INDUSTRIAL A N D ENGINEERING CHEMISTRY
April, 1926
401
Fertilizer Trade Developments* By O t t o Wilson MUNSRYBUILDING, WASEINGTON,D. C.
OLLOWING the vast derangements caused by the war, international trade in general has shown a strong tendency t o work back into the well-worn pre-war channels. Old connections between customer and seller are gradually reestablished, old advantages in underlying economic conditions again assert themselves. I n the production and trade in chemical fertilizers, as in other fields, this tendency has been noticeable, particularly with the return of Germany to something like her pre-war energy. But important changes in international trade currents have also developed in the last eight years, brought about not alone by the effects of the war but also by internal changes in the chemical industries themselves. For the United States the readjustment has meant a swing back to the point where the ratio between imports and exports of chemical fertilizers and materials now stands about as it did before the war. Prior to 1914 the average yearly value of our foreign purchases of these materials was about $40,700,000, and that of our sales abroad was $10,700,000, the latter being about 26 per cent of the former. In 1925 our imports totaled $78,000,000 and our exports $17,300,000, or 22 per cent. Imports have thus almost doubled, and exports have increased 70 per cent, in value. This gain, however, has been in large part simply a price increase. For example, the total 1925 tonnage of exports, 1,147,000 tons, was some 12 per cent less than the average of the five years preceding the war. Outstanding features of our post-war production and trade in this field have been the swift fading of the war-born potash industry; the growth of Chilean nitrate imports after a great falling-off following the war; the halting recovery of our export trade in phosphate rock, which is yet far below pre-war figures; the rapid rise of an export trade in sulfate of ammonia; the recent expansion of imports of synthetic nitrogen salts from Germany; and the gradual growth of our synthetic nitrogen industry.
F
Nitrogenous Fertilizers
I n the world trade in nitrogenous fertilizers the most conspicuous development in the post-war period has been the striking advance of the synthetic nitrogen industry in Germany. I n that and other countries the necessities of war forced a concentration of attention on the production of nitrogen salts, both from the air and as industrial by-products, and much experimentation with new processes. With the coming of peace several countries outside of Germany discontinued air-fixation operations because of the expense. But in Germany the impetus given to the industry had brought it to the point where its products could compete on more than even terms with Chilean nitrates, and the synthetic products have now forged ahead of the natural deposits of the South American desert. I n the year 1925, according to the annual report of Aikman (London), Ltd., the nitrogen content of the total world production of synthetic nitrogen products was about 480,000 long tons, about 17 per cent more than the 1924 output. That of the Chilean nitrates marketed was 377,000 tons, a gain of 6l/4 per cent over 1924. The strong demand in 1925 thus absorbed the offerings of both the synthetic and the natural products without lowering prices, and postponed for 1
Received March 2, 1926.
a while the inevitable struggle to see which shall be displaced when the market does not have room for both. When the struggle becomes acute it is fairly evident which will have to give way. Germany, which bought three-quarters of a million tons of Chilean nitrates annually before the war, now supplies her domestic needs with her own synthetic nitrogen and is reaching out into the markets of the other large nitrogen users. In order to meet this competition Chileans will be forced to reduce costs, by cutting the present export duty of 3.38 pesos gold per metric quintal ($12.17 per metric ton) and by introducing more economical production methods, and it is uncertain whether with even these reductions they can hold their own in sharp competition. Actual figures of comparative production costs of synthetic and natural nitrogen salts are obviously difficult to obtain. The costs of synthetic production vary widely among the different processes and in different countries. A year ago a United States Government expert reported that the Nitrogen Syndicate of Germany had gone on record as stating that the products of the Haber-Bosch process in that country were selling 30 per cent below Chilean nitrates. Another American authority, referring to production in this country, says: Although actual costs of fixation are not available for any of the fixation processes, there is every reason t o believe t h a t nitrogen products from the synthetic ammonia process can be sold in successful competition with Chilean nitrate and byproduct coke-oven sulfate at the present time. It seems very probable also that reductions in the price of these two nitrogen products occasioned by the competition of air-nitrogen products can be successfully met through improvements in the synthetic process.*
About two-thirds of Germany’s output of fixed nitrogen comes from two big plants producing ammonia by the HaberBosch process, about one-fourth is ammonium sulfate from coke and gas plants, and most of the remainder comes from smaller plants producing calcium cyanamide by the FrankCar0 process. The air-nitrogen fixation industry has been very largely the result of a war and post-war development. I n 1913 the one Haber plant in operation produced only about 7000 tons of fixed nitrogen, and the two cyanamide plants 5000 to 7000 tons of nitrogen. Ammonium sulfate from coke and gas plants furnished 110,000 tons, or about 93 per cent of the total domestic output. The rest of Germany’s needs were supplied by heavy imports from Chile, amounting in 1913 to 747,000 net tons of nitrate, and by calcium nitrate from Norway, 48,000 tons, the nitrogen content of these being calculated, respectively, a t 119,490 tons and 8184 tons.3 I n 1925 Germany purchased 24,428 tons of Chilean nitrate, but her reexports to her neighbors in Europe, chiefly Russia, and to other countries, were 15,428 tons. She still retains a few thousand tons for special uses, but her role in this trade is now chiefly that of middleman. I n the Chilean statistics for 1924, for example, Germany is credited with purchases of 94,441 tons, whereas her own statistics show imports of only 11,574 tons. The difference apparently represents the amounts passed on to other countries.
* Braham, U. S. Dept.
Commerce, Trade Information BUZZ. 240 (1924). ‘From a manuscript review of the nitrogen fixation industries of Germany by U. S. Trade Commissioner William T. Daugherty, which is on file and available for inspection in the Department of Commerce a t Washington.
INDUSTRIAL A-VD ENGINEERING CHEMISTRY
402 Table I-Trade
in Fertilizers in Last Two Years Compared with War a n d me-War Trade Average 191C-14° Value
Tons Nitrogenous : Calcium cyanamide Sodium nitrate Sulfate of ammonia Potash: Chloride crude (muriate) Sulfate, &rude Kainite Manure salts Other potash
Average 191Fr19° Tons Value Imgorts
b
Sulfate of ammonia Phosphate rock: High-grade hard rock Land pebble Other Superphosphates (acid phosphates) a Fiscal years. b Not separately stated. c Four-year average.
546,000 69,000
$17,61:,000 4,208,000
1,173pOOO 18,000
$46 21; 000 1:195:000
204,000 44,000
6,805,000 1,769,000
22,000 5,000
940,000 267,000
575,000
3,513,000
37,0000
316,0000
Exports b
6
b
1,231,000
9,130,000
42,000 169,000 12,000
......
......*
.....
During the fertilizer year ending with LIay, 1926, Germany’s production of synthetic nitrogen products is estimated at a probable 400,000 tons of nitrogen. It is uncertain how much of this will have been found available for export at the end of the year. Recently i t has been announced that the German Government is extending credit assistance to the Nitrogen Syndicate (which controls the entire output of the country, including by-product sulfate of ammonia) by which domestic users will be enabled to take more of the product, leaving a smaller margin for export. The exporttrade, however, is being actively pushed. sales of the chief export product of the &ber process, ammonium 1921 sulfate, have grown remarkably in recent years. they were only 11,600 tons, and in 1922, 13,700 tons. I n 1923 they amounted to 119,000 tons but fell back to 1O4,OOO tons in 1924. Last, year, homTever, they more than trebled, jumping to 344,380 tons valued a t $20,325,000. The chief buyers and the amount each one took are in Table 11. Table 11-Exports
of A m m o n i u m Sulfate from Germany in 1925 Metric tons Japan 142,609 Netherlands 88,260 Denmark 38 436 Spain 19:523 United States Czechoslovakia 13,789 16,415 11,435 Cuba
EXPORTED TO:
There is also a considerable export of cyanamide and some other salts. I n Chile’s export trade the large hole left by the withdrawal of Germany has been filled to a considerable extent by much larger shipments to the United States* This appear from the figures in Table 111. Table 111-Exports
of Nitrates from Chile 1913 1924 Metric tons Metric tons
E X P O R T E D TO:
United States United Kingdom Germany France Belgium Netherlands Egypt Other countries TOTAL..
630,790 1,004,979 629,298 121,472 118,690 100,379 12,300 120,431
960,411 854,308 94,441 46,029 15,062 27 211 81:263 254,677
..... 2,738,339
2,333,402
I
Vol. 18, KO.4
The large shipments recorded as coming to the United States in 1924 were considerably bettered in 1925. According to United States import figures the total 1925 trade in nitrates, practically all from Chile, was 1,112,000tons, having a value of $52,531,000, 13 per cent greater in quantity than in 1924. The 1925 imports, however, were still far below the war-time trade, although they were twice as large in amount and three times as large in value as the average before the war (Table IV).
-1924Tons
Value
-1925-
76,000 987,000 6,000
$3,688,000 47,169 000 3421000
98,000 1,112,000 24,000
$4 689 000 52:531:000 1,326,000
129,000 376,000 155,000 226,000 46,000
3,972,000 2,857 000 914:OOO 2,218 000 480:OOO
161,000 69 000 183:OOO 384,000 24,000
5,194,000 2 686 000 1:173:000 3,677,000 321,000
Tons
Value
b
118,000
6,919,000
123,000
6,749,000
386,000 842 000 117:OOO
151,000 686,000 12,000
1,814,000 3,210,000 97,000
... . . . .
159.000 698,000 13,000
2,283,000 3,287,000 107,000
46,000
589,000
67,000
1,077,000
Table IV-Imports of Sodium Nitrate i n t o the United States. Year Tons Value Average 191C-14a 546,000 $1 7,6 15,000 Average: 1915-19O 1,173,000 46,215,000 1920 1,322,000 63 121 000 1921 369,000 17:983:000 1922 542,000 26 153 000 1923 892,000 41:956:000 1924 987,000 47,169,000 1925 1,112,000 52,531,000 Fiscal years*
The steady climb of the nitrate trade with Chile in the last five years is to be accredited largely to favorable agricultural conditions in the chief fertilizer-using sections of this count’ry. During most of this period cotton prices have been very favorand the Of the South have been able to buy liberally Of prized product* They have also been willing to pay very good price% the average import valuation per ton being nearly 50 per cent higher than that before the war. Should cotton prices fall to the low level of five years ago we may expect, as then, a heavy slump in nitrate purchases. so far Chile’s naturalproduct has been able to hold the. field in our fertilizer trade against the synthetic products. With the German industry showing the way, there has been, in the United States and other countries, a growing interest in production of synthetic nitrogen salts. But heretofore the output of the few plants operating has gone to fill other demands than that of fertilizer manufacture because of the much higher prices obtainable. It is reported, however, that prices are now being materially reduced, and that ammonia and the other nitrogen materials will and be diverted to fertilizer The United States now has four synthetic nitrogen plants in operation, with a daily output of about 50 tons of nitrogen. During the present year others are expected to begin producing, raising the total daily capacity to about 100 tons. Our imports of nitrogenous fertilizer materials other than Chilean nitrates, compared with the purchases from South America, are not very large. The chief article is calcium cyanamide from Canada, largely from the Niagara Falls installation. Total imports of cyanamide in 1925 amounted to 98,000 tons having a value of $4,689,000. From Germany we are getting an increasing amount of nitrogen products. For example, our total imports of ammonium sulfate in 1925 were 23,762 tons, valued a t $1,325,743. This was four times the 1924 amount, and the increase came very largely from Germany, which sent US, according to our import statistics, 19,637 tons last year. Another import which is attracting much attention is the so-called “leuna saltpeter,” or ammonium-nitrate-sulfate, from Germany. Our government statistics are now classifying this separately, but heretofore it has been hidden in the classification “All other nitrogenous fertilizers,” which in-
INDUSTRIAL A N D ENGINEERING CHEMISTRY
April, 1926
creased from 47,575 tons in 1924 to ’72,792 tons in 1925. Of last year’s imports 25,000 tons were credited to Germany and are said to be mostly this double ammonia salt. I n our export trade the post-war period has been marked by the surprisingly rapid growth in sales of sulfate of ammonia, m+hichnow goes abroad in larger amounts than phosphate rock and superphosphates (Table Y). Table T’-Exports of A m m o n i u m Sulfate from the United States Year Tons Value $7,433,000 1920 60,000 6 098 000 1921 103,000 147 000 1922 8’737’000 154:OOO 11:118:000 1923 6,919,000 1924 118,000 I925 6,749,000 123,000
This trade is very largely with Japan, the Philippines, and the Dutch East Indies, and appears to have ariaen as a direct result of the shutting off of former sources by the war. Potash
When Germany was bottled up by the blc Ickading fleet she was sending us about 1,000,000 tons of potash a year. Thrown on our own resources we developed a number of latent source:. Satural brines from lakes in Xebraska and other sources yielded (1918) 149,000 tons of crude potash. From the d u d from cement mills 13,000 tons were obtained, from seal\-eed 14,000 tons, from distillery waste 12,000 tons. All told. we produced 207,000 tons of crude potash in 1918, 20 to 2.5 per cent of our requirements. With the coming of peace these war-born industries practically collapsed in the face of the comparatively low-priced imports from Europe. Rut a certain small production has continued, and we are now producing a t the rate of about 180 tons a day. The chief source is Searles Lake, Calif., which is yielding about 120 tons a day of almost pure potaqciuni chloride, having a K20 content of 60 per cent. A Baltimore industrial alcohol plant is the chief source of byproduct potash from manufacturing. The actual presence of potash in immense quantities in the United States is a well-recognized fact. The only difficulty lies in estracting it so that it can be sold in competition with the mineral deposits of Europe. Government experts believe that this will be accomplished only by developing potash as a by-product, leaving the direct cost of mining and handling to be borne by other products of the potash-bearing material^.^ There appears to be a good economic foundation for a large future industry. Table V‘I-Potash r
1914“ Chloride. crude (muriiite)
Sulfate o i potash
Kaini?e l l a n u r e qalts
Other potash
{ { Tons Value Tons
{value Tons f value Tons {value
... ... ... ... ...
.. .. b b
France has thus benefited to the extent of some $3,000,000 worth of trade with the United States alone, through her acquisition of German potash deposits as a result of the mar. T o avoid competition in foreign trade between the two countries, the potash producers of France and Germany effected an agreement in May, 1925, by which the export market was to be divided on the basis of 70 per cent to German production and 30 per cent to French. With centralized control and elimination of competition the directors of the European industry are thus in a position to impose whatever prices on foreign buyers they choose to make. Thus far, however, the agreement of last May has brought no price rise in its \Take. The German potash industry is in a thriving condition, Not only has the export trade assumed large proportions, but the German farmers themselves have been using much larger quantities. As a result the 1925 output of potash was greater than in 1913, in spite of the reduced holdings because of the war. Last year’s total output for Germany was 1,225,455 metric tons, whereas in 1913 it was 1,110,000 tons. I n 1924 it was 542,000 tons. An American consular report, however, forecasts a possible decline for 1926. The larger part of the German production is consumed by German agriculture, the financial position of which is said to be unfavorable. Control of German potash production is thoroughly centralized. The Potash Syndicate holds the entire industry in its hands, and has been pursuing a policy of improving its equipment and closing down the less profitable mines. The Government has helped to make the policy effective by prolonging for three years the regulation forbidding the opening of new potash mines, which expired December 31, 1925. Out of 220 pits already opened only 90 are now being worked, but the syndicate has greatly increased the production of each of these plants, and the concentration has materially lowered production costs-in the case of one of the largest plants, it is said, by as much as 50 per cent. Kern potash deposits have been discovered in Poland, and production is growing in importance. I n the first nine months of 1925 the mines turned out 143,000 metric tons of crude salts, of which 97,000 tons were sylvinite and 45,000 tons kainite. During the same period of 1924 the total output was only 55,000 tons. Phosphates Although our exports of phosphate fertilizers were higher in 1925 than for several previous years, all the important
Imports i n t o the United States fx‘omL France and Germany Y-FROM GERMAN 1924 1925 1914a 1924 48,000 35 000 236,000 72,000 57,885,000 5 1,472,000 $1,062:000 62,185,000 6,000 8,000 44,000 66,000 $ 246,000 $ 323,000 $1,828,000 $2,459,000 81 000 a37 000 69,000 69 000 $ 483:OOO $ 502,000 $2,555:000 $ 387:OOO 84,000 95,000 257 000 129 000 S 798,000 $ 951,000 52,69::000 $1,242:000 31,000 15,000 8,000 b 5 287,000 $ 164,000 $ 104,000
-FROMFRANCE-
Fiscal year.
403
1925 108,000 $3,523,000 59 000 $2,277:000 108 000 $8 6?9:000 259 000 82,369:OOO 3,000 $ 104,000
b Figures not availabie.
At the moment the reports of Texas potash deposits are attracting much attention. Borings have revealed a stratum of potash minerals a few inches thick. Much more exploration is necessary before it can be known whether these deposits are of commercial importance. Potash comes from Europe chiefly in four forms. The amounts and value of imports from France and Germany in the last two years as compared with the pre-war trade are s h o r n in Table VI. 4 Turrentine. Fox, and Whittaker, TEIS JOURNAL, 17, 1177 (1925); Turrentine, Ibid., 16, 1192 (1924).
classes except acid phosphates are still below pre-war figures. I n the twelve months immediately preceding the beginning of the war in Europe our sales of phosphate rock abroad totaled $10,617,000 in value. This was a normal figure, as the average exports for the five (fiscal) years 1910-14 were 1,231,000 tons having a value of $9,130,000. Following the war this figure was again approached in 1920, when exports of this rock went to 1,069,000 tons valued a t $10,570,000. But that was an extraordinary year, and the trade has not come near that level since. I n 1925 the exports of phosphate rock were 870,000 tons
INDUSTRIAL A N D ENGINEERING CHEMISTRY
404
having a total value of $5,677,000. The decrease has occurred both in the shipments of the high-grade hard rock and in those of rock in the form of pebbles. The trend of the trade in the two chief classes of exports in the last six years as compared with the (fiscal) year 1914 is shown in Table VII. Table VII-Exports of Phosphate Rock from t h e United States HIGH-GRADE HARDROCK LANDPBBBLES Tons Value Tons Value Year 1914O 475,000 $4,753,000 1,001,000 $5,858,000 1920 345,000 4,496,000 693,000 5,594,000 1921 183,000 2,593,000 544,000 4,628,000 3,269,000 2 549 000 513,000 1922 202,000 1923 194,000 2:478:000 631,000 3,273,000 3 210 000 1,814,000 656,000 1924 151,000 1925 159.000 2.283.000 698.000 3:287:000 a Fiscal year. ~
As in the years before the war,’Germany is much the largest buyer of the high-grade rock. I n 1914 her purchases were somewhat more than half the total exports, and that proportion has been maintained in the current trade. The only other buyers are also countries of western Europe, Belgium, the Netherlands, Sweden, and Poland. This is in line with pre-war conditions, as all our exports a t that time also went to Europe.
Vol. 18, No. 4
While Europe also takes about five-sixths of our shipments of land pebbles, the beginning of an export trade has been established with Cuba, Canada, Japan, British South Africa, and one or two other countries. Of the European buyers Germany is well in the lead, but the trade is more widely scattered than in the case of the costlier hard rock. Spain is an important customer. I n the export trade in acid phosphates the post-war period has witnessed first a heavy slump and then a gradual recovery. Immediately following the war there was much activity in this field, and our sales to foreign countries mounted rapidly. I n 1919 we sent abroad 87,000 tons of this material and received for it $2,775,000. I n 1920 the total shipments fell to 81,000 tons but better prices brought the total value to $2,950,000. Then there was a swift decline, and in the next year we exported only 4000 tons valued a t $96,000. The succeeding years have seen a steady growth in the trade, which brought exports in 1925 to a total quantity of 67,000 tons and a total value of $1,077,000. Except for scattering amounts to a number of countries these exports go entirely to Canada and Cuba.
Is Commercial Synthetic Rubber Probable?’ By L. E. Weber 729 BOYLSTON ST., BOSTON, MASS.
HE increase in the price of crude rubber has been responsible for arousing once again considerable interest in synthetic rubber. I n a period of declining rubber prices, such as we have witnessed during the last ten years, the question of synthetic rubber receives scant attention. It is remarkable how quickly interest is stimulated by a reversal in the price trend of the raw material. There is probably some difference of opinion as to whether or not it can be claimed from the commercial standpoint that crude rubber has been synthesized successfully. During the war as much as 40 tons per month of a product designated as synthetic rubber were manufactured, but the material was satisfactory only for hard-rubber articles. It was in no sense a substitute for rubber intended for use in soft-cured articles, because the vulcanized product was not only lacking in elasticity but was also very short-lived. These deficiencies were in a measure counteracted by adding to the synthetic product in small amounts materials designated as “elasticators,” but the remedy was only partially successful.
T
Methods of Manufacture
The manufacture of synthetic rubber consists of two distinct operations: (1) the manufacture of the parent hydrocarbon, and (2) the polymerization of the hydrocarbon. The hydrocarbons that have been proposed for the synthesis of rubber are butadiene, isoprene, and methyl isoprene. These substances are all diolefins, the two latter being homologs of butadiene. CHa
CHz
CH
C.CHa
CH I
LH
CHz Butadiene
CHz Isoprene
I/ I1
II II
CHz
II I C.CHa 1 I
C.CHa
CHa Methyl isoprene
1 Presented by title before the joint meeting of the Division of Rubber Chemistry and the Akron Section of the American Chemical Society, Akron, Ohio, February 22 and 23, 1926.
The nomenclature of these hydrocarbons is unfortunately somewhat confusing since butadiene is also known as erythrene and also as divinyl. Accordingly, we find reference to isoprene as either methyl butadiene or methyl divinyl. Similarly, methyl isoprene, in addition to being known as dimethyl butadiene, is also designated frequently as dimethyl erythrene. These alternative names for the same substances have given the impression that many more hydrocarbons have been employed in the synthesis of rubber than is actually the case. The fact is that, with rare exception, the parent hydrocarbon has been either methyl butadiene or dimethyl butadiene-that is to say, isoprene or methyl isoprene-attempts using butadiene having been very infrequent. Other hydrocarbons, in effect, have not received consideration. Accordingly, only the more important methods by which isoprene and methyl isoprene have been produced will be discussed. Isoprene It has been known for many years that isoprene is obtained upon the destructive distillation of crude rubber and also of turpentine. It is natural, then, that turpentine should have been given serious consideration as a raw material for the production of isoprene. The attempts to convert turpentine into isoprene were, however, not crowned with any degree of success, owing to the fact that the yields obtained were always small. Furthermore, as the work with turpentine progressed, it became more and more evident that its use as a starting point in the synthesis of rubber was unsound from the economic aspect, the supply of turpentine being entirely inadequate to meet the demand which would ensue if the synthesis were successful. With the realization of these basic objections to turpentine, attention was given to raw materials which were more abundant and less expensive. The petroleum hydrocarbons, coal tar, and starch met these economic requirements. The petroleum hydrocarbons were not regarded as promising on account of their chemical inactivity and accordingly were
