March 2022

History of the HPI

History of the HPI: The 1940s: Global conflict, FCC, 100 octane, synthetic rubber—Wartime necessitates advancing technologies

Hydrocarbon Processing continues its look at the history of the hydrocarbon processing industry (HPI).

Nichols, Lee, Hydrocarbon Processing Staff

Hydrocarbon Processing continues its look at the history of the hydrocarbon processing industry (HPI). The first installment detailed the origins of the global refining and petrochemical industries. In the February issue, major refining and petrochemical discoveries of the 1930s were discussed, including the discovery of catalytic cracking and polyethylene; the evolution of coking and gasification; the production of polystyrene, nylon, polyester, resins, epoxies and polyurethane; and the inception of the jet engine.

The following will detail how the HPI continued to evolve during the 1940s.

The onset of fluid catalytic cracking (FCC)

In 1936, Eugene Houdry started up the first Houdry unit at Sun Oil’s Marcus Hook refinery in Pennsylvania (U.S.). The novel fixed-bed catalytic cracking unit was instrumental in evolving the gasoline production process. For example, approximately 50% of the 15,000-bpd unit produced high-octane gasoline, which was double the production of conventional thermal processes.24 However, the novel Houdry process—a significant advancement vs. the thermal cracking process—was unable to satisfy increasing global demand for gasoline from vehicles and the aviation industry.

In the early 1940s, Standard Oil of New Jersey and Davison Chemical (the company would later become W. R. Grace & Co.) collaborated on developing powered catalyst and an improved catalyst circulation design vs. the Houdry process. The companies were joined by the Massachusetts Institute of Technology (MIT) and M. W. Kellogg.23

Through significant research, MIT professors Warren Lewis and Edwin Gilliland improved Houdry’s design. One of the major changes was improving catalyst circulation—the new design enabled the catalyst to pass through both the reactor and regenerator. Their patent was the basis for Standard Oil of New Jersey’s 100-bpd pilot plant in Baton Rouge, Louisiana (U.S.).23 The newly designed pilot plant was tested and, after a few modifications, was shut down and redesigned into a full commercial unit. On May 25, 1942, Powdered Catalyst, Louisiana 1 (PCLA) Model 1 went online (FIG. 1), marking the first use of a commercial catalytic cracking process using powdered catalyst.23 The plant’s catalyst was supplied by Davison’s Curtis Bay Works facility in Maryland, which also began operations in May 1942—three months later, The Refiner and Natural Gasoline Manufacturer, the forerunner to Hydrocarbon Processing, was retitled Petroleum Refiner; the name change reflected the significant advancements and broader scope of petroleum processing. The Curtis Bay plant was the world’s first synthetic FCC production facility, and, in 1947, Davison established the refining industry’s first technical services facility for fluid cracking catalysts.47 

FIG. 1. View of Standard Oil of New Jersey’s PCLA Model 1 plant in Baton Rouge, Louisiana—the first use of a commercial catalytic cracking process using powdered catalyst. Photo courtesy of the American Chemical Society.

Over the next 2 yr, several new FCC units were built in the U.S. The new refining process helped to significantly increase production of gasoline motor fuel and aviation gasoline, which was crucial in aiding the Allied powers in World War 2 (WW2).

The world engages in conflict

On September 1, 1939, Germany invaded Poland. The invasion caused European allies to mobilize against Germany, setting off the largest and bloodiest conflict in human history. Central to both the Allies and Axis powers’ military operations was the ability to produce refined fuels. Oil and refined fuels were imperative during the war. Without fuel (gasoline and aviation gasoline), tanks could not run, planes would not fly, battleships and other marine vessels are trapped in port, and thousands of other vehicles (e.g., jeeps) become obsolete. Oil was also indispensable for lubricating guns and machinery both in the field and to fuel domestic industrial manufacturing.

The Allies—especially the U.S.—controlled most of the world’s oil production. Conversely, Germany lacked any kind of oil production, which was a major factor that eventually led to its demise. However, Germany did have a substantial amount of coal reserves. To fuel its war machine, Germany primarily used coal conversion processes for synthetic-fuels manufacturing. More than 90% of Germany’s aviation gasoline and half of its total domestic petroleum products production came from synthetic fuel plants.48 These plants primarily used the Bergius process and the Fischer-Tropsch process, among others.

Japan suffered from the same challenge as Germany. The country had no oil production and virtually no refining system to produce fuels for its war effort. Japan did have major coal reserves and tried to venture into synthetic fuels production; however, it lacked the technical expertise and specific alloys and catalytic metals required for synfuel production.49

Once the U.S.—the primary supplier of oil and finished products to Japan—cut off oil supplies to the island nation, Japan began a strategic military offensive in the South Pacific, seizing oil fields developed by Royal Dutch Shell in the Dutch East Indies (i.e., Indonesia) and Borneo, which also contained 90% of the world’s natural supply of rubber.49 However, the Axis powers could not compete against the manufacturing juggernaut of the Allied nations.

Several new technologies and initiatives were integral in the Allied war effort against the Axis powers. These included the production of 100-octane aviation gasoline, a boost in domestic refined fuels capacity, a more efficient way to produce pure toluene and cooperation for the development of synthetic rubber.

100 octane: A decisive advantage in aerial superiority. In the mid-1930s, U.S. aviator Jimmy Doolittle joined Shell Oil Co. as Aviation Manager. His primary responsibility was to develop aviation fuels for military and civilian applications. Up until this time, both automobiles and aircraft ran off 87-octane gasoline levels. However, the lower-rated fuel severely affected aircraft engine performance, negatively impacting speed, climb rate, service ceiling and overall performance, especially at higher altitudes. Higher octane aviation gasoline (i.e., 100 octane) could fuel high-performance aircraft engines, boosting the performance of fighter planes.

After lobbying the U.S. Congress, Doolittle convinced the U.S. Army to adopt 100-octane aviation fuel as the standard fuel for aircraft. However, the fuel was extremely expensive to produce and prohibitively high to sell—the cost of 100-octane fuel was approximately $20/gal vs. less than $0.20/gal for regular automobile gasoline.50 The solution to this challenge came from a new process in operation at the Marcus Hook refinery in Pennsylvania (U.S.). The process was a catalytic cracking process developed by a French engineer: Eugene Houdry.

The Houdry process was greatly enhanced by octane-boosting processes, the most notable being invented by Russian-born chemists Herman Pines and Vladimir Ipatieff. Ipatieff, the Director of Chemical Research at Universal Oil Products (UOP) and a professor at Northwestern University in Chicago, was responsible for the development of solid phosphoric acid—a highly active refining catalyst created by treating silica with phosphoric acid.51 The catalyst was instrumental in increasing octane levels of gasoline. Ipatieff worked closely with fellow UOP colleague Herman Pines in the 1930s. The pair were instrumental in developing new polymerization, alkylation of aromatic compounds (i.e., alkylation)—Phillips (later called ConocoPhillips) invented the hydrofluoric acid (HF) alkylation process in the early 1940s to produce high-octane aviation gasoline52—and isomerization of paraffins (i.e., isomerization) to boost octane levels in aviation gasoline to 100. These new processes enabled the U.S. refining industry to produce affordable high-octane aviation gasoline, which would play a decisive role in WW2.

By 1940, the U.S. was producing more than 4.2 MMgpm of 100-octane aviation gasoline53—the standard fuel for the U.S. Air Force (referred to as the U.S. Army Air Corp prior to entrance in WW2). As war was declared in Europe, the U.S. gained its first customer for 100-octane aviation gasoline: Great Britain. The high-octane fuel powered Rolls-Royce Merlin engines inside British Hurricane and Spitfire fighter planes (FIG. 2), enabling them to gain a decisive advantage over the German Luftwaffe—most of Germany’s fighter planes ran on 87-octane aviation gasoline. The 100-octane aviation fuel was an invaluable asset that helped Britain push back German air attacks during the Battle of Britain and aided Allied powers in establishing air superiority (FIG. 3).

FIG. 2. The British Spitfire used 100-octane fuel-powered Rolls-Royce Merlin engines, enabling them to gain a decisive advantage over the German Luftwaffe during the Battle of Britain in WW2. The U.S. significantly boosted 100-octane fuel production, enabling the Allies to gain air superiority against the Axis powers. Photo courtesy of the Imperial War Museum.
FIG. 3. WW2 poster stressing the importance of high-octane aviation fuel. Spoken by U.S. Chief of Naval Operations Ernest King, the slogan “Oil is ammunition” was used for promotional posters during the conflict. Source: U.S. National Archives and Records Administration.

TNT. Trinitrotoluene (TNT) was first discovered by German chemist Julius Wilbrand in 1863. However, the first use of the material was for yellow dye. Approximately 30 yr later, German chemist Carl Häussermann discovered its explosive properties.54 TNT was used by Germany and other militaries starting in the early 1900s.

According to literature,55 Standard Oil Development (the company would later become Exxon) detected toluene in product streams from thermal reforming experiments on a petroleum-based naphtha. This discovery led to a new source to produce a significant amount of pure toluene. However, the produced product did not meet nitration-grade requirements. Upon using catalytic reforming, the process produced a 99+% toluene stream that could be nitrated.55 From 1940–1945, toluene production in the U.S. topped 484 MMgal, with nearly half being produced by Standard Oil’s subsidiary, Humble Oil and Refining Co. Approximately 15% was produced by Shell.56 This significant increase in production enabled the Allied powers to receive a steady stream of explosive materials.

Synthetic rubber. Although the discovery of synthetic rubber dates to the late 1870s (French chemist Gustave Bouchardat created a polymer of isoprene), the first true synthetic rubber was created and patented by German chemist Fritz Hofmann in the early 1900s.57 During WW2, the Allies were nearly cutoff from supplies of natural rubber—the Japanese occupied rubber producing areas in Southeast Asia, which represented 90% of the world’s natural rubber production.58 Without rubber, Allied vehicles and planes could not be built or repaired.

As a solution, the U.S. government partnered with four rubber companies—B. F. Goodrich, Firestone Tire and Rubber Co., Goodyear Tire and Rubber Co, and the U.S. Rubber Co. (the company would later become Uniroyal)—to find a solution to the rubber supply crises. However, to produce synthetic rubber, butadiene—its basic raw material—is needed. To produce much-needed supplies of butadiene, several U.S. refiners built new facilities to produce the product that would be used to increase synthetic rubber production.

Researchers at the four big tire companies set out on new processes to increase synthetic rubber production in the U.S. In 1940, while working at B. F. Goodrich, Waldo Semon—the inventor of an improved process for PVC production—invented a process for the copolymerization of butadiene with methyl methacrylate. The cost-effective synthetic rubber produced was marketed under the name Ameripol. Goodyear produced its own synthetic rubber—the process was patented by Ray Dinsmore—called “Chemigum.” The other rubber companies patented processes to increase synthetic rubber production, as well.59

However, in 1942, synthetic rubber producers were needed to boost production to aid the Allied war effort. The four rubber companies, along with the U.S. government, agreed upon a common process to produce synthetic rubber called GR-S (government rubber styrene), which was similar to Bina S developed by Germany. By 1945, the U.S. increased GR-S production to approximately 920,000 tpy.59 Due to this manufacturing juggernaut, Allied forces did not suffer from a shortfall in synthetic rubber for military equipment and vehicles.

Cyanoacrylates. In 1942, Harry Coover—while working at the Eastman Kodak company in the U.S.—was conducting experiments with cyanoacrylates. He was attempting to develop materials to build clear plastic gun sights for the Allies in WW2. However, while working with the materials, he noticed that it stuck to everything, making it very difficult to work with. According to literature, moisture caused the chemicals to polymerize, and since virtually all objects have a thin layer of moisture on them, bonding would occur in nearly every testing instance.60 Since the material was highly adhesive, the researchers rejected the commercial use of it.

It was not until 1951 that Coover and fellow researcher Fred Joyner recognized the potential of cyanoacrylates as a quick bonding substance. His team was researching heat-resistant polymers for jet airplane canopies. These tests showed the unique adhesive properties of cyanoacrylate—the adhesive required no heat or pressure to bond.60 Several years later, Eastman Kodak sold the material as Eastman 910, later marketing the material as it is known today: Super Glue. The material—still in use today for many applications—has a unique story in that it was discovered by accident, twice.61

Silicones. Although discovered in the 1850s, commercial silicones research and development would not take off until the 1930s. Early research was conducted by American chemist James Franklin Hyde while working at Corning Glass Works (FIG. 4). By using English chemist Frederic Stanley Kipping’s procedure for creating organic silicon compounds, Hyde was able to create a synthesized fluid that hardened into a rubbery mass.62 Kipping pioneered work in silicone polymers, even coining the name “silicone” in 1904.

FIG. 4. James Franklin Hyde works with a colleague on experiments in the Corning Glass Works’ lab. Photo courtesy of Dow Corning.

Hyde’s discovery enabled Corning to produce high-temperature motors and generators. Silicones were used extensively in ships and planes during WW2 as a cable and wire insulator.62 Hyde’s work created the first commercially useful silicone product and led to the formation of the Dow Corning Corp. in 1943—a JV between Dow Chemical Co. and Corning Glass Works. The company’s primary focus was to develop silicone products, including manufacturing products for the U.S. military in WW2. The company’s first product was Dow Corning 4, an ignition sealing compound that made high-altitude flight possible. The compound prevents corona discharge, enabling aircraft to remain at 35,000 ft for 8 hr. This benefitted the Allied powers since planes could be flown to the UK and North Africa vs. transporting them by ship, significantly reducing the risks of them being bombed and destroyed by Axis forces.63,64

Silicone continues to be widely used in many different industries and applications, including in automotive, construction, energy, electronics, chemicals, coatings, textiles and personal care, among others.

Unconditional surrender and post-war discoveries

On May 7, 1945, Germany unconditionally surrendered to the Allies. Japan did the same on September 2, 1945. These events marked the end of the 7-yr global conflict.

The end of the European conflict also saw the breakup of the largest chemical and pharmaceutical company in the world, IG Farben. The company was formed in 1925 as a merger of six chemical companies—BASF, Bayer, Hoechst, Agfa, Chemische Fabirik Griesheim-Elektron and Chemische Fabrik vorm. Post WW2, the company was broken into several different entities. Agfa, BASF and Bayer continued operations. Hoechst acquired several other companies over the next several decades, as well as spinning off portions of its business into independent companies, such as Clariant. Hoechst is presently a subsidiary of the French pharmaceutical company Sanofi.

Although WW2 had ended, the global refining and petrochemicals industries were just beginning. New technologies and discoveries continued to be made through the rest of the 1940s.65 In 1947, American chemical engineer Vladimir Haensel conducted experiments using platinum catalysts for upgrading petroleum. However, at the time, the use of platinum catalyst was thought to be impractical and uneconomical due to the costs of the precious metal. Haensel’s research showed that using miniscule amounts of platinum (0.01%) was enough for an effective process.66,67 This research led to a novel process to produce gasoline with a higher octane rating: Platforming. Haensel’s Platforming process also generated a higher yield of aromatic hydrocarbons, which are used in manufacturing plastics.66,67 The process was commercialized by UOP, and the first Platforming unit (FIG. 5) was built in 1949 at Old Dutch Refining Co.’s refinery in Michigan (U.S.). The Platforming process was instrumental in the eventual removal of lead from gasoline.

FIG. 5. Vladimir Haensel (left) developed the Platforming process. The first Platforming unit (right) went online in 1949 at Old Dutch Refining Co.’s refinery in Michigan (U.S.). Photo courtesy of Honeywell UOP.

The 1950s

Post-WW2 saw a significant increase in oil consumption and economic development in Europe and the U.S. New chemical and refining discoveries would continue to improve the lives of people around the world. The evolution of the global refining and petrochemicals industry in the 1950s will be examined in the April issue of Hydrocarbon Processing. This includes the discovery of polypropylene, high-density polyethylene, new catalyst designs, the first use of a computer control system in refining operations and several other advancements in refining and chemicals production technologies. HP

LITERATURE CITED

  1. W. R. Grace, “Our History,” online: https://grace.com/about-grace/our-history/
  2. U.S. Department of Energy, “Early days of coal research,” Office of Fossil Energy and Carbon Management, online: https://www.energy.gov/fecm/early-days-coal-research
  3. Mawn, P., “Oil and War,” Defense.info, October 24, 2018, online: https://defense.info/re-thinking-strategy/2018/10/oil-and-war/
  4. Spoonts, S., “How high-octane gasoline saved untold Allied pilots during WWII,” SOFREP, November 2021, online: https://sofrep.com/news/filler-up-how-high-octane-gasoline-saved-untold-allied-pilots-during-wwii/
  5. Jacoby, M., “Vladimir Ipatieff is the catalysis superhero you’ve never heard of,” Chemical and Engineering News, May 2019, online: https://cen.acs.org/people/profiles/Vladimir-Ipatieff-catalysis-superhero-ve/97/i19
  6. ConocoPhillips, “Our history: 1930–1949,” online: https://www.conocophillips.com/about-us/our-history/1949-1930/
  7. Shell, “High octane,” online: https://www.shell.com/business-customers/aviation/100years/more-uptime/high-octane.html
  8. Wikipedia, “TNT,” online: https://en.wikipedia.org/wiki/TNT
  9. Thinnes, B., “The military and the hydrocarbon: A love affair of over 100 years,” Hydrocarbon Processing, July 2012.
  10. Miller, K., “How important was oil in World War 2?” Columbian College of Arts and Sciences, George Washington University, online: https://historynewsnetwork.org/article/339
  11. Stern Rubber Co., “Origins of synthetic rubber before World War 2,” January 2015, online: https://sternrubber.com/blog/origins-synthetic-rubber-world-war-2/
  12. Wendt, P., “The control of rubber in World War 2,” The Southern Economic Journal, January 1947.
  13. American Chemical Society, “U.S. Synthetic Rubber Program, 1939–1945,” August 1998, online: https://www.acs.org/content/acs/en/education/whatischemistry/landmarks/syntheticrubber.html#:~:text=Semon%2C%20built%20a%20100%2Dpound,%2C%20Ohio%2C%20that%20same%20year
  14. Lemels on-MIT, “Harry Coover,” online: https://lemelson.mit.edu/resources/harry-coover
  15. Hiskey, D., “Super Glue was invented by accident, twice,” Today I Found Out: Feed Your Brain, August 2011, online: http://www.todayifoundout.com/index.php/2011/08/super-glue-was-invented-by-accident-twice/
  16. Wikipedia, “James Franklin Hyde,” online: https://en.wikipedia.org/wiki/James_Franklin_Hyde
  17. Dow history, “1930–1942: Researches,” ATF, online: https://www.atf.ru/en/about/about-atf/istoriya-dow-corning/
  18. Thomas, N. R., “Frederic Stanley Kipping—Pioneer in silicon chemistry: His life and legacy,” Springer, August 2010, online: https://link.springer.com/content/pdf/10.1007/s12633-010-9051-x.pdf
  19. Wikipedia, “IG Farben,” online: https://en.wikipedia.org/wiki/IG_Farben
  20. Gembicki, S., “Vladimir Haensel,” The National Academies of Sciences, Engineering and Medicine, 2006, online: https://www.nap.edu/read/11807/chapter/10
  21. Wikipedia, “Vladimir Haensel,” online: https://en.wikipedia.org/wiki/Vladimir_Haensel

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