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.
There are four domestic producers of cresylic acid with recovery and
refining units at Pittsburgh, Pa., Philadelphia, Pa., Indianapolis,
Ind., and Follansbee, W. Va. The last three mentioned are refining
plants operated in conjunction with a number of tar distillation units
widely scattered throughout the country. These units usually recover
crude tar-acid fractions in the distillation of tar and ship them to
these refining plants for separation and refining. All in this group are
purchasers of coal tar. The fourth producer operates a byproduct recovery
unit in connection with the company’s coke-oven operations. Part of the
coal tar produced is distilled to recover the several products, including
creosote oil, tar acids, and naphthalene, and the residual pitch is mixed
with the remaining undistilled tar and used for fuel. The shortage of tar
acids and naphthalene in 1936 caused this producer to begin the topping
of tar.
Foreign production.
The cresols are produced in the United Kingdom, Germany, France, the
Netherlands, Belgium, and other European countries. Coal tar recovered
in the United Kingdom is principally gas tar, which is much richer in
tar acids than coke-oven tar, the principal source in the United States.
This is true because low temperature carbonization of coal yields greater
quantities of tar acids than are obtained in the tar from byproduct coke
ovens. Exports to the United States are chiefly mixtures which can enter
as crude cresylic acid.
Production of cresol in Germany in recent years is shown in table 69.
TABLE 69.—_Cresol: German production, in specified years_
-------+------------
Year |1,000 pounds
-------+------------
1929 | 23,814
1931[1]| 15,435
1933 | 11,780
1934 | 10,476
-------+------------
[1] Includes 2,866,000 pounds of separated ortho, meta, and para
cresols.
Source: Consular reports.
German imports and exports of cresol, in recent years, are shown in table
70.
TABLE 70.—_Cresol: German imports and exports, in specified years_
----+--------+--------
Year|Imports |Exports
----+--------+--------
|_1,000 |_1,000
| pounds_| pounds_
1929| 2,037 | 8,494
1930| 1,277 | 6,712
1931| 1,874 | 7,980
1932| 1,541 | 3,669
1933| 1,832 | 4,970
1934| 1,960 | 6,345
1935| 2,117 | 8,528
1936| 3,737 | 4,531
1937| 1,787 | 4,423
----+--------+--------
Source: Consular reports (1929-33) and official German statistics
(1934-37).
The output of cresols in Czechoslovakia in recent years is shown in table
71.
TABLE 71.—_Cresol: Production in Czechoslovakia, in specified years_
-----+----------
Year | Quantity
-----+----------
| _1,000
| pounds_
1928 | 1,984
1931 | 1,477
1932 | 1,102
1933 | 1,599
1934 | 1,918
-----+----------
Source: Consular reports.
Cresylic acid is recovered in all the countries of Europe, Great Britain
and Germany being the leading producers and the principal exporters.
Increasing demand in these countries for synthetic resins made from
cresylic acid has greatly reduced the quantities available for export in
recent years.
Great Britain is probably the world’s largest producer of cresylic acid,
and for many years has been the principal exporter to the United States.
This position is due to the large available supply of gas-house tar, and
to an ample market for all the products of tar distillation. In 1935
the tar distilled in England, Wales, and Scotland totaled 360 million
gallons, of which 55 percent was gas-house tar.
British production of all grades of cresylic acid averages between 35
million and 42 million pounds annually, of which from 12 million to 20
million pounds are exported. Many British producers market their tar
products through pools and associations. There is a cresylic acid pool, a
phenol pool, and at least two creosote oil export associations, a pitch
marketing association, and a benzol association. One of the principal
grades of cresylic acid produced in Great Britain is “American duty-free
specification.”
Table 72 shows British exports of cresylic acid, by countries, in recent
years.
TABLE 72.—_Cresylic acid: British exports, by countries, 1933-37_
-------------------+------+------+------+------+------
Destination | 1933 | 1934 | 1935 | 1936 | 1937
-------------------+------+------+------+------+------
| Quantity (in thousands of pounds)
+------+------+------+------+------
UNITED STATES | 3,616| 5,783| 6,116|11,296|([1])
Chile | 1,381| 2,958| 2,814| 662|([1])
France | 358| 87| 214| 189|([1])
Japan | 632| 203| 685| 2,002|([1])
All other countries| 5,464| 6,965| 7,333| 9,250|([1])
+------+------+------+------+------
Total |11,451|15,997|17,162|23,399|26,697
+------+------+------+-------------
| Value (in thousands of dollars)
+------+------+------+------+------
UNITED STATES | 147| 277| 255| 620|([1])
Chile | 28| 89| 87| 31|([1])
France | 21| 5| 20| 14|([1])
Japan | 38| 20| 43| 118|([1])
All other countries| 189| 307| 330| 537|([1])
+------+------+------+------+------
Total | 422| 698| 734| 1,321| 2,262
-------------------+------+------+------+------+------
[1] Not available.
Source: Official British statistics.
Imports into the United States.
_Rates of duty._—Prior to September 8, 1916, the cresols were imported
free of duty. Since that date they have been subject to the tariff
treatment shown in table 73.
TABLE 73.—_The cresols: Rates of duty upon United States imports, 1916-37_