Sulfur fertilizers

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. 

Sulfur-Coated Fertilizers. Sulfur-coated urea technology (SCU) was developed in the 1960s and 1970s by the Tennessee Valley Authority, now called the National Fertilizer and Environmental Research Center. A commercial-scale demonstration plant (9.1 t/h) was put in operation by TVA in late 1978. Sulfur was chosen as the principle coating material because of its low cost and its value as a secondary nutrient. 

Mudahar, M.S., J.S. Kanwar Fertilizer Sulfur and Food Production, Klnwer Academic Publishers, Norwell, MA, 1986. 

In the manufacture of fertilizers, sulfuric acid is used to digest phosphate rock (largely Ca3(P04)2 and Ca5(P04)3F) to make phosphoric acid or the calcium salts such as Ca(H2P04)2-Some of the phosphoric acid is also used to make ammonium phosphate. More details on the manufacture of fertilizer were presented in Chapter 13. 

J.S. Kanwar, Fertilizer Sulfur and Food Production. Kluwer Academic Publishers, U.S., and... 

Sulfuric acid is one of the world s most important industrial raw materials. In the United States, more sulfuric acid is produced than any other industrial chemical. Most sulfuric acid is used in the production of phosphate fertilizers. Sulfuric acid is also important in extracting metals from ore, oil refining, waste treatment, chemical synthesis, and as a component in lead-acid batteries. Sulfuric acid is so important that economists use its production as a measure of a nation s industrial development. 

Randle, W.M., Lancaster, J.E., Shaw, M.L., Sutton, K.H., Hay, R.L., and Bussard, M.L. 1995. Quantifying onion flavor compounds responding to sulfur fertility-sulfur increases levels of alk(en)yl cysteine sulfoxides and biosynthetic intermediates. J Amer Soc Hort Sci J20(6) 1075-1081. 

The CPI industry manufactures alcohols, detergents, synthetic rubber, glycerin, fertilizers, sulfur, solvents, and feedstock for the manufacture of drugs, nylon, plastics, paints, polyesters, food additives and supplements, explosives, dyes, and insulating materials. The petrochemical industry uses about 5% of the total supply of oil and gas in the US. 

SO2 removed from the tail gas using by-product processes yields a material that has reuse potential or market value (either directly or after further processing). Such by-products include commercial-grade gypsum, fertilizer, sulfuric acid, and S02-rich gas that can be subsequently converted to concentrated (93-98% H2SO4) sulfuric acid. 

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. 

Essentially all the ammonium sulfate fertilizer used in the United States is by-product material. By-product from the acid scmbbing of coke oven gas is one source. A larger source is as by-product ammonium sulfate solution from the production of caprolactam (qv) and acrylonitrile, (qv) which are synthetic fiber intermediates. A third but lesser source is from the ammoniation of spent sulfuric acid from other processes. In the recovery of by-product crystals from each of these sources, the crystallization usually is carried out in steam-heated sa turator—crystallizers. Characteristically, crystallizer product is of a particle size about 90% finer than 16 mesh (ca 1 mm dia), which is too small for satisfactory dry blending with granular fertilizer materials. Crystals of this size are suitable, however, as a feed material to mixed fertilizer granulation plants, and this is the main fertilizer outlet for by-product ammonium sulfate. 

The sustained world popularity of NSP results from simplicity of production and high agronomic quaHty as a carrier of available P2O5, calcium, sulfur, and usually some incidental micronutrients. In terms of agronomic value for large numbers of crops, no phosphate fertilizer has been shown to be superior to NSP. It is likely to remain in strong demand in parts of the world where simplicity of production or sulfur fertilization has high priority and where transportation costs are not prohibitive. 

There are numerous variations of the wet process, but all involve an initial step in which the ore is solubilized in sulfuric acid, or, in a few special instances, in some other acid. Because of this requirement for sulfuric acid, it is obvious that sulfur is a raw material of considerable importance to the fertilizer industry. The acid—rock reaction results in formation of phosphoric acid and the precipitation of calcium sulfate. The second principal step in the wet processes is filtration to separate the phosphoric acid from the precipitated calcium sulfate. Wet-process phosphoric acid (WPA) is much less pure than electric furnace acid, but for most fertilizer production the impurities, such as iron, aluminum, and magnesium, are not objectionable and actually contribute to improved physical condition of the finished fertilizer (35). Impurities also furnish some micronutrient fertilizer elements. 

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. 

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 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. 

A smaller factor in ozone depletion is the rising levels of N2O in the atmosphere from combustion and the use of nitrogen-rich fertilizers, since they ate the sources of NO in the stratosphere that can destroy ozone catalyticaHy. Another concern in the depletion of ozone layer, under study by the National Aeronautics and Space Administration (NASA), is a proposed fleet of supersonic aircraft that can inject additional nitrogen oxides, as weU as sulfur dioxide and moisture, into the stratosphere via their exhaust gases (155). Although sulfate aerosols can suppress the amount of nitrogen oxides in the stratosphere... 

Sulfur, another inorganic petrochemical, is obtained by the oxidation of hydrogen sulfide 2H2S + O2 — 2H2 0 + 2S. Hydrogen sulfide is a constituent of natural gas and also of the majority of refinery gas streams, especially those off-gases from hydrodesulfurization processes. A majority of the sulfur is converted to sulfuric acid for the manufacture of fertilizers and other chemicals. Other uses for sulfur include the production of carbon disulfide, refined sulfur, and pulp and paper industry chemicals. 

An additional mole of ammonium sulfate per mole of final lactam is generated duting the manufacture of hydroxylamine sulfate [10039-54-0] via the Raschig process, which converts ammonia, air, water, carbon dioxide, and sulfur dioxide to the hydroxylamine salt. Thus, a minimum of two moles of ammonium sulfate is produced per mole of lactam, but commercial processes can approach twice that amount. The DSM/Stamicarbon HPO process, which uses hydroxylamine phosphate [19098-16-9] ia a recycled phosphate buffer, can reduce the amount to less than two moles per mole of lactam. Ammonium sulfate is sold as a fertilizer. However, because H2SO4 is released and acidifies the soil as the salt decomposes, it is alow grade fertilizer, and contributes only marginally to the economics of the process (145,146) (see Caprolactam). 

The value of langbeinite as a fertilizer is enhanced because, in pure form, it contains 18.8 wt % potassium, 11.7 wt % magnesium, and 23.0 wt % sulfur. AH three elements are essential nutrients for plant growth. Commercial grades contain ca 97 wt % mineral the remaining 3 wt % consists of water-insoluble clays and residual sodium chloride. 

Economic Aspects and Uses. Almost all ammonium sulfate is used as a fertilizer for this purpose it is valued both for its nitrogen content and for its readily available sulfur content. In 1986/1987 United States consumption of ammonium sulfate was 0.57 million metric tons (34) world consumption during the same period was estimated at 13.3 million metric tons. In North America ammonium sulfate is largely recovered from caprolactam production. 

Ammonium sulfate is a good fertilizer for rice, citms, and vines, and can be especially useful for some sulfur-deficient or high pH soils. Nonfertilizer uses include food processing, fire control, tanning, and catde feed. 

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. 

By-Products and Waste Disposal. A by-product of sulfamic acid manufacturing is fuming sulfuric acid or dilute sulfuric acid. The amount of sulfuric acid (as 100% H2SO is 1—1.5 times as much by weight as the sulfamic acid product. This by-product also contains ammonium salts and is therefore normally used as raw material for fertilizer (see Fertilizers). 

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