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Phosphorus Chemicals W A L T E R J . RILEY, F o o d M d c M m y & Chemical
χ HERE are two major categories of
use of elemental phosphorus. First are the so-called acid type uses, covering all the phosphate salts. Second, there are other direct elemental uses, generally nonacid in nature, such as the produc tion of phosphorus chlorides and sulfide. In making this analysis it was neces sary to eliminate a number of compli cating factors. One of these is wet phosphoric acid made from rock and sulfuric acid. While primarily pro duced for triple superphosphate manu facture, wet acid does find its way into chemical phosphates and is included in statistics reported by Facts for In dustry, our primary data source. In addition, TVA's elemental phosphorus goes into triple super and other fertilizers. The general procedure employed was to tabulate the data on individual prod ucts available from Facts for Industry, to estimate productions where data were lacking, to convert the pounds of anhydrous material to phosphorus by means of theoretical conversion factors, to plot and rationalize these data either by major individual compounds or by groups of compounds of lesser signifi cance, and finally to estimate die percentage coming from elemental phosphorus.
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tween 1955 and 1960, maintaining the per capita consumption at t h e histori cal level of between 25 and 2 6 pounds. It w a s estimated that by 1960 total synthetic detergents would represent 72% of this market, or a total of 3.32 billion pounds. In turn, it was esti mated that unbuilt light duty liquid synthetics would b e 1 1 % of the total synthetic market and that solid for syn thetics would be 8 9 % of the total synthetics by 1960. A n e w class of synthetics, buut heavy duty liquids, now being introduced in the market, will ultimately affect this conventional pattern. This is discussed in more detail subsequendy. It will be noted in Figure 1 that t h e curves for total synthetics and solid synthetics are di verging slightly because of the rela tively rapid growth of liquid light duty
An appraisal of the major categories of present a n d future uses of elemental phos phorus portends ex panded markets for this commodity . · . as r e ported before Chemical Market Research As sociation synthetics. Because of this it is pref erable to project the uses for sodium tripoly and tetrasodium pyrophosphate on the basis of the projected solid synthetic curve. In making projections (Figure 2 ) , it was assumed that the ratio of phos phorus equivalents of these two mate rials to solid synthetics would stay essentially constant, as they have been during the last five years. It was esti mated that 82% of the phosphorus used for the production of these quantities of these materials comes from elemental phosphorus. Thus, it is estimated that the total elemental phosphorus require ment for these two compounds will
Table I.
Miscellaneous Sodium Phosphates. P 4 1951 1952 Monosodium phosphate 3.3 3.5 10.2 Disodium phosphate 13.9 19.2 25.8 Trisodium phosphate 30.2 31.8 Sodium hexametaphosphate 6.4 6.0 Sodium acid pyrophosphate Total P 4 Equivalent 81.4 68.9 ( 8 0 % from elemental phosphorus)
Equivalents—Founds X 10 e 1953 1954 1955 1960 4.6 3.6 3.7 12.7 11.2 11.6 19.6 19.1 18.3 35.1 31.8 32.1 8.5 7.9 7.0 72.7 73.6 80.5 95
Chief Uses The largest single use of elemental phosphorus today is for the production of sodium tripolyphosphate (39.2%) and tetrasodium pyrophosphate (6.6% ) which, in turn, are used primarily as builders for solid heavy duty deter gents. ^ nsequently, to project the use of these two important compounds it is necessary t o consider such factors as population growth, the probable long-term consumption of soap and detergents, the relative breakdown of the use of each of these, and the break down belween solid and liquid light duty synthetic detergents (Figure 1 ) . Total soap and detergents were as sumed to increase at the same rate that population is expected to increase b e 5312
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O C T . 29. 1 9 5 6
Calcium Phosphates P 4 Equivalents—Pounds X 10 6 1960 1951 1952 1953 1954 1955 Dicalcium phosphate 76.8 23.8 47.3 55.5 31.9 (37.8) ( from elemental Ρ ) 25.0 e 24.6 e 25.0° 22.2 20.0 Monocalcium phosphate 2.2 e 2.2 α 2.0 tt 2.0° 2.0° Tricalcium phosphate 56.1 104.0 82.7 45.8 Total Ρ Equivalent 65.0 100.0 from elemental Ρ β Estimated Table II.
Table III.
Phosphorus Chlorides Phosphorus Equivalents—Pounds X 1 0 e I960 1951 1952 1953 1954 1955
Phosphorus trichloride Phosphorus oxychloride Total P 4 Equivalent
2.7 2.3 5.0
2.1
2£
4.4
3.1 2.8 5.9
4.1 5.4 9.5
7.0 6.3 13.3
*26
have increased from a level of 269 million pounds to 329 million pounds by I960. Miscellaneous sodium phosphates were treated much in the same fashion and the elemental phosphorus require ment for this group was estimated to increase from 64 to 76 million pounds by 1960 (Table I ) .
Colcium Phosphates The calcium phosphates presented a particularly difficult problem. Produc tion statistics for dicalcium phosphate, the major compound in this category, include sources from by-product pro duction from gelatin, elemental phos phorus production, and wet acid pro duction. The major consumption of dicalcium phosphate is in animal feeds, with considerably smaller quantities go ing into such pharmaceutical applica tions as dental abrasives. There is considerable discrepancy between the total production reported by Facts for Industry and the estimated consump tion in the animal feed industry, the latter being much lower than Facts for Industry would indicate. Consultation with several members of the chemical industry and the animal feeds industry failed t o resolve this discrepancy, and no other major uses for dicalcium phos phate were uncovered. In addition, one major producer of dicalcium phos phate from wet acid has withdrawn from production this year. As a con sequence it was necessary to use a very arbitrary approach in resolving all these factors. In making the projections on total production of all calcium phosphates (Table I I ) , it was assumed that monocalcium and tricalcium phosphate would grow at a rate equivalent to our population growth. For dicalcium phosphate it was estimated that the current production from elemental phosphorus was equivalent to 39 mil lion pounds of phosphorus, of which roughly 33 million pounds was for animal feeds. A synthetic curve based on the growth of the feed industry and gradual attainment of the goals recom mended by the USDA for phosphorus supplementation was constructed, lead ing to an estimate of 100 million pounds of phosphorus for all calcium phos phates b y 1960, an increase of 35 mil lion pounds over 1955. Other miscellaneous phosphates, in cluding principally ammonium and po tassium phosphates, were estimated to increase in proportion to population
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Figure 2 . OCT. 29,
1956
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The second major use categoryDirect Elemental Phosphorus U s e s includes TVA*s production of calcium metaphosphate from phosphate rock and elemental phosphorus. It was as sumed that this production level would remain static at about 27 million pounds. The largest use of elemental phos phorus in this category is for the pro duction of phosphorus chloride, oxychloride, sulfide, and oxide. Produc tion statistics are only available on the two chlorides (Table III). Recent growth has been extremely rapid, a little more than doubling between 1953 and 1955. In projecting the growth through 1960 it was assumed that the interim growth would b e equal to the present level. The current level of 17 million pounds of phosphorus for oxide and sulfide was estimated to increase about 35% to a level of 23 million pounds of phosphorus b y 1960, giving a total 1960 projection of 49 million pounds of phosphorus for this category. The remaining categories, including phosphorus sales, alloys, and miscel-
from a current level of 2.4 to 2.6 mil lion pounds of phosphorus. TVA's elemental phosphorus going into triple superphosphate was esti mated to remain static at about 31 million pounds of phosphorus. Sales of phosphoric acid for nonfertilizer use, while primarily a differ ence figure, are rational in terms of our knowledge of the industry and interpretations of interplant transfers and sales.
ducers show considerable interest in converting to the production of diam monium phosphate. It w a s assumed that the principal interest in this con version would lie in the states of Illi nois and Indiana and the area west of the Mississippi. Thirty-five per cent of the total capacity was assumed in projecting the 1960 requirement of elemental phosphorus to a level of 31.5 million pounds, roughly a. tenfold increase.
N e w Use in Fertilizers Data on consumption for fertilizers are available from the Fertilizer Year Book. These fertilizer uses break down into three applications, all of which are relatively new acid uses by the fertilizer industry. These include direct application in irrigation water or to the soil, either as acid or in the form of liquid mixed goods, and as solid diammonium phosphate. In projecting these uses the area primarily west of the Mississippi was considered as the economic one for growth potential. Direct application of acid to the soil or in irrigation waters was only projected at a modest rate equivalent to population growth from 7.0 to 7.6 million pounds by 1960. Liquid mixed goods, however, were projected on a basis of this total area's projected consumption of available mixed P 2 O s , reaching the same percent age of liquid mixed goods to total mixed goods available P 2 0 3 as is cur rently used in California and Texas (6.97c). While this may sound like a conservative estimate, it represents a sixfold increase from 4.3 to 27.5 million pounds in the use of elemental phos phorus for this type of application and one which can probably be attained by sound marketing techniques. By-product ammonium sulfate pro
G Elemental Phosphorus Consumpt Ion—Pounds X 10 1960 1955 771.0 586 Total 657.0 493 Acid type uses 114.2 Direct elemental uses 93 657.0 493 Acid type uses Sodium tripoly277.0 230.0 phosphate Tetrasodium pyro 52.0 38.7 phosphate 76.0 Miscellaneous sodium 64.4 phosphates* 100.0 Calcium phosphates 6 65.0 2.6 Other phosphates 0 2.4 TVA ( triple super ) 30.8 30.8 118.6 Acid sales 62.0 52.0 47.7 Non fertilizer 66.6 14.3 Fertilizer 7.6 Direct application 7.0 27.5 Mixed goods 4.3 Diammonium 3.0 31.5 phosphate 114.2 93 Direct elemental uses 27.2 TVA (calcium meta phosphate ) 49.0 30.3 Ρ Chlorides, sulfide, oxide Ρ Sales 2.0 2.0 Ρ Alloys 12.0 13.0 Miscellaneous 21.5 23.0 β Includes: Mono-, di-, and trisodium phosphates; sodium acid pyrophosphate and sodium hexametaphosphate. 5 Includes: Mono-, di-, and tricalcium phosphates. c Includes: Potassium and ammonium phosphates.
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Table IV.
MARKETS laneous, were all projected at a rate equivalent to population growth, giving a total i 9 6 0 requirement o f elemental phosphorus of about 1 1 4 million pounds for direct elemental ixses. Total elemental phosphorus con sumption is predicted to iracrease from a 1955 level of 586 milliosa pounds to 771 million pounds, a n increase of 185 million pounds or, roughly, -32% (Table IV). The major growth is in acid-type uses, increasing from 4 9 3 million to 657 million pounds b y 19630, a growth of 164 million pounds or approximately 3 3 % . Direct elemental mises are ex pected to increase from a level of 93 to 114 million pounds, an increase of 21 million pounds or almost 2ί3%. Publicly and privately armnounced ex pansions will more than irake care of the 1960 requirement o f elemental phosphorus (Figure 3 ) .
New Developments A final word about some major new developments which, while they may not modify the total projected picture appreciably, can have a major impact on some of the materials now produced. The first of these is t h e development of liquid heavy duty detergents. The products now being marketed are re ported to use complex potassium phos phates as builders becauase of their high solubility and low tendency to revert to o-phosphate. It is still too soon t o predict the ex tent to which these new heavy duty liquids will find market acceptance. On the basis of our analyses of the level of potassium phosphate in these products and manufacturers' recom mendations for use, a 1% replacement of the synthetic detergent market would require 3.1 million pounds of phosphorus for the production of these potassium phosphates. A^ correspond ing net loss of about 1 million pounds of phosphorus would restait from dis placement of sodium tripolyphosphate by these complex potassimja phosphates. Another development is the substitu tion of phosphoric a c i d for dicalcium phosphate in animal feeds. In essence the manufacture of dicalcium phos phate is being transferred from present producers to the f e e d manufacturer's mixer. This development is sound on nutritional, economical, and practical bases. While this -will n*ot affect the total phosphorus requirement in this use it will unquestionably reduce the consumption of dicalcium phosphate.
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