THEMAIN ENTRANCE VILLE,
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O F T H E EMERYLABORATORIES OF
SHELL DEVELOPMENT COMPANYIs SHOWN AT THE RIGHT; BELOW Is A U N I T FOR T H E SEMISCALE EXPERIMEKTAL PRODUCTIOX OF HIGH-BOILIKG ALCOHOLS
ment made a t the Sam Rem0 ConETROLEUM as a vital necessity BENJAMIN T. BROOKS ference of 1920, Japan and Germany in the economy Of in114 East 32nd Street, New York, N. Y. were among the have-nots until the dustrial nations has increased last few months. Until February, enormously since 1914. Russia and the 1942, Japan owned or controlled only sufficient petroleum United States are the only ones which produce their requireproduction to supply one third of the peacetime requirement of oil within their own territory, and since 1914 the role ment of her navy, assuming no industrial or other consumpof petroleum in world power politics has vastly increased. I n tion whatever. 1907 D’Arcy endeavored to interest American oil companies The first World War saw the shift from coal to oil fuel in in the great fields in Persia without result, and it was not the British and American navies, the first tanks, the first small until the summer of 1914 that his company succeeded in obbombing and fighter planes, the first motorized infantry in the taining sufficient British capital to develop these fields. little taxicab army of Gallieni. Since 1920, however, American oil companies have actively The present war finds the common uses of petroleum by the participated in developing the fields in Iraq, Bahrein and armed forces vastly increased as to quantity, and in addition Arabia, Venezuela, Colombia, Dutch East Indies, and other the oil industry has shouldered the production of the new 100countries, and have built refineries of important capacities octane aviation fuel, of toluene, and, in the last few months, in France, Rumania, Bahrein Island, Aruba, and Sumatra. of synthetic rubber to meet the military and civilian requireAlthough American oil companies were excluded from some ments of rubber, for ourselves as well as our allies. of these countries for a time by the British-French oil agree798
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July, 1942
INDUSTRIAL AND ENGINEERING CHEMISTRY
The ability to satisfy these new war needs is due to the fact that since 1912 the petroleum industry has greatly increased its staff of trained research and engineering personnel as well as production. In 1940,as compared with 1914,the American petroleum industry produced five times as much crude and thirteen times as much gasoline, had nineteen times the tonnage of tankers and twenty times the trained research personnel. The number of research workers in the petroleum industry is now about 6000,of which about 45 per cent are highly trained scientific men. There are 563 research workers for every 10,000 wage earners in the refining branch of the business, almost twice the ratio in the chemical industry (7).
Synthetic Rubber
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Germany the government stepped in and subsidized this research of the I. G. Farbenindustrie laboratories. Here the research was continued, without government aid, interest, or encouragement, mainly by Standard Oil Company of New Jersey and also by Shell Development Company, Phillips Petroleum Company working with Goodrich Tire and Rubber Company, and Universal Oil Products Company. I n Germany and Russia the synthetic rubber research was kept alive as a military necessity. I n the United States it was encouraged by the Stevenson monopoly plan, the high prices (sometimes more than $1.00 per pound) paid here for natural rubber, and the prospect that if our supplies of natural rubber were cut off, our oil and gasoline business as well as civilian transportation and military requirements would suffer. It was obvious, however, that since the cost of producing plantation rubber had come down steadily from about 24 cents per pound in 1912 to 7-9 cents in 1939, synthetic rubber in the United States was not likely to go beyond the research stage, except in an emergency such as the present one. As frequently noted recently in the press, the Standard Oil Company of New Jersey made an agreement with the German I. G. in 1929; one of the provisions gave the New Jersey company the right to operate in the United States under the I. G. patents on synthetic rubber, as well as full information regarding the research relating to these patents. In view of the fact that the acquisition by American companies of foreign patents has been portrayed in the press as an impropriety or worse, it may be pointed out that if the Standard Oil Company of New Jersey or some other American company had not acquired the American rights to make synthetic rubbers of the Buna S and Buna N type, no American company could have undertaken the manufacture of such products in the United States prior to December, 1941,except as a willful infringer, subject to heavy penalties if convicted. We expected also to have our patents respected abroad. There is every prospect that we shall be almost entirely dependent upon synthetic rubber for about ten years unless we acquiesce in the Japanese possession of Malaya or they are obliging enough to leave the rubber plantation undamaged when defeated. Also it appears possible that synthetic rubber may be produced a t a cost comparable with that of plantation rubber delivered in the United States. There has been steady improvement in the quality of the cured finished products made from synthetic rubbers. Butyl,
The production of synthetic rubber, or its essential raw material butadiene, has become one of the major war responsibilities of the petroleum industry. No other industry possesses both adequate trained technical personnel and the raw material required for the manufacture of 800,000 to 1,000,000tons of synthetic rubber. The necessary butadiene for this quantity of rubber can be manufactured by petroleum refineries without sensibly affecting the price or available supply of other petroleum products; in fact, the hightemperature cracking processes largely employed for this purpose are also a factor in making the large quantities of 100-octane aviation gasoline required by the United Nations. There has been a vast amount of research on synthetic culminating finally in the successful rubber since 1912 (n), work of the last five years in which the oil industry has played much the greater part. There is a certain timing, not unlike organic growth, in such developments. No matter how great the necessity, synthetic rubber could not have been produced in 1914-18 to satisfy our needs of even that time. The necessary foundation work laid by research had not then been carried out. Other processes not necessarily related to synthetic rubber had to be developed first. Thus one of our important raw materials of both synthetic rubber and 100-octane gasoline is the butane fraction of natural gas gasoline. I n 1912 the first samples of such gasoline were being produced by crude compression methods, and the butanes were lost by “weathering” in vented tanks before shipment or use. The art of fractional distillation had then hardly been applied to petroleum products, and the large-scale separation of hydrocarbons-butane and iRobutane, for example-had not been done. Cracking in 1914-18, relative to our present knowledge, was then in its infancy and catalytic dehydrogenation (12,19),butane+ butene + butadiene, was unknown. I n 1912 Duisberg, of the German Badische Company, exhibited a t the International Congress of Applied Chemistry in New York a pair of automobile tires made of synthetic rubber. This was pure showmanship, however, since only about 2300 tons of synthetic rubber were made in Germany during 1914-18. It was known as methyl rubber and was made from dimethylbutadiene derived from acetone (27). Yet up to 1936 synthetic rubber appeared to be so unsatisfactory for tires that chemists both in the United States and Germany seriously c o n s i d e r e d abandoning t h e project. I n ONE OF THE ORIQINALBURTON STILLS (No LONGER IN USE)
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Long after gasoline had become of major economic importance as a motor fuel, its physical properties, gravity, volatility, and color were considered to be the only useful properties; this notion was demolished by the studies of Midgley and Boyd (do), which led t o the discovery of the effect of tetraethyllead, and by the later studies of Edgar (4)and others. I n the winter of 1940-41 the average premium grade of gasoline sold in the United States had an octane rating (18) of 80.2 (C. F. R.). Just thirty years ago the Burton cracking process came into commercial operation at Khiting, Ind. This was the first real attempt to make the output of the major refinery products flexible, following demand. Responding to the stimulus of the success of the Burton process and also to the demands on the industry as a result of the war, the petroleum business began to go scientific, a change which has continued a t an accelerated pace up to now. Thus, according to Brown ( 7 ) , one major company employed six trained research workers in 1910, thirteen in 1920, thirty in 1924, ninety-seven in 1931 and one hundred fifty in 1940. The study of cracking led to the greatly improved processes of Dubbs, Roy and Walter Gross, and Holmes and Manley in the early 1920’s. Unreserved acknowledgment must be made of the role of engineers, geologists, physicists, and other specialists, particularly the engineers of the equipment manufacturers, during the renaissance years of 1920-30 when the petroleum industry was practically made over. The outstanding engineering achievements are too well known t o need recounting, although some of them, such as the pipe still and the bubble-cap fractionating tower, were almost incredibly delayed. Not until about 1924 did this type of fractionation find general and somewhat reluctant acceptance in the petroleum industry. But one noteworthy feature of this going-scientific period is that engineers, too, went scientific. Interesting exhibits would be typical data books of some of the major companies as compared with such a collection for 1914. Inspection of such a BUTYLRUBBER,A 100 PER CENT PETROLEUM PRODUCT book for 1940 would reveal the fact that about 80 per cent of ( T i g h t ) , Is IN GOODCONDITION AFTER THREE MILLIONFLEX- the data have been determined originally or more accurately URES, WHILENATURAL RUBBER (left) FAILED UKDER THE SAME since 1920. An enormous amount of effort and expense has COXDITIONS been expended in determining such data, without which modern equipment design would be impossible. Painstaking research thus bears a generally acknowledged symbiotic relaEvery great war has stimulated new technological develoption to good engineering. ments, many of which have been important enough to result In 1914 cracked gasolines were generally regarded as inin major economic dislocation after the war. It is probable ferior to straight-run gasolines and were usually drastically rethat the manufacture of synthetic rubber from petroleum fined with large losses. I n the early 1920’s their superior hydrocarbons is one of these major economic readjustments antiknock value was recognized and led to more rational which will endure after the war. refining methods; the use of antioxidants (19) nearly eliminated refining loss except in the case of high-sulfur cracked Gasoline gasoline, in which acid treatment a t low temperatures was It is eloquent testimony to the detachment of the academic found to be advantageous (14, 24). mind that until about 1920 most textbooks of organic chemNobody knows what the octane rating of gasoline commonly istry did not mention gasoline, a material of vast importance used in 1914-18 was. Aviation gasoline was solely straighta t least since 1900 and amounting to about 54 per cent of all run gasoline from selected crudes. I n the early 1930’s it aprefinery production; upon it the entire automotive industry peared that an aviation gasoline of 87 octane rating was about depends, and it has been the subject of research by hundreds the limit for large-scale production (3, 15, 17), using selected or thousands of the former readers of these quaint textbooks. straight-run gasolines with 3 cc. of tetraethyllead per gallon. Some of these guides to organic chemical literature mentioned Much credit is due the United States Army Air Corps for enpetroleum, and, if so, usually stated that petroleum was a mixcouraging the study and manufacture of aviation fuels of ture of paraffins, CnH2,+ 2, the word “paraffin” meaning inert. the order of 100 octane value, used first in a small way by the Finis. Army in 1935. The great increase in power and performance An editor of The American Chemist wrote in 1871 of the from 100-octane fuel mas fully appreciated by them ( 1 ) . The report which Silliman made in 1855 of his study of Pennsylconfidence of the Army Air Corps that the oil industry could vania petroleum: “In reading this report now, after sixteen solve the problem of manufacturing 100-octane fuel in adeyears of experience in the development of this important inquate quantities was shown when the engines of Army planes dustry, we are struck with the fact that its author very nearly were standardized for this fuel. Up to the outbreak of the presexhausted the subject, and anticipated and described most of ent war, however, foreign aviation authorities refused to follow the methods of treatment which have since been adopted by our example and regarded such fuel as only an interesting manufacturers.’’ experiment, even though the chemists of the Anglo-Iranian rubber (d6), an invention from the research laboratories of the Standard Oil Company of New Jersey, is made by the polymerization of isobutene with small proportions of butadiene. Heretofore it has been regarded as too soft for tires and inferior for this particular purpose to Buna s, the copolymer of butadiene and styrene. However, when cured and compounded, it is extremely resistant to deterioration by air oxidation, and recent results indicate that it can be successfully employed for tires. Its cost has been estimated as low as 12 cents per pound, and since the raw material is chiefly isobutene the process of manufacture is simpler, isobutene being much easier to produce than butadiene.
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Oil Company (2, 5) were pioneers in the development of alkylation by the cold concentrated sulfuric acid method. The research staffs of Anglo-Iranian, Humble Oil and Refining Company, Shell Development Company, Standard Oil Development Company, and The Texas Company cooperated in developing the process, and submitted a joint report at the meeting of the American Petroleum Institute in November, 1939 (9). The task of producing and purifying the large quantities of butane and isobutane required for conversion into aviation gasoline for our war program was made relatively easy by the experience gained in the liquefied petroleum gas business, which reached a volume of only 1,000,000gallons in 1927 but by 1941 had attained a volume of 446,000,000 gallons (2f). Although the first 100-octane fuel used by the Army Air Corps was made by polymerizing isobutene to isooctene, followed by hydrogenation, the large volumes of such fuel now being produced are made possible only by the discovery of alkylation (2) and selective catalytic polymerization (8, 16). Also, the quantity of alkylate which could be produced was a t first limited by the amount of isobutane available in natural gas gasoline and refinery products and the olefins in cracked gases from refinery operations; but almost as soon as the need for large production became apparent, it was found possible to isomerize n-butane to isobutane (8) and catalytically dehydrogenate simple paraffins to olefins (f 9, 13). Also in 1939 the manufacture of neohexane (2,2-dimethylbutane) by the thermal coupling or alkylation of isobutane and ethylene was announced (11, 29); this product had an A. S. T. M. octane number of 94.5 (without tetraethyllead). Research on catalytic processes has resulted also in the c a t a l y t i c reforming or “hydroforming” p r o c e s s (26) installed commercially in 1941, by which either high-octane gasoline or aromatic hydrocarbons, including toluene, can be produced. C a t a l y t i c cracking is exemplified in the Houdry p r o c e s s (10)a n d S t a n d a r d Oil of New Jersey’s fluid catalytic process, announced last year.
Toluene from Petroleum In 1914-18 small a m o u n t s only of toluene were made from petroleum. I n England the effort w a s concentrated upon producing it from certain crude oils from Borneo which are unusual for their content of aromatic hydrocarbons. T h e pro-
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duction of toluene in the United States during 1914-18 was practically limited to about 18,000,000 gallons annually from the coking of coal. As contrasted with the earlier World War period, the manufacture of pure toluene, readily nitrated to TNT, is being manufactured from petroleum without difficulty in the quantities desired by the military authorities. The large quantities of T N T required in the present war for depth bombs, aerial bombs, and shells could not be produced except for the toluene now being made from petroleum.
Synthetic Chemical Manufacture
Until recent years the manufacture of organic chemicals from petroleum was regarded as too small, relatively, to interest the executives of the petroleum industry. And it is a curious fact that for many years the attempts to solve the synthetic rubber problem were concentrated upon making isoprene from turpentine, butadiene by the pyrolysis of cyclohexane (from the hydrogenation of benzene, a process contributing somewhat to our present synthetic rubber program), butadiene from 1,3-butylene glycol, and dimethylbutadiene from acetone through pinacone (27‘). Fortunately the manufacture of synthetic organic chemicals from petroleum had been given serious attention by a few companies before the task of making butadiene for a million tons of synthetic rubber was undertaken. The perspective has altered a great deal. Aside from synthetic rubber, the war demand for many products is being met to a large extent by the oil industry. Ethyl alcohol is now b e i n g m a d e from ethylene in three plants, and a fourth will be in production in a few weeks. Ethyl alcohol can be made from ethylene more cheaply than by the fermentation of any raw material except abnormally low-price molasses. Synthetic ethyl alcohol is here to stay. As in many chemical enterprises, one process is closely interrelated to a series of others. The same plant which makes and separates pure ethylene for synthetic ethyl alcohol may also convert ethylene to ethyl chloride, heretofore made from alcohol, and this in turn is utilized in the manuf a c t u r e of t e t r a ethyllead. The same cracking plant which makes ethylene inevitably produces propylene and may also yield THE BAYWAY REFINERYOF STANDARDOIL butadiene. PropylDEVELOPMENT COMPANY
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series of high-molecular-weight polymers, including a saturated rubberlike product and viscous oils useful in improving the viscosity characteristics of lubricating oils. It is also used in the manufacture of tert-butylphenol, a raw material for modified Bakelite resins, and one company has produced from it no less than seventy other chemical products of commercial interest. Isobutene and butadiene are by far the most valuable individual hydrocarbons now known. Several well-known chemical companies, not petroleum refiners, are utilizing petroleum products, fractions, or cracked gases in the manufacture of synthetic materials. The glycol series is well known. Another company manufactures amyl alcohol, acetates, and amines from pentane and another has developed the manufacture of the commercially new nitroparaffins. None of these synthetic products were made on a large scale during the last war.
Lubricants
MULTIPLEFOUR-BALLMACHINEFOR RESEARCHO N TEE WEAR-PREVENTING PROPERTIES OF LUBRICANTS AT SHELL DEVELOPMENT COMPANY’S LABORATORIES ene is converted to isopropyl alcohol and the latter into acetone by catalytic dehydrogenation. The production of isopropyl alcohol has grown from 37,500 gallons in 1922 to 32,000,000 in 1940, and acetone, which formerly sold for 10 to 20 cents per pound has been marketed at 5 cents. The large-scale production and purification of ethylene also has a special potential significance during the present war. I n 1914-18 all of the mustard gas (dichloroethyl sulfide) made in Germany and by the Allies was from ethylene derived from alcohol. Germany introduced mustard gas into the art of war and for a time enjoyed the monopoly of its use, but when the German plants were inspected after the Armistice, the manufacturing capacity of the mustard gas plants built in allied countries was found to be thirty-four times the German production capacity (23). This was partly due to the discovery of the Pope-Levinstein process of treating ethylene with sulfur chloride. If mustard gas should be used in the present war, the petroleum industry could readily furnish ethylene in abundance, and the bottleneck, if any, would be chlorine, not ethylene. I n the last war a serious shortage of glycerol developed. Should this happen again, glycerol can readily be made from propylene. In the last war ethylene glycol had not been manufactured on a large scale. It finds an important place in the present war program as a cooling fluid in liquidcooled aircraft engines, as well as in replacing alcohol as an antifreeze material for military and civilian motor vehicles. Acetone, mentioned above, is used in the manufacture of one type of smokeless powder; i t is utilized in one important process for the manufacture of acetic anhydride, the conversion by pyrolysis t o ketene and then to the anhydride. The importance of isobutene in the manufacture of Butyl rubber and aviation gasoline has been mentioned. In the 1920’s no industrial use was made of this olefin except as fuel with other residual refinery gases. I n 1929 several tank cars of tert-butyl alcohol were manufactured, incidental to the production of sec-butyl alcohol, but the tert-butyl alcohol found no important use. Isobutene is also converted to a
The problem of lubricating large airplane engines over long flights has been solved, and the manufacture of greatly improved lubricants in adequate quantities has been made possible through research. In the last war we used substantially what Nature gave us in the lubricating oils contained in various crude petroleums. The industry has since learned how to produce lubricating oils of the best viscosity characteristics from many crudes by the various methods of solvent extraction (9) and manufactures superior “extremepressure” lubricants for gears, very heavy duty bearings, and tool cutting. The liquid propane method of dewaxing and deasphalting residual oils is also a development of the last decade (6). The interest of petroleum executives in research is well shown by the cordial support given the research projects carried out, under the supervision of the American Petroleum Institute, with funds given by Universal Oil Products Company, by John D. Rockefeller, and, since 1930, by various oil companies. These projects were started in 1924. They were planned to be fundamentally scientific in character so as not to conflict with any company interest; it was believed that thereby centers of interest in petroleum research would be created (for example, in universities) which would endure. This expectation has proved well founded, as shown by the many valuable researches subsequently carried out a t Princeton, Pennsylvania State, Ohio State, California Institute of Technology, Northwestern, Massachusetts Institute of Technology, the National Bureau of Standards, and elsewhere. The sum total of petroleum and fundamental research on chemical and other matters of interest to petroleum technologists is, however, overshadowed by the vast amount of research done in the laboratories of the industry itself. It is also noteworthy that much of the research carried out in company laboratories which is of scientific value has been published in the scientific and technical journals. This liberal policy regarding publication can be explained only by the common belief in the protection afforded by our patent system and the integrity of the courts. The criticism of our patent system as favoring monopolies loses much of its force in view of the liberal licensing practices of the oil companies. All departments of the petroleum industry have gone scientific. The use of geophysical methods in finding oil-bearing structures began in this country about 1922. Wallace Pratt states that, of 163 major fields of more than 20,000,000 barrels ultimate recovery discovered by petroleum geologists, 155 were found between 1910 and 1939. Four major fields were discovered in 1920-29 and sixty-one in 1930-39 by the aid of geophysics. The same authority states that in 1939 the following types of geophysical study were used by field parties in the United States:
INDUSTRIAL AND ENGINEERING CHEMISTRY
July, 1942 Method of Exploration Seismic Torsion balance Gravimeter Magnetic Eleatrical Electrical well log Soil gas analysis
Number of Field Parties 226 40 40 26 13 50
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The study of crude oil emulsions has resulted in widespread use of the electrical and chemical precipitation methods. It has been estimated that the amount of crude petroleum recovered by these two methods amounts to at least 90,000,000 barrels annually. Many of the noteworthy accomplishments of petroleum technologists have been the result of groups of men rather than individuals. This was recognized in the Award for Chemical Engineering Achievement in 1939 to the Standard Oil Development Company. The same cooperative group effort characterizes many of the technical staffs of American oil companies. In 1938 Walter Teagle wrote: “The operation of the world’s oil industry is now very largely in the hands of technical experts, geologists, physicists, chemists, and engineers. This change in the complexion of the responsible operating personnel has occurred more rapidly perhaps than in any other field of comparable importance. This cooperation is typical of the present spirit in the industry, and in this instance, as in many others, is the foundation on which a solution of the peculiar problems of our industry must rest.’’ This is no small part of the strength with which the American petroleum industry is meeting the problems put upon it since December 7, 1941.
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What of 19721 If the technologists of the oil industry cannot forecast the next thirty years in the light of the last eighty years, who can? We have noted that only shortly prior to 1910 the most farseeing and largest American oil companies were not interested in foreign oil fields and apparently did not visualize the growth of our industry in the ensuing thirty years. We now produce and consume as much petroleum in one year as we did in the total of the first forty years of the industry-that is, up to 1900. Every important oil-producing state has passed its peak of production with the exception of Texas. The enormously thick sedimentaries of that great state now produce 36 per cent of our domestic production. What will our industry be like in 19721 Extrapolated from past history we shall still be producing some oil from present productive areas and probably some new areas yet to be developed; but we shall be much more dependent upon foreign sources such as Mexico, Venezuela, the fields of the Middle East, and perhaps even Russia. Price levels may be high enough long before 1972 to make a shale oil industry profitable, the known reserves of which are enormous. Judging by the events of the past ten years, a much greater percentage of our oil will go into the manufacture of synthetic organic chemicals. This is definitely indicated. Much more petroleum will be consumed in essential uses, such as motor fuel, and less as fuel in ways which coal can serve; this change is noted in recent years. Processes such as hydrogenation of heavy residual oils t o gasoline will undoubtedly be used much more. Although the oil business of 1972 will be concerned with motor fuels, airplane fuels, and lubricants, the use of petroleum for chemical synthesis of rubber, plastics, solvents, and a vast assortment of important special chemical products will come about through continued research. That the American petroleum industry is able to give vastly greater aid
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to the prosecution of the war and the manufacture of direly needed materials than was possible in 1914-18 is due to the research carried out in the company laboratories in the intervening twenty years. Literature Cited (1) Alden, R. C.,Natl. Petroleum News, June 6 , 1940,R-231. (2) Anglo-Iranian Oil Co. et al., Oil Gas J . , Nov. 17,1939, 104. (3) Bamard, D . P., S. A. E. Journal, 41,415 (1937). (4) Beatty, H. A., and Edgar, Graham, in “The Science of Petroleum”, Vol. IV, p. 2927 (1938). (6) Birch, S., Dunstan, A. E., et al., IND.ENQ. CHEP., 31, 1080 (1939). (6) Bray, V. B., and Bahlke, W. H., in “The Science of Petroleum”, Vol. 111, p. 1966 (1938). (7) Brown, €3. K., News Ed. (Am. Chem. Soc.), 18, 347 (1940). (8) Burgin, Groll, and Roberts, Natl. Petroleum News, Sept. 7, 1938, R-432. (9) Ferris, S.W.,in “The Science of Petroleum”, Vol. 111, p. 1876 (1938). (10) Fitzgerald, G. F., Chem. & Met. Eng., 46,196 (1939). (11) Frey, F. R.,and Hepp, H. J., IND.ENQ.CHEM.,28, 144 (1936). (12) Grosse, A. V., and Ipatieff, V. N., Ibid., 32,268 (1940). (13) Grosse, A. V., Ipatieff, V. N., Egloff, G., and Morrell, J. C., Refiner Natural Gasoline Mfr., 18,478 (1939). (14) Halloran, R. A., in “The Science of Petroleum”, Vol. 111, p. 1798 (1938). (16) Heron, S. D.,Natl. Petroleum News, Nov. 17,1937,R-307. (16) Howes, D.A,, in “The Science of Petroleum”, Vol. 111, p. 2045 (1938). (17) Hubner, W. H.,and Egloff, G., Oil Gas J., March 31, 1938, 103. (18)Lane, E. C.,U. S. Bur. Mines, Rept. Investigation 3576 (1941). (19) Mardles, E . W. J., in “The Science of Petroleum”, Vol. IV, p. 3033 (1938). (20) Midgley, T., Jr., and Boyd, T. A., J. IND.ENQ.CHE~M.. 14,894 (1922). (21) Oberfell, G. G., Oil Gas J., Jan. 15,1942,22. (22)Oberfell, G.G.,and Frey, F. E., Ibid., Nov. 23,1939,60. (23)Pope, W.J., J . Chem. Soc., 115, 397 (1919). (241 Robinson. C. I.. U. 8. Patent 910.584 (1909). (25j Smith, D.J., and Moore, L. W., Natl.’PetrOleum News, April 2, 1941,R-98. (26) Sparken, W.J., Lightbrown, I. E., Turner, L. B., and Frolich, P. K., IND.ENQ.C H ~ M32, . , 731 (1940). (27) Whitley, G. S.,and Kats, M., Ibid., 25, 1204,1333 (1933). PR~DS~DNTED under the title “Thirty Years of Petroleum Reseeroh” before the Division of Petroleum Chemistry a t the 103rd Meeting of the A M ~ R I C A N CHEMICAL SOCIETY, Memphis, Tenn.
SHELL DEVELOPMENT COMPANY’S AUTOMATIC APP.4R.kTUS FOR STUDYING OXIDATION CHARACTERISTICS OF HYDROCARBOSS
