16. RAW MATERIALS FOR ALKYD RESINS

The alkyd resins are made chiefly from phthalic anhydride and glycerin. Phthalic anhydride in turn is made from naphthalene. Polybasic acids such as maleic, succinic, etc., may also be used with glycerin to form alkyd resins. Naphthalene, phthalic anhydride, maleic and other polybasic acids, and glycerin are discussed in the order named.

NAPHTHALENE

The discovery of naphthalene in coal tar was made simultaneously by Garden and Brande in 1819, and its composition was determined by Faraday in 1826 and later by Laurent in 1832. Naphthalene is almost invariably a constituent of the products obtained when organic matter is heated to comparatively high temperatures. For example, it is formed in small quantities when acetylene, alcohol, acetic acid, benzene, or toluene are heated to high temperatures. Together with certain aromatic hydrocarbons it is formed in the cracking of petroleum and in the hydrogenation of petroleum fractions. Naphthalene is a constituent of the principal varieties of tar produced from coal in the manufacture of gas and coke under ordinary conditions, but not of low-temperature tar. It is present in coal gas although its presence must be kept as low as possible to avoid blocking service pipes in cold weather. The proportion in gas tar varies with the kinds of coal used and is greater the higher the temperature used during carbonization; it usually amounts to 4 to 6 percent but is sometimes as much as 10 percent. In tars obtained from byproduct coke ovens the proportion of naphthalene and other aromatic hydrocarbons depends on the type of oven used. Byproduct coke-oven tar averages 10 to 11 percent naphthalene; blast-furnace tar contains only very small amounts.

Processes to synthesize naphthalene were described as early as 1873 by Aronheim, in 1876 by Wroden and Znatowicz, and in 1884 by Baeyer and Perkin. English Patent No. 26,061 of 1898 claims that it may be obtained by heating barium carbide with barium hydroxide to a high temperature. None of these processes has become of commercial importance.

Recovery of naphthalene.

Naphthalene is recovered in the distillation of coal tar, in the fraction boiling at 180° to 250° C., in the creosote oil fraction boiling at 240° to 270° C. and most abundantly in the carbolate or middle oil fraction boiling at 200° to 250° C. When these fractions are allowed to cool most of the naphthalene crystallizes out and is separated by draining and hot-pressing. This crude material is partially purified by washing with hot caustic soda solution to remove tar acids and then with mineral acid to remove basic substances. Refined naphthalene is obtained by subliming, or preferably by distilling the crude product.

Description and uses.

The Tariff Act of 1930 defines crude naphthalene as naphthalene solidifying under 79° C. after the removal of all water present; and refined naphthalene as that having a solidifying point at or above 79° C. after the removal of all water present.

Crude grades, melting between 70° and 78.5° C., are found in commerce as yellow, red, or brown crystalline solids. These grades are used in the manufacture of phthalic anhydride and other coal-tar intermediates; in the manufacture of lampblack; to enrich illuminating gas and sometimes motor fuel; in synthetic tanning materials; and in certain insecticides. Probably its most important outlets are as a raw material for phthalic anhydride (see p. 98) and refined naphthalene.

Refined grades, melting above 79° C., are marketed as white, crystalline lumps or flakes. Their principal uses are in the manufacture of intermediates, dyes, medicinals, solvents, and textile assistants; as moth repellants; as a lubricant when mixed with rapeseed oil; to remove the “bloom” from lubricating oils; as a preservative for rubber goods and animal skins; and in explosives (trinitro naphthalene). In 1936 more than 75 coal-tar intermediates made from naphthalene were commercially produced in the United States. Of the 75 million pounds of these intermediates produced in that year, 31 million pounds were phthalic anhydride, an important component of synthetic resins of the alkyd type.

United States production.

Crude naphthalene is produced in the United States by byproduct coke-oven operators, gas works that produce their own coal tar, and also by firms that purchase coal tar and distill it. Statistics of production by groups are shown in table 33.

Table 33.—Crude naphthalene: United States production, 1918-37

Year By producers of tar By purchasers of tar Total production

Quantity Value Unit value Quantity Value Unit value Quantity Value Unit value

1,000 pounds Per pound 1,000 pounds Per pound 1,000 pounds Per pound

1918 40,138 $1,281,440 $0.032 40,138 $1,281,440 $0.032

1919 12,612 327,201 .030 12,612 327,201 .026

1923 11,872 $201,824 $0,017 41,453 652,148 .016 53,325 853,972 .016

1925 9,239 92,389 .010 34,135 519,773 .015 43,374 612,162 .014

1926 7,747 100,709 .013 45,166 494,986 .011 52,913 595,695 .011

1927 8,303 91,331 .011 45,298 470,806 .010 53,601 562,137 .010

1928 ¹12,182 146,186 .012 35,180 395,059 .011 47,362 541,245 .011

1929 ¹19,761 316,182 .016 19,502 366,491 .020 39,263 682,673 .017

1930 ¹12,640 151,681 .012 18,617 304,574 .020 31,257 456,255 .015

1931 ¹7,623 76,229 .010 13,311 199,665 .015 20,934 275,894 .013

1932 ¹4,632 41,690 .09 8,961 125,453 .014 13,593 167,143 .012

1933 ¹6,618 66,181 .010 24,003 360,040 .015 30,621 426,221 .014

1934 ¹10,743 139,665 .013 27,179 489,222 .018 37,922 628,887 .016

1935 ¹12,937 168,185 .013 34,716 624,890 .018 47,653 793,075 .017

1936 ¹37,552 600,836 .016 51,984 1,195,632 .023 89,536 1,796,468 .020

1937 ¹60,797 1,215,942 .020 55,182 1,545,100 .028 115,979 2,667,522 .023

¹ Crude and refined. Refined naphthalene included here is probably small so that the figures here and those for total production are substantially accurate.

Source: Bureau of Mines and U.S. Tariff Commission.

Refined naphthalene is obtained from domestic crude, imported crude, and recently from petroleum cracking and hydrogenation. Table 34 shows the annual production and sales of refined naphthalene since 1916. The difference between the figures for the quantity produced and that sold represents the amount used by refiners in the manufacture of other products.

Table 34.—Refined naphthalene: United States production and sales, 1917-37

Year Production Sales

Quantity Value Value Quantity Value Value

1,000 pounds 1,000 dollars Per pound 1,000 pounds 1,000 dollars Per pound

1917 35,343 2,334 $0.07

1918 28,112 2,163 .08

1919 17,625 1,161 .07

1920 30,231 2,309 .08

1921 13,554 13,183 741 $0.056

1922 17,420 14,060 794 .057

1923 28,184 21,871 1,271 .058

1924 15,324 11,961 603 .050

1925 17,581 12,508 610 .049

1926 18,072 12,456 576 .046

1927 21,233 (¹)

1928 24,992 (¹)

1929 31,144 21,120 1,027 .049

1930 31,956 20,171 949 .047

1931 34,959 21,260 829 .039

1932 25,825 18,877 783 .041

1933 42,708 28,658 1,065 .037

1934 38,730 21,257 1,100 .052

1935 46,564 28,761 1,212 .042

1936 52,694 30,499 1,841 .060

1937 52,194 29,657 1,893 .060

¹ Not publishable.

Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.

Organization of the industry.—There are 10 domestic producers of crude naphthalene, operating 52 tar-distilling plants in the following States: Ohio (7), Pennsylvania (6), Illinois and New York (5 each), Alabama, Minnesota, and New Jersey (3 each), Missouri, Rhode Island, Wisconsin, Utah, West Virginia (2 each), and Michigan, Massachusetts, Maryland, Kentucky, Oregon, Connecticut, Tennessee, Indiana, Virginia, and Washington (1 each). Although these plants do not all recover naphthalene as such, they are equipped to recover a crude mixture of naphthalene and tar acids for shipment to a central extracting and refining plant. The principal producing plants are located in Pennsylvania (2), New Jersey (2), Illinois (1), Indiana (1), and West Virginia (1).

The purchasers of tar produced 77 percent of the total output of crude naphthalene in 1935 and 58 percent in 1936.

There are 8 producers of refined naphthalene located in the following States: New Jersey (3), Pennsylvania (2), California, Indiana, and Ohio (1 each).

Trend of production.—Although the United States is the largest producer of coal tar, the limited demand for the main products of tar distillation (creosote oil and pitch) has tended to restrict the amount distilled, thereby reducing the output of naphthalene and the tar acids to a point where the domestic output was not sufficient to meet our requirements. As a result, large quantities of these products have been imported. In 1936 we produced 560 million gallons of coal tar, containing from 400 million to 500 million pounds of naphthalene.[17] In the same year we distilled about 300 million gallons of tar, containing 230 million to 270 million pounds of naphthalene,[17] and our actual recovery of crude naphthalene was 89,536,000 pounds.

Early in 1935 the price of crude naphthalene was about 1.5 cents per pound or 15 cents per gallon, at which level there was little incentive to isolate it from the various fractions of tar distillation. Late in 1935 and in 1936 a serious shortage in naphthalene prevailed, largely because of increased demand by synthetic resin makers but also because of restrictions on exports from certain European countries. The price of the crude then advanced in domestic markets to from 2.5 to 3 cents per pound, with the demand greatly exceeding the supply. Between 1930 and 1936 the apparent consumption of crude naphthalene (production plus imports) increased from 59 million to 129 million pounds, or more than 100 percent. During the same period production increased from 31 million to 89 million pounds; and imports increased from 27 million pounds in 1930 to 48 million pounds in 1935 but declined to 40 million pounds in 1936.

Domestic producers of naphthalene are increasing their output, and they state that continued prices of 2.5 to 3 cents per pound for naphthalene solidifying at about 75° C. or slightly higher will stimulate production sufficiently to meet all present and near-future requirements. Estimates obtained in the summer of 1936 from the large tar distillers and a petroleum refiner indicate that production was appreciably greater in 1937 than in 1935. These estimates included the potential output of two new tar distillation plants under construction, the topping of large quantities of tar (hitherto used as fuel without removing any of the products), the recovery of appreciable quantities of naphthalene by several petroleum refiners, and increased output by other producers.

Imports of crude naphthalene in 1937 amounted to 52,664,277 pounds valued at $1,133,157, or 2.2 cents per pound.

World production.

The output of naphthalene in the principal producing countries, in 1933 and 1935, is shown in table 35. Most of these statistics were estimated from the output of tar or of other distillation products given in official reports of the countries or in consular reports.

The figures in table 35 indicate that the output in 1935 was an increase of about 100 million pounds over 1933 or 41 percent. Notwithstanding this sharp increase in world production, consumers had difficulty in obtaining their requirements. It is believed that the world output in 1937 substantially exceeded that in 1935.

Table 35.—Naphthalene (all grades): World production, by countries, 1933 and 1935

[In thousands of pounds]

Country 1933 1935

Germany 109,148 145,530

Great Britain 45,750 ¹55,000

UNITED STATES 30,620 47,653

France 30,000 ¹33,000

Netherlands ¹15,000 ¹15,000

Belgium 11,025 ¹25,000

Czechoslovakia 6,835 10,805

U. S. S. R. ¹10,000 ¹15,000

Poland ¹5,000 ¹8,000

Spain ¹1,250 ¹2,000

Italy ¹2,500 ¹3,000

Canada ¹2,000 ¹3,000

Total 269,128 362,988

¹ Estimated.

Source: Official statistics of the several countries and consular reports.

Germany.—Germany is the largest producer of naphthalene and the third largest producer of coal tar. With increased production of coal tar and intensive efforts to recover the maximum of naphthalene there has been a larger output of naphthalene in recent years, but increased consumption has created a scarcity in Germany as in all other important producing countries. As a result, greatly reduced quantities are available for export, a situation that is in marked contrast to earlier periods when superabundant production created a marketing problem. The manufacture of phthalic anhydride for alkyd resins is requiring increased quantities of naphthalene.

The demand for alkyd resins has been given a marked impetus by the development of a new standardized linseed oil varnish substitute known as El Varnish, the use of which is required by the Control Board for Industrial Fats in Germany for certain interior and exterior painting (see p. 77). Increased requirements for other important purposes such as intermediates, dyes, black pigments, and explosives have also contributed to the scarcity of naphthalene. In order to conserve domestic supplies, the Reich Government, from December 1935 until late in 1937 prohibited its export without special permit. The prospect of continued strong domestic demand apparently will curtail for an indefinite period the quantities available for export.

The international scarcity of naphthalene resulted in a sharp increase in its price in Germany as elsewhere. The export embargo augmented the domestic German supply, although a shortage still existed and large consumers found it difficult to secure adequate amounts. The shortage of foreign exchange greatly curtailed imports of naphthalene from nearby countries.

The German Government issued a decree requiring that beginning July 1, 1936, the entire national output of coal tar should be delivered to plants equipped for the recovery of tar products distilling up to 240° C. (naphthalene boils at 218° C.). This measure assured maximum recovery of benzol, toluol, xylol, solvent naphtha, phenol, cresol, xylenol, other tar acids, and naphthalene. The decree contemplated an official list of distillation units, and all tar producers were required to report to the official trade control board for mineral oil their monthly output, quantities distilled, and quantities delivered to other distillation plants.

German production, imports, exports, and apparent consumption of naphthalene are shown in table 36. Production increased from 108 million pounds in 1928 to 146 million pounds in 1935; imports decreased from 9 to 4 million pounds; exports decreased from 48 to 22 million pounds; and apparent consumption increased from 69 to 128 million pounds in the same years.

Table 36.—Naphthalene: German production, imports, exports, and apparent consumption, 1928-37

[In thousands of pounds]

Year Production Imports Exports Apparent consumption¹

1928 108,173 9,471 48,332 69,312

1929 124,362 8,032 39,739 92,655

1930 103,194 3,892 34,614 72,472

1931 92,169 2,403 39,077 55,495

1932 90,626 952 29,720 61,852

1933 109,148 7,483 31,842 84,783

1934 132,300 8,641 35,044 105,891

1935 145,530 4,246 22,169 127,603

1936 (²) 493 8,153 (²)

1937 (²) 33 24,966 (²)

¹ Production plus imports, minus exports.

² Not available.

Sources: Consular reports (production); Der auswartige Handel (imports and exports).

Imports of naphthalene into Germany in past years have been supplied by nearby countries, notably the Saar (which became an integral part of Germany in February 1935), Belgium, Czechoslovakia, Poland, the Soviet Union, and others. The United States has been the most important foreign market for German naphthalene, taking from 50 to 75 percent of the total quantity exported. Other important buyers were Belgium, Italy, Japan, and France. Table 92 (see p. 144) shows the quantity and value of imports and exports by countries in recent years.

Great Britain.—The recovery and distillation of coal tar in Great Britain is highly developed. The annual output of tar, principally gas-works tar, is somewhat smaller than in the United States, although the quantities distilled for the recovery of separate components exceed the quantities distilled in the United States. In 1935 the tar distilled in England and Wales totaled 330 million gallons and in Scotland, 31 million gallons, or a combined total of 361 million gallons as compared with about 280 million distilled in this country.

Production of naphthalene in Great Britain is shown in table 37.

Table 37.—Naphthalene: Production in Great Britain, in specified years

Year Production

1,000 pounds

1924 13,730

1930 41,400

1933 45,750

1935¹ 55,000

1936¹ 70,000

¹ Estimated.

Source: Consular reports.

Table 38 shows exports of naphthalene from Great Britain in recent years. The United States has been the best customer, in most recent years taking 50 percent or more of the total exported. Our imports from Great Britain have been entirely crude naphthalene, duty-free.

Imports of naphthalene into Great Britain are not shown separately in official statistics. It is known that the Netherlands exported small quantities to Great Britain in 1929 and 1933.

Table 38.—Naphthalene: Exports from the United Kingdom

Year Quantity Value

To all countries To United States To all countries To United States

Pounds sterling Dollars¹ Pounds sterling Dollars¹

1,000 pounds 1,000 pounds

1928 5,132 (²) 20,607 100,278 (²) (²)

1929 9,185 4,312 32,348 157,110 12,558 60,993

1932 11,132 7,514 26,869 94,205 14,274 50,046

1933 14,718 10,480 38,172 161,728 19,604 83,059

1934 11,955 6,492 35,226 177,514 13,025 65,637

1935 14,490 7,999 49,939 244,789 18,413 90,256

1936 26,332 13,412 120,372 598,357 46,158 229,447

¹ Conversion to dollars at annual average quotations of the Federal Reserve Board.

² Not available.

Source: The Trade of the United Kingdom, 1929 and 1936.

Belgium.—The distillation of coal tar is one of the oldest and most important branches of the Belgian chemical industry. Approximately 90 batteries of byproduct-coke ovens, with a total of 3,000 ovens are in operation. Practically all of the coal tar produced in these operations is distilled for the recovery of the several products. The output of naphthalene is shown in table 39.

Table 39.—Naphthalene: Belgian production, 1928-35

Year Quantity

1,000 pounds

1928 26,000

1929 26,500

1930 24,200

1931 22,000

1933 12,000

1935¹ 25,000

¹ Estimated.

Source: Consular reports.

Belgian imports and exports of naphthalene, by countries, are shown in tables 93 and 94 (see pp. 146, 147). Belgium is a net importer of crude naphthalene and a net exporter of refined naphthalene. In 1937, it imported 9 million pounds and exported 6.7 million of crude; it imported only 19 thousand pounds and exported 14 million pounds of refined.

Czechoslovakia.—The annual output of naphthalene in Czechoslovakia is shown in table 40.

Table 40.—Naphthalene: Czechoslovak production, in specified years, 1928-35

Year Quantity

1,000 pounds

1928 5,733

1930 6,174

1931 2,205

1932 1,543

1933 6,835

1934 9,040

1935 10,805

Source: Consular reports.

France.—Naphthalene is produced in France by a number of manufacturers, most of whom consume their production in their own factories. The French output is said to be insufficient to meet domestic requirements. Estimated production is given as approximately 30 million pounds annually. Appreciable quantities are imported from nearby countries. Imports from Belgium in recent years average between 1 million and 3 million pounds.

Poland.—Production of crude naphthalene in Poland is shown in table 41.

Table 41.—Crude naphthalene: Polish production, 1928-36

Year Quantity

1,000 pounds

1928 4,708

1929 5,257

1930 3,925

1931 3,486

1932 3,704

1933 4,795

1934 7,705

1935 5,021

1936 2,836

Source: Consular reports.

The Netherlands.—Statistics of production are not available. Exports in recent years, however, have averaged about 10 million pounds annually. It is believed that the production of crude naphthalene exceeds 15 million pounds a year.

Table 95 (see p. 148) shows Netherland imports and exports of naphthalene by countries in recent years. Imports in 1937 amounted to 2 million pounds and exports to 15 million pounds.

Canada.—Statistics of production are not available. The annual output of crude naphthalene is estimated at 2 to 3 million pounds.

Imports of refined naphthalene are usually about 1 million pounds (see table 96, p. 150). Exports are probably small, although in 1929 and 1934 those to the United States alone were over 1 million pounds.

The Soviet Union.—Statistics of production of naphthalene in the Soviet Union are not available. The annual output has been estimated at 10 million pounds in 1933 and 15 million pounds in 1935. Exports have increased substantially in recent years, those to the United States from 1 million pounds in 1934 to 6 million pounds in 1935. Exports to Germany were 361 thousand pounds in 1933; 1 million pounds in 1934; and 531 thousand pounds in 1935.

Japan.—Japanese production of naphthalene has been small compared with the output of other tar products. The output of crude naphthalene in 1934 was reported to have been 381 thousand pounds. Expansion of the byproduct coking industry in Japan and Manchuria has increased the production of coal tar, byproduct ammonia, and benzol. Japan has imported large quantities of naphthalene in recent years, principally from Germany and Belgium. The increased consumption in Europe may so reduce supplies from these sources as to cause Japan to increase the recovery at home.

Japanese imports of naphthalene from principal sources, are shown in table 97 (see p. 150). In 1936, 12.6 million pounds were imported.

United States imports.

Rates of duty.—Prior to September 8, 1916, all grades of naphthalene were imported free of duty. Since that time crude naphthalene has remained free but refined naphthalene has been subject to the tariff treatment shown in table 42.

Table 42.—Naphthalene: Rates of duty upon imports into the United States, 1916-38

Period Rate of duty Authority

Crude Refined

To Sept. 8, 1916 Free Free Free under par. 452 of the act of 1913 and under 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. (Title V, prohibited imports for 3 months 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 Crude, free under par. 1549 and refined dutiable under par. 27 of the Tariff Act of 1922.

Sept. 22, 1924, to June 17, 1930. do. 40 percent ad valorem and 7 cents per pound.¹ Ad valorem rate on refined reduced as provided for in Tariff Act of 1922.

June 18, 1930, to Apr. 30, 1935. do. do. Crude, free under par. 1651 and refined dutiable under par. 27 of Tariff Act of 1930.

May 1, 1935, to— do. 20 percent ad valorem and 3½ cents per pound.¹ Refined reduced under trade agreement with Belgium.²

¹ Ad valorem based on American selling price or United States value.

² Generalized to all countries which do not discriminate against United States products.

Under the Tariff Act of 1930, crude naphthalene is on the free list[18] and refined naphthalene is dutiable at 7 cents per pound and 40 percent ad valorem on the basis of American selling price, since it is competitive with refined naphthalene produced in this country.[19] Under the trade agreement with Belgium, effective May 1, 1935, the duty on refined naphthalene was reduced to 20 percent[20] ad valorem and 3½ cents per pound on imports from that country. Under the Trade Agreements Act this reduction applies also to imports from all other countries which do not discriminate against commerce of the United States. In July 1938 Germany was the only one not receiving the reduced rate, exports from that country being subject to the rates specified under the Tariff Act of 1930.

Import statistics.—Table 43 shows imports of crude naphthalene (solidifying at less than 79° C.) and table 44 of refined naphthalene (solidifying at or above 79° C.) The unit invoice values of imports of refined naphthalene in 1924, 1926, 1927, 1928, and 1935 indicate that the imported product was probably not naphthalene as recorded but one of its derivatives provided for elsewhere in paragraph 27.

Table 43.—Crude naphthalene (solidifying at less than 79° C.): United States imports for consumption, in specified years, 1919-37

Calendar year Rate of duty Quantity Value Value per pound

1,000 pounds

1919 Free 3,239 $92,265 $0.028

1920 do. 15,012 530,219 .035

1923 do. 20,992 575,702 .027

1924 do. 5,267 96,491 .018

1925 do. 1,980 26,593 .013

1926 do. 6,963 126,088 .018

1927 do. 6,576 131,436 .020

1928 do. 19,926 357,679 .018

1929 do. 35,007 598,718 .017

1930 do. 27,667 397,292 .014

1931 do. 30,971 318,578 .013

1932 do. 27,002 234,557 .009

1933 do. 42,786 451,019 .010

1934 do. 47,995 669,383 .014

1935 do. 48,455 643,249 .013

1936 do. 39,806 785,396 .020

1937¹ do. 52,664 1,133,157 .022

¹ Preliminary.

Source: Foreign Commerce and Navigation of the United States.

Table 44.—Refined naphthalene (solidifying at or above 79° C): 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 15 percent + 2½ cents per pound. 7,650 $384 $0.050 64.8

1920 do. 3,697,562 416,172 .112 37.2

1923 55 percent + 7 cents per pound 9,605 194 .020 401.6

1924 do. 4,549 1,147 .252 82.8

1925 do.

1926 40 percent + 7 cents per pound 424 125 .295 63.7

1927 do. 18,668 3,077 .165 82.5

1928 do. 27 6 .222 71.5

1929 do. ⎫ None

1930 do. ⎪

Jan. 1-June 17 do. ⎪

June 18-Dec. 31 ⎬

1931 do. ⎪

1932 do. ⎪

1933 do. ⎭

1934 do. 66 6 .091 116.7

1935 do.¹ 99 31 .313 62.4

1936 20 percent + 3½ cents per pound² 30 20 .667 50.5

1937³ do.² 5,055 1,085 .215 36.3

¹ From Germany. No imports under trade agreement rate.

² Belgo-Luxemburg trade agreement rate.

³ Preliminary.

Source: Foreign Commerce and Navigation of the United States.

Table 45 shows the principal sources of our imports of crude naphthalene in recent years. Germany was the principal source until 1936; the United Kingdom, previously the next most important source, was first in 1936 and 1937. In the last three years appreciable quantities have been received from Poland, Czechoslovakia, and the Soviet Union, hitherto unimportant sources.

Table 45.—Crude naphthalene (solidifying under 79° C.): United States imports for consumption from principal sources, in specified years

Source 1929 1931 1933 1934 1935 1936 1937¹

Quantity in thousands of pounds

Germany 21,931 17,444 20,797 22,219 15,742 2,712 12,129

Belgium 2,531 253 4,970 7,314 2,388 2,025 1,995

United Kingdom 8,096 11,339 15,704 6,968 10,689 16,301 17,594

Poland and Danzig 5,766 5,075 1,969 2,312

Canada 1,488 331 223 1,073 76 255 734

Netherlands 44 937 1,092 621 1,344 3,794 3,359

Czechoslovakia 2,984 6,960 6,595 6,414

U. S. S. R. 1,050 6,158 5,145 7,091

All other countries 918 667 22 1,010 1,038

Total 35,007 30,971 42,786 47,995 48,455 39,806 52,664

Value

Germany $382,078 $170,463 $242,501 $326,607 $230,820 $75,314 $287,901

Belgium 48,508 2,506 57,243 90,424 31,375 55,503 51,227

United Kingdom 124,427 123,890 135,853 78,968 123,545 273,964 340,760

Poland and Danzig 89,002 63,992 35,439 55,184

Canada 23,344 3,808 2,729 18,703 1,169 4,093 7,941

Netherlands 614 11,837 12,693 8,739 19,724 105,404 93,045

Czechoslovakia 44,371 98,099 120,529 128,197

U. S. S. R. 12,569 74,354 97,815 146,331

All other countries 19,747 6,074 171 17,335 22,571

Total 598,718 318,578 451,019 669,383 643,249 785,396 1,133,157

Value per pound

Germany $0.017 $0.010 $0.012 $0.015 $0.015 $0.028 $0.024

Belgium .019 .010 .012 .012 .013 .027 .026

United Kingdom .015 .011 .009 .011 .012 .017 .019

Poland and Danzig .015 .013 .018 .024

Canada .016 .011 .012 .017 .015 .016 .011

Netherlands .014 .013 .012 .014 .015 .028 .028

Czechoslovakia .015 .014 .018 .020

U. S. S. R. .012 .012 .019 .021

All other countries .022 .009 .008 .017 .022

Average .017 .010 .011 .014 .013 .020 .022

Percent of total quantity

Germany 62.7 56.3 48.6 46.3 32.5 6.8 23.0

Belgium 7.2 .8 11.6 15.3 14.9 5.1 3.8

United Kingdom 23.1 36.6 36.7 14.5 22.0 41.0 33.4

Poland and Danzig 12.0 10.5 5.0 4.4

Canada 4.3 1.1 .5 2.2 .2 .6 1.4

Netherlands .1 3.0 2.6 1.3 2.8 9.5 6.4

Czechoslovakia 6.2 14.4 16.6 12.2

U. S. S. R. 2.2 12.7 12.9 13.4

All other countries 2.6 2.2 2.5 2.0

Total 100.0 100.0 100.0 100.0 100.0 100.0 100.0

¹ Preliminary.

Source: Compiled from official statistics of the United States Department of Commerce.

United States exports.

Exports are not shown separately; it is doubtful if any naphthalene is exported. Demand in the United States has exceeded domestic production.

Competitive conditions.

The commercial development and widespread application of surface coatings and finishes made from alkyd resins, in which phthalic anhydride and glycerin are the principal components, has resulted in a world-wide shortage of naphthalene, which is a raw material used in making phthalic anhydride. In recent years about one-half of domestic requirements of crude naphthalene have been imported (see table 46) from Europe, principally Germany and the United Kingdom. Increased demand for the same purposes, in these countries, has so reduced the quantities available for export as to create a serious shortage in the United States. Germany placed an embargo on exports late in 1935 and continued it until late in 1937.

Table 46.—Crude naphthalene: United States production, imports, and apparent consumption in specified years

Year Production¹ Imports² Apparent consumption³ Percent supplied by imports

1,000 pounds 1,000 pounds 1,000 pounds

1923 53,325 20,992 74,317 28

1927 53,601 6,577 60,178 11

1929 39,263 35,007 74,270 47

1931 20,934 30,971 51,905 60

1932 13,593 27,002 40,595 66

1933 30,621 42,786 73,407 58

1934 37,922 47,995 85,917 56

1935 47,653 48,455 96,108 50

1936 89,536 39,806 129,342 31

1937⁴ 115,979 52,664 168,643 31

¹ From table 33.

² From table 43.

³ Production plus imports.

⁴ Preliminary.

Vast quantities of naphthalene potentially available in this country were not recovered because of the low prices prevailing until 1936. Since then an increase in the price of crude naphthalene from 1.55 cents to 2.5 cents and 3 cents per pound has stimulated production and has led to additional recovery.

PHTHALIC ANHYDRIDE

Description and uses.

Phthalic anhydride is an aromatic polybasic organic acid anhydride made from naphthalene by vapor phase catalytic oxidation. It is marketed as white needle-shaped crystals or flakes having a melting point of 130° to 131° C. and boiling at 284° to 285° C. It is the cheapest and most widely used aromatic organic acid. Its most important use is in the manufacture of synthetic resins of the alkyd type. Other important uses are in dye intermediates; in phenolphthalein; in benzoic acid; in dyes such as indigo, phloxines, rhodamines, erythrosines; and in esters such as dibutyl phthalate (widely used as a plasticizer in nitrocellulose lacquers and films and of interest as a greaseless lubricant), diethyl phthalate (used as a perfume fixative and denaturant of alcohol), dimethyl phthalate (used as a plasticizer in cellulose acetate films), and diamyl phthalate (used as a plasticizer). Important new processes using phthalic anhydride as a raw material include the syntheses of anthraquinone, substituted anthraquinones, and benzoyl benzoic acid.

Before the World War phthalic anhydride was made by heating naphthalene with sulphuric acid in the presence of mercury; the sulphuric acid acted as an oxidizer, and sulphur dioxide and carbon dioxide were liberated. This process was used in Europe and in the United States to produce the small quantities of phthalic anhydride needed for the manufacture of certain dyes and intermediates. It proved highly unsatisfactory as to operation; the yield varying widely from batch to batch. The sales price of the phthalic anhydride produced at that time was as high as $4.25 per pound, whereas it is 12 to 14 cents per pound today.

In September 1916, Gibbs and Conover, working in the Color Laboratory of the Bureau of Chemistry and Soils, United States Department of Agriculture, developed a process for the synthesis of phthalic anhydride by the direct vapor phase catalytic oxidation of naphthalene. This work was done under the United States Government’s wartime investigation of the manufacture of intermediates and dyes. Gibbs and Conover were granted United States Patent No. 1,285,117 covering the basic process, and the invention was assigned to the people of the United States. This process revolutionized the manufacture of phthalic anhydride, causing the market price to drop to $2.85 per pound in 1918, to 46 cents per pound in 1920, and to 13 cents in 1930. With each decline in price new outlets were found, and domestic production increased practically every year, rising from 227,000 pounds in 1918 to 23,500,000 pounds in 1935.

By a remarkable coincidence the same basic process was developed in Germany, by Alfred Wohl, in the laboratories of the Interessen Gemeinschaft Industrie A. G. (German I. G.), at almost the same time that Gibbs and Conover made their discovery. In 1920 Wohl applied for a United States patent covering this process, claiming invention in the summer of 1916. There was some doubt whether his discovery had been made 2 months earlier or 3 days later than that of Gibbs and Conover, but in July 1934 the United States Court of Customs and Patent Appeals rendered a decision in favor of the German inventor, allowing Wohl’s claim filed with the German patent office on June 28, 1916. Therefore, Wohl’s claim covering the air oxidization process was upheld and he was granted United States Patent No. 1,971,888, issued August 28, 1934 and assigned to the German I. G.

Several domestic firms began commercial production of phthalic anhydride about 1918 under the patent of Gibbs and Conover and have since operated the process continuously. Such manufacturers are presumably protected from possible patent litigation and the payment of royalties under the Wohl patent by section 3 of the so-called Nolan Act of 1921, which states: “No patent granted or validated ... shall affect the right of any citizen of the United States or his successor in business to continue the manufacture, use, or sale commenced before the passage of this Act, nor shall the continued manufacture, use, or sale by such citizen ... constitute an infringement.”

United States production.

Table 47 shows the production and sales of phthalic anhydride from 1917 through 1937.

Table 47.—Phthalic anhydride: United States production and sales, 1917-37

Year Production Sales Unit value

Quantity Value

Pounds Pounds

1917 138,857 138,857 $587,240 $4.23

1918 227,414 227,414 648,650 2.85

1919 290,677 290,677 290,037 .99

1920 796,210 796,210 362,431 .46

1921 202,471 202,471 79,162 .39

1922 1,629,182 1,317,625 461,944 .35

1923 2,343,802 2,091,100 596,508 .29

1924 2,787,308 2,277,073 556,265 .24

1925 3,900,332 3,560,429 701,840 .20

1926 4,379,108 3,446,175 604,949 .18

1927 4,549,820 4,064,476 686,946 .17

1928 6,030,854 5,445,432 888,156 .16

1929 9,168,946 7,450,037 1,147,953 .15

1930 6,693,001 5,614,012 724,909 .13

1931 (¹)

1932 6,259,000 5,695,000 663,000 .12

1933 14,075,844 11,593,716 1,271,887 .11

1934 20,680,379 13,511,253 1,575,787 .12

1935 23,421,558 17,931,662 2,105,134 .12

1936 31,244,378 22,905,873 2,824,471 .12

1937 45,210,784 17,565,905 2,492,473 .14

¹ Not available.

Source: Compiled from annual reports of the Tariff Commission on dyes and other synthetic organic chemicals in the United States.

There are six domestic makers of phthalic anhydride, with producing units at Bridgeville, Pa., Buffalo, N. Y., Philadelphia, Pa., Deepwater Point, N. J., Saint Louis, Mo., and Detroit, Mich. Five of these firms have been producing in commercial quantities continuously for a number of years and it is therefore believed that these companies may continue to produce without the payment of royalties. New producers using this process, however, might be at a disadvantage unless licensed to operate without the payment of royalties by the owner of the patent.

The production of phthalic anhydride has increased remarkably since the discovery of the vapor phase catalytic process of manufacture. Until 1922 the only large outlet was the coal-tar dye industry. The development of new uses for phthalic esters, principally dibutyl phthalate, increased the demand during the period 1922-28. With the drop in price of phthalic anhydride, resins made from it and glycerin became of commercial interest and about 1929 their production began to increase sharply. Most of the increased output since that year is accounted for by its use in alkyd resins. As previously stated, surface coatings made from these resins are now applied to practically all “indoor” surfaces, both wood and metal, and to “outdoor” use on metal. Largely as a result of the growing popularity of surface coatings of the alkyd type the domestic production of phthalic anhydride exceeded 45 million pounds in 1937 and may reach 50 million pounds in 1938. This estimate is based on the present trend of consumption of alkyd resins and current use therein of phthalic anhydride. Should other polybasic acids be used in greater proportion the estimate would have to be revised. Considerable research work is being done on certain polybasic acids, with very promising results in some instances. Maleic anhydride is being used commercially, as are adipic acid, malic acid, and succinic acid. Other possibilities include such acids as citric, tartaric, sebacic, fumaric, and oxalic.

Production in other countries.

Phthalic anhydride is manufactured in Germany, England, France, Italy, and Japan, but no statistics of foreign production or of international trade are available. The output in Germany is known to be increasing rapidly and is believed to be the principal reason for the German embargo on exports of naphthalene.

In England there are two makers: Imperial Chemical Industries, Ltd., and Monsanto Chemicals, Ltd. The latter is a branch of the American firm of the same name.

In Italy, production was started in 1928 by the A. C. N. A. at Cengio. Capacity is given as 600,000 pounds annually, and the process is essentially the same as in this country.

Japanese production is estimated at 6 million pounds a year. Nihon Seuryo’s plant is the principal one, and the Nishijima mill, at Osaka, the next in importance.

United States foreign trade.

Imports of phthalic anhydride are dutiable under paragraph 27 at 7 cents per pound and 40 percent ad valorem based on American selling price. There were practically no imports since the World War until 1937, when 223,431 pounds were imported from England to relieve a temporary shortage.

Exports, if any, are not shown separately in official statistics.

Competitive conditions.

Phthalic anhydride is the cheapest polybasic organic acid and therefore the most widely used in the production of alkyd resins. The rapid rise in consumption of surface coatings and finishes made from these resins presages greater demand for phthalic anhydride (and glycerin) in the future, particularly if this type of outdoor finish for wood is successful.

The world-wide shortage of naphthalene, with attendant sharp increases in price, raises the question of whether there may not be partial or complete replacement of phthalic anhydride by other polybasic acids in certain types of alkyd resins. The probability of such replacement seems remote unless the use of other polybasic acids, at present much higher priced, so improves the properties of the resins as to give a superior product. Approximately 100 pounds of naphthalene are required to produce 109 pounds of phthalic anhydride. Naphthalene at 3 cents per pound gives phthalic anhydride a raw material cost of 2.75 cents per pound as compared with 1.45 cents per pound when naphthalene was 1.55 cents per pound. In other words, the increase of 1.5 cents per pound in naphthalene, meant an increase of only about 1⅓ cents per pound in the raw material cost of phthalic anhydride, and only approximately ¼ cent per pound in the raw material cost of an alkyd resin surface coating containing about 20-percent phthalic anhydride.

POLYBASIC ACIDS OTHER THAN PHTHALIC ANHYDRIDE

Maleic acid and anhydride.

Maleic anhydride is obtained as a byproduct in the manufacture of phthalic anhydride and as a major product by the vapor phase catalytic oxidation of benzene. Domestic production, still small compared with phthalic anhydride, has increased many fold during the past two or three years. In 1937 there were three producers of maleic anhydride, with an output totaling 2,114,176 pounds. The uses of maleic acid derivatives other than in making resins are minor.

Malic acid and malomalic acid.

Malic acid is widely distributed in the vegetable kingdom, occurring especially in unripe apples. Commercially it is obtained by synthesis. Domestic production was reported for the first time in 1935. Malomalic acid is formed by heating malic acid. United States Patent No. 1,091,627 covers a resin made from malic acid and glycerin which will increase the toughness of phthalate resins. United States Patent No. 1,667,198 suggests the use of malomalic acid to form resins of glass-like appearance.

Adipic acid.

Adipic acid is made by oxidation of cyclohexanol. When condensed with glycerin it yields an alkyd resin which is soft and rubbery and which does not harden when heated. Numerous patents have been granted on the preparation of adipic acid and its resins. Commercial production of adipic acid was first reported in 1935, and the output increased in 1936 and in 1937.

Succinic acid and anhydride.

Succinic acid is a white crystalline powder melting at 185° C. and boiling at 234° C., with decomposition to succinic anhydride. It may be obtained by the reduction of maleic acid. Condensation with glycerin gives a resin tougher and more flexible than is obtained with phthalic anhydride.

In 1937 there were two commercial producers of succinic acid. It is believed that small quantities are used in combination with phthalic anhydride in alkyd resins.

Fumaric acid.

Fumaric acid is a white crystalline powder obtained by the prolonged heating of or by the action of mineral acids on maleic acid. Fumaric acid and maleic acid are structurally identical and the former decomposes at about 280° C., forming the latter. In 1937 there was one domestic maker of fumaric acid.

GLYCERIN

Description and uses.

Glycerin (glycerol) is a clear, colorless or almost colorless, odorless, syrupy, hygroscopic liquid. It is obtained as a byproduct of the soap and fatty acid (oleic acid or red oil and stearic acid) industries. Other sources are insignificant; glycerin can be produced by the fermentation of carbohydrates such as molasses, but when glycerin prices are low this process is not profitable. The chief commercial grades of crude glycerin are “soap lye” glycerin, a byproduct of the soap industry, containing about 80 percent glycerin, and “saponification” grade, a byproduct of the fatty acid industry, containing about 88 percent glycerin. Chemically pure grades contain about 95 percent and dynamite grades about 98.5 percent glycerin. Other grades include “30° yellow distilled” containing about 96 percent glycerin.

The uses of glycerin are extremely varied, the most important being in the manufacture of alkyd resins and ester gums; in the manufacture of nitroglycerin and dynamite; as a moistening, antiseptic, and sweetening agent in tobacco; in pharmaceutical and medicinal preparations; and in certain soft drinks, soaps, and inks.

United States production.

The output of both the crude and the refined has increased in recent years, reaching new highs in 1937. Chemically pure glycerin constitutes about 60 percent of the total refined output and dynamite and other grades about 40 percent. In the production statistics shown in table 48, grades such as yellow distilled are included with the dynamite grade. Since large soap makers refine their own crude glycerin, the sale of crude is only a small part of the total output.

Table 48 shows domestic production of glycerin by grades and table 49 production for sale.

Table 48.—Glycerin: United States production by grades, in specified years, 1919-37

[In thousands of pounds]

Census year Crude 80 percent basis Refined

Chemically pure grade Dynamite 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

Year Crude¹ Refined

Quantity Value Value per pound Quantity Value Value per pound

1,000 pounds Cents 1,000 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

1931² 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 1935 1936 1937⁴

Imports Exports Imports Exports Imports Exports Imports Exports Imports Exports Imports Exports

Crude:

UNITED STATES¹ 8,782 (²) 4,988 (³) 13,722 (³) 4,092 (²) 8,686 (²) 10,171 (²)

United Kingdom 1,702 2,662 4,778 2,951 472 2,825 1,119 2,365 2,322 3,070 (²) (³)

Germany 4,120 2,313 5,232 2,939 4,746 1,599 4,091 326 8,247 122 13,567 578

France 1,269 7,962 426 3,488 (²) 862 (²) 1,176 (²) 164 (²)

Netherlands 5,133 859 3,027 2,300 2,605 3,796 5,441 4,912 7,185 5,644 9,127 6,865

Refined:

UNITED STATES 1,966 328 2,776 (³) 2,214 (³) 69 3,354 3,448 1,146 7,535 1,375

United Kingdom 2,519 9,926 822 19,834 230 19,134 2 15,032 12,991 (³) 16,029

Germany 102 10,092 57 3,562 224 3,818 108 1,571 30 1,155 71 100

France 178 3,989 109 1,246 51 12,249 4 12,118 10 9,269 9 17,750

Netherlands 618 8,337 1,144 6,620 1,008 5,955 694 5,516 739 8,885 500 10,961

Belgium 534 758 1,193 429 1,206 2,360 998 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 imports¹ for consumption 1919-20 and 1923-37

Calendar year Rate of duty Quantity, 1,000 pounds Value Unit value Computed ad valorem rate, percent

Crude

1919 1 cent per pound 3,564 $417,774 $0.117 8.5

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 Various² 8,686 936,312 .108 7.7

1937³ do 10,171 1,716,351 .169 4.8

Refined

1919 2 cents per pound 39 4,471 .114 17.5

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 Various² 3,447 594,036 .172 8.5

1937³ 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

Calendar year Rate of duty Quantity Value Unit value Computed 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 Various¹ 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

1937² 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

1937¹ 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

Pounds Cents per 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

1937² 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 Production¹ Imports² Exports³ Apparent consumption⁴

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

1937⁶ (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.