Rock phosphates

Never found free in nature, it is widely distributed in combination with minerals. Phosphate rock, which contains the mineral apatite, an impure tri-calcium phosphate, is an important source of the element. Large deposits are found in Russia, in Morocco, and in Florida, Tennessee, Utah, Idaho, and elsewhere. 

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. 

Vanadium is found in about 65 different minerals among which are carnotite, roscoelite, vanadinite, and patronite, important sources of the metal. Vanadium is also found in phosphate rock and certain iron ores, and is present in some crude oils in the form of organic complexes. It is also found in small percentages in meteorites. 

Uranium, not as rare as once thought, is now considered to be more plentiful than mercury, antimony, silver, or cadmium, and is about as abundant as molybdenum or arsenic. It occurs in numerous minerals such as pitchblende, uraninite, carnotite, autunite, uranophane, and tobernite. It is also found in phosphate rock, lignite, monazite sands, and can be recovered commercially from these sources. 

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. 

Phosphate ores Phosphate plastici Phosphate rock... 

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 ... 

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... 

Production Technology. A moderately high (33.5% 2 5 BPL) grade of phosphate rock is required for the production of a product that contains 20% available P2 5 Significant process variables in the manufacture of NSP are Hsted in Table 5. 

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. 

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... 

The complete chemistry of TSP production has been studied and reported in great detail (34). As in the production of NSP there are also reactions with impurity minerals. In fact, the increasing amounts of such impurities in U.S. commercial phosphate rocks, especially those from Florida, are now reflected in somewhat lowered amounts of citrate-soluble P2O5 product. The range of constituents in commercial TSP from wet-process acid and phosphate... 

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. 

Production of nitric phosphates is not expected to expand rapidly ia the near future because the primary phosphate exporters, especially ia North Africa and the United States, have moved to ship upgraded materials, wet-process acid, and ammonium phosphates, ia preference to phosphate rock. The abundant supply of these materials should keep suppHers ia a strong competitive position for at least the short-range future. Moreover, the developiag countries, where nitric phosphates would seem to be appealing for most crops except rice, have already strongly committed to production of urea, a material that blends compatibly with sulfur-based phosphates but not with nitrates. 

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 ... 

Some commonly used primary nutrient fertilizers are incidentally also rich sources of calcium. Ordinary superphosphate contains monocalcium phosphate and gypsum in amounts equivalent to all of the calcium originally present in the phosphate rock. Triple superphosphate contains soluble monocalcium phosphate equivalent to essentially all the P2 5 product. Other fertilizers rich in calcium are calcium nitrate [10124-37-5] calcium ammonium nitrate [39368-85-9] and calcium cyanamide [156-62-7]. The popular ammonium phosphate-based fertilizers are essentially devoid of calcium, but, in view of the natural calcium content of soils, this does not appear to be a problem. 

Table 14. World Reserves and Resources of Phosphate Rock ...

At the present rate of world phosphate rock consumption (150 x 10 t/yr), the total world reserve (Table 14) is sufficient for about 200 years, and the resource would be sufficient for nearly 900 years. At expected increased rates of consumption, the reserves and resources are adequate for at least 150 years and 700 years, respectively. At projected rates of consumption, the high grade reserves in Florida probably will be exhausted by the year 2000. Rock production from the Florida reserve presentiy constitutes about 80% of all United States production and about one-third of world production (106). This rate of depletion is causing increased interest in western United States reserves which represent nearly 80% of present U.S. total reserves. 

Bilhons of metric tons of phosphate rock also are present offshore in the oceans, eg, best estimates are that a biUion tons of pellets that may contain about 30% P2 5 present in a Baja California—Mexico deposit alone. Other areas in the world that contain large, unevaluated amounts of phosphate include AustraUa, Alaska, Africa, the Near East, Pern, Colombia, Brazil, the People s RepubHc of China, MongoHa, and the former Soviet Union. 

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. 

Calcium. Calcium is the fifth most abundant element in the earth s cmst. There is no foreseeable lack of this resource as it is virtually unlimited. Primary sources of calcium are lime materials and gypsum, generally classified as soil amendments (see Calcium compounds). Among the more important calcium amendments are blast furnace slag, calcitic limestone, gypsum, hydrated lime, and precipitated lime. Fertilizers that carry calcium are calcium cyanamide, calcium nitrate, phosphate rock, and superphosphates. In addition, there are several organic carriers of calcium. Calcium is widely distributed in nature as calcium carbonate, chalk, marble, gypsum, fluorspar, phosphate rock, and other rocks and minerals. 

Flotation or froth flotation is a physicochemical property-based separation process. It is widely utilised in the area of mineral processing also known as ore dressing and mineral beneftciation for mineral concentration. In addition to the mining and metallurgical industries, flotation also finds appHcations in sewage treatment, water purification, bitumen recovery from tar sands, and coal desulfurization. Nearly one biUion tons of ore are treated by this process aimuaHy in the world. Phosphate rock, precious metals, lead, zinc, copper, molybdenum, and tin-containing ores as well as coal are treated routinely by this process some flotation plants treat 200,000 tons of ore per day (see Mineral recovery and processing). Various aspects of flotation theory and practice have been treated in books and reviews (1 9). 

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). 

In the geochemistry of fluorine, the close match in the ionic radii of fluoride (0.136 nm), hydroxide (0.140 nm), and oxide ion (0.140 nm) allows a sequential replacement of oxygen by fluorine in a wide variety of minerals. This accounts for the wide dissemination of the element in nature. The ready formation of volatile silicon tetrafluoride, the pyrohydrolysis of fluorides to hydrogen fluoride, and the low solubility of calcium fluoride and of calcium fluorophosphates, have provided a geochemical cycle in which fluorine may be stripped from solution by limestone and by apatite to form the deposits of fluorspar and of phosphate rock (fluoroapatite [1306-01 -0]) approximately CaF2 3Ca2(P0 2 which ate the world s main resources of fluorine (1). 

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). 

Sulfide collectors ia geaeral show Htfle affinity for nonsulfide minerals, thus separation of one sulfide from another becomes the main issue. The nonsulfide collectors are in general less selective and this is accentuated by the large similarities in surface properties between the various nonsulfide minerals (42). Some examples of sulfide flotation are copper sulfides flotation from siUceous gangue sequential flotation of sulfides of copper, lead, and zinc from complex and massive sulfide ores and flotation recovery of extremely small (a few ppm) amounts of precious metals. Examples of nonsulfide flotation include separation of sylvite, KCl, from haUte, NaCl, which are two soluble minerals having similar properties selective flocculation—flotation separation of iron oxides from siUca separation of feldspar from siUca, siUcates, and oxides phosphate rock separation from siUca and carbonates and coal flotation. 

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. 

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