Magnesite and Magnesia

Magnesium is the eighth most abundant element in the earth's crust and the third most plentiful element in seawater. It is found in more than sixty minerals and in brines and seawater as a magnesium salt. One of the more important magnesium minerals is magnesium carbonate, MgCO3, with a theoretical maximum magnesia, MgO, content of 47.6%; this carbonate form represents the world's largest source of magnesia. The next most used sources for magnesia are magnesia-rich brines and seawater, where it occurs as magnesium sulfate and magnesium chloride. Other commercially important magnesium-bearing minerals are dolomite, CaMg(CO3)2, which serves the aggregate industry as well as the chemical industry; brucite, Mg(OH)2, which is used in the production of both caustic and sintered magnesia; olivine, ([MgFe]2-SiO2), which serves the refractory and heat storage industries; talc, (H2Mg3(SiO3)4), which serves several industries as a filler and as an ingredient in cosmetics; and serpentine, (H4Mg3SiO9). All these minerals are of commercial value because of the desirable characteristics given to them by magnesia and by its placement in the crystal structure. These minerals are the starting raw materials for a wide range of products. These include the production of magnesium metal, and several grades of magnesia used for the production of both sintered magnesia for refractory manufacture and lighter fired caustic magnesia, the latter is used in fluxes, fillers, insulation, cements, decolorants, fertilizers, chemicals, in the treatment of waste water including pH control, and in the removal of sulfur compounds from exhaust stacks. Magnesite is one of several major minerals possessing a dual character, i.e., non-metallic industrial mineral because of its principal end use as a calcined/dead burned raw material in non-metallic end products and magnesium metal. A large percentage of the magnesia used to produce magnesium metal comes from seawater1 brines. The total primary metal production worldwide is about 350 ktpy. This report reviews magnesite solely as an industrial non- metallic raw material. Magnesite for most refractory purposes must have a content of sintered magnesia above 85%, with a preference for those sources that have the potential for 90 to 98% magnesia values. Dolomite, used in large tonnages because of its physical properties in the construction industry, also has a use in the chemical and the refractory industry. In its calcined form, dolomite is used as a slag addition in the making of steel, and it is used in a high-purity calcine to precipitate magnesium hydroxide from brines or seawater. The precipitated magnesium hydroxide is intermediate for the production of deadburned clinker for refractories and the production of magnesium metal. In many cases the high-purity magnesium hydroxide obtained by precipitation with calcined dolomite, or in some cases limestone, has supplanted much of the world's production of magnesia from the natural mineral magnesite. This is especially true of the United States and in major industrialized areas of Europe and Japan. The best known of the minerals directly and widely exploited for its magnesia content is magnesite (MgCO3), one of the calcite group of rhombohedra1 carbonates, which includes calcite (CaCO3), siderite (Fe2CO3), and rhodocrosite (MnCO3), among others. The members of this group enter into a wide range of substitutional solid solutions when the positive ions have similar radii. The radii of magnesium and iron ions are within 6% of each other; hence magnesite and siderite form a complete series, of which the mineral breunnerite (ferroan magnesite) is a well known end member. The radii of calcium ion is 36% larger than that of magnesium ion and only limited substitution exists at each end of the MgC03-CaCO3 series. Dolomite is not a member of the calcite group, but it occurs when calcium and magnesium ions alternate in equal number in an ordered structure among carbonate ions. The result of this relationship is that calcite and dolomite are commonly found intermixed with magnesite. They occur, commonly, as identifiable crystal entities, which can be separated to a varying degree from the magnesite by benefication techniques. Magnesite, when pure, contains 47.8% MgO and 52.2% CO,. The pure mineral is found occasionally as transparent crystals resembling calcite. Magnesite principally contains variable amounts of the carbonates, oxides, and the silicates of iron, calcium, manganese, and aluminum. Although the genesis of natural magnesite deposits can be complex, it is distinguished in nature in two distinct physical forms, namely crystalline, (with a wide range of visible crystal sizes) and cryptocrystalline, sometimes referred to as amorphous, where the crystal size is not detectable to the eye and will range from 1 to 10 pm. The two types not only differ in crystal structure but in the sizes of the deposits and in modes of formations. The crystalline form has a Mohs hardness of 3.5 to 4.0. The color range is from white to black with shades of yellow, blue, red, or gray. The color is not a significant indicator of purity but in a given deposit an experienced person can often roughly grade the magnesite by observing color and crystallinity. Macrocrystalline deposits occur in relatively few, but generally large, deposits on the order of several million tons. The ore shows a marble-like crystal structure and belongs to the sedimentary or metasomatic groups of origin. The cryptocrystalline variety of magnesite frequently occurs in many small deposits, although there are exceptions. Cryptocrystalline magnesite is typically massive with no cleavage and is sometimes descriptively called bone magnesite. The fracture is usually conchoidal, with a hardness of 3.5 to 5.0. The color is mainly white, but it can have tints of yellow, orange, or buff. Accessory silaceous minerals such as serpentine, quartz, or chalcedony are usually present. Calcium minerals are normally absent or in low concentration, this contrasting with the macrocrystalline form where calcium minerals are almost invariably present and some- times in high concentration. The specific gravity of cryptocrystalline magnesite ranges between 2.90 and 3.00, whereas the value of pure crystalline magnesite is 3.02. In actuality, the normal specific