February 2022

100th Anniversary

History of the HPI: The 1930s: Catalytic cracking, polyethylene, synthetic fibers, resins and jet engines

The hydrocarbon processing industry (HPI) has a rich history of discovery, challenges, breakthroughs, trial and error, collaboration and success. Hydrocarbon Processing continues its reflection on the history of the HPI.

Nichols, Lee, Hydrocarbon Processing Staff

The hydrocarbon processing industry (HPI) has a rich history of discovery, challenges, breakthroughs, trial and error, collaboration and success. Hydrocarbon Processing continues its reflection on the history of the HPI. In the January issue, a detailed analysis was provided on the origins of the modern refining and petrochemicals industries. This included the discovery of kerosene, the construction of new refineries around the world, the production of the first synthetic plastics, the rise of the internal combustion engine (ICE), oil demand’s exponential growth during and after World War I (WWI) and how thermal cracking evolved refining processing. The following will detail how the HPI continued to evolve during the 1930s.

The discovery of catalytic cracking

After serving in WWI in the French artillery division and later in the tank corps, French engineer Eugene Houdry worked in his father’s steel business. Outside of work, Houdry had an interesting hobby, racing cars. Through these endeavors, he began to develop a passion for improving engine performance.

With the significant increase in gasoline demand after WWI, many forecasters feared that thermal cracking was unable to satisfy future global demand. Like many other researchers around the world, Houdry was trying to develop a new way to develop high-performance fuels.

In the late 1920s, he and French scientist E. A. Prudhomme developed a three-step process to convert lignite to gasoline. However, a major problem with the process was that the catalysts would get coated with carbon, lessening their effectiveness. To solve this challenge, Houdry used Fuller’s earth (a naturally occurring aluminosilicate), which effectively produced gasoline from lignite.24 However, pilot plant demonstrations yielded less than expected results and the process was deemed uneconomical.

Unable to secure additional financial backing, Houdry moved to the U.S. and eventually started working with Socony-Vacuum and Sun Oil Co. to perfect his process. In 1936, the first Houdry Unit began commercial operations at Sun Oil’s Marcus Hook refinery in Pennsylvania—it was the first fixed-bed catalytic cracking unit.23 Approximately 50% of the 15,000-bpd unit produced high-octane gasoline, which was double the production of conventional thermal processes.24 Around the same timeframe (circa 1938), the alkylation process was commercialized in the U.S. The process produced high-octane aviation gasoline, which saw significant demand increase during World War 2 (WW2). The process was then used in the 1950s to produce blending components for automotive fuel.

The catalytic cracking process was later improved upon by Warren Lewis and Edwin Gilliland while working for Standard Oil of New Jersey (U.S.). According to literature,25 the improved process included a continuously circulating fluidized catalyst made of fine zeolite powder. Houdry’s fixed-bed unit gave rise to research and development by other companies that led to the invention of the fluid catalytic cracking process in the 1940s.

Coking and gasification evolve

The first delayed coker was built in 1929 by Standard Oil of Indiana (the company would later become bp). The Burton thermal cracking process produced coke that would be sent to a vertical coke drum. However, cleaning the vertical coke drum required arduous manual labor. It was not until the late 1930s that Shell introduced hydraulic decoking at its refinery in Wood River, Illinois (U.S.), which used high-pressure water to clean coke drums. This process enabled refineries to use two coke drums for continuous operation.26 Over the next several decades, coking would become a staple in refining operations.

In the mid-1930s, Lurgi GmbH (now a part of Air Liquide) invented a novel coal gasification process. The pressurized, dry-ash, fixed-bed gasifier would use coal to produce synthesis gas (syngas). The first commercial Lurgi dry-ash gasification plant started operations in 1936, and the process is still in use today.

Polyethylene: An accidental discovery

In 1933, while working at Imperial Chemical Industries (ICI) in Northwich, England, Eric Fawcett and Reginald Gibson stumbled upon a white, waxy substance during experiments they were conducting on ethylene and benzaldehyde. The experiments included heating the mixture to 170°C at an extremely high pressure—more than 1,900 bar—in an autoclave. However, the reaction was a safety hazard due to the explosive nature and research was halted.

Two years later, ICI scientists Michael Perrin, John Paton and Edmond Williams began to conduct additional research on Fawcett and Gibson’s discovery. In this iteration, the scientists repeated Fawcett and Gibson’s test but focused solely on ethylene. What the three did not know was that the pressure vessel used leaked, leading to a loss of pressure. Once the reaction was completed, the trio noticed a white powdery substance remained—one lab technician described the substance looked like a lump of sugar.27 The scientists had accidentally stumbled upon polyethylene, which would revolutionize society.

Over the next several years, ICI perfected the process and found practical uses for the material (the first item ever made with PE was a walking stick28) that would not only produce products to modernize society but also aide the Allies in WW2.

ICI produced the first ton of PE in 1938 (FIG. 1). In 1939, the first commercial-scale PE plant went into operation. The 100,000-tpy plant was instrumental in producing PE on an industrial scale. Within the next few years, many PE plants went into operation, primarily to aide in the allied war effort. PE was used extensively as insulating material for radar cables during WW2. The material was lightweight, which enabled Britain to install radar in their fighter planes, providing a significant technical advantage in long-distance air warfare.27,28 Due to this wartime advantage, the production of PE for insulated cabling was highly-secretive. It was not until post WW2 that the production of PE was commercialized. Within several years, PE production capacity significantly increased and would later become the world’s most used thermoplastic.

FIG. 1. A commemorative sample of the first ton of PE produced by ICI in 1938. The initials G. F. are that of George Feachem, a chemist that was on duty the night PE was produced in laboratory tests in 1933. According to family members, Mr. Feachem kept this token in his wallet until his death. Photo courtesy of BBC History of the World.

New chemical discoveries with lasting legacies

Several new chemical discoveries took place in the 1930s that have provided the global population with new products to improve standards of living. These included the discovery and production of polystyrene, polyepoxide, nylon, polyester and neoprene.

Polystyrene. Although discovered in the late 1830s, styrene—which would lead to the production of polystyrene—would not be commercialized for nearly 100 yr. In 1839, German chemist/pharmacist (referred to as an apothecary) Eduard Simon distilled an oily substance from storax, a resin from a sweetgum tree. He noticed several days later that the material—which he called styrol—thickened into a jelly-like substance. Thinking the reaction was due to oxidation, Simon termed the substance styrol oxide.29 However, it was not until 80 yr later that a practical use was found for the material.

In the 1920s, research/writings by German chemist Hermann Staudinger led to the invention of polystyrene. Staudinger demonstrated that thermally processing styrol produces macromolecules, which he characterized as polymers. His technical research/writings would eventually lead Staudinger to be awarded the Nobel Prize for Chemistry in 1953.

Commercialization of styrene polymers began in the early- to mid-1930s by IG Farben in Germany and Dow Chemical in the U.S.—styrene production increased significantly in both Germany and in the U.S. during WW2 to produce synthetic rubbers to aide in the war effort. In the late 1930s, Dow Chemical engineer Ray McIntire was experimenting with a polystyrene process developed by Swedish inventor Carl Munters. By accident, McIntire created foam polystyrene which expanded approximately 40 times in size.30 Dow would later commercialize this discovery as expanded polystyrene, better known and marketed under the name Styrofoam.

Neoprene and nylon. While focusing on research conducted by Staudinger and Belgian-born priest and chemistry professor Julius Nieuwland, Wallace Carothers’ polymers research group at DuPont discovered two major chemical applications: neoprene and nylon. While a professor of chemistry at the University of Notre Dame (U.S.), Nieuwland focused his research on acetylene chemistry, which led to the discovery of divinyl acetylene—a jelly-like substance that hardens into an elastic compound similar to rubber.31 DuPont purchased the patent rights to this new discovery, and Nieuwland joined Carothers’ research team to conduct further research and testing on practical applications for this and other polymer applications. One of Carothers’ colleagues, Arnold Collins, discovered neoprene while conducting further research on divinyl acetylene. Through several testing methods, Collins soon discovered a mixture that produced a clear homogeneous mass that bounced. The product—chloroprene—was used to produce the polymer polychloroprene, which later became the new synthetic rubber neoprene.

Neoprene was first marketed in 1931 under the name DuPrene; however, the product was re-envisioned since it contained an odor due to the manufacturing process. By the mid- to late-1930s, the improved product—suitable for many applications (construction, automotive, medical equipment, fabrics, electrical equipment, textiles, among others) and marketed under the generic name neoprene—generated substantial revenues for DuPont.

After the discovery of neoprene, Carothers’ team turned their sights on producing synthetic fibers. By the mid-1930s, Carothers produced fibers comprised of amine, hexamethylene diamine and adipic acid. However, water produced during the condensation reaction process would fall back into the mixture, preventing the creation of more polymers. After adjusting the process, Carothers produced strong, elastic fibers.32 The new material was called polymer 6,6 (or nylon 66) since the two monomers that comprise the substance each contained six carbon atoms (FIG. 2). Nylon first became a household product as women’s hosiery, later being used in the U.S. war effort to produce parachutes and tents. Over the next several decades, nylon would be used extensively as a combined fabric in fashion and apparel, as well as in several industrial applications—the global nylon industry market size is forecast to reach more than $46 B by the late 2020s.33 

FIG. 2. Carothers demonstrates the elasticity of neoprene. Photo courtesy of the Science History Institute.

Polyester. Carothers’ research also led to the discovery of polyester in the early 1930s. However, the discovery of nylon pushed additional research on polyester to the backburner. It was not until the late 1930s that British scientists John Winfield and James Dickson expanded on Carothers’ work on synthetic fibers. Their research would eventually lead to the development of polyethylene terephthalate (PET) in 1941, which they marketed under the name Terylene. DuPont would later purchase the rights of the British scientists’ discovery and develop a new synthetic fiber in the mid-1940s they called Dacron. In the early 1970s, PET began to be used in the production of plastic bottles, and today, PET is the fourth most produced polymer after PE, polypropylene and polyvinyl chloride.

Resins, epoxies, polyurethane and Plexiglas. The DuPont company was not finished with major polymer discoveries of the 1930s. In 1938, Roy Plunkett was assigned to research chlorofluorocarbon refrigerants to find a better way to refrigerate food. Much like the discovery of PE, an accident led to the discovery of another important product still in use today. Plunkett stored 100 lb of tetrafluoroethylene gas in small cylinders at dry-ice temperatures [approximately –78°C (–109°F)] before chlorinating it. When he opened the cylinder, instead of gas pouring out, Plunkett noticed a white powder had formed (FIG. 3).34 Further investigation found the substance to be heat resistant and had a low surface friction. DuPont polymer scientists determined that the tetrafluoroethylene gas polymerized to produce the material, which DuPont would later market under the name Teflon.

FIG. 3. Plunkett (far right) and colleagues reenacted the discovery of Teflon in 1938. Photo courtesy of the Hagley Museum and Library.

In 1936, while working at Monsanto Chemical Co., William Talbot produced melamine formaldehyde by polymerizing formaldehyde with melamine. This new substance was a thermosetting plastic that was very good at maintaining strength and shape. Melamine resins were used for many different applications, including in utensils, plates, furniture, cups, bowls, laminates, toilet seats, automotive and epoxy coatings, among others.35

Within the next 3 yr, other significant chemical discoveries were made. In 1936, British chemists John Crawford and Rowland Hill discovered polymethyl methacrylate (PMMA) while working at ICI in England. PMMA is a clear thermoplastic resin that is more transparent than glass and 6x–7x more resistant to breakage than glass.36

Around the same time, German chemist Otto Röhm conducted experiments with methyl methacrylate (MMA). One experiment involved polymerizing MMA between two layers of glass in a water quench. The result was a clear plastic sheet that was lighter than glass but much less prone to shatter. Röhm’s chemical company—Röhm and Hass AG—soon marketed the material under the name Plexiglas (FIG. 4). According to literature, the first major applications of the new plastic were for aircraft windows and bubble canopies for gun turrets during WW2.37 After this discovery, several companies around the world developed their own PMMA products under various proprietary names. Röhm and Hass AG’s business lines were eventually acquired by different multinational businesses, including Dow Chemical, Arkema and Evonik.

FIG. 4. After discovering Plexiglas, Röhm and Hass AG marketed the material by saying, “The light and weather-resistant, practically unbreakable, flexible and easily formable Plexiglas is made from a new, viscous synthetic resin.” Photo courtesy of Evonik Industries.

In 1936, while working with synthetic resins to produce dental prosthesis, Swiss chemist Pierre Castan developed a solid by reacting bisphenol A with epichlorohydrin and curing it with phthalic anhydride. Castan’s invention—epoxy resin—was first used for dental fixtures and casings,38 later being licensed by Ciba Ltd., which would become one of the largest epoxy resin producers in the world.

Around the same timeframe, Sylvan Greenlee was conducting his own research on epoxy polymers in the U.S. by reacting epichlorohydrin with bisphenol A. His research created the epoxy resin bisphenol A diglycidyl ether (DGEBA or commonly abbreviated as BADGE), which would become the most widely used commercial-grade resin in the world. Epoxy resins are presently used in many industrial and commercial applications, including paints and coatings, adhesives, electrical systems and electronics, marine and aerospace applications, and many more.

While epoxy resins research and development were being implemented in Switzerland and the U.S., German chemist Otto Bayer was setting his sights on polymer research at IG Farben in Leverkusen, Germany. In 1937, Bayer created a new polymer by reacting 1,8 octane diisocyanate with 1,4 butanediol.39 This new material was named polyurethane, which would later be used in many applications, including in construction, furniture, insulation, coatings, adhesives, sealants, elastomers, moldings, appliances, automotive, apparel and many more.

Ingenuity takes to the skies

Prior to designing engines, British engineer and inventor Frank Whittle was an airplane apprentice and pilot at the Royal Air Force (RAF) College Cranwell. Although garnering the reputation as a low-flying daredevil and aerobatics stuntman (not in a positive light), Whittle had an eye for airplane engine designs. In his graduation thesis Future Developments in Aircraft Design, Whittle believed that the evolution in flight would not be better propeller designs but the use of improved combustion engines for propulsion. In addition, he believed that airplanes would be able to fly faster (more than 500 mph) and farther at higher altitudes due to low air density.40,41 However, when Whittle provided his concepts to the RAF, they were rejected as impracticable. Despite being rejected by his superiors, Whittle continued to publicize his jet engine concept and filed a patent for his engine design two years later in 1930. According to literature, the concept was a two-stage axial compressor feeding a single-sided centrifugal compressor, what he referred to as a “turbojet.”42 Whittle continued to work on building his jet engine designs over the next several years, forming Power Jets Ltd. in 1936 (FIG. 5).

FIG. 5. Whittle and his colleagues work on the first jet engine. Photo courtesy of Getty Images.

Unbeknownst to Whittle, German physicist and engineer Hans von Ohain was developing a similar jet engine in Germany. Ohain joined aircraft industrialist Ernst Heinkel to design the Heinkel-Strahltriebwerk 1 (HeS 1) engine—German for Jet Engine 1. The first tests of HeS 1 were conducted in 1937. Although the tests were successful, the high-temperature burn—the engine ran off hydrogen fuel—scorched the metal, leading Heinkel and Ohain to switch to gasoline as fuel. Several changes were made to the design, and on August 27, 1939, test pilot Erich Warsitz flew a plane equipped with a HeS 3b centrifugal-flow turbojet engine—the latest iteration.43 This historic day marked the world’s first jet-powered aircraft flight.

Although Ohain beat Whittle to the first jet engine test flight, Whittle continued to improve his designs. As WW2 started, he received additional financial backing from the UK Air Ministry. In 1940, the first British jet-powered plane—the Gloster E.28/39—was flown using Whittle’s W1A engine.44 As war raged in Europe, the UK Air Ministry was ordering several thousand jet engines per month. By 1944, Whittle’s engine design—produced by Rolls Royce—was used in the first British fighter planes, the Gloster Meteor, that could reach speeds of 600 mph.45

Over the next several years, jet engine designs continued to be optimized, primarily for military aircraft. However, on July 27, 1949, the world’s first jet-propelled airliner made its test flight in England.46 This historic occasion marked the first use of a jet-powered passenger plane, which would revolutionize travel. Over the next several decades, the jet-powered passenger plane would enable passengers to travel faster and farther in a shorter duration and build a nearly $200-B industry to carry billions of people each year to various destinations around the world.

The 1940s

As the world engages in conflict, demand for gasoline and chemical products soar to aid in the war effort. Post-WW2 will usher in new technological advances for producing higher octane fuels and chemical products that will increase the standard of living for hundreds of millions around the world. The industry’s milestones of the 1940s will be discussed in the March issue of Hydrocarbon Processing. HP

LITERATURE CITE

24. Sun Co., “The Houdry Process for the catalytic conversion of crude petroleum to high-octane gasoline,” April 1996, online: https://www.acs.org/content/acs/en/education/whatischemistry/landmarks/houdry.html.
25. Wikipedia, Eugene Houdry, online: https://en.wikipedia.org/wiki/Eugene_Houdry.
26. Ellis, P. and C. Paul, “Tutorial: Delayed Coking Fundamentals,” AIChE Spring National Meeting, New Orleans, Louisiana, 1998, online: http://coking.com/wp-content/uploads/sites/2/2013/11/DelayedCokingFundamentals.pdf.
27. Jagger, A., “Polyethylene: Discovered by accident 75 years ago,” ICIS, May 2008, online: https://www.icis.com/explore/resources/news/2008/05/12/9122447/polyethylene-discovered-by-accident-75-years-ago/.
28. BBC News, “History of the world: The first piece of polythene,” September 2010, online: http://news.bbc.co.uk/local/manchester/hi/people_and_places/history/newsid_9042000/9042044.stm.
29. Britannica, “Styrene,” Encyclopedia Britannica, December 2020, online: https://www.britannica.com/science/styrene.
30. PN staff, “History of the world in 52 packs,” Packaging News, December 2015, online: https://www.packagingnews.co.uk/features/comment/history-of-the-world-in-52-packs-20-polystyrene-22-12-2015.
31. Wikipedia, “Neoprene,” online: https://en.wikipedia.org/wiki/Neoprene#History.
32. PBS, “Nylon is invented 1935,” A Science Odyssey: People and Discoveries, online: http://www.pbs.org/wgbh/aso/databank/entries/dt35ny.html.
33. Research and Markets, “Global nylon market size, share and trends analysis 2021–2028,” PRNewswire, October 2021, online: https://www.prnewswire.com/news-releases/global-nylon-market-size-share—trends-analysis-2021-2028—nylon-6-accounts-for-highest-revenue-share-301389960.html.
34. Historical Biographies, “Roy J. Plunkett,” Science History Institute, December 2017, online: https://www.sciencehistory.org/historical-profile/roy-j-plunkett.
35. Gilani, N., “What is melamine formaldehyde?”, Sciencing, April 2017, online: https://sciencing.com/melamine-formaldehyde-6495357.html.
36. Encyclopedia.com, “Polymethyl methacrylate,” November 2021, online: https://www.encyclopedia.com/science/academic-and-educational-journals/polymethyl-methacrylate.
37. Britannica, The editors of Encyclopedia, “polymethyl methacrylate,” Encyclopedia Britannica, December 2018, online: https://www.britannica.com/science/polymethyl-methacrylate.
38. Plastics Historical Society, “Pierre Castan,” online: http://plastiquarian.com/?page_id=14266.
39. Plastics Historical Society, “Otto Bayer,” online: https://plastiquarian.com/?page_id=14264.
40. Wikipedia, “Frank Whittle,” online: https://en.wikipedia.org/wiki/Frank_Whittle#Development_of_the_turbojet_engine.
41. Whittle, F., Future Developments in Aircraft Design, thesis, Royal Air Force College Cranwell, 1928.
42. Wikipedia, “History of the jet engine,” online: https://en.wikipedia.org/wiki/History_of_the_jet_engine#Pre_World_War_II.
43. Gavrieli, K., N. Salim and A. Yanez, “The jet engine: A historical introduction,” Stanford University, online: https://cs.stanford.edu/people/eroberts/courses/ww2/projects/jet-airplanes/planes.html.
44. Encyclopedia.com, “The development of jet engines,” November 2021, online: https://www.encyclopedia.com/science/encyclopedias-almanacs-transcripts-and-maps/development-jet-engines.
45. Dunn, J., “The RAF told him it would never work but 80 years ago genius Frank Whittle tested the world’s first jet engine that shrank the world and won the war,” Daily Mail, April 2017, online: https://www.dailymail.co.uk/news/article-4401004/The-man-tested-jet-engine-80-years-ago.html.
46. This Day in History, “First commercial jet makes test flight,” The History Channel, online: https://www.history.com/this-day-in-history/first-jet-makes-test-flight.

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