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By Charles C. Hawes

DETERMINATION OF SILICA OXIDE iron ores usually are found in intimate association with silica and phosphorus compounds. Their quantitative separation and purification sometimes present difficult problems to the chemist. Silicic acids may represent various degrees of dehydration. They are exeedingly weak, but combine with metallic oxides and form some of the most stable oxides in nature, the silicates. When iron ores are treated with hydrochloric acid, they yield practically all their iron. However, apart from rare exceptions, varying amounts of insoluble residues of silica, alumina, lime, magnesia and compounds of phosphorus, sulphur, titanium, chromium and others will be left. If the oxides of silicon, aluminum and titanium are present in small quantities, the insoluble residue is generally very small, but the presence of these oxides is more usual in larger quantities. Therefore, only a special treatment can break the bond between these elements. Ore Residues Acids remove the soluble constituent of the ore, leaving the insoluble residue, which chemically is rock or gangue and must be treated accordingly. Alkali carbonates are used frequently to break up the residue, but other fluxes have also been recommended, such as a number of lead and boron salts. The introduction 0f these salts, which offers certain advantages, requires, however, their removal before the other constituents can be analyzed, and this elimination is sometimes difficult. Usually in quantitative analysis silicates are dissociated by fusing them in a platinum crucible with sodium carbonate, thereby forming sodium silicate, Na2SiO3, sodium aluminate, Na2Al204, sodium titanate, Na2TiO3, and carbonates of other elements. All the carbonates are soluble in hydrochloric acid, but also some silicic acid is formed that must be rendered insoluble. To this end the solution is evaporated several times, as the first evaporation still leaves as much as 5 per cent of the silica soluble. Even after a number of evaporations, minute quantities of silica may be found with the iron and alumina present. Perchloric Acid as an Agent for Dehydrating Silicic Acid Perchloric acid, HC104, (60 per cent), has been used for years as a solvent, but few chemists have used it to dehydrate silica. It is derived from anhydrous perchloric C1207, which is most unstable and dangerous. Perchloric acid is a strong oxidizing agent, which boils at 203°C. It is more effective in rendering silica insoluble than any other known agent, and most rapid in action. After perchloric acid is added to a mixture containing silicic acid, the resultant solution is

Jan 1, 1945

By Marshall D. Himes

The Pima mine, Pima County, Ariz., a 53,500-tpd copper mine, is located 17 miles south of Tucson, Ariz. The mine is in a sequence of Paleozoic and Mesozoic sediments striking east-north-east and dipping southeasterly. These sediments are intruded by a Tertiary quartz monzonite porphyry. The Paleozoic Permian (?) dolomites, limestones, and sandstones have been altered to calc-silicate skarn, marble, and quartzite. The overlying Mesozoic Triassic (?) clastic sediments have undergone some recrystallization and hydrothermal alteration. The clastic metasediments are divided into three distinct lithologic units: lithic arenite, arkose, and interbedded and overlying black argillite. Three types of hydrothermal alteration in the clastic rocks are propylitic alteration (epidote, chlorite, and quartz, with or without sericite), quartz-sericite alteration, and potassic alteration (K-feldspar, quartz, and sericite, with or without chlorite and calcite). The porphyry has undergone potassic alteration. Dominant structures are an east-west postmineral fault in the western part of the pit, and strong low angle faulting and shearing which truncates the ore body at depth. The two joint sets, one parallel to bedding and the other at right angles to bedding are prominent in the mine. Faulting is in two dominant directions, one striking northwest, dipping northeast, and the other striking northeast, dipping northwest. Economic mineralization is prediminantly disseminated pyrite and chalcopyrite, and molybdenite-quartz veinlets. There are less important amounts of magnetite, hematite, sphalerite, galena, tennantite, and bornite. Mineralization is believed to be both structurally and chemically controlled.

Jan 1, 1974

By F. F. Aplan

INTRODUCTION The production of coal is a major part of the mining industry. In recent years the production of clean coal has exceeded 600 million tons per year and is reported to have reached 660 million tons in 1977. Some data on the magnitude and utilization for the year 1975 is given in Table I. In that year 648 million tons of soft coal were produced and of this 267 million tons or 41% approximately was produced by mechanical cleaning. Of the 374 million tons of raw coal sent to the preparation plant, 28.6% or 107 million tons was discarded as refuse. In the same year approximately 6 million tons of anthracite were produced and nearly all of this was cleaned. Table I also gives coal utilization statistics for 1975. Excluding the approximately 20% that goes to the coke ovens or to export, the vast bulk of our production is used for steam power generation and a lesser amount for captive production of industrial power and process steam. While much of the nation's coal (e.g. strip mined western, sub-bituminous coal) may be removed from the ground in relatively pure form by modest selective mining techniques, other coal requires preparation in order to remove ash and sulfur constituents and produce an acceptable steam or coking coal. Preparation is often a valuable adjunct to mining in that rather non-selective, low cost, bulk mining techniques may be used underground while the preparation plant is used to reject refuse at low cost above ground. The principal reason for the use of coal preparation is to convert raw coal into an acceptable commercial product by removing the high ash and high sulfur refuse material.

Jan 1, 1979

By Paul Cook

THE ore deposit of the Buckhorn Mines Co., Buckhorn, Nev., is peculiar in being a shallow kaolinized mass of material with basalt walls, and having apparently no direct connection with any of the usual gold-bearing rocks. The average ore contains 16 per cent. waiter of hydration, and the cyaniding of this hydrous clayey material offered unusual difficulties as compared with the typical gold quartz ores of Nevada. The orebody was thoroughly developed; then the mill was built according to the latest cyanide .practice, with such changes as were thought to be demanded by the peculiar nature of this ore. Upon starting the mill, the ore proved more difficult to handle than had been anticipated. It is hoped that an account of how these difficulties were met may prove of interest to anyone having a clayey ore to handle and to the profession in general.

Jan 9, 1916

By J. David Lowell

On a low desert ridge six miles south of Cairo lie the remains of the world's earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radio- carbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy.

Jan 1, 1970

By Corliss R. Kinney

Since the first atomic bomb exploded over Japan, a great deal of speculation has been published about the use of atomic energy instead of coal for the production of power. Atomic energy, in time, may displace coal for this purpose, but atomic energy will not displace coal in supplying chemical raw materials to the rapidly expanding carbon-chemicals market. Modern civilization demands large quantities of carbon compounds and the logical source of many of these is coal. Consequently, many progressive operators are considering the possibilities of the utilization of coal as a chemical raw material as never before. Furthermore, the demand for clean, smokeless, and ashless fuels will continue to increase and the only way to handle coal under those conditions is to take it apart, just as crude petroleum is taken apart. One can readily imagine where the petroleum industry would be now if it had insisted on selling customers only crude oil, perhaps emulsified with a little salt water to correspond to the moisture and mineral matter in raw coal. The time seems to be coming at an accelerated Dace when mine operators will find that competing for a highly selective fuel market by producing a larger tonnage at smaller cost will be less profitable than to increase the value of a smaller tonnage many fold by producing something more valuable to industry and civilization than raw coal. For example, about 750,000 tons of carbon black selling for $50 to $60 per ton was produced in the United States in 1945. This tonnage is insignificant compared with the total production of coal in the United States, but a very tidy tonnage, together with the coal necessary to operate the process, for any mine operator fortunate enough to obtain a method of producing a better carbon black from coal. From the point of view of tonnage, the manufacture of coke of various kinds and its by-products is at present the most important source of carbon chemicals from coal. Nearly 20 per cent of the coal mined in this country is used for this purpose. A large proportion of the coke is used for the production of iron and steel, but even in this operation a considerable part of the coke is used for a chemical purpose; that is, the reduction of the ore to metallic iron. In addition, large quantities of coke are used in manufacturing many important products that find their way into the market. Possibilities of Acetylene One of the important chemicals manufactured from coke is calcium carbide, from which many products are made. One of these is acetylene. This hydrocarbon can also be manufactured from natural gas or from waste oil-refinery gas and these industries will probably offer competition for the manufacture of acetylene. Coke-oven gas can be used for making acetylene and should receive consideration

Jan 1, 1947

By E. G. Leonardon, Irving B. Crosby

ElectRical prospecting by potential methods has been applied to mining problems for some years and determinations of the depth to bed rock have been made, but so far as is known it has not been used previously in the solution of civil engineering problems, such as investigating the foundations of dams. During the past winter and spring the senior author has been engaged as consulting geologist in studying the site of a large dam on the upper Connecticut River and has had the satisfaction of introducing electrical prospecting to foundation problems. The valley across which the dam is to be built is underlaid by a deeply buried preglacial gorge which is filled with glacial deposits. An extensive drilling campaign was in progress, but the work was unusually slow and expensive on account of the number of boulders in the overburden. The necessity of speeding up the work was pressing and it was decided that much of the needed information could be obtained by geophysical methods. After investigating the various methods and conferring with the company engineers and with the consulting engineer, Albert Crane, a contract was made with the Schlumberger Electrical Prospecting Methods, and an observer with apparatus was sent to the dam site the first of April, 1928. The problem was to determine the depth to rock at various points in order to prepare a contour map of the bed-rock surface and outline the buried gorge in the vicinity of the dam site. Over one hundred determinations of depth have been made and the bed-rock topography is now known in considerable detail. In addition, some information has been obtained about the nature of the overburden. The drilling has been continued; in fact, two additional drills have been put to work, and the electrical determinations have been checked at several points. At one of these the depth to rock given by the electrical work was 142 ft. and the drill found rock at 147 ft., an error of less than 4 per cent. The electrical work has also been checked by the geological study, and it has been found that when the electrical determinations are in agreement with the geological expectations they are probably reasonably accurate. When the electrical interpretation of the subsurface topography is incon-

Jan 1, 1929

By N. M. Langdon

In considering the magnificent success of Mr. Gayley's bold experiment of applying dry blast to the blast-furnace, whereby a saving of 20 per cent. of fuel per ton of iron is effected, the question arises whether still further economy in fuel is possible, and, if so, how it is to be attained. The manner in which the heat generated in the furnace is utilized in the production of pig-iron may be determined, by the method of Bell and Gruner, for any furnace for which the necessary data are obtainable ; and the study of the operation, under various conditions, of a number of furnaces, for which such information has been worked out, should enable us to form some conclusion on the subject. The tables and calculations here given cover the operations of several furnaces reported in our Transactions ; also the two furnaces using natural and dry blast ill Mr. Gayley's experiment, for which the heat-equation has been worked out by Prof. Joseph W. Richards in his admirable discussion ' of Mr. Gayley's paper, The Application of Dry Air Blast to the Manufacture of Iron, and, finally, various hypothetical furnaces. The full list is as follows : A. Isabella furnace, with natural blast. B. Isabella furnace, with dry blast. The data stated for A and B in Table 111. are those given by Professor Richards, except that the heat-units are given for one unit of iron instead of 100 units, and some items of heat supplied, as stated by Richards, have been subdivided, the total being the same as given by Richards. (Columns A and B are introduced in Table 111. for comparison with C and D.)

Jan 1, 1910

By Arthur A. Brant

Let us start back as far as possible, to the beginnings of this universe, some 5 billion or more years ago. This is a time interval that can be crudely underestimated by the moon-earth tidal friction effects that have increased the length of the day by about 1/1000 second per century-from a 5 to 7 hour day to its present 24-and have moved the moon away at 5 inches per year to its present 240,000 miles. The oldest stony meteorites from interplanetary space give an age dating of some 4.6 billion years, approximating the time of formation of our earth. Further, certain stars pulsate, the period of pulsation being related to their absolute brightness. Measuring apparent brightness and comparing, gives the distance away. Thus Hubble and Shapley of Harvard, from 1925 on, were able to show that the universe reached as far as our telescopes could scan. The Doppler shift of the hydrogen red lines could only mean that the nebulae, or galaxies, were moving away at velocities increasing with their distances, by 180 km/ sec velocity increase for every million light year's distance. In short, the universe is expanding like an exploded bomb.

Jan 4, 1964

By William Colby

INCREASING governmental control of human activities seems inevitable. Within the present generation railroad rates and the public sale of water, gas and electricity have been subjected to rigid regulation. The field of control is slowly but surely being enlarged, and it is the object of this paper to outline in brief space this tendency toward increased governmental regulation, as far as mineral resources are concerned. Our, dual form of government complicates the problem. We must deal not only with the powers of the Federal Government, but also with those of the individual States. In order to approach this question intelligently we must have some conception of the powers and jurisdiction of the States and the United States, respectively, over mineral lands and mineral production. Starting with the Federal Government we find it never owned any public domain within the States that formed a part of the thirteen original colonies and, for historical reasons, the same is true of Tennessee and Texas. The Mid-Western States were erected out of the public domain which was acquired by the United States through cession from the original States or by purchase from foreign nations. Congress early in the last century adopted a policy of leasing public lands containing lead deposits in a portion of this Mid-Western territory, but later abandoned that policy and disposed of such public, lands, mineral and non-mineral, outright so that they long since have practically all passed into private ownership and become subject to the general jurisdiction of the respective State governments. In the great public domain lying west of the Mississippi River, and in portions of some of the Southern States, the Federal Government adopted a new mineral land policy following the discovery of gold in California. (Acts of Congress of 1866, 1870, and 1872.) The mineral lands within these States, instead of being disposed of on the game basis as agricultural lands, as occurred in the Mid-Western States, were segregated from agricultural lands and sold under special laws intended to encourage mining, giving the miner the free right to locate and work these mineral lands without paying any royalty to the Federal Government. A miner could also obtain at slight expense a complete

Jan 1, 1930

By R. R. Hawthorne, H. F. Dunlap

A method of calculating formation water resistivities from chemical analyses is presented which is somewhat faster and more accurate than previously described methods. For 26 formation water samples taken from wells in the Texas Gulf Coast, the average deviation of calculated from measured water resistivities was 3.3 per cent, with an average bias of + l.l per cent in the calculated values. This compares with average deviations of 4.6 per cent and 7.8 per cent, with corresponding average biases of +3.2 per cent and -6.3 per cent, for the two methods previously described in the litera-

Jan 1, 1951

By Fred C. Bond

AN improved method of measuring the surface area of a comminution product down to any desired particle size has been developed. The method is largely graphical, and requires relatively little calculation. It can be used with materials containing large amounts of clay, or excess fines of any kind. The surface area S is expressed in terms of square meters per100 c.c. of solids. This expression is based upon volume rather than weight, and is considered to be more suitable for crushing and grinding problems, where the machines ordinarily are operated under constant volume conditions. It has the advantage that surface areas of different materials can be compared directly, even though their specific gravities may be unknown. The "specific surface" of a material, or the number of square centimeters of surface area per gram, is equal to 100S divided by the specific gravity. Particle diameters are expressed in microns, K being the diameter of the largest particle present and L the grind limit, or lower size limit of the particles formed directly by grinding. The value of K does not always coincide exactly with the diameters of the largest particles retained on the coarsest testing sieve, since the largest particles formed in crushing and grinding are often slabby, or have other irregular shapes. L has been chosen as 0.700 microns, or number 27.5 in the size number series,1 for reasons to be explained later. S is the total surface area of all particles larger than L microns in diameter. When a homogeneous comminution product is separated into fractions whose diameters bear a constant geometrical relationship [p] to each other, and the log per cent weight retained upon each size and passing the next larger size is plotted against the log diameter, a straight line results, which is called the distribution line, and which has a slope in called the distribution modulus. The distribution line can be extended to any desired limiting size, and the total surface area of all particles larger than that size can be calculated. The equation of the distribution line is w = Cxm [I] where w is the per cent weight retained on each successive sieve; x is the particle diameter; and C is the per cent weight retained on an opening of unit diameter.2 Theoretically, the distribution line can be extended to include infinitely small particles. When it is so extended, and the assumption is made that no fine particles are present other than those accounted for by the equation; the log per cent cumulative weight passing any series of sizes, plotted against the log diameter passed, will result in a straight line lying parallel to and above the plotted distribution line.

Jan 1, 1941

By Lester Uren

Beginning with theoretical concepts of oil drainage, this paper demonstrates that the flow of petroleum into a well from a stratum of oil-saturated sand of uniform texture increases with the diameter of the well. This conclusion is supported by experimental evidence. It appears that if a well may be reamed to a diameter of 20 ft. within the oil sand, its production will be approximately doubled. A novel method is proposed for forming and supporting a cavity of such proportions within the oil-producing stratum. PETROLEUM occurs, in nature, as a fluid saturating the pore spaces between the grains of porous rocks or aggregations of rock particles such as sand, sandstone, conglomerate, shale, limestone, etc. The oil, under the influence of gas pressure, hydrostatic pressure, gravity, earth pressure, and, perhaps, other natural forces, is caused to flow through the porous "reservoir rock" into wells penetrating the stratum in which the oil occurs. The principal moving force is the pressure of dissolved or occluded natural gas within the oil, though this;, force is assisted by gravity and by the hydrostatic or buoyant pressure of ground water about the edges of the "pool." The wells, providing outlets to the surface, are centers of reduced pressure and the flow of rock fluids into a particular well is usually an expression of the difference in pressure existing between the space within the well and that of the stored oil .within the reservoir rock. The greater this differential pressure, the more rapidly will oil flow from the source rock into the well. Opposing movement of the oil from the reservoir rock into the well are certain natural forces related to the rock structure, such as pore friction and capillarity, and certain others related to the physical properties of the oil, such as viscosity and adhesion. The differential pressure between the well and the boundaries of the area drained by it must be sufficient to overcome the forces opposing flow if there is to be movement of oil into the well. If by any device the resistance to movement of the oil may be reduced, the oil will flow into the well at a more rapid rate and the effective area of drainage will be increased.

Jan 10, 1924

By M. E. Kukura, L. G. Stevens

As described in a previous presentation and in various patents, the Minerals Sciences Div. of UOP, Inc., has developed a modified reduction roast ammonia leach process for nickel laterites. This process gave considerable improvement in extraction over the conventional Caron approach as practiced in Cuba, Australia, and the Philippines. This greatly improved response was obtained with a wide variety of ores. This paper describes the pilot plant flowsheet and reviews the design features unique to the UOP process. Operating results from pilot plant campaigns are compared with bench scale results. Operating problems and their solutions are also discussed.

Jan 1, 1976

By Harrison Schmitt

IN the practice of ore finding the geologist is continually confronted with the question of oreshoot extension, so that the general problem seems worthy of systematic investigation. This problem appears when the reserves are estimated and when the advisability of deepening the shaft comes up. Moreover, there is need for lower development cost to keep pace with cost reductions in other departments, or even to offset a rising cost of ore finding or ore following. This can be gained by close geologic control of the development; and much of the geology involved is that bearing on the downward, upward, and horizontal extensions of shoots. Furthermore, the purchase of a mine or prospect often depends directly on the question of shoot extension; because it is seldom that the ore is fully developed and the purchase price is almost invariably based largely on "possible" and geologically prospective ore. Most current methods for estimating '(possible" and the more nebulous classes of ore are crude and indecisive. In the following pages the extension of oreshoots is the major theme, although the more basic subject, the general art of ore finding, is given some space. (A) Direct Methods of Extension Prediction (I) Extrapolation and Interpolation of Shoots by Use of Conventional Geologic and Assay Plans, Projections and Cross-sections There is little need for stressing the desirability of detailed geologic plans, assay plans, projections, and cross-sections as a basis for the study and extension prediction of shoots. Underground and surface mapping, in most cases, ought to be done in exhaustive detail. All features of obvious bearing should be mapped and it is good practice to record all possible details, some of which may become significant when studied in the ensemble. It should be emphasized that the mapping should be done with an impartial mind, with interpretation reduced to the minimum. The symbols of the map can be made to distinguish observed facts from interpretation.

Jan 1, 1929

By Edmund C. Pechin

THE iron trade of America seems on the point of a new departure. After years of struggling against heavy odds, patient endurance in periods of depression and loss, fears and hopes alternating as failure or success seemed to be the penalty or reward ; wanting in sufficient capital, embarrassed by reason of imperfect knowledge and lack of skilled labor, confronted by a powerful foe-every doubt has at last vanished, physical and mechanical difficulties have been largely overcome, capital has become more abundant and remunerative, the excellence of our product has been everywhere established, - and the peculiarities of American character-pluck, energy, and perseverance -have at last placed the trade upon a foundation so broad and stable that upon it we begin to erect the structure of a world-wide business. Concerning the future of the iron trade in the United States there can be but little doubt. The growing scarcity and constantly increasing cost of raw material in Great Britain, their loss of labor by emigration, the social disturbances among the working-classes, assuming a more threatening attitude on each new outbreak ; the rapidly decreasing value of money, in consequence of the enormous production of gold and silver, combine to forbid any return to former prices, and indicate that a point has been reached beyond which any marked increase of production is improbable. The same causes are operating to a greater or lesser extent upon the Continent. . In the meanwhile the growing wants of humanity are rapidly outstripping these sources of supply. In addition to the steadily increasing foreign and home demand, we find, the world over, the most intense activity everywhere displayed in enterprises requiring

By J. S. Ross

Although the opinion has prevailed for several years that bottoni-hole choking under certain flow conditions should effect an increase in flow efficiencies, the use of bottom-hole chokes until recently has been limited in application mainly because of mechanical difficulties encountered in their construction. Within the past year, however, bottom-hole choking, through the development of a removable type of choke, has been applied successfully under various conditions of flow in many Mid-Continent fields. The observation of these field tests indicates that bottom-hole choking, although not applicable to all flow conditions, has an important place in the operation of oil and gas wells. This paper gives briefly the conclusions drawn from the data obtained from the experiments with this bottom-hole choke under various flow conditions, and a description of the choke and its operation. Purpose of Bottom-hole Choking Since, in a normal well, the velocity with which the column of gas is moving generally has a direct bearing upon the quantity of oil it can lift, probably the main purpose of bottom-hole choking is to accomplish an increase in the velocity of this- rising column, particularly in the lower portion of the tubing string. This it does first, by expansion of the free gas accompanying the oil; next, by liberation and expansion of some of the occluded gas normally carried in the oil to the surface; and lastly, by atomization, which results in a more intimate and uniform mixture of the oil and gas. It is apparent, then, that if this velocity, particularly in the lower portion of the flow string, at a given rate of production, is inefficiently low, owing either to an insufficient supply of gas or to excessive surface choking, and slippage takes place, bottom-hole choking should bring about an increased velocity of the gas and hence an increased lifting capacity. But if the velocity of the column of gas at this same rate of production through a surface choke alone is at or above a velocity necessary to lift the oil efficiently, increasing the velocity by bottom-hole choking would probably serve no useful purpose, other than to steady the flow by the better mixture of oil and gas and to lower delivery pressures.

Jan 1, 1932

By C. T. Van Winkle

MINE fires are always dangerous and are frequently accompanied by loss of life during the period of confusion which is apt to follow their discovery. In metal mines, fires may result from the accidental ignition of some combustible material, or they may be of spontaneous origin resulting from the rapid decomposition of sulphide. They occur frequently enough to demonstrate the need of some special equipment and a general plan for controlling them, in addition to measures for their prevention. Nearly all the large copper mines have had fires, and the methods of fighting them have been well described in recent papers, notably-by C. L. Berrien,1 R.. E. Tally,2 and others in discussion. The Copper Queen mine has many shafts, which are connected by underground workings. The deeper parts are ventilated by fans, but in the shallower portions natural ventilation through numerous connecting raises or shafts is sufficient. There have been several fires in the past few years, of which all are extinguished but one, and that is under control. These notes cover particularly the preparations that are being made-to check a new fire, partially or temporarily, and to facilitate the escape of workmen in the interval before a definite plan of fighting it can be established. A fire may occur in a shaft or station, or in some working father away. In case of fire in an upcast shaft, the gas would escape to the surface and the immediate result would probably not be dangerous to workmen, as they could escape by other shafts. In a downcast shaft, however, the gas would be distributed very rapidly throughout a large portion of the mine, and men might easily be trapped and asphyxiated. A fire in mine workings, drift, raise, or stope, would be dangerous in a degree, but the draft there is likely to be less strong than in a shaft and probably a smaller area would be invaded by the fire gases.

Jan 1, 1918

By E. T. Cox

WHILe engaged, in the year 1856, in determining the oil-bearing properties of some bituminous coals from Western Kentucky, by subjecting them to dry distillation in an iron retort, which held about a pint;, and to the neck of which were attached several bottles, for collecting the carbon oils, and washing and measuring the gas, I observed that there was a very great gain in the weight of coke thus made, over that obtained from the same coal when charred in a platinum crucible, as is usual in the laboratory for making the proximate analysis of coal. It was thought at the time that the increase of coke, by the former mode of treating the coal, was due to the pressure which the retarded gas exerted upon the solid carbon, and the possible fixing of a portion of the carbon from the volatile hydrocarbons. For the purpose of obtaining a more definite idea of the effects of pressure on the coking of coals, a series of experiments were made this spring under my direction, by my assistant, Dr. G. M. Levete. The results are highly instructive and full of interest, since they point out some peculiarities in the nature of bituminous coals which

By R. E. Cech, T. D. Tiemann

It has been shown that hydrogen may be made to serve as a rapid and eflicient reducing agent for Cu, Ni, Co, and Fe sulfides if a scavenging agent for hydrogen sulfide is intimately mixed with the sulfide particles being reduced. Accelerated reduction kinetics are demonstrated for nickel sulfide. Copper, nickel, and cobalt sulfides, when treated at certain temperatures in a combined reducing agent-scavenging agent system, are converted to voluminous masses of fibrous metal product. Studies have been carried out to determine the conditions which lead, on the one hand, to irregular poly crystalline fibers and, on the other, to long single crystal filaments a few microns in diameter. A mechanism is proposed to account for the formation of single crystal filuments. The sulfide minerals of Cu, Ni, Co, and Fe are an important source of these metals yet there has been comparatively little scientific effort devoted towards understanding reduction mechanisms of these minerals. This may be, in part, due to the fact that the most convenient reducing agents for carrying out such studies, viz., hydrogen and carbon, do not react appreciably with sulfides. We have found that the reaction of hydrogen with metal sulfides can be markedly accelerated by placing a scavenging agent for hydrogen sulfide in close proximity to the metal sulfide. A brief series of experiments demonstrating relative reduction rates is reported in this paper to illustrate the effect. With the reduction process thus accelerated we have observed an unusual type of reduction behavior on some of the sulfides investigated. Under certain conditions the metallic product of the reduction reaction takes the form of filaments growing outward from the sulfide particles. The present paper deals largely with efforts to classify the various types of growth forms observed. This study has shown that filamentary growths from sulfides take a much greater variety of forms than has heretofore been reported by Ercker,1 Hardy,2 and Nabarro and Jackson3 in their reviews of metallic growths from copper and silver sulfides. THERMODYNAMIC CONSIDERATIONS The thermodynamics for hydrogen reduction of metal sulfides is quite unfavorable. For the sulfides considered here equilibrium constants typically range from 10-3 to 10-5. These low equilibrium constants impose severe kinetic limitations on reduction since hydrogen sulfide must be transported out of the system at concentrations of only a few hundred ppm. Unless extremely high gas flow rates are employed the atmosphere surrounding any sulfide particle will always be essentially in equilibrium with the sulfide. If, however, one places an efficient scavenging agent for hydrogen sulfide in close proximity to the metal sulfide particles the concentration of H2S near the metal sulfide will be held to a very low value. This would permit the reduction reaction to proceed with little or no inhibition from a buildup of reaction product gas. It is well known that calcium oxide is capable of removing hydrogen sulfide from a hydrogen gas stream of low dew point.4 If a sufficient quantity of calcium oxide is mixed with the metal sulfide particles the reaction: CaO+H2S=CaS+ H2O [l] will substitute moisture in place of hydrogen sulfide in the gas stream and this will not affect, in a direct manner, the reaction: MeS +H2=Me + H2S [2] A convenient method of considering the thermodynamics of the combined reducing agent-scavenging agent system is to consider the atmosphere when the partial pressure of hydrogen sulfide is the same over both the metal sulfide and the scavenging agent, i.e., pH2S (1) =pH2S (2). As a consequence: pH2O (1) pH2(2) =K1K2 The chemical driving force for reduction will depend inversely upon the moisture content of the gas and will be 0 when, in the system, pH2O = pH2.K1K2. Table I lists values of the equilibrium constants for reduction and H2S scavenging reactions for a number of sulfides at several temperatures. Data are taken from Rosenqvist4,5 and Kelly.6 The equilibrium constant products calculated from this data show that the limiting level of gaseous reaction product has been increased by a factor of 10' to l04 as a result of substituting a reducing agent-scavenging agent system for a simple reducing agent system. One possible side effect which must be considered is the possibility that the moisture evolved in the scavenging reaction might cause the atmosphere in the system to be sufficiently oxidizing to favor the formation of oxide rather than metal. This possibility was examined by comparing the equilibrium constant products listed in Table I with equilibrium constants for hydrogen reduction of the respective metal oxides. It was found that for copper, nickel, and cobalt the combined reduction-scavenging reactions could not develop a sufficiently high oxidizing potential in the

Jan 1, 1970