Chapter VII: Part 7
[In thousands of pounds]
-------------+---------------+--------------------------------
| | Refined
Census year | Crude 80 +------------+----------+--------
| percent basis | Chemically | Dynamite |
| | pure grade | grade | Total
-------------+---------------+------------+----------+--------
1919 | 61,793 | 36,693 | 25,655 | 62,348
1920 | 54,688 | 32,860 | 31,571 | 64,431
1923 | 99,579 | 47,992 | 52,369 | 100,361
1924 | 95,154 | 53,243 | 37,368 | 90,611
1925 | 103,407 | 55,448 | 52,658 | 108,106
1926 | 116,369 | 64,460 | 49,579 | 114,039
1927 | 128,209 | 59,126 | 49,266 | 108,392
1928 | 130,499 | 66,419 | 46,622 | 113,041
1929 | 140,080 | 66,791 | 58,981 | 125,772
1930 | 138,675 | 69,654 | 50,974 | 120,628
1931 | 140,002 | 70,528 | 43,366 | 113,894
1932 | 133,919 | 63,624 | 41,539 | 105,163
1933 | 119,812 | 58,585 | 45,534 | 104,119
1934 | 153,115 | 80,359 | 48,553 | 128,912
1935 | 141,185 | 74,705 | 48,685 | 123,390
1936 | 154,096 | 85,386 | 47,535 | 132,921
1937 | 167,882 | 92,889 | 51,794 | 144,683
-------------+---------------+------------+----------+--------
Source: Bureau of the Census, U. S. Department of Commerce.
TABLE 49.—_Glycerin: United States production for sale, in specified years, 1919-35_
--------+-------------------------------+--------------------------------
| Crude[1] | Refined
+----------+------------+-------+----------+-------------+-------
Year | | | Value | | | Value
| Quantity | Value | per | Quantity | Value | per
| | | pound | | | pound
--------+----------+------------+-------+----------+-------------+-------
| _1,000 | | | _1,000 | |
| pounds_ | |_Cents_| pounds_ | |_Cents_
1919 | 18,228 | $2,482,779 | 13.6 | 47,377 | $11,461,213 | 24.2
1923 | 27,444 | 3,124,470 | 11.4 | 74,105 | 12,214,012 | 16.5
1925 | 30,735 | 4,258,351 | 13.9 | 94,303 | 16,991,213 | 18.0
1927 | 27,000 | 3,942,991 | 14.6 | 89,585 | 19,184,806 | 21.4
1929 | 28,790 | 2,358,031 | 8.2 | 113,140 | 12,715,641 | 11.2
1931 | 27,530 | 1,673,733 | 6.1 | 102,510 | 10,316,347 | 10.1
1931[2]| 25,964 | 1,551,573 | 6.0 | 101,615 | 10,222,850 | 10.1
1933 | 22,161 | 1,191,000 | 5.4 | 107,853 | 7,915,000 | 7.3
1935 | 24,042 | 2,366,481 | 9.8 | 121,262 | 12,984,684 | 10.7
[1] By chemical and soap manufacturing plants only.
[2] Adjusted for comparison with 1933.
Source: Bureau of the Census, U. S. Department of Commerce.
Crude glycerin is produced by about 200 soap makers and by about 12 producers of fatty acids. Soap factories are located in more than half the States, the principal ones being in Ohio, New York, Massachusetts, New Jersey, Illinois, California, and Pennsylvania; the fatty acid plants are located in five or six States, Ohio being of chief importance. Most of the smaller producers sell their output of crude glycerin. Refiners of glycerin are few in number compared to the producers of crude. The larger soap plants refine their own crude glycerin and in addition purchase crude from other plants for refining.
The process of recovering glycerin consists of chemically treating weak glycerin solutions separated from the soap or fatty acids, and then concentrating and distilling under reduced pressures. The average yield is less than 10 percent but varies from about 9 to 12 percent, depending upon the kinds of oils and fats used. When prices are high every effort is made to recover the maximum yield of glycerin; when prices are low, cost of chemical treatment and distillation makes it advisable to allow more glycerin to remain in the soap or to discard the weak solutions.
Production in other countries.
As in the United States, glycerin is produced in foreign countries, as a byproduct of the soap and fatty acid industries. The United Kingdom, Germany, and France, and recently the Soviet Union, are the leading producers. The output in each of these countries is estimated to be less than a third of the output in the United States. The British Census of 1930 reports the production of crude glycerin in the United Kingdom at 44 million pounds. Authentic statistics on production in other leading countries are not available, but most estimates show lower figures than for the United Kingdom. In some European countries the normal production of soap results in more glycerin than can be utilized.
International trade.
France is the principal net exporter of crude glycerin and the United Kingdom of refined glycerin. The Netherlands, Germany, and France are also net exporters of refined glycerin. The international trade of certain of the more important producing countries in crude and refined glycerin is shown in table 50.
TABLE 50.—_Glycerin: Imports and exports of principal countries, 1931 and 1933-37_
[In thousands of pounds]
--------------------+---------------+---------------+---------------
| 1931 | 1933 | 1934
+-------+-------+-------+-------+-------+-------
|Imports|Exports|Imports|Exports|Imports|Exports
--------------------+-------+-------+-------+-------+-------+-------
Crude: | | | | | |
UNITED STATES[1]| 8,782| ([2]) | 4,988| ([3]) | 13,722| ([3])
United Kingdom | 1,702| 2,662| 4,778| 2,951| 472| 2,825
Germany | 4,120| 2,313| 5,232| 2,939| 4,746| 1,599
France | 1,269| 7,962| 426| 3,488| | ([2])
Netherlands | 5,133| 859| 3,027| 2,300| 2,605| 3,796
Refined: | | | | | |
UNITED STATES | 1,966| 328| 2,776| ([3]) | 2,214| ([3])
United Kingdom | 2,519| 9,926| 822| 19,834| 230| 19,134
Germany | 102| 10,092| 57| 3,562| 224| 3,818
France | 178| 3,989| 109| 1,246| 51| 12,249
Netherlands | 618| 8,337| 1,144| 6,620| 1,008| 5,955
Belgium | 534| 758| 1,193| 429| 1,206| 2,360
+-------+-------+-------+-------+-------+-------
| 1935 | 1936 | 1937[4]
+-------+-------+-------+-------+-------+-------
|Imports|Exports|Imports|Exports|Imports|Exports
+-------+-------+-------+-------+-------+-------
Crude: | | | | | |
UNITED STATES[1]| 4,092| ([2]) | 8,686| ([2]) | 10,171| ([2])
United Kingdom | 1,119| 2,365| 2,322| 3,070| ([2]) | ([3])
Germany | 4,091| 326| 8,247| 122| 13,567| 578
France | 862| ([2]) | 1,176| ([2]) | 164| ([2])
Netherlands | 5,441| 4,912| 7,185| 5,644| 9,127| 6,865
Refined: | | | | | |
UNITED STATES | 69| 3,354| 3,448| 1,146| 7,535| 1,375
United Kingdom | 2| 15,032| | 12,991| ([3]) | 16,029
Germany | 108| 1,571| 30| 1,155| 71| 100
France | 4| 12,118| 10| 9,269| 9| 17,750
Netherlands | 694| 5,516| 739| 8,885| 500| 10,961
Belgium | 998| 1,945| 188| 1,981| 651| 1,858
--------------------+-------+-------+-------+-------+-------+-------
[1] Imports from Cuba and the Philippines not included in the
United States statistics. These imports, consisting of crude
glycerin, averaged about 2,200,000 pounds annually for the period
1931-37.
[2] Included, if any, with refined.
[3] Not separately reported.
[4] Preliminary.
Source: Official statistics of each country.
United States imports.
Under the Tariff Act of 1922, paragraph 43, imports of crude glycerin were dutiable at 1 cent per pound and refined glycerin at 2 cents per pound. The Tariff Act of 1930, paragraph 42, carries the same rates. Imports of crude glycerin from Cuba enjoy a preferential rate; they were dutiable at 0.8 cent per pound up to September 3, 1934, and at 0.4 cent per pound thereafter. Under the trade agreement with the Netherlands, effective February 1, 1936, the rate on refined glycerin was reduced from 2 cents to 1⅔ cents per pound (⅔ cent plus regular rate on crude, but not more than 1⅔ cents). Under the trade agreement with France, effective June 15, 1936, the rate on crude glycerin was reduced from 1 cent to 0.8 cent, which automatically further reduced the rate on refined glycerin to 1¹⁴⁄₃₀ (approximately 1.47) cents per pound. The rates under these last two trade agreements are generalized to all countries which do not discriminate against our commerce.
The amount of glycerin supplied by imports has greatly declined. Prior to the World War, imports of crude glycerin ranged from 30 million to 40 million pounds annually. After the war imports were less and after 1929 declined to comparatively small quantities, except in 1934. Imports of refined glycerin were relatively unimportant until 1924, except in 1920. They amounted to almost 11 million pounds in 1926, but declined thereafter. Some of the imports are reexported with benefit of drawback. In 1930, 1,006,164 pounds of imported crude glycerin and 396,792 pounds of imported refined were thus reexported, chiefly in the refined grades. Corresponding figures in 1932 and 1933 were 197,331 and 111,753 pounds of crude, and 40,011 and 10,056 pounds of refined.
Statistics of imports other than from Cuba and the Philippines are given in table 51. Table 52 shows imports of crude from Cuba and table 53 imports of crude from the Philippines.
TABLE 51.—_Glycerin: United States imports[1] for consumption 1919-20 and 1923-37_
-------------+-------------+---------+---------+----------+-------------
| |Quantity,| | | Computed
Calendar year| Rate of | 1,000 | Value |Unit value| ad valorem
| duty | pounds | | |rate, percent
-------------+-------------+---------+---------+----------+-------------
| Crude
+-------------+---------+---------+----------+-------------
1919 | 1 cent per | 3,564| $417,774| $0.117| 8.5
| pound | | | |
1920 | do | 22,272|2,912,430| .131| 7.7
1923 | do | 14,120|1,382,249| .098| 10.2
1924 | do | 13,659|1,413,593| .103| 9.7
1925 | do | 18,624|2,161,413| .116| 8.6
1926 | do | 26,729|3,849,222| .144| 6.9
1927 | do | 13,666|2,026,175| .148| 6.7
1928 | do | 3,889| 282,615| .073| 13.8
1929 | do | 13,681| 786,598| .058| 17.4
1930 | do | 10,022| 577,406| .058| 17.4
1931 | do | 8,782| 446,897| .051| 19.7
1932 | do | 3,952| 145,329| .037| 27.2
1933 | do | 4,988| 176,080| .035| 28.3
1934 | do | 13,722| 932,389| .068| 14.7
1935 | do | 4,092| 353,925| .086| 11.4
1936 | Various[2] | 8,686| 936,312| .108| 7.7
1937[3] | do | 10,171|1,716,351| .169| 4.8
+-------------+---------+---------+----------+-------------
| Refined
+-------------+---------+---------+----------+-------------
1919 | 2 cents per | 39| 4,471| .114| 17.5
| pound | | | |
1920 | do | 5,382|1,170,030| .217| 9.2
1923 | do | 586| 76,994| .131| 15.2
1924 | do | 1,501| 229,897| .153| 13.1
1925 | do | 2,044| 305,796| .150| 13.4
1926 | do | 10,839|2,328,936| .215| 9.3
1927 | do | 8,289|1,697,330| .205| 9.8
1928 | do | 4,218| 450,247| .107| 18.7
1929 | do | 5,358| 489,575| .091| 21.9
1930 | do | 3,137| 265,093| .085| 23.7
1931 | do | 1,966| 140,975| .072| 27.9
1932 | do | 2,348| 142,359| .061| 33.0
1933 | do | 2,776| 166,991| .060| 33.2
1934 | do | 2,214| 208,989| .094| 21.2
1935 | do | 69| 8,277| .121| 16.6
1936 |Various[2] | 3,447| 594,036| .172| 8.5
1937[3] | do | 7,535|1,827,189| .242| 6.2
-------------+-------------+---------+---------+----------+-------------
[1] Does not include products of Cuba (duty less 20 percent) and
the Philippine Islands (free).
[2] For changes in rates, see p. 105.
[3] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 52.—_Crude glycerin: United States imports (for consumption) from Cuba, in specified years, 1919-37_
-------------+-------------------+--------+-------+----------+----------
| | | | | Computed
Calendar year| Rate of duty |Quantity| Value |Unit value|ad valorem
| | | | | rate
-------------+-------------------+--------+-------+----------+----------
| | _1,000 | | |
| | pounds_| | |_Percent_
1919 |⁸⁄₁₀ cent per pound| 249|$27,023| $0.108| 7.4
1920 | do | 139| 21,941| .158| 5.1
1923 | do | 429| 47,438| .111| 7.2
1924 | do | 768| 85,971| .112| 7.2
1925 | do | 624| 73,538| .118| 6.8
1926 | do | 835|134,893| .162| 5.0
1927 | do | 1,119|170,723| .153| 5.2
1928 | do | 690| 48,963| .071| 11.3
1929 | do | 921| 60,158| .065| 12.2
1930 | do | 843| 53,905| .064|
1931 | do | 1,171| 67,709| .058| 13.8
1932 | do | 1,232| 50,147| .041| 19.7
1933 | do | 1,216| 56,737| .047| 17.2
1934 |Various[1] | 1,178| 92,692| .079|
1935 |⁴⁄₁₀ cent per pound| 2,551|228,011| .089| 4.5
1936 | do | 2,160|230,340| .107| 3.8
1937[2] | do | 2,477|381,683| .154|
-------------+-------------------+--------+-------+----------+----------
[1] Trade agreement of ⁴⁄₁₀ cent per pound, effective Sept. 3,
1934.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
TABLE 53.—_Crude glycerin: United States imports (for consumption) from Philippine Islands 1925-37_
-------------+-------------+--------------+-------+----------
Calendar year| Rate of duty| Quantity | Value |Unit value
-------------+-------------+--------------+-------+----------
| |_1,000 pounds_| |
1925 |Free | 16| $1,418| $0.089
1926 | do | 95| 12,115| .128
1927 | do | 159| 18,261| .115
1928 | do | 337| 24,327| .072
1929 | do | 250| 16,796| .067
1930 | do | 279| 18,805| .067
1931 | do | 180| 10,993| .061
1932 | do | 198| 9,150| .046
1933 | do | 268| 14,078| .052
1934 | do | 181| 14,984| .083
1935 | do | 1,579| 74,798| .047
1936 | do | 304| 32,708| .108
1937[1] | do | 793|145,348| .183
-------------+-------------+--------------+-------+----------
[1] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
France has usually been the principal source of imports of crude glycerin, but since 1935 Cuba has ranked first. Cuban imports enter at a preferential rate of duty (0.8 cent per pound on crude until September 3, 1934, when it was reduced to 0.4 cent). Receipts from the Philippines are duty-free. Imports by countries for recent years are given in table 98, page 151.
The Netherlands has generally been the chief source of imports of refined glycerin, although the United Kingdom was first in 1934 and 1935 and France first in 1937. Imports by countries for recent years are given in table 99, page 152.
United States exports.
Exports of glycerin are insignificant compared with production and are small compared with imports. They go chiefly to Mexico and Canada, and, at times, also to Cuba, the Philippines, and Chile. Geographic propinquity is probably the principal factor accounting for these exports, although it is possible that some exports are destined to foreign branch factories of an American company for making dynamite.
Crude and refined grades were not separately distinguished in export statistics, but it is known that exports consist principally, if not entirely, of the refined. In 1933 and 1934 glycerin exports were not reported. Statistics of exports are given in table 54.
TABLE 54.—_Glycerin: United States exports, in specified years, 1919-37_
-------+---------+-----------+----------
Year | Quantity| Value |Unit value
-------+---------+-----------+----------
| | |_Cents per_
|_Pounds_ | | _pound_
1919 |3,963,392| $1,190,984| 30.0
1920 |1,742,708| 429,116| 24.6
1923 |1,767,407| 318,765| 18.0
1924 |1,415,882| 237,639| 16.8
1925 |1,367,191| 282,078| 20.6
1926 | 767,698| 192,220| 25.0
1927 | 693,144| 143,700| 20.7
1928 |2,051,937| 259,100| 12.6
1929 |1,373,605| 197,986| 14.4
1930 | 607,690| 102,892| 16.9
1931 | 328,143| 48,095| 14.7
1932 | 260,339| 28,609| 11.0
1933 | ([1]) | ([1]) |
1934 | ([1]) | ([1]) |
1935 |3,353,625| 450,248| 13.4
1936 |1,146,026| 182,592| 15.9
1937[2]|1,375,036| 338,148| 24.6
-------+---------+-----------+----------
[1] Not reported separately.
[2] Preliminary.
Source: Foreign Commerce and Navigation of the United States.
Competitive conditions.
Glycerin occurs in chemical combination in animal and vegetable oils and fats. Since it is obtained as a byproduct, the output is dependent primarily upon the output of the major products, soaps and fatty acids, and its production is largely independent of demand. At low prices, however, less glycerin is recovered.
The United States usually consumes more glycerin than it produces (see table 55), whereas leading European producing nations produce more than they consume. In recent years the domestic production has apparently been approaching domestic requirements. A factor tending to decrease demand is the increasing resort to substitutes in various uses, particularly ethylene glycol, ethyl alcohol, and methyl alcohol. On the other hand, the demand in the resin industry is expanding rapidly.
TABLE 55.—_Refined glycerin: United States production, imports, exports, and apparent consumption, in specified years_
-------+-------------+----------+----------+--------------
Year |Production[1]|Imports[2]|Exports[3]| Apparent
| | | |consumption[4]
-------+-------------+----------+----------+--------------
| _Pounds_ | _Pounds_ | _Pounds_ | _Pounds_
1927 | 108,392| 8,289| 693| 115,987
1929 | 125,772| 5,358| 1,374| 129,757
1931 | 113,894| 1,966| 328| 115,531
1932 | 105,163| 2,348| 260| 107,250
1933 | 104,120| 2,776| ([5]) | 106,895
1934 | 128,912| 2,214| ([5]) | 131,126
1935 | 123,390| 69| 3,354| 120,105
1936 | 132,922| 3,447| 1,146| 135,223
1937[6]| ([5]) | 7,535| 1,375| ([5])
-------+-------------+----------+----------+--------------
[1] From table 48 (refined basis).
[2] From table 51 (refined).
[3] From table 54 (grade not specified, but chiefly refined).
[4] Production plus imports minus exports.
[5] Not available.
[6] Preliminary.
Up to 1924 (except 1920) imports consisted principally of crude glycerin, much of which was refined in the United States and included in United States production; thereafter imports of refined glycerin became important relative to the crude. Exports are insignificant compared to either production or imports.
17. RAW MATERIALS FOR TAR-ACID RESINS
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_
--------------------+-----------------------+---------+----------
| | | Average
Commercial name | Chemical name | Boiling |percent in
| |point ° C| 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| ⎫
2-4 Xylenol |2-4-dimethyl phenol | 211.5| ⎪
2-5 Xylenol |2-5-dimethyl phenol | 211.5| ⎬ .2
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| ⎫
Meta ethylphenol |3-ethyl phenol | 217.0| ⎪
Para ethylphenol |4-ethyl phenol | 218.5| ⎪
s-methyl ethylphenol|3-methyl-5-ethyl phenol| 232.5| ⎬ .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_
-----------+--------------+--------------
| Available in | Available in
Tar acid | tar produced | tar distilled
| in 1936[1] | in 1936[2]
-----------+--------------+--------------
|_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_
-----------+----------+--------------------------------+---------------
|Production| Sales |
| | | Ratio of sales
Census year+----------+----------+----------+----------+ to total
| Quantity | Quantity | Value |Unit value| production
-----------+----------+----------+----------+----------+---------------
| _1,000 | _1,000 | _1,000 | | _Percent_
| pounds_ | pounds_ | dollars_ | |
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_
--------------+-----------------
| Estimated
Produced in— |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 |2½ cents per pound plus |Under Revenue Act of 1916.
Sept. 21, 1922. | 15 percent ad valorem |
| on foreign value. |
| |
Sept. 22, 1922, to|7 cents per pound plus |Under par. 27 of Tariff Act
Sept. 21, 1924. | 55 percent ad valorem | of 1922; special provision
| on American selling | for first 2 years.
| price[1] or United |
| States value.[2] |
| |
Sept. 22, 1924, to|7 cents per pound plus |Under par. 27 of Tariff Act
Nov. 29, 1927. | 40 percent ad valorem | of 1922, rate provided
| on American selling | for period after the
| price[1] or United | first 2 years.
| States value.[2] |
| |
Nov. 30, 1927, to |3½ cents per pound plus |By Presidential proclamation
June 17, 1930. | 20 percent ad valorem | following a cost of
| on American selling | production investigation
| price[1] or United | under sec. 315 of Tariff
| States value.[2] | Act of 1922.
| |
June 18, 1930 |3½ cents per pound plus |Under par. 27 (b) of Tariff
| 20 percent ad valorem | Act of 1930.
| on American selling |
| price[3] or United |
| States value.[4] |
------------------+------------------------+----------------------------
[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_
-------+----------------------+---------+--------+----------+----------
| | | | | Computed
Year | Rate of duty | Quantity| Value |Unit value|ad valorem
| | | | | rate
-------+----------------------+---------+--------+----------+----------
| | _Pounds_| | | _Percent_
1910[1]|Free |4,507,693|$275,600| $0.061|
1911[1]| do |4,371,014| 265,780| .061|
1912[1]| do |5,686,704| 521,457| .092|
1913[1]| do |8,345,631| 688,771| .083|
1914[1]| do |8,393,216| 531,535| .063|
1915[1]| do |3,106,445| 179,685| .058|
1916[1]|([2]) |2,246,256| 154,841| .069|
1917[1]|15 percent + 2½ cents | 265,519| 17,168| .065| 53.7
| per pound | | | |
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 | 126,618| 21,389| .169| 96.4
| per pound [4] | | | |
1924 |([5]) | 176,081| 46,786| .266| 81.4
1925 |40 percent + 7 cents | 256,126| 58,958| .230| 70.4
| per pound [4] | | | |
1926 | do | 218,437| 47,351| .217| 72.3
1927 |([6]) | 500| 100| .200| 75.0
1928 |20 percent + 3½ cents | 1,653| 298| .180| 39.4
| per pound [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
1937[7]| 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_
---------+----------------------+--------+------+----------+----------
| | | | | Computed
Calendar | Rate of duty |Quantity| Value|Unit value|ad valorem
year | | | | | rate
---------+----------------------+--------+------+----------+----------
| |_Pounds_| | | _Percent_
1918 |15 percent + 2½ cents | 1,550|$2,008| $1.30| 16.93
| per pound | | | |
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 | 245,119|30,328| .124| 111.58
| per pound[2] | | | |
1924 |([3]) | 662,938|49,380| .074| 134.43
1925 |40 percent + 7 cents | 252,382|15,441| .061| 154.41
| per pound[2] | | | |
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|Production[1]|Imports[2]|Exports[3]| Apparent
| | | |consumption[4]
----+-------------+----------+----------+---------------
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_
----------------+------------+-----------------------------------
| | Sales
Type | Production +-----------+----------+------------
| | 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_
-----+------------+-------------------------------------
| | Sales
Year | Production +------------+------------+-----------
| | 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.
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Synthetic resins and their raw materialsChapter VII: Part 7
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