CHAPTER 24

MAGNESITE AND RELATED MINERALS

BY RAYMOND BIRCH* E. AND OSCAR M. WICKEN+

mineral magnesite, formerly the source of nearly all magnesia, now shares this role with brucite, dolomite, and the world's natural and artificial brines. The mineral magnesite is the normal carbonate of magnesium, MgCO,, composed when pure of 47.6 pct MgO and 52.4 pct CO,. It is one of the calcite (CaCO,) group of rhombohedra1 carbonates, which also includes dolomite, CaCO,.MgCO,, and siderite, FeCO,. Magnesite does not form an isomorphous series with calcite or dolomite; consequently, these lime-bearing carbonates commonly present in magnesite deposits are there only as mechanical mixtures. Magnesite and iron carbonates form a continuous isomorphous series and therefore are inseparable mechanically. The variety of magnesite known as breunnerite is an isomorphous mixture of iron and magnesium carbonates. Magnesite may be either crystalline or amorphous (cryptocrystalline). The former, which includes breunnerite, is often termed spathic magnesite. Crystalline magnesite varies from finely to coarsely crystalline in texture and has a hardness of 3.5 to 4. The color is white, yellowish, blue-gray to drab, red, pink, black, or mottled. It is seldom found pure but usually contains variable amounts of iron, lime, silica, and sometimes manganese. The color cannot be used as an index of purity. The cryptocrystalline variety is perhaps the more common type but the crystalline variety usually occurs in larger deposits. The amorphous type is fine grained and compact, showing no cleavage. It is usually snow white but sometimes is light to pale orange yellow or buff, owing to impurities. The fracture is conchoidal to uneven and the hardness 3.5 to 5. Silica may be present as inclusions of serpentine, quartz, chalcedony, or other minerals. The lime and iron contents are usually low. In general, amorphous magnesite is somewhat purer than the crystalline variety. The specific gravity of cryptocrystalline magnesite is 2.90 to 3.00. Pure crystalline magnesite has shown a specific gravity of 3.02 but iron

HE

+ Northwest Magnesite Co., Pittsburgh, Pennsylvania.

521

* Harbison-Walker Refractories Co., Pittsburgh, Pennsylvania.

522

INUTJSTHIAJ, MINERALS AND ROCKS

carbonate, conin~only present, raises the specific gravity; lypical figures for breunnerite are 3.08 to 3.1.3. Magnrsite dissociates on heating, by the release of carbon dioxide. The p r o d ~ ~is tmagnesia (l\/lgO). which develops, either simultaneously c or. lipor1 l'urther. heating. ;I crys~alline structure and is then known as periclase. The n ~ i r ~ e r a l periclase occurs in nature but is rather rare and is not f'ourld ill 11.ot.1iable drpnsits. When dead-burned or sintered, magnesiurrl ovitle is Y P S ~ S ~ ~ I I O I hydralion and carbonation at the temperaI ture and pressLwc1 of the, ~ t r r ~ o s p l ~ ~ r ~ .
NOMENCLATURE OF PRODUCTS

hlagnesite actually refers only to the mineral NlgCO,, but common usage applies it to most of the manufactured products with a classifying prefatory word; e.g., dead-burned magnesite and caustic magnesite. For the most part. thesc products are actually magnesia (MgO) and the universal use of this term has been urged by some. However, when magnesia froni sea water and brines made its appearance in the world's markets described as "rnagnesite," the last opport~~nity dislodge the to older terms became a lost cause. Dead-burner1 Magnesits is the granular product obtained by calcining n~agnesite,or other substa~icesconvertible to magnesia upon heating, above 1450C long enough to form dense, weather-stable granules suitable lor. use as a refractory or in refractory products (ASTM definition 'I . Ca~~sticr Magnesite is the product obtained by calcining magnesite, or other substances convertible to magnesia upon heating, at a temperature not exceeding 1200(:. From 0.5 to 7 pct ignition loss is shown by the product, depending upon the desired degree of reactivity. Generally, the lower the ignition loss, the lower the reactivity.
ORIGIN,WCCURRENCE, AND DISTRIBUTION OF DEPOSITS'3,"

The tr.ystallinc. magnesi~eis generally formed by the alteration of dolomite by rliagnesiarl solutions associated with intrusions. T h e cryptocrystalline variety is a n alteration product of serpentine or allied magnesian rocks. It is common in serpentine areas and occurs in fissures or crush zones mixed with serpentine and some opal or chalcedony, also produced by the breakdown of the serpentine. This type of magnesite generally occurs in small deposits, as in the California coast ranges and on the Grecian island of Euboea. The largest deposits of crystalline magnesite in the United States are those near Chcwelah, Washington, and near Gabbs, Nevada. They represent replacements of dolomite under the influence of later intrusive~. Probably the largest deposits in the world (also crystalline) are

MAGNESITE AND RELATED MINERALS

523

those at Veitsch, in Styria, Austria, and in Manchuria near Niehsinshan. The Austrian deposit is a replacement of dolomite formed following the intrusion of porphyry and other acidic and basic rocks. In the United States, magnesite has been mined in Washington and California for many years but resources in the latter state are running out. During World War 11, small-scale production began in Texas and large-scale operations in Nevada. In late 1947, mining had ceased at least temporarily in California and the ~roducersof that state were relying on crude magnesite shipped from Nevada to be burned in California to supplement the much greater tonnages of magnesite produced from sea water and bitterns. In Canada, a large deposit of crystalline magnesite occurs in British Columbia7 but the only deposit being worked is that associated with dolomite in the Grenville district of Quebec. For a single year, 1944, Nevada was reported to be the leading producer of magnesite. The Government-owned plant operated by Basic Magnesium Inc. and later by Anaconda Copper Co. near Gabbs, Nevada, mined, concentrated and calcined rock (in shelf roasters) to be trucked 350 miles to the magnesium-metal plant at Las Vegas. When the latter plant, which required 300 tons daily of caustic magnesite, ceased operation, sufficient ore had been developed to operate the concentrator at full capacity for 10 years. Viewed as to thcir long-time influence on the world magnesite industry, the most important deposits have been those of central Europe. This magnesite is of the crystalline breunnerite type and was formed by the replacement of limestone by the action of ascending aqueous solutions carrying magnesium and iron compounds. Of the many deposits of this type that exist in a belt through central Europe, about a dozen are large enough to be workable. The narrow belt in which they occur extends westward from Semmering, Austria, the most important occurrences being at Semmering, Veitsch, Brietenau, Trieben, Radenthein, and Dienten. The deposits are lenses, of which by far the most celebrated and most important is the one at Veitsch, near Mittendorf in Styria, Austria (its reserves were estimated at 50 years in 1946). The magnesite lens at Radenthein (estimated proved reserves, 20 years) is also of considerable extent. Although this belt comprises the major part of the workable deposits of central Europe, Yugoslavia and Czechoslovakia also are p r o d u ~ e r s . ~ ~ The USSR was the world's leading producer of magnesite before World War 11. The U. S. Bureau of Mines reported USSR average annual ~roductionof crude magnesite for the five years prior to 1939 as 535,000 tons. Comparative data in thousands of tons were 403 for AUstria, 233 for Manchuria, 157 for the United States, 134 for Greece, and

524

INDIJSTRIAZJ MINERALS AND ROCKS

83 for Czechoslovakia. Dead-burned magiiesite from Manchuria first entered the United States markets in 1936, and by 1941 accounted for 91 pct of all importations. Greece and British India are the only important producing countries whose major output is derived from cryptocrystalline magnesite. In British India. most of the production is from the Salem district, in the Madras Presidenc~.,but some supplies come from Mysore. Magnesite exportatiorls from Greece began in 1870 and that country continued to hold an important world position in the industry until World War 11. A peak productiorl was reached in 1916 at about 200,000 tons (crude rock j . Deposits large enough to have a bearing upon the future of the industry occur also in Korea, Brazil, and Argentina. Australian supplies arc adequate for her own needs.
PROSPECTING AND EXPLORATION

The conjunction of dolomitic or calcareous areas with one of igneous activity, or an area wherein serpeiitinization is abundant, are possible locations of the various magnesites. Magnesitic formations are generally more resistant to weathering than associated formations, and consequently bold outcrops characterize magnesite deposits. Newly discovered outcrops are sampled by surface chipping and by shallow trenching. Field differentiation between magnesite of commercial purity and magnesite containing excessive lime can be aided by the use of cold dilute hydrochloric acid. Calcite will effervesce under hydrocloric acid whereas magnesite will not. After a preliminary idea of the size and quality of the deposit has been obtained, diamond drilling is employed to further delineate the ore body, particularly in massive deposits. The evaluation of magnesite deposits is based on the amount of silica, lime, and alumina contained, and on the degree of dispersion of these impurities. Generally, to be of grade acceptable to the refractories industry, the magnesite prior to dead-burning must contain at least 90 pct magnesium carbonate.
MINING AND PROCESSING

The mode of mining is dependent upon the type of deposit. Massive deposits are generally worked by modified open-pit quarry methods; others are worked both by narrow surface openings and by underground drifting and stoping. Washington Washington magnesite occurs as massive replacements in dolomite. Haphazardly distributed throughout the magnesite are stringers and lenses of siliceous and calcareous impurities. The magnesite deposits are found in several places along the formation known as the Stensgar

MAGNESITE AND RELATED MINERALS

525

dolomite. Although magnesite outcroppings are numerous in this formation, only a few are being exploited. These are the Finch, Allen-Moss, Keystone, and Red Marble quarries. The Finch and Allen-Moss were the original quarries of the Northwest Magnesite Co. and until 1445 all of the production came from those two operations. In 1946, the Keystone deposit was brought into after extensive diamond drilling had outlined the ore body. Prior to the actual mining at the Keystone, a large cap of dolomite was removed in order that the Finch and Allen-Moss quarry methods could be used. At the present time (1948) the Red Marble deposit is being developed. It will be brought into production in 1949. In all cases the mining operations are similar: 20 to 30-ft levels are opened up and advanced in a series of working faces, which may be just wide enough to allow the operation of a power shovel or many times as wide. Drilling for primary rock breakage is accomplished by putting down vertical wagon drill holes from the bench above a given working level. Some secondary jackhammering and plugging is necessary to reduce the rock to sizes that can be handled by power shovels. The broken ore is loaded into trucks, which discharge into oreways. Much of the Finch rock is trucked directly to the mill. At the Finch and Allen-Moss quarries, the magnesite is withdrawn from the oreways into a train of underground cars and is transported 1000 to 2000 f t to the milling plant. At the Keystone operation, all oreways feed into one gathering oreway, which in turn discharges into an underground jaw crusher. The crushed rock is conveyed by belt several hundred feet underground and then discharged into a surface bin, which loads directly into aerial tramway buckets. The tramway delivers the ore to the milling plant near the Finch quarry, 4 miles away. Rough separation of ore and waste such as is possible with a power shovel is made at the quarry faces. Prior to 1943, most of the ore was hand-sorted but since the completion of the heavy-media concentrating plant, all hand sorting has been eliminated. Crude ore is treated as follows: The ore is brought from the various operations by aerial tramway, mine cars and conveyor belts, to a coarseore bin, or, for the Keystone ore, to the middling-ore bin. The ore is crushed by means of jaw and gyratory crushers, washed and screened by means of rotary scrubbers and vibrating screens, and the - 19 $in. fraction is discharged into the heavy-media cone feed bin. The minus $-in. sands are stock-piled for future trealment. The sized ore from the cone feed bin is beneficiated in a 20-ft diameter heavy-media cone. The floats, or waste, consisting of dolomite, quartz, and other undesirables, are rejected to a tailings pile, and the sinks, or magnesite, are crushed by gyratory and roll crushers to pass a fine screen in closed cir-

526

INI)lISTRIAI, MINERALS AND ROCKS

cuit with the crusher. Most of the crushed magnesite is then transported 5 miles by aerial tramway to the calcining plant, where it is blended wit11 iron ore and dead-burned at about 2900F in six rotary kilns, to prod~~ce "standard" dead-burned grains. Five of the kilns are 7 ft 6 in. by 125 ft long. The sixth kiln is 9 ft ( in. by 8 ft 6 in. in diameter by 5 306 f t long. The large kiln has 10 forward flow coolers. The sniall kilns have separt~te rotary aftercoolers. The standard grains are crushed and scre~nedlo a variety of sizes for different refractory applications. 'The rnagnesite that is not directly transported to the calcining plant is conveyed by conveyor belt to a flotation mill for further beneficiation. Some of the minus 4-in. screenings frorn the heavy-media mill are also treated ill the flotation mill. The fine magnesite is further reduced to minus 65-mesh size by a ball mill in closed circuit with a classifier. Pure magnesite is floated away from impurities. The magnesite concentrate is thickened, filtered, dried in a rotary drier and transported to the calcining plant by aerial tramway. At the calcining plant, the concentrates are dead-burned in an 8-ft 6-in. by 125-ft rotary kiln. This high-grade burned magnesite is cooled and stored in bins for shipment brickmaking centers. to e a s t e r ~ ~ California California rnagnesite has been reported in many places throughout the state. However, very few of the deposits are of commercial size. The magnesite is cryptocrystalline or amorphous material derived from the alteration of serpentine. Although deposits may have many stringers and lenses of impurities, the magnesite itself is very pure. Magnesite mined in California has been produced by several companies during the past several years. However, the mining of magnesite in this state has long since passed its peak and at present, according to M. Y. Seaton, Executive Vice President, Westvaco Chemical Division of Food Machinery and Chemical Corporation (private communication), no mines are operating in virgin ore. The Westvaco Chemical Division is engaged currently in working over a deposit of stock-piled ore at its Western mine. The only present milling operation in California involving natural magnesite is that of the Westvaco Chemical Division. The stock-piled ore froni the old Western mine is crushed and screened. Because the impurities other than lime are softer than the magnesite, a concentratiori of silica, alumina, and iron impurities tends to appear in the minus +-ill. fraction, which is rejected. The coarse magnesite is transported to Newark, California, for processing. All of this production is devoted to caustic magnesite.

MAGNESITE AND RELATED MINERALS

527

Nevada
The magnesite industry i n Nevada centers about 35 miles from Luning, at Gabbs, Nye County. The magnesite occurs as a replacement in dolomite. The deposits are similar to those in Washington in that both were formed by the action of igneous intrusives on the dolomitic formations. The individual deposits are smaller than those in Washington. The magnesite is similar to Washington magnesite in chemical analysis and appearance. The hydroxide, brucite, is found in substantial quantities throughout the formation in addition to the carbonate. This area was the scene of the large-scale Defense Plant Corporation plant operated by Basic Magnesium, Inc. For a time this operation, which has been well described in the l i t e r a t ~ r e , ' ~ ' ~ ~the largest was ~ ~ single producer of calcined magnesia in the country. All of its production was consumed in the manufacture of metallic magnesium. The operation of this plant was terminated in October 1944. At present only the privately owned Sierra Magnesite and Basic Refractories deposits are being operated. Westvaco Chemical Division together with Permanente Metals Corporation jointly own the Sierra Magnesite Co., which operates a quarry at Gabbs. They have been mining and shipping magnesite to the Pacific Coast since 1940.' Some of the crude ore is removed by open-pit methods from benches 20 to 30 ft high. Working faces are generally narrow because of small horizontal dimensions of individual pockets of magnesite. Generally dikes and intrusions of gangue are removed prior to ore breakage at any given face. Then, when the ore is shot down, it can be removed with a minimum of contamination. The broken ore is discharged through oreways to underground conveyorbelt haulage to the surface. Currently a large part of the production is also being mined by underground methods. All the crude ore is crushed and screened prior to shipment to the two companies' California processing centers.'' Near the Sierra Magnesite deposit is a deposit of ore consisting largely of brucite, owned and operated by the Basic Refractories Co., of Cleveland, Ohio. The mining of the deposit has been continuous since 1935. Open-pit benching is the method used. After the ore is shot down, the high-grade portion is selected for shipment to Ohio and the low-grade portion is stock-piled for future treatment.

Quebec
A deposit of high-lime magnesite is being mined by the Canadian Refractories, Ltd., at Kilmar, Quebec, about 70 miles northwest of M ~ n t r e a lThe magnesite occurs as a series of veins up to 30 ft wide. .~

528

INDUSTRIAL, MINERALS AND ROCKS

The veins dip about 8 i U from the horizontal and have a footwall of quartz monzonitc and ;I hanging wall of serpentine, diopside, and quartzite. From 1!)1'5 to 1036, the inirle was operated by narrow, deep, opencuts. Since 19 -16, tlic mine has been operated by underground methods. Shafts arc, sunk l o the desired level and drifts and crosscuts are driven into the vt:ins. The ore is lhen removed by shrinkage stoping. Chutes discharge into cars, which are individually hoisted to the surface ill a
cage.

The ore discharged from the cars is crushed to 5-in. size, washed, ant1 hand-sorted on a picking conveyor. The magnesite is then carried by locomotive haulage about a mile to the calcining plant, where large portions are stock-piled to obtain unilorm blending. Material withdrawn from this pile furnishes feed for the crushing operation. The crushed magnesite is ground dry in a ball mill to provide fine feed for the rotary kilns. Prior to 1947, all dead-burning was done in three 65-ft kilns. Now, howevel-, a 9 by 220-f~kiln is used. Early in 1949, a heavy-media plant was put into operation in order to obtain closer control over the quality of the magnesite produced. The Aluminum Company of Canada is mining a unique deposit of This brucite occurs as rough grains f16. brucite at Wakefield, Quebec.LL to ', in. in diameter, disseminated through a limestone matrix. The brucite content is about 29 pct of the weight of the rock. The ore is removed by power shovel and trucks from three or four 25 to 30-ft benches. The trucks haul the ore directly to an apron feeder ahead of the primary crusher. several closcly sized fracThe ore is crushed and screened to ~ r o v i d e tions for use as kiln feed. Two rotary kilns are used to calcine the brucitic limestone. Adequate reactivity of the limestone is assured by very careful control of the calcining operation. After calcination, the lime is crushed, screened, and slaked in a dry hydrator. The entire operation is controlled so that the discharge from the slaker consists of an impalpable dust of hydrated lime mixed with granules of magnesia. An ~roducts, after which the granair separator is used to separate the ~ w o ules are washed in a wet classifier. When this product is to be used for refractory purposes, it is dead-burned at the Kilmar plant ol Canadian Refractories: Ltd.
SYNTHETIC MAGNESITE

During the past decade the manufacture of dead-burned and caustic magnesias lrom niaierial sources other than natural magnesite or brucite has become increasingly important. In all but one of the commercial plants making synthetic magnesias, the basic reactions are alike. These reactions are the calcination or dead-burning of magnesium

MAGNESITE AND RELATED MINERALS

529

hydroxide obtained by precipitating it from magnesium salt solutions such as sea water, sea-water bitterns, or inland brines, by means of calcium hydroxide derived from oyster shells, limestone, or dolomite. For the precipitation of magnesium hydroxide, any of the magnesium salt solutions can be used with any of the sources of calcium hydroxide. The main consideration in establishing the choice of reactants is purely an economic one, depending on proximity of suitable raw materials. After the reactants are established for any given plant, however, the limitations of pumping and thickening equipment will prevent that plant from changing to reactants more dilute than those for which the plant was designed; that is, a plant using sea-water bitterns cannot change to the use of raw sea water, nor can one using dolomite change to one using limestone without sacrifice of production. However, the reverse changes would be entirely feasible. The size and capacity of equipment to handle and calcine limestone, oyster shells, and dolomite is about the same per unit of magnesia in all plants making synthetic magnesia. The same is true of operations pertaining to the calcination or dead-burning of magnesium hydroxide. However, the size of equipment to handle the magnesium salt solutions and the precipitated magnesium hydroxide varies considerably, depending on the choice of reactants. Plants using sea water and limestone or oyster shells require large sea-water softening systems and large thickening capacity for the precipitated magnesium hydroxide. Plants using sea water and dolomite require one half as much capacity for the sea-water softening and magnesium hydroxide-thickening equipment. This follows from the fact that in plants using dolomite the magnesium salt solution provides only half the magnesia. Plants using concentrated brines or bitterns require no softening equipment and relatively small thickening equipment, depending on the volume of liquid, which in turn depends on the concentration of magnesium salts. These last plants, however, sometimes require pretreatment of the brines in order to remove sulphates or other impurities. The ~roduction of precipitated magnesium hydroxide from sea water dates back to the end of the last century, when a small operation existed for a short time on the Mediterranean coast of France.g The Marine Magnesium Products Corporation, the first commercial ~roducerin this country, makes a variety of magnesium compounds in its plant at South San Francisco.] The raw materials are sea water and calcined limestone or dolomite. Analysis of the sea water, in grams per liter, is: l4

5 30

INDITSTRIAI, MINERALS 4ND ROCKS

This sea water is more dilute than that of the open ocean. The calcined lin~estone exceptionally pure and probably contains less than 2 pct is total impurities. 'The sea water cr~teringthe plant is chlorinated, to remove organic material, and then treated with a small amount of slaked lime, to precipitate bicarbonates as carbonates. After a thickening operation that removes most of the illsoluble impurities, the treated sea water is filtered by sand filters to yield a clean, softened solution. In the softening operalion, enough slaked lime is added to precipitate a small part of the magnesium ions as magnesium hydroxide. This makes for a niore voluminous precipitate. which helps to sweep out the silica and carbonattas. The softened arid clarified liquid is then combined with enough slaked linie to precipitate most of the remaining magnesium ions as magnesi~m~ hydroxide. The slurry of n~agnesiun~ hydroxide and spent sea water is thickened and washed to yield a pure magnesium hydroxide. The magnesium hydroxide is used as a raw material for the preparation of a multitude of different n~agnesium compounds. All of the production of this plant is consumed in the specialty markets requiring very pure materials. Three other plants using raw sea water are those of the Permanente Metals C:orporation at Moss Landing, California; the Northwest Magnesite Co., at Cape May, New Jersey, and the Dow Chemical Co., at Freeport. Texas. This last plant uses calcined oyster shells as the precipitant but the other two use calcined dolomite. Some differences, such as direct addition of calcined dolomite to the softened sea water instead of ~reliminaryslaking, exist among these plants, but essentially they operate on the same principles as the other plants described. One synthetic-magnesite plant, Westvaco Chemical Division at Newark, California, is steadily producing caustic and dead-burned magrlesitc from sea-water bitterns and dolomite. Until recently, oyster shells dredged out of San Francisco Bay furnished the calcium hydroxide used as the precipitant but now the company has a source of excellent dolomite, which it began to use in 1943. The analysis of the bitterns, which are a by-product from a local saltmaking operation, falls in the followirtg range:lWaCl, 12.5 to 16.0 pct; MgCl,, 6.0 to 8.7; MgSO,, 4.2 t,o 6.1; KC1, 1.4 to 1.9; MgBr,, 0.14 to 0.20. No removal of carbollate is necessary but sulphate must be removed before the precipitation of magnesium hydroxide or else the product will contain large quant,ities of calcium sulphate. The removal of sulphate is accomplished by combining the bitterns with calciunl &loride from another step in the operation. The gypsum thus precipitated is dried and sold. Part of the sulphate-free bittern is added to all the finely calcined dolomite in the first compartment of a two-

MAGNESITE AND RELATED MINERALS

531

stage combined slaker and reactor. After this mixture leaves the first compartment and enters the second, it is combined with the remainder of the bittern. The reaction, partially completed, is continued to cornpletion in reaction vessels under conditions of mild agitation. The product obtained is a semirigid, spongelike structure that thickens and filters speedily. The completely reacted slurry from the last reaction vessel is washed with softened fresh water in a series of five 55-ft thickeners. The underflow from the last thickener, containing about 2.2 Ib Mg(OH), per gallon, is sent either directly to rotary vacuum filters or to batching tanks for adjustment of composition by adding certain materials, and then to filters. In either event, the filter cake is fed into rotary kilns for the production of dead-burned magnesite and caustic calcined magnesite. The dead-burning kiln has a feed end diameter of 11 ft, a discharge end diameter of 7 ft, and a length of 190 ft. The two caustic calcining kilns are about 6 ft in diameter. One of them is 80 ft long and the other is 100 ft long. The calcining operations are carried out at a variety of temperatures, in order to produce magnesias of different degrees of activities for different uses. The dead-burning operation is carried out at temperatures in excess of 3400F, which is higher than those met with in similar commercial operations. The final products are cooled, crushed, and screened if necessary, and shipped to consumers. Three magnesia producers-the Dow Chemical Co., at Ludington, Michigan; the Michigan Chemical Corporation, at St. Louis, Michigan, and the Standard Lime and Stone Co., at Manistee, Michigan-use well brines and calcined dolomite to precipitate magnesium hydroxide, which is calcined to yield caustic calcined or dead-burned magnesite. A typical analysis of the brine is as follows: NaC1, 5.8 pct; CaCl,, 17.0; MgCl,, 9.9; KC1, 2.5; Br, 0.1; sp gr, 1.29; pH, 5 + 0.5. The brine is pumped to the surface from depths of 2500 to 3500 ft. Removal of sulphates or bicarbonates prior to precipitation of the magnesium hydroxide is not necessary. Aside from the omission of this step, the processes parallel, with minor differences, the process used by Westvaco. Certain of these plants make only caustic magnesite but others manufacture both the caustic and dead-burned products. The foregoing processes have been based on the reaction between a soluble magnesium salt and calcium hydroxide to produce magnesium hydroxide. A somewhat different process is used by the Diamond Alkali Co. at Painesville, O h i ~ where production of dead-burned magnesite ,~ was begun in 1948. By substituting calcined dolomite for calcined limestone in the Solvay process for making soda ash, the spent material from the ammonia stills consists of a slurry of magnesium hydroxide in a solu-

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INLILTSTRIAL MINERAIS AND ROCKS

tion of calcium chloride instead of calcium chloride a l o n e . T h e slurry can be thickened aricl filtered to yield magnesium hydroxide. Alternatively, thc slurry car1 be carbonated with carbon dioxide from the calcinir~gkilns to yield a solutior~of magnesium chloride, which i n turn can he reacteci with additional slaked, calcined dolomite to precipihydroxide. tate a much 1)urc.r ~rlagriesium The calcium oxide content ol' the primary dolomite is credited against the soda-ash 'branch of the operation. Only this fact makes this ari r~conorrlicalproccss, since 4.6 tons of doloniite is theoretically required to rnakc magnesium hydroxide equivalent to 1.0 ton of magnesia. IS the primary rnagncsium hydroxide is converted to magnesium chloride, which is i r ~ turn reacted with calcined dolomite, 4.6 tons of dolomite is still required, but only half of its calcium oxide content can be crcditrd to :he soda-ash operation. By co~~trast, other synthetic magnesia processes wherein half or tllr: all the magnesia is derived from the magnesium salt solution theoretically require 2.5 tolls linlestor~eor 2..3 tons dolomite per ton of magnesia. As a matter ol' ir1tt.1-est, 2.1 tons of pure, natural magnesite and will each yield 1.0 ton magnesia. 1.45 toris of pure brt~cite
POLITICAL AND COMMERCIAL CONTROL

Since magnesite as a refractory is necessary for the production of steel and nonferrous metals, abundant domestic supplies are a wartime necessity. Dead-burned magnesite was not regularly produced in the United States until World War I. Production of caustic magnesite began in California on a small scale iri 1886 but all of that was consumed on the west coast. The year 1910 was the first year in which production (rock mined) reached 10,000 tons. Production of this order continued until MTorld War I shut off supplies of dead-burned magnesite from Austria-Hungary. Production in California nearly trebled i n 1915 and by 1917 reached 2 1 1.000 tons (crude basis j . most of which was deadburned. The state of Washington, which had not previously been a producer, came into production in late 1916; it produced more than 100,000 tons the next year and subsequently has been the leading factor in the industry. Almost all of the Washington product has been shipped as dead-burned magnesite. When Austrian magnesite returned to U. S. markets following World War I, the domestic industry could not compete on a price basis and the Washington operations showed no production in 1921. However, under the tariff act of 1922, magnesite was removed from the free list, and the industry has since existed under this protection (Table 1 ) . Events related to World MTar I1 followed a similar pattern but one still differing in vital details. I n the decade preceding the war, the United States provided about two thirds of its dead-burned magnesite

MAGNESITE AND RELATED MINERALS

533

and three fourths of its caustic. When the European war shut off exports of magnesite from Central Europe, the needs for dead-burned magnesite were filled for a time by large imports from Manchuria. When these ceased, the domestic industry had already expanded its facilities to the point where no critical wartime shortage developed. It is highly questionable whether foreign producers can ever recapture any appreciable share of the United States market in view of the high quality of the products now here. The self-sufficiencyof the United States is based on the natural magnesite deposits of Washington, Nevada, and Texas, and on the synthetic-magnesite plants on the east and west coasts, as well as those based on inland brines. In 1946, the supplies of synthetic magnesite in the United States accounted for about 65 pct of all caustic magnesite produced and for about 30 pct of all the dead-burned magnesite. Since natural deposits of magnesite are exhaustible, the long-time trend will favor production based on sea water and other brines. However, for dead-burned magnesite it is likely that the deposits of Chewelah, Washington, will be the largest single factor in the industry for many years.
TABLE 1-Tar$
Rates for Magnesite under the United States Tarif Acts of 1922 and 1930, and b y Presidential Proclamation

Act or Proclamation

Tariff, Cents per Pound Crude Magnesite

15 -

Dead-burned Magnesite

Caustic Magnesite

Geneva rates effective Jan. 1, 1918. . . . . . . . . . . . Act of 1930, par. "LO. . . . . . . . . . . . . . . . . . . . . . . . Presidential proclamation, effective Dec. 10, 1927 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Act of 1924, par. 204. . . . . . . . . . . . . . . . . . . . . . . .

,,
15

% :
4 2

32 1s
o 3 15
16
8

4 2

o a

In the trade agreement with Canada, effective Jan. 1, 1936, provision was made under Paragraph 214 of the Tariff Act of 1930 for the high-lime product of that country as "dead-burned basic refractory material, containing 6 pct or more of lime and consisting chiefly of magnesia and lime." A duty of 278 pct ad valorem was established on imports of this product. Under the revised agreement with Canada, effective Jan. 1, 1939, the minimum lime content was increased to 15 pct and the duty was lowered to 20 pct ad valorem. The duty on the material containing 6 to 15 pct of lime reverted to the 30 pct ad valorem as provided for in Paragraph 214. A further revision to 15 pct ad valorem became effective Jan. 1, 1948, based on rates established through international ,agreement at Geneva, Switzerland.

INDI JSTRIAI. MINERALS AND ROCKS PRICES

Although little crude magnesite is sold, the price range is of interest as reflecting mining costs. There has been little departure in recent vears from the price of $11 to $14 per short ton that has been reported from West Coas~ miues. The price of dead-burned magnesite of furnacemaintenance grade, which had fallen to $22 f.0.b. Chewelah, Washington, in 1930, was increased to $24 in 1947 and to $27 in 1948. Deadburned nlagnesite sold as periclase grade from West Coast plants was priced at $35 (90 pct LMgO)and $65 (94 pct MgO): f.0.b. points in the early part of the war, but increases were later granted. When wartime

FIG1-CONSUMPTION DEAD-BURNED A N D CAUSTIC MAGNESITE I N TIXE IJNITED Olr STATES. Data from Minerals Yearbook. U. S. Bureau of Mines.

price controls were removed, the price of the 90 pct MgO grade rose to $40 in 1946 and to $45.50 in 1947. In most of the 10-year period ending in 1945, caustic nlagnesite sold for about $40 per ton f.0.b. West Coast shipping points but by 1947 had risen to $60 to $70.
PRODUCTION

The production of magnesite is discussed under various related headings throughout this chapter. The data necessary for a full view of production and use in the United States are shown graphically in Fig 1. Within the period 1930-1947, the dead-burned magnesite industry

MAGNESITE AND RELATED MINERALS

535

closely reflected the trends of heavy industry, particularly steel. he consumption of 31 1,000 tons in 1943 included only 9000 tons of imported magnesite. During that year, the U. S. ~roductionfrom natural magnesite rock was 186,000 tons. A fact revealed by Government data is that while only 4.1 lb of dead-burned magnesite was consumed per ton of steel in 1930, the figure had risen to 6.5 lb in 1945. Thus magnesite has improved its relative position. Domestic production of dead-burned magnesite reached an all-time ~ e a k 315,000 tons in of 1947. Caustic magnesite, the consumption of which was approximately 10,000 tons annually before World War 11, has greatly increased its market, owing to new uses. The very high level of production and consumption during the war was largely accounted for by the operations near Gabbs, Nevada, from which the plant producing metallic magnesium at Las Vegas was supplied.
TESTS AND SPECIFICATIONS

Crude Magnesite-Crude magnesite has been used in small tonnages for preparation of certain chemicals such as epsom salts but the total annual use of crude magnesite in the United States is less than 2000 tons. Caustic Magnesite-Magnesite for oxychloride cement is tested for the purpose by making test slabs of the cement. The magnesites are purchased from suppliers on the basis of character of the test specimens in addition to specifications covering chemical and physical analysis. The general specification for caustic magnesia used in cements is as follows: MgO, 90 pct min.; free CaO, 2.5 pct max.; R,O, plus SiO,, not particular but should be low; ignition loss, 3 to 4 pct; color, uniform; grain size, 90 pct minus 200-mesh. Chemically combined limes such as silicates are not harmful but free CaO causes the cements to expand and crack during setting. In 1947, the American Society for Testing Materials organized a new technical committee known as Committee C-2 on Magnesium Oxychloride Cements and the American Standards Association formed a Sectional Committee A-88 on Magnesium Oxychloride Cement Flooring.3 The scope of these two committees will cover specifications, testing, definitions, application and research pertaining to such cements. Magnesite for fertilizer is sold on the basis of MgO content; therefore most magnesia sold for this purpose has more than 90 pct MgO and much of it has more than 95 pct MgO. It should be ground but granular, should contain a minimum of free CaO, and should have an ignition loss of between 3 and 5 pct. Even though the magnesia may appear satisfactory from a chemical and physical point of view, it is extensively tested in small lots before large-scale application is made.

536

INDITSTRIAI, MINERALS ,4ND ROCKS

Specifications for caustic magnesia for use in the production o f synthetic rubber are varied, depending on the use and on arrangements between buyer and seller. Tvpical specifications are given in Table 2.

.I .\nr.r:2
\

- Typicul Sprc<ficirtiorr.s,forCrritstic Jfagrresia

Spc.rifii.:tiiori
-

I
~

Hc:ivy Caustic
~ ~

Extr:~Light (laustit:
- -

. . . . .

-~

, --

. ..

- --

Size. . . . Color. . . . %Ig(), pc.1

('$10. pet. SiO: H20::. 1wt Ignition loss, 1x.t

. . . . .

100 lilt*shI Buyer's stand;~rds . . H7.0 ~ n i n . . . . 2 . 6 ~iins. . . I. 0 nrax.

All through

i'

All tlirough 100 mesli

I3uyer's stand;lds 9 %5 min. . .LO mas. 1 1 inax. -k 5 111~);.

..

. .

The specifications for other uses of caustic magnesia are as varied as the uses. In general, high degrees of purity are required with particular emphasis placed on low CaO content. These magnesias are ground to prescribed sizes. Like most caustic magnesia, these magnesias are sold in 100-lb bags. Dead-burned .Magnesite-Dead-burned magnesite is also subjected to both physical and chemical tests. The nature of the requirements is somewhat dependent upon the uses to which the material is put. If it is to be used as grain magnesite for building up monolithic bottoms in the basic open-hearth furnace, certain characteristics are desired that would be unnecessary in dead-burned magnesite from which brick are to be manufactured. Both services require a dense, well-burned grain with a predominance of large sizes. Grains intended for the open-hearth bottom preferably contain a reasonable amount of silica (in the form of silicates), which aids the process of sintering the hearth to form a monolithic flooring. However, excessive amounts of lime and other impurities are undesirable, since magnesium oxide is the constituent that offers greatest resistance to solution by open-hcarth slag. Lime, when present in large percentages, may combine with silica to form dicalcimi silicate (2Ca0.Si02),which under certain conditions undergoes a rapid inversion that may reduce the magnesite to dust. Its complete stabilization is possible, however, and has been accomplished in products that contain it. Iron oxide, which is preferably kept low in caustic magnesite, is not an undesirable constituent in dead-burned magnesite. It aids the process of dead burning, gives a grain of greater density, and probably gives the individual grains greater powers of coherence. The major tonnage of dead-burned magnesite, used for maintenance of furnace hearths, contains 4 to 5 pct Fe,O,. In the magnesite from Austria and Czechoslovakia, this is a natural impurity present in the breunneritic type of crystalline magnesite. In the United States and Canada, the iron

MAGNESITE AND RELATED MINERALS

537

oxide is added as kiln charge in the form of finely powdered roll scale or iron ore. Synthetic magnesites contain-the same impurities as natural ones but the manufacturers have chosen to follow certain departures. Iron oxide may be added but frequently is omitted. Synthetic magnesites that contain less than 2 pct CaO frequently contain added SiO, to give a total of 5 pct, which, after burning, would in part be present as forsterite (2Mg0.Si02).This is particularly typical of the California products. The term periclase, which refers to the crystalline mineral MgO, and which predominates in all dead-burned magnesites, has come to denote generally in the trade a dead-burned, low-iron magnesite showing more than 90 pct MgO by analysis.
MARKETING, USES AND PRICES

Caustic Magnesite

As the graph of total consumption shows, the use of caustic mapesite has increased steadily since 1938. For 1946, a new peak for uses other than in the manufacture of metallic magnesium was reached over the previous high in 1924. The production for the years 1942, 1943, and 1944 includes about 6400 tons, 135,800, and 104,000 tons, respectively, of caustic magnesite used for making metallic magnesium. Aside from this wartime consumption, other factors have tended to stimulate the production of caustic magnesite. One factor is the increase in the use of magnesium oxychloride cements for interior flooring. The addition of copper powder to the cement has vastly increased resistance to weathering and cracking.12 The cement is used mainly for flooring. Such flooring is resilient, fireproof, spark-proof, and vermin-proof. It can be installed over wood, and it can be sawed and nailed without damage. Minor amounts of oxychloride cements are used in small decorative moldings, wallboard, caskets, and as an abrasive binder. The cements are prepared on the job by mixing a solution containing about 20 pct MgC1, with dry, ground, caustic calcined magnesite. Variable amounts of fillers such as wood fiber are added. In 1944, the Dow Chemical Co., Westvaco Chemical Division, and F. E. Schundler and Co. formed the Oxychloride Cement Association in Washington, D. C. This organization supplies materials and information relating to such cements. Another factor leading to increased production of caustic magnesite is the heavily increased demand for magnesium compounds in fertil i z e r ~ . ' Magnesia and magnesium compounds serve two purposes in ~ fertilizers; one is to supply Mg as such to the plant; the other is to assist in the assimilation of phosphorus. The magnesia is rarely added

5 38

INIIlJSTRIAI, MINERALS AND ROCKS

alone but is added as a constituent of a balanced, formulated fertilizer. Other major uses of caustic magnesia are in the manufacture of synthetic rubbcr. in which operation it is used for both catalyst and of filler, and in the n~anufacture magnesium chemicals. Miscellaneous uses arc as coatings for welding rods, fillers for heating elements, reagent for reduction o f silica in boilers, pharmaceutical pul-poses, glue compourids, glass constituent, and fine abrasivrs. Accurate consumption figures for these various uses are difficult to obtain, bu~. 1943 about 48 pct of I!. S. consumption was in oxychloin ride cements, 10 pct in synthetic rubber, 1 1 pct in fertilizers and 31 pct ill miscellaneous uses. Current figures are probably about 30 pct for cen~er~ts, pct for fertilizers, 1 0 pct for rubber and 35 pct for 25 miscellaneous uses. The price of' caustic magnesite depends on MgO content and preparation for. the trade. Ground and bagged magnesite generally costs aboui $6 more per ton than unground, bulk magnesite. The average price per ton for all grades of caustic magnesia, except those in the chemical grades, has increased steadily from $34.81 in 1941 to $63.81 in 1946. Dead-burned Magnesite Dead-burned magnesite is used almost entirely for the manufacture of refractories, sold as grain products or as shaped brick. These refractories are used throughout industry but find their largest markets in the steel and copper industries. The hearth of the basic open-hearth steel furnace may be built up by burning in layers of magnesite grains or by using a monolithic, cold-setting. ramming mix of magnesite grains to which a bonding agent has been added. Brick resistant to basic slags may be made of magnesite alone or of mixtures of magnesite with chrome ore or olivine. Such refractories have been greatly improved in quality, so that their use is no longer confined to hearths and side walls but has been extended to roofs of such high-temperature furnaces as the copper smelter and the openhearth steel furnace.
OTHER MAGNESIUM COMPOUNDS

Beside the magnesium oxides discussed under refractory and caustic headings, a n impressive variety of other magnesium compounds is currently being produced. The use of these compounds is increasing and continued substantial production is anticipated as new outlets are developed. Magnesium sulphate has been made by leaching serpentine and olivine with sulphuric acid, by extracting it from certain well waters, and mainly by reacting caustic magnesite with sulphuric acid. This

MAGNESITE AND RELATED MINERALS

539

last method accounts for the bulk of the ~roduction. Purity of ~ r o d u c t is governed by purity of ranTmaterials and by processing techniques. Low-grade sulphate is used for fertilizer and stock feed. High-grade sulphate is used for coagulating rayon in the Viscose process, for weighting and dyeing textiles. Special grades find use as a medicine and chemical reagent. The production of magnesium sulphate of all grades on a 100 pct MgSO, basis has been in excess of 25,000 tons per year during the period 1942 to 1947. The average value has been about $50 per ton. Magnesium chloride has been obtained from well brines, from natural salts such as carnallite, by conversion of magnesium hydroxide from sea water, and by reaction of caustic magnesite with carbon and chlorine. The largest consumption o this salt is in the manufacf ture of metallic magnesium and oxychloride cements. After curtailment of the wartime magnesium-metal program, the production of magnesium chloride decreased from a 1943 peak of 640,708 tons to 32.,137 tons in 1946. Production seemingly is stabilized at about this figure. Price has increased somewhat; in 1945, it was $32 per ton of flaked magnesium chloride; in 1946, it was $37. by Magnesium carbonate is ~ r e ~ a r e d precipitation from solutions of magnesium bicarbonate. Most of the technical grade is obtained from dolomite by use of the Pattison process, although a substantial tonnage is being produced on the West Coast by the carbonation of magnesium hydroxide. Much of this production is used in the manufacture of insulation of all types. Special grades of pure carbonate are used as rubber compounders, as ink, paint, pigment and varnish ingredients, and as an additive to prevent moisture adsorption by hygroscopic substances. The production of precipitated magnesium carbonate has decreased from 55,207 tons in 1943 to 47,423 tons in 1946. The price has fluctuated between 6&and 8$ per pound. Magnesium silicate, as part of the natural mineral olivine, is being exploited commercially for refractory purposes. Olivine is composed of forsterite, 2 MgO.SiO,, and fayalite, 2 FeO.Si0,; fayalite is the minor ingredient and generally averages about 15 pct of the olivine. Olivine is quarried on a relatively small scale. Hand cobbing and sorting may be used to remove deleterious talc and serpentine impurities. For refractory purposes, these low-melting minerals are reacted with magnesia. Olivine is a common constituent of igneous rocks, but deposits of sufficient purity to be commercial are not plentiful. Deposits in North Carolina have been worked continuously since about 1935. These deposits are contaminated in varying degrees and the ore requires close sorting for use in refractories. The state of Washington has a deposit near Bellingham that can be literally described as a "mountain of ore."

540

INIIIJSTRIAL MINERALS AN11 ROCKS

The olivine is massive and relatively unaltered. Unfortunately, the geographic locatiori has prevented anything but small, preliminary developmer~ t. Olivintl arid serpentine have been utilized as a fertilizer ingredient and as raw material for the preparation of magnesium sulphate and of chloride. hlany tho~~sands tons OF serpentine have been used in New Zealand ill recent years to increase the availability of phosphorus in phosphate lertilizer. Synthetic magnesium silicate with high absorptive properties is being ma~rufactured by Westvaco Chemical Division at its Charleston, West Virginia, plant (private communication). Substantial tonnages of this product are being made by reaction between precipitated calcium silicates and magnesium chloride solution.
BIBLIOGRAPHY
I . Anon.: Magnesium Chemicals. Chern. Eng. (Aug. 1947) 132-135. 2. Anon.: Magnesite Mining at Gabbs. Mining World (Nov. 1944) 23-26. 3. Anon.: New Committee Organized on Magnesium Oxychloride Cement Materials. Organization of Sectional Colnrriittee ASA-A88 on Magnesium Oxychloride Cement Flooring, Bull. Amer. Soc. Test. Mat. (Aug. 1947) 29-30. 4. J. M. Avery and H. F. Evatis: Modified MgO Process Yields MgCl, and Calcium Hypochlorite. Chanz. and Met. Eng. (1945) 94-96, 130-133. 5. J. M. A v e r and R. E'. Evans: Production of Magnesium at Painesville, Ohio. , Min. T ~ c h .AIME (Apr. 1945-TP 1829). 6. G. W. Bain: T ~ p e s Magnesite Deposits and Their Origin. Econ. Geol. (1924) of 19, 412-433. 7. C. E. Carnes: Mineral Occurrences in the Vicinity of Cranbook. Geol. Survey Can. Sumnlary Rept., pt. AII (1932) 98-99. 8. S. G. Chipman: From Open Pit to Underground Mining. Concrete and Quarry (Aug. 1937). 9. T. Egleston: Basic Refractory Materials. Trans. AIME (1885-1886) 14, 460. 10. M. F. Goudge: Sources of Magnesia and Magnesium in Canada. Can. Inst. Min. and Met. Trans. i1942) 45, 191 007. 11. hl. F. Goudge: Brucite Magnesia. Inl. Amer. Ceramic Soc. (1943) 27, No. 1 . 8-10. 12. D S. FIubbell: A New Inorganic Cement and Adhesive. Ind. and Eng. C h ~ r n . (193ij 29, 123-132. 13. J. Lunlsden: Magnesium, Magnesite and Dolomite. Imperial Inst. (British), Mintwal Resources Dept., London, 1939. 14. P. V. Manning: Oceans of Raw Material for Magnesium Compounds. Chenz. and Met. Eng. (March 1936) 116-120. 15. .l. S . McDowell and R. M. How-e: Magnesite Refractories. Jnl. Amer. Ceramic Soc. (March 1920) 3, 185-246. This is a good general treatise on magnesite occul.rences. mining, and utilization. 16. . W. Nielseri: Growth and Development of Gabbs Concentrator and Oxide ( ; Plant. Mining World (Dec. 1914) 27-31. 17. K. Niinom.\-: Bibliography on Magnesite Deposits of the World. Dairen, Manchuria, 1930. Manchuria Daily News. 18. J. I,. Parker: Open-Pit Mining of Magnesite Ore. Ezplosiues Engineer (JanFeb. 1945) 9-11, 31-32.

MAGNESITE AND RELATED MINERALS

541

19. M. Y. Seaton: Production and Properties of the Commercial Magnesias. Min. Tech., AIME (July 1942-TP 1496). 20. G. E. Seil, S. M. Phelps, et al.: Manufacture of Refractories and Information Concerning Their Use in the Iron and Steel Industry of Western Germany. Fiat Final Report No. 432, 1946, Office of Technical Services, Washington, D. C. 21. P. M. Tyler: Magnesite. U. S. Bur. Mines I.C. 6437 (May 1931). 22. Symposium on Magnesian Fertilizers. Amer. Chem. Soc. meeting, Chicago, Sept. 1946. Titles listed in Chem. and Eng. News (Sept. 10, 1946) 24, 2057; published in part in Soil Science (Jan. 1947) 6 3 , 1-78.