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By Clark A. Sumner, D. Arthur Burnham

A process for recovery of greater than 99% of the copper contained in acid leach solutions by sulfide precipitation using hydrogen sulfide as a hydrometallurgical reagent has been developed. The process incorporates the concept of hydrogen sulfide addition to recycled copper sulfide solids in a turbulent flow area where further precipitation or agglomeration occurs to increase the effective particle size of the copper sulfide precipitate. Because the recycled solids provide a larger number of particles upon which momentary excesses of hydrogen sulfide are absorbed, oversulfidization of the product is prevented. Copper sulfide precipitates produced in this manner in a laboratory test reactor showed greatly improved physical characteristics compared to copper sulfide precipitates obtained by conventional direct precipitation in which H2S is bubbled directly into acid leach liquor. Copper sulfide precipitates were evaluated and compared by use of filtration tests and settling rate studies. Electron microscopic examination of the solids confirmed the presence of larger particles in reactor-precipitated copper sulfide. Flotation was examined as an alternative to filtration for recovery of CuS precipitates and was found to achieve complete CuS removal without addition of collector or frothing reagents in a period of 2 min. In the same test reactor, a rapidly floatable CuS precipitate was also formed by mixing H2S with acid liquors used to leach crushed copper oxide-copper sulfide ore (LPF process). In the presence of gangue from the crushed ore, flotation of both natural and reactor-produced copper sulfides resulted in recovery of better than 90% of the copper contained in the crushed ore.

Jan 1, 1974

By Carlo Massa

THE Societá Auonima di Miniere e di Alti Fourni, familiarly known as the " Elba Company," works the rich ore-deposits of the Island of Elba under a long-term contract with the Italian Government. The ore-deposits are scattered over the eastern and southeastern coast; but as those parts of the island are not well provided with ports, the blast-furnaces were built at Portoferraio, the principal town of the island, situated on the northern shore, and possessing a magnificent natural harbor where even vessels as large as the battleships of the Italian navy can comfortably anchor. In the selection of Portoferraio. the cost of transporting the iron-ore from the different mines to the blast-furnaces has been reduced to a minimum, and shelter has been provided for the Company's flotilla of tugs and barges, as well as for the steamers carrying coal and pig-iron. The whole plant, of which a general view is given in Fig. 1, comprises 1. A discharging-pier with unloading-cranes. The ore and coal are transported from this pier by means of an aerial cable-rail¬way to the coal- and ore-storage yards. This cable-railway is supported by an iron bridge extending from the pier to the shore and by a wooden trestle extending from the shore to the yards. , 2. Blast furnaces, two in number, with all the accessory appa¬ratus, such as blowing-engines, dry purifiers, Cowper hot-blast stoves, hoists, etc. 3. Coke-ovens, two batteries, with coal-bin, crushers and boilers. 4. Engine-house containing the blast-engines and the electric generating-station. 5. Pumping-plant. 6. Narrow-gauge railways.

Mar 1, 1905

By Orville R. Lyons, A. C. Richardson

F. X. Ferney—We are pleased that this paper was presented at this meeting and thank Mr. Richardson and Mr. Lyons for their effort and work in preparing it. We agree with the authors that it was unfortunate that more comprehensive data were not available when the paper was prepared, this being particularly true since we had no knowledge that the paper was being written and could not make available data which were in our process files. Further, it is our opinion that because the data are not sufficiently comprehensive the results which are presented are erratic and will lead to false conclusions. As we see it, there are three Specific reasons why the data which are presented cannot be considered accurate. 1. The preparation plant was not at equilibrium while the samples were being taken. This is indicated by the fact that the percent of solids in the circulating water varied from 3.9 pct to 10.7 pct during the period when the plant was sampled. 2. We do not believe that the samples of Bird feed which were taken were representative and could indicatc the true feed to the filter. Evidence of this is shown in the data where the dewatered product leaving the centrifuge contains more coarse material than the feed to it, that is, material which is +6-mesh in size. 3. We question if the data concerning screen analysis in the fine sizes is accurate and would conclude (from the data) that these tests were made by a dry-screen method. We have found that wet screening is always necessary to obtain a true picture of the quantity of —200-mesh fines which is present. The test work described in the Lyons-Richardson paper was conducted some time ago and the tests were carried on during a period when the preparation plant had not ironed out all of their start-up problems. Since that time most of these problems have been corrected and now this is a smooth running, well-operated prep-

Jan 1, 1951

By Orville R. Lyons, A. C. Richardson

F. X. Ferney—We are pleased that this paper was presented at this meeting and thank Mr. Richardson and Mr. Lyons for their effort and work in preparing it. We agree with the authors that it was unfortunate that more comprehensive data were not available when the paper was prepared, this being particularly true since we had no knowledge that the paper was being written and could not make available data which were in our process files. Further, it is our opinion that because the data are not sufficiently comprehensive the results which are presented are erratic and will lead to false conclusions. As we see it, there are three Specific reasons why the data which are presented cannot be considered accurate. 1. The preparation plant was not at equilibrium while the samples were being taken. This is indicated by the fact that the percent of solids in the circulating water varied from 3.9 pct to 10.7 pct during the period when the plant was sampled. 2. We do not believe that the samples of Bird feed which were taken were representative and could indicatc the true feed to the filter. Evidence of this is shown in the data where the dewatered product leaving the centrifuge contains more coarse material than the feed to it, that is, material which is +6-mesh in size. 3. We question if the data concerning screen analysis in the fine sizes is accurate and would conclude (from the data) that these tests were made by a dry-screen method. We have found that wet screening is always necessary to obtain a true picture of the quantity of —200-mesh fines which is present. The test work described in the Lyons-Richardson paper was conducted some time ago and the tests were carried on during a period when the preparation plant had not ironed out all of their start-up problems. Since that time most of these problems have been corrected and now this is a smooth running, well-operated prep-

Jan 1, 1951

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By B. M. Larsen

Attempting to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic" and "macroscopic," depending on whether the variations in concentration of solutes or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also untlerly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all sepregation effects. Undercooling and Nuclei Formation It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus temperature. In practical terms this means that the nuclei number illcreases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. Temperature Gradients and Heat Dissipation during Freezing Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period. Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1945

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By Michael Perch, Charles C. Russell

Nearly 75 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1942

By Robert Maes, Robert de Strycker

The Cu-Sn-As systeM was studied in the region near the Cu-42 and (214-As binary diagrams, where reactions in the solid state appear, resulting from the decomposition of the y(Cu-Sn) phase and from the formation of the 7 phase (Cu,As). The techniques used were microscopic observation, thermal analysis by dilatometry, and X-vay diffraction. The formation of the 7 phase gives rise to a ternavy pevitectoid veaction; the decomposition of the y phase gives rise to five transitional reactions. The temperatures of almost all these reactions could be determined; in the most favorable cases , the accuracy of this determination was of 11.5-C. The 7 phase is stabilized by tin additions, the arsenic atoms being replaced by tin atoms up to 35 pct; this has allowed the preparation of pure j) phase and the confirmation, by extrapolation, of the conrposition of this compound in the Cu-As diagram. In the first part of this work, the solidification reactions in the Cu-Sn-As phase diagram were studied. In the copper corner, the structure of the alloys presented the evidence of reactions in the solid state: on the one hand, all the alloys containing the y phase of the Cu-Sn diagram showed, under the microscope, that this phase had formed different decomposition products after complete solidification; on the other hand, the appearance of the 7 phase of the Cu-As diagram necessitated the introduction of a peritectoid formation reaction. The study of the decomposition of the y phase has been done by preparing about forty alloys that were homogeneous y at high temperature. The formation of the 7 phase has been studied by means of a few alloys with a composition near the homogeneity field of this phase at room temperature. The part of the Cu-Sn phase diagram of interest for this study is represented by Fig. 1, with the phase designation which will be used in the remainder of this paper; it is drawn after Hansen and Anderko.' The Cu-As diagram has already been presented in Part I of this work; the significant features of this study are the existence of the arsenides CusAs and Cu5Asz, and the formation of a compound CUEAS, designated as the 7 phase, by a peritectoid reaction at about 325°C. EXPERIMENTAL METHODS The fundamental technique for the investigation of this part of the Cu-Sn-As constitution diagram was microscopic observation; the greatest part of the observed alloys has also been subjected to thermal analysis by dilatometry; a few selected alloys have then undergone an X-ray analysis by powder diffraction. Alloy Preparation. The alloys were prepared from the same products as in Part I of this study: cathode copper, arsenic with a purity better than 99.5, and tin with a purity of 99.98. The fusion of the ternary alloys was realized from

Jan 1, 1967

By F. W. Rols-Hausen, F. W. Jessen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By F. W. Jessen, F. W. Rols-Hausen

It is the purpose of this paper to present data on brines occurring in the Frio formation of the Texas Gulf Coast, and to show how their composition varies, (1) with depth below the surface, (2) with depth below the top of the formation, and (3) along the approximate strike. The brines vary in chloride content from 3,180 to 73,000 p.p.m., though the average salinity of the salt waters is shown to vary with total depth; the concentration being 35,000 to 40,000 p.p.m. at 3500 to 5500 ft., slightly less than 50,000 p.p.m. chloride at 5500 to 6500 ft. and average 38,000 to 40,000 below 6500 feet. From the analyses available, it appears that the highest concentration of salts occurs in the upper 300 ft. of the formation, while lower salinity is found with increasing depth below this point. The salt waters from wells in Starr County show less concentration of dissolved salts than in any other group of wells farther north along the strike. In all, 116 analyses from 63 fields and 14 wildcats, from depths ranging from 1300 to 11,400 ft. below the surface and from z to 3240 ft. below the top of the Frio, are recorded. Introduction Brines have been studied for many Years in an attempt to solve some of the geologic and production problems associated with the production of oil and gas. One practical application of study of . water analyses is the correlation of waters occurring above, in, or below the producing sand in the same field or throughout the same formation. The Frio formation, the series of sands and shales occurring below the Marginulina zone and above the Vicksburg, is one of the major oil and gas-producing formations in the Texas Gulf Coast. Fossils are rare or absent in the upper Frio throughout most of the area. When available, cuttings and cores, and electric logs were used to determine the top of the Frio. A change in lithology was used to determine this point in most of the wells, and fossils were used in some of the deep wells. It is realized that a change in lithology is not perfect for correlation purposes over long distances and some of the trends may be influenced by the inability to differentiate between the nonfossiliferous Marginulina zone and the Frio. It underlies virtually all the area shown on the accompanying map (Fig. I). Although it is not productive in the updip facies, it has been explored to a limited degree below I2,000 ft. Further more, toward the coast line future drilling to deeper depths should encounter this formation. Although thousands of wells have penetrated or drilled entirely through the formation, very few water samples have been secured from the many sands occurring in this formation and analyzed. Previous Investigation No previous published study has been made of the chemical composition and concentration of waters from the Frio formation. However, one water analysis

Jan 1, 1944

By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By Michael Perch, Charles C. Russell

Nearly 7 5 per cent of the total coke production in the United States in 1940 was consumed in blast furnaces. In 1939 the percentage was 69.9, and in 1938 it was 61.3. To produce a net ton of pig iron 1757 lb. of coke was required in 1940 and 1760 lb. in 1939. These figures indicate how dependent the production of pig iron is upon the production of coke. The rate of iron production is in some measure influenced by the physical and chemical characteristics of the coke. Blast-furnace operators believe that the physical properties of coke profoundly influence the operation of the furnace. Although it is true that coke of a wide variety of physical properties is used in American blast furnaces, the periodic fluctuation of these properties is one of the causes of irregularity of blast-furnace operation. The purpose of this paper is to present a broad picture of the physical properties of by-product coke that are generally considered to be important by coke-oven and blast-furnace operators. Effects of the kind of coal used, the preparation of the coal, the rate of coking, and other factors will be considered. Of all these variables, the kind of coal used is by far the most important. In this discussion use will be made of the method of coal classification by rank1 standardized by the American Society for Testing Materials. Although this method of classification has been an American standard for several years, it has not been given the attention it deserves, especially in connection with the selection of coal for production of coke. Despite the fact that many producers of blast-furnace coke are limited to some particular source or sources of coal, a good understanding of the principles involved in setting up the standard method of classification may lead to a better appreciation of the causes of changes in coke characteristics. Furthermore, where it is necessary to select new coals as a substitute for the original supply, this method of classification can be of great assistance. The data presented have been gathered from many sources, but no attempt has been made to cover the vast literature. Instead, some of the more important data have been selected to show how coals and their carbonization affect some of the physical properties of coke. It must be emphasized that generalizations concerning the behavior of coking coals are presented and that individual coals may vary widely from the specific behavior depicted. Nevertheless, it is believed that the data illustrate certain typical behaviors. Neither was it possible to cover completely all the factors involved; for example, the macroscopic constituents of coal are believed to have important effects on the physical properties of coke, but since there is little information available for such study, and since vitrain, clarain, and durain are neither

Jan 1, 1943

By K. E. Brown, F. W. Jessen

It is deemed feasible to store atomic reactor fuel wastes in salt dome cavities when the differential pressure acting on the cavity does not exceed 3,000 psi and the temperature is less than 400°F. Tests at pressure increments of 1,000 psi were conducted on a 2-in, cylindrical cavity contained in a 6-in. long X 6-in. diameter salt core. The cavity exhibited stability under pressures up to 3,000 psi and temperatures to 300°F. At temperature ranges of 100 to 400°F and with pressures of 5,000 psi and above continuous deformation of the cavity resulted. Initial movement of the salt was observed at all pressares. This was evidenced by vertical deformation and cavity size reduction. INTRODUCTION The development of storage techniques for safe disposal of atomic reactor fuel wastes is a goal of the Atomic Energy Commission. Salt domes have been used successfully for storage of liquefied petroleum gases and hence should prove to be suitable for liquid waste products of atomic reactors. The purpose of the following work is to evaluate the practicability of utilizing salt dome cavities for such wastes and to de-termine particularly the effect of pressure and temperature on a salt cavity. This work represents a part of a comprehensive study covering the over-all problem of storing re- actor fuel wastes in salt domes and/ or salt beds. The problem of accurately determining the stresses which exist in rocks in the earth's crust is indeed a complex one. Theoretical studies have differed widely in many of the basic assumptions about the physical properties of the rock itself. Some solutions of problems in underground stress analysis assume that rock is elastic, homogeneous and isotropic in character; others assume that rock possesses plastic, viscous, elasticovis-cous properties, or a combination thereof. Experimental evidence has shown that salt possesses plastic, viscous and elasticoviscous properties.' Recent work has shown that salt becomes more plastic with temperature.' APPARATUS AND PROCEDURE For experimental study a cylindrical cavity was chosen for analysis since it provided maximum volume per unit of depth with constant diameter. This particular cavity shape, allowing for irregularities, can be easily leached out of salt domes in field operations. For the purpose of approaching underground storage conditions as nearly as possible, the following factors were considered: (1) control of pressure and temperatures, (2) measurements of temperature gradients throughout salt mass, and (3) measurement of structural stability of salt cavities. In order to obtain triaxial pressure on the salt cavity without resorting to the application of fluid pressure directly on the salt mass, a system was designed whereby the same effect could be produced through axial loading only. By cutting a core to close dimensions to fit a steel test cylinder and applying axial pressure, a lateral pressure was obtained. This equipment is shown in Figs 1 and 2. A steel cylinder was made from

By Donald D. Carr, Lawrence F. Rooney

Perhaps no other mineral commodity in this volume has as many uses as limestone and dolomite. These carbonate rocks are the basic building blocks of the construction industry, the material from which aggregate, cement, lime, and building stone are made. Carbonate rocks, and their derived products, are used as fluxes, glass raw material, refractories, fillers, abrasives, soil conditioners, ingredients in a host of chemical processes, and much more. Although the use of limestone and dolomite goes back before recorded history, new uses and products are continually being found. Carbonate rocks form about 15% of the earth's sedimentary crust and are widely available for exploitation. Found extensively on all continents, they are quarried and mined from formations that range in age from Precambrian to Recent. Reserves of carbonate rock are large and will last indefinitely, although high-purity deposits may be absent or have limited availability in certain areas. Limestone and dolomite are so useful and so abundant that in 1981 about 644 million tons were produced in the United States. In fact, about 75% of all stone quarried or mined in the United States was carbonate rock. Sand and gravel was the only mineral commodity produced in greater quantity. In this chapter we have sought to provide the general reader an overview of carbonate rocks, their composition, distribution, production, and uses, with emphasis on developments since 1960. In doing so we borrowed extensively from our report on the applied geology of limestone and dolomite (Rooney and Carr, 1971). The literature on the limestone and dolomite resources of the United States and Canada is so vast and diverse that one can easily become mired down in print. We tried to list those references that are easily accessible and that provide the economic geologist with a starting point for more intensive study. The table listing selected references on limestone and dolomite resources in Canada and the United States reflects our attempt to be selective rather than exhaustive and to direct the reader to the best sources of detailed information. Geology Mineralogy The principal carbonate rocks used by industry are limestone and dolomite. Limestones are sedimentary rocks composed mostly of the mineral calcite (CaCO3) and dolomites are sedimentary rocks composed mostly of the mineral dolomite (CaCO3 • MgCO3). Aragonite (CaCO3), which has the same chemical composition as calcite but a different crystal structure, is economically important only in modern deposits, such as oyster shells and oolites. Aragonite is metastable and alters to calcite in time. Some other carbonate minerals, notably siderite (FeCO3), ankerite (Ca2MgFe (CO3)4), and magnesite (MgCO3), are commonly found associated with limestones and dolomites but generally in minor amounts. Because of their similar physical properties, the carbonate minerals are not easily distinguished one from the other. Specific gravity,

Jan 1, 1983

By E. C. Carris

THE loading of bituminous coal mechan¬ically was recognized about the year 1900, but during the following 28 years less than 5 per cent of the bituminous pro¬duction in the United States was loaded by mechanical means. During the past i6 years, however, the usage of some form of mechanical loader has had a very rapid and accelerated growth, until at present production of bituminous coal by mechanical means has reached an all¬time high of approximately 46 per cent, and is still increasing. This rapid growth in the use of the mechanical loader has been supplemented by an increase in mechanical cleaning. The importance of mechanical cleaning of coal was recognized many years before the mechanical loader was introduced, because of the impossibility of cleaning manually the sizes below 2 in., and the increasing competition from other fuels. Utilization of mechanical loaders without mechanical cleaning on the surface for at least one or more sizes is the exception, rather than the rule. One exception is a mine that employs caterpillar-mounted mobile loaders exclusively, and mines the entire seam without any selectivity, and yet loads and ships six grades of coal of the very highest quality without mechanical cleaning. Such a fortunate situation can exist only where mining conditions are ideal, where top and bottom are exceptional and there are no impurity partings, and where there is loader height. The conversion from hand loading to mechanical loading has definitely intro¬duced many problems in the preparation plant of yesterday and in the modern streamline plant as well. Many of these problems have been solved by good, sound, conscientious initiative on the part of the plant personnel, with minor expendi¬tures; the solution taking the pattern of rearranging and improving the equipment at hand. Other problems have caused, and are causing, considerable concern and difficulty. LARGE IMPURITIES The removal of large quantities of large impurities from the lump coal, and their handling and disposal, is definitely a troublesome and costly problem. The cost of manually removing the impurities from the picking table alone, based on the actual recovered lump coal, can reach a cost of 42 cents per ton or more. In the design of future plants it would be wise to give this phase of preparation considerably more time and thought, particularly if the seam of coal contains one or more heavy partings and the mining procedure is all seam. This same caution applies to seams that may not contain heavy partings but have poor and heavy draw-slate top, which falls with the coal during the mining cycle. One of the more recent of the modern preparation plants has answered this problem by installing a rock crusher under the picking table in such a manner that the impurities can be diverted by gravity directly to the crusher. This reduces the

Jan 1, 1946

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper describes the field opeturluns at the Fry in situ combustion project in Crawford County, 111. Field operations may be divided into three phases—-preliminary engineering studies of 1960 and 1961, ignition, and, finally, operation of the test. The Fry combustion project was a pilot test of cocur-rent in situ combustion on a 3.3-acre inverted five-spot. In the summer of 1960, air injection tests were conducted using old wells in the area and a new air injection well drilled especially for the test. In the summer of 1961, four new oil wells were drilled on a 3.3-acre pattern for the pilot test. All old wells in the near vicinity of the pilot test were abandoned to preclude any possibility of gas escaping to adjacent formations. A compressor plant was also installed at the test site in 1961. Air injection tests and other engineering studies were made. At the conclusion of these tests, ignition was accomplished with a 40 kw electrical igniter. Operation of the Fry combustion test was little different from the usual oilfield operation with the exception of the high rate of air injection. No difficulty was found with the openhole completion. There were no unusual corrosion or emulsion problems until bottom-hole temperatures exceeded 150F. Four cores were drilled into the burned-out portion of the reservoir with no mechanical difficulties. INTRODUCTION A cocurrent or conventional in situ combustion test was conducted on the Fry unit of the Marathon Oil Co., in Crawford County, Ill. Besides testing combustion in the Fry type of reservoir, the test was intended to evaluate various operating procedures. This paper presents a discussion of the Fry combustion test field operations. The geology of the reservoir and the test performance are discussed in other papers.'.' HISTORY OF THE FRY UNIT The Fry unit consists of 11 leases totaling 337 acres in an area in which oil was originally discovered in 1906. Production from this reservoir, as from all Robinson sand reservoirs in the area, was very high during the first few years. As the dissolved-gas energy was dissipated, early attempts to retard the decline consisted of vacuum, air, and gas repressuring, and recently, most of the area has been subjected to water flooding. Following early air repressuring, the Fry waterflood unit was formed and water flooding initiated in July, 1952. In the area in which the Fry combustion test was conducted, a peripheral water flood of a 160-acre area was developed as shown in Fig. 1. Between 1956 and 1960, it became apparent that the water flood was unsuccessfd. In looking for a suitable site for an in situ combustion test, the Marathon Oil Co. selected the Fry unit as possessing those features most desirable for such a research project. Field operations associated with the Fry combustion test began in the spring of 1960.

Jan 1, 1966

By R. A. Nadler and

Specimens of Ti-155A (Ti-5Al-1.3Fe-1.3Cr-1.2Mo), Ti-6Al-4V and Ti-4Al-3Mo-1V were hydrogenated, aged to high strength levels, and subjected to notched stress-rupture tests and tensile tests at two strain rates. Both Ti-6Al-4V and Ti-155A were relatively unaffected by hydrogen in amounts exceeding those found in commercially -produced material. Inconsistencies in the data and a relatively low initial level of ductility prevented an accurate determination of the hydrogen tolerance for aged Ti-4Al-3Mo-1V, but there was no evidence that this alloy was any more susceptible to hydrogen embrittlement than Ti-155A and Ti-6A1-4V. THE metallurgical literature has been considerably enriched in the past five years by the publication of the results of many investigations which were concerned with the effects of hydrogen on titanium and its alloys. Although it is not the authors' intention to provide a complete literature survey of this vast field, it is worthwhile to summarize briefly some of the important factors which influence the embrittling phenomenon in a - B alloys. Some of the influencing factors are those of strain rate, temperature, and composition. Hydrogen embrittlement in a - B titanium alloys is now believed to be a strain-induced phenomenon, and whether or not embrittlement occurs at high hydrogen levels depends largely upon whether sufficient time is available for hydride precipitation. This condition is fulfilled by tensile testing at very slow strain rates or by rupture testing smooth or, preferably, notched specimens over relatively long periods. Conveniently, maximum embrittlement occurs at or near room temperature. The presence B - stabilizing elements, in amounts sufficiently small to prevent an all -B or nearly all -P condition, promotes hydrogen embrittlement and this tendency is believed to be related to the amount of a - B interfacial area present. Aluminum, by increasing the solubility of hydrogen in A titanium, greatly reduces the danger of hydrogen embrittlement, while oxygen has been shown to have detrimental effects.' The preceding discussion is based on experimental work performed on annealed a - P alloys. This early work has shown that annealed Ti-6A1-4V and Ti-155A are relatively insensitive to the embrittling effects of hydrogen.' Although no work has been reported on annealed Ti-4A1-3Mo-lV, the alloy would be expected to exhibit somewhat the same insensitiv-ity as Ti-155A. In sharp contrast to the voluminous literature on annealed titanium alloys is the paucity of reported investigations on materials receiving commercial heat-treatment cycles. To date, the most notable contributions in this field have arisen from two separate investigations on Ti-3Mn-1Fe-1Cr-1V-lMo, the so-called 3Mn comple~. These investigations

Jan 1, 1961

By F. S. McNicholas

IN the writer's opinion the term "block caving" has been rather loosely applied to a general principle of mining, and therefore detailed classification of caving methods and draw, together with the characteristics required for each method, will fill a desired need. Selection of caving method should be made only after a study of all governing conditions, such as size of orebody, lateral and vertical extent of ore-body, attitude, treatment demands, possible resultant pressures, and cost and profit comparison of methods. Successful caving methods can be classified under six main headings: (1) Full-protected block caving, (2) semi-protected block caving, (3) unprotected block caving, (4) full-panel caving, (5) half block-panel caving, (6) block-panel caving. The methods and factors governing choice of method are shown in Table I. Full-protected Block Caving Full-protected block caving consists of develop-ing, undercutting, and drawing to exhaustion a block of ore of predetermined size without coordination of mining or draw with adjoining areas. The block is mined and drawn as an independent unit (Fig. 1). Full-protected block caving demands that mining and draw cannot be done against unconsolidated capping in adjoining caved and exhausted blocks. Two sides of block are against solid. Caved capping must be allowed to consolidate for a suitable period, usually not less than one year. Pillars may be left in lieu of consolidated capping (Fig. 2). The advantages of full-protected block, caving are: (1) A definite area is developed, mined, and drawn as a unit so that all work may be completed, the block drawn to exhaustion in the minimum length of time, and the area then abandoned. (? Production is not restrained because of coordina1, on with adjoining areas. (3) Records of draw and caved reserve of ore are good. Upon abanwnment of the block, accountability for production is closed out with no carry-over to adjoining areas. The disadvantages of full-protected block caving are: (1) Side dilution from the draw adjacent to the consolidated capping may be serious, particularly where capping does not consolidate sufficiently in the allotted time. (2) Boundary weakening is needed on the solid sides of the block except in weak rocks. (3) Maximum cantilever and compression effect to aid caving and fragmentation may not be secured since the draw should proceed from the solid to the consolidated capping to minimize side dilution. However, undercutting from the loose (caved capping) to the solid with a slight initial draw in the same manner will develop cantilever effect. (4) A period of at least one year, more is usually desirable, must be allowed for caved capping ,to consolidate before mining the adjoining block, depending upon the characteristics of the capping. (5) Capping may not consolidate sufficiently in the time that can be allowed. Full-protected block caving is indicated where: (1) The ground is weak and heavy and workings

Jan 1, 1952

By J. L. Bruce, G. W. Nicolson

THE country rock of the Mavrovouni mine of the Cyprus Mines Corp. is hydrothermally altered, disintegrated pillow lava, with very little tensile strength ("short" ground). In places, especially when wet, it is heavy ground, though not extremely heavy except where movement has been caused by underlying or nearby stoping operations. Damage by caving from roof or sides of galleries is not sudden but progressively faster when the size of the cave increases as a result of the fall of small pieces. CEMENT AND CONCRETE LININGS During early operations, galleries in the country rock were supported by customary mine-timbering methods. Available timber, however, was of poor quality and of relatively high price, and replacements were frequent and expensive. Furthermore, the massive sulphide ore bodies required large volumes of fresh air for ventilation and cooling, and it was therefore desirable to provide smooth-lined galleries with low resistance for the introduction of air to the ore bodies. It was also desirable to eliminate hazards of fire in shafts and underground workings insofar as this would be practical. Cement and concrete were relatively cheap, and plans for using these in support of shafts, underground galleries, raises, and chutes, were developed steadily. Circular shafts with diameters ranging from 10 to 15 ft were adopted for all permanent shafts and airways. In places these were lined with concrete poured behind sectional pressed-steel forms especially constructed for this purpose. In other places, they were lined with precast-concrete blocks. It was found that such precast concrete of good quality could be produced on mass production scale and delivered at the mine from most favorable point of manufacture, at a cost of about 25 cents per cubic foot of concrete. This refers to prewar costs. As the use of concrete blocks in circular lined galleries was developed, it was found that there were very great advantages in the reduction of air resistance as compared with customary timber supports. After best methods had been developed, it was found that breakage and replacements were extraordinarily low, averaging only about 1 ½ pct per year during a period of about 15 years. Furthermore, it has been possible to reclaim for re-use a very large percentage of the concrete blocks from abandoned galleries. During the history of the operations precast-concrete blocks have been used for lining shafts, raises, ore chutes, galleries, and shaft stations, ranging from 3 to 16 ft id. The thickness of lining has varied from 5 to 10 in.; with I2 in. thickness in a few cases. Junctions of two galleries at angles ranging from about 30 to 60° are usually made of poured concrete behind sectional forms, or of a combination of poured concrete and precast blocks. In nearly all cases it has been found advisable to make the point of the wedge at the junction, of

Jan 1, 1947