in this issue
Revisiting the first cracker, in West Virginia, as shale rekindles interest
2:40 PM MDT | September 9, 2014 | —Lindsay Frost
The discovery of a cheaper and more efficient way to directly produce ethylene by George Curme in 1919 laid the foundation of the modern chemical industry. Applications for ethylene quickly spread beyond what had been originally conceived, including various plastic products used in several growing industries. The new technology of steam cracking from hydrocarbons to produce ethylene, and its derivatives—including ethylene glycol (EG), ethylene oxide (EO), and ethyl alcohol—would fuel the rise of US industry. It started with the first major commercial ethylene plant at Clendenin, WV, in 1920, built by Union Carbide. Carbide is now part of Dow Chemical.
Raw materials eventually dwindled in the area, and most petrochemical production gradually shifted to the US Gulf Coast. However, the cycle has come full circle thanks to shale. The Marcellus Shale extending from New York through Pennsylvania, Ohio, and West Virginia has prompted announcements of new crackers in the area. Shell Chemical is considering investment at Monaca, PA; Odebrecht and its affiliate Braskem are evaluating a cracker at Parkersburg, WV. Smaller start-ups, such as Aither Chemical, are also trying to raise financing for cracker projects. Shale is proving that history does, in fact, repeat itself.
After producing calcium carbide, Union Carbide’s founders formed the company in the late 1800s to sell the chemical, according to Peter Spitz’s Petrochemicals: The Rise of an Industry. Although ethylene was discovered long before in Europe—specifically Germany with coal as the feedstockthe key figure in this cheaper production method that spurred the development in the 1920s was George Curme, an American scientist who studied in Germany for many years. He returned to the United States in 1914 to begin work with the Mellon Institute, funded by the Prest-O-Lite company, which was absorbed into Union Carbide in 1917. During his work at the institute, he discovered that chemicals made from acetylene could be made more cheaply from ethylene because this route avoids the costly step involving calcium carbide manufacture. His first target was ethanol production, Spitz says.
Several feedstocks had been considered for ethylene manufacture—and some were successful. After Congress dropped the tax on grain alcohol in 1900, alcohol became the feedstock to make ethylene. However, once World War I started, alcohol became a critical material for food and explosives, so ethylene production via alcohol was shelved. Attention then turned to natural gas and ethane feedstocks, Spitz says. The abundantly available natural gas deposits in many states, including Texas, Oklahoma, New York, Pennsylvania, Ohio, and West Virginia, were now being taken into consideration. Low temperature fractionation was needed to separate ethane from other natural gas constituents, and if ethane could be successfully cracked, people could separate ethylene from uncracked ethane, Spitz says.
Warren Woomer, president of Manufacturing Management Services—a consulting firm for several industries—and a former Union Carbide employee, says Curme changed industry with this discovery. “Curme is kind of the father of the ethylene business,” Woomer says. “Curme made a statement in 1918 about the possibilities of all of the different chemicals you can make from ethylene. He was a big proponent of exploring the uses of ethylene.”
The next step for Curme was finding a partner—and Linde, with its refrigeration technology, fit the bill. After merging in 1917 with Prest-O-Lite and the National Carbon Company, Carbide was now the United Carbide and Carbon Co.—with its selling point being the new ethylene cracking technology. In 1920, Carbide and Carbon Chemicals Corp. was established with the goal of commercializing the production of a number of aliphatic chemicals. After experimentation at Linde’s plant near Buffalo, NY, the team needed to choose a site for the new plant—somewhere with ethane-rich gas and relatively cheap land to build on, according to Spitz. They came across West Virginia, specifically the Kanawha Valley region, because of its light hydrocarbon and condensate-rich natural gas. Technically, the first petrochemical plant was brought online in December 1920 by Standard Oil, the predecessor to ExxonMobil, at Bayway, NJ, producing isopropyl alcohol from refinery propylene, according to A History of the International Chemical Industry, by Fred Aftalion. However, it was Curme’s work and the West Virginia plant that proved the most fruitful.
“The chemical industry follows available raw materials,” says Kevin DiGregoria, executive director of the Chemical Alliance Zone—a nonprofit focused on industry growth in West Virginia—and a former Union Carbide employee. “In the late 1800s and before that, West Virginia had a lot of brine and salt. We also had coal, but natural gas and oil [are] what brought Union Carbide to the area. In those early days, we were not making ethylene from ethane yet, but the acetylene by-product was ethylene, and Curme figured out what we could make with ethylene.”
At the time, gas production in West Virginia was about 240 billion cubic feet/year, though in the 1920s oil and gas field operations were still primitive, with minimal processing to condition raw crude oil coming from the well, Spitz says. However, this West Virginian stream full of ethane and propane caught the eye of Union Carbide, which purchased a site at Clendenin in 1920. The company began work on developing the production system, preliminarily focusing on a more efficient method of carrying out the weathering process, i.e. bringing the stabilizing column to the correct freezing temperature for cracking.
After multiple failures, the Carbide team completed the project, and it went onstream in the summer of 1921. “The system developed at Clendenin is the precursor for thousands of plants built later to separate light hydrocarbon components in natural gasoline as well as to manufacture ethylene, propylene, and other light olefins,” Spitz says.
After this initial success, it was time to manufacture at commercial scale. The company spotted an abandoned Rollins Chemical plant at South Charleston, WV. This marked the first US plant specifically designed to produce ethylene, Spitz says. The plant was linked to a chlorohydrin unit, where the all of the ethylene output was converted in a single reactor sized at 10,000 lbs/day. Between 1921 and 1939, annual production of synthetic organic chemicals based on petroleum rose from 21 million lbs to 3 billion lbs, Spitz says. Throughout the 1920s, Union Carbide was producing ethylene, EO, and EG near Charleston, WV. By 1934, the company could make 50 derivatives from petroleum-based ethylene and propylene.
“Small-scale work was successful, and when there was a fire in the Buffalo plant, they started looking for larger facilities where there was the highest concentration of ethane in the natural gas,” Woomer says. “It so happens that in this part of West Virginia there’s about 6% ethane in natural gas; in other parts of the country, the number is considerably less. So, they found the Clendenin plant, and they thought that they could go ahead and buy the plant and use the plant to manufacture ethylene and propylene. Their main focus was to make the small ethylene plant, and they never considered making a large manufacturing plant.”
The biggest seller from the Clendenin and Charleston plants were pyrofax gas, Woomer says, which went into homes and burned easier than other gas available at the time. This gas gave Carbide a good source of cash to begin building the company. After derivatives were being produced, more uses were discovered, including the use of EG for glycol dinitrate to create more stable dynamite. Carbide also created cellosol and isopropynol, which was used to make acetone. Antifreeze for automobiles was another big discovery from the plants.
“We have a historically strong chemical industry in this state [because of] our raw materials,” DiGregoria says. “You can get ethane out before you can also use the natural gas for heating. It’s a double whammy. Ethane is used to make 70% of chemicals. We are essentially sitting on large raw material sources and close to end markets.” Woomer says the concentration of natural gas in the area is 90% methane, 6% ethane, 3% propane, and 1% butane.
Though the company had faced several challenges in the beginning, including inefficient separation and few roads between Charleston and Clendenin, its success continued. However, when the region’s natural gasrich areas started to dry, opportunities were searched for elsewhere—particularly in US Gulf Coast and Mideast.
“In the early 1970s, the price of petroleum was cheaper on the Gulf Coast. A lot of the cracking operations were shut down; Institute, WV, operations were shut down in 1972, and then all the manufacturing went to the Gulf Coast,” Woomer says. “But we [West Virginia] had all of the facilities still making the derivatives. They shipped ethylene oxide from the Gulf up here. We later built other derivative plants but continued in the Kanawha Valley—with the Marcellus Shale gas with [a] high ethane concentration years later.”
The US chemical industry has regained competitiveness in recent years as hydraulic fracturing fueled a surge in unconventional oil and gas production, including Marcellus, which has some of the most attractive economics. This development has shined light on West Virginia once again.
“We have talked to a number of companies interested in building crackers in West Virginia over the last four years. Not all are overseas, but most are,” DiGregoria says. “I would suggest eventually one to three crackers in this area will be built in the next 510 years.”
The most recent cracker announcement in the region have been by Oderbrecht and its Braskem affiliate. Oderbrecht in January closed a previously announced acquisition of Sabic’s site at Washington, WV, for the Appalachian Shale Cracker Enterprise (Ascent) project. Oderbrecht purchased the site for $11 million for the Ascent project that would include an ethane cracker, three polyethylene plants, and associated infrastructure for water treatment and energy cogeneration. Shell has an extended option to buy a Monaca, PA, industrial site that it has been evaluating for an ethane cracker since March 2012. This extension is the third—and final—on the option to buy, Shell says.
Marcellus is an advantaged location, Woomer says. A 500-mile radius around Charleston, WV covers several key US and Canadian markets, including New York; Detroit; Savannah, GA; Newport News, VA; and Memphis, TN. The region sits on a number of rail lines and barges that move through the Ohio River and the Mississippi River. “I’m very optimistic about this area,” Woomer says. “There is a good economic reason for [companies] being here and continuing to grow.”
DiGregoria says the region’s history contributes to its attractiveness, and current R&D there stems from innovation from the 1920s. However, the companies make their investment decisions based on potential profit, not the history of the region.
“The region’s history is something you can use to attract attention, but decisions are made in board rooms on whether they can make money,” DiGregoria says. “The fact that we had the first cracker is icing on the cake, but that’s not why companies are making their decisions.”
Today, the Kanawha Valley area continues to grow as an important production area, and industry is growing there because of shale gas deposits and location. DuPont, NL Industries, Bayer, BASF, FMC, Monsanto, and more large chemical companies have operated in the region at some point in the past 100 years.
The region also has strong innovation heritage. “Innovations [developed] around the world’s first cracker [commercial] in Clendenin helped Union Carbide create its South Charleston, WV, technical center, which sprang into one of the world’s top research and development centers,” DiGregoria says. “If you look at the top 500 chemicals produced globally, 200300 were thought of there. This technical park is now used as a basis of innovation to the future. And now, the story continues, with a new incubator solely focused on chemical-based technology.”