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]
-------------+---------------+--------------------------------
| | 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_