Rocks acidity

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... 

Element Atomic number Earth crust Basic rock (Ba salts) Intermediate rock Acid rock (granites)... 

Carbonate-rock acid-rain reaction stiochiometry is best examined using a mathematical model of the ionic species present in a dilute carbonate solution. Appropriate models have been recently developed and are used with an electronic digital computer. Although a discussion of the application of mineral-reaction modeling is outside the scope of this paper, several recent publications explain its use in the study of carbonate-mineral reactions in aqueous solution (9-11). A reaction model, such as PHREEQE (11), the model used in this study, incorporates changes in gas-solution and solution-solid equilibria, as well as ionic equilibria in solution, in arriving at a final equilibrium-solution composition (. ... 

Filterability of the rock-acid slurry is one of the most important characteristics of a phosphate rock for use in phosphoric add production. Factors influencing filterability are complex and not completely understood. However, if a plant is to be designed to use a specific rock, an acceptable filtration rate can... 

CaO P205 in Rock Rock Acid Rock, %P20s Rock Acid % Total P2O5 ... 

White phosphorus may be made by several methods. By one process, tri-calcium phosphate, the essential ingredient of phosphate rock, is heated in the presence of carbon and silica in an electric furnace or fuel-fired furnace. Elementary phosphorus is liberated as vapor and may be collected under phosphoric acid, an important compound in making super-phosphate fertilizers. 

Wagner s solution (phosphate rock analysis) dissolve 25 g citric acid and 1 g salicylic acid in water, and make up to 1 liter. Twenty-five to fifty milliliters of this reagent prevents precipitation of iron and aluminum. 

Uranium is present in small (50—200 ppm) amounts in phosphate rock and it can be economically feasible to separate the uranium as a by-product from the cmde black acid (30% phosphoric acid) obtained from the leaching of phosphate for fertilizers (qv). The development and design of processes to produce 500 t U Og per year at Ereeport, Louisiana have been detailed (272). 

Extraction of Nonmetallic Inorganic Compounds. Phosphoric acid is usually formed from phosphate rock by treatment with sulfuric acid, which forms sparingly soluble calcium sulfate from which the phosphoric acid is readily separated. However, in special circumstances it may be necessary to use hydrochloric acid ... 

Minerals. Supplementation of macrominerals to mminants is sometimes necessary. Calcium and phosphoms are the minerals most often supplemented in mminant diets. One or both may be deficient, and the level of one affects the utilization of the other. Limestone, 36% calcium, is commonly used as a source of supplemental calcium. Dolomite, 22% calcium oyster sheUs, 35% calcium and gypsum, 29% calcium, are sources of calcium. Bone meal, 29% calcium, 14% phosphoms dicalcium phosphate, 25—28% calcium, 18—21% phosphoms and defluorinated rock phosphate, 32% calcium, 18% phosphoms, are sources of both calcium and phosphoms. Diammonium phosphate, 25% phosphoms phosphoric acid, 32% phosphoms sodium phosphate, 22% phosphoms and sodium tripolyphosphate, 31% phosphoms, are additional sources of phosphoms (5). 

Direct Application Rock. Finely ground phosphate rock has had limited use as a direct-appHcation fertilizer for many years. There have been widely varying results. Direct appHcation of phosphate rock worldwide amounts to about 8% of total fertilizer phosphate used, primarily in the former Soviet Union, France, Brazil, Sri Lanka, Malaysia, and Indonesia. The agronomic effectiveness of an apatitic rock depends not only on the fineness of the grind but also strongly on the innate reactivity of the rock and the acidity of the sod performance is better on more acid sods. Probably more than half of the potentially productive tropical sods are acidic, some with pH as low as 3.5—4.5. Certain phosphate rocks may thus become increasingly important as fertilizer in those areas. The International Fertilizer Development Center at Muscle Shoals, Alabama is active in researching this field (30). 

NSP is produced by the reaction of phosphate rock and sulfuric acid. This reaction quickly yields a soHd mass containing monocalcium phosphate monohydrate and gypsum, CaSO 2H20, according to the simplified equation... 

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). 

Cost Fa.ctors, The dehvered costs of the phosphate rock and sulfuric acid raw materials often account for more than 90% of the cost of producing NSP, thus the production cost varies considerably with plant location. Because the rock is richer in P2O5 than is the low analysis NSP product, NSP need not be produced near the phosphate mine. However, deUvery of sulfuric acid and shipment of product to market are important cost factors. Most United States NSP plants have been located east of the Mississippi river, with concentration in the southeastern and extreme southern parts of the country where the largest use of the product has occurred. Production and use of the product also has been high in California. 

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. 

Chemistry ndProperties. The chemistry of phosphoric acid manufacture and purification is highly complex, largely because of the presence of impurities in the rock. The main chemical reaction in the acidulation of phosphate rock using sulfuric acid to produce phosphoric acid is... 

In addition to the main acidulation reaction, other reactions also occur. Free calcium carbonate in the rock reacts with the acid to produce additional by-product calcium compounds and CO2 gas which causes foaming. Other mineral impurities, eg, Fe, Al, Mg, U, and organic matter, dissolve, the result being that the wet-process acid is highly impure. 

Nitric acid acidulation of phosphate rock produces phosphoric acid, together with dissolved calcium nitrate. Separation of the phosphoric acid for use as an intermediate in other fertilizer processes has not been developed commercially. Solvent extraction is less effective in the phosphoric—nitric system than in the phosphoric—hydrochloric system. Instead, the nitric acid acidulate is processed to produce nitrophosphate fertilizers. 

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. 

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. 

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