INDUSTRIAL A N D ENGINEERING CHEMISTRY
August, 1927
of a nitrogen institute in the United States. One of the functions of such an institute would undoubtedly have t o do with propaganda. Just what forms this propaganda should take in America is a question outside the scope of
917
this paper. The fact remains, however, that the per capita consumption of nitrogen in this country is low. Education of the prospective user of nitrogen cannot fail to have a beneficial influence upon the demand for this substance.
Trade in Synthetic Resins and Their R a w Materials’ By Otto Wilson MUNSEYBUILDING,WASHINGTON, D. C.
I
N STUDYING the remarkable expansion in the use of synthetic resins, an expansion which has doubled their output in four years, we are impressed once more with the interdependence of modern industries. The radio, springing up overnight, found ready a t hand these most useful of plastics and profited greatly by them, and they have played an appreciable part in the 100 per cent increase in automobile output since the war and in the steady growth of the electrical industry. Demands from these and a great variety of other industries have in turn raised the manufacture of resins to a position of commercial prominence from which they look forward to a far greater growth in the years ahead. Because of the centralized manufacture of the resins in this country the Government for the most part has been unable to publish figures showing the annual production. Sales and production figures are available only for the years 1920, 1921, and 1922. Since 1922 they have been incorporated with the returns for synthetic tanning materials. The total for these two classes of manufactures combined shows a rapid rise, registering a gain in the three years preceding 1926 of nearly 60 per cent. Most of this gain may be attributed to the resins. Table I - P r o d u c t i o n a n d Sales of S y n t h e t i c P h e n o l i c R e s i n s a n d S y n t h e t i c T a n n i n g Materials MANUFACTURERS PRODUCTION SALES Pounds Value Pounds Value 1918: Resins 4,233,400 $2,642,100 a 0 Tanning materials 1919: Resins Tanning materials 1920: Resins Tanning materials 1921: Resins Tanning materials 1922: Resins Tanning materials 1923: Resins Tanning materials 1924: Resins Tanning materials 1925: Resins Tanning materials 1926: Resins Tanning materials a h-ot stated. b Preliminary.
‘;I
3,794,500
2,381,400
a
a
4 4
4,659,700 3,410,200 3,142,900 233,700
a a
a a
3 4
1,643,800 1,902,600
5
5,944,100 1,910,500
a
4
a
6,415,900 1,981,600
4,315,200 103,600
$1
9,763,700
a
10,068,400
5,816,600
12,778,100
a
12,745,500
8,818,000
14,687,100
a
13,896,600
8,698,800
14,107,000b
a
14,325,000b
7,647,0006
:}
1 ,” 1
1,674,500 81,352,200 1,721,400 141,000
Recently announced preliminary returns for 1926 show a slight falling off in total production of these commodities as compared with the previous year, and a decrease in total value of sales but a gain in quantity of sales. But that, of course, does not necessarily imply a decrease in resin production. The figures in Table I, gathered and published by the United States Tariff Commission, show the output and sales 1
Received April 8, 1927.
of these resins and of synthetic tanning materials for t h e last nine years. Of the various forms in which these resins are marketed, the molding powders and laminated blocks, tubes, etc., make up by far the larger part of the totals given in Table I. No figures hare been made available to the public which would indicate the proportions of the total represented by these classes or by the resins in the forms of varnishes, cements, or the hard transparent article, except that the one large manufacturing company gave as its total output of the last-named product in 1925 about 178,000 pounds, only a small fraction of the whole manufacture of resins. Foreign Competition
Born in America, the synthetic resin industry was early established on both sides of the Atlantic. But its development here has been a response to domestic demands, and except in the importation of raw materials it has figured little in foreign trade. Synthetic resins are not listed separately among the country’s exports, but sales to foreign countries are of no great consequence. The only recent year for which statistics of the trade were published was 1922, when 128,000 pounds valued a t $13,000 were exported, nearly all to Canada. The principal channel through which they find their way abroad is in the form of the great variety of manufactures into which they enter, and these are not distinguished statistically from similar articles made from other materials. I n the import trade the resins of foreign manufacturers are effectually held back a t the border by the high duties, particularly by the provision in the 1922 Tariff Act for American valuation as a basis for computing ad valorem duties. The present rate is 7 cents per pound and 45 per cent. Even at this rate there is a certain small trade (Table 11). Table 11-Imports of S y n t h e t i c Resinsa YEAR POUNDS VALUE 1919 1114 $ 2860 1920 2681 2479 1921 1420 2366 1922 2518 3498 1923 3183 10512 1924 8756 4183 1925 1537 889 1926 1298 1649 a Figures since 1922 are for “resin-like products’’ prepared from coal-tar derivatives.
The tariff, however, does not cover articles made from the hard, amber-like form of these resins, and in these lines competition from abroad has been keenly felt. After the war the manufacture of beads and smokers’ articles, such as cigar and cigaret holders, from synthetic resin for awhile achieved encouraging results. But presently similar imported goods began to displace them, and salesmen for the American articles were met everywhere by the statement that the foreign goods could be had at far lower prices than they could quote. American manufacturers in these lines were practically driven from the market. On the ground of unfair competition a number of firms
9 18
INDUSTRIAL A N D ENGINEERING CHEMISTRY
requested the President to bar these goods from entry into the United States, asserting that they were identical in composition with those made from materials and processes covered by United States patents, and in many cases were represented to be of a material covered by a United States trademark. On the recommendation of the U. S. Tariff Commission a temporary order was issued prohibiting the entry of these goods, and in May and June, 1926, extended hearings were held to determine whether this order should continue in force. I n December an order was issued permitting .the entry of these articles after December 6, the date when the first two synthetic resin patents, taken out seventeen years before, expired, but making an exception of multicolored articles, on which further hearings were held early in 1927. The final decision of the commission, dated May 25, 1927, upheld the claims of the complainants. It recommended that synthetic phenolic resins and articles made wholly or in part from them, as covered by two specified basic patents, should be excluded from entry into the United States, as well as articles made from any kind of synthetic phenolic resins unless they were marked so as to distinguish them clearly from articles made of such resins produced by the Bakelite Corporation. The decision was not unanimous, two of the five commissioners dissenting wholly or partly on the grounds that the patents concerned were in dispute and that the commission's right to assume their validity, under the circumstances, was doubtful. A s disclosed in the hearings, European costs of producing these goods are one-half to two-thirds lower than the American cost. The reasons for this large difference have not been officially ascertained, but very apparently they lie chiefly in lower manufacturing costs, which make up the larger part of the total production cost. Processes in Europe involve greater use of hand labor than those in this country, and in the chief competing countries, including Czechoslovakia, Austria, and Germany, labor costs are much less than here. RAW MATERIALS
The sources of supply of the chief raw materials used in resin manufacture-formaldehyde, phenol, and cresylic acid-are adequate to meet the demand, and the principal concern with regard to them has related to prices. Formaldehyde and phenol are produced increasingly as the result of synthetic processes, and there is no shortage of the material which yields cresylic acid. Formaldehyde
Domestic production of formaldehyde has been adequate, and there has been no necessity for calling on foreign sources. The mounting demand for the synthetic resins has pushed formaldehyde production up sharply in the last two or three years. The total annual output is now three or four times the pre-war average. I n 1925 the gain in output over the previous year was 20 per cent, and the preliminary figures for 1926 show that the increase still continued in that year. Table I11 shows how rapidly the manufacture has been advancing. a n d Sales of F o r m a l d e h y d e in t h e U n i t e d States PRODUCTION SALES YEAR Pounds Pounds Value b $ 655,000 8,426,200 1914" 3,938,300 19,663,800 25,006,800 19190 651,700 6,056,500 9,657,400 1921" 1,676,400 16,140,000 23,958,000 1922 2,474,500 18,854,500 24,081,200 1923 1,971,100 20,542,400 26,155,200 1924 1,895,900 23,391,600 31,455,700 1925 2,050,9008 22,552,200C 31,953,200~ 1928 Census Bureau figures; all others from U.S. Tariff Commission. b Not available. c Preliminary,
T a b l e 111-Production
Vol. 19, No. 8
Although formaldehyde has many other uses, the synthetic resins now constitute probably its most important outlet and the growth in output is to be attributed in large degree to the demands from that source and from the manufacture of indigo. A new factor which is likely to affect permanently the course of formaldehyde prices appeared in 1925. This was the entry into the markets of synthetic methanol from Germany. While fluctuations in prices of methanol and formaldehyde do not closely parallel each other, there is naturally a relationship between the two. With methanol selling a t $2.00 to $2.50 per gallon immediately after the war, formaldehyde sales showed an average valuation of about 20 cents. Methanol in the last two or three years has been much reduced in price and formaldehyde sales have had an average value of 8 to 10 cents. Synthetic methanol manufacture has been begun in this country, and its influence and that of the imported article will undoubtedly be in evidence in the future course of formaldehyde prices. Phenol
I n the production of phenol in this country the synthetic article now very much holds the center of the stage. It is estimated that in 1925 more than three-fourths of the total manufacture was produced by the synthetic process. This development has been due very largely to the advance of the synthetic resins. Their rise rapidly used up the large surplus left over from the war, and when it had vanished manufacturers were faced with a possible shortage, since the output from the distillation plants was insufficient for their growing needs. The Tariff Act of 1922 put a heavy increase of duty on phenol, and the next year the manufacture of the synthetic article, which in 1918 had turned out more than 100 million pounds but had been suspended since the war, was resumed. So rapid was the increase in output that a total of more than 10 million pounds was recorded for 1924 and of nearly 15million pounds for 1925. But this apparently was an overproduction, and the preliminary returns for 1926, recently announced, show a decided falling off. The course of production and sales since the war as compared with our two war years is shown in Table IV. Table IV-Production a n d S a l e s of P h e n o l in the U n i t e d S t a t e s o YEAR PRODUCTION SALES Pounds Value Pouiids Value Unit value b $0.37 1917 64,146,500 $23,715,800 b b 0.35 1918 106,794,300 37,270,300 b b 0.10 1919 1,543,700 155,600 b ... ... ... 1920 0.14 292,600 yj 4i,boo ... 1921 b 268,300 0.21 1,266,600 1,286,000 1922 0.27 b 589,800 2,180,200 3,310,900 1923 0.30 b 2,505,500 8,273,600 10,521,900 1924 0 .21 b 1,771,300 8,524,200 14,734,100 1925 b 987,000~ 0.18 5,480,0000 8,691,000~ 1926 U. S Tarlff Commission, "Census of Dyes and Other Synthetic Chemicals." b Not stated e Preliminary.
A development that is being watched with much interest is the prospective manufacture of phenol by a new synthetic process. It is more direct than the one now in use and promises to reduce the cost of production. The process has been patented, but has not yet been made the basis of commercial manufacture. The resumption of phenol manufacture in this country and the charging of a high rate of duty have kept imports comparatively low. Formerly most of our supplies came from abroad. Until 1916 phenol was admitted free and in pre-war days 80 or 90 per cent of our requirements came from abroad, mostly from England and Germany. The existing rate of 40 per cent and 7 cents has more than reversed this proportion, although there is still a trade of some importance (Table V).
INDUSTRIAL AND ElYGI.VEERI.VG CHE*MISTRY
August, 1927 Table V-Imports YEAR 1917 191s 1919 1920 1921 1922 1923 1924 1925 1926
of Phenol into the United States CRYSTAL Pounds 30,700 148,300
... ...
250 349,500 126,600 176,100 256,100 2 18,400
LIQUID Pounds 3 14,600 134,400 2,100 1,000 147,'ioo 2,800 44 1,600 QS,700
25,900
Since the war phenol imports have come very largely from England. The raw material from which it is obtained in that country is derived from coke ovens, gas houses, and blast furnaces. The coke ovens, operated in connection with coal mine:: or steel mills, have been undergoing the same change as in this country, and a recent official statement gave the proportion of by-product ovens in 1924, as disclosed by a census survey, as about 75 per cent of the total. I n the gas houses the coal gas process largely prevails, in contrast to the practice in this country where water gas has for the most part taken the place of coal gas. Tar from coal gas is much richer in the tar acids than that from water gas, and England can produce much more of them than she needs. The 1924 census showed an output of coke-oven and blastfurnace tar of some 500,000 tons, from which more than 3 million pounds of carbolic acid were obtained. KO figures are to be had which would show what proportion of the total output in England is represented by these amounts. British raw-material costs in making phenol are somewhat lower than in this country, and labor and other costs are very much lower. An investigation made in 1923 showed t h a t the American cost of production, including that of both natural and synthetic phenol, was 142.5 per cent of that of the largest producer of refined phenol in England. Cresylic Acid
Although in synthetic resin manufacture cresylic acid is practically interchangeable with phenol, conditions of production and trade are materially different. It is not made synthetically, the whole supply coming from tar distillation. As commercial production in this country is in the hands of a single large concern, with twenty or twenty-five plants, annual figures of output cannot be given. There has, however, been a marked increase within the last two or three years.
919
Prior to the passage of the Tariff Act of 1922 all cresylic acid entered free. The normal importation was heavy, averaging some 8 or 9 million pounds a year. In 1920 the trade reached its peak with a total of 10,600,000 pounds, including cresol and distillates of tar containing a considerable proportion of cresol, the whole being valued a t $957,000. The use of war-time phenol greatly reduced the import trade. The 1922 Tariff Act put a heavy duty on refined cresylic acid but pemitted the crude still to come in free. The line was drawn by assuming that crude cresylic acid would fall in that class of tar products distilling less than 5 per cent tar acids below 190"C. Foreign manufacturers apparently have been able to control their processes so that grades of cresylic acid can be produced which will fall in that class but which can be easily refined to higher grades. Although domestic production has considerably increased since 1922, imports have continued to come in to the extent of some 2 million pounds a year, nearly all free of duty. Within the last year cresylic acid imports have shown a big gain, the 1926 trade being nearly three times that of the year before. Imports of cresylic acid were not separately classified under that name before 1924. For the last three years crude cresylic acid imports and those of distillates yielding less than 5 per cent tar acids under 190' C., all of which are admitted free, have been as shown in Table VI. Table VI-Imports YEAR 1924 1925 1926
of Crude Cresylic Acid, Etc. TARDISTILLATES YIELDING LESS THAN 5 PER CENTT A R CRESYLIC ACID ACIDSUNDER 190' C. Pounds Value Pounds Value 2,327,500 $157,600 2,440,400 $151,900 2,163,600 122,700 5,994,800 367,700 5,802,900 331,600 3,136,800 197,000
Refined cresylic acids subject to duty are classified as tar distillates yielding 75 per cent or more of tar acids below 215' C. Imports for the three years have been as follows: YEAR 1924 1925 1926
POUNDS 378,400 135,800 7,200
VALUE $38,800 29,000 4,200
Cresylic acid can be produced in England a t much lower cost than in this country. A recent inquiry revealed a n average cost about one-half that of American manufacture.
Estimation of Organic Matter in Sewage and Effluent' Modification of Adeney's Acid Dichromate Method By W. E. Abbott LABORATORY OF CHIEFSANITATION CHEXIST,SHANGHAI MUNICIPAL COUNCIL, CHINA
RGANIC substances can be oxidized rapidly and almost completely to carbon dioxide by a mixture of potassium dichromate and sulfuric acid a t a high temperature. Several methods have been described for estimating the carbon in organic substances by the use of this oxidizing mixture, the carbon dioxide evolved being absorbed and weighed. Small amounts of carbon monoxide are produced, however, and must be oxidized either by passing the mixed gases with air over heated platinized asbestos or by some other means. Several years ago Adeney found that many organic substances were completely oxidized by prolonged digestion
0
1
Received March 28, 1927
with a concentrated mixture of sulfuric acid and potassium dichromate a t the temperature of the water bath. Moreover, a t this temperature there was no appreciable spontaneous loss of oxygen from the dichromate such as occurred a t higher temperatures. It was thus possible to use a measured amount of potassium dichromate and to titrate the excess a t the conclusion of the digestion. The loss represented the oxygen required to oxidize the organic matter to carbon dioxide and water. I n other words, the method promised to be the means of estimating the oxygen which a polluted liquid would consume during the complete conversion of its organic matter to carbon dioxide, water, and ammonia. Unfortunately, this reaction could not be
