term zeolite—microporous, aluminosilicate minerals—was first coined by Swedish mineralogist Axel Fredrik Cronstedt in 1756.107 Cronstedt, who is most noted for discovering the elements nickel and scheelite (later to be known as tungsten), discovered zeolite after heating the mineral stillbite (tectosilicate minerals of the zeolite group) with a blowpipe flame. The process produced a large amount of steam from water that had been absorbed by the mineral.107,108 After observing the reaction, Cronstedt coined the mineral “zeolite” from the Greek words “to boil” and “stone.”107

Modern research and development of synthetic zeolites were pioneered by individuals such as New Zealand-born chemist Richard Barrer (his work in adsorption and synthesis began the era of synthetic zeolites); Robert Milton, Donald Breck and T. B. Reed at Union Carbide (their work during the late 1940s/early 1950s led to the discovery of synthetic zeolites A, X and Y); and Jule Rabo and Edith Flanigen who both worked with Milton’s team at Union Carbide. Rabo led the catalyst research group at Union Carbide from 1957–1961 and played a key role in the discovery of the catalytically active ingredient used worldwide in the catalytic cracking of gasoils to produce gasoline.109 Flanigen was instrumental in the development of zeolite Y. In his historical perspective on zeolite research, Milton described Flanigen as a world expert on zeolite synthesis and the first to synthesize high-silica Y with silica/alumina rations above 4, the first to remove aluminum from zeolite lattices without loss of structure, and responsible for identifying and evaluating the myriad of samples from Union Carbide’s investigation of sedimentary zeolite deposits in the Western U.S.109 Dr. Flanigen’s work was detailed in the Industry Pioneers segment published in the April issue of Hydrocarbon Processing.

In the 1950s, while working at Mobil Oil, American chemical engineers Charles Plank and Edward Rosinski were researching various catalysts. During their research, they decided to test zeolite as a catalyst for catalytic cracking. Plank and Rosinki’s research on zeolite catalysts showed superior activity and selectivity, which led to dramatically higher gasoline yields during the cracking process. According to literature, the increased gasoil conversions could also be obtained without increasing gas or coke yields—two unwanted byproducts of cracking.110,111

The two chemists submitted their patent—Catalytic cracking of hydrocarbons with a crystalline zeolite catalyst composite—to the U.S. Patent Office in July 1960.111 The patent submission and subsequent literature written by Plank described the catalyst as consisting of a finely divided crystalline alumino-silicate, having uniform pore openings between 6 ångströms (Å) and 15 Å, dispersed in an inorganic oxide matrix with a low sodium content.111,112

The technology patent was approved on July 7, 1964. Plank and Rosinski’s patent laid the foundation for modern catalytic cracking. Due to its molecular structure, zeolite catalysts are extremely effective in the reaction process—they have higher performance at lower pressures.

Five years after Plank and Rosinski’s patent was approved, Robert Argauer and George Landolt—the two also worked at Mobil Oil—were the first to synthesize high-silica zeolite, which was commercially named Zeolite Socony Mobil-5 (ZSM-5). The two submitted the technology for a U.S. patent in 1969. The patent submission Crystalline zeolite ZSM-5 and method of preparing the same provided a detailed analysis of the novel crystalline aluminosilicate zeolite and its usefulness in cracking and hydrocracking processes, as well as within other refining processes (e.g., alkylation, isomerization) and petrochemical products production.113 ZSM-5 catalysts are still used in refining and petrochemical plants around the world.

FIG. 3. Rosinski (left) and Plank (right) demonstrate their invention of zeolite catalyst prior to being inducted into the National Inventors Hall of Fame in 1979. Photo courtesy of the National Inventors Hall of Fame.
FIG. 3. Rosinski (left) and Plank (right) demonstrate their invention of zeolite catalyst prior to being inducted into the National Inventors Hall of Fame in 1979. Photo courtesy of the National Inventors Hall of Fame.

New petrochemical products/processes enhance everyday life

Several new petrochemical products were discovered in the 1960s. These included Kevlar, linear low-density polyethylene (LLDPE) resins, a more cost-effective process to produce acrylonitrile and stretched polytetrafluorethylene (PTFE), which came to be known as Gore-Tex. With the significant expansion in the global petrochemical industry, Petroleum Refiner retitled the technical publication to Hydrocarbon Processing and Petroleum Refiner in 1961, then adopted the name Hydrocarbon Processing in June 1966. The publication’s title—Hydrocarbon Processing—represented the integration of the global refining and petrochemical industries and the technical processes and operational know-how that are synonymous with refinery and petrochemicals production.

Acrylonitrile. The origins of acrylonitrile trace back to 1893 when French organic chemist and pharmacist Charles Moureu was the first to synthesize acrylonitrile. However, acrylonitrile did not find a commercial use until the 1930s—industrial producers used the material in applications such as acrylic fibers for textiles and synthetic rubber.114

Although the use of acrylonitrile was extremely effective in several applications, production was expensive and included multistep processes. In the late 1950s, the Standard Oil Co. (Sohio, later bp) discovered a cheaper processing route through selective catalytic oxidation to produce acrylonitrile. This research effort was led by Franklin Veatch. Veatch proposed that converting light refinery gases (e.g., aliphatic hydrocarbon propane) to oxygenates could be profitable. In 1953, funding was approved, and Veatch and his team began research efforts. With only 6 wk left of funding, Veatch’s research team made a vital discovery when conducting a test run on propylene over a modified vanadium pentoxide oxidant, resulting in the production of acrolein—an additional oxidation step would produce acrylic acid.114

In 1955, the Sohio research team began testing oxidants as direct oxidation catalysts, leading to the process of converting propylene to acrolein in a single catalytic reaction step—the process used a bismuth phosphomolybdate catalyst.114 According to literature, acrylonitrile was produced by feeding propylene, ammonia and air over the bismuth phosphomolybdate catalyst. The process resulted in ammoxidation (i.e., the Sohio process), which produced a 50% yield of acrylonitrile, with acetonitrile and hydrogen cyanide as coproducts.114,115

Approximately 4 yr after the start of research, the Sohio process was commercialized and a new $10-MM, 47.5-MMlb/yr plant was constructed in Lima, Ohio (U.S.). The plant was commissioned in early 1960. Upon the success of the Lima plant, Standard Oil Co. began licensing the Sohio process for the cost-effective production of acrylonitrile.

Acrylonitrile is used in numerous applications that touch the everyday lives of people around the world. It is a key ingredient in acrylic fibers (used in the production of clothing, carpeting, industrial yarns, blankets and drapes, among several other applications); in acrylonitrile-butadiene-styrene to produce appliances, automobile components, sports equipment, telephone and computer casings; specialty chemicals; polyols; nitrile rubber to produce fuel hoses, automotive belts and hoses; plastic resins; and adhesives and coatings.114 The global acrylonitrile market reached approximately $12 B in 2020, with forecasts showing growth to more than $16 B by the late 2020s.116,117

Kevlar. After graduating college in the mid-1940s, American chemist Stephanie Kwolek took a job with DuPont. During the 1950s/1960s, Kwolek’s focus was on research and development of new synthetic fibers capable of performing in extreme conditions. Her initial researched focused on aromatic polyamides—a type of polymer that can be made into strong, stiff and flame-resistant fibers.118 This work extended into the study of the polymers poly-p-phenylene terephthalate and polybenzamide. The focus of her team’s research was to discover a new lightweight, strong fiber to use for light, strong tires (FIG. 4).119

FIG. 4. Stephanie Kwolek and others of the DuPont group that developed Kevlar. From left to right: Kwolek, Herbert Blades, Paul Morgan and Joseph Rivers. Photo courtesy of DuPont.
FIG. 4. Stephanie Kwolek and others of the DuPont group that developed Kevlar. From left to right: Kwolek, Herbert Blades, Paul Morgan and Joseph Rivers. Photo courtesy of DuPont.

During one experiment in 1965, Kwolek noticed the solution she was working on had a cloudy, thin and opalescent look when stirred, along with a low viscosity. According to literature, she also noticed that under certain conditions, many rodlike polyamides would line up in parallel (i.e., form a liquid crystalline solution), which could be spun into oriented fibers.120 Upon testing the solution in a spinneret, Kwolek noticed that the fibers that were created were incredibly stiff and strong—these fibers had a high tensile strength-to-weight ratio (i.e., this new substance was five times stronger than steel on an equal weight basis).119 Her discovery created a whole new field of polymer chemistry, which eventually led to the creation of modern Kevlar in 1971.

Kevlar’s first commercial use was as a replacement for steel in racing tires in the 1970s. Since then, Kevlar has been used in more than 200 applications, including sporting and safety equipment, cables/ropes, boats, airplanes, motor vehicles, satellites, household items, and, most notably, in bullet-proof vests. In fact, on the day Kwolek passed away (June 18, 2014), DuPont announced that the one millionth Kevlar bullet-proof vest had been sold.121 For her contribution to polymer research, Kwolek was the first woman to earn the Lavoisier Medal for Technical Achievement from DuPont.

LLDPE. In 1954, DuPont Canada was split off from its parent company Canadian Industries Ltd. The new company’s first objective was to establish a research laboratory in Kingston, Ontario, Canada to identify new growth businesses, one of them being new applications for polyethylene (PE) production. The Kingston Research Center team focused on producing low-density resins by incorporating large amounts of alpha-olefin comonomers.122 However, the product produced from pilot plant testing—which later became known as LLDPE—behaved differently than conventional low-density resin processes at the time, along with several other production challenges. Despite these setbacks, DuPont Canada greenlighted an investment in a new PE production plant.

Due to the economic market conditions in the late 1950s, DuPont Canada could only invest capital in one PE production plant. This facility—located in Corunna, Ontario (outside Sarnia)—could produce both high- and low-density PE (HDPE/LDPE).122 The 275-MMlb/yr St. Claire River (SCLAIR) site—commissioned in 1960—used the same process produced in pilot plant testing by the Kingston Research Center team; thus, establishing the first commercial plant to produce LLDPE. The resin—named SCLAIR after the production site’s location—was found to be stiffer, more heat resistant and tougher than conventional LDPE.123 Several modifications to optimize the process were completed over the next several years, providing resins that would fetch premiums beyond commodity market prices.122 The plant was so successful that DuPont Canada added a second PE production line at the Corunna site in 1976, followed by licensing the SCLAIRTECH process worldwide in 1980—the technology can produce a range of products from LLDPE to HDPE.124 DuPont Canada’s PE business, including the St. Claire PE plant, was eventually purchased by Nova Chemicals in 1994.

In the 1970s/1980s, several other companies began to produce their own LLDPE resins. These included Dow Chemical, Union Carbide and bp Chemicals, among others. Union Carbide’s LLDPE technology’s origins emerged from research and development on a low-pressure, gas-phase fluidized bed process to produce HDPE. This process—known as the UNIPOL PE process (now licensed by Univation Technologies)—came to fruition in 1968 with the startup of the G-1000 plant in Seadrift, Texas (U.S.). The UNIPOL process extended its reach into LLDPE production in 1977.125 By the late 1980s, more than 70% of the world’s LLDPE production was produced via gas-phase polymerization—the basis of the UNIPOL process.123 Today, several additional companies license their own LLDPE process, including Borealis, Chevron Phillips Chemical, INEOS and LyondellBasell, among others. LLDPE is used in many consumer goods such as plastic grocery/trash bags, shrink wrap, toys/playground and plastic gardening equipment, tubing, flooring and many other applications. Over the past 60 yr, the LLDPE market has significantly expanded, with forecasts showing the global LLDPE market will exceed $65 B by the mid-2020s and increase to more than $85 B by 2030.126,127

Gore-Tex. In the late 1950s, Bill Gore left his job at DuPont to pursue detailed research and analysis on the untapped potentials of PTFE.128 The polymer PTFE was discovered by accident in the late 1930s by Roy Plunkett who was working at DuPont at the time. This discovery eventually led to the development of Teflon—the discovery of PTFE and the subsequent creation of Teflon was detailed in the History of the HPI segment published in the February issue of Hydrocarbon Processing.

In 1969, Bill’s son Robert (Bob) conducted experiments by heating rods of PTFE and stretching the material. However, on one such occasion, primarily out of frustration, he yanked the heated PTFE rod, causing it to stretch about 800%. After analysis, he noticed that the resultant material was incredibly strong, microporous (the structure was approximately 70% air), and contained several key benefits, such as low water adsorption and good weathering properties.128,129 The expanded PTFE (ePTFE) was given the name Gore-Tex and sold commercially in the 1970s as a breathable, waterproof and windproof fabric for clothing (e.g., jackets).129 Gore-Tex (ePTFE) found use in many applications over the ensuing decades, including in insulation, medical implants, high-performance fabrics, gloves, footwear and even on astronauts’ spacesuits.

The PLC revolutionizes industrial automation

The invention of the PLC originated within the automotive industry. In the late 1960s, Bedford Associates—from Bedford, Massachusetts (U.S.)—was awarded a contract from GM Hydramatic [the automatic transmission division of General Motors (GM)]. GM wanted to replace its hardwired relay systems with a better electronic device.130 Hardwired relay systems had several disadvantages: several relays were needed to control a single device, improper wiring of only one relay could cause the machine or entire system to shut down, systems were hard to troubleshoot and fix, and needed changes to the system often required reconfiguring the entire system.131

In 1968, the founder of Bedford Associates, Richard (Dick) Morley (known as the father of the PLC), unveiled the world’s first PLC, the Modicon 084 (FIG. 5)—the technology was named Modicon (MOdular DIgital CONtroller) 084 since it was the company’s 84th project.132 The creation of the PLC meant that large banks of relays could be replaced by a single device. It also contained enough memory to retain loaded programs in the event of a power outage and worked well in harsh conditions.131

FIG. 5. The Bedford Associates group, who formed Modicon in 1968 after developing the world’s first PLC, the Modicon 084. Left to right: Dick Morley, Tom Boissevain, George Schwenk and Jonas Landau. Photo courtesy of Schneider Electric
FIG. 5. The Bedford Associates group, who formed Modicon in 1968 after developing the world’s first PLC, the Modicon 084. Left to right: Dick Morley, Tom Boissevain, George Schwenk and Jonas Landau. Photo courtesy of Schneider Electric

Bedford Associates soon adopted the company name Modicon and began to market PLCs. The company was also responsible for the invention of the Modbus in the late 1970s—Modus is a data communications protocol that enables electronic devices to communicate with each other.133

Modicon was acquired by Gould Electronics in 1977 and then by AEG in 1989. The company eventually became part of Schneider Electric in 1994 with the merger of AEG and Groupe Schneider—the merger took the name Schneider Electric in 1999.134

The invention of the PLC created a new era in automation technology. Today, PLCs are incorporated into refining and petrochemical plant operations to help monitor plant equipment, among other production actions. HP

LITERATURE CITED

96   Noble, P. G., “A short history of LNG shipping, 1959–2009,” Society of Naval Architects and Marine Engineers, February 10, 2009, online: https://higherlogicdownload.s3.amazonaws.com/SNAME/1dcdb863-8881-4263-af8d-530101f64412/UploadedFiles/c3352777fcaa4c4daa8f125c0a7c03e9.pdf

97   Sullivan, F. W., V. Voorhees, A. W. Neeley and R. V. Shankland, “Synthetic lubricating oils relation between chemical constitution and physical properties,” Industrial and Engineering Chemistry Research, June 1931.

98   AMSOIL, “The history of synthetic oil (and AMSOIL),” December 26, 2019, online: https://blog.amsoil.com/the-history-of-synthetic-oil-and-amsoil/

99  Bried, E., H. F. Kidder, C. M. Murphy and W. A. Zisman, “Synthetic lubricant fluids from branched-chain diesters physical and chemical properties of pure diesters,” Industrial and Engineering Chemistry Research, April 1947.

100 Wikipedia, “United States Naval Research Laboratory,” online: https://en.wikipedia.org/wiki/United_States_Naval_Research_Laboratory

101 Wikipedia, “Amsoil,” online: https://en.wikipedia.org/wiki/Amsoil

102 Mobil, “One great oil. One great story,” online: https://www.mobil.com/en/lubricants/about-us/mobil-1/one-great-oil-one-great-story#:~:text=More%20than%2040%20years%20ago,the%20widest%20range%20of%20temperatures

103 Wikipedia, “Seven Sisters,” online: https://en.wikipedia.org/wiki/Seven_Sisters_(oil_companies)

104 OPEC, “Brief History,” online: https://www.opec.org/opec_web/en/about_us/24.htm

105 Kuwait National Petroleum Co., “Shuaiba refinery,” online: https://www.knpc.com/en/our-business/petroleum-refining/shu#:~:text=The%20first%20National%20Oil%20Refinery,was%20The%20Company’s%20first%20Refinery.

106 Gulf Petrochemicals and Chemicals Association, “Key milestones and achievements in the Arabian Gulf’s petrochemical landscape,” online: https://www.gpca.org.ae/history/

107 Wikipedia, “Zeolite,” online: https://en.wikipedia.org/wiki/Zeolite#Catalysis

108 Wikipedia, “Axel Fredrik Cronstedt,” online: https://en.wikipedia.org/wiki/Axel_Fredrik_Cronstedt

109 Milton, R. M., “Molecular sieve science and technology: A historical perspective,” American Chemical Society, July 1989, online: https://pubs.acs.org/doi/pdf/10.1021/bk-1989-0398.ch001

110 Wikipedia, “Charles J. Plank, online: https://en.wikipedia.org/wiki/Charles_J._Plank

111 Plank, C. and E. Rosinski, “Catalytic cracking of hydrocarbons with a crystalline zeolite catalyst composite,” U.S. Patent No. 3,140,249, July 7, 1964, online: https://patentimages.storage.googleapis.com/c6/9d/ad/6a751ff6983d30/US3140249.pdf

112 Plank, C., “The invention of zeolite cracking catalysts—A personal viewpoint,” Heterogeneous Catalysis, June 3, 1983.

113 Argauer, R. J., M. Kensington and G. R. Landolt, “Crystalline zeolite ZSM-5 and method of preparing the same,” U.S. Patent No. 3,702,886, November 14, 1972, online: https://patentimages.storage.googleapis.com/1f/b9/43/ff5945c7fbd9eb/US3702886.pdf

114 American Chemical Society, “The Sohio acrylonitrile process,” September 13, 1996, online: https://www.acs.org/content/dam/acsorg/education/whatischemistry/landmarks/acrylonitrile/sohio-acrylonitrile-process-commemorative-booklet-1996.pdf

115 Granado Institute of Polyacrylonitrile Technology (IGTPAN), “The Sohio process,” online: https://www.igtpan.com/Ingles/processo.asp#:~:text=In%20the%20SOHIO%20process%2C%20propylene,cooled%20in%20aqueous%20sulfuric%20acid.

116 Grand View Research, “Acrylonitrile market analysis report, 2020–2027,” February 2020, online: https://www.grandviewresearch.com/industry-analysis/acrylonitrile-acn-market

117 Reports and Data, “Acrylonitrile market: Forecasts to 2028,” August 2020, online: https://www.reportsanddata.com/report-detail/acrylonitrile-market

118 Wikipedia, “Stephanie Kwolek,” online: https://en.wikipedia.org/wiki/Stephanie_Kwolek

119 Wikipedia, “Kevlar,” online: https://en.wikipedia.org/wiki/Kevlar

120 Science History Institute, “Stephanie L. Kwolek,” December 9, 2017, online: https://www.sciencehistory.org/historical-profile/stephanie-l-kwolek

121 Houston Chronicle, “Kevlar inventor dies as millionth bulletproof vest sold,” June 20, 2014, online: https://www.houstonchronicle.com/news/article/Newsmakers-Kevlar-inventor-dies-as-millionth-5568812.php

122 The Free Library, “The SCLAIR story,” Chemical Institute of Canada, 1997, online: https://www.thefreelibrary.com/The+SCLAIR+story.-a019232866

123 Plastics Technology, “No. 6—LLDPE,” October 1, 2005, online: https://www.ptonline.com/articles/no-6—-lldpe

124 Nova Chemicals, “Sarnia/Lambton plant facilities,” online: https://www.novachem.com/locations/sarnia-lambton-on-canada/plant-facilities/

125 Univation Technologies, “History of the UNIPOL PE technology,” online: https://www.univation.com/en-us/unipol/polyethylene-technology-history.html

126 Market Watch, “Linear low-density polyethylene market research report,” February 20, 2021, online: https://www.marketresearchengine.com/reportdetails/linear-low-density-polyethylene-market

127 Reports and Data, “Linear low-density polyethylene market,” online: https://www.reportsanddata.com/report-detail/linear-low-density-polyethylene-lldpe-market

128 Gore-Tex, “Our history,” online: https://www.gore-tex.com/technology/history

129 Wikipedia, “Gore-Tex,” online: https://en.wikipedia.org/wiki/Gore-Tex

130 Wikipedia, “Programmable logic controller,” online: https://en.wikipedia.org/wiki/Programmable_logic_controller#Invention_and_early_development

131 Process Solutions blog, “A brief history of programmable logic controllers,” May 19, 2020, online: https://processsolutions.com/a-brief-history-of-programmable-logic-controllers-plcs/

132 Schneider Electric, “Modicon history,” online: https://www.se.com/in/en/about-us/events/modicon.jsp

133 B+B SmartWorx, “14 frequently asked Modbus questions,” online: https://www.bb-elec.com/Learning-Center/All-White-Papers/Modbus/The-Answer-to-the-14-Most-Frequently-Asked-Modbus.aspx#:~:text=Modbus%20is%20a%20communication%20protocol,supplying%20information%20are%20Modbus%20Slaves

134 Schneider Electric, “Modicon is now Schneider Electric,” online: https://www.se.com/uk/en/about-us/company-profile/brands/modicon.jsp#:~:text=The%20history%20of%20Modicon&text=In%201977%20Modicon%20was%20acquired,as%20Schneider%20Electric%20in%201999

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