Fertilization with sulfur

In alkaline soils, acidification is required and realized by fertilization with sulfur or... 

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. 

Prevention of Soil Crusting. Acid-based fertilizers such as Unocal s N/Furic (a mixture of urea with sulfuric acid), acidic polymers such as FMC s Spersal (a poly(maleic acid) derivative originally developed to treat boiler scale) (58), the anionic polyacrylamides described previously, as weU as lower molecular weight analogues such as Cytec s Aerotil L Soil Conditioner, have all been used successfully in at least some circumstances to prevent the formation of soil cmsts. It is difficult to prove benefits in the laboratory, and field tests may give variable results depending on local weather conditions. 

Products are granular, free-flowing, and dust-free by nature, since no flow conditioner dust is used as with sulfur-coated fertilizers. They possess excellent abrasion resistance and handling integrity. Since the outer coating is a hard polymer, the products do not leave waxy residues on material handling and apphcation equipment. 

Ammonium sulfate fertilizer is made by reacting ammonia with sulfuric acid. In many parts of the world, calcium sulfate is in mineral form convertible to ammonium sulfate by combining it with ammonia and water - a virtually limitless source of sulfur. 

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 ... 

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. 

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 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. 

Merseburg A process for making ammonium sulfate fertilizer from gypsum. The gypsum is slurried with water and ammonium carbonate solution added. Calcium carbonate precipitates and is removed, any excess of ammonium carbonate is neutralized with sulfuric acid, and the solution is concentrated until it crystallizes ... 

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. 

The calcium sulfate by-product separates as either the dihydrate or the hemihydrate, depending on the conditions. The process originates from the work of J. B. Lawes in 1842 who patented a method of making a fertilizer by treating bones with sulfuric acid. Many variations are practiced today. See also Dorr and Haifa. 

By reacting apatite with sulfuric acid, phosphoric acid and gypsum will result. Most phosphoric acid is produced in this way and is normally used as raw material (green acid) to produce fertilizers. A small amount, however, is further refined to phosphoric acid of food grade quality. 

Balanced chemical reactions are critical to the chemical industry. Plant managers must know the amount of reactants necessary to yield a product to keep production lines moving. If reactants or products are not pure, this must be taken into account. Alternative reactions can be examined to find the most cost-effective process. For example, a fertilizer may be produced using one process with sulfuric acid as a reactant or another process that starts with ammonium carbonate. Working through the balanced equations for each process would help decide which process to adopt. 

Minerals of economic importance within sedimentary formations include, hut are not limited to fluorite, barite, phosphorite, and oolitic hematite. Fluorite is utili/ed us a flux in steelniakiitg and when of high quality as lenses and prisms in the optical industry. Barite is an essential mineral used m gas- and oil-well drilling. Phosphorite, a product of chemical precipitation from seawater, when ircaled with sulfuric acid, produces superphosphate fertilizer, (.killtic hematite deposits of extensive size are important sources of iron ore. 

Two major methods are utilized for the production of phosphoric acid from phosphate rock. The wet process involves the reaction of phosphate rock with sulfuric acid to produce phosphoric acid and insoluble calcium sulfates. Many of the impurities present in the phosphate rock are. also solubilized and retained in the acid so produced. While they are of no serious disadvantage when the acid is to be used for fertilizer manufacture, their presence makes the product unsuitable for the preparation of phosphatic chemicals. 

Several other processes for producing alumina based on ores other than bauxite have been announced. One process uses alunite, a hydrous sulfate of aluminum and potassium. It is claimed to be capable of producing 99% pure alumina from alunite containing only 10 to 15% alumina, compared with bauxite that assays 50% alumina. The alunite is crushed, dehydroxy-lated by heating to 750°C, ground, and treated with aqueous ammonia. Filtration removes the alumina hydrate, and potassium and aluminum sulfates are recovered from the filtrate (to be used as fertilizer constituents). The alumina hydrate is treated with sulfur dioxide gas, and the resulting aluminum sulfate is converted to alumina by heating in a kiln. 

Silica is present in the mineral as an impurity, and it reacts with hydrofluoric acid to yield silicon tetrafluoride, which can be converted to fluorosifi-cic acid, an important source of fluorine. More than half of the phosphoric acid that is produced by the reaction of phosphates with sulfuric acid is converted directly to sodium or ammonium phosphates to be used as fertilizer thus, purity is not a concern. 

The major use of phosphate is to supply phosphorous, one of the three essential plant foods, nitrogen, phosphorus, and potassium. Phosphate rock extraction from its ore, and its subsequent conversion into fertilizer materials and industrial chemicals, is a relatively mature art. Single superphosphate, a mixture of monocalcium monohydrate and gypsum formed by the reaction of sulfuric acid with phosphate rock, has been used as a fertilizer since the mid-1800s. Phosphoric acid, derived by the treatment of phosphate rock with sulfuric acid so as to produce gypsum in a separable form, was manufactured in many locations by batch and countercurrent decantation methods in the 1920s. 

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