Mar., 1912
T H E JOCRSAL OF I N D U S T R I . 4 L
If a sufficiently large and permanent outlet for sul- cheaply- from clay would be of inestimable advantage. furic acid, on the one hand, and elementary sulfur on the other can be assured reasonably near the sources of supply, the metallurgical industry itself can be safely relied upon to meet the demands and find the way to supply them.
MISCELLANEOUS MINERAL WASTES. By CHAS L. PARSONS.
As the hour is so late and I have brought out a good many applications in the preceding discussion, and as a considerable portion of the subject is alreadlin type for the February number of THIS J O U R N A L , under the title, “Mineral Wastes : The Chemists’ Opportunity,” I will present a few additional facts in the form of brief notes. There are several kinds of waste-waste of material, waste due to inefficient methods of preparation, waste b y use of unsuitable material, waste from lack of use of abundant material. One of the great losses taking place a t the present time in this country is through the destruction of valuable metals due to electrolysis induced b y leakage of electric currents. The loss is difficult t o estimate, but i t undoubtedly means millions of dollars a year. A good example of waste due to inefficient methods, of which there are many, is the failure t o utilize modern methods in the hardening and tempering of steel. One of our large manufacturers of steel blades, making a t the present time some 3 0 0 , o o o blades a day, has reduced their cost in the last few years, through the employment of an expert, b y more than half. They use now some three tons of steel per week and the blades were formerly hardened by using sixty-five machines, utilizing gas and blast for the heating process, running day and night and requiring fifteen men for their control. This company is now using six electrically heated furnaces, giving double the capacity, in an 8-hour day, with two men doing everything. For purposes of tempering, the blades are dipped, seventy pounds a t a time, into an electrically heated salt bath and held for a definite time a t a temperature definitely controlled with pyrometers. Per contra, another of our largest manufacturers of small steel articles is still to my knowledge hardening each article separately b y blacksmiths b y hand, getting a much more variable result a t many times the cost. They, too, are working up hundreds of thousands of dollars’ worth of material each year. Examples illustrating this kind of waste could be almost indefinitely multiplied. ALUMIh’UhI.
Twenty years ago aluminum sold for five dollars
a pound; today it can be bought for less than twenty cents and still is obtained only from one ore, bauxite, the deposits of which are far from inexhaustible. Bauxite has many other uses and is needed for the manufacture of alum and aluminum salts in the chemical industries. Any method for producing aluminum
Several new patents have recently been issued, experiments are under way in this country and a prominent chemist of this Society tells me that he expects one of these processes t o become a success. The methods of mining bauxite have apparently been but little studied. There are reputed to be considerable deposits in Wilkinson County, Georgia, that may pay for further exploitation. Aluminum has grown from a consumption of 83 pounds in 1883 to 4 7 , 7 3 4 ) o o o in 1910. A RS E S I C .
According t o Harkins and Swain, about thirty tons of arsenic trioxide go out of the stack of the Washoe Smelter daily. This means perhaps 80 to go per cent. of the total arsenic coming into the plant and amounts to over 10,000tons a year t h a t is being thrown o u t into the atmosphere from this one smelter alone. Similar losses are taking place in almost every smelting plant in the country and there is little doubt t h a t 2 j , 0 0 0 tons of arsenic go to waste each year. The amount recovered in 1911 increased nearly 300 per cent. over 1910, chiefly due to requirements put upon smelters for its collection. Although its price has been greatly reduced, the over-supply is not being fully taken care of. It is used in large quantities in combination with lead as an insecticide and it would seem worth while t o have experiments inaugurated t o determine if arsenic sulfide or calcium sulfarsenite, both of which are probably quite harmless to plants, may not be substituted as an insecticide, giving a much cheaper material, using more arsenic and conserving lead. It should be noted particularly that any proposed insecticide must be effective as a poison but must not injure the foliage of the plant upon xi-hich i t is placed. A K T I J I 0S Y .
Some losses of antimony are taking place from the flues of our smelters, but the loss is not so severe as with arsenic. Antimony lithophones are stated t o have been successful in Germany, made by treating barium carbonate and antimony sulfite. The oxide itself may be used as a white paint and sodium metantimonate is a valuable constj tuent of enamels. I t s use, however, is forbidden abroad in enamels placed on cooking utensils, but so far these enamels have not been extensively prohibited in the United States. AS B EST 0S . The uses of asbestos are rapidly increasing and are a real conservation of lumber and a protection against fire loss. Asbestos shingles and asbestos lumber are of the utmost importance and their use should be encouraged. This country however, produces a t the present time but a very small proportion of the asbestos i t uses, although very extensive deposits are known to exist in Wyoming. Anything that enables man to supplant wood with a non-combustible and cheap material is of the utmost importance to the country, for i t is not only much less destructible from atmospheric agencies, but tends always to decrease our enormous fire losses.
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THE J O U R N A L OF I N D U S T R I A L A N D E - V G I N E E R I S G C H E M I S T R Y . BARITE.
Large and extensive deposits of barite occur in Missouri, Nevada and California, but transportation costs still make it possible t o import more cheaply a large supply of this valuable mineral from abroad. It is used in large quantities in the production of lithophone and in paints and should a t least be made to supply a goodly portion of the Western demand for this material. BISMUTH.
The uses of bismuth are growing and if i t could be obtained more cheaply, these uses would be very greatly increased. Inquiries have been recently received by the author for alloys of bismuth and lead which were needed by the ton if a low enough price could be obtained. Large quantities are being wasted in this country. Probably 3000 pounds per day are going out of the stacks of our western smelters and i t is understood that one or two of our smelting companies are already installing processes for obtaining this material and placing i t in greater amounts upon the American market. I n 1 9 1 0 nearly threefourths of the domestic supply was imported. Bismuth is not a desirable constituent in lead and €or many purposes for which lead is used the bismuth must be separated. The bismuth now produced in this country is obtained as a by-product in refining lead. The lead is melted and allowed t o crystallize, the mother liquors becoming richer and richer in bismuth. Finally these mother liquors are refined electrolytically and the bismuth recovered from the slimes. BKOMINE,
CHLORIKE AND IODINE.
There is apparently an over-production of both bromine and chlorine in this country and new uses are desired as an outlet for these elements. Bromates are incidentally made in the production of bromides and so far have had but little market. Potassium bromate, however, is an excellent oxidizing agent and it would seem as if its use for this purpose might be greatly extended. One to two pounds of potassium bromate added to each ton of solution of potassium cyanide in the cyanide process for gold is certain t o keep the bath “sweet” provided the bath is kept alkaline with lime. Any sulfides, sulfocyanides or ferrocyanides tending t o reduce the value of the dissolved oxygen are apparently prevented from forming by the presence of potassium bromate. Chlorine can now be obtained cheaply in liquid form and can be supplied either in regular cylinders, in cheap cylinders which do not need t o be returned, or in tank cars if desired. Processes are also being exploited which produce the chlorine on the ground electrolytically, which, while cheapening the application, tends also t o reduce the market of the works producing chlorine as a regular product. A possible use for chlorine is for chlorinating certain pyroligneous tars from wood to be used in the preservation of wood. I t may be possible also to make cheap, noncombustible solvents b y chlorinating certain petroleum residues like the cheap solar oil of Texas, which can now be disposed of for only about two cents a
Mar., 1912
gallon. Such solvents, especially if they do not attack metals, are greatly needed. Immense quantities of chlorine in the form of calcium chloride are being run off as a waste from the ammonia soda process works of the country. One plant alone now produces 2 8 0 metric tons of calcium chloride per day, 90 per cent. of which is a total waste. Ten per cent. is, however, evaporated and used in granulated form chiefly in refrigerating plants and t o be spread on roads t o lay dust. This material is also found to be of very great advantage if sprinkled in coal mines, as i t tends t o keep the coal dust moist and thereby greatly diminishes the danger of explosions. Any non-hygroscopic substance added t o water used to sprinkle coal dust in mines has little more effect than a diluent. Water itself quickly evaporates from coal dust in dry mines owing t o the ventilating currents that must pass continually through these mines. If calcium chloride is added, the moisture is, of course, retained. The price of iodine is reputed to be one that is highly artificial. I t is certain that the output could be many times multiplied with little effort and the price greatly lowered if new uses could be found. CADMIUM.
As western spelter contains an average of a t least 0.3 per cent. cadmium and the production was 230,169 tons in 1910, there were, accordingly, 690 tons of cadmium sold as an impurity in zinc in that year. Cadmium is easily distilled fractionally from zinc and is an undesirable impurity. I t is especially bad if the zinc is t o be used for the manufacture of lithophone. Flue dust from brass works carries from about I 1/4 per cent. to I I/Z per cent. cadmium, which is about 5 1/2 per cent. of the zinc actually present. On this basis there are some 400 pounds of cadmium lost each day in the flues of the brass works of JT7aterbury, Conn. The United States imported 4000 pounds in 1 9 1 0 and produced about 5300 pounds, the price varying from sixty to seventy cents per pound. I t is reported that furnaces capable of producing 1000 pounds a month are about ready to operate. New uses for cadmium are desired. At present its chief use is in glass manufacture and as a constituent of easily fusible alloys. If cheaper, it could be used extensively as a yellow pigment. I t is stated that cadmium sulfide was formerly used as a yellow paint for horse cars, as i t was necessary since they were kept in horse barns where hydrogen sulfide was more or less prevalent. Now that trolley cars have been substituted for horse cars the cheaper lead chromate can be used to paint cars yellow. Cadmium has also found some use as a constituent of a silver-cadmium plating alloy. E SAM E LS.
General information in regard to the preparation and constituents of enamels should be made public. They are of the utmost importance for special uses. They offer an outlet for such materials as antimony oxide, arsenic oxide, zirconium oxide, etc., and serve as a protective material conserving metals as well as greatly aiding proper sanitary conditions. They
can be sold a t a very much cheaper price than a t the present time. Furthermore, enamel brick and tile can be greatly improved and much of the work now done by hand can be done b y machine. F u L L E R 's E A R T H . The imports of English earth are regularly increasing in spite of the duty. Domestic production is still used chiefly for petroleum, while imported earth is used for edible oils. The deposits of fuller's earth in the South, especially in Georgia, South Carolina and Alabama, are almost unlimited, and there is no good reason why any- foreign earth should be imported. Deposits in Arkansas and Texas are also being exploited, Domestic earth could be easily produced at a profit a t one-half the present price if a sufficient output could be maintained. Several of the domestic earths bleach edible oils much better than the English. Lack of knom-ledge of methods of preparation for the market is one of the chief reasons why they are not now used and also some manufacturers do not yet know how to remove from edible products the slight taste these earths are apt to impart. ISF US 0 R I A L E A R T H ,
Probably the largest deposits in the world occur in Lompoc, California. The deposits there are almost inexhaustible and are remarkably free from iron and other impurities. I t is used in making light terra cotta brick. jn the beet sugar industry to assist in filtration and as an insulating material for covering boilers, The material in pure form has been rather hard to obtain in the past, b u t this immense deposit, much of R-hich is still open to exploitation, should encourage new uses for the material. LEAD.
Van Hise states that the losses of lead are 15 per cent. to 2 0 per cent. left in the mines, ~j per cent. lost in concentration and I j per cent. to 2 0 per cent. lost in smelting. A large part of the lead mined is applied where i t is never recovered; namely, in paints and as a filler for rubber. Perhaps thirty million pounds of lead carbonate were used as a filling for rubber goods in 1910. TIX.
There is but little tin produced in the United States, although there is distinct promise of an Alaskan supply and the output of the Texan mines is increasing. This is greatly needed, for in spite of the real conservation of the detinning recovery process, a large part of the tin produced is again lost each year. NICKEL.
Practically all of the nickel used in the United States is imported from Canada in the form of nickel-bearing mattes and ores. Nickel is also obtained as a secondary product in the electrolyte refining of copper to the extent of a few tons annually. Large quantities of this metal are, however, known t o exist in Idaho and a n immense deposit of a lox-grade, hydrous nickel magnesium silicate occurs at Webster, N. C. This latter deposit contains millions o f tons, but owing t o its low-grade character
no method of economically working the material has yet been found. Of course, the same statement was true of similar ores of copper ten years ago, but these nickel ores have the disadvantage that they apparently are not amenable t o ordinary methods of gravity concentration. PI%TROLLUM.
Large quantities of so-called solar oils occur in the Texas petroleums, which would appear to be too good t o be used for fuel but which are not light enough to be distilled for kerosene. Uses for these oils are being sought. Many million gallons of the lighter petroleum products, lying between true gasoline and natural gas, are annually lost by evaporation from the open mouths of petroleum wells and from open stbrage tanks. PLAT I h-U 11 AS D P A L L.4 11I U 11,
Owing to the craze of the rich for platinum in jewelry and its use in dentistry, the price of this metal, which is now absolutely essential to scientific research, has been trebled in recent years. One of our producing companies is now obtaining about 1 5 0 ounces of mixed platinum palladium per month which contains about 1 2 0 ounces of palladium. Platinum is being sought more and more in the West and is being conserved in the refining plants, although, as a rule, smelters do not as yet allow anything for it in ores. Every effort should be made to develop the platinum industry and to induce careful search for it and recompensation when found. The Rambler Mine, which was supposed to have run out, has apparently struck ore again. This ore formerly carried about $14 worth of platinum per ton. Palladium is used in making the dividing scales of delicate, astronomical instruments and also in jewelry. Its price per ounce is about the same as platinum but i t has the advantage of lighter specific gravity. Platinum is also being conserved by the substitution of a nickel chromium alloy wire covered with platinum for the entrance wire of electric bulbs and other purposes where pure platinum was formerly used. R .i D I U M.
This material is greatly desired b y the medical fraternity and is important for the treatment of certain diseases. Foreign governments have taken i t up, b u t nothing has been done in the Vnited States, although two companies are now experimenting on its production. Large deposits of carnotite, a lowgrade uranium ore, are found in Colorado, also recently in Oregon, and there is every reason t o suppose that exploitation of two mines known to contain pitchblend would produce an output of this valuable, but very rare material. Our government might well take up the study of this problem both from the mining standpoint and from the producing standpoint with the hope of perfecting the methods of obtaining radium from the ore and of adding to our stocks of the material, as it is important from the standpoint of the public health. The price of radium is now about $80 per milligram of two million power. The production was 1 . 9 2 grams in 1 9 1 0 , which sold for about S I j o , o o o .
I88
T H E J O C R S a 4 L OF IA\-DLISTRIAL A N D E S G I . Y E E R I S G CHEAIIISTRI’. RARE EARTHS.
There are a large number of the rarer elements of which comparatively little is known. Even the minerals which contain them are little known and i t is impossible t o state how extensively they occur in the West, for they may have been overlooked as worthless. This is especially true of such elements as tungsten, vanadium, titanium, tantalum, thallium, thorium, beryllium and the twenty or more elements of the cerium and yttrium earths. No one can say what a n exploitation of this field might lead to, but it is through pure scientific investigation of such problems as these t h a t many industries have been developed, perhaps the most noteworthy recent industry being that of the Welsbach incandescent gas light. In the production of thorium from monazite b y far the larger part of the associated materials goes t o waste. Cerium makes up perhaps 30 per cent. of these losses. An application has recently been found in the pyrophoric alloys, which give off innumerable sparks when scratched. I t is also probable that cerium oxide, lanthanum oxide and others, which occur in these waste materials, will become of special value as refractories, for they are among the most infusible materials known. Cerium is also finding a use in the form of cerium fluoride in the flaming arc and there is little doubt that these uses may be greatly extended. The properties of some of its compounds t o act as perhaps the strongest oxidizing substances known may open new uses for this element. Furthermore, there appears t o be a fruitful field for research in the applications of these rare elements in the production of special enamels. R E F R A CTO R I ES
.
The refractory industry offers an especially promising field of research. Many metallurgical furnaces have to be relined much more frequently than would seem t o be necessary and the operation put out of commission for weeks while this relining is being carried on. A specific instance recently came to my attention where the life of the furnace was increased from six months to over two years simply by a careful study of the texture of the refractory brick used and the development of methods for decreasing their porosity. Great improvements have taken place in the last few years, but little careful scientific study has been given to the problem. Bauxite bricks offer an especially promising field if their breaking up under contraction and expansion can be controlled, which is by no means improbable. Also i t is quite possible t h a t the best fire clays can be greatly improved and brick made from them approaching bauxite brick in composition by the addition of alumina t o the clay from which they are made. S E L E K I U .M.
Up t o a year oritwo ago no important use for selenium was known, although for some three or four years it had been secretly used in the glass industry. It is now well known that it is used for coloring glass red and for decolorizing glass by the use of small amounts t o neutralize the green of ferrous iron. I t
Mar
,
1912
is obtained as a by-product in the refining of copper. Apparently about twenty tons per year are now utilized, which amount could be greatly increased if a larger market mas found. As the price has recently been greatly reduced i t is hoped that new uses will be found soon. SULFUR.
The tremendous losses of sulfur from our western smelters has been too often dwelt on t o need much additional space here. O n the basis of the calculations of Harkins and Swain, the flue gases of the largest smelter in the United States are carrying off daily sulfur dioxide and sulfur trioxide, equivalent t o 1,977,570long tons of chamber acid, or more than enough t o supply the total acid consumed in the whole fertilizer industry in this country. This L b u t a fraction of the actual sulfur wastes. ZINC.
The immense losses of zinc have already been described in the discussion of the paper on “Zinc Losses in Brass Manufacture.” ZIRCOXIA.
Zirconium oxide is important and some unworked American deposits are known. There appears t o be a real field for this material as a refractory in replacing valuable tin oxide in enamels. NEW USES.
New uses for unused material is as important in conserving mineral waste as any other one thing and there is a n almost unlimited field. Calcium and silicon occur all around us by the millions of tons and can now be produced a t a reasonable price if uses therefor can be found. If extensive uses were found, the prices could be greatly reduced from present cost. Tellurium is going to waste in quantity from the copper refineries and from the plants working up gold telluride ores. Absolutely no use is now known for this material, though many tons per year could be easily obtained. Molybdenum occurs in this country in some quantities, but no good method is known which has proved itself capable of commercially separating i t from the gangue. Chemical firms have been willing t o pay as high as’ 8700 per ton for pure imported foreign material, but known uses are small. Molybdenum can replace tungsten in steel, but has the disadvantage of volatilizing out of the steel by oxidation even under the blacksmith’s hammer. I t is especially important in making permanent magnets and only about one-third as much is required to harden steel as when tungsten is used. I t can be obtained for electrical heating purposes in the form of ribbon or wire and on account of its ductility and high melting point is used as a support for the tungsten wire in incandescent-electrical lamps. Tungsten is finding more and more applications and with a cheapened supply will undoubtedly become one of our most important minor metals. I t s use in tool steel and in incandescent lamps is rapidly increasing t o the great conservation of efficiency in mechanical processes and energy in lighting.
