Modern Petroleum Research 1 E. C. Williams, Shell Development Co., Emeryville, Calif. HE oil industry in comparatively recent years has changed from a rather crude art, by which an abundant raw material was converted by the simplest processes into a few products which would burn or slip, into one of the neat scientific industries of the day. That, incidentally, has enormous consequences in the realm of higher management. Commercial, financial, and political acumen alone are no longer sufficient foundation for the direction of this industry. The days, when oil, like coal, might be regarded as a heaven-sent raw material which had only to be produced, graded, and sold into a receptive market, have gone, and with each year that passes the industry takes its place more and more in that company of scientific industries whose success depends on the ability and vision of our research
T
E. C. Williams
workers and on highly scientific control of the industrial operations themselves. There are unpleasant shocks awaiting those charged with the conduct of our industry who either are not well informed on, or are unreceptive to, what is going on in several of the leading research laboratories of today. In the research laboratories, also the days of empirical trial and error, or playing hunches, are past. The industry needs, and is willing to support, genuine scientific research; nothing less will provide the groundwork from which to go Upper.
General View, Glycerol lUnit
Right Hand. Automatically Con· trolled Hydrolyming Unite 1 From an address before the annual leetinjt of the American Petroleum Institte, Chicago. I1L, November 16. 1938.
690
forward. Whoever tries to solve the current problems of the industry, or to carry it into new fields, finds himself depending on a fundamental knowledge of such matters as the mechanism and kinet ics of reactions and the theory of catalysis, and on the basic chemical thermodynamic and physical properties of the materials with which we have to deal. To take only a few examples. In the study of lubrication, a subject still little understood, in which the demands of engineers press close on the ability of the oil scientist to produce, we are concerned primarily with what happens in that infinitesimallv small no-man's land which borders on the surfaces of oil and metal; where oil is not simply oil and metal does not behave according to one's ordinary ideas of metals. This subject is taking the highest endeavors of our most distinguished physicists to unravel. They are attempting to tell us now what truths lie hidden behind the mystery which we cloak, or fail to cloak, by that accommodating word "oiliness." By the new research tools of electron diffraction, x-ray, cathode-ray oscillograph, and sensitive temperature measurements of tiny areas of surface, we try to probe into details of the molecular arrangement within these infinitely small layers and to follow the course of their rapid movements. Out of these researches is already coming more certain knowledge of the way in which lubricants work and what must be done to meet the exacting demands of modern engineering. The methods of catalysis are becoming a normal procedure of our industry and are used to change hydrocarbon molecules from what they happen to be to what we wish them to be. But the truth of catalyst behavior is still largely hidden from us. Here, again, although commercial development does not need to wait, nor does wait on complete understanding of whys and wherefores, we are striving for such
DECEMBER 10,1938
NEWS EDITION
Hydrolysis) Unite for Organic Chlorides knowledge because with it we hope to go further, more quickly, and more surely. Only recently in our own laboratories we have been able to show that catalytic activities of certain metals towards hydrogénation, for example (and no doubt it will prove to be so for other reactions), are directly associated with the orientation of the metal crystals along definite crystal axes with respect to the substrate. We are able now in a controllable manner to produce films of metal in which all the crystals possess a single orientation—a fact provable by x-ray and electron diffraction analysis. It has been shown that such orientation is directly to be correlated with catalytic activity to such a degree that, whereas formerly we have been led to believe in the existence of minute spots of high activity, now we believe that such spots are only incidental and due to a casual occurrence of metal crystals with suitable orientation. We have it in our power to produce at will surfaces in which, by virtue of controlled orientation, all spots are active. This represents a new and striking advance in our knowledge of catalytic activity (we shall publish these results shortly in the proper place, together with the methods by which such orientation is controlled). We shall seek methods to control the orientation of crystals in different planes, and expect to find that towards a particular reaction some orientation is active, others not. It is not beyond possibility that having now a rational method of examination, we may succeed in showing, in those cases where certain catalysts have the power to accelerate different reactions, often to our embarrassment and disgust, that such versatility on their part may be due to the existence in the surface of groups of differently oriented crystals, ifthisis so, and if we should be able to orient all crystals in any one of their possible directions, we would hope to be able to curb the promiscuity of such catalysts and force them to perform selectively and exclusively the particular functions that we may desire of them. This would.
indeed, be a tremendous advance. Although this latest stage has not yet been reached, the path is clearer than it has been; perhaps some fog is lifting. It is by such researches that the foundations for industrial development are laid, and although it is the opinion of some that such fundamental work might be left to the universities, I do not subscribe to that view. It is for our industry to foster whatever lies at the root of its own advances, and we are sorely in need of knowledge which even our most distinguished academic workers are unable to supply. Before long we shall be tracing the transferences of organic radicals by tagging them radioactively, as the biochemists now tag elements and trace them through the living body. One particular phenomenon which we can appreciate ana wonder at is the bombardment of metal surfaces heated to temperatures as high as 1400° C. with butane, without the butane suffering any cracking or other change whatever. Then, by introducing with the butane or onto the surface of the metal so little water vapor as to maintain merely a molecular layer on the metal, the same butane is completely dehydrogenated at far lower temperatures. There we have some indication of the degree of control which it is possible to achieve over hydrocarbon behavior under the most extreme conditions. Some of these fundamental aspects of modern research in oil are more farreaching even than some of the more publicized developments which are becoming well known in commercial practice. Probably the most impressive happening of the last year or two is the commercial development of truly synthetic gasolines for use in the highest octane motor fuels. This development already is having important influence on the design of engines which will power the aircraft of the future. But so much has already been said on this subject that I will not discuss it here except to say that since a few years ago, when we made available to the industry
631 the first 100 octane undoped fuel for military and naval use, we have been intensely active, as have others, in exploring methods by which such fuels may be manufactured in the huge quantities which will be needed for both military and commercial flying. The original process of 1034 has been entirely supplanted on a commercial scale by one which doubles the yield of 100 octane fuel from available raw materials, and we anticipate within the near future seeing existing processes again supplanted, with again a redoubling of present supplies. This will prove an important factorperhaps a determining one—in the progress of engine design, particularly with respect to the competition between Diesel, and gasoline engines for long-distance aircraft. These advances have been made possible only by painstaking researches in the laboratory, from which has come a far greater knowledge of the chemistry of petroleum hydrocarbons, and of the methods and mechanisms of their rearrangements, than existed even in the schools of organic chemistry a few years ago. We are carrying out now on a commercial scale processes which the scientific textbooks have not yet recognized as possible. Another aspect of oil research is the recognition of oil as a basic material of chemical industry. Great strides in this direction have been made during the past few years, and much has been written on that subject. Developments already known, as, for example, the manufacture of alcohols, glycols, ketones, esters, ethers, acetylene, acetic add, etc., will not be considered here except to mention that, with the entry of the oil industry into this field, an altogether higher leva
632
INDUSTRIAL AND ENGINEERING CHEMISTRY
of scientific standards and scientific control of manufacturing operations has been found necessary than previously existed in the normal activities of the oil industry. These higher standards have reflected to the benefit of the oil industry as a whole. Only one example of recent progress showing the possibilities of oil as a basic chemical material will be cited—namely, the synthesis of glycerol from petroleum. We have had in operation now for more than a year a small commercial plant producing glycerol from petroleum gases. The quality of the product is equal to, if not better than, the finest grades of glycerol on the market, and the cost of production leaves a comfortable margin for profitable commercial operation at present price levels, which are already on the low side. It was only two years ago that a recognized authority stated he believed a practical process for the synthesis of glycerol, while highly desirable from a world economic point of view, must be regarded as so difficult as not to be in the cards. It is a problem which has engaged the attention of research workers, both academic and industrial, for many years. There are several methods by which this synthesis has been proposed, first and most obvious by the hydrolysis of 1,2,3trichloropropane. The fact that trichloropropane, if made, is difficult to hydrolyse is, however, not such a stumbling block as the fact that it cannot be economically manufactured (as, for example, by the direct chlorination of propane, or by the further chlorination of 1,2-dichloropropane, which could easily be obtained by adding chlorine to propylene). Trichloropropane can be made in a pure state by adding chlorine to allyl chloride. Allyl chloride appears, therefore, the only commercially likely starting point for the manufacture of 1,23-tricnloropropane. Glycerol may also be made by the hydrolysis of dichloro- or monocnlorohydrin. Both these chlorohydrins are made by the addition of hypochlorous acid to allyl chloride or allyl alcohol, respectively· So here again the key material is seen to be allyl chloride. By many similar arguments and experiments the conclusion was reached that allyl chloride is the key to glycerol synthesis. The stumbling block, however, was that no satisfactory process existed for the manufacture of allyl chloride. It is true that some allyl chloride can be made by the decomposition of dichloropropane, which, as already explained, can be made by the addition of chlorine to propylene. We have investigated this method thoroughly, but the reaction is only partially controllable in the direction desired and economically not satisfactory. We, therefore, had to find some other method for the synthesis of allyl chloride, and have found it in the direct subetitu· tion of chlorine into the propylene molecule in such a way that the unsaturated bond remains unaffected. This is, of course, diametrically opposed t o what
everyone believes about the behavior of chlorine relative to double bonds. The clue was given to us, although it later proved to be a wrong one, by some earlier work on the chlorination of isobutylene. It was found, surprisingly enough, that when isobutylene was chlorinated at ordinary temperature the chlorine did not enter to any appreciable extent into combination at the double bond, but by substitution attached itself to one of the saturated carbon atoms. (The methallyl chloride and alcohol so produced are now available commercially.) We have explored for several years the mechanisms of such chlorinations but have still to regard this substitution reaction in the case of isobutylene as unique. It was, in fact, not the clue to the substitutive chlorination of propylene. In the course of that work, however, we investigated chlorination reactions in generaTover a rather wide range of organic hydrocarbons, particularly with a view to detennining what it was that controlled addition or substitution reactions and, if possible, ways of directing them. There are several means available for accelerating, or perhaps modifying, the course of a cluoris&tion reaction—for example, radiatioû by acttaic light; presence of a catalyst; induction of substitution by a concurrent reaction of chlorine addition, a mechanism very thoroughly studied by Professor Stewart and coworkers. It was found that none of the first three influences gave the result anticipated, and we found nothing in the literature to guide us on the influence of temperature. We found it possible, by chlorinating olefins (in this particular case propylene) at temperatures between 400° and 600° C , to limit the reaction almost entirely to one of substitution. The chemical and mechanical hazards of such operation would seem to be insurmountable, and it is of course very easy to get complete inflammation of the reacting materials with a yield of nothing but carbon and hydrochloric acid. The mechanical difficulties of such procedures also, when the reactions are not rightly conducted, are considerable. However, when conditions are correctly chosen, the desired reaction proceeds smoothly in the direction desired, with yields of allyl chloride amounting to 80 per cent of tneory on both the propylene and chlorine. It is quite possible eventually to obtain yields as high as 85 to 90 per cent of allyl chloride, the remainder being some isomeric vinyl chloride, some disubstituted olefins, and a very little dichloropropane. · The allyl chloride so made may then be transformed to glycerol by three alternative processes: either conversion to 1,2,3tricbioropropane by addition of chlorine, or to dichlorohydrin by chlorohydrination. or by preliminary hydrolysis to allyl alcohol followed by chlorohydrination to glycerol monochlorohydrin. All these processes have been worked out, as also has the electrolytic chlorohydrination of allyl alcohol.
VOL. 16, NO. 23
The hydrolysis of allyl chloride or of glycerol chlorohydrins is itself a difficult technical problem, since so many byproducts may be formed by slight variations of conditions, particularly of acidity or alkalinity, during hydrolysis. We have found it necessary to devise automatic controls operated by tungsten, calomel, and glass electrodes at various points throughout the plant. These, in turn, regulate continuously through motordriven valves the streams of organic chlorides and alkali. The refining of the crude glycerol presents also new features not encountered in the refining of glycerol from fat, but these also have been satisfactorily overcome. When we remembered that certain of the intermediate products, particularly allyl chloride and alcohol, are highly toxic materials, we feared that the glycerol so produced might contain toxic or irritant impurities. However, these points have been tested in our pharmacological laboratories and it has been found that even under such severe tests as filling the stomach to capacity with synthetic glycerol, or injecting glycerol in quantity into the muscles, no 01 effects were produced, indeed less than is caused by U. S. P. glycerol. From the economic point of view we have to recognize that glycerol is now a by-product of the soap industry. Its price is, therefore, subject to wide fluctuation, as would be expected of a product which must be thrown away if not sold. The market price for the highest grades of glycerol has fluctuated over a period of years from 10 cents per pound, or even a little lower a t the depth of the depression, to 60 and 70 cents per pound under war conditions. A year ago the price was 30 cents per pound; now it is, I think, around 13 cents per pound. The average over any long period of years is around 15 to 16 cents. The value of synthesizing glycerol from petroleum, therefore, lies m the possibility which it gives of stabilizing prices of a universally used commodity. It would not be anybody's intention to compete with existing supplies to the extent of reducing prices to unprofitable levels, but we have processes which, if it were necessary, could produce the whole world requirements of glycerol from petroleum gases. This is sure to ex* ercise a stabilizing influence on a fluctuating commodity. At the same time, if the capacity of existing sources should fall below requirements, the petroleum industry could step quickly into the breach.
Government Chemists Needed As
NOTED in
the
NEWS
EDITION
of
Λ . November 20 (page 608), the United States Department of Agriculture needs several principal chemists and principal chemical engineers at $5000 a year to direct the work in the four new regional laboratories which are to be set up. Ap plications must reach the Civil Service Commission, Washington, D. C , by December 27 (December 30 if applicant lives in Colorado or states westward).
NEWS EDITION
DECEMBER 10,1938
Council Votes to Termi nate Trust Agreement BS following communication was Tsent to every member of the Council
The ballot to be valid must be received in this office on or before Wednesday. November 23. Please detach and mail in enclosed stamped envelope. Sincerely yours, CHARLES L. PASSONS, Secretary
on November 2,1938:
To the Council of the American Chemical This communication is being sent to you for letter ballot by advice of counsel. The Board of Directors at the time of the reincorporation of the SOCIETY were unanimously of the opinion that the Permanent Endowment Fund trust agree ment entered into December 19,1930, be
This ballot was counted on November 25 by a committee consisting of Charles L. Parsons, Secretary, and two other members, H. E . Howe and A. H. Emery, appointed by the President as required by the Constitution of the SOCIETY,
with the following result: Approved. 234; Disapproved· 5.
tween the AMERICAN CHEMICAL SOCIETY
and the United States Trust Co. of New York should be terminated and the funds otherwise invested and controlled by the board itself through our Finance Com mittee, as is done with all other SOCIETY funds. The trust instrument provides that: This trust shall be terminated only when the Council of the SOCIETY shall recommend such termination to the Board of Directors of the SOCIETY; the Board of Directors shall by a two-thirds vote approve such ter mination; and such termination shall be duly approved at a general meeting of the SOCIETY held after notice of such meeting and of the proposed termination of this trust given at least four months prior to such meeting. Our own counsel and counsel of the United States Trust Co. of New York are agreed in terminating this trust agreement by taking the following steps:
633
Notice t o Members Washington, D. C , December 3, 1938 OTICE is hereby given that the Board
N
of Directors of the AMERICAN CBBMI-
CAL· SOCIETY has unanimously approved
the above vote of the Council and that the matter wiO be presented for the approval or disapproval of the whole membership at the General Meeting of the SOCIETY to be held in Baltimore· Aid., on April 3,1939. CHABLBSL. Γ
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N o m i n e e s f o r A . C S . Officers τ THE ballot which has just been Β counted, the members of the AMERI CAN CHBMICAL· SOCIETY have nomi
nated for President-elect Gustav Egloff, S. C. Lind, E. Emmet Reid, and H. S. Taylor; for Councilors-at-Large George D. Beal, Henry Gilman, Arthur W. (1) By having the Council of the SOCIETY Hixson, Harry N. Holmes, John R. John recommend such termination to the son, Carl S. Marvel, R. Norris Shreve, and Harold C. Urey: for Directors (First Board of Directors, after which Arthur J. Hill and C. R. Downs, (2) The Board of Directors shall approve District) (Third District) E. K. Bolton, A. S. such termination by a two-thirds Richardson, and E. R. Weidlein, and vote, following which Director-at-Large, Thomas Midgley, Jr., (3) Notice shall be given to the member and Walter S. tandis. ship four months prior to the next Ballots are now in the hands of mem general meeting of the SOCIETY, that bers of the Council. The result of the such recommendation by the Council election will be reported in the NEWS and such approval by the board will EDITION of December 20.
Suppressed Patents (?) To the Membere the American Chemical Society: kT THE recent hearings on the l \ . McFarlane Bill for the Com pulsory licensing of Patents. I, as your representative, was asked more than once as to the rumor that is so extant throughout the country that patents worthy of development are being unethically held to prevent business development by others, or pigeonholed by the owners to pro tect investments under obsolete procedure. Although, of course, I had heard these rumors, since they frequently appear in the public press, I stated that I knew of no such cases. This matter of the suppression of patents is one of great importance to the American people, and if the Tumors are true, they should be in· formed thereof. By suggestion of the Chairman of the Board of Direc tors and with the approval of the President of the SOCIETY, I am pub lishing this notice with a request to every member of the SOCIETY, among whom there are hundreds of inventors and thousands of em ployees engaged in research leading to invention, to inform our Com mittee on Patents through me, or direct to the Chairman thereof, of any such suppression of patented invention or discovery of which they have actual knowledge· Such information, to be effective, must of course be accompanied by defi nite statement in sufficient detail for presentation to any congressional committee on patents before whom a representative of this organization may appear. It is suggested that, if possible, the number of the patent should be given, and that the reason for the alleged suppression be stated in detail. CHABLES L. PARSONS, Secretary
be submitted to the SOCIETY for ap-
approval at the general meeting, and (4) The SOCIETY at its general meeting shall vote such approval by appropri ate resolution, and (5) Notice of these various steps shall be given to the United States Trust Co. over the signature of the Secretary of the SOCIETY, attested by the seal of the SOCIETY, with a demand that the trust be terminated and its assets be turned over to the Treasurer of the SOCIETY.
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Bogert Address Available for Students T THE request of several of our leading chemistry teachers, who wished to use them as text material for their stu dents, a number of separates were struck off of the public address of Marston T. Bogert given at the Milwaukee meeting of
A
the AMERICAN CHEMICAL SOCIETY and
>rinted on page 553 of the NEWS EDITION
Îor October 20.
Photostats o f Broadcasts WING to lack of funds the Publicity Committee of the Philadelphia Sec tion of the A. C. S. regrets that it cannot supply fre® copies of its "Mysteries of Chemistry" radio broadcasts. However, if anyone desires a photostat of the manuscript reduced to 4 pages on 1 sheet, size 8.5 X 11 inches, it will be sup plied at cost. Orders for photostats accom panied by check or money order of $1.00 per broadcast should be sent to A. J. Nydick, 1421 Chestnut St.. Philadelphia, Pa.
O
Several hundred of these Any membere of the AMBBICAN CHEMI are still available and may be obtained in If this action is to be taken by the whole lots of 100 for $5.00 a hundred. Orders CAL SOCIETY desiring to write a broadcast SOCIETY on April 3, 1939» it is necessary with remittance should be sent to diaries (someone will be provided to read the lines that ballot be sent immediately to the L. Parsons, Secretary, 728 Mills Bldg., of an absentee writer, but the author of Council, which ballot is attached below. Washington, D . C. the manuscript will receive due recogni tion over the air) should communicate Will you kindly give' this your attention with O. F. Roller, Jr.. Chairman, Pub and mail to me in the enclosed ballot en licity Committee, Philadelphia Section, velopes, which are stamped "COUNCIL." N o 1938 N o b e l A w a r d i n 4817 Resent St., Philadelphia, Pa. Please be sure that this ballot is hot con Chemistry fused with the ballot that has just gone The schedule of broadcasts as listed on to all members of the SOCIETY covering ORD has come from Stockholm that page 602 of the November 20 issue of the the election of officers. no Nobel Prise in Chemistry will be KEW8 EDITION is correct, except that It is the unanimous opinion ofUhe Di awarded in 1938, but that the prize money the broadcast on December 24 will be "The rectors that this trust agreement should be will be placed in the general fund of the Chemistry of Christmas" by D. L. Gibson, instead of the one previously listed. terminated. award. The AMERICA* CBHOCAL SOCIETY assumes no responsibility for the statements and opinions advanced by contributor· to its publications. Piiblishedby the AMEBICA» CHXMTCAL· βοαχττ. Publication Office, 20th et Northampton 8ts.· Easton, Pa. Editorial Office, Room 706. Mills Building, Washington, D. C : Telephone, National 0848; Cable, Jieehem (Washington). Advertising Department. 882 West 42nd St., New York, N. Y.'K Téléphone· Bryant 9-4430. Entered as second-class matter at the Post Office at Easton, Pa., under the Act of March 8,1870, as 48 times Edition monthly on the first; Analytical Edition monthly on the 15th; News Edition on the 10th and 20th. Acceptance for mailii postage provided for in section 1108. Act of October 8. 1917. authorised July 13. 1918. _ BuBecMtrnon to nonmembers. XKPUSMUAI» AH» Esennstmo C m o m r complète· 86.00 per year; foreign postage 82.40· except to countries L lag mail at American domestic rates; Canada, 80 cents. Analytical Edition alone, 82.50 per year; foreign postage, 60 cents; Canada 20 cents. News L i tton alone, 81.60 per year (single copies· 10 cents); foreign postage. 60 cent·; Canada, 20 cents. Subscriptions, changée of address, and claims for lost copies should be sent to Charles L. Parsons· Secretary· 728 MiD· Building. Washington, D. C.
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