Formaldehyde: A Statistical Review J O H N R.
SKEEN
A p r o d u c t i o n capacity of 900 m i l l i o n p o u n d s of f o r m a l d e h y d e a n n u a l l y m a y prove i n a d e q u a t e t o m e e t t h e n e w d e m a n d s of greatly increased p r o d u c t i o n of t h e r m o s e t t i n g resins L HE capacity to produce formaldehyde has expanded almost without interruption since the earliest days of the industry. Within a few months, private plants alone will be able to make about 900 million pounds annually (37% by weight), or almost five times that of only a decade ago. Until recent months, the supply was insufficient for the demand. This situation affected the production of phenolic, melamine, urea, and other resins; chemicals such as ethylene glycol, hexamethylene tetramine, and pentaerythritol; and handicapped operations in the dye, drug, leather, and fur industries. This year new facilities sufficient to make over 135 million pounds of formaldehyde will be completed. As this capacity anticipates the greatly increased production of thermosetting resins, especially the phenolics, the present adequate supply of formaldehyde may be only temporary. With the beginning of the European war in 1939, the need for formaldehyde was sharply increased for the manufacture of certain vat dyes and thermosetting resins, particularly for new construction. The armed services soon required the chemical to make hexamine for nitration into the explosive R D X . I t is probable that over 380 million pounds of formaldehyde were diverted from private plants t o war purposes in 1943, and formaldehyde was placed under complete allocation early in the year. With the end of World War II, capacity exceeded the need and production was curtailed. The inadequacy of the potential supply, however, did not become apparent until a year later. Then the rapid expansion of the resin industry made demands for formaldehyde which could only be satisfied by a correspondingly remarkable increase in formaldehyde facilities. The necessary raw materials are low cost synthetic methanol or, alternatively, the lower boiling petroleum gases. Natural or wood methanol is not usually employed in the process. Methanol is oxidized with air a t temperatures u p to 600° C. Silver is the most generally used catalyst although several plants employ an iron-molybdenum oxide combination giving a higher yield but a t the expense of higher circulation. Such petroleum gases as methane, ethane, propane, and butane have been oxidized for 20 years t o yield formaldehyde as well as methanol and other coproducts. While formaldehyde was first prepared just 90 years ago by A. Butlerov, it was not until 1868 that it was identified. A. W. 3344
Hofman passed a mixture of methanol and air over a heated platinum wire and this method became the basis for subsequent procedures. Platinized asbestos was soon used and later replaced by copper gauze. The German firm of Mercklin and Lôsemann, located near Hanover, first began commercial production in 1889. At least five other operations started in Middle Europe shortly afte>. Uses were few at first. Some worthy of mention were the hardening of gelatin films, the preparation of paraformaldehyde, the synthesis of hexamine, anhydroformaldehyde aniline, and a few médicinale and dyes. About 1900, the demand was increased when the value of formaldehyde as a disinfectant was recognized. At this time, too, formaldehyde was needed for the production of phenylglycine, an intermediate for making indigo. Upon the organization in 1910 of the General Bakélite Co., a market was created in the new field of plastics. The syntans of Edmund Stiasny of Austria appeared also, and four domestic firms were consuming formaldehyde to make these products by 1920. New uses appeared rapidly, as illustrated by the production of formaldehyde sodium hydrosulfite, consumed extensively in dyeing and printing; in anhydroformaldehyde-p-toluidine, a rubber accelerator; as a grain-tightening agent for leather, and for a miscellany of uses in cosmetics. By 1940, over 130 million pounds of Table I.
formaldehyde were required by the plastics industry, nearly 16 million pounds for t h e synthesis of ethylene glycol, and about 14 million pounds for making hexamine. T h e drug and dye industries accounted for almost 13 million pounds as did the producers of leather and furs. As war progressed, all demands increased although only "vital industry*' was amply supplied. Thus, the consumption in plastics doubled by 1943 and over 70 million pounds were converted into ethylene glycol. Consumption in hexamine reached 115 million pounds from civilian sources alone and pentaerythritol accounted for nearly 30 million pounds more. Generally, other outlets were not supplied in amounts exceeding peacetime levels, or they were actually curtailed. In order to supply skyrocketing demands, industry doubled its capacity by the end of 1941. The War Production Board then sponsored additional increases totaling 195 million pounds. Among the latter were the Cherokee Ordnance Plant a t Danville, Pa., and the Morgan town Ordnance Plant, originally begun b y Du Pont as a private enterprise in 1939. The combined capacities of these two plants amounted to about 500 million poimds of formaldehyde annually (37% equrv >nt). Both are present!}' maintained in standby condition. Domestic production was begun by the Buffalo Alcoline Works in 1901 with equipment bought from t h e Van Heyden Co. of Germany. Two years later, this equipment was purchased b y the Heyden Chemical Works and installed a t Garfield, N . J.
Formaldehyde: Domestic Supply and Price Unit:
1,000 pounds of 3 7 % (by wt.)
Domestic Supply*
Price· Imports e Exports* Production t» SO.085 1914 14 n.a. 8,426 0.097 2.898 26.155 1924 23,257 0.091 2.588 51,786 1929 49,198 0.072 3,769 40,763 1930 36,994 0.060 2.905 n.a. 1931 0.060 2,103 n.a. 1932 0.060 2.373 52,236 1933 49,863 0.060 2.598 n.a. 1934 0.060 0.4 2.498 n.a. 1935 0.059 0.0 1.844 n.a. 1936 0.058 2.865 n.a. 1937 0.058 1,765 n.a. 1938 0.058 3.926 134,479 1939 130,553 0.058 5.710 180,885 1940 175,175 0.055 2.139 309,912 92* 1941 307,865 0.055 3.785 347,463 1942 343,678 0.055 5,217 522,920 1943 517,703 0.054 9,235 522,440 1944 513,205 0.032 10.744 509,602 1945 498,858 .. 0.032 11.065 460,048 1946 448.983 .. 13.312 0.036 615,853/ 1947 602,541 3.856 0.037 165,531 1948 (1st quarter) 161,675 .9 4.110 0.042 160,061 (2nd quarter) 155,951 β Production plus imports less exports. bc 1914-46: Tariff Commission, Annual Reporta; 1947-48: Facta for Industry, series 6-2-50, 6-2-55. Foreign Commerce and Navigation, Department of Commerce. à 1924-46: Foreign Commerce and Navigation; 1947-48: Report N o . PT410, Department of Commerce. « 1914: "contract price," approximate only; 1924—: Bureau of Labor Statistics; 1924-44: bbl., works; 1945-: tanks, works. / A revision of a previously reported figure (513,868).
CHEMICAL
AND
ENGINEERING
NEWS
Table II.
Formaldehyde : Producers, Plants, and Capacities 0
Capacity unit: million pounds of 3 7 % (by wt.) Plant Capacities'* Plants* Producers & Existing σ New Plants/ Total· (number) (number) 5 130 130 3 1936 5 3 1937 172 18 190* 6 4 1938 190 190 6 4 1939 233 1 234 7 5 1940 346 12 358 8 6 1941 398 71 469 9 7 1942 551 6 557 11 9 1943 555 555 10 8 1944 561 561 10 8 1945 599 45 644 13 11 1946 678 65 743 15 11 1947 778 96 874 i 18 14 194S a From announcements, reviews, and industry survey. «> 1938: Kay-Fries; 1940-41: Commercial Solvents, Rohm & Haas; 1942: Bakélite: 1943: Thomas Keery, Celanese; 1944: Thomas Keery discontinued; 1946: Durez, Casein, Geo. I. Trey ζ ; 1947: Agnew plant of Commercial Solvents Toledo plant of D u Pont; 1948: Monsanto, Spencer, McCarthy. c Uncertainties whether some plants "came in*' at the end of one year or the beginning of another; dis continuance after start-up is not considered. «* Existing at year-end, see e . * Error believed to be =*= 10% consistent with c and probably much less for late years. / Initial capacity as rated or installed and differs from ultimate potential capacity; error believed to be on the low side. ο Capacity of existing plants at year end. h May be as low as 175 million pounds. * May be slightly over 900 million pounds; earlier reports give as high as 1 billion pounds, a value which does not appear to be justified by present evidence. While representing production primarily from methanol, capacities of three producere from petroleum gases are included: Celanese, Cities Service, Com mercial Solvents.
Following another German process, Har rison Brothers began production in Phila delphia in 1904. In this year, also, Roessler and Hasslacher Chemical Co. (acquired by Du Pont in 1930) began operations through its subsidiary, the Perth Amboy Chemical Works. No new producers seem to have appeared for nearly 20 years.
There were short-lived projects of the Delta Chemical and Iron Co., the MinerEdgar Co., the Norvell Chemical Corp., and the Rednovol Chemical Products Co. Through its subsidiary the Cities Service Co. began coproduct production at Tallant, Okla., in 1927. Heyden, Du Pont, and Cities Service have remained in con
Groves Outlines Chemists' Atom Itniib Role A STAFF REPORT
J. HE the
Western Connecticut Section of
AMERICAN CHEMICAL SOCIETY cele
brated its one hundredth meeting by a record turnout of almost 200 members and guests. The gathering, which in cluded most of the section's past chairmen since its founding 12 years ago, heard Lt. Gen. Leslie R. Groves, wartime head of the atomic bomb project, speak on the 1 'Chemists' Important Role in the De velopment of the Atomic Bomb." The scene for the gathering was the Picadilly Restaurant, historic landmark in Stam ford, Conn., the home city of the section. Gen. Groves, now an executive of the Remington Rand Co., arrived at the meeting fresh from Miami Beach, Fla., where on the previous evening he had addressed the national convention of the American Legion on the subject of Ameri ca's atomic preparedness. Ή. J. Wing of Northam-Warren Co. and chairman of the Western Connecticut Section in troduced General Groves. The general opened his address with a mild rebuke to the chemists for allowing "all of the scientific glory to go to the physicists" for the progress of the war time atomic bomb project. He pointed out the helpful contribution made to the undertaking by the chemists, among whom he said was Dr. Conant of Harvard, VOLUME
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tinuous production over the years. In 1938, Kay-Fries Chemical, Inc., began operations. Shortly after, Rohm and Haas was producing at Bristol, Pa., as was the Bakélite Corp. at Bound Brook, N. J. Two small plants employing natural methanol have operated in late years. The Thomas Keery Chemical Co. produced in small amount in 1943 while the George I. Treyz Co. began three years ago. Probably the most dramatic development is represented by the Celanese Corp. of America with its plant at Bishop, Tex. This coproduct enterprise has expanded since 1943 until Celanese is today the third largest producer of formaldehyde. Producers new to the field in the past two years include the Casein Co. of America at Springfield, Ore.; Durez Plastics and Chemicals, Inc., at North Tonawanda, Ν. Υ.; and the Commercial Solvents new plant at Agnew, Calif. In operation last year was the new plant of Du Pont at Toledo. Monsanto Chemi cal Co. began this year at Springfield, Mass. It is expected that the Spencer Chemical Co. will be producing at Calumet City, 111., before the end of 1948 as well as the McCarthy Chemical Co. at Winnie, Tex. However, now as in the past, Hey den and Du Pont remain the largest pro ducers of formaldehyde, and by a wide margin. preparation of raw materials for the diffu sion process, the barrier problem, and the purification and separation of plutonium. The ability of the chemist and chemical engineer as technical planners and opera tors, the general said, was proved in the fact that the "gaseous diffusion plant worked perfectly from the daywit was turned on," a result that many scientists never believed possible. The speaker concluded this part of his discussion by praising the role of the instrument engineers, much of whose training had originally been along chemical lines. "Instrument engineering worked perfectly," the general said, and whenever an instrument and a man dis agreed in an observation, the instrument was found invariably to be correct.
"a scientist not worried about precedent." At the outset of the project, the general observed, it was very difficult to get the scientific men on the project to "leave the blackboard stage and decide upon a definite approach to the problem." Once this theoretical stage was passed, Gen. Groves continued, the need for "good chemists" capable of putting theory into practice, became even more pronounced. "It is hard," the general declared, "to get men at the top who have a sound fundamental knowledge." Fortunately for the project, the H. J. Wing, Northam-Warren Co., chairman of Western speaker declared, Connecticut Section, ACS, and Gen» Groves of Renting" men like Conant and ton Rand, and former head of Manhattan Project Tolman were avail able; "two men upon whom I depended the most." Gen. Groves then proceeded to give brief accounts of many of the chemical problems that arose on the project and the manner in which chemists and chemi cal engineers resolved them. Among these, he said, were the
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8,
1948
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