literature resources - American Chemical Society

History of the Petroleum Chemicals Industry RICHARD F. GOLDSTEIN

Downloaded by STANFORD UNIV GREEN LIBR on February 22, 2013 | http://pubs.acs.org Publication Date: June 17, 1954 | doi: 10.1021/ba-1954-0010.ch035

The British Oxygen Co., Ltd., Research & Development Department, Morden Rd., London, S.W.19, England

The petroleum chemicals industry was started and developed in America at the end of the first world war. In the first stage, an industrial aliphatic chemicals industry was developed utilizing olefins obtained from hydrocarbon cracking. The products were either new industrial chemicals, such as ethylene glycol, or were established products where petroleum had become the most economical starting material. The outbreak of the second world war led to the second stage of major expansions. Other types of hydrocarbons became as important as the olefins. Methane from natural gas has largely displaced coal processes for ammonia and methanol. The simple aromatics formerly isolated as coal processing by-products are now manufactured from petroleum. In addition, completely new industries have been created for the production of synthetic rubbers, fibers, detergents, etc., largely based on petroleum raw materials. Many by-products of petroleum refining can also be regarded as petroleum chemicals. Since the second world war other countries have developed petroleum chemicals from the available raw materials but have advanced only to the first stage of the American pattern.

Petroleum chemicals are defined as products intended for chemical markets, manufac tured from petroleum or natural gas, or isolated as by-products i n the working up of petro leum. Petroleum chemicals fulfill two functions. They provide alternative and more econo mic routes to existing chemicals already made from other raw materials, and they lead to new industrial chemicals. The reactions of and outlets for chemicals more economically synthesized from petroleum have already been worked out, although perhaps not com pletely, i n connection with the older routes. Those countries not favored with petroleum as an economic raw material have had to make use of alternative sources for these chemi cals. I n surveying the literature, i t is, therefore, necessary to take account of the history of those petroleum chemicals which have been made from alternative sources. The reac tions of methane are the same whether it is obtained from natural gas or as a by-product of the hydrogénation of coal or as a fraction i n the liquefaction of coke oven gas; depending on the source, the economics may be quite different. I n view of the vast field now comprised within the term petroleum chemicals, i t is necessary to restrict this historical survey to the highlights and to leave aside many i n teresting and potentially important lines of work.

Petroleum Chemicals in America, 1920 to 1940 The petroleum chemicals industry i n the U . S . A . was created from research work car ried out during the first world war. I n the 1920's and 1930's i t was mainly concerned 321

In LITERATURE RESOURCES; Advances in Chemistry; American Chemical Society: Washington, DC, 1954.


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with the methods of making and of using the simple olefins—ethylene, propylene, and the butylènes. The first olefin, ethylene, was made b y direct cracking of liquid petroleum fractions or of propane. Propylene and the butylènes were obtained either simultane ously with ethylene i n these direct cracking processes or as by-products of refinery opera tions, particularly as these became more and more chemical processes with the adoption of thermal reforming and later of catalytic cracking. F o r separation of the olefins, reliance was placed largely on efficient fractional distilla tion under pressure, using techniques now familiar to the petroleum industry; the unusual feature was the low temperature required for concentration of ethylene. The main ole fin reactions developed were hydration with sulfuric acid to give the alcohol, which was then dehydrogenated to the corresponding aldehyde or ketone, and conversion to the ole fin oxide b y reaction with hypochlorous acid. The ready commercial availability of the olefin oxides led to a continuous stream of new products, such as glycols, glycol ethers, and alkanolamines. This indicates the two-fold function of petroleum chemicals; the hydration of ole fins led to alcohols and to the family of derivatives of alcohols already made from other sources and, on the other hand, the olefin oxides and their derivatives were new industrial chemicals not previously made. Ethylene was and, i n fact, still is the most important olefin. Although i t is believed that 2-propanol was actually the first petroleum chemical, as i t was made on a limited scale i n the early days of production, the outstanding feature of this period was the launch ing of the derivatives of ethylene oxide into the industry and their establishment on a firm and proved basis. These chemicals found new uses mainly i n the automobile industry. Ethylene glycol was the basis of the first permanent antifreeze, while the glycol ethers were used i n the new surface coatings being developed for automobiles. Simultaneously, ethanol was being made from ethylene b y hydration with sulfuric acid, using a process the chemistry of which had been worked out many years before but which had never been economically successful. The bulk utilization of ethylene was soon followed b y that of propylene and then by the butylènes, which were converted to ketones v i a the alcohols made b y the same hydra tion step as for ethyl alcohol. The ketones and their derivatives also found outlets i n the automobile and solvents industries. These developments progressed steadily up to the outbreak of the second world war. This can be shown i n Table I, from U . S . Tariff Commission reports on synthetic organic chemicals, which shows how the number of ethylene and propylene chemicals marketed by only one firm, Carbide and Carbon Chemicals Co., increased between 1926 and 1939. The figures are approximate. Table I.

Number of Individual Aliphatic Compounds from Olefins Made by Carbide & Carbon Chemicals Co. Year 1926 1929 1934 1939

Number of Compounds Derived from Ethylene Propylene 5 15 35 41

2 4 15 27

Total 7 19 50 68

Derivatives of the butylènes had been introduced from about 1930, though not b y the company named. A t the same time, other work was i n hand which was the basis of many of the later developments dealt with i n the following section.

Petroleum Chemicals in America, 1940 to 1952 Whilst the first world war was responsible for the creation of the petroleum chemicals industry, the second world war led to its widespread expansion, Firstly, more types of hydrocarbons were used as the raw materials of the industry. Secondly, the end uses were enlarged from the limited outlets of the first period. In LITERATURE RESOURCES; Advances in Chemistry; American Chemical Society: Washington, DC, 1954.


GOLDSTEIN—HISTORY O F THE PETROLEUM CHEMICALS INDUSTRY

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The techniques of preparation and of separation of hydrocarbons were improved. New construction materials led to cracking being conducted under more severe conditions, to increase the amount of olefins produced. This also permitted a change from propane to ethane as the raw material for ethylene synthesis. Aromatics became available from petroleum naphthenes. Diolefins and acetylene were also manufactured from petroleum sources. Methods of separation of hydrocarbons became more diversified. Fractional distil lation was improved b y the use of azeotropic and extractive distillation. Continuous adsorption on solids such as active charcoal or silica gel was established. Liquid-liquid solvent extraction, already used i n petroleum refining, was adapted to the concentration and purification of some of the raw materials for petroleum chemicals; finally, the forma tion of physical complexes, the so-called clathrate compounds, which permit separation of hydrocarbons of different shapes, is being developed as a new separation method, now known as extractive crystallization. Olefins were the main building blocks of the industry during the first period. T h e second period brought into the picture the paraffins, the diolefins, acetylene, and the aro matic hydrocarbons. T h e magnitude of utilization of the olefins increased pari passu with that of the other hydrocarbons, but they were no longer the only type. Although the initial work had i n some cases been carried out earlier, important new olefin reactions established since 1940 were: Direct oxidation of olefins to olefin oxides, partly replacing the hypochlorous acid route (discovered in Europe in 1929). Direct hydration of olefins to alcohols without the use of sulfuric acid (known for many years but never successful until the discovery of new catalysts in Europe at the end of the second world war). Reaction of olefins with carbon monoxide and hydrogen, leading directly to primary alco hols with one more carbon than the initial olefin (discovered in Germany in 1938). High temperature substitutive chlorination of olefins, leading to synthetic glycerol and to new intermediates for the plastics industry (discovered in America, 1935 to 1939).· Methane from natural gas was used as a source of petroleum chemicals for making synthesis gas (carbon monoxide and hydrogen) and hydrogen, b y reaction with water (methane-steam process) or with oxygen (methane-oxygen process). Methane from natural gas thus became the raw material for synthetic methanol and for synthetic a m monia. The synthetic ammonia synthesis had been worked out i n Germany just before the first world war and synthetic methanol followed i n the 1920's, both from coal. S i m i larly the methane-steam and methane-oxygen processes were European developments using by-product methane from coke oven gas separation or from coal hydrogénation. I n America methane has now largely displaced coal as the raw material for synthetic methanol and ammonia. I t is being used as the starting material for the synthesis of liquid fuels, using an improved method of conducting the Fischer-Tropsch process, which will give a considerable tonnage of petroleum chemicals as coproducts. Toward the end of this second period, methane is being established for the manufacture of petroleum acetylene, again using a European process of the 1930's, which used methane from coal. Propane and butane are directly oxidized with air to a range of oxygenated com pounds, principally formaldehyde, methanol, and acetaldehyde. This is a development of work initiated i n the 1930's, although an oxidation process of this type was first tried out in America i n 1926. A t the same time as the lower paraffins were being pressed into service, the second world war led to the manufacture of aromatics from petroleum. New methods of isolat ing, isomerizing, and dehydrogenating petroleum naphthenes were devised on the basis of petroleum techniques. During the war, manufacture of toluene and xylene was estab lished; since then, benzene has been added, because the growing demands of the chemical industry could not be met from the conventional source, coke-oven tar. Simultaneously with this diversification of types of hydrocarbons, new industries were being created which turned to petroleum for many of their raw materials. These included synthetic rubbers, synthetic fibers, plastics, and detergents. Synthetic rubber led to the development of specific petroleum routes to butadiene, In LITERATURE RESOURCES; Advances in Chemistry; American Chemical Society: Washington, DC, 1954.


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from η-butane and 1- and 2-butenes, and to styrene, from benzene and ethylene. The techniques used were refinements of those already established b y the petroleum industry for the manufacture of high octane gasoline. The growth of synthetic fibers has led to the devising of syntheses from petroleum of the chemical intermediates required for this new industry. Leaving aside acetic anhy dride from ethylene v i a synthetic ethanol and from propylene v i a acetone, already estab lished and used for cellulose acetate i n the 1930's, nylon has called for the isolation of petroleum cyclohexane and for the discovery of a route from butadiene to nylon salt; Dacron for the isolation of p-xylene from petroleum xylene, and the nitrile fibers for the synthesis of acrylonitrile from ethylene or acetylene. Plastics require such a wide variety of raw materials that i t is difficult to select the major petroleum chemical developments. Styrene, v i n y l chloride, and polyethylene from ethylene, formaldehyde from petroleum methanol, and urea from petroleum ammonia are the chief contributions of petroleum chemicals. Detergents, which now rival soap i n demand, are based largely on petroleum; the variety of structures which confer detergent properties have led to some interesting syn theses. A l k y l aryl sulfonates are made by alkylation of benzene either with chlorinated kerosene or with a highly-branched olefin made from propylene. Long chain olefins for secondary sulfates were made from paraffin wax. Secondary a l k y l sulfonates were made by direct sulfonation of paraffins with sulfur dioxide and chlorine, a reaction discovered in America i n the 1930's.

Other Countries Aside from one or two relatively minor operations, there was no petroleum chemicals industry outside America until after the second world war. The potential importance of the new chemical industries based on petroleum then led to the creation of petroleum chemical industries i n several European countries and i n Canada. I n the few years avail able, i t is not surprising that most of these countries are still i n the first stage of American development; that is to say, their industries are directed primarily to making and using the lower olefins. There are two factors which distinguish operations i n some of these countries from American practice. I n the absence of natural gas, petroleum chemicals have to be made from imported liquid hydrocarbon fractions. Compared with America, many of the Europeans countries are relatively well placed on aromatic compounds as by-products from coal processes and the relative price structure may not make manufacture of aromat ics from imported oil attractive. The United K i n g d o m has, at present, the largest petroleum chemicals industry out side America. I t is based wholly on imported liquid fractions and directed very largely to manufacture and use of olefins. The position i n France is similar, but i n Italy, with new natural gas discoveries and no coal, manufacture of chemicals from methane is of equal importance. Canada can hardly be termed the most recent entrant to this field, as she participated in the manufacture of synthetic rubber from petroleum during and since the second world war. The postwar developments so far have, however, been on the E u r o pean pattern.

By-Products The main by-products from petroleum refining are oxygen compounds, nitrogen com pounds, and sulphur compounds. The principal oxygen compounds are phenols and naphthenic acids. These are pres ent only i n particular crude oils i n significant amounts. By-product petroleum phenols have been industrial products i n America since the 1930's, but the literature on their com position is limited. Naphthenic acids were found i n considerable quantities i n the early days of the oil industry i n crude oils from Roumania and from Russia. These have, therefore, been worked upon i n Europe before the first world war; this work is associated with the name of von Braun. In LITERATURE RESOURCES; Advances in Chemistry; American Chemical Society: Washington, DC, 1954.


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Nitrogen compounds are present only i n certain crude petroleums and have not at tracted much attention. M o s t work on their composition has been done i n America by Bailey. The main interest i n sulfur compounds is their removal i n order to upgrade the quality of petroleum fractions. M u c h literature is therefore to be found i n petroleum refining on the removal of hydrogen sulfide, mercaptans, and sulfides since the 1920's. Compara tively little information is available on the composition of mercaptans present i n petro leum products; if wanted for industrial purposes, they are usually synthesized. I n recent years the recovery of sulfur from the hydrogen sulfide present i n natural and refinery gases has reached the status of a major industry. The processes used, however, employ meth ods worked out i n the nineteenth century i n the coal gas industry for the removal and use of hydrogen sulfide. I n the petroleum industry, this process was first used i n Iran before the second world war; i t is now being widely adopted i n America, partly because of the sulfur shortage and partly to avoid effluent nuisance. Industrial sulfur compounds also occur at the other end of the refining industry, in working up of white oils and related prod ucts. Manufacture involves drastic treatment with sulfuric acid, giving rise to sulfonic acids, which are useful on account of their surface active properties. They have been known for many years, but their constitution is still uncertain.

Alternative Routes to Petroleum Chemicals The importance of alternative routes to petroleum chemicals was discussed at the beginning of this paper. The position on the more important chemicals is summarized in Table I I . This is intended as a guide on where to look i n the literature on petroleum chemicals made from raw materials other than petroleum. Table II.

Alternative Routes to Principal Petroleum Chemicals Petroleum source

Chemical Methane

Natural gas

Ammonia Methanol

Methane Methane

Ethylene

Ad hoc cracking of gaseous or liquid hydrocarbons

Acetylene

Methane

Ethylene glycol

Ethylene

Ethanol Acetaldehyde

Ethylene Synthetic ethanol. Coproduct of paraffin gas oxidation Propylene

Acetone Glycerol Butadiene

Propylene 1- and 2-Butenes, ethanol

Aromatic hydrocarbons

Aromatic rich fractions, naphthene rich fractions

Synthetic

Alternative Sources, Europe (Except Where Stated) Coal, as by-product of separation of coke oven gases (1920-30) or of coal hydrogénation (1930-40) From coal via producer gas (1910-20) From coal via producer gas (1920-40); from methane (from coal) by methane-steam and methane-oxygen processes (1930-40). Dehydration of ethanol (original route). By-product in fractional distillation of coke oven gas (1925-35). Hydrogénation of acetylene (1940-45). Calcium carbide (original route). Methane from coal by partial combustion and by arc process (1935-45) From ethylene made as above (1925). In America from coal via carbon monoxide and formaldehyde (1935-40). Fermentation of molasses (original route). Fermentation ethanol or acetylene from carbide (190010). Wood distillation (original process). Pyrolysis of acetic acid (1920-30) or ethanol (1930) or by acetylene-steam reaction (1930-40). By-product of soap manufacture (original process). Ethanol (1915); acetaldehyde via 1,3-butanediol (192030); acetylene and formaldehyde from coal via 1,4butanediol (1940-45); from 2,3-butanediol by fermentation (1940-45). By-products of coal tar distillation.

Selected Bibliography TEXTBOOKS, ENCYCLOPAEDIA, REVIEWS

B r o o k s , B . T . , " C h e m i s t r y of t h e N o n - b e n z e n o i d H y d r o c a r b o n s , " N e w Y o r k , R e i n h o l d P u b l i s h i n g C o r p . , 1st e d . , 1 9 2 2 ; 2 n d e d . , 1950. D u n s t a n , A . E . , N a s h , A . W . , B r o o k s , B . T . , T i z a r d , H . , et al, " S c i e n c e o f P e t r o l e u m , " L o n d o n , Oxford U n i v e r s i t y Press, Vols. I - I V , 1938; V o l . V , 1950. E l l i s , C , " C h e m i s t r y of P e t r o l e u m D e r i v a t i v e s , " N e w Y o r k , R e i n h o l d P u b l i s h i n g C o r p . , 1st ed., 1934; 2 n d ed., 1937. F a r a d a y Society Discussions, " H y d r o c a r b o n C h e m i s t r y , " 1939; " O x i d a t i o n , " 1946; " T h e L a b i l e M o l e c u l e , " 1947; " H e t e r o g e n e o u s C a t a l y s i s , " 1950; " H y d r o c a r b o n s , " 1951. London. T h e F a r a d a y Society. F o e r s t , W . , éd., " U l l m a n n ' s Enzyklopâdie der T e c h n i s c h e n C h e m i e , " B e r l i n , U r b a n a n d Schwartzenberg, 1928-32, 1951-.


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ADVANCES IN CHEMISTRY SERIES Friedlânder, P . , " F o r t s c h r i t t e d e r T e e r f a r b e n f a b r i k a t i o n , " B e r l i n , S p r i n g e r ( N o issues since V o l . 2 2 , 1935). G o l d s t e i n , R . F . , " P e t r o l e u m C h e m i c a l s I n d u s t r y , " L o n d o n , E . & F . N . Spon, 1949. G r u s e , W . Α . , a n d S t e v e n s , D . R . , " C h e m i c a l T e c h n o l o g y of P e t r o l e u m , " 2 n d e d . , N e w Y o r k , a n d L o n d o n , M c G r a w - H i l l B o o k C o . , 1942. I n s t i t u t e o f P e t r o l e u m , Reviews of Petroleum Technology, L o n d o n , I n s t i t u t e o f P e t r o l e u m , 1 9 3 7 K i r k , R . E . , a n d O t h m e r , D . F . , e d . , " E n c y c l o p a e d i a of C h e m i c a l T e c h n o l o g y , " N e w Y o r k , Interscience E n c y c l o p a e d i a , Inc., 1947-. S a c h a n e n , A . N . , " C h e m i c a l C o n s t i t u e n t s of P e t r o l e u m , " N e w Y o r k , R e i n h o l d P u b l i s h i n g C o r p . , 1945. T h o r p e , J . F . , a n d W h i t e l e y , Μ . Α . , " T h o r p e ' s D i c t i o n a r y of A p p l i e d C h e m i s t r y , " 4 t h e d . , L o n d o n , N e w Y o r k , a n d Toronto, Longmans, Green & Co., 1937-.


JOURNALS, AMERICAN

Chemical Abstracts. Chemical and Engineering News. Chemical & Metallurgical Engineering ( u p t o J u l y 1 9 4 6 ) Chemical Engineering ( f r o m A u g u s t 1 9 4 6 ) . Chemical Engineering Progress ( f r o m 1 9 4 7 ) . Chemical Industries ( u p t o J a n u a r y 1 9 5 1 ) . Chemical Industries Week ( J a n u a r y t o J u n e 1 9 5 1 ) . Chemical Week ( f r o m J u n e 1 9 5 1 ) . Industrial and Engineering Chemistry. National Petroleum News. Oil and Gas Journal. Petroleum Processing ( f r o m S e p t e m b e r 1 9 4 6 ) . Petroleum Refiner. Transactions of the American Institute of Chemical Engineers ( u p t o D e c e m b e r 1 9 4 6 ) . JOURNALS, U . K . AND

EUROPE

Angewandte Chemie. Brennstoff Chemie. Journal of the Institute of Fuel. Journal of the Institute of Petroleum Technologists ( u p t o 1 9 3 8 ) . Journal of the Institute of Petroleum ( f r o m 1 9 3 9 ) . Petroleum Times. SELECTED ARTICLES

B r o o k s , B . T . , Ind. Eng. Chem., 16, 1 8 5 ( 1 9 2 4 ) . B r o o k s , B . T . , Chem. Met. Eng., 44, 18 ( 1 9 3 7 ) . B r o o k s , B . T . , Ind. Eng. Chem., 31, 5 1 5 ( 1 9 3 9 ) . Fortune, 24, 5 6 S e p t e m b e r ( 1 9 4 1 ) . G o l d s t e i n , R . F . , Petroleum Times, 51, 5 2 4 (1947) and s u b s e q u e n t l y a t 3 - t o 6 - m o n t h i n t e r v a l s . W i l s o n , R . E . , Chemistry and Industry, 1939, 1 0 9 5 MISCELLANEOUS

D a v i e s , M . , " P h y s i c a l P r i n c i p l e s of G a s L i q u e f a c t i o n a n d L o w T e m p e r a t u r e R e c t i f i c a t i o n , " L o n d o n , N e w Y o r k , a n d T o r o n t o , L o n g m a n s , G r e e n & C o . , 1949. R u h e m a n n , M . , " S e p a r a t i o n of G a s e s , " L o n d o n , O x f o r d U n i v e r s i t y P r e s s , 1st ed., 1 9 4 0 ; 2 n d e d . , 1949. R E C E I V E D March 3, 1953. Presented before the Division of Chemical Literature and the Division of Petroleum Chemistry, Symposium on the Literature of Chemicals Derived from Petroleum, at the 123rd Meeting of the A M E R I C A N C H E M I C A L S O C I E T Y , LOS Angeles, Calif.


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