The Future of the Chemistry of Petroleum - ACS Publications

happiness, ease, and comfort to mankind. The Future of the Chemistry of Petroleum. By James F. Norris. hfASSACHtiSETT5 INSTITUTE OF TECHNOLOGY,...
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October, 1916

I-\-DUSTRIAL A-YD ESGINEERISG C H E M I S T R Y

an ordinary wood chair in constant use runs from about $1.00 to $3.00 per year, which justifies a reasonably high first cost of the metal chair. Conclusion

These seem to be the directions in which, in the light of present knowledge, the light metals ail1 make the most prog-

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ress in the near future. However, the intensive scientific study of their production and utilization has only just begun, and there may be many new developments in the near future that will open still other avenues of growth and usefulness. This is the lure of scientific research-the striving for the discovery of the unknown which, in its success. brings new happiness, ease, and comfort to mankind.

The Future of the Chemistry of Petroleum By James F. Norris hfASSACHtiSETT5

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I N S T I T U T E OF

HE outlook i;, bright for the rapid development of the chemistry of petroleum. The increasing appreciation of the value of science to the industry leads to confidence in what is ahead, and one approaches with enthusiasm a look into the future. The use of chemistry, geology, and physics in the detailed study of petroleum in all its aspects will greatly enhance the value of this important product, both financially and from the point of viem- of furnishing the world with useful substances. I t is a fundamental fact in industry that a detailed knowledge of the properties of the raw material used is essential for the best results. This knowledge has been lacking in the case of petroleum and the first task of the chemist is to acquire it. I n the future the study will not be limited to the investigation of those properties that come into play in handling petroleum by the methods now in use, but attention will be paid to the enriching of our knowledge of the fundamental chemistry of the hydrocarbons and their many types of derivatives related in any way to the parent compounds. The subject must be approached from this point of view if marked advance is to follow. A very promising start has been made in this direction, and it takes no prophet of the first rank to forecast the success of the research program lately undertaken under the auspices of the American Petroleum Institute. Up to the present the work is being financed by the father of the petroleum industry and one progressive company But it will not be long, in the judgment of the writer, before the organizations forming the institute will be mhole-heartedly behind the plan. What can be expected in the immediate future? What problems need the first attention? The study of the genesis of petroleum is of more than academic or geological interest ; for when we know the way or ways in which S a t u r e has produced such a valuable substance. we may be in a position to duplicate the processes or improve upon them. The chemist, geologist, and physicist will cooperate in this study. The chemist will furnish the facts in regard to the components of the raw materials from the several sources. The geologist will describe the history and nature of the rock formations that yielded the deposits, and the cahanges that these formations have undergone. The physicist will bring t o bear on the problem his knowledge of the value of the pressure, capillary action, and physical forces involved, and with the chemist find out the effect of these forces on the probable,ultimate source of the petroleum studied. We shall see as a result new or improved theories of the genesis of petroleum based on wide observation-theories that can be suhjected to experimental examination. While this work is in progress new knowledge will be accumulating in university laboratories that may help to solve the problem. The study of the chemical action produced by the alpha particles emitted by radium when they come into contact

TECHNOLOGY, C A M B R I D G E , MASS.

with molecules may seem far afield from petroleum; but recent work shows that this type of energy changes methane into a mixture of compounds that resemble crude petroleum. This observation taken along with the fact that helium occurs in the natural gas from certain sources makes the study of radioactivity from this point of view of the first importance. It may turn out that one type of petroleum a t least had its origin in vegetable matter that was converted into marsh gas and finally into higher hydrocarbons. The formation of hydrocarbons from vegetable material through action of bacteria or other agencies will some day be studied, and the results may lead to important industrial developments. Heptane is produced by a certain type of tree and other hydrocarbons have been shown to have a vegetable origin. Some day me shall know more of such chemical processes. The world must eventually turn for help to the tropics with their limitless supply of energy in the form of sunlight; and petroleum or something to do the work now done by petroleum will be made from the vegetable material so abundantly and quickly supplied with energy from the sun. The study of the genesis of petroleum will lead to the discovery of facts that will help in devising systematic methods for the search of new deposits. The progress already made leads to confidence in the future. The physicist with his torsion balance and seismograph is now as necessary as the geologist in prospecting for new fields. The future will see added interest in the study of oil shales which will eventually prove t o be an important source of power. This field is a fascinating one for study, as much chemical work is to be done. Problems Awaiting the Chemist

Let us now turn our attention specifically to the problems before the chemist. One of the most pressing needs is a definite knowledge of the composition of the various types of petroleum. The time is propitious for a reexamination of this problem. The pioneer work in this very difficult field was carried out when there was little knowledge of the physics or chemistry of the components of the material being studied. The use of distillation, solubilities, and test for unsaturation by unreliable methods could not advance the subject very far. But today the established laws and experimental methods of physical chemistry are tools that make the attack of the problem a hopeful one. With temperatures a t command as low as the boiling point of hydrogen and with the use of accurate criteria of the purity of crystalline substances, it is possible to obtain definite knowledge impossible twenty years ago. The old-fashioned method of fractional distillation has been replaced by one based upon the significance of vapor pressures of mixtures. It will not be long before the technologist knows more about the composition of the material with which he is working

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The processes now used in converting crude petroleum into commercial products involve, in many cases, chemical transformations. The nature of most of these is unknown, but the immediate future will see a change. The study of the influence of heat on the breaking of bonds that link carbon and carbon atoms and carbon and hydrogen atoms in molecules will make it possible to understand and control the cracking of petroleum. The study of the influence of Twious catalysts on such decompositions will give us new means to produce the compounds best adapted to the particular use to which they are to be put. The study of the behavior of pure hydrocarbons when brought into reaction with oxygen under the conditions that exist in a combustion engine will make possible a more efficient fuel. We shall learn about the stepwise oxidation of complex molecules; find out which bond is first severed, where the oxygen enters the molecule; and learn why compounds containing branched chains and certain types of unsaturation do not knock. We shall find out the proper fuel for the best results, arid with our knowledge of the composition of the different crudes and the way each component behaves when it undergoes decomposition under a variety of conditions, we shall be able to set up processes for the preparation of gasoline that will make present-day practice look like the crude and impractical operations of the alchemists. The study of lubrication by the physicist and the chemist will lead to the manufacture of lubricants for each particular purpose according to the physical properties required and the particular chemical constitution of the molecules that produce these properties. ' The study of the nature of the sulfur compounds in petroleum and their chemical behavior will give an impetus t o the changing technology of the refining of petroleum from this point of view. The detailed study of the unsaturation produced during the process of cracking will solve the gumming problem. Instead of destroying the compounds that offend in this way, we shall put them to important uses. Petroleum as Raw Material for Organic Chemicals

The most brilliant part of the picture of the future of petroleum chemistry is, in the writer's judgment, the assured development of petroleum as the raw material of a widely diversified organic chemical industry. It is not bold to predict that before long the production from petroleum of chemical substances for uses other than the lubrication and the production of heat and power will exceed in amount the products of the coal-tar industry. The synthetic production from petroleum of many of the aliphatic compounds so widely used is a thing of the future. It has been shown that a large number of alcohols can be readily manufactured from petroleum. These have been the sources from which a great variety of compounds have been prepared. Partial oxidation of petroleum produces acetaldeyde, allyl alcohol, and other substances a t a very low cost. The former will be a source of acetic acid, plastics, and other substances with extensive uses. Allyl alcohol makes synthetic glycerol a possibility. The cracking of petroleum will yield products from which can be formed hydrocarbons capable of polymerization to plastics related t o rubber. I n fact, petroleum is a source from which many of the industrially important aliphatic compounds can be made, and future work will demonstrate that most of these can be manufactured at a low cost. What has been done is but an indication of what is ahead. Petroleum can be readily corn-erted into unsaturated

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hydrocarbons, halogen compounds, and oxygen derivatives. The opening up of the hydrocarbon molecule in these ways makes i t possible to use the well-known synthetic methods, and others to be devised, to build up for commercial use many of the compounds which have already found a place in industry. But more than this-compounds not yet known and others that have never been studied as possible industrial products on account of the difficulty and cost of preparation will come into general use. Every substance has unique properties which adapt it to some particular purpose. Given an adequate supply a t a reasonable cost and eventually it will find its place. I recall distinctly the preparation of ethylene glycol which I carried out as a student. The process was a long one, the yield was unsatisfactory, and the small amount obtained was prized as evidence of much time and labor spent. It would have taken a lively imagination, which I did not possess, to picture the ethyl ether of the glycol as a commercial solvent of most striking properties. Almost four years ago I purchased 100 grams of tertiary butyl alcohol for $16. It was a matter of economy to pay this price rather than to expend the labor necessary to make it. Who would have foreseen then that the alcohol would soon be available in thousand-gallon quantities? When one has seen what chemistry can do with petroleum, the fear of undue optimism vanishes. But we must not be content to utilize only our present knowledge. We must develop aliphatic chemistry in all its branches. We must study more closely organic molecules-learn about the forces that hold the atoms together and how to control these forces a t will. The problems are fascinating ones, and I foresee with clearness great activity in this rich field. It is impossible to picture this or that particular advance, except where logic leads us from what we know now. But brilliant achievements not even dreamed of are ahead. A Source of Life's Luxuries-Petroleum

May I be pardoned if I let imagination run away with my thoughts in closing this very inadequate consideration of the future of petroleum chemistry. It is a beautiful afternoon and you decide to take a ride in the country. The gas tank on your car is examined. It is only partially filled and you will travel a long distance. But you know it will be adequate, for your engine runs at a high compression and your synthetized no-knock fuel makes possible many miles per gallon. The lubricating oil is all right although it has not been replaced for months. You admire the new finish on the car. The lacquer is brilliant, does not scratch, and possesses the correct adhesive and elastic properties-petroleum. You look over the tires; they scarcely show wear after the many miles they have traveled-petroleum. You examine the artificial leather with which the car is upholstered; i t is remarkable how it has withstood wear and the sun and heat; it is pliable and soft-petroleum. The windshield and windows are as clear as crystal; no cracks, no danger of breaking-petroleum. The panel containing the recording instruments looks like polished ebony-petroleum. You wipe off a little grease from the engine and wash your hands with a marvelous soap-petroleum. Finally you start. Soon there is a detour;, the road is being broadened and there is much blasting-petroleum. You pass a plant for the manufacture of ammonia for fertilizer where large amounts of hydrogen are used-petroleum. You stop at a drug store for a little refreshment. You order a n exhilarating drink with the taste and odor of fresh fruit-petroleum. You finally ask for ice cream; it is delectable and smooth-petroleum. You look about and

October, 1926

I S D U S T R I A L A S D ENGIWEERISG C H E M I S T R Y

as a chemist examine some of the newer drugs. If you ever need something to give you additional vim to meet a physical or intellectual emergency, if you prove restless a t night and want a mild soporific, if diabetes ever takes hold of you, if you want a mild antiseptic for household use, if you want to’remove grease from a delicate fabric, if you need a n internal lubricant, in fact, if you want the help so abundant in a modern drug store, you will find it here and in many cases i t will go back to petroleum. You jump aboard the car again and admire the durability

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of the floor covering-petroleum. It is time for a cigaret. The tobacco contains just the right amount of moisture, held by a trace of a liquid of the proper hygroscopic properties-petroleum. You pass a hospital and think of the wonderful new anesthetics that have none of the bad after-effects of chloroform or ether-petroleum. You finally return home and spend the evening working on your income tax return. You are surprised to find what a large sum you must pay: you are rapidly getting rich-petroleum.

Future Trends in Iron and Steel Production By John A. Mathews CRCCIBLE STlCEL C O M P A N Y O F .%YERICA, N E W Y O R K ,

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HE title suggests the question as to how long in the

future the remarks apply. Let us assume that a period more or less near to 1976 is intended. Standing a t the middle of the second century of our national independence, it is much easier to look back to the wonderful achievements of the past fdty years than to predict what is to be a half-century hence. It is not intended to weary the reader with columns of uncertain figures based upon a study of the statistics of the past. Nevertheless, we can hardly escape giving some thought to the question of ‘~HOTV much?” The answer to this question is wrapped up in the consideration of certain trends or tendencies which may be of weight in future years and to which it may be profitable to give attention. The hazards of prophecy are many. Not later than seventyfive years ago Overman wrote: “In Pittsburgh attempts have been made to manufacture steel. But we doubt whether a n article of good quality can ever be produced in that region.” A single prophecy like that may well make one cautious. Sir Robert Hadfield, in his presidential address before the Faraday Society in 1914, reproduced a chart showing pig-iron production from the year 1500 to 1904 with an estimate up to the year 2000 A. D. At the time he spoke the 1912 statistics were available and his estimates of less than ten years’ standing were about 33 per cent below actual production. At present, some twenty years later, production is only 7 per cent above his estimate. Taken from his curve the world’s output for 1976 will be about 120 million tons. The question is-shall we make it, and if so, where? Our share a t present rates of production would be about one-half, or 60 million tons. Blast-Furnace Efficiency

The present estimated blast-furnace capacity in the United States is already 53,500,000 tons, so we are well on our way, and we have produced in single years over 40 million tons. We therefore have available now 33 per cent excess capacity over our greatest past demand, and about the same proportion exists for the production of ingots and castings. I n view of recently published rates of earnings on invested capital in the industry, i t would seem well if no new capacity were built for about twenty-five years. This does not mean that replacements and renewals should not be made or that we should fail to recognize what Mr. Carnegie aptly termed “depreciation due to the advance of the art.” The obsolete must go; efficiency must be maintained; but why increase capacity? Such a large percentage of total pig iron is used molten direct from the furnace and by the original maker that the

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position of many so-called merchant furnaces has not been enviable of late. These are frequently in isolated locations and most of their product is shipped to local foundries scattered over wide areas. I n many respects the blast furnace is extremely efficient; yet the amount of coke consumed is about twice what is actually necessary to reduce, carburize, and melt the product. Can the other 50 per cent be utilized? I n the highly integrated plant much of it can be and is utilized. Mr. Franchot has called attention to the blast furnace from the point of view of a gas producer, and intimates that if all the energy of the coke were utilized pig iron might assume the role of a by-product. There are plants in Sweden where it is hard to say whether steel is a by-product of the wood industry or whether wood products are by-products of the steel industry. If Franchot’s assumptions are true, then there should be a migration of merchant furnaces to centers of population where coke, pig iron, gas, and electricity will all be made in large publicservice plants and the iron will then have a more local market. Coke consumption per ton of pig iron will not be so important if all the energy of the coke can be accounted for in some marketable form. Reasons for Decline in Pig-Iron Production

It was pointed out that in 1912 pig-iron production was 33 per cent greater than Hadfield’s estimate while in 1925 it was only 7 per cent in excess. Will this decline continue and may it reach a point below the estimate in 1976? In the writer’s opinion there are several reasons why this may be so, a t least so far as our own production is concerned. Let us consider these reasons. Decline in Pig Iron per Capita Ratio The pig iron per capita ratio has not increased appreciably since 1910. Prior to that time the ratio increased enormously-e. g. : Year 1860 1870 1880 1890

Pounds 53 98 160 298

Year 1900 1910 1920 1925

Pounds 425 624

597

628 (estimated)

Population will not increase so rapidly during the next fifty years as during the period 1876-1926, especially if our policy on immigration continues. The birth rate usually declines with advancing civilization, education, wealth, and culture. These circumstances should tend to lower the future demand below present-day ideas. N o Increase i n Exports Our exports of iron and steel have never assumed a large proportion of the total production, probably not over 5