Superphosphate production

Large quantities of amnioniated superphosphates are made in the United States of America, containing up to 6 per cent. NH3, and made by treating the superphosphate with ammonia or merely by mixing in ammonium sulphate into the superphosphate. Products are used for manurial purposes. 

Data on fertilizer consumption, annually data on superphosphate production , monthly. 

Plants for superphosphate production represent the msdn sources of fluorine emissions. The inital raw materials (natural phosphates) always con-... 

The fortunate evolution of superphosphate production was due to an equally fortunate combination of natural resources and geographic and political circumstances from the... 

Triple superphosphate production—Triple superphosphate (TSP) is a fertilizer material with a phosphorus content of over 40%, measured as phosphorus pentoxide (P2O5). 

In about 1840 treatment of phosphate rock wath sulfuric acid yielded an effective phosphate fertilizer, which was called superphosphate. TTie first successful commercial superphosphate production was started by Lawes in England in 1842. Others followed, and by 1853 there were 14 manufacturers in the United Kingdom and several in other countries. By 1870, 80 factories were operating in the United Kingdom. 

Several variations of the basic process have been evolved, one of the options being to precipitate the calcium sulphate as dihydrate (x = 2), hanihydrate (x= 1/2) or anhydrite (x = 0). In the most used dihydrate process, the acid is usually obtained at a concentration of about 32% P2O5. Evaporation is used to increase the concentration to 40-42% P2O5 (as required for ammonium phosphate manufacture) or 52-54% P2O5 - merchant grade (as required for superphosphate production). During... 

The superphosphate products are much more soluble than the parent phosphate minerals. The HF produced as a byproduct of superphosphate production can create air pollution problems. 

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. 

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... 

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. 

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. 

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. 

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. 

A significant concern in all nitration plants using mixed acids centers on the disposal method or use for the waste acids. They are sometimes employed for production of superphosphate ferti1i2ers. Processes have also been developed to reconcentrate and recycle the acid. The waste acid is frequently first stripped with steam to remove unreacted HNO and NO. Water is then removed by low pressure evapori2ation or vacuum distillation. 

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