Phosphoric rock

In the case of the processing of phosphoric rock, worker exposure can occur in areas of mining, transportation, loading and unloading of the raw material in the manufacturing industries and in the waste produced and accumulated along the industrial units. Uranium is associated with phosphate and in some mines the ratio is a thousand pounds of phosphoric rock for a pound of uranium (Santa Quit6ria s Mine—Brazil). 

Beyond dewatering, however, is the possibility of decontaminating polluted sediments of which there is an abundance of sites and situations. For decontamination the addition of activated carbon, charcoal, or phosphoric rock is possible in which pollutants are adsorbed onto the soil particles and remain in the fabric enclosure while the effluent is decontaminated to the necessary degree. Examples of a number of polynuclear aromatic hydrocarbons and chlorinated chemicals were presented in this regard. 

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. 

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). 

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... 

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. 

Chemistry and Properties. TSP is essentially impure monocalcium phosphate monohydrate, Ca(H2P0 2 20, made by acidulating phosphate rock with phosphoric acid according to... 

Economics. In contrast to NSP, the high nutrient content of TSP makes shipment of the finished product preferable to shipping of the raw materials. Plants, therefore, are located at or near the rock source. The phosphoric acid used, and the sulfuric acid required for its manufacture, usually are produced at the site of the TSP plant. As in the case of NSP, the cost of raw materials accounts for more than 90% of the total cost. Most of this is the cost of acid. 

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. 

Nitrophosphates are made by acidulating phosphate rock with nitric acid followed by ammoniation, addition of potash as desired, and granulation or prilling of the slurry. The acidulate, prior to ammoniation, contains calcium nitrate and phosphoric acid or monocalcium phosphate according to the foUowiag equations ... 

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. 

The ores of most importance are fluorspar, CaF2 fluorapatite, Ca (P0 2Fj cryoHte [15096-52-3], Na AlF. Fluorspar is the primary commercial source of fluoiine. Twenty-six percent of the world s high quaHty deposits of fluorspar are ia North America. Most of that is ia Mexico. United States production ia 1987—1991 was 314,500 metric tons, most of which occurred ia the Illinois-Kentucky area. Imported fluorspar ia 1990—1991 represented about 82% of U.S. consumption 31% of U.S. fluorspar imports were from Mexico and 29% from China compared to 66% from Mexico ia the 1973—1978 period. The majority of the fluorine ia the earth s cmst is ia phosphate rock ia the form of fluorapatite which has an average fluorine concentration of 3.5%. Recovery of these fluorine values as by-product fluorosiHcic acid from phosphate production has grown steadily, partially because of environmental requirements (see Phosphoric acid and THE phosphates). 

The large amount of fluorine values released from phosphate rock in the manufacture of fertilisers (qv) gives a strong impetus to develop fluorine chemicals production from this source (see Phosphoric acid and the phosphates). Additional incentive comes from the need to control the emission of fluorine-containing gases. Most of the fluorine values are scmbbed out as fluorosiUcic acid, H2SiPg, which has limited useflilness. A procedure to convert fluorosihcic acid to calcium fluoride is available (61). 

Alternative Processes. Because of the large quantity of phosphate rock reserves available worldwide, recovery of the fluoride values from this raw material source has frequently been studied. Strategies involve recovering the fluoride from wet-process phosphoric acid plants as fluosiUcic acid [16961-83-4] H2SiFg, and then processing this acid to form hydrogen fluoride. 

The majority of the fluorine ia the earth s cmst is present in the form of the phosphoms fluoride fluoroapatite [1306-05 ] Ca (P0 2F- Phosphate rock deposits contain an average concentration of 3.5 wt % fluorine. During phosphate processing these fluorine values are partially recovered as by-product fluorosihcic acid. The amount of fluorosiUcic acid recovered has grown steadily, in part because of environmental requirements (see Phosphoric acid and THE phosphates). 

Wet-process acid is manufactured by the digestion of phosphate rock (calcium phosphate) with sulfuric acid. Depending on availabiHty, other acids such as hydrochloric may be used, but the sulfuric-based processes are by far the most prevalent. Phosphoric acid is separated from the resultant calcium sulfate slurry by filtration. To generate a filterable slurry and to enhance the P2O5 content of the acid, much of the acid filtrate is recycled to the reactor. 

Hydroxyapatite, Ca2Q(PO (OH)2, may be regarded as the parent member of a whole series of stmcturaHy related calcium phosphates that can be represented by the formula M2q(ZO X2, where M is a metal or H O" Z is P, As, Si, Ga, S, or Cr and X is OH, F, Cl, Br, 1/2 CO, etc. The apatite compounds all exhibit the same type of hexagonal crystal stmcture. Included are a series of naturally occurring minerals, synthetic salts, and precipitated hydroxyapatites. Highly substituted apatites such as FrancoHte, Ca2Q(PO (C02) (F,0H)2, are the principal component of phosphate rock used for the production of both wet-process and furnace-process phosphoric acid. 

Phosphorus [7723-14-0] is a nonmetaUic element having widespread occurrence in nature as phosphate compounds (see Phosphoric acid and phosphates). Fluorapatite [1306-03-4], Ca F(P0 2> is the primary mineral in phosphate rock ores from which useful phosphoms compounds (qv) ate produced. The recovery from the ore into commercial chemicals is accompHshed by two routes the electric furnace process, which yields elemental phosphoms and the wet acid process, which generates phosphoric acid. The former is discussed herein (see Furnaces, electric). Less than 10% of the phosphate rock mined in the world is processed in electric furnaces. Over 90% is processed by the wet process, used primarily to make fertilisers (qv). 

The largest-volume phosphoms compounds are the phosphoric acids and phosphates (qv), ie, the oxide derivatives of phosphoms ia the + 5 oxidation state. With the exception of the phosphoric acid anhydride, P O q, and the phosphate esters, these materials are discussed elsewhere (see Phosphoric acids and phosphates). An overview of phosphoms compounds other than the phosphoric acids and phosphates is given herein. These compounds constitute a large variety of phosphoms compounds that are either nonoxide derivatives or derivatives of phosphoms ia oxidation states lower than + 5. These phosphoms compounds are manufactured only from elemental phosphoms (qv) obtained by reduction of naturally occurring phosphate rock (calcium phosphate). 

Many plants outside of North America pfill or granulate a mixture of ammonium nitrate and calcium carbonate. Production of this mixture, often called calcium ammonium nitrate, essentially removes any explosion hazard. In many cases calcium nitrate recovered from acidulation of phosphate rock (see Phosphoric acid and the phosphates) is reacted with ammonia and carbon dioxide to give a calcium carbonate—ammonium nitrate mixture containing 21 to 26% nitrogen (23). 

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. 

Phosphates. The primary constituent of phosphate rock is fluorapatite, Ca3FP2022- Industrial phosphates including phosphate fertilizers (qv), phosphoric acid, and calcium phosphates (11) (see Phosphoric acid and the phosphates) are obtained from the large deposits of fluorapatite found in Florida in the United States, and in Morocco. Because phosphate rock is too insoluble to be useful as a fertilizer, it is converted to superphosphate [12431 -88-8] Ca(H2P0 2 CaSO, by H2SO and to triple superphosphate [7758-23-8] by H PO (l )- Phosphoric acid may also be... 

Rare earth oxides and phosphors Ceramics (AI2O3) and glasses Mining ores and rocks Superconductors and precursor materials Thin films... 

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... 

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