Eugene Houdry, Catalytic Cracking, Charles G. Moseley The Ohio State University at Lima, Lima. OH 45804 I t is generally known that Allied bombing of Axis fuel production and distribution facilities caused fuel shortages which contributed to their loss to the Allies in World War I1 (1,2); however, it is not generally known that another very important factor in the Allied victory was their ability to mass produce an aviation gasoline which was superior to that of the Axis nations. The role of chemistry and of a mechanical engineer named Eugene Houdry in providing the superior Allied aviation gasoline is an interesting story. Aviation method octane numbers for the best mass-produced Axis and Allied aviation gasolines were 87-90 and 100+, respectively ( 3 4 ) . While this difference in octane numbers mav seem small. use of the bieher octane easoline nroduced significant improvement in most combat-rehed pe;formance factors for a typical World War I1 airplane. Examples of the improvements are a 15-30% increase in engine power for take-off and climbing (61, a 15-20% decrease in cruising fuel consumption with a similar increase in range (7),a 25% increase in payload (8,9), a 10%increase in maximum speed (10, l l ) , and a 12%increase in service ceiling ( 1 0 , l l ) . The basic reason for the superioritv of the 100 octane aviation gasoline is that i t was m&h more resistant to knocking than the 87 octane fuel and thus allowed use of more efficient, higher compression ratio engines (12). The importance of this superior fuel is indicated by the statement made in 1943 by Geoffrey Lloyd, Great Britain's Petroleum Secretary, that he did not feel Britain could have won the Battle of Britain without 100 octane aviation gasoline (13). The primary reason that the Allies were able to mass produce 100 octane aviation gasoline was that they had available products from catalytic cracking processes that were brought into commercial oueration in the United States -~~ in the late ~ - -~~~~ - ~ 1930's and early 19'40's. Although several important catalytic cracking urocesses were develoued durine this oeriod. the one which was commercialized first and the only one which was in production before World War I1 began was due primarily to the work of Eugene Houdry (14). Eugene Houdry was horn near Paris, France, on April 18, 1892, and received a degree in mechanical engineering from the Ecole des Arts et Metiers in 1911 (15,16). Upon graduation, he worked for the family steel business only a short time before being called to duty in World War I. After the war, he returned to the family business but also took up automobile racing as a hobbv. Through this activitv he became aware of the efforts of a N i c e pharmacist andinventor, E. A. Prudhomme, to produce gasoline from lignite. His orocess involved catalytic hydrngennt ion of carbon monoxidk produced hy the water gaq reaction of limite. Houdw was excited bv the potential valie of this procels to ~rance,whichwas th& experiencing one of its recurrent fuel shortages. Thus. in 1923. he organized a group to work with Prudhomme in an attempt to develop a commercial catalytic process t o make gasoline from lignite. The hydrogenation process showed little promise, but much better results were obtained with catalytic cracking. In spite of many difficulties, including a break with Prudhomme, the group succeeded, and in 1929 the plant began production. Unfortunately, although the process worked; i t did not prove to be economical, and the group was forced to shut down the plant after a short time. ~
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Houdry then began to pursue seriously development of catalytic cracking of crude oil, a process which he had first studied in 1925 with some success. By 1927 he had found a clay-Woe, -~~ . .. . silica-alumina catalvst which could crack even heavy, hard-LO-crack crude8 tn produce high quality gasoline. Houdrv also found a solution to the oroblem exoerienced hv all craiking catalysts: deactivation Eaused by gradual act;. mulation of carbon deoosits on the catalvst surface. He dip. . covered that introducing air to the reactbr and burning the carbon off the catalyst produced both catalyst regeneration and an important source of heat for the process heat balance (17). Houdry immediately began to seek support for developing his process, but most of the oil companies he contacted were indifferent; however, in 1930 he reached an agreement with the Vacuum Oil Company to develop jointly his catalytic cracking process. The initial test runs carried out a t Vacuum Oil's Paulsboro, New Jersev. refinerv were successful. and in 1931 Houdry, his French as&ciates,gnd Vacuum Oil formed the Houdrv Proress Corooration to continue thc develoonlent: however, after spending almost $1,000,000 to comme;cializ~ the process without complete success, Vacuum Oil began to lose interest as the depression deepened and the new management acquired in the 1931 merger with Standard Oil of New York began to function. Thus, Houdry sought and received the company's permission to seek financial support from other sources. After being turned down by numerous oil and equipment manufacturing companies, he reached an agreement with Sun Oil Company in 1933 to finance further research and development of the process. Houdry, his associates, and Sun Oil engineers worked together for more than two years and spent more than $2,000,000 to work out the details of a practical commercial process. The process which they developed utilized several fixed-bed reactors of silica-alumina catalyst and was semicontinuous with some reactors on stream while the others were being purged and regenerated (18). Socony-Vacuum began operating a semi-commercial, 2000-barrel-per-day plant for cracking light gas oil a t its Paulsboro, New Jersey, refinery in June 1936. Sun Oil brought on stream a full scale commercial 15,000-barrel-per-day plant for cracking heavy gas oil at its Marcus Hook, Pennsylvania, refinery in April 1937. Ry 1939, the two companies had operating or G d e r ionstruction-f~teen units with a total charging capacity of almost 220,000 barrels per day. During 1940 the units were improved by modifying the cooling system and switching from a natural clay catalyst to a superior synthetic silica-alumina catalyst developed by Houdry (14). The Houdry units offered refiners several advantages over competitive thermal cracking units including slightly lower operating cost, better ability to control the amounts of fuel oil and gasoline produced, and a much greater ability to crack heavy gas oils to gasoline; however, the chief advantage of the Houdry units was the higher quality of the products which they produced. Typical research oe&e numbers for gasoline from the Houdry process and the best thermal processes were 88 and 72, respectively. In addition, the heavier-than-gasoline product from the Houdry process (No. 2 furnace oil) was more ~
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valuable than the corresponding product from the thermal processes (heavy fuel oil) (14). From a national point of view, the most important benefit of the Houdry units was the advantages they offered in producing 100 octane aviation gasoline. The Army had initially tested 100 octane aviation gasoline in 1934 and found it to be far superior to the standard 87 octane aviation gasoline then in use (8); however, the supply of this new fuel was quite limited since it could be made only by adding required amounts of tetraethyl lead and high octane compouents such as isooctane (2,2,4-trimethylpentane),isopentane, or alkylate to aviation-base gasoline produced from relatively scarce high grade crudes. Fortunately, just before World War I1 began, the Houdrv units ereatlv increased the national caoacitv to produce 160 octane aviation gasoline. They provided in auantitv both a better aviatiou-base easoline for blendine with k g h o&ne compouents and by-product gases suitable for feeding to alkylation and other processes to produce the required high octane components. Use of the higher octane Houdrv orocess easoline tvoicallv cut in half the amount of expen&; high octane biehding components required to oroduce 100 octane aviation gasoline (15.19). By early 1942 all of the ~ o i d r units y were being used exclusivelv for oroduction of aviation easoline, and bv 1944 twenty:nine bf the units with a daily charging capacity of 375,000 barrels were in operation ( 1 4 ) . Houdry became an American citizen soon afwr American entrv into World War I1 and directed his efforts toward meeting the the critical national need for synthetic rubber. His efforts resulted in a new single-step catalytic process for dehydrogenating butane to butadiene (20). Two other improved catalytic cracking processes, both of which were continuous. were broueht into commercial oroduction in theearly 194b'y in time 1;)contrihute significa"tly Stanto the World War 11 aviation easolinesuoolv .. . (14.21). . dard Oil of New Jersey had higun work on catal&cbydroeenation and crackine of heavv oils in the 1920's and had worked on a continuous fluid catalytic cracking process as earlv as 1934. The orocess involved feedine continuouslv with the b i a~ powdered catalyst which could be transported as a fluid when aerated. The companv completed pilot olant development early in 1940, and b&aus;of the-threat of war carried out a "flash" build-UDfrom the small pilot plant t o capacity. three commercial units of 12,000-barrels-~er-da~ The first unit went on stream May 25,1942, a t Jersey Standard's Baton Rouge, Louisiana, refinery (22). Even before the Houdry fixed-bed process was commercialized, Socony-Vacuum bad begun work on a continuous catalytic cracking process which utilized a moving bed of pelleted catalyst traveling between a separate reactor and regenerator. Pilot-scale testing of this Thermafor catalytic cracking (TCC) process was begun in January 1941, and again, because of war concerns, a direct scale-up to two 10,000-barrel-per-day semi-commercial units was carried out. The units went on stream in October 1943 a t the Beaumont, Texas, refinerv of the Maenolia Petroleum Comoauv. . - . a Soconvvac"u;h affiliate (2i). Even with the hieh aualitv aviation-base easoline oroduced by the Houdry, flGid'cat&tic, and ~ ~ C ? p r o c e s i e mass s, production of 100 octane aviation gasoline would have been
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impossible without large amounts of high octane blending components produced by alkylation, isomerization, polymerization, and hydroforming processes. In many cases, as m construction of catalvtic crackine units. dramatic scale-uns from pilot to commer>ial scale u n k were carried out in order to increase oroduction as auicklv as oossible. The coo~erative efforts of the ~ e t r o l e u m ~ d m i ~ i s t r &for i o nWar ( P ~ w and ) the American oil comoanies resulted in a verv ranid increase in production of 100snd 100+ octane aviation gssoline from about 40,000 barrels per dav in 1911 toabout 200.000 barrels per day by ~ e c e m b k r1943. Production peaked at about 373,000 barrels per day in 1944 (23). The imoortance of Houdry's catalytic cracking process is indicated by the fact that it was used to p r o d u ~ e ofthe 9 ~ Allied aviationgasoline for the tirst two yearsof American participation in World War 11 116) ,-.,. Houdry continued to work on improved cracking processes after World War I1 and in 1948 introduced the continuous moving-bed Houdriflow process (24). He retired as president of Houdry Process Corporation in 1948 but two years later formed Oxy-Catalyst, Inc. to pursue an interest in use of oxidation catalysts for reduction of air pollution. He was awarded more than 70 oatents and numerbus awards for his mnnv ~~~. scientific a c h i e b e n t s . His awards included the 1948 pot; Metal from the Franklin Institute 1161. the 1959 Perkin~~Medal (25), and the 1962 ACS Award in 1nd"strial and Engineering Chemistry (26). Houdry received the awards not only for developing his catalytic cracking processes, his synthetic cracking catalyst, and his butane dehydrogenation process but also for beginning a catalytic revolution which led to much greater use of catalvsis in industrial chemical orocesses. The man who was known to many as.'Mr. ~atalysis"died onJuly 18.1962, ar. the age of 70 after a short illness (27,2d). ~
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Literat1ure- wrea ^"- ~' (1) Spaa,r,A.,"lnsidetheThirdReich?MacMillanPublishingCo..lne.,NewYork, 1970, pp. 350-351. (2) Krsmmer, A,, Tech. & Cult., 19,394 (1978). 13) French,S. J.,Sci. Amer, 166,167 119421. 14) Van Winkle, M.,"Avistion Gasoline Manufacture? Istod..Mffirsar Hill Bookcompany. Inc.,NewYark, 1944.p.28. . F., Not1 Petroleum N o w , 37, R851 (1945). (5) Faragher, W 16) Science, 87.9 11938). 17) Ref. 141, p. 252. 18) ForIune. 27,154 (1943). (9) Ickos,H. L.,"Fightin'Oil..'Alfred A. Knopf Co.,New York, 1943, p,116. (10) Leaver. G. A,, Oil & Gos J , 40,88 11942). (11) Eg1off.G..J.CHEM.EDUC., 18,582 11941). 112) Ret ( 4 1 , 236. ~ 113) ad. ( 9 1 , ~111. . 114) Williamson, H. F., Andrcano, R. L.,Dam. A. R., and Klase. G. C.,"The American Petroleum Industry," Northwestern University Press.Evanaton, 1963, Volume 11. pp. 61M20. 115) Fortuna, IS. 56 (1938). 116) Chem. Eng. Neurs.26.3339 (1948). 117) Ref. (141, P. 614. 118) Houdry. E.. Bun, W. F..Pew. A. E., Jr., and Peters.W. A.. JI., O i l & Gos J.,37,40
I241 (25) (26) 127) (28)
Pefmleum Reliner, 28.110 11949). Chem. En& News. 37.76 11959). Chem. Eng. Newa. 40.90 11962). Faragher, W. F., Cham. Ind. (London), 1870 11962). Chrm. Eng. Nelur, 40,130 (1962).
