17. RAW MATERIALS FOR TAR-ACID RESINS
Reading edition
The first tar-acid resins were made from phenol and formaldehyde. As a result this group of resins is frequently spoken of as phenolic resins. This is true despite the fact that coal-tar acids other than phenol, particularly the cresols and xylenols, are used in large volume today.
THE TAR ACIDS
The term coal-tar acids is applied to certain organic compounds either obtained from or known to be present in coal tar. Probably the best known is phenol or carbolic acid, produced in large quantities in the United States and abroad. Others of commercial importance are ortho, meta, and para cresol and the xylenols. All of these are definite chemical compounds available as such or in mixture with other tar acids. Cresylic acid is a term widely used in commerce for almost any mixture of tar acids. Formerly it was used to designate a mixture of ortho, meta, and para cresols in the proportions in which they are found in coal tar. The higher boiling tar acids (listed in table 56 below the xylenols) have little or no commercial importance at this time.
Table 56 lists the tar acids by commercial name, chemical name, boiling point of the pure compound, and average percentage present in coal tar. Boiling point is shown because the several tariff classifications covering tar acids under the acts of 1922 and 1930 (pars. 27 and 1651) depend upon distillation range (boiling points) for classification and assessment of duty (see pp. 119 and 124).
Table 56.—Tar acids: Commercial and chemical names, boiling points and average percentage present in coal tar
Commercial name Chemical name Boiling point ° C Average percent in coal tar
Phenol Phenol 181.5 0.7
Orthocresol 2-methyl phenol 190.8 .4
Metacresol 3-methyl phenol 202.8 .4
Paracresol 4-methyl phenol 201.8 .3
2-3 Xylenol 2-3-dimethyl phenol 218.0 ⎫ .2
2-4 Xylenol 2-4-dimethyl phenol 211.5 ⎪
2-5 Xylenol 2-5-dimethyl phenol 211.5 ⎬
2-6 Xylenol 2-6-dimethyl phenol 212.0 ⎪
3-4 Xylenol 3-4-dimethyl phenol 225.0 ⎪
3-5 Xylenol 3-5-dimethyl phenol 220.0 ⎭
Ortho ethylphenol 2-ethyl phenol 206.5 ⎫ .5
Meta ethylphenol 3-ethyl phenol 217.0 ⎪
Para ethylphenol 4-ethyl phenol 218.5 ⎪
s-methyl ethylphenol 3-methyl-5-ethyl phenol 232.5 ⎬
Iso pseudocumenol 2-3-5-trimethyl phenol 233.0 ⎪
Mesitol 2-4-6-trimethyl phenol 219.5 ⎪
Pseudocumenol 2-4-5-trimethyl phenol 234.0 ⎭
Source: Ellis, Chemistry of Synthetic Resins.
Since the quantities of tar acids present in coal tar are small (see table 56), it is usually uneconomical to distill coal tar completely unless the creosote oil and pitch can be marketed profitably. Beginning in 1936, production of tar acids in the United States was increased by the practice of topping. Topping is the recovery in tar distillation of the light fractions only, leaving a residual thin enough to flow through the pipe lines to supply fuel to open hearth and other type furnaces. These light fractions contain the naphthalene and tar acids. The practice permits recovery of these products from tar to be used as fuel, thus providing a new alternative intermediate between the two older practices of either complete distillation or using the undistilled tar as fuel.
In the United States, consumption of most of the tar acids greatly exceeds the quantities extracted from tar, necessitating large production of synthetic phenol and importation of large quantities of the cresols and xylenols. The calculated amount of these tar acids present in the tar produced in this country vastly exceeds present day requirements. Table 57 shows the approximate amounts of the several tar acids contained in the coal tar produced and distilled in 1936. These estimates are based on a 1936 production of coal tar of 560,385,578 gallons and a distillation of 292,140,249 gallons. The calculation is made by using the percentage of tar acids in tar shown in table 56 and converting the gallons to pounds in accordance with the specific weights of the pure tar acids. Actual production of all tar acids in the United States in 1936 was about 29 million pounds.
Table 57.—Tar acids available in coal tar produced and distilled in 1936
Tar acid Available in tar produced in 19361 Available in tar distilled in 19362
1,000 pounds 1,000 pounds
Phenol 34,912 18,200
Orthocresol 19,277 10,050
Metacresol 19,277 10,050
Paracresol 14,290 7,450
Xylenols 10,200 5,316
Others 25,200 13,290
1 560,385,578 gallons.
2 292,140,249 gallons.
The several tar acids are discussed in detail under the following heads:
(a) Phenol.
(b) The cresols, xylenols, and cresylic acid.
(c) Synthetic tar acids other than phenol.
PHENOL
Description and uses.
Phenol (commonly called carbolic acid) is a tar acid obtained from two sources: (a) From one of the fractions recovered in the distillation of coal tar, a byproduct resulting from the manufacture of coke in byproduct ovens, and from the manufacture of coal gas; (b) from benzol, by synthesis. The second source has been the more important since 1923. Phenol, when pure, is a colorless substance of interlaced or separate needle-shaped crystals with a characteristic aromatic odor. It is corrosive to the skin and to mucous membrane. When pure it is water white, melts at about 42° C., and boils at about 181.5° C. It was discovered in 1834 by Runge.
Phenol is used today chiefly as a component of tar-acid resins. It is also widely used as an antiseptic and disinfectant, in the manufacture of explosives (picric acid and ammonium picrate), and as an intermediate for certain dyes and medicinals. Salicylic acid and its derivatives—aspirin, salol, and methyl salicylate (artificial oil of wintergreen)—are important medicinals made from phenol. Another use is in the extraction of lubricating oils. The relative importance of these various uses in recent years is indicated by table 58, which gives the estimated domestic consumption of phenol by uses in 1936-37.
Table 58.—Phenol: Estimated consumption by industries, 1936-37
Use Percent of total consumption
Synthetic resins 60-65
Extraction of lubricating oil 5
Insecticides and disinfectants 10
Dyes and intermediates 5
Other 15-20
United States production.
Prior to 1914 United States production of phenol averaged about a million pounds a year and was entirely the natural product obtained from distillates of coal tar. Increased demand during the World War was met by several synthetic phenol processes, which utilized in part the vast quantities of benzol available. Our output of phenol reached 64 million pounds in 1917 and 107 million pounds in 1918. When the armistice was signed stocks on hand in the United States totaled between 35 million and 40 million pounds, estimated at three times the annual consumption at that time for nonmilitary purposes. As a result the price dropped from about 45 cents to 6 cents a pound, and the synthetic plants were closed.
The limited quantities of phenol available to synthetic resin makers prior to and during the World War caused much concern to that industry and led to research work for substitutes, work resulting in the development of many new and modified types of resins in which tar acids other than phenol were used. But notwithstanding the use of these other tar acids the increased demand for synthetic resins used up the accumulated stocks of phenol sooner than was expected.
Of the phenol produced in the United States from 1919 through 1923 a large part was natural phenol but the rapid increase in demand and the improvement of processes for synthetic phenol had by 1923 resulted in four companies beginning production of the synthetic article. The rapid increase in output, from about 3 million pounds in 1923 to about 15 million pounds in 1925, was almost entirely in synthetic phenol. Since then a large part of the domestic production has continued to be synthetic, although the production of natural phenol since 1935 has been about four times that of 1929.
Adequate quantities of coal tar are usually available to produce sufficient natural phenol to meet a substantial part of our requirements, if it were all recovered, but the quantity actually produced is determined in part by the demand for other coal-tar products, and in part by the value of the tar as fuel. More than 50 percent of the tar produced has been burned as fuel, principally at the coke ovens or nearby steel mills.
The domestic production and sales of phenol, natural and synthetic combined, are shown in table 59.
Table 59.—Phenol: United States production and sales, in specified years, 1918-37
Census year Production Sales Ratio of sales to total production
Quantity Quantity Value Unit value
1,000 pounds 1,000 pounds 1,000 dollars Percent
1918 106,794 106,794 37,270 $0.35
1919 1,544 1,544 156 .10
1923 3,311 2,180 590 .27 66
1925 14,734 8,524 1,771 .21 58
1926 8,691 5,480 988 .18 63
1927 8,041 4,595 684 .15 57
1928 10,227 7,746 912 .12 76
1929 24,178 19,939 2,248 .11 83
1930 21,147 17,715 1,976 .11 84
1931 17,981 14,002 1,446 .10 78
1932 13,965 12,181 1,269 .10 87
1933 33,220 27,923 2,881 .10 84
1934 44,935 36,241 3,887 .11 81
1935 43,419 34,575 3,431 .10 80
1936 48,724 40,942 4,235 .10 84
1937 65,690 57,176 6,153 .11 87
Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.
Grades produced for resins.—Increased production of phenol in recent years is largely due to the demand from makers of synthetic resins. A number of grades are regularly produced for this purpose, though it is believed that the technical grade is the principal one used in resins. The several grades are as follows:
(1) USP.—Either natural or synthetic. This grade contains not less than 98 percent phenol.
(2) Technical.—Various grades containing from 80 to 95 percent phenol, of which the two most important are 82-84 percent and 90-92 percent.
(3) Mixtures.—Containing from 30 percent to 80 percent phenol and the remainder of the isomeric cresols.
Producers.—Natural phenol is obtained in the distillation of coal tar and to a smaller extent in the purification of ammonia liquors in coke and gas plants. In 1937 there were four producers of natural phenol with plants located at Philadelphia, Pa., Follansbee, W. Va., Indianapolis, Ind., and Pittsburgh, Pa. All these are tar distillers recovering creosote oil, pitch, cresylic acid, naphthalene, and other crudes from coal tar.
Synthetic phenol is made from benzene, either by sulfonation followed by alkaline fusion, or by chlorination and subsequent heating under pressure with caustic soda. It is produced in large quantities by two firms, one at Midland, Mich., and the other at St. Louis, Mo. A third producer is building a plant at North Tonawanda, N. Y., using a process recently developed in Germany. Operation of this unit will probably start late in 1938.
World production.
Natural phenol is recovered in practically all European countries and in Japan. Germany and the United Kingdom are the principal producers and have also been the leading exporters. Synthetic phenol was made in Germany as early as 1900, and during the World War. Plants for synthetic phenol recently installed are now in operation in Germany, Great Britain, Belgium, and Italy.
Table 60 shows the average annual world production of phenol in recent years by countries. Half of the total was produced in the United States.
Table 60.—Phenol: Estimated average annual production, by countries, 1933-35
Produced in— Estimated annual production
1,000 pounds
UNITED STATES 41,000
United Kingdom 18,000
Germany 10,000
Poland 3,000
Japan 3,000
Czechoslovakia 1,000
Belgium 2,000
France 2,000
Italy 1,500
Spain 700
Total 82,200
Source: Consular reports.
In the United Kingdom, where tar distillation is a well developed and highly organized industry, large quantities of gas-works tar, rich in phenol and other tar acids, are available. Prior to the World War the United Kingdom was the principal source of phenol, and of the other products of tar distillation. During the war several synthetic processes of commercial importance were developed, but they were discontinued after its close. A new synthetic unit has recently been installed in England and is now in operation. Increasing consumption of phenol in synthetic resins during the last decade, particularly in the last several years, has changed the United Kingdom from an exporter to an importer of phenol. Estimated consumption of phenol in the United Kingdom is given as 20 million pounds annually—principally in synthetic resins, and in lesser quantities in dyes, intermediates, antiseptics, and disinfectants.
In Germany the phenol recovered in 1936 amounted to about 20 million pounds, and recently three commercial units have been installed for the production of synthetic phenol, one with a reported daily output of 11,000 pounds.
Natural phenol is also recovered in Belgium, France, the Netherlands, Czechoslovakia, Poland, Italy, and Spain. Synthetic phenol has recently been produced for the first time in Belgium and Italy. The quantities normally produced in these countries are small and are supplemented by imports from Great Britain and Germany.
The production of phenol in Japan has increased rapidly and has been sufficient since 1930 to meet domestic requirements. The estimated output increased from 300,000 pounds in 1927 to more than 3 million pounds annually in recent years. The Miike Dyestuffs Works is reported to be producing synthetic phenol.
United States imports.
Rates of duty.—Prior to September 6, 1916, phenol was imported free of duty. Since that date it has been dutiable at the various rates shown in table 61. Under the act of 1930 the rate of duty is 3½ cents per pound and 20 percent ad valorem on the American selling price (the wholesale price of a similar competitive article manufactured in the United States).[21]
Table 61.—Phenol: Rates of duty upon imports into the United States, 1916-37
Period Rate of duty Authority
To Sept. 8, 1916 Free Free under Tariff Act of 1913 and previous acts.
Sept. 9, 1916, to Sept. 21, 1922. 2½ cents per pound plus 15 percent ad valorem on foreign value. Under Revenue Act of 1916.
Sept. 22, 1922, to Sept. 21, 1924. 7 cents per pound plus 55 percent ad valorem on American selling price1 or United States value.2 Under par. 27 of Tariff Act of 1922; special provision for first 2 years.
Sept. 22, 1924, to Nov. 29, 1927. 7 cents per pound plus 40 percent ad valorem on American selling price1 or United States value.2 Under par. 27 of Tariff Act of 1922, rate provided for period after the first 2 years.
Nov. 30, 1927, to June 17, 1930. 3½ cents per pound plus 20 percent ad valorem on American selling price1 or United States value.2 By Presidential proclamation following a cost of production investigation under sec. 315 of Tariff Act of 1922.
June 18, 1930 3½ cents per pound plus 20 percent ad valorem on American selling price3 or United States value.4 Under par. 27 (b) of Tariff Act of 1930.
1 As defined in subdivision (f) of section 402, title IV, act of 1922.
2 As defined in subdivision (d) of section 402, title IV, act of 1922.
3 As defined in subsection (g) of section 402, title IV, act of 1930.
4 As defined in subsection (e) of section 402, title IV, act of 1930.
Import statistics.—Imports for consumption are shown in tables 62 and 63. Table 62 shows imports of phenol or carbolic acid and table 63 imports of “all distillates of tars yielding below 190° C. an amount of tar acids equal to or more than 5 percent.” Imports under the latter classification prior to 1928 were probably chiefly phenol. Phenol imports consist entirely of the natural product.
Table 62.—Phenol: United States imports for consumption, 1910-37
Year Rate of duty Quantity Value Unit value Computed ad valorem rate
Pounds Percent
19101 Free 4,507,693 $275,600 $0.061
19111 do 4,371,014 265,780 .061
19121 do 5,686,704 521,457 .092
19131 do 8,345,631 688,771 .083
19141 do 8,393,216 531,535 .063
19151 do 3,106,445 179,685 .058
19161 (2) 2,246,256 154,841 .069
19171 15 percent + 2½ cents per pound 265,519 17,168 .065 53.7
1918 do 283,337 62,497 .221 26.3
1919 do 2,061 264 .128 34.5
1920 do 1,040 244 .235 25.8
1921 do 250 142 .568 19.4
1922 (3) { 280,224 30,414 .109 38.0
{ 69,310 16,102 .230 85.1
1923 55 percent + 7 cents per pound4 126,618 21,389 .169 96.4
1924 (5) 176,081 46,786 .266 81.4
1925 40 percent + 7 cents per pound4 256,126 58,958 .230 70.4
1926 do 218,437 47,351 .217 72.3
1927 (6) 500 100 .200 75.0
1928 20 percent + 3½ cents per pound4 1,653 298 .180 39.4
1929 do 433,385 44,226 .102 54.3
1930 do 500 115 .230 39.4
1931 do 2,365 639 .270 33.0
1932 do None
1933 do 3,440 641 .186 38.8
1934 do None
1935 do 2,605 211 .081 63.0
1936 do 71,429 8,302 .116 50.1
19377 do 32,238 3,767 .117 50.0
1 Fiscal year.
2 15 percent ad valorem and 2½ cents per pound effective Sept. 9, 1916.
3 55 percent ad valorem and 7 cents per pound, effective Sept. 22, 1922.
4 Ad valorem based on American selling price or United States value under acts of 1922 and 1930.
5 Ad valorem reduced to 40 percent effective Sept. 22, 1924.
6 Duty reduced to 20 percent ad valorem and 3½ cents per pound effective Nov. 30, 1927.
7 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 63.—All distillates of tar yielding below 190° C. an amount of tar acids equal to or more than 5 percent: United States imports for consumption, 1918-37
Calendar year Rate of duty Quantity Value Unit value Computed ad valorem rate
Pounds Percent
1918 15 percent + 2½ cents per pound 1,550 $2,008 $1.30 16.93
1919 do 3,170 4,587 1.45 16.73
1920 do 85,474 36,041 .422 20.93
1921 do 16,240 11,811 .727 18.43
1922 (1) 350,764 42,912 .122 46.27
1923 55 percent + 7 cents per pound2 245,119 30,328 .124 111.58
1924 (3) 662,938 49,380 .074 134.43
1925 40 percent + 7 cents per pound2 252,382 15,441 .061 154.41
1926 do 1,102 5,236 4.75 41.47
1927 (4) 2 16 8.00 40.88
1928-37 None
1 55 percent ad valorem and 7 cents per pound, effective Sept. 22, 1922.
2 Ad valorem based on American selling price or United States value under acts of 1922 and 1930.
3 Ad valorem reduced to 40 percent, effective Sept. 22, 1924.
4 Duty reduced to 20 percent ad valorem and 3½ cents per pound, effective Nov. 30, 1927.
Source: Foreign Commerce and Navigation of the United States.
United States exports.
Exports of phenol have not been separately shown in official statistics since 1924. In that year they went chiefly to Panama, Japan, Cuba, and Mexico. Table 64 shows exports from 1918 to 1924, inclusive, as furnished by the Department of Commerce.
Table 64.—Phenol: United States exports, 1918-24
Year Quantity Value Unit value
Pounds
1918 6,477,841 $2,666,634 $0.412
1919 1,243,841 363,744 .292
1920 2,151,475 388,047 .180
1921 249,658 35,994 .144
1922 223,146 23,223 .104
1923 232,830 34,389 .148
1924 51,364 8,016 .156
Source: Commerce and Navigation of the United States.
Appreciable quantities of phenol have been exported in recent years to Japan and China, and to Great Britain and other European countries. Export statistics, collected by the U. S. Tariff Commission from the several domestic producers, show the following quantities exported in recent years.
Table 65.—Phenol: United States exports, 1934-36
Year Quantity Value Unit value
Pounds
1934 2,622,900 $329,269 $0.126
1935 2,921,835 322,933 .111
1936 1,258,244 148,501 .118
Source: Data obtained by the U. S. Tariff Commission through questionnaires.
In 1934, the principal destinations in order of importance were China, Italy, and Canada; in 1935 Germany, China, Japan, and Belgium; and in 1936 China, Belgium, and the Netherlands.
Competitive conditions.
Before the World War our average annual consumption of phenol was 5 million pounds, of which about 80 percent was imported from Great Britain and Germany. These countries produced phenol in excess of their consumption, and phenol was on the free list in the United States.
In September 1916 phenol became dutiable. The demand was increasing rapidly because of the use of phenol in the manufacture of picric acid, an explosive. To meet the wartime demand at home and abroad large scale production of synthetic phenol sprang up in the United States. But the end of the war not only shut off the largest part of the demand but left the producers with large stocks on hand. The price dropped sharply and the production of synthetic phenol ceased.
Since 1922 there has been a gradually increasing demand for phenol in the United States, chiefly for use in the manufacture of synthetic resins, and production has increased to meet this demand as shown in table 66.
Table 66.—Phenol: United States production, imports, exports, and apparent consumption in specified years, 1918-37
[In thousands of pounds]
Year Production1 Imports2 Exports3 Apparent consumption4
1918 106,794 285 6,478 (5)
1919 1,544 5 1,244 (5)
1923 3,311 372 233 3,450
1925 14,734 919 (6) (7)
1926 8,691 220 (6) (7)
1927 8,041 1 (6) (7)
1928 10,227 2 (6) (7)
1929 24,178 433 (6) (7)
1930 21,147 1 (6) (7)
1931 17,981 2 (6) (7)
1932 13,965 (6) (7)
1933 33,220 3 (6) (7)
1934 44,935 2,623 42,312
1935 43,419 3 2,922 40,500
1936 48,724 71 1,258 47,537
1937 65,690 32 (6) (7)
1 From table 59.
2 From tables 62 and 63.
3 From tables 64 and 65.
4 Production plus imports minus exports.
5 Not calculated because of importance of stocks on hand.
6 Not available.
7 Not available because of absence of export figures. Exports probably negligible up to 1929; substantial in 1933.
The manufacture of synthetic phenol was revived about 1923. Imports were quite small as compared with production, especially after 1927. At first this was probably due primarily to the protection given by the duty which had been increased in 1922.[22] But with the increase in volume of production in the United States the price decreased and since 1933 the United States producers have enjoyed a substantial export business. It may therefore be doubted that in recent years there would have been any substantial imports even if phenol had been free of duty.
THE CRESOLS, XYLENOLS, AND CRESYLIC ACID
Reference to table 56, page 109, will show that, as distillation of coal tar proceeds and the temperature of distillation is increased, the phenol fraction is followed in order by the three cresols and then by the six xylenols. Each of these tar acids is a definite chemical compound with definite physical properties. Consideration of them as raw materials for synthetic resins is complicated by the fact that they are generally used in mixtures and that the commercial term, cresylic acid, applied to many of these mixtures has no definite relationship to the precise chemical terminology. Yet since the term cresylic acid is so widely used in commerce, since the tariff provides for imports under that name, and since the statistics available are in part in terms of cresylic acid and in part in terms of cresols and xylenols it is impossible to present the complete picture on the basis of the correct chemical terminology.
Description and uses.
The cresols.—The cresols are isomeric tar acids obtained from coal tar by fractional distillation. Their combined content averages about 1 percent of domestic coal tar. The total cresol content is divided in about the following proportions: 40 percent metacresol, 35 percent orthocresol, and 25 percent paracresol. The cresols are marketed in a number of types and grades including mixtures of ortho, meta, and para; mixtures of meta and para; separated ortho, meta, and para; and also in mixtures with phenol and the xylenols.
Metacresol (chemically, 3-methyl phenol) is a colorless to yellow liquid with a phenol-like odor. When pure, it melts at 11° C., boils at 202.8° C., and has a specific gravity of 1.03. It is used in the manufacture of synthetic resins, photographic developers, explosives, disinfectant soaps, paint and varnish removers, to remove ink from newsprint, to soften and reclaim rubber, and in intermediates for dyes and perfume materials.
Orthocresol (chemically, 2-methyl phenol) is a colorless, crystalline product with a phenol-like odor, melting at 30° C., boiling at 190.8° C., and having a specific gravity of 1.04. It is used in the manufacture of coumarin (flavor), antiseptics, disinfectants, and fumigants. It is not used to any extent in synthetic resins.
Paracresol (chemically, 4-methyl phenol) is a colorless, crystalline substance with a phenol-like odor, melting at 35° C., boiling at 201.8° C., and having a specific gravity of 1.03. It is used in the manufacture of intermediates, dyes, disinfectants, and fumigants, in medicine, and in mixture with metacresol in synthetic resins. Domestic production of synthetic paracresol was announced early in 1938 by Swann & Co., Birmingham, Ala.
Metaparacresol is a combination of approximately 60 percent meta and 40 percent para cresol obtained in the fractional distillation of mixed cresols. The ortho isomer is distilled off, leaving a residue of metaparacresol. It is widely used in the manufacture of synthetic resins.
Cresol.—The term cresol used without further qualification indicates a mixture of the three isomers in substantially the same proportions in which they are found in coal tar. The United States Pharmacopoeia describes cresol, a mixture of isomeric cresols obtained from coal tar, as a colorless or yellowish to brownish-yellow or a pinkish, highly refractive liquid, becoming darker with age and on exposure to light. It is widely used in synthetic resins, antiseptics and disinfectants, and in medicine.
The xylenols.—Shortly after the original patents on Bakelite resins expired extensive research was begun for raw materials that would give different properties to the resultant resins. This work led to a study of the high-boiling tar acids, and methods of recovery for some of them were commercially developed. Among those obtained from coal tar are the six isomeric xylenols, methylethyl phenol, and one of the trimethyl phenols (see table 56). Coal tar contains about 0.2 percent xylenols and 0.5 percent other high-boiling tar acids.
The principal uses for these products have been in the preparation of high-phenol coefficient disinfectants, and recently in the replacement of phenol and cresols in synthetic resins. It was found, for example, that 3: 5 xylenol reacts with formaldehyde faster than either metacresol or phenol. Numerous patents have been granted on the use of these high-boiling acids in the production of synthetic resins.
The xylenols, when pure, are colorless, crystalline substances boiling between 211° and 225° C. They are usually marketed in mixtures containing from 50 to 80 percent xylenols and 20 to 50 percent cresols. There is commercial production of at least one of the separated xylenols (3: 5). An appreciable part of our imports of crude cresylic acid and of our production of cresylic acid contains high percentages of the xylenols.
Other high-boiling tar acids.—The other high-boiling tar acids are ortho ethylphenol, meta ethylphenol, para ethylphenol, methyl ethylphenol, and the three isomeric trimethyl phenols. Several of these have been isolated from coal tar. All of them, when pure, are crystalline compounds with boiling points ranging between 206° and 235° C. There has been little, if any, commercial production of this group up to this time. They are known, however, to have very high phenol coefficients, a property which would make them suitable for use in disinfectants. Little is known as yet concerning their application in synthetic resins.
Cresylic acid.—Cresylic acid is a generic term now applied to mixtures of tar acids in widely varying proportions. As defined in the literature and as formerly used in commerce the term identified a mixture of ortho, meta, and para cresols in the proportions in which they occur in coal tar. This proportion is approximately 40 percent metacresol, 35 percent orthocresol, and 25 percent paracresol. But in recent years the designation cresylic acid has been applied to all sorts of mixtures of tar acids boiling above 190° C. Practically every maker of synthetic resins, antiseptics, and disinfectants has his own specifications for cresylic acid; it may be any mixture in almost any proportions of the three cresols, the six isomeric xylenols, and the higher boiling tar acids. Imports of crude cresylic acid are understood to be largely xylenol mixtures containing low percentages of the cresols. This loose application of cresylic acid in recent years is due to the increased commercial application of the high-boiling tar acids, especially the xylenols.
Under the Tariff Act of 1930 refined cresylic acid, that having a purity of 75 percent or more, is dutiable under paragraph 27 at 3½ cents per pound and 20 percent ad valorem based on American selling price or United States value; while crude cresylic acid, that having a purity of less than 75 percent, is free under paragraph 1651. The provision in paragraph 27 reads, “cresylic acid which on being subjected to distillation yields in the portion distilling below two hundred and fifteen degrees centigrade, a quantity of tar acids equal to or more than 75 per centum of the original distillate.” Under this provision cresylic acid may include an endless number of combinations of tar acids and may or may not contain any of the isomeric cresols. Of the 17 or more tar acids known to exist in coal tar (see table 56), only 8 have boiling points above 215° C. It would seem to be more accurate and more in line with present day usage to have the tariff drop the designation cresylic acid in favor of more definite terms based on composition, such as cresols and cresol mixes, xylenol and xylenol mixes, etc.
About 60 percent of our consumption of cresylic acid is in synthetic resins and the remainder in the manufacture of insecticides, antiseptics, disinfectants, and other coal-tar products, such as intermediates for dyes, plasticizers for nitrocellulose, etc.
United States production.
The cresols.—There is large production of cresol, metaparacresol, and orthocresol in the United States. Commercial production of paracresol was reported for the first time in 1934, and of metacresol in 1935.
Statistics of domestic production and sales are publishable only for the year 1934 because of the small number of producers. The output in that year is shown in table 67. Production has increased appreciably since then.
Table 67.—Meta, ortho, and para cresols: United States production and sales, 1934
Type Production Sales
Quantity Value Unit value
Pounds Pounds
Cresol 8,929,836 8,559,048 $572,738 $0.07
Metaparacresol 2,033,424 1,692,149 101,324 .06
Orthocresol 835,016 (1) (1)
Paracresol (1) (1) (1)
1 Not publishable; figures would reveal operations of individual firms.
Source: Dyes and Other Synthetic Organic Chemicals in the United States. U. S. Tariff Commission.
The trend of domestic production of the several cresols is upward. In 1937 the output of all grades and types of cresols was 13,745,271 pounds with sales of 13,251,345 pounds, valued at $1,071,965. The practice of topping coal tar will greatly increase the output of the cresols as well as of other tar acids and naphthalene.
There are five domestic producers of cresol, three each of orthocresol and metaparacresol, and two of metacresol and paracresol. All except one of these makers recover natural phenol, cresylic acids, and other tar acids. Refining plants are located at Pittsburgh, Pa., Philadelphia, Pa., Indianapolis, Ind., and Follansbee, W. Va. Domestic production of synthetic paracresol was first announced in 1938.
The xylenols.—There has been a large domestic production of mixed xylenols in recent years. These mixtures, containing from 50 to 80 percent xylenols, are marketed as cresylic acid. Statistics of domestic production, and sales are therefore included in table 68. It is estimated that the output of xylenols and xylenol mixtures in 1935 exceeded 750,000 pounds and exceeded 1,250,000 pounds in 1937. At least one of the separated xylenols (1: 3: 5) has been produced commercially in the United States since 1935, but statistics of its production are not publishable.
Other high-boiling tar acids.—There was no reported domestic production of the other high-boiling acids prior to 1935 and the data obtained for that year are probably incomplete. Estimated output was 200,000 pounds in 1935, 250,000 pounds in 1936, and 300,000 pounds in 1937. These estimates are based on production of mixtures of high-boiling acids.
Cresylic acid.—Domestic production and sales statistics for so-called crude cresylic acid are not publishable. It is known, however, that production of the crude is small compared with our output of refined cresylic acid. It is usually more economical for the producer to prepare the mixture of tar acids to the specifications of the purchaser, rather than to leave part of the refining operations to be performed by the latter. The fact that imports of cresylic acid are chiefly of crude is largely due to the different tariff treatment of crude and refined.
Domestic production of refined cresylic acid was confined to one or two firms until 1928, when there were four makers. Statistics of production and sales are not publishable for the years prior to 1929, though it may be stated that the annual domestic output increased each year to supply the increased demand. Table 68 shows production and sales from 1929 to 1934, inclusive. Data for later years are not publishable.
Table 68.—Refined cresylic acid: United States production and sales, 1929-37
Year Production Sales
Quantity Value Unit value
Pounds Pounds Per pound
1929 14,601,534 $0.10
1930 17,305,308 16,026,407 $1,267,155 .08
1931 10,994,000 10,305,000 652,000 .06
1932 8,060,000 4,805,000 251,000 .05
1933 13,813,941 11,975,441 626,496 .05
1934 10,949,860 9,230,255 489,231 .05
1935 (1) (1) (1)
1936 (1) (1) (1)
1937 (1) (1) (1)
1 Not publishable; figures would reveal operations of individual firms.
Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.
As previously stated, the composition of cresylic acid has gradually been changed from a mixture of the isomeric cresols to mixtures of cresols, xylenols, and high-boiling tar acids. The cresols, formerly included under cresylic acid statistics, are now shown separately. For this reason the data in table 68 do not fully reflect the increased output of these tar acids in recent years. Statistics for years prior to 1931 probably include all of the tar acids except phenol, while those for subsequent years do not include the separated cresols. In 1934 the production of refined cresylic acid was 10,949,860 pounds, and in addition recovery of the several cresols amounted to 11,798,276 pounds making a total of 22,748,136 pounds as compared with a total of 14,601,534 pounds in 1929 and 17,305,308 pounds in 1930.
During 1936 and the first part of 1937 a serious shortage of cresylic acid existed in the domestic market owing to increased demand by synthetic resin makers. The output in 1936 exceeded that in 1935 and the production in 1937 was appreciably higher than in 1936. These increases are due to the recovery of appreciable quantities at several new distillation plants, the topping of large amounts of tar hitherto not processed, and increased production by present recovery units.
There are many grades of cresylic acid, most of which are prepared by mixing or blending to individual specifications. Every large consumer apparently has his own specifications. In addition to these special mixtures there are the following standard blends:
(1) Ninety-nine percent high-boiling, straw color.
(2) Low-boiling, straw color.
(3) Special resin grade, high-boiling.
There are four domestic producers of cresylic acid with recovery and refining units at Pittsburgh, Pa., Philadelphia, Pa., Indianapolis, Ind., and Follansbee, W. Va. The last three mentioned are refining plants operated in conjunction with a number of tar distillation units widely scattered throughout the country. These units usually recover crude tar-acid fractions in the distillation of tar and ship them to these refining plants for separation and refining. All in this group are purchasers of coal tar. The fourth producer operates a byproduct recovery unit in connection with the company’s coke-oven operations. Part of the coal tar produced is distilled to recover the several products, including creosote oil, tar acids, and naphthalene, and the residual pitch is mixed with the remaining undistilled tar and used for fuel. The shortage of tar acids and naphthalene in 1936 caused this producer to begin the topping of tar.
Foreign production.
The cresols are produced in the United Kingdom, Germany, France, the Netherlands, Belgium, and other European countries. Coal tar recovered in the United Kingdom is principally gas tar, which is much richer in tar acids than coke-oven tar, the principal source in the United States. This is true because low temperature carbonization of coal yields greater quantities of tar acids than are obtained in the tar from byproduct coke ovens. Exports to the United States are chiefly mixtures which can enter as crude cresylic acid.
Production of cresol in Germany in recent years is shown in table 69.
Table 69.—Cresol: German production, in specified years
Year 1,000 pounds
1929 23,814
19311 15,435
1933 11,780
1934 10,476
1 Includes 2,866,000 pounds of separated ortho, meta, and para cresols.
Source: Consular reports.
German imports and exports of cresol, in recent years, are shown in table 70.
Table 70.—Cresol: German imports and exports, in specified years
Year Imports Exports
1,000 pounds 1,000 pounds
1929 2,037 8,494
1930 1,277 6,712
1931 1,874 7,980
1932 1,541 3,669
1933 1,832 4,970
1934 1,960 6,345
1935 2,117 8,528
1936 3,737 4,531
1937 1,787 4,423
Source: Consular reports (1929-33) and official German statistics (1934-37).
The output of cresols in Czechoslovakia in recent years is shown in table 71.
Table 71.—Cresol: Production in Czechoslovakia, in specified years
Year Quantity
1,000 pounds
1928 1,984
1931 1,477
1932 1,102
1933 1,599
1934 1,918
Source: Consular reports.
Cresylic acid is recovered in all the countries of Europe, Great Britain and Germany being the leading producers and the principal exporters. Increasing demand in these countries for synthetic resins made from cresylic acid has greatly reduced the quantities available for export in recent years.
Great Britain is probably the world’s largest producer of cresylic acid, and for many years has been the principal exporter to the United States. This position is due to the large available supply of gas-house tar, and to an ample market for all the products of tar distillation. In 1935 the tar distilled in England, Wales, and Scotland totaled 360 million gallons, of which 55 percent was gas-house tar.
British production of all grades of cresylic acid averages between 35 million and 42 million pounds annually, of which from 12 million to 20 million pounds are exported. Many British producers market their tar products through pools and associations. There is a cresylic acid pool, a phenol pool, and at least two creosote oil export associations, a pitch marketing association, and a benzol association. One of the principal grades of cresylic acid produced in Great Britain is “American duty-free specification.”
Table 72 shows British exports of cresylic acid, by countries, in recent years.
Table 72.—Cresylic acid: British exports, by countries, 1933-37
Destination 1933 1934 1935 1936 1937
Quantity (in thousands of pounds)
UNITED STATES 3,616 5,783 6,116 11,296 (1)
Chile 1,381 2,958 2,814 662 (1)
France 358 87 214 189 (1)
Japan 632 203 685 2,002 (1)
All other countries 5,464 6,965 7,333 9,250 (1)
Total 11,451 15,997 17,162 23,399 26,697
Value (in thousands of dollars)
UNITED STATES 147 277 255 620 (1)
Chile 28 89 87 31 (1)
France 21 5 20 14 (1)
Japan 38 20 43 118 (1)
All other countries 189 307 330 537 (1)
422 698 734 1,321 2,262
1 Not available.
Source: Official British statistics.
Imports into the United States.
Rates of duty.—Prior to September 8, 1916, the cresols were imported free of duty. Since that date they have been subject to the tariff treatment shown in table 73.
Table 73.—The cresols: Rates of duty upon United States imports, 1916-37
Period Rate of duty Authority
Less than 75 percent pure 75 to 90 percent pure 90 percent or more pure
To Sept. 8, 1916. Free Free Free Free under par. 452, Tariff Act of 1913, and under previous acts.
Sept. 9, 1916, to Sept. 8, 1921. do do 15 percent ad valorem and 2½ cents per pound. Revenue Act of 1916.
Sept. 9, 1921, to Sept. 21, 1922. do do 15 percent ad valorem and 2 cents per pound. Emergency Tariff Act of 1921. From May 28, 1921, to Sept. 21, 1922, imports prohibited except when not obtainable in sufficient quantities or on reasonable terms as to quality, price, and terms of delivery.
Sept. 22, 1922, to Sept. 21, 1924. do 55 percent ad valorem and 7 cents per pound.1 55 percent ad valorem and 7 cents per pound.1 Free under par. 1549 and dutiable under par. 27 of Tariff Act of 1922.
Sept. 22, 1924, to June 17, 1930. do 40 percent ad valorem and 7 cents per pound.1 40 percent ad valorem and 7 cents per pound.1 Same; ad valorem reduced to 40 percent under provisions of the Tariff Act of 1922.
June 18, 1930, to date. do do 20 percent and 3½ cents per pound.1 Free under par. 1651 and dutiable under par. 27 of the Tariff Act of 1930.
1 Ad valorem based on American selling price or United States value.
Under the Tariff Act of 1930 metacresol, orthocresol, and paracresol as such or in mixture, if less than 75 percent pure, would be imported free under paragraph 1651.[23] If from 75 to 90 percent, they are dutiable under paragraph 27 at 7 cents a pound and 40 percent based upon American selling price.[24] And if 90 percent pure or more, they are dutiable under paragraph 27 at 3½ cents per pound and 20 percent, based upon American selling price.[25]
The duties on cresylic acid in recent years are shown in table 74. Under the Tariff Act of 1930, cresylic acid less than 75 percent pure is free under paragraph 1651.[23] If more than 75 percent pure it is dutiable under paragraph 27 (b) at 3½ cents per pound and 20 percent, based on American selling price.[26]
Table 74.—Cresylic acid: Rates of duty upon United States imports, 1916-37
Period Rate of duty Authority
Less than 75 percent pure 75 percent pure or more
To Sept. 8, 1916. Free Free Free under par. 452 of Tariff Act of 1913 and previous acts.
Sept. 9, 1916, to Sept. 8, 1921. do 15 percent ad valorem and 2½ cents per pound. Revenue Act of 1916.
Sept. 9, 1921, to Sept. 21, 1922. do 15 percent ad valorem and 2 cents per pound. Emergency Tariff Act of 1921. From May 28, 1921, to Sept. 21, 1922, imports prohibited except when not obtainable in sufficient quantities or on reasonable terms as to quality, price, and terms of delivery.
Sept. 22, 1922, to Sept. 21, 1924. do 55 percent ad valorem and 7 cents per pound.1 Free under par. 1549 and dutiable under par. 27 of the Tariff Act of 1922.
Sept. 22, 1924, to Aug. 18, 1927. do 40 percent ad valorem and 7 cents per pound.1 Same; ad valorem reduced to 40 percent under provisions of the Tariff Act of 1922.
Aug. 19, 1927, to June 17, 1930. do 20 percent ad valorem and 3½ cents per pound.1 Duty reduced by Presidential proclamation.
June 18, 1930, to date. do 20 percent ad valorem and 3½ cents per pound.1 Free under par. 1651 and dutiable under par. 27 of the Tariff Act of 1930.
1 Ad valorem based on American selling price or United States value.
Import statistics.—Imports of the separated and mixed cresols are combined in official statistics. Table 75 shows imports of the cresols “90 percent pure or more.” There have been no recorded imports of less pure grades.
Tables 76, 77, and 78 show, by principal sources, imports of metacresol, orthocresol, and paracresol, as obtained from invoice analyses by the United States Tariff Commission. The sum of the three tabulations does not equal the total shown for all cresols in table 75. The difference in 1934 of 38,744 pounds valued at $12,906 is accounted for by mixed cresols. Undoubtedly the differences in other years may be similarly accounted for.
Table 75.—Metacresol, orthocresol, and paracresol, 90 percent pure or more: United States imports for consumption, 1920, and 1923-37
Calendar year Rate of duty1 Quantity Value Unit value Computed ad valorem rate
Pounds Percent
1920 2½ cents per pound + 15 percent 2,444 $2,230 $0.912 17.7
1923 7 cents per pound + 55 percent 8,754 5,410 .618 66.3
1924 { do 15,326 1,995 .130 108.8
{ 7 cents per pound + 40 percent 1,000 663 .663 50.6
1925 do 34,874 5,741 .165 82.5
1926 do 105,238 15,040 .143 89.0
1927 do 174,094 35,054 .201 74.8
1928 do 207,897 33,638 .162 83.3
1929 do 227,974 32,098 .141 89.8
1930:
Jan. 1-June 17 do 131,134 14,973 .114 101.3
June 18-Dec. 31 3½ cents per pound + 20 percent 71,183 11,762 .165 41.2
Total, 1930 202,317 26,735 .132 74.9
1931 do 151,571 26,901 .177 39.7
1932 do 83,848 18,530 .221 35.8
1933 do 48,511 16,205 .334 30.5
1934 do 124,598 34,361 .276 32.7
1935 do 65,468 18,290 .279 32.5
1936 do 83,273 27,686 .332 30.5
19372 do 167,278 36,227 .217 36.2
1 Ad valorem rate based on American selling price or United States value under the Tariff Acts of 1922 and 1930.
2 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 76.—Metacresol: United States imports for consumption by principal sources, in specified years
Imported from 1929 1931 1933 1934 1935 1936 19371
Quantity (pounds)
United Kingdom 113,057 916 15,769 21,054 6,500 6,800 40,878
Germany 3,235 4,432
All other countries 21,106 311,025
Total 117,398 916 20,201 21,054 6,500 6,800 51,903
Invoice value
United Kingdom (4) (4) $5,264 $8,400 $2,645 $2,589 $6,951
Germany (4) (4) 1,548
All other countries (4) (4) 34,200
Total 6,812 8,400 2,645 2,589 11,151
Invoice unit value
United Kingdom (4) (4) $0.334 $0.399 $0.407 $0.380 $0.170
Germany (4) (4) .349
All other countries (4) (4) .381
Average .337 .399 .407 .380 .215
Percent of total quantity
United Kingdom 96.30 100.0 78.06 100.0 100.0 100.0 78.76
Germany 2.76 21.94
All other countries 2.94 321.24
Total 100.00 100.0 100.00 100.0 100.0 100.0 100.00
1 Preliminary.
2 Netherlands.
3 Switzerland.
4 Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
Table 77.—Orthocresol: United States imports for consumption, by principal sources, in specified years
Imported from— 1929 1931 1933 1934 1935 1936 19371
Quantity (pounds)
United Kingdom 105,790 79,198 19,548 25,855 29,120 33,816 112,108
Germany 82,859 5,914 10 10
France 4,480
All other countries 30,600
Total 219,249 85,112 19,548 25,865 29,130 38,296 112,108
Invoice value
United Kingdom (2) (2) $1,591 $2,707 $2,529 $3,178 $14,940
Germany (2) (2) 4 4
France 336
Total 1,591 2,711 2,533 3,514 14,940
Invoice unit value
United Kingdom (2) (2) $0.081 $0.105 $0.087 $0.094 $0.133
Germany (2) (2) .400 .400
France .075
Average .081 .105 .087 .092 .133
Percent of total quantity
United Kingdom 48.25 93.05 100.0 99.96 99.97 88.30 100.00
Germany 37.79 6.95 .04 .03
France 11.70
All other countries 13.96
Total 100.00 100.00 100.0 100.00 100.00 100.00 100.00
1 Preliminary.
2 Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
Table 78.—Paracresol: United States imports for consumption, by principal sources, in specified years
Imported from— 1929 1931 1933 1934 1935 1936 19371
Quantity (pounds)
United Kingdom 2,587 458 6,972 16,889 16,625 32,666 14,338
Netherlands 11,243
Germany 8,818 11,023 6,076
France 13,228 5 6 4
Total 2,587 11,701 6,972 38,935 27,653 38,748 14,342
Invoice value
United Kingdom (2) (2) $2,652 $4,797 $4,485 $10,739 $5,415
Netherlands (2) (2)
Germany (2) (2) 1,921 3,090 3,079
France (2) (2) 3,626 7 7 3
Total 2,652 10,344 7,582 13,825 5,418
Invoice unit value
United Kingdom (2) (2) $0.380 $0.284 $0.270 $0.329 $0.378
Netherlands (2) (2)
Germany (2) (2) .218 .280 .506
France (2) (2) .274 1.400 1.167 .750
Average .380 .266 .274 .357 .378
Percent of total quantity
United Kingdom 100.0 3.92 100.0 43.38 60.12 84.30 99.97
Netherlands 96.08
Germany 22.65 39.86 15.68
France 33.97 .02 .02 .03
Total 100.0 100.00 100.0 100.00 100.00 100.00 100.00
1 Preliminary.
2 Not available.
Source: Invoice analyses, compiled by U. S. Tariff Commission.
The processes for recovery of the cresols (fractional distillation) usually yield products more than 75 percent pure and most of the consumers of mixed or prepared cresols require products of high purity. This explains why there are no imports less than 75 percent pure, notwithstanding that they are duty-free under paragraph 1651.
Under the act of 1930 cresols of 90 percent or greater purity are assessed for duty at 20 percent ad valorem and 3½ cents per pound while cresols 75.1 to 89.9 percent pure are assessed for duty at 40 percent ad valorem and 7 cents per pound. Naturally, since the duty on imports below 90 percent pure is double that on imports over 90 percent pure there are no imports of the former.
Imports of crude cresylic acid are shown in table 79 and those of refined cresylic acid in table 80. Imports by principal sources are shown in tables 81 and 82, for crude and refined, respectively.
Table 79.—Crude cresylic acid: United States imports for consumption, 1924-37
Year Quantity1 Value Unit value
Pounds
1924 2,327,528 $157,643 $0.068
1925 2,163,557 122,742 .057
1926 5,702,740 331,550 .058
1927 9,136,516 567,802 .062
1928 10,687,109 678,177 .063
1929 17,856,765 952,110 .053
1930 9,009,674 501,418 .056
1931 4,937,078 244,631 .050
1932 4,077,700 164,379 .040
1933 5,523,733 178,824 .032
1934 7,163,511 284,051 .040
1935 6,849,113 265,485 .039
1936 13,476,427 722,575 .054
19372 16,360,213 1,219,268 .075
1 Conversion factor—8.5 pounds to gallon.
2 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 80.—Refined cresylic acid: United States imports for consumption, in specified years, 1919-37
Calendar year Rate of duty Quantity Value Unit value Computed ad valorem rate
Pounds Percent
1919 2½ cents per pound plus 15 percent. 2,061 $264 $0.128 34.5
1920 do. 1,040 244 .235 25.7
1923 7 cents per pound plus 55 percent1 2,815 257 .091 131.7
1924:
Jan. 1-Sept. 21 do.1 62,869 15,169 .241 84.0
Sept. 22-Dec. 31 7 cents per pound plus 40 percent1 378,777 29,066 .077 131.2
Total 441,646 44,235
1925 do.1 98,672 23,618 .239 69.2
1926 do.1 25,932 4,748 .183 78.2
1927:
Jan. 1-Aug. 18 do.1 1,322 978 .740 49.5
Aug. 19-Dec. 31 3½ cents per pound plus 20 percent.1 610,488 37,896 .062 76.4
Total 611,810 38,874
1928 do.1 976,180 70,513 .072 68.5
1929 do.1 22,343,529 183,324 .078 64.7
1930 3½ cents per pound plus 20 percent.1 1,275,872 96,047 .075 66.5
1931 do.1 3707,105 42,156 .060 78.7
1932 do.1 4641,899 37,326 .058 80.2
1933 do.1 121,634 9,164 .075 66.5
1934 do.1 23,964 1,497 .062 76.0
1935 do.1 16,602 1,128 .068 71.5
1936 do.1 512 40 .078 64.8
19375 do.1 46,479 5,122 .110 51.8
1 Based on American selling price or United States value.
2 Drawback paid on 44 percent.
3 Drawback paid on 80 percent.
4 Drawback paid on 105,285 pounds.
5 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Table 81.—Crude cresylic acid: United States imports for consumption, from principal sources, in specified years, 1929-37
Imported from— 1929 1931 1933 1934 1935 1936 19371
Quantity (pounds)
United Kingdom 13,981,259 3,809,293 5,060,925 6,927,865 6,753,003 12,344,924 12,704,108
Germany 3,874,400 1,073,491 357,034 217,965 95,727 626,833 2,499,391
Netherlands 1,106 54,294 22,066 17,468
All other countries 283,708 17,681 383 3487,202 1,156,714
Total 17,856,765 4,937,078 5,523,733 7,163,511 6,849,113 13,476,427 16,360,213
Value
United Kingdom $739,385 $190,333 $165,986 $276,989 $262,137 $661,781 $954,953
Germany 212,652 51,643 8,666 6,263 3,325 33,068 184,887
Netherlands 73 2,655 551 1,190
All other countries 23,621 799 23 326,536 79,428
Total 952,110 244,631 178,824 284,051 265,485 722,575 1,219,268
Unit value
United Kingdom $0.0529 $0.0500 $0.0328 $0.0400 $0.0388 $0.0536 $0.0752
Germany .0549 .0481 .0243 .0287 .0347 .0528 .0740
Netherlands .0660 .0489 .0250 .0681
All other countries .0432 .0452 .0602 .0545 .0687
Average .0533 .0495 .0324 .0396 .0388 .0536 .0745
Percent of total quantity
United Kingdom 78.3 77.2 91.6 96.7 98.6 91.60 77.65
Germany 21.7 21.7 6.5 3.0 1.4 4.65 15.28
Netherlands 1.1 .4 .13
All other countries 1.5 .3 (4) 3.62 7.07
Total 100.0 100.0 100.0 100.0 100.0 100.00 100.00
1 Preliminary.
2 Canada.
3 Canada and France.
4 Less than one-tenth of 1 percent.
Source: Compiled from official statistics of the United States Department of Commerce.
Table 82.—Refined cresylic acid: United States imports for consumption, from principal sources, in specified years, 1929-37
Imported from— 1929 1931 1932 1933 1934 1935 1936 19371
Quantity (pounds)
Great Britain 1,855,844 604,404 456,783 121,634 23,464 16,602 46,379
Germany 212,918 102,701 185,028 512
All other countries 274,767 88 500 100
Total 2,343,529 707,105 641,899 121,634 23,964 16,602 512 46,479
Value
Great Britain $144,630 $35,041 $24,607 $9,164 $1,412 $1,128 $5,101
Germany 14,699 7,115 12,714 $40
All other countries 23,995 5 85 21
Total 183,324 42,156 37,326 9,164 1,497 1,128 40 5,122
Unit value
Great Britain $0.078 $0.058 $0.054 $0.075 $0.060 $0.068 $0.110
Germany .069 .069 .069 $0.078
All other countries .087 .057 .170 .210
Average 0.78 .060 .058 .075 .062 .068 .078 .110
1 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
In 1931 practically all imports of refined cresylic acid were from the United Kingdom and consigned to one importer in New York. In 1932 about 73 percent of the total dutiable imports were consigned to the same firm. From these data and from a conference with representatives of the importer it would appear that the imports were not cresylic acid in its original meaning (a mixture of cresols in their natural proportions), nor in the broadened commercial meaning (including with the cresols, xylenols and higher boiling tar acids), but were chiefly a product consisting largely of a single cresol separated from its two isomers. Treasury Decision 46146, effective March 11, 1933, closed the classification of refined cresylic acid to products of this type and imports thereafter under this head have been much smaller. After 1927 substantial amounts of the imports were reexported with benefit of drawback.
The imports of crude cresylic acid are also not of the type which the domestic producer would sell by that name. Far from being a straight run mixture of the cresol and higher boiling tar acids, they are usually a mixture of fractions which have been separated, and then chosen and combined so that they will meet both the tariff requirement (i. e., less than 75 percent of the total product will distill over at 215° C.) and the specifications of the purchasers. Customer’s specifications are so drawn that the product will fill his special needs or can easily be broken down by fractional distillation in this country into elements, one or more of which will be so usable. Thus although imported crude cresylic acid must keep within the limitations set by the tariff it approaches as nearly as possible the type of cresylic acid which, if produced in this country, would be termed refined, since it was produced to meet the specifications of the consumer.
United States exports.
Exports of the cresols and of cresylic acid are not shown in official statistics and exports of these products as such are probably negligible, but there are appreciable exports of antiseptics, insecticides, and disinfectants in which they are incorporated, as well as of products or parts of products molded of resins made from cresylic acid.
Competitive conditions.
British coal tar is principally of gas-house origin and contains a higher percentage of tar acids (cresylic acid and phenol) than coke-oven tar, the principal kind recovered in the United States. The recovery of these tar acids from either kind of tar is usually not practicable, unless the distiller can dispose of the major products, creosote oil and pitch. British distillers have in the past ordinarily had a market for all their products; exporting large quantities of creosote oil to the United States, pitch to continental Europe, and tar acids and naphthalene to the United States, Germany, and other countries. Domestic distillers have sold cresylic acid, creosote oil, naphthalene, etc., in local markets in competition with duty-free imports from the United Kingdom, the Netherlands, Belgium, and Germany, but have found it difficult to dispose of pitch. The domestic production of coal tar ordinarily exceeded 600 million gallons, approximately one-half of which has been burned as fuel. Since the profit in distilling depends upon the markets for all of the joint products of the distillation, the large amount remaining undistilled can be understood.
The domestic production of cresylic acid may be expected to increase substantially, for several reasons: (1) The principal foreign producing countries have decreased exports because of increased demand for some of the coal-tar distillation products at home; (2) increased world prices; and (3) the development of topping, which allows the production of tar acids and naphthalene from coal tar without complete distillation.
Imports of refined cresylic acid are unimportant because the duty on the refined is high relative to the duty-free condition of the crude. Most of the imports of refined are either reexported or used in the manufacture of one proprietary antiseptic. The principal domestic market for cresylic acid is as a raw material for synthetic resins, and most of the domestic refined and most of the duty-free imported crude is now consumed by this industry. It may therefore be said that practically all imports of cresylic acid are duty-free and that, while they are sometimes refined by the consumer, they compete directly with domestic production of refined grades.
Phenol, already discussed, is closely related to cresylic acid—in chemical composition, in production by distillation from coal tar, and in use as a raw material for synthetic resins. To a considerable extent the proportions of phenol and cresylic acid used in the manufacture of tar-acid resins can be altered to take advantage of the changing price differential between the two.
All of the separated or mixed cresols are produced in commercial quantities in this country. Consumption in the United States, especially of types and grades used in synthetic resins, has increased appreciably in recent years, and is supplied chiefly by domestic production. A comparison of the quantity and value of domestic production and of imports in 1934 is shown in table 83.
Table 83.—The cresols: Comparison of production and imports, 1934
Product Production Imports
Quantity Value Unit value Quantity Value Unit value
Pounds Pounds
Metacresol (1) (1) 21,054 $8,400 $0.399
Paracresol (2) (2) $0.350 38,935 10,344 .266
Metaparacresol 2,033,424 $122,005 .060 (1) (1)
Orthocresol 835,016 66,801 .080 25,865 2,711 .105
Orthometapara cresol 8,929,836 625,088 .070 38,744 12,906 .333
Total 11,798,276 813,894 124,598 34,361
1 None, production reported for first time in 1935.
2 Not publishable.
Sources: Production, Dyes and Other Synthetic Organic Chemicals in the United States; imports, invoice analyses, U. S. Tariff Commission.
SYNTHETIC TAR ACIDS OTHER THAN PHENOL
Certain synthetic tar acids other than synthetic phenol are used commercially in the manufacture of synthetic resins in the United States. Among these are para tertiary amyl phenol, para tertiary butyl phenol, ortho phenyl phenol, para phenyl phenol, and resorcinal.
Para tertiary amyl phenol.
Para tertiary amyl phenol is made by reacting amylene with phenol in the presence of sulphuric acid as a catalyst. At ordinary temperatures it is a solid, melting at about 88° C. and boiling between 250°-265° C. Its use is of increasing importance as a component in tar-acid resins, especially in oil-soluble varnish resins. Owing to its phenol coefficient of approximately 60, it is also used as a germicide, fumigant, and insecticide. Commercial production was reported for the first time in 1933. Since then the output has increased appreciably each year, accompanied by material reductions in sales prices.
According to United States Patent No. 1,800,295, dated April 14, 1931, a resin fast to light and soluble in oils is obtained by heating 82 parts of p-tertiary amyl phenol with 90 parts of formaldehyde, in the presence of sodium hydroxide. This substituted phenol resin passes slowly into the infusible state, thus permitting better control of the reaction.
Para tertiary butyl phenol.
Para tertiary butyl phenol is a white solid with an aromatic odor, melting at approximately 100° C. It is a new commercial product and is used in resins for paints and varnishes. It is the most important resin material in this group.
Phenyl phenols.
Both ortho and para phenyl phenol are commercially produced and are used to some extent in resins to replace phenol. The ortho isomer is a white solid boiling at 284° C. and melting at about 56° C. It is used chiefly as a germicide, though small quantities are used in resins.
Para phenyl phenol is a white solid melting at about 165° C. and boiling at 322° C. Commercial production was reported for the first time in 1933. The output has increased each year since and the selling price has gradually declined.
Resorcinol.
Resorcinol, usually obtained by fusing meta benzene disulphonic acid with caustic soda, is a colorless, crystalline substance with a peculiar odor. It melts at 119° C. and boils at 276° C. It is used in medicine, in the manufacture of intermediates and dyes, and to some extent in synthetic resins. Resorcinol condenses with formaldehyde at such a rapid rate that some means must be applied to slow up the reaction. It is used to increase the rate of condensation of tar-acid resins and to reduce the danger of sticking or undercure.
Domestic production of resorcinol has decreased in recent years. Its relatively high cost is probably an important factor in limiting its use in synthetic resins.
FORMALDEHYDE
Description and uses.
At ordinary temperature and pressure formaldehyde is a gas. It enters commerce as formalin, an aqueous solution containing 40 percent formaldehyde by volume (37 percent by weight) and from 6 to 14 percent methyl alcohol. It is generally made by the oxidation of methyl alcohol. Commercial formalin contains polymers which tend to precipitate in water solution; these are kept in solution by allowing from 6 to 14 percent methyl alcohol to remain in the solution.
The principal use of formaldehyde is in the manufacture of synthetic resins. Other uses are (in the order of their importance): In the manufacture of synthetic indigo; in the manufacture of hydrosulphite; as a disinfectant, deodorant, and preservative; as a fungicide; in embalming fluids; in tanning leather; and in the manufacture of coated paper and wallpaper.
United States production.
The domestic output of formaldehyde has increased with the increased demand by resin makers. Production and sales in 1937 were more than double those in 1930. There are three domestic makers, two of which produce methyl alcohol, the raw material. Their plants are located in New Jersey and Oklahoma.
Statistics of production and sales are shown in table 84.
Table 84.—Formaldehyde: United States production and sales, in specified years
Year Production Sales
Quantity Quantity Value Value per lb.
1,000 pounds 1,000 pounds
1914 (1) 8,426 $655,174 $0.078
1919 25,007 19,664 3,928,322 .200
1921 9,657 6,056 651,681 .108
1922 23,958 16,140 1,676,401 .104
1923 24,081 18,855 2,474,506 .131
1924 26,155 20,542 1,971,053 .096
1925 31,456 23,392 1,895,913 .081
1926 31,953 22,552 2,050,967 .091
1927 29,920 24,597 2,256,534 .092
1928 38,718 27,934 2,491,615 .089
1929 51,786 (2) (2)
1930 40,763 (2) (2)
1931 (1) (1) (1)
1932 (1) (1) (1)
1933 52,236 46,424 2,122,925 .046
1934-37 (2) (2) (2)
1 Not available.
2 Not publishable; figures would disclose operations of individual firms.
Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.
Production in other countries.
Formaldehyde is produced in England, Germany, France, Czechoslovakia, Italy, Sweden, the Soviet Union, Japan, and Canada. Production data are not available but Germany and England are probably the leading foreign producers. Estimated productive capacity in the Soviet Union is given as 10 million pounds annually; in Japan 6.5 million pounds; in France 4 million pounds; and in Italy 3 million pounds.
United States imports and exports.
Imports of formaldehyde have been negligible since 1920 when 428,444 pounds, valued at $210,191, were imported. There were no imports from 1928 until 1935, when 375 pounds valued at $72 were imported from Canada. In 1936 imports amounted to 20 pounds, valued at $14, from Switzerland.
The United States exports about 5 percent of its production of formaldehyde. Canada is the principal destination of exports, and prior to 1934 Japan was an important market. Table 85 shows exports of formaldehyde to principal markets, in recent years.
Table 85.—Formaldehyde: United States exports to principal markets, in specified years, 1929-37
Exported to— 1929 1931 1933 1934 1935 1936 19371
Quantity (pounds)
Canada 19,321 716,132 1,095,847 1,236,103 1,493,993 1,105,277 1,187,661
Japan 1,464,763 622,407 729,875 11,250
Netherlands Indies 626,689 650,875 344,725 71,375 200 335,275
United Kingdom 303 345,896 305 2
China 29,030 229,760 215,050 572,700 598,342 459,490 938,700
All other countries 448,063 339,777 332,101 433,068 334,100 279,289 403,236
Total 2,588,169 2,904,847 2,373,178 2,597,846 2,497,810 1,844,258 2,864,872
Value
Canada $4,405 $36,471 $46,611 $58,348 $83,805 $53,062 $50,780
Japan 124,411 33,395 43,254 562
Netherlands Indies 42,807 38,462 15,536 2,866 13 13,411
United Kingdom 510 18,629 192 1
China 3,354 13,019 11,998 27,407 28,239 19,258 34,274
All other countries 49,742 22,709 18,966 23,444 18,676 16,520 20,498
Total 225,229 162,685 121,021 125,297 133,586 88,854 118,963
Unit value
Canada $0.228 $0.051 $0.043 $0.047 $0.056 $0.048 $0.043
Japan .085 .054 .059 .050
Netherlands Indies .068 .059 .045 .040 .065 .040
United Kingdom 1.683 .054 .630 .500
China .116 .057 .056 .048 .047 .042 .037
All other countries .111 .067 .057 .054 .056 .059 .051
Average .087 .056 .051 .048 .053 .048 .042
Percent of total quantity
Canada 0.8 24.7 46.2 47.6 59.8 59.9 41.4
Japan 56.6 21.4 30.7 .4
Netherlands Indies 24.2 22.4 13.3 2.8 11.7
United Kingdom 11.9
China 1.1 7.9 9.1 22.0 24.0 24.9 32.8
All other countries 17.3 11.7 14.0 16.7 13.4 15.2 14.1
Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0
1 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
The competitive situation with respect to formaldehyde is determined largely by the output and price of the raw material, methanol. The United States produces large quantities of synthetic and natural methanol and is a net exporter of that product. Both methanol and formaldehyde are produced in many foreign countries, and foreign production is expanding. Although methanol is now the main, if not the sole, raw material utilized in making formaldehyde, plants for making the latter direct from natural gas, or from petroleum gas hydrocarbons are contemplated or actually under construction. Should such processes develop to an appreciable extent, the competitive situation of the United States may change, but in such case it is unlikely that this country would be so affected as to change its position as a moderate exporter.
HEXAMETHYLENETETRAMINE
Description and uses.
Hexamethylenetetramine is a white crystalline powder made by the interaction of formaldehyde and ammonia. It is used in tar-acid resins to replace formaldehyde, though its higher cost has limited its use to small proportions as a finishing or hardening agent. Other uses are as an internal antiseptic in medicine (marketed under trade names such as Urotropin, Cystogen, Aminoform, Urisol, and Cystamin), as an accelerator in the vulcanization of rubber (a declining use), and in artificial cork. During the World War it was used in gas masks as an absorbent for phosgene.
United States production.
The domestic production of hexamethylenetetramine declined during the depression, but has been increasing in the last few years. Production in 1937, however, was still below that of 1929. Statistics of production are shown in table 86.
Table 86.—Hexamethylenetetramine: United States production and sales, 1923, and 1925-37
Year Production (quantity) Sales
Quantity Value Unit value
Pounds Pounds
1923 1,381,073 1,155,083 $974,877 $0.84
1925 1,657,993 1,506,286 994,458 .66
1926 1,495,220 (1) (1)
1927 1,315,213 (1) (1)
1928 1,661,645 (1) (1)
1929 2,368,020 (1) (1)
1930 1,871,690 (1) (1)
1931 (2) (2)
1932 (2) (2)
1933-37 (1) (1)
1 Not publishable; figures would disclose operations of individual firms.
2 Not available.
Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.
Hexamethylenetetramine is made by two firms in New Jersey and by one in West Virginia. The raw materials utilized are formaldehyde and liquid or anhydrous ammonia. One company makes its own requirements of both, and another makes its own formaldehyde. Most of the production of hexamethylenetetramine is sold, marketed in barrels, drums, kegs, and cans.
Production in other countries.
Hexamethylenetetramine is made in a number of foreign countries, with Germany probably the leading foreign producer. Exports from Germany declined from 445,000 pounds in 1931 to 182,000 pounds in 1934, the decline being due chiefly to the expansion of production in countries previously large importers, particularly the United Kingdom, Japan, Czechoslovakia, and France.
United States imports and exports.
Imports of hexamethylenetetramine to the United States are shown in table 87.
Table 87.—Hexamethylenetetramine: United States imports for consumption, 1923-37
Calendar year Rate of duty Quantity Value Unit value Computed ad valorem rate
Pounds Percent
1923 25 percent 47,373 $24,722 $0.522
1924 do 3,826 3,998 1.045
1925 do 20,771 10,453 .503
1926 do 23,481 10,237 .436
1927 do 3,417 1,715 .502
1928 do 5,898 1,643 .279
1929 do 5,562 1,857 .334
1930:
Jan. 1-June 17 do
June 18-Dec. 31 11 cents per pound
1931 do
1932 do 1,103 336 .305 36.1
1933 do 1,103 293 .266 41.4
1934 do 612 273 .446 24.7
1935 do
1936 do 7,496 1,510 .201 54.6
19371 do 10,895 8,197 .200 54.9
1 Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Imports of hexamethylenetetramine in 1928 came principally from the United Kingdom, the remainder from Germany. In 1929 they came wholly from Germany; in 1932 and 1933 from Belgium; and in 1934 principally from Canada, with the rest from the United Kingdom. In 1936 Belgium supplied 7,166 pounds valued at $1,368 and Germany 330 pounds valued at $142.
Exports of hexamethylenetetramine are not shown in official statistics. It is known, however, that some has been exported, and that in 1933, at least, exports exceeded imports.
Competitive conditions.
Hexamethylenetetramine is made from formaldehyde and ammonia, of which there are ample supplies in the United States. The market for hexamethylenetetramine is limited, and imports are small. It is made in numerous foreign countries, Germany being probably the principal potential competitor.
FURFURAL
Furfural is an aldehyde found in oat hulls, rice hulls, corn cobs, bran, and other farm waste products. Commercially it is obtained in the United States from oat hulls and in the Soviet Union from the husks of sunflower seeds. It is a colorless liquid, boiling at 158° to 162° C. and freezing at minus 38° C. Its principal use is in synthetic resins, of which tar acid-furfural is probably the most important. These resins are used in molding, for impregnating, and in coatings. Furfural is also used as a solvent for cellulose ethers and esters, natural gums and resins, and in the manufacture of derivatives useful as rubber chemicals.
Domestic production is entirely by one firm, located in Iowa. Production and sales statistics are not publishable, but the maker has stated that consumption is in “terms of millions of pounds per year.”