Commercial Chemical Development of Butadiene HISTORY AND IMPLICATIONS JAMES H. BOYD 250 Park Ave., New York 17, N. Y . 4
a
T h i s is the third in a series of papers dealing with the case history of the commercial chemical development of butadiene (the 1,3-isomer) in the United States. The first paper dealt with handling and transportation ( I ) and the second with specifications (2). This paper gives the chronoIogy of the development and indicates the limitations as well as the importance of the role played by commercial chemical development.
T
R
H E American commercial development of butadiene stems from two fundamental facts. First, rubber is an unsaturated hydrocarbon. Secondly, in petroleum the United States has a very large supply of t h e raw material necessary for the manufacture of the unsaturated hydrocarbons needed for synthetic rubber. The butadiene development in the United States had definitely begun before the rubber demands of World War I1 tremendously increased its rate and magnitude. The earlier development of petroleum hydrocarbon processing in the United States was an essential factor contributing t o the later spectacular accomplishment of the government synthetic rubber program under the auspices of Rubber Reserve Company. Collateral developments were also significant, particularly the development of carbon black. I n retrospect it is clear t h a t the techniques of commercial development markedly accelerated the commercialization of butadiene progress once the value of the butadiene-acrylonitrile copolymer, Perbunan, had been demonstrated in the United States in 1937. However, the techniques of commercial development were not responsible for the industrial germination of synthetic rubber on which the butadiene development hinged. These techniques do not create the demand for new chemicals but, rather, are tools for speeding and simplifying their introduction to commercial use and consumption. The more freely these tools can be modified and adapted to the task at hand the greater is their utility. The successful commercial development of butadiene, and probably this is true for any chemical, rested not only on the perception and intelligent effort applied to its introduction to industry but even more basically upon a favorable economic environment, a factor relatively uninfluenced by the application of the techniques of commercial chemical development. Commercial development is thus only a n important aid t o progress in chemical industry and not a primary cause thereof. COMMERCIAL HISTORY OF BUTADIENE
Chance played an important part in the earliest commercial interest in butadiene. Quite independently several large industrial organizations began private butadiene manufacture as a result of their interest in ethylene. Certainly the first butadiene produced in quantity in the United States was incidental‘to the production of ethyl’ene by the cracking of light hydrocarbons and 80 was termed “coproduct butadiene.’, This coproduct butadiene was recovered from the cracker effluent as a concentrate and then purified. Later the Shell Chemical Company developed and privately used a process for the manufacture of butadiene as
the main product. These activities led to the commercially significant events given in Table I. CYLINDER BUTADIENE
A vital contribution to the commercial development of butadiene was its availability in cylinders for experimental work. Prior to late 1938 the butadiene used in synthetic rubber research was prepared by those using it. This was troublesome and impeded polymerization research. I n the fall of 1938, Dow Chemical Company made its first shipment of cylinder butadiene and later produced over 20,000 pounds in its pilot plant (16). In December 1939, Shell Chemical Company began shipping, from its main product pilot plant, cylinder butadiene made by the deUp to t h e hydrohalogenation of chlorinated refinery *butenes. termination of this operation in January 1942, Shell shipped a total of 248,313 pounds in cylinders t o various polymerization laboratories. Carbide and Carbon Chemicals Corporation made its first cylinder shipment of coproduct butadiene November 16, 1940 (5). Early in 1942 Phillips Petroleum Company included 99% pure butadiene in its line of hydrocarbons for experimental purposes. I n 1944 Phillips offered a more highly purified butadiene from a segregated supply for the Rubber Reserve research program in order to eliminate the effect of small differences in composition of butadiene drawn from several sources. At t h e same time Phillips made available a research butadiene with a cryoscopic purity of 99.72% ( I S ) . These several sources and types of cylinder butadiene were highly important for the support of polymerization research and the development of butadiene product specifications and analytical procedures. TANK CAR BUTADIENE
The first recorded bulk shipment of commercial butadiene was by tank truck on February 5 , 1941, from Carbide’s plant a t South Charleston, W. Va. (S). Tank truck shipment was made to avoid both the delay of accumulating a tank car load and the slower rail transit. I n March 1941, Dow, Carbide, and Phillips each made their initial tank car shipments of coproduct butadiene on the 15th, 18th, and 21st, respectively ( 3 , 16). The simultaneity of these initial shipments is remarkable in view of t h e widely different ethylene interests of Dow for styrene, of Carbide for aliphatic chemicals, and of Phillips for a thermal alkylation synthesis of neohexane. Standard Oil Company of New Jersey shipped their first tank car of coproduct butadiene in January 1942, made incidentally to the manufacture of ethylene for chemicals. Also in January 1942, the first tank car of main product butadiene made in the United States was shipped by Shell from their private plant. Practically all of this butadiene was used in acrylonitrile or N-type rubber manufacture. GOVERNMENT OPERATIONS
The importance of these private operations t o the government synthetic rubber program cannot be overstressed despite the disparity in magnitude of the private and government operations a s
2925
2926
TABLE I. Company Source of butadiene Shipment of butadiene First cylinder First tank truck First tank car
Carbide and Carbon Chemicals Corp. Manufacture of ethylene begun in 1923 November 16, 1940 February 5 , 1941 March 18, 1941
PRIVATE
BUTADIENE DEVELOPMENT
Dow Chemical Co.
Phillips Petroleum Co.
Shell Chemical Co.
Manufacture of ethylene begun in 1936
Manufacture of ethylene begun in 1939
Main product begull in 1942
Fall 1938
March 1942
December 1939
IViarch 15, 1941
~ a r ‘ c h21, 1941
J a n u a r s 1942
TABLE11. COMPARATIVE
SIZE O F PRIVATE AND
Conipsny
Carbide and Carbon Chemicals Corp.
Approximate private plant capacity (17) Government plant, demonstrated capacity ( 1 8 )
5,000 252,000
a
Vol. 41, No. 12
INDUSTRIAL AND ENGINEERING CHEMISTRY
...
... J a n i a r y 1942
GOVERNMENT BUTADIENE OPERATIONS I N 1945
(Short tons per year) Doiv Chemi- Phillips Petrocal Co. leum Co. 2,700
Standald Oil Co. of Neu Jersey l I a n u f a c t u r e of ethylene begun in 1942
2,000 45,000
Shell Chemical Go. 8,000 56,000
Standard Oil Co. of New Jersey
12,000
83,000a
Other
Total
aitibob
~51,000
29,700
Includes operations of affiliated companies,
shown in Table 11. The importance lay in the anticipatory development of know-how on manufacturing, transportation, handling, and specifications plus making available the butadiene necessary for experimental and commercial polymerization. IKDUSTRIAL HISTORY
The contributions of the major industrial pioneers in this field are outlined below. Coproduct butadiene is believed to have been first produced by Carbide and Carbon Chemicals Corporation in 1923. The butadiene was not then recovered as altention was centered on the utilization of the ethylene in chemicals manufacture. Probably initially the butadiene went unnoticed save as a gum former in the gasoline fraction. However, Carbide began study of butadiene as a primary product in 1930 ( 3 ) . About this time the existence of the normal butane-butadiene azeotrope, troublesome in butadiene purification, was recognized by Perkins and navies (1%). Simultaneously Chlorex (dichloroethyl ether)-extractive distillation for diolefin separation from olefins and paraffins was being developed (64). This process was among those used in the government butadiene program. In 1937 to 1938 certain butadiene derivatives renewed Carbide’s interest in butadiene production methods. In February 1940 extensive research was begun on making butadiene from ethyl alcohol. Initial bulk shipment of coproduct butadiene was by tank truck on February 5, 1941, and the first tank car followed on March 18, 1941. Production of government butadiene from ethyl alcohol began January 29, 1943. In 1935, Dow Chemical Company began cracking oil to obtain ethylene for the manufacture of styrene. Butadiene was formed incidentall? ( 1 1 ) . The demand for butadiene for synthetic rubber became apparent in 1937 ( 1 6 )and attention was directed to its recovery and subsequent purification by the ammonia azeotrope process. The supply of cylinder butadiene for laboratory rubber synthesis began with a 200-pound shipment in the fall of 1938. This is probably the earliest instance of supply of experimental quantities of purified coproduct butadiene in this country. Though the material analyzed 99% butadiene it did not polymerize and infrared analysis shon-ed 2% acetylenes in the product. Process improvements resulted in polymerizable butadiene and 20,000 pounds of cylinder butadiene were produced in this pilot unit. Dow’s first tank car of butadiene from the purification plant was shipped on March 15, 1941. Dox did not operate a government butadiene plant. Phillips Petroleum Company’s interest in butadiene began about 1928 (16) and was initially directed toward the dehydrogenation of paraffins as a route to butadiene manufacture. However, it was ethylene manufacture for neohexane synthesis begun in 1939 which first provided a source of coproduct butadiene for the budding N-rubber industry. Thls butadiene was purified by the furfural extractive distillation process later used in the govern-
ment program. Phillips also adapted t o butadiene its techniques for the handling and transportation of liquefied petroleum gas ( 1 ) . Another later contribution was the supply of several grades of cylinder butadiene for research and of qynthetic hydrocarbon gas mixtures for Rubber Reserve’s elaborate analytical program. Phillips’ first tank car was shipped March 21, 1941, and manufacture of government butadiene began September 12 1943. Shell Chemical Company was the major early source of bottled butadiene for polymerization research and from December 1939 t o January 1942 shipped 248,313 pounds from their pilot plant. This material as well as subsequent private plant production a t Houston, Tex., was made by the chlorination of 1- and 2-butene5 follov ed by dchydrohalogenation to butadiene and purification with acetone extractive distillation. This was the only main product butadiene produced in the United States prior to the government program. The process produced large quantities of hydrogen chloride and later proved uneconomic in competition with the vast government operations. The first tank car of Shell butadiene was shipped from Houston in 1942. Production of government butadiene began July 27, 1943. The Standard Oil Company of Kew Jersey and its affiliated companies began their study of butadiene with research on its synthesis from acetylene in 1932 (8). Later i!ork was directed to the development of a butadiene supply for their o m rubber manufacture. Significant process achievements were the butylene dehydrogenation to butadiene and its purification M ith copper ammonium acetate. Ethylene manufacture for rhemical operations began in January 1942 and the first tank car of coproduct butadiene was shipped that same month. Initial government butadiene production began March 27, 1943. As a war measure, during 1940 to 1946, The United Gas Improvement Company produced a butadiene concentrate for purification elsewhere. Others, including Universal Oil Products Company, were interested in butadiene manufacture but did not contribute to its commercial development. To date butadiene has had but little industrial use in other chemical syntheses so that its future now rests solely on the new highly publicized cold rubber (19, 21). PRICE AND PRODUCTION DATA
From 1941 until 1943 the demand for butadiene for N-rubber manufacture exceeded the private supply. Under these conditions the price of butadiene varied from 18 cents to 25 cents per pound .depending on the source. These price differences disappeared shortly after January 1943 when government production of butadiene from ethyl alcohol began. In order t o conserve tank cai transportation both private and government butadiene production were pooled and so allocated as to eliminate “cross hauls.” The price remained a t 18 cents per pound until curtail-
INDUSTRIAL AND ENGINEERING CHEMISTRY
December 1949
Even the German methyl rubber of World War I would not have made too poor a showing had carbon black and the knowledge of its use been available as the data in Table V show. Curiously also, the performance of the new cold rubber in processing and in use varies significantly with the specific carbon black employed
ment in GR-S production below the volume level of government low cost butadiene production again permitted a free market in private butadiene when the price dropped t o 12 cents per pound and later t o 11.5 cents per pound. As already indicated this price history is not typical of chemical development. Some production and average value data (10) are given in Table I11 in which government and private butadiene figures are combined.
(14, 19).
ROLE OF COMMERCIAL DEVELOPMENT
This commercial history of butadiene is straightforward but in order to evaluate the role played by the relatively new techniques of commercial chemical development it is helpful to look into the past. The commercial development of butadiene is so closely linked with synthetic rubber t h a t i t is instructive t o consider the latter’s history as tabulated chronologically in Table IV which presents the author’s choice of the most significant events leading to the commercial development of butadiene. For brevity, omissions have been made which others may question. Those wishing additional detail are referred to Midgley (4), Howard ( 8 ) , Fisher ( 7 ) , Sebrell (20), and the detailed historical review by Whitby and Katz (23). There are probably two outstanding discoveries in this list. First, naturalrubber is a hydrocarbon, whence it follows that physically similar materials will also probably be hydrocarbons. Secondly, a butadiene copolymer, which alone is of most limited utility, becomes commercially valuable when reinforced with carbon black. Because rubber is a hydrocarbon it can be based on petroleum while carbon black is made chiefly from natural gas, both fortunately abundant in the United States. The importance of carbon black can scarcely be overemphasized.
AND VALUEOF BUTADIENE TABLE 111. PRODUCTION
Year 1938 1939 1940 1941 1942 1943 1944 1945
Produo tion, Millions of Lb. 0.002 0.007 0.37 5.9 24 364 1212 1247
TABLE IV. Year m
1820 1882 1912 1928 approx. 1931 1933 1Q33 1934 1937 1937 1941 1943 1948
Av. Value per Lb.
Ratio of Alcohol t o Petroleum Butadiene
$1.09 0.35 0.36 0.21 0.19 0.36
2.5
0.34 0.21
1.6 0.6
... ...
Remarks Cylinder Cylinder Cylinder First tank car shipment All private production Production of butadiene from alcohol begins
SYNTHETIC RUBBER CHRONOLOGY Discovery
01
Achievement
Rubber found to be a hydrocarbon (6) Synthetic rubber clearly foreseen (23) Einulsion polymerization discovered (89) Butadiene selected as the diene monomer Neoprene announced-an nil resistant rubber (23) Buna S-general purpose rubber (28) Carbon black with Buna S (28) Perbunan-oil resistant rubber ( 9) U. S. imports Perbunan (8) U. S. commercial development of butadiene begins (16) Initial bulk shipment of butadiene (3) Government butadiene production begins ( f7) Cold rubber production ( 8 1 )
Country England England Germany Germany U. 9. Germany Germanv German$ 9.
u. u. s. u. s. U. S. u. 5.
2921
,
Also necessary were collateral developments in styrene and acrylonitrile manufacture in order t o have them available when needed for copolymers with butadiene. In 1935, Dow began the manufacture of styrene for plastics (6, 11 ). Acrylonitrile knowhow derived from long range plastic and chemical interests though its initial manufacture in 1941 by American Cyanamid Company and by Rohm and Haas was justified by its use in IG-rubber. The diverse ethylene interests leading t o coproduct butadiene, the development of carbon black, styrene, and acrylonitrile, coupled with the polymerization know-how and rubber processing know-how were all necessary t o create commercial value in butadiene. It is obvious t h a t the commercial development techniques earlier discussed, while significant, played but8 a minor part in this. Really, interest in butadiene was derived basically from the original interest in rubber because of its remarkable elastic properties. Rubber consumption followed the growth of the automobile industry in the United States. The growing dependence of the industrial nations on automotive transportation increased interest in synthetic rubber but it was not until the oil-resistant rubbers were developed t h a t synthetic rubber became self-supporting. The techniques of commercial development were not applied to butadiene until 1937 when Perbunan was first imported into the United States and the supply of cylinder butadiene for experimental polymerization actively began. The importation of Perbunan was a t least in part occasioned by the need for a replacement for Neoprene whose manufacture was interrupted by a plant explosion (8). This interruption stimulated the synthesis of butadiene rubber which led to the manufacture of coproduct butadiene and then t o the solution of the commercial problems arising in its transportation and handling and in drafting product specifications. The history of butadiene development has political as well as commercial implications. T h e chain of events beginning in 1826 leading t o the butadiene development was not planned. The synthesis of butadiene rubber was t h e result of man’s freedom to satisfy both his curiosity as t o the nature of things and his ambition t o be independent of his terrestrial environment. The techniques used in the commercial development of butadiene could have been fully developed only under free enterprise for their value depends on the equality of buyer and seller, an equality which does not exist in a planned economy. The synthesis of rubber from butadiene was a product of human imagination as were the solutions of the problems arising in its commercial development. Human imagination is most productive where given individual scope. These development techniques are helpful in discovering new uses for chemicals although they do not create them. They are an accelerator though not a cause of chemical development. Properly applied, these techniques can greatly shorten the time required t o bring a new chemical into routine commercial use. ACKNOWLEDGMENT
TABLE V. EFFECT OF CARBON BLACBADDITIONS I N VULCANIZATES OF
NATURAL AND GERMAN SYNTHETIC RUBBERS (7)
Natural rubber Methyl rubber W Buna S
Pure Gum Stock Ultimate tensile Elongastrength, tion, lb./sq. in. % 4125 710 425
..
510
Carbon Black Stock Ultimate tensile Elongastrength, tion, lb./sq. in. % 5000 650 2415. 4200
530 650
Acknowledgment is gratefully made to many friends in industry who helpfully contributed data and suggestions used herein. LITERATURE CITED
(1) Boyd, J. H., IND.ENG.CHEM,,40, 1703 (1948). (2) Ibid., p. 1964. (3) Carbide and Carbon Chemicals Corp., “Buna 8 Synthetic Rubber,” 1943.
INDUSTRIAL AND ENGINEERING CHEMISTRY
2928
(4) Davis, C. C., and Blake, J. T., “Chemistry and Technology of
(7) (8) (9) (10) (11) (12) (13)
Rubber,” New York, Reinhold Publishing Corp., 1937. Dow, W. H., IND.ENG.CHEM.,34, 1267 (1942). Faraday, M., Quart. J . Sci., 21, 19 (1826). Fisher, H. L., Am. SOC.Testing Materials Marburg Lecture, 1941. Howard. F. A., “Buna Rubber,” New York, D. Van Nostrand Co., 1947. Konrad, E., and Tschunkur, E., U. S. Patent 1,973,000 (1934). Manufacturing Chemists’ Assoc., “Chemical Facta and Figures,” 2nd ed., Washington, D. C., h‘lfg. Chemists’ Assoc., 1946. Mitchell, J. E., Jr., Trans. Am. I n s t . Chem. Engrs., 42, 293 (1946). Perkins, G. A , , and Davies, J. d.,U. S. Patent 2,271,092 (1942). Phillips Petroleum Co., Bull. 103 (1944).
Vol. 41, No. 12
(14) I b i d . , 265 (1948). (15) Phillips Petroleum Co., “Phillips and Synthetic Rubber,” 1943. (16) Poffenberger, N., et al., Trans. Am. Inst. C h m . Engrs., 42, 815 (1946). (17) Rubber Reserve Co., “Report on the Rubber Program 19401945,” Feb. 24, 1945. (18) I b i d . , Supplement No. 1 (April 8, 1946). (19) Schulze, W. A,, et al., Oil Gas J . , 46, 128 (March 1945). (20) Sebrell, L. B., IND.ENC.CHEM.,35,738 (1943). (21) Shearon, W. H., Jr., and McKensie, J. P., I b i d . , 40, 769 (1948). (22) Tschunkur, E., and Bock, W., U. S. Patent 1,938,730-1 (1933). (23) Whitby, G. s.,and Kata, bI.,IND. ENG.CHmf., 25, 1204, 1338
(1933). (24) Young, C . O., and Perkins, G. A., G. S.Patent 1,948,777(1934). RECEIVED June 15,
1949.
Organic Dehydration Reactions Using Activated Bauxite -
HEINZ HEINERIANNl, R. W. WERT, AND W. S. W. MCCARTER Porocel Corporation, Philadelphia, Pa. Activated bauxite is an abundant and relatively inexpensive catalyst for drying and for dehydration reactions in organic chemistry. Activated bauxite has been found to be equal or superior to the various forms of activated alumina now widely used for drying and to catalyze dehydration reactions. A number of well known dehydration reactions are described in which activated bauxite is substituted for activated alumina as a catalyst. The yield obtained in dehydration reactions is shown to be affected by such variables as reaction temperature, activation temperature, and iron content of the bauxite.
D
RYING and dehydration reactions in organic chemistry using inorganic desiccants as regenerable agents have been frequently described and are widely used. Among the most frequently mentioned desiccants are silica gel, thoria, tungsten oxide, and alumina. The alumina catalysts described in the literature are usually either alumina gels or forms of “activated alumina.” Relatively little work has been done with activated bauxite as a catalyst for this type of reaction. Yet bauxite, a naturally occurring hydrated alumina containing minor amounts of kaolinite, anatase, and ferric oxide, is interesting as an abundant and inexpensive catalytic agent. The bauxites used in the work described in this paper n‘ere of either -4rkansas or South American origin and had chemical and physical properties previously described (15, 19). Some typical chemical analyses are given below: % FetOs
% Si02
Ti02 1.30
Bauxite I 0.76 4.40 Bauxite I1 1.28 13.99 1.92 9.50 Bauxite I11 2.73 3.44 Bauxite I V 5.65 9.40 3.40 Bauxite V 18.60 6.40 2.60 a Column includes figures for NarO, KzO, etc.
% A1203 92.20
yo Undetermined“ 1.34
82.83 84.33 80.70
0 0
68.00
4.40
0.85
Iron content was varied by selection and blending of ores. The bauxites were thermally activated, either by large scale (18) or by laboratory procedures (16). Results of this work show that bauxite, in addition t o being an excellent drying agent (3, Q), is generally equivalent to other forms of alumina for con1
Present address, Houdry Process Corporation, iMarcus Hook, Pa.
densation reactions and that its iron content has in certain cases a promoting influence. APPARATUS AND PROCEDURE
Most of the dehydration reactions described in this paper were carried out by passing the reactants in either gaseous or liquid phase and a t atmospheric pressure through a bed of activated bauxite. The reaction chamber consisted of a Pyrex glass tube 3.75 em. in diameter and 105 cm. long. The catalyst bed of 100 t o 200 ml. was held in place by glass moo1 plugs and was preceded by a layer of glass beads t o serve as a preheating zone. The reactor ITas heated in an electric tube furnace of conventional design. Catalyst temperatures were measured by a thermocouple placed in a n axially located thermowell; furnace temperatures were controlled by means of a therniostatic regulator. Liquid reactants were charged from a calibrated buret to the reactor head by means of a n adjustable bellows pump, while gaseous reactants were admitted through a flowmeter. The reactor was connected to a water condenser, a receiver, and a dry ice stabilizer. Uncondensable gas was metered. The products obtained were, if possible, separated into aqueous and nonaqueous layers and idcn tificd by one or more of the following procedures: fractional distillation, the preparation of derivatives, refractive indexes, aaeotropic distillation, density, and acid number. INTRAMOLECULAR DEHYDRATIONS
Dehydration of Ethyl Alcohol. The dehydration of an aqueous solution of ethyl alcohol or of 95 to 99% alcohol can occur in three ways-viz., drying to absolute alcohol, dehydration to diethyl ether, or formation of ethylene. Under proper operating conditions bauxite will influence the reaction in such a manner that ’any one of these three compounds can be obtained as the main reaction product. DRYING.Derr (IO) has proposed a vapor phase process for drying ethyl alcohol to absolute alcohol in the presence of alumina adsorbent. Some ethylene may be produced as a by-product. The authors’ experiments show that very satisfactory vapor or liquid phase drying can also be obtained with activated bauxite as the adsorbent. In order to obtain absolute alcohol, long periods of intimate contact are necessary. A t atmosphcric temperature, liquid space velocities of less than 0.1 volume per volume per hour are required t o give absolute alcohol. Some dehydration of alcohol to ethylene always occurs. The amount of ethylene formed increases rapidly with increasing temperature, Thus, the heat of wetting, when alcohol first
