Superphosphates

Industrially. phosphoric(V) acid is manufactured by two processes. In one process phosphorus is burned in air and the phos-phorus(V) oxide produced is dissolved in water. It is also manufactured by the action of dilute sulphuric acid on bone-ash or phosphorite, i.e. calcium tetraoxophosphate(V). Ca3(P04)2 the insoluble calcium sulphate is filtered off and the remaining solution concentrated. In this reaction, the calcium phosphate may be treated to convert it to the more soluble dihydrogenphosphatc. CafHjPOjj. When mixed with the calcium sulphate this is used as a fertiliser under the name "superphosphate . 

The routes by which mineral phosphates are processed into finished fertilizers are outlined in Eigure 7. World and U.S. trends in the types of products produced are shown in Eigures 8 and 9, respectively. Most notable in both instances is the large, steady increase in the importance of monoammonium and diammonium phosphates as finished phosphate fertilizers at the expense of ordinary superphosphate, and to some extent at the expense of triple superphosphate. In the United States, about 65% of the total phosphate appHed is now in the form of granular ammonium phosphates, and additional amounts of ammonium phosphates are appHed as integral parts of granulated mixtures and fluid fertilizers. 

Fig. 8. World trends in types of phosphate fertilizers consumed, where (—) represents ammonium phosphates and multinutrient compounds (— normal superphosphate ( ), triple superphosphate and (— —), basic slag and raw rock.

Normal Superphosphate. From its beginning as the first commercial phosphate fertilizer, normal superphosphate (NSP), also called ordinary or single superphosphate, has continued among the top fertilizers of the world (Fig. 8). Use of normal superphosphate decreased steadily on a percentage basis because of growing production of more concentrated materials, but grew on a P2 s basis to a maximum of 6.7 x 10 t... 

Table 5. Process Variables in the Manufacture of Normal Superphosphate...

A modification of the NSP production process involves use of a mixture of sulfuric and phosphoric acids. The resultant product is referred to as enriched superphosphate and can contain up to 40% P2O5. The usual P2O5 content of enriched superphosphate is about 27%. 

Triple (Concentrated) Superphosphate. The first important use of phosphoric acid in fertilizer processing was in the production of triple superphosphate (TSP), sometimes called concentrated superphosphate. Basically, the production process for this material is the same as that for normal superphosphate, except that the reactants are phosphate rock and phosphoric acid instead of phosphate rock and sulfuric acid. The phosphoric acid, like sulfuric acid, solubilizes the rock and, in addition, contributes its own content of soluble phosphoms. The result is triple superphosphate of 45—47% P2 s content as compared to 16—20% P2 5 normal superphosphate. Although triple superphosphate has been known almost as long as normal superphosphate, it did not reach commercial importance until the late 1940s, when commercial supply of acid became available. 

Worldwide, triple superphosphate, over the period 1955 to 1980, maintained about a 15% share of the phosphate fertilizer market (Fig. 8). World consumption for the year ended June 30, 1991 (9) was equivalent to 3.6 x 10 t of P20, which was about 10% of world fertilizer P2O5 consumption. In the United States, consumption for the year ended June 30, 1990 (Fig. 7) was equivalent to about 240 x 10 t of P20, which represented only 6% of U.S. fertilizer P2O5 consumption. 

Simplicity of production, high analysis, and excellent agronomic quaUty are reasons for the sustained high production and consumption of TSP. A contributing factor is that manufacture of the triple superphosphate has been an outlet for so-called sludge acid, the highly impure phosphoric acid obtained as a by-product of normal acid purification. 

Fig. 11. Dorr-Ohver type slurry process for manufacture of granular triple superphosphate. Courtesy of TVA.

Since about 1968, triple superphosphate has been far outdistanced by diammonium phosphate as the principal phosphate fertilizer, both in the United States and worldwide. However, production of triple superphosphate is expected to persist at a moderate level for two reasons (/) at the location of a phosphoric acid—diammonium phosphate complex, production of triple superphosphate is a convenient way of using sludge acid that is too impure for diammonium phosphate production and (2) the absence of nitrogen in triple superphosphate makes it the preferred source of phosphoms for the no-nitrogen bulk-blend fertilizers that frequendy are prescribed for leguminous crops such as soy beans, alfalfa, and clover. 

Monoammonium Phosphate. Monoammonium phosphate [7722-76-1] (MAP), NH4H2PO4, has become second only to diammonium phosphate as a phosphate fertilizer material of trade. During the year ended June 30, 1990, monoammonium phosphate used ia the United States furnished 985 thousand t of P2O5 as compared to 1.5 million t furnished by diammonium phosphate and 240 thousand t by triple superphosphate (Fig. 7). Monoammonium phosphate furnished 25% of total P2O5 consumption. 

Plasticity, and hence granulation efficiency, varies considerably with the nature and proportion of feed materials. Pure salts, such as potassium chloride and ammonium sulfate, lend Httle or no plasticity and thus are difficult to granulate. Superphosphates provide good plasticity. The plasticity of ammonium phosphates depends chiefly on the impurity content of iron and aluminum. The higher the impurity the greater the plasticity. In some cases, binders such as clay are added to provide plasticity. 

Steam granulation is practiced in Europe, AustraUa, and elsewhere, chiefly in small plants in which superphosphate, either ordinary or triple, is a primary ingredient. However, for many of the larger operations, superphosphates have been replaced by ammonium phosphates as the principal P2 s source, and granulation procedures involving chemical reactions are employed in Europe as well as in the United States. 

Fig. 18. TVA-type cogranulation process with preneutralizer, as used for production of granular mixed fertilizers. Feed materials such as ammonium sulfate, ammonium nitrate, urea, superphosphates, sulfuric acid, and potash are used.

Some commonly used primary nutrient fertilizers are incidentally also rich sources of calcium. Ordinary superphosphate contains monocalcium phosphate and gypsum in amounts equivalent to all of the calcium originally present in the phosphate rock. Triple superphosphate contains soluble monocalcium phosphate equivalent to essentially all the P2 5 product. Other fertilizers rich in calcium are calcium nitrate [10124-37-5] calcium ammonium nitrate [39368-85-9] and calcium cyanamide [156-62-7]. The popular ammonium phosphate-based fertilizers are essentially devoid of calcium, but, in view of the natural calcium content of soils, this does not appear to be a problem. 

Some of the principal forms in which sulfur is intentionally incorporated in fertilizers are as sulfates of calcium, ammonium, potassium, magnesium, and as elemental sulfur. Ammonium sulfate [7783-20-2] normal superphosphate, and sulfuric acid frequendy are incorporated in ammoniation granulation processes. Ammonium phosphate—sulfate is an excellent sulfur-containing fertilizer, and its production seems likely to grow. Some common grades of this product are 12—48—0—5S, 12—12S, and 8—32—8—6.5S. 

Resources of Sulfur. In most of the technologies employed to convert phosphate rock to phosphate fertilizer, sulfur, in the form of sulfuric acid, is vital. Treatment of rock with sulfuric acid is the procedure for producing ordinary superphosphate fertilizer, and treatment of rock using a higher proportion of sulfuric acid is the first step in the production of phosphoric acid, a production intermediate for most other phosphate fertilizers. Over 1.8 tons of sulfur is consumed by the world fertilizer industry for each ton of fertilizer phosphoms produced, ie, 0.8 t of sulfur for each ton of total 13.7 X 10 t of sulfur consumed in the United States for all purposes in 1991, 60% was for the production of phosphate fertilizers (109). Worldwide the percentage was probably even higher. 

Calcium. Calcium is the fifth most abundant element in the earth s cmst. There is no foreseeable lack of this resource as it is virtually unlimited. Primary sources of calcium are lime materials and gypsum, generally classified as soil amendments (see Calcium compounds). Among the more important calcium amendments are blast furnace slag, calcitic limestone, gypsum, hydrated lime, and precipitated lime. Fertilizers that carry calcium are calcium cyanamide, calcium nitrate, phosphate rock, and superphosphates. In addition, there are several organic carriers of calcium. Calcium is widely distributed in nature as calcium carbonate, chalk, marble, gypsum, fluorspar, phosphate rock, and other rocks and minerals. 

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