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

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.

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

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

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

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

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