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MAGNESIUM COMPOUNDS

Vol 15

Magnesium Carbonate
Occurrence. Chemical reactions in the system MgOCO2H2O result in a series of normal carbonates which include the following
mineral species: magnesite [13717-00-5], MgCO3; barringtonite [5145-48-2], MgCO32H2O; nesquehonite [14457-83-1], MgCO33H2O; and lansfordite [61042-72-6], MgCO35H2O. These reactions also produce a series of basic, ie, hydroxyl-containing, magnesium carbonates having the general formula xMgCO3yMg(OH)2zH2O. This basic carbonate series includes artinite [12143-96-3], MgCO3Mg(OH)23H2O; hydromagnesite [12072-90-1], 4MgCO3Mg(OH)24H2O; dypingite [12544-02-4], 4MgCO3Mg(OH)25H2O (34); and an unnamed octahydrate [75300-49-1], 4MgCO3Mg(OH)28H2O (35,36). Hydromagnesite is the most stable of the basic carbonates at ambient temperatures, humidities, and partial pressures of CO2. In its natural form magnesite is a member of the calcite group of rhombohedral carbonates. It is the most common species of the naturally occurring magnesium carbonate minerals. The other magnesium carbonate species are rare in occurrence compared to magnesite (37). Because of the similar sizes of the ionic radii of magnesium and iron, magnesite forms a complete solid solution series with the mineral siderite [14476-16-5], FeCO3. The mineral which forms the species intermediate between magnesite and siderite is known as breunnerite, (Mg,Fe)CO3. Properties. The physical properties of the normal magnesium carbonates are given in Table 3, those of the basic magnesium carbonates in Table 4. Magnesium carbonate is insoluble in CO 2-free water. The solubility products, Ksp, for magnesium carbonate and some hydrates follow (38). Compound magnesite MgCO3H2O barringtonite nesquehonite Solubility product, Ksp
1:0 105 2:7 105 2:3 105 8:9 106

Table 3. Physical Properties of Magnesium Carbonates Parameter mol wt crystal system space group lattice constants, nm a b c angle, degree b Z density, calculated, g/cm 3 hardness, Mohs' color melting point, C index of refraction d heat of formation, H298, kJ/mol free energy of formation, G298, kJ/mol
a
d

Magnesite 84.32 hexagonal R3c 0.46332 1.5015

Barringtonite 120.35 triclinic

Nesquehonite 138.37 monoclinic P21/n 1.2112 0.539 0.77697

Lansfordite 174.4 monoclinic P21/n

0.9115 0.6202 0.6092 94.00 95.53 108.87 4 2.825 colorless 1.458, 1.473, 1.501

90.42 4 1.837 2.5 colorless to white 1.412, 1.501, 1.526


1726:3

1095:8 1012:1

6 3.009 3.55.0 white c 402480 1.510, 1.700

1.730 2.5 white 1.456, 1.476, 1.502


2199:5

Refs. 3,30, and 3741. Number of formulas per unit cell. c Material decrepitates. d To convert J to cal, divide by 4.184.
b

Table 4. Physical Properties of Basic Magnesium Carbonates Parameter mol wt Artinite 196.70

Hydromagnesite 467.67

Dypingite 485.69

Octahydrate 539.74

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

MAGNESIUM COMPOUNDS

Vol 15

crystal system space group lattice constants, nm a b c angle, degree b Z density, calculated, g/cm3 hardness, Mohs' color index of refraction
a b

monoclinic C2 or C2/M 1.656 0.315 0.622 99.15 2 2.039 2.5 white 1.488, 1.534, 1.556

monoclinic P21/C 1.011 0.894 0.838 114.58 2 2.254 3.5 white 1.458, 1.473, 1.501

monoclinic

white 1.412, 1.501, 1.526

white to gray 1.456, 1.476, 1.502

Refs. 3,30 and 3741. Number of formulas per unit cell.

The relatively high solubility of magnesium bicarbonate, Mg(HCO3)2, at low temperature and high partial pressures of CO2 permits the separation of magnesium compounds from impurities. The high degree of solubility of magnesium bicarbonate was first utilized in the mid-nineteenth century in the Pattison process to prepare pure magnesium compounds from calcined dolomite [17069-72-6] (42). Normal, hydrated, and the basic magnesium carbonates react with acids to yield salts which can be recovered by crystallization (43). Magnesium carbonate forms many double salts, some of which are listed in Table 5.
a

Table 5. Double Salts of Magnesium Carbonate Salt MgCO3MgCl27H2O MgCO3MgBr28H2O MgCO3MgBr27H2O MgCO3NH4CO34H2O
a

CAS Registry Number [11140-13-9] [75198-49-1] [75198-50-4] [22450-55-1]

Salt MgCO3K2CO38H2O MgCO3KHCO34H2O MgCO3Rb2CO34H2O MgCO3Na2CO3

CAS Registry Number [75198-51-5] [19154-48-4] [75198-52-6] [19086-68-1]

Ref. 44.

Because of this solid solution, natural magnesite contains varying amounts of iron which can affect the ultimate use of the material. Small amounts of calcium and manganese may also be present. Production. Naturally occurring magnesite is widely distributed throughout the earth's crust and is used as a starting raw material for the production of magnesia, MgO, and other magnesium compounds (45,46). It occurs as crystalline magnesite, and in the cryptocrystalline forms. Economically exploitable deposits of natural magnesium carbonate occur in many countries. The world's leading producers of natural magnesite in 1991 included Australia, 231,000 metric tons; Austria, 667,000 t; Brazil, 245,000 t; Canada, 174,000 t; China, 1,050,000 t; Greece, 240,000 t; India, 257,000 t; Russia, 2,205,000 t; Spain, 205,000 t; Slovakia, 726,000 t; Turkey, 309,000 t; Ukraine, 1,345,000 t; United States, 100,000 t; the Yugoslav republics, 240,000 t; and the various republics of the Commonwealth of Independent States of the former Soviet Union (44). North Korea is reported to have a production capacity of 2;000;000 t=yr. In the Americas, natural magnesite deposits are currently being mined at Gabbs, Nevada; Mount Brussilof, British Columbia; and Brumado, Bahia, Brazil (47). Deposits of magnesite are also known to exist in Washington state and in the province of Quebec. Benefication. The purity of naturally occurring magnesite ores are quite variable. The ores can range from nearly pure magnesite to magnesite intermixed with other carbonate mineral species, quartz, clay minerals, and other aluminosilicates. The purity of the mined ore can be increased by several processes of mineral benefication (see MINERAL RECOVERY AND PROCESSING). Selective mining practices can produce a relatively good quality of industrial-grade magnesium carbonate. Ores can also be upgraded by means of heavy media separation. High quality magnesium carbonate is produced by means of froth flotation (qv) (48). Manufacture. Synthetic forms of magnesium carbonate and basic magnesium carbonates can be produced by the carbonation of magnesium hydroxide slurries. Anhydrous magnesium carbonate, MgCO3, can be prepared in aqueous systems only under very high partial pressures of carbon dioxide (qv), CO2 (49). Magnesium carbonate trihydrate, synthetic nesquehonite, is formed under normal conditions of temperature and pressure regardless of the methods of preparation (50). If the carbonation of magnesium hydroxide slurry is carried out at 345 517 kPa (50 75 psi) and at temperatures below 50 C, the more soluble bicarbonate is formed and is then separated from the other reaction products by means of filtration with subsequent crystallization. The trihydrate form is recovered from the filtrate by decarbonation under vacuum or by filtration. Boiling the bicarbonate solution or drying the trihydrate precipitate at about 100 C produces the basic magnesium carbonate 4MgCO3Mg(OH)24H2O, a synthetic version of the naturally occurring mineral hydromagnesite. Hydrated and basic magnesium carbonates can also be produced from calcined dolomite, CaOMgO, or half calcined dolomite, MgOCaCO3, by means of slaking, carbonation, filtration, and decarbonation. Magnesium carbonate trihydrate can be produced from calcined dolomite dust by means of the Judd process (51). In this process the calcined dolomite kiln dust is first slaked to hydrate the CaO. Deliming of the solution is achieved through precarbonation. The magnesium-rich solution is then carbonated, pressure carbonated, decarbonated, filtered, and finally dried. The principal producers of synthetic normal magnesium carbonates and basic magnesium carbonates are J.T. Baker Inc., Philipsburg, New

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

MAGNESIUM COMPOUNDS

Vol 15

Jersey; GTE Corp., Sylvannia Chemicals Division, Towanda, Pennsylvania; Mallinkrodt Specialty Chemicals, St. Louis, Missouri; Marine Magnesia, San Francisco, California; Morton Specialty Chemicals, Manistee, Michigan; and Ube Chemical Industries, Tokyo. Economic Aspects. The 1991 world production of natural magnesites was 9.97 million metric tons; in 1992 world production of natural magnesite and other minor magnesium carbonates was estimated to be 12.5 million metric tons (52). In 1990 the United States consumed 2821 metric tons of synthetic, precipitated magnesium carbonate with a value of $703,000 (52). The prices quoted in July 1993, for light technical-grade magnesium carbonate ranged from $0.73 to $0.78 per pound and for USP grade the price range was $0.74 to $0.80 per pound (53). Uses. Thermal decomposition of any of the species of normal and hydrated magnesium carbonates produces magnesia, MgO, the physical and chemical properties of which are determined by the purity of the original natural magnesite, the method of magnesite ore benefication, the temperature, and degree of calcination. Many of the Austrian magnesite deposits contain breunnerite, (Mg,Fe)CO3. The presence of up to 6% iron as Fe2O3 limits the use of this form of natural magnesite to the production of low quality magnesia refractory brick. The physical properties of magnesia prepared by calcination of basic magnesium carbonate are available (54). Natural magnesites are calcined at temperatures approaching 2100C (dead burned) for the production of synthetic periclase, MgO, a refractory material used in the steel industry. Magnesites that are calcined at 500550C (light burned) find use as magnesium supplements for animal feed (see FEEDS AND FEED ADDITIVES), as components of oxysulfate cement (qv), in sugar (qv) processing, and in the flue-gas scrubbing of gaseous SO2 emissions (see SULFUR REMOVAL AND RECOVERY). Natural magnesites are used in the pollution control industry as acid neutralizing agents and in gaseous SO2 scrubbers (see AIR POLLUTION CONTROL METHODS). The only processing that the natural magnesite receives for these applications is crushing and screening to a uniform size. Precipitated magnesium carbonate and basic magnesium carbonates are calcined to produce magnesia having surface areas of ca 200 m2 =g. These high surface area magnesias are used as thickening agents in the sheet molding of rubber and as scorch retarders in chloroprene rubbers (see RUBBER, COMPOUNDING). Precipitated carbonates are useful as extenders in paint (qv) and pigments (qv). Specially prepared spherical magnesium carbonate finds use as an extender in spray paints (55). Crystalline magnesium carbonate has found use in various optical applications. Precipitated carbonates are used in smoke suppressants, fire-extinguishing compounds, flooring products, ceramics (qv), specialty inks (qv) for high speed printers, and as granular filtering media (see FLAME RETARDANTS). USP-grade anhydrous magnesium carbonate is used as a flavor impression intensification vehicle in the processed food industry (see FLAVORS AND SPICES). Basic magnesium carbonates are used as free flowing agents in the manufacture of table salt, as a bulking agent in powder and tablet pharmaceutical formulations, as an antacid, and in a variety of personal care products (see PHARMACEUTICALS). Health and Safety Factors. Magnesium carbonates and its basic hydrated forms have minimal toxicological effects when encountered at normal exposure levels. However, in response to the possible adverse effects of long-term exposure to magnesium carbonate dust, the ACGIH has established a TLV TWA of 10 mg= m3 for magnesite dust that contains no asbestos (qv) fibers and less than 1% free silica (56). These compounds are best utilized within a conscientiously applied program of industrial hygiene (qv).

Kirk-Othmer Encyclopedia of Chemical Technology (4th Edition)

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