Sulfuric acid phosphate fertilizer

Agriculture is the largest industry for sulfur consumption. Historically, the production of phosphate fertilizers has driven the sulfur market. Phosphate fertilizers account for approximately 60% of the sulfur consumed globally. Thus, although sulfur is an important plant nutrient in itself, its greatest use in the fertilizer industry is as sulfuric acid, which is needed to break down the chemical and physical stmcture of phosphate rock to make the phosphate content more available to plant life. Other mineral acids, as well as high temperatures, also have the abiUty to achieve this result. Because of market price and availabiUty, sulfuric acid is the most economic method. About 90% of sulfur used in the fertilizer industry is for the production of phosphate fertilizers. Based on this technology, the phosphate fertilizer industry is expected to continue to depend on sulfur and sulfuric acid as a raw material. 

The use of sulfuric acid in automobile batteries, however, does not account for its production in such vast quantities. The largest single use for sulfuric acid is fertilizers, especially a sulfuric-acid/phosphate-containing-rock mixture called superphosphate. Because phosphorus is a major mineral nutrient needed by plants and because phosphorus is a major component of bones, bone meal was once a commonly used fertilizer. Today, however, phosphate rock, treated with sulfuric acid to become more soluble, can be used, too. 

Sulfur is a component of black gunpowder, and is used in the vulcanization of natural rubber and a fungicide. It is also used extensively in making phosphatic fertilizers. A tremendous tonnage is used to produce sulfuric acid, the most important manufactured chemical. 

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. 

Nitric Phosphate. About 15% of worldwide phosphate fertilizer production is by processes that are based on solubilization of phosphate rock with nitric acid iastead of sulfuric or phosphoric acids (64). These processes, known collectively as nitric phosphate or nitrophosphate processes are important, mainly because of the iadependence from sulfur as a raw material and because of the freedom from the environmental problem of gypsum disposal that accompanies phosphoric acid-based processes. These two characteristics are expected to promote eventual iacrease ia the use of nitric phosphate processes, as sulfur resources diminish and/or environmental restrictions are tightened. 

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. 

Although tetrafluorosilane can be readily produced by the action of hydrogen fluoride on sihca, its production is a by-product of HF production by the reaction of fluorospar and sulfuric acid and as a by-product from phosphate fertilizer production by the treatment of fluoroapatite with sulfuric acid (171). The most significant U.S. production is by IMC-Agrico at Uncle Sam, Louisiana. 

Sulfuric acid is the most important sulfur-containing intermediate product. More than 85% of the sulfur consumed in the world is either converted to sulfuric acid or produced direcdy as such (see Sulfuric acid and sulfur trioxide). Worldwide, well over half of the sulfuric acid is used in the manufacture of phosphatic fertilizers and ammonium sulfate for fertilizers. The sulfur source may be voluntary elemental, such as from the Frasch process recovered elemental from natural gas or petroleum or sulfur dioxide from smelter operations. 

The need for acid concentrators exists because many uses of sulfuric acid do not lead to its consumption. Instead, the acid is diluted and partially degraded and contaminated. In the past, large amounts of acid were disposed of either by usiag it ia the phosphate fertilizer iadustry to dissolve phosphate rock or by neutralization and subsequent discharge to waterways. 

Historically, consumption of sulfuric acid has been a good measure of a country s degree of iadustrialization and also a good iadicator of general busiaess conditions. This is far less vaUd ia the 1990s, because of the heavy sulfuric acid usage by the phosphate fertilizer iadustry. Of total U.S. sulfuric acid consumption ia 1994 of 42.5 x 10 metric tons, over 70% went iato phosphate fertilizers as compared to 45% ia 1970 and 64% ia 1980 (144). Uses other than fertilizer have grown only slowly or declined. This trend is expected to continue. Production and consumption trends ia the United States are shown ia Tables 9 and 10. 

As of 1993—1994, over 70% of sulfuric acid production was not sold as such, but used captively to make other materials. At almost all large fertilizer plants, sulfuric acid is made on site, and by-product steam from these sulfur-burning plants is generally used for concentrating phosphoric acid ia evaporators. Most of the fertilizer plants are located ia Florida, Georgia, Idaho, Louisiana, and North Carolina. In the production of phosphate fertilizers, the primary role of sulfuric acid is to convert phosphate rock to phosphoric acid and soHd calcium sulfates, which are removed by filtration. 

Because sulfuric acid has its greatest use in fertilizers, trends in that industry have a significant effect on the sulfuric acid business. Owing to a weak U.S. doUar in the early 1990s and high demand for fertilizer abroad, a considerable portion of U.S. phosphate fertilizer production was exported. High fertilizer exports are expected to continue until Thkd World countries can meet thek own demands. 

Phosphate fertilizer complexes often have sulfuric and phosphoric acid production facilities. Sulfuric acid is produced by burning molten sulfur in air to produce sulfur dioxide, which is then catalytically converted to sulfur trioxide for absorption in oleum. Sulfur dioxide can also be produced by roasting pyrite ore. Phosphoric acid is manufactured by adding sulfuric acid to phosphate rock. The... 

Fluorides and dust are emitted to the air from the fertilizer plant. All aspects of phosphate rock processing and finished product handling generate dust, from grinders and pulverizers, pneumatic conveyors, and screens. The mixer/reactors and dens produce fumes that contain silicon tetrafluoride and hydrogen fluoride. A sulfuric acid plant has two principal air emissions sulfur dioxide and acid mist. If pyrite ore is roasted, there will also be particulates in air emissions that may contain heavy metals such as cadmium, mercury, and lead. 

The oxoacids and oxoanions of phosphorus are among the most heavily manufactured chemicals. Phosphate fertilizer production consumes two-thirds of all the sulfuric acid produced in the United States. 

Phosphoric acid is the parent of the phosphates, which contain the tetrahedral P04 anion and are of great commercial importance. Phosphate rock is mined in huge quantities in Florida and Morocco. After being crushed, it is treated with sulfuric acid to give a mixture of sulfates and phosphates called superphosphate, a major fertilizer ... 

Sulfuric acid is the most heavily produced inorganic chemical worldwide, the annual production in the United States alone being more than 4 X 1(J10 kg. The low cost of sulfuric acid leads to its widespread use in industry, particularly for the production of fertilizers, petrochemicals, dyestuffs, and detergents. About two-thirds is used in the manufacture of phosphate and ammonium sulfate fertilizers (see Section 15.4). 

Uses The highest value inorganic acid marketed in the U.S. and second in value to sulfuric acid. Used primarily for the preparation of salts used as fertilizers (ammonium and calcium salts), water softeners and detergents, animal feeds, and baking powder. Food-grade phosphoric acid is used to acidify soft drinks, e.g.. Coca Cola. Organic phosphates are used in flame retardants. 

The element phosphorus, like nitrogen, is essential to plant and animal life. Although phosphorus was not identified and isolated until 1669, phosphorus-containing materials have been used as fertilizers since ancient times, usually from bird droppings, fish, and bone. The first phosphoric acid was made by treating bone ashes with sulfuric acid. This marked the beginning of the commercial fertilizer industry. Eventually, mined phosphate rock, a poor fertilizer by itself, was substituted for bones as a raw material for phosphoric acid in the mid-1880s. 

C04-0146. The largest single use of sulfuric acid is for the production of phosphate fertilizers. The acid reacts with calcium phosphate in a 2 1 mole ratio to give calcium sulfate and calcium dihydrogen phosphate. The mixture is crushed and spread on fields, where the salts dissolve in rain water. (Calcium phosphate, commonly found in phosphate rock, is too insoluble to be a direct source of phosphate for plants.) (a) Write a balanced equation for the reaction of sulfuric acid with calcium phosphate, (b) How many kilograms each of sulliiric acid and calcium phosphate are required to produce 50.0 kg of the calcium sulfate-dihydrogen phosphate mixture (c) How many moles of phosphate ion will this mixture provide ... 

Ammonia synthesis is the second largest chemical process, after the production of sulfuric acid (see also Chapter 1). It accounts for about 1 % of the total human-related energy consumption. Roughly 80 % of the ammonia produced is used for fertilizers (either as liquid ammonia or as more easily handled salts such as ammonium nitrate, ammonium phosphate, etc.) and, as such, ammonia synthesis is indispensable for our society. Other applications of ammonia are nitrogen-containing... 

In the fertilizer manufacturing scheme, the wet process phosphoric acid most commonly ensues from dissolution of sedimentary phosphate rock in sulfuric acid. Such acid solution contains around 1 g 1 1 uranium which is recovered as the byproduct. This task is accomplished by three well-proven extraction processes, some salient details of which are presented in Table 5.10. 

Sulfide ores usually contain small amounts of mercury, arsenic, selenium, and tellurium, and these impurities volatilize during the ore treatment. All the volatilized impurities, with the exception of mercury, are collected in the dust recovery systems. On account of its being present in low concentrations, mercury is not removed by such a system and passes out with the exit gases. The problem of mercury contamination is particularly pertinent to zinc plants since the sulfidic ores of zinc contain traces of mercury (20-300 ppm). The mercury traces in zinc sulfide concentrates volatilize during roasting and contaminate the sulfuric acid that is made from the sulfur dioxide produced. If the acid is then used to produce phosphatic fertilizers, this may lead to mercury entering the food chain as a contaminant. Several processes have been developed for the removal of mercury, but these are not yet widely adopted. 

Most of the sulfuric acid produced by the chemical industry is used to make fertilizers. Fertilizers are produced using phosphorous, an essential nutrient that plants need to grow well. Phosphate is found in rocks, and these rocks are more soluble, or more easily dissolved, in water when broken down with sulfuric acid. Treating phosphate rocks this way releases phosphorous in a form that plant roots can absorb. 

A "fertilizer-grade" product is obtained by treating phosphate rock with sulfuric acid. 

The product, Ca(H2P04)2, is more soluble than the phosphate. Sulfuric acid is produced in the largest quantity of any compound, with production that approaches 100 billion pounds annually. Approximately two-thirds of this amount is used in the production of fertilizers. The mixture containing calcium dihydrogen phosphate and calcium sulfate (gypsum) is known as superphosphate of lime, and it contains a higher percent of phosphorus than does calcium phosphate. 

The manufacture of fertilizers was discussed in Chapter 14. Phosphate rock is digested with sulfuric acid to convert CaC03 into a more soluble form that contains a higher percentage of phosphorus. Sulfuric acid is used as a catalyst in alkylation reactions, petroleum refining, manufacture of detergents, paints, dyes, and fibers, and other processes. It is also used as the electrolyte in the lead-acid battery that is used in automobiles. Sulfuric acid is an enormously important chemical commodity that it would be hard to do without. 

Den A batch process for making the fertilizer superphosphate. The den is the vat into which the mixture of phosphate rock and sulfuric acid is dumped after mixing. There is also a continuous-den process. Not to be confused with DEN [Deutsch - Englisch - Norwegische Gruppe], a fertilizer cartel operated in the three countries from which the name is derived from 1929 to 1930. See also Davison, Oberphos. 

Oberphos A version of the superphosphate process for making a fertilizer by treating phosphate rock with sulfuric acid, which yields a granular product. Used in the United States and Canada, but superseded in the United States by the Davison process. 

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