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
Con­tributed by ACS

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
Con­tributed by ACS

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
Con­tributed by ACS

50 Years of Catalysis

1st DECADE: 1949 — 1958

  • Late 1940s to Early 1950s — Robert M. Mil­ton and Don­ald W. Breck, Union Car­bide, develop com­mer­cial syn­the­sis for zeo­lites — A, X, and Y types.
  • Late 1940s — Eugene Houdry devel­ops mono­lithic plat­inum cat­a­lyst sys­tem for
  • Early 1950s — Treat­ing exhaust gases from inter­nal com­bus­tion engines, founds — and begins com­mer­cial oper­a­tions at Yard­ley, Penn­syl­va­nia. Houdry is later inducted into the Inventor’s Hall of Fame.
  • June 11, 1949 — First meet­ing of orga­ni­za­tion that became the Catal­y­sis Club of Philadel­phia was held at the Uni­ver­sity of Penn­syl­va­nia. Paper were pre­sented by R. C. Hans­ford (Mobil), A. G. Oblad (Houdry), A. V. Grosse (Tem­ple U), T. I. Tay­lor (Colum­bia U.) and K. A. Krieger (U. Penn­syl­va­nia). A. Farkas, orga­nizer of this sym­po­sium, was selected chair­man of a com­mit­tee to form a per­ma­nent organization.
  • Decem­ber 1949 — Prof. Paul Emmett pre­sented a lec­ture at Tem­ple Uni­ver­sity and after­wards the Catal­y­sis Club of Philadel­phia was offi­cially formed, elect­ing A. Farkas chair­man and A. Oblad as Secretary-Treasurer. Almost one hun­dred signed up as members.
  • 1949 — First com­mer­cial oper­a­tion of UOP’s Plat­form­ing Process for naph­tha reform­ing, Old Dutch Refin­ing, Muskegon, Michi­gan; patents for Pt-Cl-Al2O2 cat­a­lysts to Vladimir Haensel.
  • 1949 — P. W. Sel­wood pub­lished his first paper on nuclear induc­tion and begins a series of clas­sic pub­li­ca­tions on the appli­ca­tion of mag­netic tech­niques in catal­y­sis. The results are sum­ma­rized in his book [P. W. Sel­wood, “Adsorp­tion and Col­lec­tive Para­mag­net­ism,” Aca­d­e­mic Press, 1962.]
  • March 2, 1950 — The Bylaws of the Catal­y­sis Club of Philadel­phia, as writ­ten by Grace Kennedy (wife of Robert Kennedy, promi­nent catal­y­sis sci­en­tist at Sun Oil), were adopted and still serve as the model for later formed clubs/societies.
  • 1950 — MILESTONE MEETING: The Dis­cus­sions of the Fara­day Soci­ety, Het­ero­ge­neous Catal­y­sis, No. 8, 1950. Top­ics included:
    • O. Beeck, Relates % d-character of metal and cat­alytic activ­ity for eth­yl­ene hydrogenation.
    • D. D. Eley, Cal­cu­lates the heat of adsorp­tion of hydro­gen on metals.
    • G. M. Schwab, Alloy cat­a­lysts for dehydrogenation.
    • D. D. Dow­den and P. W. Reynolds, Elec­tronic effects in catal­y­sis by metal alloys.
    • P. W. Sel­wood and L. Lyon, Mag­netic sus­cep­ti­bil­ity and cat­a­lyst structure.
    • M. W. Tamele, Sur­face chem­istry and cat­alytic activ­ity of silica-alumina catalysts.
  • John Turke­vich, H. H. Hubbell and James Hillier, Elec­tron microscopy and small angle X-ray scattering.
  • 1950 — Lin­ear rela­tion­ship between quino­line chemisorp­tion and cat­alytic activ­ity for gasoil crack­ing — G. A. Mills, E. R. Boedeker and A. G. Oblad, JACS, 72, 1554 (1950).
  • 1950 — Hydro­formy­la­tion cat­alytic species iden­ti­fied as HCo(CO)4 — I. Wen­der, M. Orchin and H. H. Storch, JACS, 72, 4842 (1950).
  • 1951 — A. Wheeler defines role of dif­fu­sion in deter­min­ing reac­tion rates and cat­alytic selec­tiv­ity — Advan. Catal., 3, 250–326 (1951).
  • 1951 — Paul Emmett uti­lizes 14C radioiso­tope in Fischer-Tropsch mech­a­nism stud­ies — New York Times reports that “Gulf Oil sci­en­tist makes radioac­tive gasoline.”
  • 1953 — Naph­tha reform­ing involves dual func­tional cat­a­lysts — mech­a­nism for reform­ing with these cat­a­lysts — G. A. Mills, H. Heine­mann, T. H. Mil­liken and A. G. Oblad, Ind. Eng. Chem., 45, 124 (1953).
  • 1953 — Karl Ziegler dis­cov­ers a cat­a­lyst sys­tem for poly­mer­iz­ing eth­yl­ene at low tem­per­a­ture and pres­sure to pro­duce lin­ear, crys­talline poly­eth­yl­ene– Nobel Prize awarded to Ziegler in 1963.
  • 1954 — Gue­lio Natta invents stere­ospe­cific poly­mer­iza­tion of propy­lene to pro­duce crys­talline polypropy­lene– Nobel Prize awarded to Natta in 1963.
  • 1954 — “Begin­ning” of cat­a­lyst char­ac­ter­i­za­tions using instru­ments with i.r. spec­tra for CO adsorp­tion on cop­per (R. P. Eis­chens, W. A. Pliskin and S. A. Fran­cis, J. Chem. Phys., 22, 1786 (1954)). This pio­neer­ing work soon included approaches to char­ac­ter­ize active sites for adsorp­tion on metal, metal oxide and acidic sites as well as dis­tin­guish­ing Brøn­sted and Lewis acid sites.
  • 1954 — John P. Hogan and R. L. Banks, Phillips Petro­leum, dis­cov­ers chro­mia cat­a­lyst for poly­eth­yl­ene production.
  • 1954 — B.F. Goodrich (S. E. Horne) and Gulf Oil announce use of Ziegler cat­a­lyst to poly­mer­ize iso­prene to dupli­cate nat­ural rubber.
  • 1955 — Sasol begins com­mer­cial oper­a­tion of Fischer-Tropsch cir­cu­lat­ing fluid bed reactors.
  • 1956 — Phillips Process — high pres­sure (500 psi) in hot sol­vent with sup­ported chro­mia cat­a­lyst did not, on the sur­face, look attrac­tive com­pared to Ziegler-Natta; how­ever, engi­neer­ing advances, cheap and high activ­ity cat­a­lyst, and ever increas­ing scale made the Phillips Process the world’s lead­ing source of polyethylene.
  • 1956 — First Inter­na­tional Con­gress on Catal­y­sis held in Philadel­phia — more than 600 atten­dees. Orga­niz­ing the Inter­na­tional Con­gress on catal­y­sis was con­ceived by the Catal­y­sis Club of Philadel­phia and received endorse­ment from the Catal­y­sis Club of Chicago, the Uni­ver­sity of Penn­syl­va­nia, and the National Sci­ence Foun­da­tion. [At the end of the acknowl­edg­ments it is noted the the orga­ni­za­tion of the Con­gress was planned by RL Bur­well, Jr, A Farkas, AV Grosse, H Heine­man, WR Kirner, KA Krieger, JM Mav­ity, AG Oblad and CL Thomas. The orga­niz­ers included peo­ple from Chicago.]
  • 1957 — On June 18, Her­cules opens the first Zigler cat­a­lyst based plant in the U.S.
  • 1958 — Merox Mer­cap­tan Oxi­da­tion Process _ UOP.
  • 1953 to 1959 — Patents granted in these years led to the com­mer­cial pro­duc­tion of three sig­nif­i­cant lin­ear poly­olefins: high-density poly­eth­yl­ene (1955– 56 by Hoechst, W.R. Grace, Her­cules and Phillips), polypropy­lene (1957–8 by Her­cules, Mon­te­can­tini and Hoechst) and stereo-specific rub­bers (1958–9 by Goodrich-Gulf, Phillips and Shell).

 

2nd DECADE: 1959 — 1968

  • 1960’s — Major advances in het­ero­ge­neous photocatalysis
  • 1960’s — Cat­alytic advances to allow low-temperature water-gas shift
  • 1960s — Sci­en­tific Design devel­oped processes to make chlo­ri­nated sol­vents and maleic anhy­dride. A major break­through was the devel­op­ment of a cat­a­lyst to oxi­dize p-xylene into puri­fied ter­phthalic acid.
  • 1960s — Devel­op­ment of the con­cepts of demand­ing and facile metal cat­alyzed reac­tions — intro­duced by Boudart and cowork­ers. M. Boudart, Adv. Catal., 20, 153 (1969)
  • 1959 — Obser­va­tion of olefin metathe­sis at Phillips Petro­leum — R. L. Banks and G. C. Bai­ley, Ind. Eng. Chem. Prod. Res. Dev., 3, 170 (1964); R. L. Banks, “Dis­cov­ery and Devel­op­ment of Olefin Dis­pro­por­tion­a­tion (Metathe­sis)” in “Het­ero­ge­neous Catal­y­sis: Selected Amer­i­can His­to­ries,” (B. H. Davis and W. P. Het­tinger, Jr., Eds.), ACS Symp. Series, 222, 403 (1983)).
  • 1959 — Dabco (trimeth­yl­ene diamine) was intro­duced by Houdry Corp. as a cat­a­lyst for the pro­duc­tion of ure­thane foams from iso­cyanates and alcohols.
  • 1959 — Nalco intro­duces 1/16″, and later 1/32,” extru­date CoMo– alu­mina hydrotreat­ing cat­a­lysts and intro­duced in Exxon Bay­town refinery.
  • 1960 — Eth­yl­ene to acetalde­hyde — Wacker Chemistry
  • 1960 — UOP intro­duces Hydrar Process for con­vert­ing ben­zene to cyclohexene.
  • 1960 — Com­ple­tion of Sohio’s acry­loni­trile plant at Lima, Ohio, based upon cat­a­lyst dis­cov­ered by J. D. Idol.
  • 1961 — Par­ing reac­tion in hydro­c­rack­ing, R. F. Sul­li­van, C. J. Egan, G. E. Lan­glois and R. P. Sieg, JACS, 83, 1156 (1961).
  • 1962 — Steam reform­ing with NiK2Al2O3
  • 1962 — Obser­va­tion of reversible bind­ing of H2 and C2H4 by Vaska’s Com­plex, IrCl(CO)(PPh3)2, L. Vaska and J.W. DiLuzio, JACS, 84, 679 (1962).
  • 1962 — Jour­nal of Catal­y­sis, the first sci­en­tific jour­nal devoted solely to catal­y­sis, begins pub­li­ca­tion with J. H. de Boer and P. W. Sel­wood as editors.
  • 1962 — Descrip­tion of “Vaska’s Com­plex,” the first to show reversible bond­ing of hydro­gen and ethene within the coor­di­na­tion sphere (L. Vaska and J. W. D. Luzio, JACS, 84, 679 (1962)).
  • 1963 — Sachtler proves, using 14C-labeled propene, that a p-allyl com­plex is formed dur­ing propene oxi­da­tion (W. M. H. Sachtler, Rec. Trav. Chim., 82, 243 (1963)).
  • 1963 — Ammox­i­da­tion of propene to acrylonitrile.
  • 1963 — The­o­ret­i­cal model for describ­ing ele­men­tary redox reac­tions for elec­trodes (R. A. Mar­cus, J. Phys. Chem., 43, 679 (1963)).
  • 1964 — Intro­duc­tion of rare earth metal sta­bi­lized X-zeolite for cat­alytic crack­ing by Mobil Oil — C. J. Plank, E. J. Rosin­ski and W. P. Hawthoren, 3, 165, (1964). Plank and Rosin­ski in the Inven­tors Hall of Fame.
  • 1964 — Olah announces “Magic Acid,” a mix­ture of HF and SbF5 reacts with hydro­car­bons to pro­duce sta­ble car­bo­ca­tions that are observ­able using NMR. G. Olah awarded the 1994 Nobel Prize in Chemistry.
  • 1964 — Olefin metathe­sis announced [R. L. Banks and G. C. Bai­ley, Ind. Eng. Chem, Prod Res. Dev., 3 170 (1964)] com­mer­cial­ized in 1966.
  • 1964 — Mech­a­nism for hydro­c­rack­ing — H. L. Coon­radt and W. E. Gar­wood, Ind. Eng. Chem., Process Design Dev., 3, 38 (1964).
  • 1964 — K. Tamaru sum­ma­rizes tran­sient cat­alytic stud­ies empha­siz­ing IR tech­niques (Adv. Catal., 15, 65 (1964)).
  • 1964 — Spillover of Hydro­gen from Pt/Al2O3 to WO3 (S. Khoobiar, J. Phys. Chem., 68, 411 (1964)).
  • 1964 — Bly­holder (J. Phys. Chem., 68, 2772 (1964)) sug­gested that CO adsorp­tion on tran­si­tion met­als can be described by a mol­e­c­u­lar orbital pic­ture of two con­tri­bu­tions to bond­ing, par­tial dona­tion of CO-5s charge to metal ds orbitals and back dona­tion from metal dp to CO 2p* anti­bond­ing orbitals.
  • 1964 — Startup by Mon­santo of the world’s first biodegrad­able deter­gents plant based upon C10-C14 lin­ear olefins obtained by selec­tive cat­alytic dehy­dro­gena­tion of n-paraffins.
  • 1965 — Wilkinson’s homo­ge­neous hydro­gena­tion cat­a­lyst, J.F. Young, J.A. Osborn, F.H. Jar­dine and G. Wilkin­son, Chem. Com­mun., (1965) 131. G. Wilkin­son is the 1973 Nobel Lau­re­ate in Chemistry.
  • 1966 — ICI devel­oped a moderate-pressure, low-temperature methanol syn­the­sis process employ­ing a Cu-ZnO/Al2O3 cat­a­lyst in a gas-recycle reactor.
  • 1966 — Intro­duc­tion of con­cept of hard and soft acids and bases to catal­y­sis (R. G. Pear­son, Sci­ence, 151, 172 (1966)).
  • 1966 — Devel­op­ment of a method to cal­cu­late the coor­di­na­tion num­bers of sur­face atoms in the sta­ble forms of small metal par­ti­cles (R. van Hard­e­veld and A. van Mont­foort, Sur­face Sci., 4, 396 (1966)).
  • 1967 — Intro­duc­tion of first bimetal­lic naph­tha reform­ing cat­a­lyst — Pt-Re-Al2O3 — need for pre­sul­fi­da­tion of a naph­tha reform­ing catalyst.
  • 1967 — Catal­y­sis Reviews begins pub­li­ca­tion with H. Heine­mann as editor.
  • 1967 — Atlantic Rich­field and Hal­con (for­merly Sci­en­tific Design) formed a joint ven­ture, Oxi­rane, to pro­duce styrene, propy­lene oxide and tert-butyl alcohol.
  • 1967 — Sum­maries of Lin­ear Free Energy Rela­tion­ships (LFER) in Het­ero­ge­neous Catal­y­sis (M. Kraus, Adv. Catal., 17, 75 (1967); I. Mochida and Y. Yoneda, J. Catal., 7, 386 (1967)).
  • 1968 — Shape selec­tive catal­y­sis — Selecto­form­ing with erionite.

 

3rd DECADE: 1979 — 1988

  • 1970’s — Rh-catalyzed hydro­formy­la­tion of propene.
  • 1970’s — Improved selec­tiv­ity for oxi­da­tion of ethene to eth­yl­ene oxide using Cs (or Cl) pro­moted Ag catalysts.
  • 1970’s — Intro­duc­tion of use of con­trolled atmos­pheric trans­mis­sion elec­tron microscopy for cat­a­lyst char­ac­ter­i­za­tion and kinet­ics of catalysis.
  • 1972 — Exten­sive stud­ies of metal alloy cat­a­lysts by Sin­felt and cowork­ers results in demon­stra­tion of dif­fer­ent activ­ity pat­terns as alloy com­po­si­tion changes for the hydrogenol­y­sis of ethane to methane and dehy­dro­gena­tion of cyclo­hexane to ben­zene (J. H. Sin­felt, J. L. Carter and D. J. C. Yates, J. Catal., 24, 283 (1972)).
  • 1974 to 1975 — UOP Purzaust Auto Exhaust Treat­ment sys­tem accepted by Chrysler and is installed on 1975 models.
  • 1974 — F. Sher­wood Roland and M. Molina dis­cover chlorine-catalyzed ozone deple­tion in the atmosphere.
  • 1975 — B. Del­mon orga­nizes the first meet­ing for the Sci­en­tific Basis for the Prepa­ra­tion of Het­erog­neous Catalysts.
  • 1975 — State of dis­per­sion of small Pt and Pd metal par­ti­cles in zeo­lites (P. Gal­leyot et. al., J.Catal., 39, 334 (1975)).
  • 1975 — Demon­stra­tion that poi­sons of metal­lic cat­a­lysts are selec­tive, decreas­ing rates of structure-sensitive and structure-insensitive reac­tions dif­fer­ently (R. Mau­rel, G. Leclercq and J. Bar­bier, J. Catal., 37, 324 (1975)).
  • 1976 — Mobil Oil man­age­ment announces the dis­cov­ery of methanol-to-gasoline con­ver­sion using their ZSM-5 zeo­lite cat­a­lyst (Chemtech, 6, 86–9 (1976)).
  • 1978 — Dis­cov­ery of the strong metal sup­port inter­ac­tion (SMSI) and its role in alter­ing the adsorp­tive prop­er­ties of the metal func­tion. (S. J. Tauster, S. C. Fung and R. L. Garten, JACS, 100, 170 (1978)).
  • 1979 — Ten­nessee East­man selects rhodium as cat­a­lyst for pro­duc­ing acetic anhy­dride from coal.

 

4th DECADE: 1979 — 1988

  • 1980’s — Intro­duc­tion of SCR (Selec­tive Cat­alytic Reduc­tion) for NOx con­trol on sta­tion­ary power generators.
  • 1980’s — New cat­alytic tech­nol­ogy com­mer­cial­ized in the U.S. dur­ing the 1980’s (J. Armor, Appl. Catal., 78, 141 (1991)).
  • 1980’s — Union Car­bide and Shell develop the UNIPOL process for lin­ear low-density poly­eth­yl­ene, which allows pre­cise con­trol over the product’s mate­r­ial prop­er­ties. The process was extended to polypropy­lene in 1985.
  • 1980’s — Demon­stra­tion that strongly elec­troneg­a­tive ele­ments rel­a­tive to nickel mod­ify chemisorp­tive behav­ior far more strongly than a sim­ple site– block­ing mech­a­nism would allow, sup­port­ing an elec­tronic effect (D. W. Good­man, “Chem. Phys. Solid Surf.,” Springer-Verlag, 1986, pp. 169–195.
  • 1980’s — Exper­i­men­tal evi­dence demon­strat­ing the restruc­tur­ing of sur­faces dur­ing cat­alytic reac­tions — e.g., the con­ver­sion of eth­yl­ene to eth­yli­dyne with expan­sion of the metal atoms around the car­bon atom (R.J. Koest­ner, M. A. Van Hove and G. A. Somor­jai, Surf. Sci., 121, 321 (1982) and show­ing the par­al­lel restruc­tur­ing of Pt and oscil­la­tion in CO oxi­da­tion (G. Ertl, Ber. Buns. Phys. Chem., 90, 284 (1986)).
  • 1980 — Very rapid ethene poly­mer­iza­tion by homo­ge­neous cat­a­lyst (CP2 Zr (CH3)2 acti­vated with cocat­a­lyst alu­mi­nox­ane) (H Sinn et. al., Angew. Chem., 92, 396 (1980)).
  • 1981 — Applied Catal­y­sis begins pub­li­ca­tion with B. Del­mon as Editor-in-Chief.
  • 1981 — Adsor­bate induced restruc­tur­ing of sur­face (M.A. van Hore et.al., Surf. Sci., 103, 190, 218 (1981)).
  • 1981 — Intro­duc­tion of con­straint index as a diag­nos­tic test for shape selec­tiv­ity using crack­ing rate con­stants for n-hexane and 3-methylpentane (V. J. Frilette, W. O. Haag and R. M. Lago, J. Catal., 67, 218 (1981)).
  • 1982 — Def­i­n­i­tion of Energy Pro­file for Ammo­nia Syn­the­sis (G. Ertl in “Solid State and Mate­r­ial Sci.”, CRC Press, 1982, 349).
  • 1982 — The first of a series of sil­i­caa­lu­minophos­phate mol­e­c­u­lar sieves pre­pared by Union Car­bide (now part of UOP).
  • 1982 — The con­cept of tran­si­tion state selec­tiv­ity for zeo­lite catal­y­sis intro­duced (W. O. Haag, R. M. Lago and P. B. Weisz, J. Chem. Soc., Farad. Disc., 72, 317 (1982)).
  • 1983 — Ash­land Petro­leum intro­duces RCC (Reduced Crude Crack­ing) with 40,000 blb/day plant.
  • 1983 — Enichen sci­en­tists report the use of tita­nium sil­i­calite (TS-1) as a cat­a­lyst for selec­tive oxi­da­tions with aque­ous hydro­gen per­ox­ide, includ­ing olefin epox­i­da­tion (M. Tara­masso, G. Pereyo and B. Natari, U.S. 4,410,501).

 

5th DECADE: 1989 — 1999

  • 1990’s — Fischer-Tropsch as a source of alpha-olefins.
  • 1990’s — Com­bi­na­to­r­ial approaches to cat­a­lyst screen­ing and new cat­a­lyst dis­cov­ery (e.g., K. D. Shimizu et al., Chem. Eur. J., 4, 1885 (1998)).
  • 1990’s — Selec­tive oxi­da­tion of ben­zene to phe­nol using (Fe) ZSM-5 catalyst.
  • 1992 — Com­mer­cial use of non-iron cat­a­lyst for ammo­nia synthesis.
  • 1992 — Syn­the­sis of MCM-41, the first uni­formly struc­tured meso­porous alu­mi­nosil­i­cate, announced by Mobil Oil (J. S. Beck, et al., JACS, 114, 10834 (1992).
  • 1994 — Top­ics in Catal­y­sis begins pub­li­ca­tion with Gabor Somor­jai and Sir John Thomas as Co-Editors.
  • 1995 — Intro­duc­tion of oxone cat­alytic con­verter for air­plane air purification.
  • 1996 — Cat­alytic con­verter selected by Fel­lows of the Soci­ety of Auto­mo­tive Engi­neers as one of the top ten achieve­ments in the auto indus­try dur­ing the past 100 years.
  • 1996 — Global Overview of Catal­y­sis — A Series of Reports for many coun­tries begins to appear in Applied Catal­y­sis A: General.
  • 1996 — MagnaCat Process for sep­a­ra­tion and remov­ing aged FCC cat­a­lyst oper­ates at a com­mer­cial scale.
  • 1996 — Mem­bers of orig­i­nal acry­loni­trile research team (l to r; J. L. Calla­han, G. C. Cross, E. C. Mil­berger, E. C. Hughes and J. D. Idol (F. Veatch, deceased)) at ded­i­ca­tion of plant site as National His­tor­i­cal Land­mark by the ACS.
  • 1999 — UOP Cyclar Process for the pro­duc­tion of aro­mat­ics for LPG.

 
Con­tributed by Burt Davis
Uni­ver­sity of Ken­tucky Cen­ter for Applied Energy Research
2540 Research Park Drive, Lex­ing­ton, KY 40511–8410
For more details and PDF files go to http://crtc.caer.uky.edu/history.htm.