Petroleum Chemistry

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INDUSTRIAL AND ENGINEERING CHEMISTRY

the improvement of yields. I n the early eighties, Standard employed George Saybolt, probably the first full-time chemist t o be hired by the petroleum industry, to work on the standardization of product specifications and teqt mrthods. T h e real need for chemists in the refining industry became :ipparent in 1885, whtrn the Lima, Ohio, field was discovered. Everything made from this high-sulfur oil had a skunklike smell. The only use t h a t could be found for i t \vas boiler fuel in intlustries that ivere unconcerned with odor. It sold for 14 ccnts a barrc.1 compared to Pennsylvania crude a t $2.25. The ansiver t o the wlfur question was found by chemists. Herman Fr:isc-h came to Cleveland and developed a process for eliniinating sulfur by adding copper oxide t o the oil charged in the refinery. Standard purchased his patents and also employed tn-o chemists, Clarmce I. Robinson arid William 31,Burton, t o work on improvements. Burton, the first P1i.D. chemist in the petroleum industry: \vorked a t the nr\v Standard Oil refinery at \Tliiting, Ind. (2). The firpt products of the Khiting refiner?- were discouraging; the kerosene still had the strong smell of Lima crudr. Burtori set t o work in hie eniall laboratory on the second story of a f:irni house and in due time solved the sulfur problcni through improvements in the Fr:tsch process. He expanded his laboratory staff t o include G o r g e IT. Gray in 1896 and Robert E. Humphrej-s in 1900. Thc experience with Lima crude h:id given thc, petroleum industrj- a real lesson in the value of rcsearch and technology and spurred the industry on to modern refining processes. For\v:rrd-looking pc.trolcum men on the \T-eFt (’oast were also

Labels o n bottles of Kier’s Rock Oil amiounced thut petroleum possessed “wonderful medical iGrtues”

Vol. 43, No. 4

beginning to appreciate the value of science in the oil industry at about the same time ( 2 4 ) . K h e n the Union Oil C 0 . was organized in California in 1890, $2500 was appropriated for a l a b ratory. I n 1891, Frederick Salathc, a Swiss chemist who had claimed t o have a process which would refine the stuhborn California crude into a water-n-hite illuminant, was emplo>-ed a t the unheard-of salarl- of 810,000 per year. IIe was succeeded in 1893 hy S. F. Peckham, a University of California clieniist. .%t this time, the kerosene produced from California crude could not compete on equal terms with eastern oils, :ind Peckham had t o start on the ground floor. He told the directors: “The trouble with California crude is t h a t no one k n o w m y t h i n g about it. TTe d o not know what x e are working on and the results of our labor thus far have been sort of thrusts in the dark.” Progress was made, however, arid the Union Oil refinery succeeded in making good comniercial products. 111 1003, Clarence I. Robinson set u p the first special research laboratory of the industry at the Standard Oil C o . , Rayonne, X,I. Burton and his laboratory staff. which included R . I- hcst adapted t o their p:trticular prol,lems. Pome of the liquid phase processes either developed or put into operation during this period n-ere those of Cross, Dubbs, Fleming, Holmes->\laxiley (Texas Co.), Isom (Sinclair Refining Co.), Jenkins, and the ”tube and tank” process (Standa2.d Oil Co., Y7ew Jemey). Thew were also a number of vapor

I n 1865.wells and ofices of the Shoe a n d Leather Peiroleuin Co. occupied the side of a Pemsylvaizia hill

Large numbers of oil barges were anchored helter-sl;dtr r i n the Allegheny River in the early oil rush days

I n 1908, this battery of shell stills was operated at the B a y w a y refinery of Standard Oil of l’ew Jersey 81 1

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INDUSTRIAL AND ENGINEERING CHEMISTRY

phase processes, including those developed by Alexander, General Petroleum C o w . (Kashburn), Greenstreet, Hall, Parker, Ramagr, and Rittnian. -4lthough many of these vapor phase methods were p u t into commercial oI;eration, they were not so successful as the liquid phase processes. The McL4fee (Gulf Refining Co.) process is of interest because i t was the first example of commercial catalytic cracking. T h e first succesaful continuous method of cracking heavy oils was the Dubbs process, which could be operat,ed for over 20 days u-ithout a shutdown, as compared to about 2 days for the batchtype processes. T h e Dubbs process introduced the principle of “clean circulation,” which almost entirely eliminated coke deposits. In addition, it was the basis for the founding of the Vniversal Oil Products Co., the first company devoted wholly to research, development, engineering, and service. Toluene, Too. While t’he leading product of all of these processes was gasoline, the General Petroleum Corp. had a petroleum cracking process for making toluene, baqic material for TST ( 1 6 ) . During World K a r I, toluene ir~stallations costing S5,000,000 liere built a t General Petroleum’s Los -4ngeles refinerj- and a t Standard Oil of California’s plant near Sail Francisco. These two plants produced 3,000,000 pounds of toluene a month. Prior t o 1920, chemical treatment of gasoline was simple. It usually consisted only of washing with caustic soda or sodium plumbite solution, or treating with sulfuric acid followed by an alkaline wash. The latter treatment was used on all cracked gasolines. With the development of cracked gasoline, the necessity of solving the odor and color problems became more apparent. Although odor and color in cracked gasoline actually were not an indication of inferiority, consumers used these properties as their criteria for judging quality. Need for a Petroleum Division. Although the number of chemists employed in the oil industry waq small, there was yroning recognition of their importance in many branches of the industry. For example, Standard of Indiana’s chemical staff had grown from three in 1900 to thirteen in 1920 (9). Refiners had learned t h a t crude oils vary widely in their chemical composition and should be processed accordingly. The changing niarkers of the industry also called for research on new procorses. Xot orily was more gasoline needed but better gasoline. IG101vledge of the chemistry of the product showed promise of piuiiding a n s ~ i e r e to the problenis. The same was true of lubricants. The iiidu,Gtry w i also ~ beginning to appreciate the n w d for babic research. In 1911, the Gulf Refining Co. established a program of industrial fvIlo\\-,*liipsin petroleuni a t Rlellon Institute. This state of affairs existed when on January 1.5, 1915, Ilalph R . M a t t h e w wrote to Charles L. Parsons, secietary of the A~IERICAS CHEMICALSOCIETY, suggesting the formation of a new division devoted entirely to petrolcum ( 1 4 ) . Hcretofore, all papcrr dealing with petroleum had been prcsented before the Division of Industrial and Engineering Chemistry. Although Parsons n-as in favor of the formation of a petroleum division, he was fearful t h a t an insufficient number of members would be interrstcd and t h a t the petroleum industry would be reluct’ant, t o meet for the exchange of technical information. The urgent problems of World War I served to postpone further considerat’iori of the matter until 1920. 1920-1 940

Founding of the Petroleum Division. .4t the spring meeting of the AMERICANCHEMICALSOCIETYa t St. Louis in 1920, a number of chemists interested in a petroleum division again approached Parsons. H e suggested a survey t o determine whether a sufficient number of members would support such a division. Following up this suggestion, Matthews wrote t o his former professor, F. G. Cottiell, who was then director of the Bureau of Mines, t o ask for help from the Petroleum Division

Vo!. 43, No. 4

of the bureau. The matter was turned over to E. \.T;. Dean a t Pittsburgh and N. *4.C. Smith a t Washington. &an discussed the matter with W. .4. Hamor of Mellon Institute and obtained the wholehearted support of a number of chemists from t h a t institution. At the same time, Smith was working with Parsons to secure a list of representative chemists whose opinions should be asked. In February 1921, a questioiinaire was sent out t o determine interest (11). Ailthough the usual resistance t o a n y new organization was encountered froin a few who were active in other .societies interested in petroleum, the general response was excellent. Plans were immediately made t o hold a n organizational nieeting a t the Rochester ,4.C.S. meeting in April 1921. .4n attractive program was provided under the guidance of W.A . Gruse of Mellon Institute. T. G. Delbridge of the Atlaiitic Refining Co. was selected chairman and W. A. Gruse, secretary-treasurer, of the new seetion. While the nienibers were wrangling over the amount of dues to be assessed, C. F. Mabery of the Case School of ;\pplied Science illustrated his opinion t),v giving the treasurer $300. Alniost everyone followed his esaniplc, and this amount 5v:is them officially approved as the annual dues. Other matters scttl(,tl at the time included plans for the fall meeting a t N e w Turk arid a decision to furnish each inenibor with abstracts prvviour t o the meetings. Following the S t b w York mwting, a t which twelve papers w’re presented, a meeting WIIS scheduled for Birmingham in t.he ,spring of 1922. At the Birmingham meeting, the A.C.S. Council voted i o give the Petroleum Section divisional status, providcd acwptable bylaws were submitted a t the fall meet,ing a t PittPburgh (1922). The Council approved t’he bylaws submitted a t that t,inie and thus t,he Division of Petroleum Chemistry became a nJalit,j-. The first divisional officers were: T. G. Dclbridge, chairman; D. K. French, vice chairman; W.A . Gruse, secnxtarytreasurer; W.H. Fuln-eiler and E. W.Dean, executive conimitttv.

Significance of Early Programs. T h e titles of the papers at the early meetings of the Petroleuni Division indicate some of the important problems of the time ( 1 7 ) . Among the highlights of the first program was C. F. Mabery’s paper on “Petroleum Hydrocarbons T h a t Cannot Be Distilled,” one of the first reports on attempts to separate heavy hydrocarbons. llenibers iii attendance recall t h a t the blackboards Y(-ere covered with molecular formulas illurt,rating the giant compounds which 3Ialicxry disrussed. Thc paper on “Viscosity-Teni~ratule C’urvcs of FracrionF of TJ-pica1 iimerican Crude Oils” b v E. W. 1)c:in and F. IT, Lane as a forerunner of the classic I>wn and Davis v-i.scosity tables. Keen foresight v a s displayed by Sidney Born in his psper on “Petroleum, a R a n Material for Our Chemical Industries.!’ He called attention t o the possibility of using olefins from cracked gases to make alcohols. I11 addition, he st,ressed the important? of butadiene, predicting i t $ use as a synthetic rubber. The status of chemistry in thc petroleuni industry ~V:IS effectively summarized in B. T. Brooks’s paper, “Fonie Cheniical Considerations of Petroleum Refining” (8). He qucstionctl whether, i n practice, there was actually such a thing as a chemical technology of petroleum. Besides lauding the philosophy which had inspired the founding of t,he Petroleum Division, hr d r e ~ attention t o the need for more chemists in the oil industry and for the increased publication of research findings in the petroleuni field. He scoffed a t the “supposed value of secrecy” and stated t h a t “delay in publication sufficient for patent protection is reasonable but, beyond this, there is no excuse for the burying of scientific information in private office records.” Brooks stressed the importance of doing more work in nonbenzenoid chemistry. H e believed t h a t unsaturated hydrocarbons were not well enough understood and t h a t contemporarj. practices used in removing them resulted in great losses. The

problems of resin and t a r formation were also considemd. I k emphasized the necessity for stmudyingpolymerization reactions aF: a possible aource of lubricating oils. Research, he bcslievcd, \TWF the answer t o the iyfincr’s problem. How very right was hi, conclusion t h a t “economies . . . will more t,han cover the sum total of the cost of all petroleum investigations, even should thew investigations be undertaken on a very large scale indeed!” No discussion of the oracles who were present a t the initial meeting would be complete without a word on Thomas llidgley. Jr. Actually, the Petroleum Division did not hear until the, next year about his discovery of the use of tetraethyllead as an antiknock compound. rlbout the implications of antiknock properties and his predictions of increased nlileage through higher vonipiyssion ratios, Midgley said nothing t o the Rochester meetiiig. However, the distinct aroma of polecat vhich proclaimed hiF presence gave an inkling of things t o come. On questioning hy sonic of the more courageous members, he reiealrd that he had Iwen ivorking on diethyl t,c,lluridesand selenides i l l hiF s c ~ ~ r c h fiir aiit,ikriock compounds. The prograni at Yew York in the fall of 1921 attracted attentiori from distant areas because of the discussion on crude oil t.inulsions. One chemist came all the way from California t o 1’n.sriit a paper, and gratified t,he founding fathers of the division I)? saying that he had learned R great, deal mon‘ than he had given. Outstanding at the Birrninghani meeting in the spring of 1022 \\-asa paper on “The Pioneer’s Field in Petroleum Researcli” I)g Van H. l l a n n i n g of t,he A\nic,rican Petroleum Institutc. H(, listed 70 problems which needed investigation, and laid particu1:i r upon the necessity for studies of the physical arid cheincal constitution of petroleum. The immediat,e effect of his allpaal was the formation of a committee within the Petroleum Division to cooperate with Alarming. This paper also had a long-range effect aii one of thc first in M series of appeals which led t o thp establishnieiit ( i f the American Petroleum Institute’s fundaiii~ntalresearch projects a t leading universities in 1926. These projects, originally sponsored by grants of $250,000 each from John D. Rockefeller and the Universal Oil Products Co.. h a r e been of utmost importance in obtaining basic data in petroleum chemistry. Rapid Expansion and Improvement. The progre.+ of the petroleum industry during t,he two decades folloit-ing the birth 1 1 1 the Division of Petroleum Chemistry advanced motor transportation t o P. new high level. B y 1940, crude production had been more than tripled (to 1,328,000,000 barrels) through [letter production methods and the discovery of vast new field.; in Texas, Oklahoma, and California. Separation processes in t lie refinery advanced greatly through the ever-increasing Eriio\vl(~dyr~ of the physical properties of individual hydrocarboni. An;ilyticnl studivs ~i-cregreatly facilitated b y the introduction [ i f such equipment as the Podbielniak distillation apparatus. The cracking art \xis undcrgoirig rapid development throughout this period. Continuous processes, such as the improved Cross, Dubbs, Holmes-lIanley, and “tube and t:ink” processes, gradually superseded the original butch proccdurcls ( 7 ) . Some new vapor phase proceesef, including the Gyro process of the Pure Oil Co.. were also put into operation during this period. With these chuiiges came many new developments in equipmelit. Operating pressures, which had originally been 75 pounds per square inch, were increased to as high as 1000. Time of operation was lengthened, and it was possible t o build increasingly larger unite ( 9 ) ; the original Burton unit,s charged about 200 barrels per day and ran for only 48 hours without a shutdown, nhile by 1938, cracking units of 45,000-barrel capacity were in existence and runs Kere over 100 days. Catalytic Processes Introduced. T h e foregoing discussion indicated only the existing thermal processes. Although these constituted almost the entire cracking capacity before 1940,

Distillatton c q u i p m o i f i a i r x d tri zmcatigation of nc w petroleum process at thT Calajotstlia 1-h~r arch C o i p .

Houdry catalytic cracking unit supplies pilot plant data required ;for later design calculations

813

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INDUSTRIAL AND ENGINEERING CHEMISTRY

intensive research on catalytic processes for cracking and other hydrocarbon conversions was going on during the thirties. Catalytic polymerization was installed in 1934 for the conversioii of gases from cracking operations into high octane motor gasoline. T h e first catalytic cracking process was the Houdry fixd-bed. -4 unit of 200-barrels-per-day capacity was institllrd by thil Socony-Vacuum Oil Co. in 1934, arid a large unit was built nithin a few years by the Sun Oil Co. About 1938, till anothc~I~ catalytic process, called alkylation, made its appearance. Thiprocess enabled refiners t o make a high octane aviation fuc.1 conipoileiit from refinery gases. These processes ushered in a I ~ C I V vra of refining which as t o F a c h full scale proportions in thc, nest decade. These technical achievements, along Lvith automotive brought about major advancement in gasoline qualit concept of antiknock properties was introduced about 1922 with the announcement of the use of tetraethyllead as an mtiknock compound. The octane scale v a s devised a few yrars later. Furthermore, petroleum chemists had become aware of thi. fart that cracked gasolines had much better antiknock prolwrties. Higher octane motor gasoline \vas also made available through thermal reforming processes. Stimulated by aviation riaquirements, methods were sought to make gasoline of still higher octane rating. Through hydrogenation processes, the industry \vas able to supply limited quantities of 100-octane gasoline (lb’), h u t the octane number of most of the commercial aviation gasoline did not exceed 87 until alkylation proccsscs were p u t into operation. Another notable improvement in gasoline quality has been made possible through the use of antioxidants r2ither than sulfuric acid in preventing the formation of gum. The sulfuric acid treatment results not only in the removal of some high octane hydrocarbons b u t also in the formation of undesirable polymers a n d acid sludges. I n contrast, antioxidants eliminate gum formation by preventing oxidation, without the simultaneous removal of hydrocarbons. Moreover. antioxidants do not catalyze the formation of pol3-mers or sludges. Chemistry in Lubricant Manufacture. ,\lthough Inbricant~ are a smaller volume product of petroleum than gasoline, their quality is of equal importance. -1number of important advances in the field of lubricants rverc made during the twenties anti thirties. A4bout 1920, the centrifugal separator was introduced in dewaxing operations. Solvent dewasing began t o replace the plate press a n d centrifuging methods in 1927. T h e first process used benzene-acetone; a process utilizing propane was installed in 1931 and another using benzene-methyl ethyl ketone appeared in 1934. Gron-ing recognition of t h r importance of viscosity cam^ into the picture about 1925, when the industry became hig cerned over the cold-starting prohlrnis. By 1930, index \vas an established ynrdstick of the lubricant industrJ-. Solvent treating of luljricants FIBS initiated in 192!), T q - i t l i phenol as the solverit. -4 chlorex unit was installed iri 1!)32. a plant for furfural operatioil in 1033, and the first Duo-Sol (cresylic acid-propane) process in 1934. Propane deaephaltiiig was introduced in 1936. The first synthetic lube oil, ivliich n’:is the polymerizatiori product of cracked wares, appearctl in 1O30. rlpplication of high pressure hydrogenation to 1ul)ricating oil stocks began in 1932, with resultant improvement in qua lit^,. T h e use of chemical additives has played an inrreapingly i i i r portant role in improving the quality of lubrica~its. Shortlj. after 1920, the practice of adding small quantities of oleic. arid from vegetable and animal oils to impart oiliness came into use. Particularly noten-orthy was the introduction of oxidation inhibitors about 1928. T h e first use was in “lifctime” turbine oils, and since that time much progress has been made in the development of antioxidants for many types of oils. Pour-point depressors m-err introduced in 1930. ITse of viscosity index improvers began about 1933. The first of these was polyisobutyl-

Vol. 43, No. 4

ene, a p r d u c t derived from cracked gases. Others are ni:rde either wholly or in part from petroleum chemicals. In 1935, corrosion inhibitors and detergents vere first used. In 1!)3!), a combination detergent-inhibitor additive was introduwrl. The ne\v silicone antifoam agents appeared about 1911. Petroleum Division Advances with Industry. Tho a c i v , t ~ ~ c ~ . ; in gasoline and lubricating oil technology were aided immtvt*rlrably by tlie programs and tliscusbions providcd by the Divi>iott of I’etroleurn Chemistry. The great interest which had arist,ri in the chemical composition of petroleum products is evidenceti 1))- a Symposium on Properties of Pure Hydrocarbons h f o r e the tlivkion in 1923. The rising interest in luhricants during this pc>i,iodgave impetus t o a Symposium on Luhricntion in 1926 a t Tulm. The surcEss of this meeting is attested by the fact th:it attcmdnnce v a s higher than a t the general meeting of thr, docicty. The treating, handling, and application of gasoline,, :I$ i r ~ c l l:is s1wcial problems, were discussed in various symposia on “Pctrolrum and I t s Products” (1924), “Corrosion” (1825 J . “Sulfur in Pc~troleumand I t s Derivatives” (1927), and ”Comiiustion” (1029). Int,erest in the properties of hydrocarbons increased during the thirties. Symposium on Physical Properties of Hgdrocarbon Mixtures was presentrtl in the spring of 1933, a Symposium on Hydrocarbon Decomposition in the fall, and a Symposium on Chriracteristic Properties of Hydrocarbons and Their Derivatives as Related to Structure in 1937. Members PXchanged information on the developments in motor fuels at, the Symposium 0x1 Motor Fuels in 1936 and a t many general sessions. Increasing attention was also given t o the use of petroleum >is a source m:iterial for chemicals. Symposia were held on thr: “Chrmical Uti1iz:ttion of Petroleum Hydrocarbons” in 1937 and 0x1 “Plastics and Resins from Hydrocarbons” in 1939. .%I1 thcsc forward steps 1vei-e the result of the progressivenws of the pctrolcuni industry. Figures from the Standard Oil C‘o, (Indiana) are indicative. College-trained chemical personnel :tt that company had increased from 13 in 1920 t o 97 in 1931 : i r ~ c l had reached 150 in 1938 (9). The Standard Oil Co. (Selu. ,Jf,rwy), which c~rnploysthe largest number of scientists of any company in t h e industry, had formed a subsidiary company t o rch and development in 1922, a pattern which ha\ rincc becri folloiv-cd by many othrr rompanies (f5). The mrmbcrship of the I’etroleum Division kept pace. Thi. original membership of 30 increased to 337 in 1930 and 660 i r l 1940. T h e division also broadened its activities ( 1 4 ) . Tht~ custom of holding a division dinner was established iu 1021 arid has becn continucd throughout the ?.ears. These dinners have nlivays Ixen successful and have heen one of the, most pleasant soci:il event? at national meetings. Since the spring meeting in 1030, all papers have heen preprinted in full and distrihutt~tl to mcmlic~rsof the division prior to the meeting. 1940-1 950

Special Wartime Problems.

Mlien iTorld K a r I1 cam’,

~lir

terIinic2tl knowledge of tlie pc~trolcumindustry had reached a

highly advanced stage. -1s a result of concentrated researcli a i i d the ewhange of information through such orgaiiizatioiir :LX the Ilivirion of Petroleum (‘hemistry, the industry ~ v a qeuffic,ieiiil>-up t o date t o cope ivith the imperative problcms prewntcd by thc. war. The demands involved the production not only uf gwatly increased quantities of oil but also of entire,ly new produc~ts( 1 9 ) . The war brought about rapid commercializatioxi of the many pro( es ivhich have revolutionized the iridustry. T h c most outstanding contributions to the war effort \vew aviation gwoline, toluriie, and butadiene for synthetic rubbpr. Even before Prarl Harbor, -1merican oil companies n-ere eupplying the Allied powers with large volumes of 100-octane gasoline thr. iniport:i~ice of which is best illustrated by its effect 011 tho

Battle of Britain. The greater power and maneuverability of planes fueled b y 100-octane gasoline enabled British fliers to turn the tide of this battle against t h e S a z i air armada, which ran on 91-octane fuel. As t,he war progressed, aviation gasoline exceeded the 100-octane scale and new definitions had t o be set up t o describe it. Peak production of aviation gasoline reached 550,000 barrels per day. The largest single factor in this increase of quality and quantity of aviation gasoline was alkylation. A total of 56 alkylation plants were in operation by the end of the war. T h e rapid comnierci;dization of other catalytic processes was necessary for the production of sufficient raw materials for alkylation. The ailswer was found in isomerization processes, which w r c ready for comniercinl application a t t h a t time. Quantity production of other coniponents of aviation gasoline. such as isopentane and cumene, also required special processes. Production of base stocks was greatly enhanred by the widespread installation and improvenient of catalj-tic cracking procedures. The new Fluid Flow and T C C processes, which were comniercialized in 1942, had the decided advantages of permitting continuous operation and more econoniical use of catalyst. Fluid Flow units have been operated over 600 continuous days. Because of the ingenuity of petroleum chemists, enough toluene was available to provide for the utilization of ten times as mucth T K T during World K a r I1 as was consumed during World R-ar I. In 1939 when war broke out in Europe, the coal tar industry was the sole source of toluene. Alarmed a t the liniited quantities available from t h a t source, the industry took rapid steps to manufacture a nitration grade toluene from petroleum. The hydroforming process (catalytic reforming in the presence of hydrogen), which had been undergoing development since 1933, was p u t into operation and proved highly successful. During the &-st year of operation, the initial plant alone produced twice the previous peak rate of the coal tar industry. If petroleum chemists had not found ways of making butadiene in enormous quantities, the American stockpile of natural rubber would have been exhausted before World War I1 had been won. I n 1940, synthetic rubbers from petroleum had been developed and were in small quantity production for specialty uses. Foreseeing the disaster t h a t would occur should the Japanese cut off our supplies of natural rubber, work was begun on large scale production of butadiene. Out of this came the dehydrogenation processes for converting butane and butylene into butadiene, and a \Thole new industry was created in a short period of time. Also of considerable importance was t,he development of extraction processes for separating pure butadiene. Production of butadiene from petroleum reached one billion pounds in the postxvar y r a r of 1946. This quantity of butadiene permits the production of GR-S rubber in sufficient quantities t o make the Gnited States almost rlntirely independent of foreign supplies. .Ilthough GR-S constitutes the bulk of synthetic rubber production, the oil industry has developed other rubbers which arc particularly well suited for certain purposes. Perbunan rubber, which is oil-resistant, self-sealing, and flexible in extreme cold, was of high importance during the war. Butyl rubber, which became a commercial realit,\- in 1911, is far superior to the natural product for tire inner tubes. Lubricating oil :end grc~nsc~ technology also showed many rapid advances during the war. Our troops required machines that would run under the most severe weather condit,ions. Products were needed for every kind of use-whether in airplanes flying a t 60" below zero or in heavy tanks operating in desert heat. An increasing number of chemical additives came into use as well as synthetic lubricants. Although many scientific discoveries during the war period were necessarily held secret, the Petroleum Division continued t o provide programs on nonsecret subjects. RIang features of the catalJ-tic processes which had recently come into widespread

Catalytic cracking unit and storage tanks dominate fhc scene at Humble Oil refinery, Baytown, Tex.

V a c u u m distillation columns are a n important part of Shell Chemical's hexylene glycol plant 815

11-e were discussed. Papers on reaction mechanisms a n d catalyst ..tudies were also presented. h Symposium on Catalysis in t,he Pctroleum Industry was held in 1944. A number of the fundnmental studics on hydrocarbons, contributed by those engugrd in the h.P.1. rtjsearch projrcts, were presented before the division. “Bench Scale Techniques” were discussed a t a sj-mposiuni i n 1941. Because of the cron-ded condition of transportat,ion flicilities and hotels, no national meetings of t,lie Society n-err held in 1945, b u t the Pctroleum Division contribut,id a full program of papere :is a “Meeting in Print.” Postwar Increase in Demands. Despite many predictions tliat markets for petroleum products would decreav after the iwsation of hostilities, demands n-ere higher than ever before. Crude oil pt,otluct ion has increased from 1,325,000,000 barrels in 1940 t o an estimatcd 2 billion plus in 1950. ;\rotor fuel productioti ha.: i n c r e a d about 2 5 5 qince 1945 a n d over 4.57, xhive t l i t s p r c n nr ycar, 1941. The number of motor vehiclc1i:ti incrc,awcl :ahout 5 0 5 t o a total of 48,000,000. Both coniiiic.rci:il nut1 Iirivate flying are more popular now than c r e r ix,fore. The ovt~r-:iIlrt~sult~ lins licen a i 1 iiici r not onlyin t,he quantity l)ut a190 in the quality of g:isolitic Prwent-day autoniobilt,; rc’quirc inrich higlicr oct:rnc g:iwlinr than did the prewar niodcln Thil bcst prewar iJ conserved. Since 1925 there has tieen a continuow incrcn-(1 i n tlie octane numhrr :ind compression ratios of autonioliilt+ wliich has wsultcd in Ibotter efficirncy. Today 50% niorc iiiilcs:ige is cibt:iincd from each gallon of gasoline ( I O ) . ir1crc:i-e in the cjii:ility o f Livi:]tion gasoline e n a b l e ~ I R I I P ~ t o carry grratcir pa)-lo:iti~;ind opcixte at highrr speed? nnd v i t h iJI’ttc’r iii;itieuvc.rni)ilil~. 1lit, g r c tt,it ~ rise in t1c~nl:irirlfor prtroleunl products lias been

Phillips Petroleum uses these fractionhting columns in the production of liquefied petroleum gas

1

r .

in the di3till:ite EuPIs, xvhich include Diesel oil and liglil heating oil. Productioii of distill:it(’s has almost doubled from 172,800,000 Iiarrpls in I!Ml t o 332,800,000 barrels in 1950. The use of Diesel cngines by 1,:iilronds is 1:ii~gclyrcaponsiblt: for the growth in the Diesel oil iii:irktst. The rise in Ileatirig oil consumption can be attributed nininly t o the n.idcspre:id installation of oil burners for home Ileatirig. snon :IF burners were available after the imr, niany home on-ners took advantage of oil heating, which ixquires less manual 1:ibor and is c l ~ ~ : i i iand c ~ r more easily regulated than cmil henting. It is e$tim:itrcl th:it about 5,000,000 homes :ire i i o ~ v1io;itcd with oil. (hrcx of t iiix iiiolt, rapidly rsp:iriciing l~rnnclic~s of thc oil intluntry is tlict liqucficd petrolcum gas industry. Aci~ording ti> t h e l’hillips l’ctrultauni Co.. iinc of tlie most activr in this iiiilustry, pt,o,ii.i(.iiim i3 about ten tinies grr:tter tlinn in 1040. E d i n a t e d l%jO 1)roductiijii is 3 billion gallon^. xu stt)ry of t h ’ oil induPtry would l)o coiiipkte without n x n tion of asphalt, n-hich is produced t o the estent of ovrr 9,000,000 tons a yc:ir. Kowad:tyc, about $1070 of thc surfacing of d l I W T V highn-aye is of nsplialt, construction. Broad Expansion Program. T o niivLt lie demands for increased quantities and qualities of petroleum products after the war, the petroleum induitry has carrii,d out a $12,000,000,000 expansion program. Iieiinery capacity has been brought to 6,700,000 harrt9ls pc.r day. Of major importance is the fact t’hat prscticall?, : i l l neiv crncking installations have been cntnlytic. Compared t n thermal cracking, catalytic cracking produces more gasoliric and distillate fuel oils for which demand is high, a n d f;ir kiss residual oil for which demand is relatively low. It

Catalytic cracking unzt prod uces high-octane q o d i n r crt Gulf Oil’s Philndplphia. Pa.. r4finPry

At Bishop, Tex.,Celanese Corp. of &4merica turns out large variety of chemicals f r o m petroleum 816

xlsi, lit~i~iiiits much greater flexiliility, so t h a t gasoline yields can I)e illcreased in summer, while the percentage of heating oils can

be inciyased in wintertime. 1 - e iiistallations ~ of auxiliary processes such as polymerizution have also been iniportant in producing greater yields of high yuulit!- products. Reforming processes for raising the octane iiuniber of natural and straight-run gaeolines are also of consequence in meeting demands. Reccaritly a new catalytic reforming process called Piatforming i w s put into commercial operation. .Xirother factor rrhich is of high importance in meeting t h e demands for high quality gasoline is a great increase in facilities for producing tetraethyllead. K i t h an increase in motor fuel consumption and iniprovementP i n automotive engines, there have been corresponding increases i n quantitie3 and qualities of lubricating oils. Annual production has gone from about 35,000,000 barrels prewar t o 50,000,000 1)arrels in 1950. Present-day lubricants are tailor-made for ppecific uses. Synthetic lubricants and greases, such as esters. siiosanee, and phosphates developed during the war, and inorv recently all-purpose greases, a combination of lithium and cster type?, l m w come into the picture. Increasing use is being made of additives and some new ones have been developed-for esample, high Icvcl detergents diicli appeared in 1947. From tlie n-as fraction reniovrd during the deivasing operztion, the pctrolcum industry produces over 1300 tons per day of refiiicd \\--axes which are empluytd iii numerous applications, Kinging all the way from the coating of paper milk contaiiicrs t o tlie production of automobile poli91ies. Fantastic Growth of Petroleum Chemicals. For many years, litllt’ tiiought was given to petroleum as a source of cheniicnls t)e-l ::icohol, and about TOY0 uf the ethyl alcohol and methanol is ricLrived therefrom. Some alcohols of higher molecular weight :wt- niaclcs from the liquid products of cracking by the Oxo proceps. Ethylene glycol, another high tonnage product, is derived from petroleum gases. A large vari of chlorinated and nitrated products is also made from tlie g One of the outstanding ac1iirvenit:iits is the manufacture of glycc~rolfrom propylene. This process is also of importance l w u u i e of the many by-products, vhich include all~-lconipounds and the soil fumigant, D-D. hnother major technical ndvariceinent is the manufacture of phthalic anhydride by the osidation of o-sylene derived froiii catalytic cracking or hydroforming. Similarly, terephthalic acid is made from p-xylene. hroniatic hydrocarbons are also being produced in increasing quantities from petroleum. Formerly benzene waE produced alniost entirely by the coke-oven industry, which is geared to pig iron production. Present demands for benzene exceed the quantities available from that. source and increases in supply necessarily come from petroleum. In 1950, about 10,000,000 ,gallons a r e being made 1)y modified hydroforming processes xiid

Sight has descended upon the Richmond refinery o j S t a n d a d Oil Co. of California

Brilliant liglats illutniriafe a section of the Bayway refinery of Standard Oil Co. o j N e w Jersey

Fractionators and Hortonspheres for butadiene storage are located at Humble’s Baytown, Tex., rejinery 817

818

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

Vol. 43, No. 4

wl\vays under study, mith the result t h a t improvement8 are coni t is expected that the new Platforming process will further stantly being made. Similar activity in relation to other major augment the benzene supply. Thew processes can also produce products such as fuel oils, Diesel oils, and lubricants is also taking large quantities of other aromatics such as toluene and xylcnrs. place. The great variety of products which the petroleum indurThe petroleum chemicals have a r i d e variety of uses. The try supplies to agriculture has given rise t o special agricult~urnl largest volume consumer is the synthetic rubber industry, which research units. For instance, the Shell Development ( ' o ~ has utilized as much as one billion pounds of butadiene per year. operates esperimental farms in connection with its agricu1tiir;il T h e agricultural industry is another important market. I t depends on the petroleum industry for large quantities of in1:i horatorj-. Entirdy new factors are constantly arising t o act as a chaliengc~ secticides, soil fumigants, weed killers, fertilizers, and other to t h r i d u s t r y . .An r s a m p k is thr jet plane. Much work haa , products. heen tione on fuels for jrts and Eatisfactory ones have been prt)The skyrocketing plastics industry uses enormous amounts of clucttd, but a numbrr of prohlems remain unsolved. Out of thc a wide variety of petroleum chemicals Fuch as ethylene. T h r w research now going on will coni? tailor-made jet fuels arid pro(*is also a large potential market for petroleum-drrived i)ensi.tic, ;11 ( w e s for making them, just as special products and procesws plastics and resins based on styrene, phrnol, and other aromati(. ivvro found for high quality aviation gasoline. substances. Another problem a h i r h The synthetic detergent has recently attracted much industry, which has rrached Officers of the Division of Petroleum Chemistry, attrntion is synthetic. fuels one hillion pounds per year, 1921-1 951 from natural gas, c'oal, or is another large volume oil shale. \Thile the oil inconsumer. Of the active %retar>Chairman Year dustry is confident that ingredients used, petroleum I\-,.iGruse . T. Ci. Delbridgc 1921-1922 p