Alex Mills: The catalyst chemist

George Alexander Mills

George Alexander Mills

, Age 90 of Hockessin, DE died April 28, 2004 at Christiana Hospital in Newark. He was born March 20, 1914 in Saskatoon, Saskatchewan, CN and became a U.S. citizen in 1942. He was a resident of Swarthmore, PA for 28 years; Bethesda, MD for 12 years; and Newark and Hockessin, DE for 20 years.

Dr. Mills was a chemist for over 40 years, making major contributions to industrial catalytic processes, particularly hydrocarbon fuels and petrochemicals including DABCO for polyurethanes. He was executive director of the Center for Catalytic Science & Technology at the University of Delaware until 1984; chief of the Coal Division Bureau of Mines; director of the Office of International Cooperation Fossil Energy at the Department of Energy in Washington, DC; and director of research at Houdry Process Corporation (Air Products) in Marcus Hook, PA.

He received the Henry H. Storch Award from the American Chemical Society; the Pioneer Award from the American Institute of Chemists; and the E.V. Murphree Award in chemistry from Exxon Mobil Research. He was elected to the National Academy of Engineering. He was author and
co-author of 143 articles in technical publications and held 60 U.S. patents. Dr. Mills was president of the Catalysis Society of North America from 1969-73. He served as chairman of both, the Fuels Division, ACS and the Petroleum Division,ACS at different times. He was chairman of the Philadelphia Catalysis Club during the organization of the First International Congress on Catalysis (Philadelphia, 1954-56). Finally he and his work were greatly influenced by his close cooperation with Eugene Houdry.

He received a BS and an MS from the University of Saskatchewan and a PhD from Columbia University, where he studied with Nobel Prize winner Harold Urey.
 
Contributed by Thanks to The News Journal (Delaware)

The Fluid bed reactor for cracking petroleum

The first commercial circulating fluid bed reactor, PCLA #1 (Powdered Catalyst Louisiana), went on stream on May 25, 1942, in the Baton Rouge Refinery of the Standard Oil Company of New Jersey (now Exxon Corporation). This first use of powdered catalysts in continuous operation allowed the efficient cracking of heavy gas oils to meet the growing demand for high-octane fuels. PCLA #1 was dismantled in 1963 after 21 years of successful operation. Today, more than 350 fluid bed reactors, including PCLA #2 and PCLA #3, are in use worldwide for the manufacture of fuels, chemical intermediates, and plastics.

The creation and development of the fluidized bed reactor system for catalytic cracking of petroleum was a cooperative effort that involved many talented scientists and engineers. The group, estimated at one thousand, represented the largest single concentration of scientific effort, up to that time, directed toward a common goal. Later during World War II, this effort was surpassed only by the radar and Manhattan projects in the United States.

Warren K. Lewis and Edwin R. Gilliland obtained patent coverage for the fluid bed idea. Professor Lewis was chairman of the Chemical Engineering Department at MIT and was one of the best known chemical engineers in the country. The patent describing the circulating catalyst fluid bed reactor-regenerator named Donald L. Campbell, Homer Z. Martin, Egar V. Murphree and Charles W. Tyson inventors, all employed by the Standard Oil Development Co. These patents were licensed to all the members of the Catalytic Research Associates.
 
From the American Chemical Society website. Read more at ACS Educational Portal:
The Fluid Bed Reactor
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The beginnings of the catalysis society in USA & the world

History of the Catalysis Society in USA

 
In 1949, a group of 7 scientists met in Philadelphia to discuss the possibility of holding regular meetings in the field of catalysis; they formed the Philadelphia Catalysis Club. In 1954-56 the Catalysis Club organized the 1st International Congress on Catalysis (ICC), which was held in Philadelphia in 1956 (attendance of over 600 persons). By 1965 several other catalysis clubs had been organized in the USA and together they formed the Catalysis Society of North America. The first national meeting of the catalysis society of North America was held in 1969. The recent 19th North American Catalysis Society meeting was held in Philadelphia in June 2005 with almost 1,100 attendees over 4.5 days of presentations in 6 parallel sessions. The ICC eventually spawned the International Association of Catalysis Societies (IACS). Separately, regional and national catalysis societies (such as EFCATS (Europe) and APACS (Asia)) have formed around the world as members of the IACS.
 
Contributed by Heinz Heinemann & John Armor
14 June 2005.

Sohio Acrylonitrile Process

Acrylonitrile is used to produce plastics that are impermeable to gases and are ideal for shatterproof bottles that hold chemicals and cosmetics, clear “blister packs” that keep meats fresh and medical supplies sterile, and packaging for many other products. It is also a component in plastic resins, paints, adhesives, and coatings. The acrylonitrile in those products was made by a process discovered and developed in the 1950s by scientists and engineers at The Standard Oil Company, or Sohio.

In 1957, Sohio researchers developed the “Sohio Acrylonitrile Process,” an innovative single-step method of production that made acrylonitrile available as a key raw material for chemical manufacturing worldwide. Sohio’s groundbreaking experimentation and bold engineering brought plentiful, inexpensive, high-purity acrylonitrile to the market, a principal factor in the evolution and dramatic growth of the acrylic plastics and fibers industries. Today, nearly all acrylonitrile is produced by the Sohio process, and catalysts developed at the Warrensville Laboratory are used in acrylonitrile plants around the world. Sohio became part of The British Petroleum Company p.l.c. in 1987. The acrylonitrile manufacturing and catalyst and licensing businesses are now part of INEOS.

The process is a single-step direct method for manufacturing acrylonitrile from propylene, ammonia, and air over a fluidized bed catalyst. Today, nearly all acrylonitrile is produced by the Sohio process, and catalysts developed at the Warrensville Laboratory are used in acrylonitrile plants around the world. James L. Callahan, a research associate at Sohio, coordinated catalyst research and development, including the discovery of improved methods of catalyst manufacture. James D. Idol, Jr., a research associate who supervised and carried out research and feasibility testing, holds the basic patent for the process.
 
For more details, see the ACS Edu­ca­tional Por­tal: The Sohio Acrylonitrile Process
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Mobil Research Team Inducted into the New Jersey Inventors Hall of Fame

Mobil research team, Clarence Chang, Dr. Anthony Silvestri and William Lang, were charged with doing exploratory research to open new frontiers in fuel and petrochemical technology. In 1972, while conducting an investigation of the reaction pathways of polar organic compounds on acidic zeolites, the key experiment was conceived that led to the discovery of the conversion of methanol to hydrocarbons, including gasoline-range, high-octane aromatics, over the synthetic zeolite ZSM-5.

This discovery became the basis of the Mobil Methanol-to-Gasoline (MTG) Process, the first synfuel process to be commercialized in 50 years, and sparked worldwide interest and research that continues to this day. In 1985, it was commercialized in New Zealand as the Gas-to-Gasoline Process, in response to the Arab Oil Embargo and the ensuing energy crisis. The process operated successfully for a decade before being suspended due to the end of the energy crisis and declining crude oil prices. However, because methanol can be made from any gasifiable carbonaceous material, such as coal and biomass, the MTG process may again play a vital role in a future of dwindling oil and gas resources.

This patent and associated patents revealed a new way to manufacture gasoline, bringing greater security and self-sufficiency to gasoline-reliant consumers, nations and the world at large. A graduate of Harvard, Clarence D. Chang is the author of over 60 papers and encyclopedia chapters, as well as a book, Hydrocarbons from Methanol. For his discovery, he was awarded the American Chemical Society 1992 E.V. Murphree Award and the North American Catalysis Society 1999 Eugene J. Houdry Award among other honors. He holds over 220 U.S. patents.

Dr. Silvestri authored or co-authored about 60 papers. In recognition of his professional accomplishments, Dr. Silvestri received the New York Catalysis Society Award for Excellence in Catalysis in 1984 and was named a Penn State Alumni Fellow in 1995. He holds 28 U.S. patents.
 
Contributed by Clarence D. Chang, Anthony J. Silvestri and William H. Lang
Mobil Central Research

Hydrogenation of Fats and Oils

This is a huge business (worldwide consumption of fats and oils was ~180 billion pounds in 2000) in which hydrogenation catalysts (first patented in 1902 in Germany) are used to control the shape, size and distribution of double bonds in fatty acids which allows one to modify the chemical stability and physical behavior of fatty acids or glycerides. Naturally occurring oils from soybeans, peanuts, coconut, cottonseed, sunflower seeds, corn, etc are used for many household products, such as margarine, cooking and salad oils, baking dough, etc. The partial hydrogenation of natural oils to shortenings, salad oils, toppings and various other edible products is among the largest application for hydrogenation catalysts, often Nickel based. Fatty acids, both natural and synthetic pervade many areas of industrial activity and are used in products such as detergents, cosmetics, candles and crayons. Vegetable oils derived from fatty acids and glycerol are build upon long chains of esters (glycerides) with varying levels of unsaturation (up to 3 double bonds per ester chain. Highly unsaturated chains are prone to oxidation (becoming rancid) in air, while partial hydrogenation improves their stability and consistency. Soy, cottonseed, and corn oil have different levels of C16 and C18 ester chains with varying levels of unsaturation. The function of the hydrogenation catalyst is to partially hydrogenate and isomerize double bonds in the ester chains, thus altering the chemical stability and plastic properties of the oils, while avoiding “over-hardening.”

Sources for more information:

  1. Fundamentals of Industrial Catalytic Processes, by R. Farrauto and C. Bartholomew, Blackie Academic, New York, 1997, pp 441-447.
  2. Hydrogenation of Fats and Oils: Theory and Practice, H. Patterson, AOCS Press, Champaign, IL, 1994

 
Contributed by John Armor
30 December, 2002

Engelhard Scientists Honored For Auto-Emission Technology Breakthrough

ISELIN, NJ, November 11, 2004— Local Engelhard scientists who invented a novel technology that enables automakers to cost effectively comply with increasingly stringent engine-emission standards, are recipients of a 2004 Thomas Alva Edison Patent Award.

The Research & Development Council of New Jersey presented Harold Rabinowitz, Ron Heck and Zhicheng Hu with the award which recognizes dedication to research and development that leads to truly innovative breakthroughs.

Rabinowitz, Heck and Hu were honored at the R&D Council’s annual awards dinner on November 11, 2004 at New Jersey’s Liberty Science Center.

“This invention is one of the critical enablers for a substantial increase in the efficiency of catalytic emission control without a significant increase in cost,” said Mikhail Rodkin, director of research and development, Environmental Technologies. “It’s also a good example of the ingenuity of Engelhard scientists in the face of a formidable technical challenge and market pressures.”

In the early 1990s, auto-emission systems typically contained two catalysts located under the vehicle floor away from the engine. Placing the catalysts there protected them from the extreme heat of engine exhaust gases, but led to a long warm-up time and high “cold-start” emissions (those during the first two minutes following ignition). To compensate for low catalytic activity at low temperatures, the catalysts had to contain significant amounts of precious metals, typically platinum and rhodium. The three Engelhard scientists invented a close-coupled catalyst system that changed this paradigm.

The essence of the discovery made by Rabinowitz, Heck and Hu was to employ a palladium catalyst with substantially no additional oxygen storage component in the first close-coupled position, followed by downstream catalyst that includes an oxygen storage component. This enabled the use of the more thermally stable and lower-cost palladium in the close-coupled catalyst without adversely affecting catalytic activity.

To date, close-coupled catalysts have been installed on an estimated 10 million vehicles worldwide. Their use has enabled many SUVs to have emissions comparable to those from automobiles.

Eger Murphree and the Four Horsemen: FCC, Fluid Catalytic Cracking

Donald Campbell, Homer Martin, Eger Murphree and Charles Tyson, who were known for their development of a process still used today to produce more than half of the world’s gasoline. These “Four Horsemen” were part of the Exxon Research Co. The world’s first commercial Fluid Catalytic Cracking facility began production for Exxon in 1942. The Fluid Catalytic Cracking process revolutionized the petroleum industry by more efficiently transforming higher boiling oils into lighter, usable products.

Their notable US Patent No. 2,451,804: A Method of and Apparatus for Contacting Solids and Gases describes their milestone invention. Over half the world’s gasoline is currently produced by a process developed in 1942 by the “Four Horsemen” of Exxon Research and Engineering Company. The world’s first commercial Fluid Catalytic Cracking facility began production for Exxon on May 25, 1942. The Fluid Cat Cracking process revolutionized the petroleum industry by more efficiently transforming higher boiling oils into lighter, usable products. When Exxon’s first commercial cat cracking facility went on-line in 1942, the U.S. had just entered World War II and was facing a shortage of high-octane aviation gasoline. This new process allowed the U.S. petroleum industry to increase output of aviation fuel by 6,000% over the next three years. Fluid Cat Cracking also aided the rapid buildup of butadiene production, which enhanced Exxon’s process for making synthetic butyl rubber–another new technology vital to the Allied war effort. By the 1930s, Exxon began looking for a way to increase the yield of high-octane gasoline from crude oil.

Researchers discovered that a finely powdered catalyst behaved like a fluid when mixed with oil in the form of vapor. During the cracking process, a catalyst will split hydrocarbon molecule chains into smaller pieces. These smaller, or cracked, molecules then go through a distillation process to retrieve the usable product. During the cracking process, the catalyst becomes covered with carbon; the carbon is then burned off and the catalyst can be re-used. Campbell, Martin, Murphree, and Tyson began thinking of a design that would allow for a moving catalyst to ensure a steady and continuous cracking operation. The four ultimately invented a fluidized solids reactor bed and a pipe transfer system between the reactor and the regenerator unit in which the catalyst is processed for re-use. In this way, the solids and gases are continuously brought in contact with each other to bring on the chemical change.

This work culminated in a 100 barrel-per-day demonstration pilot plant located at Exxon’s Baton Rouge facility. The first commercial production plant processed 13,000 barrels of heavy oil daily, making 275,000 gallons of gasoline.

Considered essential to refinery operation, Fluid Cat Cracking produces gasoline as well as heating oil, fuel oil, propane, butane, and chemical feedstocks that are instrumental in producing other products such as plastics, synthetic rubbers and fabrics, and cosmetics. During today’s Fluid Cat Cracking process, a boxcar load of catalyst is mixed with a stream of oil vapor every minute. It is this mixture, behaving like a fluid, that moves continuously through the system as cracking reactions take place. Fluid Cat Cracking currently takes place in over 370 Fluid Cat Cracking units in refineries around the world, producing almost 1/2 billion gallons of gasoline daily. It is considered one of the most important chemical engineering achievements of the 20th century. Fluid Cat Cracking technology continues to evolve as cleaner high-performance fuels are explored.
 
Contributed by National Inventors Hall of Fame website
1999

Early Automotive Exhaust Catalysts

When catalysts were first put on American vehicles in the fall of 1974 (1975 model year), their function was to catalyze the oxidation of CO and unburned and partially burned hydrocarbons to CO2 and H2O. All that was needed was to be sure that there was enough O2 present when the A/F ratios were too low to provide it ‘naturally’. For some vehicles, there was enough O2 present in the exhaust at most operating conditions to meet the emission standards (especially the easier 49-state Federal standards) and there was no extra hardware (or software) needed. On other vehicles, or in California in general, more O2 was needed when the A/F ratios were low than was in the exhaust, and provisions were made to add O2 by a ram air venturi horn or by an engine driven air pump, delivering air to the inlet to the catalytic converter. Doing this during startup of the engine would hinder the warmup of the catalyst, and there would have been some sort of control to prevent delivery of the extra air to the converter until some time had elapsed or some temperature had been achieved. In the simplest system, the air delivery might have been activated by the same control that closed the choke.

Meeting the NOx standards in the late 70s led to the three-component control catalysts, which were capable of using the CO, H2 and hydrocarbons in the exhaust entering the converter to reduce the NOx to N2 while they were being removed by reaction with the NOx and O2. However, removal of all three pollutants depended on providing an exhaust mixture with just exactly enough reductants as oxidants; this required the A/F ratio of the air/fuel mixture being exactly that required to theoretically burn all of the fuel to CO2 and H2O, or stoichiometric. This was achieved with a closed-loop system which included an oxygen sensor exposed to the gas leaving the catalyst that provided a voltage signal proportional to the deviation of the exhaust mixture from stoichiometry, and a feedback system (computer) to effect a change in the rate of feeding fuel to the engine to drive the exhaust composition (and sensor output) back to stoichiometry. The oxygen sensor was developed as the best way to do this, although work was done to try to develop CO sensors, etc., as alternatives.

Their are a number of good reviews which describe these changes, including those by Lester, Taylor, Hegedus, Briggs, etc. I would particularly suggest, for your purposes, L. L. Hegedus and J. J. Gumbleton, CHEMTECH, 10 (10) 630 (1980).
 
Contributed by George Lester
Adjunct Professor, Northwestern University and President, George Lester, Inc.
1200 Pickwick,
Salem, VA 24153
Phone 540 375 3154
Fax 540 387 2787
Skygeorge@aol.com

Cracking of crude petroleum to gasoline

The first full-scale commercial catalytic cracker for the selective conversion of crude petroleum to gasoline went on stream at the Marcus Hook Refinery in 1937. Pioneered by Eugene Jules Houdry (1892-1962), the catalytic cracking of petroleum revolutionized the industry. The Houdry process conserved natural oil by doubling the amount of gasoline produced by other processes. It also greatly improved the gasoline octane rating, making possible today’s efficient, high-compression automobile engines, During World War II, the high-octane fuel shipped from Houdry plants played a critical role in the Allied victory, The Houdry laboratories in Linwood became the research and development center for this and subsequent Houdry inventions.

The invention and development of gasoline-fueled motor vehicles has had a profound influence on human history providing transport for industrial products and employment for millions and determining where and how we live, work, and play. In the United States today, more than half of the 300 million gallons of gasoline used each day to fuel more than 150 million passenger cars is produced by catalytic-cracking technology. High-octane gasoline paved the way to high compression-ratio engines, higher engine performance, and greater fuel economy.

The most dramatic benefit of the earliest Houdry units was in the production of 100-octane aviation gasoline, just before the outbreak of World War II. The Houdry plants provided a better gasoline for blending with scarce high-octane components, as well as by-products that could be converted by other processes to make more high-octane fractions. The increased performance meant that Allied planes were better than Axis planes by a factor of 15 percent to 30 percent in engine power for take-off and climbing; 25 percent in payload; 10 percent in maximum speed; and 12 percent in operational altitude. In the first six months of 1940, at the time of the Battle of Britain, 1.1 million barrels per month of 100-octane aviation gasoline was shipped to the Allies. Houdry plants produced 90 percent of this catalytically cracked gasoline during the first two years of the war.
 
For more details, see the ACS Edu­ca­tional Por­tal: The Houdry Process
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