Calcium sulfate sulfuric acid production

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. 

Calcium sulfate is formed as a byproduct in industrial processes such as flue gas desulfurization and the production of zinc, fluoride, organic acids and phosphoric acid, in amounts of many million tons per year. In this study the attention is focussed on calcium sulfate from the production of phosphoric acid for fertilizer applications. It is precipitated, from solution after digestion of phosphate ore by addition of sulfuric acid according to [1] ... 

Sulfuric acid is a very important commodity chemical, and indeed, a nation s sulfuric acid production is a good indicator of its industrial strength. World production in 2001 was 165 million tons, with an approximate value of US 8 billion. The major use (60% of total production worldwide) for sulfuric acid is in the "wet method" for the production of phosphoric acid, used for manufacture of phosphate fertilizers as well as trisodium phosphate for detergents. In this method, phosphate rock is used, and more than 100 million tonnes are processed annually. This raw material is shown below as fluorapatite, though the exact composition may vary. This is treated with 93% sulfuric acid to produce calcium sulfate, hydrogen fluoride (HF) and phosphoric acid. The HF is removed as hydrofluoric acid. The overall process can be represented as ... 

Subsequently, inorganic chemical production expanded and diversified into other areas. Anhydrite (calcium sulfate) was mined for use in sulfuric acid production, nitric acid and fertilizer production was introduced, and later organic chemicals and polymer production began, expanding to nearby Wilton. Ammonia and mineral acids are still manufactured to this day on the Billingham site. 

Normally, a slight excess of sulfuric acid is used to bring the reaction to completion. There are, of course, many side reactions involving siHca and other impurity minerals in the rock. Fluorine—silica reactions are especially important as these affect the nature of the calcium sulfate by-product and of fluorine recovery methods. Thermodynamic and kinetic details of the chemistry have been described (34). 

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. 

Production Technology. Processes for extraction of P2O3 from phosphate rock by sulfuric acid vary widely, but all produce a phosphoric acid—calcium sulfate slurry that requires soHds-Hquid separation (usually by filtration (qv)), countercurrent washing of the soHds to improve P2O3 recovery, and concentration of the acid. Volatilized fluorine compounds are scmbbed and calcium sulfate is disposed of in a variety of ways. 

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. 

The reaction of formate salts with mineral acids such as sulfuric acid is the oldest iadustrial process for the production of formic acid, and it stiU has importance ia the 1990s. Sodium formate [141-53-7] and calcium formate [544-17-2] are available iadustriaHy from the production of pentaerythritol and other polyhydric alcohols and of disodium dithionite (23). The acidolysis is technically straightforward, but the unavoidable production of sodium sulfate is a clear disadvantage of this route. 

If the hydrogen could be reduced, the coproduction of hydrogen and valuable side products, eg, sulfur, sulfuric acid, and calcium sulfate, from H2S could become economically competitive. 

Opa.nte. There are two methods used at various plants in Russia for loparite concentrate processing (12). The chlorination technique is carried out using gaseous chlorine at 800°C in the presence of carbon. The volatile chlorides are then separated from the calcium—sodium—rare-earth fused chloride, and the resultant cake dissolved in water. Alternatively, sulfuric acid digestion may be carried out using 85% sulfuric acid at 150—200°C in the presence of ammonium sulfate. The ensuing product is leached with water, while the double sulfates of the rare earths remain in the residue. The titanium, tantalum, and niobium sulfates transfer into the solution. The residue is converted to rare-earth carbonate, and then dissolved into nitric acid. 

Naphthalenesulfonic Acid. The sulfonation of naphthalene with excess 96 wt % sulfuric acid at < 80°C gives > 85 wt % 1-naphthalenesulfonic acid (a-acid) the balance is mainly the 2-isomer (P-acid). An older German commercial process is based on the reaction of naphthalene with 96 wt % sulfuric acid at 20—50°C (13). The product can be used unpurifted to make dyestuff intermediates by nitration or can be sulfonated further. The sodium salt of 1-naphthalenesulfonic acid is required, for example, for the conversion of 1-naphthalenol (1-naphthol) by caustic fusion. In this case, the excess sulfuric acid first is separated by the addition of lime and is filtered to remove the insoluble calcium sulfate the filtrate is treated with sodium carbonate to precipitate calcium carbonate and leave the sodium l-naphthalenesulfonate/7J(9-/4-J7 in solution. The dry salt then is recovered, typically, by spray-drying the solution. 

When boric acid is made from colemanite, the ore is ground to a fine powder and stirred vigorously with diluted mother Hquor and sulfuric acid at about 90°C. The by-product calcium sulfate [7778-18-9] is removed by settling and filtration, and the boric acid is crystallised by cooling the filtrate. 

By-Product Calcium Sulfate. There are many iadustrial chemical processes that produce by-product calcium sulfate in one of its forms. Whereas the most common is the neutralization of spent sulfuric acid, many of those processes do not produce a commercially useful by-product because of contaminants, particle size, or volume produced. There are, however, six chemical processes that do produce sufficient volume to have potential commercial value. Each is named after its chemical process. 

More recendy, the molten caustic leaching (MCL) process developed by TRW, Inc. has received attention (28,31,32). This process is illustrated in Eigure 6. A coal is fed to a rotary kiln to convert both the mineral matter and the sulfur into water- or acid-soluble compounds. The coal cake discharged from the kiln is washed first with water and then with dilute sulfuric acid solution countercurrendy. The efduent is treated with lime to precipitate out calcium sulfate, iron hydroxide, and sodium—iron hydroxy sulfate. The MCL process can typically produce ultraclean coal having 0.4 to 0.7% sulfur, 0.1 to 0.65% ash, and 25.5 to 14.8 MJ/kg (6100—3500 kcal/kg) from a high sulfur, ie, 4 wt % sulfur and ca 11 wt % ash, coal. The moisture content of the product coal varies from 10 to 50%. 

Some products are precipitated from the fermentation broth. The insoluble calcium salts of some organic acids precipitate and are col-lec ted, and adding sulfuric acid regenerates the acid while forming gypsum (calcium sulfate) that constitutes a disposal problem. An early process for recovering the antibiotic cycloserine added silver nitrate to the fermentation broth to precipitate an insoluble silver salt. This process was soon obsolete because of poor economics and because the silver salt, when diy, exploded easily. 

Manufacture Mined phosphate rock is reacted with sulfuric acid. The product phosphoric acid is isolated as a 28-35% solution by filtering off the insoluble calcium sulfate co-product. CasfPOJj + SHzSO 2H3P04 + 3CaS04 phosphate sulfuric gypsum rock acid... 

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 ... 

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 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. 

A basic step in hydrofluoric acid manufacture is the reaction of sulfuric acid with fluorspar (calcium fluoride) to produce hydrogen fluoride and calcium sulfate. Spent alumina is also generated by the defluorination of some hydrofluoric acid alkylation products over alumina. It is disposed of or sent to the alumina supplier for recovery. Other solid residuals from hydrofluoric acid alkylation include any porous materials that may have come in contact with the hydrofluoric acid. 

Sulfur Emissicms Sulfur present in a fuel is released as SO2, a known contributor to acid rain deposition. By adding limestone or dolomite to a fluidized bed, much of this can be captured as calcium sulfate, a dry nonhazardous solid. As limestone usually contains over 40 percent calcium, compared to only 20 percent in dolomite, it is the preferred sorbent, resulting in lower transportation costs for the raw mineral and the resulting ash product. Moreover, the high magnesium content of the dolomite makes the ash unsuitable for some building applications and so reduces its potential for utilization. Whatever sorbent is selected, for economic reasons it is usually from a source local to the FBC plant. If more than one sorbent is available, plant trials are needed to determine the one most suitable, as results from laboratory-scale reactivity assessments are unreliable. 

As stated earlier in this paper, FGD wet scrubbers can produce either calcium sulfite (the typical product) or calciiun sulfate. The DDO crystallizer is advantageous for either product. The following industrial case history describes the production of calcium sulfate dihydrate (or gypsum) product fi om an industrial in-plant weak sulfuric acid liquor using a DDO crystallizer configuration. 

Calcium sulfate crystals were precipitated in a Continuous Mixed Suspension Mixed Product Removal (CMSMPR) crystallizer by mixing of calcium phosphate and sulfuric acid feed streams. The formed calcium sulfate hydrate (anhydrite, hemihydrate and dihydrate) mainly depends on the temperature and the solution composition. The uptake of cadmium and phosphate ions in these hydrates has been studied as a function of residence time and solution composition. In anhydrite, also the incorporation of other metal ions has been investigated. The uptake was found to be a function of both thermodynamics and kinetics. 

All phosphorus fertilizers come from wet process phosphoric acid or directly from phosphate rock. Normal superphosphate, triple or concentrated superphosphate, and ammonium phosphate are the three common types used. Normal or ordinary superphosphate (NSP or OSP) is mostly monocalcium phosphate and calcium sulfate. It is made from phosphate rock and sulfuric acid and is equated to a 20% P2O5 content. It led the market until 1964. The production of normal superphosphate is similar to that for the manufacture of wet process phosphoric acid (Chapter 2, Section 3) except that there is only partial neutralization. Normal superphosphate is no longer used to any great extent. The following reaction is one example of an equation that represents this process. 

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