Search Documents

By Leslie W. Austin

ROTARY kiln operators will agree that some of the most severe conditions a refractory must stand occur in the hot zone of a kiln burning Portland cement, dead burn dolomite, magnesite, periclase, and similar materials. Frequently the operator is faced with factors beyond his control which drastically shorten the life of refractories. Shutdown due to mechanical failure can be serious if the period is of sufficiently long duration to cause the dropping of coating or the loosening of the lining. A change in slurry can affect the coating and cause ring buildup. A change in type of fuel and its effect upon the flame can cause a shift in location of the hottest zone. Weekend shutdowns or any other interruption can cause the operator trouble and may damage the refractories, since stopping and starting a rotary kiln is certainly more difficult than stopping and starting a motor. Some operators have tried to set an estimate of damage for each shutdown in equivalent days of running time. Conditions affecting the refractory may be roughly grouped in four classes: chemical attack, mechanical stress, thermal shock, and abrasion. Chemical Attack: The drive to obtain maximum production through a kiln demands maximum operating temperatures, temperatures which are limited more by the ringing up or melting of the clinker. This can cause interface temperatures at the junction of coating and refractory which require the use of a basic kiln block to withstand the chemical attack. Chemical changes take place within the refractory itself, especially in chemically bonded or unburned kiln blocks: These changes cause the formation of the ceramic or burned bond. Migrating liquids or fluxes from the kiln charge have an effect within the refractory and lead to mineral or glass formation. The alkalies, sodium and potassium, migrate into the refractory as silicates, chlorides, sulphates or other salts. They may move under capillary action or may be caused to move by volatilization with condensation in the cooler portion. Mechanical Stress: Concentrated stress may be caused by several factors or combinations thereof. 1-The rings of refractories must be kept tight and rigid within the kiln, and this alone demands considerable force to hold the blocks in place. So that the force will not be concentrated, the blocks should fit the circle as perfectly as possible, with the faces in contact overall. 2-As the kiln is heated, thermal expansion takes place at the hot end of the kiln block. Since this disturbs the plane face it too can cause a concentrated stress at the two ends of the block, and shearing stress can be set up within the brick itself because of the difference in expansion between the two ends. 3-If a lining becomes loose and moves in the shell very severe stress can be set up, and as the kiln rotates this load changes and gives the effect of repeated loading. Permanent expansion of the refractory can also cause severe loading. 4-Not least important, flexing of the kiln is frequently the cause of concentrated stresses. Thermal Shock: Thermal shock, the result of heating and cooling too rapidly, occurs on starting and stopping or when a large patch of coating drops, exposing the bricks. Again, its destructive effect is often the result of phase change, liquid to solid or the reverse; dense refractories loaded with glass-forming impurities are particularly susceptible. Thermal shock is a problem with refractories set in the wall or roof of a stationary furnace, and becomes even more serious in a rotary kiln, the tendency to spall being magnified with movement and concentration of stress. Uniform rate of feed and loading insures both better coating and a more uniform stress. Abrasion: If the refractories do not take a coating, abrasion can become a most destructive factor. Movement of the lining in shell or movement of loose blocks causes abrasion, which is also most destructive if the refractories do not take a coating. An analysis of the problem of basic lining for the hot zone reveals, therefore, a number of desirable characteristics: high refractoriness, basic chemical reaction, resistance to spalling, good strength at all stages, ability to take coating, true sizing, volume stability, and abrasion resistance. Increased demand

Jan 1, 1952

By R. E. Jenkins

The Bell Canyon member of the Delaware Mountain group has yielded quite a large number of fields in which completion and production problems have been numerous and complex. Reserves are difficult to estimate due to the problem of evaluating the formation water saturation, and the feasibility of water flooding is questionable. Extensive laboratory investigations were undertaken to determine if normally measured rock and contained fluids properties could account for many of the peculiar characteristics of the formation. A statistical study or routine core-analysis data was made. Capillary-pressure data were obtained by several techniques. Fresh-water and brine permeabilities were measured and relative permeabilities of oil, water and gas were determined. Some qualitative wetta-bility tests were performed, and the petrography of a few thin sections was studied. The results of this work are presented, with typical or average data shown for each test. The permeability -to- water characteristic of the Delaware was found to be abnormally poor. Correlations of laboratory and field performance data indicate high water saturations in much of the formation. Pore geometry is highly uniform. INTRODUCTION The Delaware formation has undergone extensive exploration and development in the past few years. This has resulted in the discovery of quite a number of fields—producing oil for the most part. A large percentage of the productive wells have produced water along with the oil. Often there is no apparent pattern for the percentage of water cut experienced. In several instances vertical displacments of over 200 ft have been established between communicating wells in which the formation appears to be about the same, yet the structurally high wells yield a much higher water cut than the lower wells. Drill-stem tests have contributed little to well completion because they nearly always show small amounts of water (usually mud filtrate), regardless of what is produced later in the life of the well. Other formation evaluation methods have had no more than limited success in indicating ultimate productivity. Consequently, predicting the type of fluid productivity of Delaware wells has been very difficult. Hydraulic fracture treatments are almost universal, and unstimulated Delaware wells have not exhibited the productivity that normally would be expected of wells with the specific permeabilities encountered. Some operators have indicated that their Delaware wells need frequent re-stimulation. The uncertainty of reservoir water saturations reported for the Delaware has made difficult the task of evaluating oil in place in the reservoirs and estimating primary recovery. The unreliability of this data also will cause feasibility studies for water flooding or other secondary-recovery methods to be problematical. Several opinions have been voiced to explain why the Delaware performs as it does. Chronically poor well completions, dynamic water and tilted water tables, capillary inequi-libria, peculiar relative permeability characteristics and oil-wetness are among the suggested reasons. The dual purpose of this paper is (1) to describe the principal rock characteristics, and (2) to present an evaluation of those characteristics so that approaches can be made to explain the irrational behavior of wells completed in the Delaware. STUDY OF ROUTINE CORE-ANALYSIS DATA A statistical study of routine core-analysis data has been made to relate fundamental rock properties and characteristics of the formation to well productivity. For the most part, well production data were obtained from operators and augmented by production data from commercial information services. Only data which were available in detail and which were considered to be accurate were used. The core data used were obtained on samples from the perforated or open interval only and, thus, may not always represent the total productive interval in a well. All the core-analysis data included in this study are from the Bell Canyon member of the Delaware and were obtained by "plug-type" techniques, as opposed to whole-core or full-diameter techniques. Porosity values were obtained by the summation-of-fluids technique, permeability values are air permeabilities corrected for slippage to an equivalent liquid permeability, and the oil and water contents were determined by means of a high-temperature downdraft retort. All the procedures used are discussed at length in Ref. I. The core-analysis data were sorted

By J. E. Andersen, J. Halpern, C. S. Samis

In the presence of oxygen, galena is oxidized in an aqueous medium containing sodium hydroxide, in accordance with the following reaction: PbS + 2O2 + 3OH ? HPbO2 + SO4 = + H2O A novel method was devised for following this reaction which takes place in an autoclave under oxygen pressure, by measuring the concentration of HPbO2- in the solution with a cathode ray polarograph employing stationary platinum electrodes. Using this procedure a study was made of the kinetics of the reaction, in which the effect of a number of variables, including temperature, oxygen pressure, NaOH concentration, and agitation, on the rate, were determined. The results of this study are described and discussed, in terms of possible mechanisms for the reaction. IT is known that sulphide minerals can be oxidized in aqueous media in the presence of oxygen under pressure. Reactions of this type can be classified in two categories depending upon whether the products of oxidation are insoluble or soluble in the aqueous medium. An example of the first type of reaction is the oxidation of pyrite in alkaline solutions, giving rise to an insoluble iron oxide. The kinetics of this reaction have been investigated and its mechanism established.' It has been applied in the oxidation of iron sulphides present in refractory gold ores to improve the subsequent recovery of gold by cyanida-tion.' The second type of reaction finds application where it is desired to recover the metal by leaching during oxidation. In this case a medium is selected in which the oxidized mineral is soluble. For example, nickel, copper, and cobalt sulphide ores can be treated by oxidation in the presence of a solution of ammonia dissolving the nickel, copper, and cobalt as the metal ammine sulphate salts.:' A similar treatment has also been reported to apply to zinc sulphide ores.' It is known that lead sulphate is soluble in solutions of sodium hydroxide or ammonium acetate. It should therefore be possible to dissolve the lead from galena ores by aqueous oxidation with oxygen under pressure using either of these solutions. The applicability of the ammonium acetate treatment has been investigated and confirmed in a recent study.' The present paper describes the results of a similar study in which the kinetics of the oxidation of galena in sodium hydroxide solutions have been investigated. The object of this investigation was pri- marily to obtain information of a fundamental nature relating to the kinetics and mechanism of this reaction. The use of pulps of comminuted ore in a study of this type is undesirable because of the difficulty in controlling and measuring the surface area. The measurements were therefore made using galena crystals of measured surface area and in this way absolute reaction rates were obtained. The reaction was found to proceed as follows: PbS + 2O2 + 3OH ? HPbO2 + SO4 + H2O [I] The products are sodium plumbite and sodium sulphate salts which dissolve in the aqueous solution. The reaction studies were carried out in an autoclave in which a desired pressure of oxygen was maintained. The reaction was followed by measuring the concentration of lead in the solution with a cathode ray polarograph. The results obtained in this investigation are presented and discussed in the present paper. Experimental Materials: The crystals of galena were obtained from Violamac Mines, Sandon, B. C. The following impurities were indicated by spectrographic analysis carried out by the Provincial Assay Office, Victoria, B. C.: Sn, 0.02 to 0.2 pct; Sb, 0.07 to 0.7; Zn, 0.01 to 0.1; Si, Fe, Mg, As, less than 0.05 pct; Ag, 126 oz per ton, the latter determined by standard fire-assaying procedure. After cutting a specimen measuring approximately 5x7x12 mm, the crystal surfaces were ground parallel to the 100 axes using No. 2 emery, washed with water, and the dimensions were measured with a micrometer. Oxygen gas was of commercial grade and supplied in cylinders by Canadian Liquid Air. Solutions were made up with chemicals of chemically pure grade and distilled water. Equipment: Autoclave: The autoclave used in these studies was constructed of stainless steel and

Jan 1, 1954

By Max Y. Seaton

The scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. Nomenclature The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at ali but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical .and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatmerit of magnesium hydroxide precipitated from magnesium-containing brines; prod- ucts that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and irow-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase— materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximatcly 17,000 tons, "bout 95 Per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for manY Years past. Utilization As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (1) as dead-burned grain magnesite for the construction and maintenance of the hearths Or bottomS of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By Max Y. Seaton

The scope of this paper will be limited to finished materials that contain a large preponderance (around 80 per cent or more) of magnesium oxide. The large and commercially important production of refractory dolomite and modified dolomites is not discussed here, and the production of magnesium basic carbonate for use as a heat insulator is barely mentioned. The discussion is confined mainly to magnesias produced in comparatively great quantity by direct processing of naturally occurring raw materials and hence excludes secondary or highly purified products such as pharmaceutical products or U.S.P. light and heavy calcined magnesias of commerce. Nomenclature The nomenclature of the magnesia products that will be discussed is somewhat confusing, in that it is customary in the trade to designate as "calcined magnesite" the materials that result from the calcining of magnesite to temperatures that remove the contained carbon dioxide. The finished product, therefore, is not magnesite at ali but simply a more or less pure magnesium oxide or magnesia. Furthermore, partly for statistical .and partly for commercial reasons, it has been customary, during recent years, to classify as "calcined magnesite" products that result from the heat-treatmerit of magnesium hydroxide precipitated from magnesium-containing brines; prod- ucts that, obviously, have no relationship whatever to magnesite. In the listing of magnesia-containing materials, tonnages of which are regularly reported by the Bureau of Mines, reports ordinarily are made under two headings: "caustic calcined" magnesite, in which all of the varieties of products treated at relatively low temperatures are lumped; and "dead-burned" magnesite, in which are included both high-purity and low-purity, and particularly both high-iron and irow-iron, materials that have been so heat-treated that the magnesium oxide occurs predominantly as crystalline periclase— materials used almost entirely for refractory purposes. In 1940 the apparent domestic consumption of "caustic calcined" magnesite was approximatcly 17,000 tons, "bout 95 Per cent of which was produced in this country. The apparent consumption of "dead-burned" magnesite was approximately 172,000 tons, some 82 per cent of which was domestically produced. In both total quantity and percentage of material produced within the United States, these figures are record highs for manY Years past. Utilization As indicated by these figures, the major tonnage outlet for magnesia is the refractories industry, in which magnesia is employed principally in three ways: (1) as dead-burned grain magnesite for the construction and maintenance of the hearths Or bottomS of basic open-hearth furnaces; (2) in the form of refractory magnesite bricks and shapes; and (3) as a chemical

Jan 1, 1942

By Keith Leonard Sutherland

THIS paper is a study of the differential flotation of the sulphide minerals in the presence of salts of silver, lead and zinc. In practice, accidental activation due to these salts is more important than their use as reagents to replace copper sulphate. The general method of investigation has been based upon contact tests, the temperature of 35°C. being chosen in conformity with earlier work. Potassium ethyl xanthate and potassium amyl xanthate were selected as collectors and pure sulphide minerals were used. The experimental procedure has been outlined in earlier papers and all solutions were kept carbonate-free.'' Contact, or spreading of an air bubble, at a mineral surface indicates the presence of an adsorbed collector film. PURITY OF REAGENTS The xanthates were purified in the usual manner.1 Neither the cyanide nor the sodium hydroxide solutions contained sufficient carbonate to give a precipitate with barium chloride solution. The silver sulphate was prepared from pure silver nitrate by evaporation with concentrated sulphuric acid until there was no evidence of brown fumes. This solution was diluted and the difficultly soluble sulphate washed with water so that unchanged nitrate was dissolved. The resultant crystal-line powder was pure white. The lead and zinc salts were prepared by dissolving especially pure lead and zinc in C.P. nitric and sulphuric acid solution and the crystals drained. The standard solutions were checked by titration. It was felt desirable to use the sulphate radical wherever possible, but since lead sulphate was insufficiently soluble for the purpose of the experiments, it was necessary to use some other lead salt. A.R. copper sulphate was used without further purification. RESULTS The results are presented in the accompanying figures; the areas of noncontact (nonflotation) are shaded in Figs. 8, 9, 10 and 11; in the remainder they lie to the right of the curve. Zinc Sulphate The curves in Fig. I are to be compared with those for Fig. 2, for which zinc sulphate is absent. This comparison shows that the influence of the zinc ion is usually small. Its influence is more marked, however, for chalcopyrite in the absence of cyanide. The influence of zinc sulphate is also marked for copper-activated sphalerite, for which tests were made only in the absence of cyanide. The results are of importance in the separation of pyrite from copper-activated sphalerite when zinc sulphate is added in the lead flotation section (p. 204 of ref. I). Sphalerite does not adsorb the collector (i.e., become floatable) under the conditions chosen.

Jan 1, 1942

By R. W. Shoenberger, J. D. Clendenin, W. L. McMorris, N. Schapiro, B. R. Kuchta, A. A. Terchick, R. J. Gray, J. G. Price

INTRODUCTION * The United States is fortunate in having enormous reserves of metallurgical-grade coals. Although these coals are better in quality and more accessible than most coals found throughout the rest of the world, the best grades of these coals are being depleted. Consequently, more efficient exploration tools and techniques, such as advanced methods of core drilling and logging, correlation by palynology,** stratigraphy, paleontology and petrography are being used to help assess the extent and quality of the remaining coal reserves. Exploration and assessment of new and existing coal properties become of utmost importance in determining (1) the economic justification for mining the coal, (2) the optimum design of the preparation plant and (3) the most effective use of the coal. Fortunately, the cost of mining coal has remained stable because of better mine planning, more efficient operations and increased mechanization of mining operations. However, increased mechanization raises the amount of impurities in the coal mined, and this requires more and better coal beneficiation to meet the more stringent quality requirements set by the market. Besides, mechanical miners also produce relatively fine coal and, to ensure maximum liberation of impurities, much of the coal presently being used must be crushed to a finer size prior to preparation. The bulk of all coals presently used in this country is mechanically cleaned, much of it at a lower specific gravity than in the past. This necessitates the use of new and improved processes and equipment for coal washing and recovery, such as heavy-medium cyclones and vessels, and froth flotation cells. However, because wet-cleaning processes are pre- dominant in the United States and fine coal retains large amounts of moisture, the increased production of cleaned fine coal accentuates the need for new or improved methods and equipment for dewatering and drying this coal. The larger amounts of coal being beneficiated and the use of new and improved beneficiation processes will aid in controlling and ultimately eliminating sources of pollution. Modem coal markets demand coals that meet rigid specifications. Most coals are purchased under contracts that specify moisture, ash, and sulfur contents, or heating value, depending upon the end use. There has also been a growing trend toward specifying other properties, including particle size and coking capability. These specifications may include not only the * Editor's note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections prepared by each individual as has been done in other chapters. ** Palynology is the study of plant microfossils, especially spores, pollen, and other types of fossils not usually studied by paleontologists.

Jan 1, 1968

By Kenneth K. Humphreys, F. R. Zachar, A. G. Gilbert

INTRODUCTION by F. R. ZACHAR and A. G. GILBERT Coal producers are not only faced with the problems of mining coal, but must also decide to what extent they can invest capital and what operating and maintenance expense they can afford, after mining, to market their product in sufficient volume and at a reasonable profit. Regardless of whether the operator is contemplating a new operation or merely considering expanding present facilities, market requirements, ability to make a product meeting requirements, probable costs and possible future changes in raw coal or finished product must be considered. In addition, such items as flow sheet, structural designs, storage facilities, etc, must be examined individually and collectively. In estimating preparation costs to meet predetermined market specifications, the operator must calculate the economics of present preparation practices to anticipate the increase to total production which results when the quality of the finished product is increased. The consumers of coal are continually seeking to obtain the best and most adaptable product for their money. Regardless of whether coal is used for coking, industrial requirements, electric power generation, domestic fuel or for other purposes, it will be scrutinized from such standpoints as delivered cost, suitability for utilization in certain equipment, ease of ash disposal, adaptability to material handling system plans and its potential for generating dust problems. Utilities, due to large capacity volume requirements, are generally in a position to select coal that will result in the lowest over-all cost per million Btu. Freight costs, paid by the utility, are important and are given utmost consideration when a coal is under consideration. Steel companies, whether producing or purchasing coking coal, are continually seeking coal that will result in lowering the cost of pig iron production. Since it is usually necessary to clean to lower specific gravities, say 1.40, to turn out a product meeting metallurgical requirements, it follows that a high ash "middling" product is created. These low quality middlings do not command a good price. Therefore, unless the metallurgical coal can command sufficient realization to carry or subsidize the middlings, the operator may be ahead economically to prepare steam coal at a higher specific gravity. While the "unit-train" rate reductions have been helpful to the economy of the coal industry, the establishment of these rates has made mandatory the installation of storage and rapid car loading facilities at mines and plants shipping utility coal (see Chapter 15). A study of the economics

Jan 1, 1968

By Richard Franchot

From an efficiency viewpoint, the greatest loss of energy to the blast furnace is in its failure to convert more than about a third of the coke carbon from carbon monoxide to carbon dioxide. This result has usually been ascribed to a necessity of a 2:1 excess of CO in order to reduce iron. It has, however, been proved that iron is completely reduced by equal volumes of carbon monoxide and carbon dioxide. Hence there is room for the hypothesis that vaporization, as cyanid, of accumulated alkalis is a serious primary factor limiting the ratio of ore to coke. Observed cyanid vapor concentrations and those measured by the variations of the nitrogen-oxygen ratio in the hearth gases form the basis for a quantitative explanation of the furnace action. As EVERYBODY knows, the blast furnace is a gas producer. As to the reason for this, people are not so well agreed. The significance of the fact is obvious, for the extent to which the fuel leaves the furnace as combustible gas measures poor economy in iron smelting; while good efficiency in this respect means poor gas. The furnace thus works at cross purposes. The present trend of the steel industry is toward. a primary use of the blast furnace as a gas producer with pig iron as a byproduct. Needless to say, this trend is away from improvement in iron making. The production of more and better iron in a given furnace consuming a given amount of coke would seem, at least, to involve a decrease in the relative proportion of the combustible gas. The possibility at the same time, however, of making more and better gas need not necessarily be excluded. (The more the furnace acts as gas producer, the bigger is the sulfur problem.) Whatever the object, it would seem desirable to have a, clear, comprehensive, mathematically exact estimate of why and how the blast furnace functions, to the large degree that it now does, as a gas producer. The literature does not give a definite answer to the question. That for which explanation is sought is the fact that only a minor part, usually not more than a third, of the coke carbon burned is oxidized to carbon dioxide; that the development in the furnace of the fuel energy is thus limited usually to little more than 50 per cent.; that it requires about twice as much fuel coke to make a ton of iron as is indicated by the rela-

Jan 7, 1925

By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By J. Rogers, H. F. A. Hergt, K. L. Sutherland

IN 1938 Ralston4 reviewed the many attempts to find a satisfactory collector for the separation of cassiterite from its ores and in 1944 Dean and Ambrose2 summarized some further attempts. Generally, soaps and amines are effective but nonselective collectors. We have discovered that reagents containing either the polar group -SO4- or _S03- are excellent collectors for cassiterite and promise to be selective.1 The response to these reagents of cassiterite and of minerals commonly associated with it was studied, using the captive-bubble technique. Using these fundamental data, the practicability of separation and concentration of tin was investigated by flotation tests in a 2000gram Denver cell. EXPERIMENTAL METHODS Reagents All inorganic reagents were of Analar grade. The preparation and purification of sodium cetyl sulphate, cetyl trimethyl-ammonium bromide, laurylamine and cetylamine have been previously described.5 The other collectors were commercial surface-active agents, which were used without purification. Tests Captive-bubble Tests and Cylinder Flotation Tests have been previously described.5-10 The full lines shown in the figures relating solution composition to contact (flotation) distinguish solutions in which contact (flotation) is possible from those in which it is not. The curve is derived by successive approximation and the accuracy is ±0.2 pH units and ± 5 mg. per liter of collector or depressant. Solution compositions for which it was shown experimentally that contact or flotation is possible are marked by a circle, those for which it is not possible, by a cross, and those for which it is doubtful by a cross within a circle. It is assumed that at all other solution compositions within (without) the curve, contact or flotation is possible (not possible). After testing in the collector solution, the mineral was removed, washed, and tested by the captive-bubble method in water, or floated in a cylinder with frother only. In this way the composition of solutions in which a mineral was conditioned but in which properties of the collector solution prevented contact or flotation can be defined. The composition of solutions in which conditioning was possible lie between the full and broken curve, and the experimental results are indicated by a square. The curves show the limits of composition of solutions in which flotation in a cell would be possible but many factors other than those considered in these tests determine recovery and grade of a given mineral in practice. Flotation Tests in 500 and 2000-gram Denver Submachines.--Melbourne tap water, containing 12 parts calcium, 6 parts

Jan 1, 1947

By Jan Law

Problems of oil recovery are attacked from the approaches dictated by the two strikingly dissimilar complexes that comprise an oil reservoir—the fluid complex and the interstitial complex. Knowledge of the fluid complex, due to labors in the fields of fluid mechanics and physical chemistry, has far outdistanced knowledge of the interstitial characteristics of the sand complex. This paper is concerned with the latter and applies the technique of statistics to petrographic facts—namely, porosity and permeability—dealing with what might be called petrometry. Statisticians have long worked within the problem of reconstruction of a universe oi variables by means of samples that comprise a small percentage of the universe from which the samples were drawn. Core-analysis data comply with the requisite of random sampling as stipulated by theoretical statistics. A basic concept of statistics employs t.he following substitution: 1. The results of sampling are arranged as a frequency distribution. 2. The observed frequency distribution is compared with a mathematically precise distribution. 3. If a sufficiently good agreement is found between the two, the precise distribution is substituted in all subsequent operations involving characteristics of the sampled material. This mathematically precise distribution is also known as the normal curve, curve of error, the probability, the Gaussian, and the bell-shaped curve and is describable with but two figures. Further, these two figures, the arithmetic average and the standard deviation, are subject to mathematical manipulation. This paper demonstrates that, in some cases in the Dominguez field of Southern California, if sufficient core-analysis samples are taken over not too great a thickness of sediments, the resultant permeability and porosity assemblages give satisfactory agreement with ilormal curves. It is shown that the indications are strong that oil wells wherein a satisfactory agreement is found are predictable as to productivity. Since the predictions are made by employing the laws of chance that are operative within sedimentation, it follows that the mechanism by which the predictions were made is a basic concept of reservoir mechanics. Therefore, tentative examples are given of the application of normal curves to the solution of problems of primary and secondary recovery. Nature of Permeability Frequency Distributions Core-analysis data are made available as a tabulated depth vs. permeability profile. The nature of the distribution of permeability values within a given strati-graphic interval may be approximated from an array constructed with samples plotted in the order of their appearance with depth (accession number) against their permeability value in millidarcys. A wide variation in the nature of the distribution of K (permeability) values for

Jan 1, 1944

By A. C. Losekamp, J. B. Conway

Thermal-expansion data for, tungsten, rhenium, tantalum, .molybdenum, niobium, W-25 pct Re, Ta-10 pct W, ant1 Mo-50 pct Re are presented covering the range from room tempature to 2500°C. In these measureMents, made in a resistively heated tungsten tube furnace operating in a helium atmosphere, data for rod and sheet specimens were found to be identical; in addition, arc-cast and sintered tungsten were found to yield essentially identical results. Optical rneasurenlents of thermal expansion .made in any atmosphere other- than vacuum are subject to a refraction error which can be quite substantial. Specimens tested in helium appear shorter than when tested in racuum and hence a special correction factor must be applied to the helium data in order to obtain accurate results. WHILE it is true that linear thermal-expansion data for many of the refractory metals have been measured to very high temperatures, it is also true that except in a few instances the data from various investigators are not in good agreement. This is particularly evident in the case of tantalum and niobium although some tungsten data have been reported which differ by as much as 40 pct from the data of other investigators. Due to the sensitivity of both tantalum and niobium with respect to impurity absorption during exposure to high temperatures, it is probable that this single factor accounts for the majority of the discrepancies in the thermal-expansion data for these metals. However, this same factor can probably not be employed to explain the existing differences in the tungsten data. In all probability, these are due to errors in the measurement technique, to material composition variations, or to changes which take place in the material during the heating process (e.g., additional densifica-tion resulting from heating a sintered specimen above the original sintering temperature). In view of the discrepancies which exist in the linear expansion data reported for many of the refractory metals, the current study was initiated in an attempt to resolve such differences. Also, no high-temperature linear thermal-expansion data were found to be available for several refractory metals. Providing such data was another objective of the current investigation. MATERIALS In this study test specimens were employed in either rod or sheet form and in several instances both arc-cast and sintered material were employed. Material compositions are presented in Table I. Helium gas was fed to the furnace at a rate of about 0.5 SCFH and no special purification procedures were employed. However, the helium contained less than 50

Jan 1, 1967

By J. M. Dahl, L. H. Van Vlack

STAFF: Editor, Gerhard Derge Associate Editor, Paul G. Shewman Carnegie lnstitute of Technology Schenley Park Pittsburgh, Pa. 15213 Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Jack H. Scoff, President; Richard C. Cole, Post-President; Harold B. Emerick, President-Elect; Ralph L. Hennebach, Treasurer; Robert W. Shearman, Secretary; Donald A. Parks, Assistant Secretary; Leslie S. Wilcoxson, Assistant Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairman; T. E. Dancy, H. B. Emerick, P. R. Gouwens, R. E. Grace, J. H. Jackson, H. H. Johnson, A. E. Lee, Jr., R. R. Nosh, R. D. Pehlke, and Paul Queneau. Review and selection of monuscripts is under the supervision of the following Publications Committees: Extractive Metollurgy Division: R. E. Grace, Chairman; G. M. Bell, D. W. Bridges, J. M. Cigon, G. W. Healy, T. A. Henrie, R. D. Holli-day, C. E. O'Neill, C. S. Sami s, A. W. Schlech-ten, and Charles Shull . Iron and Steel Division: R. D. Pehlke, Chairman; T. P. Floridis, Arnulf Muon, G. R. St. Pierre, E. T. Tuckdogon, L. H.Von Vlack, and J. M. Uys. Institute of Metals Division: H. H. Johnson, Jr., Chairman; J. B. Clark, Vice Chairman; M. R. Achter, G. F. Bolling, J. O. Brittain, G. P. Conard, II, L. A. Girifolco. G. T. Hahn, J.P. Hirth, L. Himmel, G. T. Horne, George Krauss, C. F. Leitton, Jr., J. D. Livingston, R. D. Monning, H. M. Otte, S. V. Radcliffe, R. E. Reed-Hill, H. C. Rogers, O. Sherby, M. T. Simnod, G. R. Speich, E. A. Steigerwold, R. A. Swolin, W. A. Tiller, W. R. Upthegrove, J. B. Wagner, Jr., Derek Walton, H. W. Weart, W. W. Webb, and D. WiIsdorf. Published monthly by the American lnstitute of Mining, Metollurgicol, and Petroleum Engineers, Inc., 345 East 47th Street, New York, N. Y. 10017. Telephone PLAZA 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement mode or opinion expressed in its publications . . . Copyright 1965 by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustrial Arts Index, and Chemical Abstracts . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 233, Number 1.

Jan 1, 1965

By G. K. Engelhart

A multi-stage counterflow process developed in Germany preheats dry pulverized portland cement raw materials held in suspension in rotary kiln waste gases. Capacity of the first kiln installed for this purpose in the United States has been increased from 860 to 1500 bbl per day, with fuel reductions from 1,100,000 Btu to 650,000 or 700,000 Btu per bbl. Sixty percent of total waste gas is used. As full use of the gas stream is approached, additional kiln production and fuel economy may be expected. EFFECTIVE use of rotary kiln waste gases to preheat dry pulverized materials has been demonstrated in full-scale operation at the Allentown Portland Cement Co. plant, Evansville, Pa. Pulverized raw materials are preheated in suspension in the gas stream in a multi-stage counterflow process which draws the gases through a series of cyclone collectors. Upon entering the first cyclone stage the material, continuously delivered and suspended in the gas stream, is successively collected and re-suspended until it discharges through the kiln feed pipe. Gas and material contact time is thus prolonged, providing a high degree of heat recuperation with a very low temperature differential between gas and material at the final stage. The suspension preheater, developed by Klock-ner-Humboldt-Deutz AG of Cologne, Germany, was first installed at the Norddeutsche Huette plant, Oslebshausen, Germany. Similar preheaters are now in operation at three other German cement plants. The first American installation, at the Allentown Portland Cement Co. plant, was designed and manufactured by Fuller Co. of Catasauqua, Pa., Humboldt's licensee for the United States, Canada, and Mexico. Design of this installation is essentially the same as the German original, but provision was made for varying the method to adapt the process to specific objectives of American portland cement production. Differences between German and American cement clinker production practices are directly related to differences in three primary production cost items: fuel, labor, and power. Because fuel costs are high in Germany and elsewhere in Europe, thermal efficiency has been the first objective of European cement producers and manufacturers of rotary kilns. The Germans have developed such recuperative equipment as the present suspension preheater, the Miag calcinator, and the Lepol kiln, the invention of 0. G. Lellep. In North America labor is the principal cost item, although rising fuel costs are of growing concern. High clinker production is therefore of first importance. Recent installations of longer dry process cement kilns have been disappointing, failing to make satisfactory reductions in exit gas temperatures when production is held at an acceptable level. The Humboldt suspension preheater satisfies both

Jan 1, 1955

By D. J. DeLazaro, D. W. Levinson

Observations were made of the isothermal transformation and quench and reheat transformation characteristics of binary titanium alloys containing nominally 6 wt pct and 10 wt pct Mn at temperatures of 700°, 600°, 500°, and 400°C. A large change in electrical resistivity attends the beta to alpha transformation in these alloys. The correlation between the resistivity and microstructure provides a very sensitive means of following the transformation. IN a recent paper, Wyatt' determined the electrical resistivity of several grades of unalloyed titanium metal as a function of temperature. In addition to the expected discontinuity accompanying the a-B transformation, it was shown that s-Ti has a much larger temperature coefficient of resistance than 8. The result would be a very large change in resistivity attending ß?a: transformation if it were possible to retain the ß structure at room temperature in pure titanium. From these data, it was reasoned that this very large resistance change should accompany the decomposition of the ß phase in alloys in which the ß phase can be retained by quenching to room temperature from the ß field. This effect is illustrated schematically in Fig. 1. Binary Ti-Mn alloys containing more than 5 wt pct Mn can be quenched to retain ß from the ß field. While the ß phase would be expected to transform in these alloys to a + TiMn via a eutectoid reaction,' it has been observed that the eutectoid decomposition does not occur readily in hypoeutectoid alloys, but rather the decomposition of the ß occurs by rejection of proeutectoid a only." Thus, the resistivity should show a marked decrease, as the a: phase is rejected from ß and a study of the resistivity of solution treated and isothermally transformed or quenched and reheated alloys should provide an excellent means of establishing the transformation kinetics of these alloys at various temperatures. The usual metallographic method of determining the transformation temperature-time characteristics of alloys of this type is very satisfactory for deter- mining the time required to initiate the rejection of the a phase at temperatures relatively close to the ß/a: + ß boundary when the rejected a is coarse, and a typical Widmanstaetten structure is produced. The metallographic method is less satisfactory for this purpose at lower temperatures where a fine nodular decomposition product is observed and is very unsatisfactory for the determination of the time required to complete the transformation at any temperature. Accordingly, specimens were prepared for resistivity measurements in order to determine the transformation characteristics of the alloys.

Jan 1, 1955

By George Hulst

PRIOR to 1914, there was little demand for antimony in this country; its use was limited almost entirely to the manufacture of type and bearing metals. Practically no antimony ore was mined here, the market being supplied principally from China, and the alloy was produced by a direct mixing of lead and antimony. The great world war, with its demand for shrapnel in hitherto undreamed of quantities, precipitated a great boom in the price of antimony. Nominally quoted at 6 c. to 7 c. in 1914, the price increased by leaps and bounds to 45 c. in March, 1916. Under the stimulus of high prices many shall mines were opened, for it became profitable to work ores containing as low as 20 percent. antimony. High-grade sulfide ores (stibnite), containing 55 per cent. to 60 per cent. antimony, were received from Bolivia, China, and Alaska. Low-grade sulfide ores, running from 20 per cent. to 45 per cent., were produced in Nevada, California, Idaho, Utah, and Mexico; much of this ore was fairly rich in silver. The principal oxide ores came from Mexico and Oregon. The following analyses are representative of various types of antimony ore: Se Pn Cu Ao Au SIC), Fe S CAO ZN As Oxide Ore 25.09 46.02 0.95 0.40 10.98 0.30 0.22 Sulfide ore 5.5.20. 15.12 1.05 19.87 ? 0.40 0.25 Sulfide Ore 37.16 11.30 0.10 34.0 7.60 0.50 17.05 7.40 0.36 0.10 Sulfide Ore 41.55 15.00 0.20 76.0 0.04 5.60 0.25 18.17 0.85 0.25 0.10 The International Lead Refining Co. fortunately was equipped to handle these ores through residue and blast furnaces. The charge consisted of a variety of sulfide ores containing Sb 20 to 60 per cent. and Si02 6 to 45 per cent., oxide ores containing Sb 20 to 40 per cent. and SiO2 10 to 45 per cent. Secondary materials, such as battery plates, battery mud, lead oxide, paint, etc., together with refinery skims, softener skims, and other refinery byproducts, were treated along with the antimony ore to furnish the lead required. All silver-bearing antimony ores were treated in the residue furnace, the sulfur, iron, and copper forming matte that carried part of the silver, the balance going into lead bullion. The

Jan 9, 1919

By J. N. Hobstetter, J. J. Becker

Deformed copper single crystals exhibited, upon annealing, a recrystallized twinned grain with a twin plane parallel to an active deformation plane, rotated approximately 22" about its pole, or else did not recrystallize at all. If extraneous deformation was not carefully removed, no simple orientation relationship was found. RECRYSTALLIZATION textures have been a subject of practical interest for many years, but any real understanding of their formation will have to start with a study of the recrystallization of carefully deformed single crystals. Some efforts have been made in this direction,'-' but much more experimental information is needed before a satisfactory picture of the crystallography of recrystallization can be formed. This paper reports a few results in copper single crystals. The crystals studied in this investigation were grown by the Bridgman method," and their orientations determined by the back-reflection Laue technique." Some specimens were simply deformed in compression, others were sheared, and still others tested in a rotating-grip device, in attempts to remove end constraints. The details of their deformation behavior are described elsewhere.' The deformed specimens were annealed and the orientations of the recrystallized grains were determined optically, as described by Barrett and Levenson.8 Compressed Specimens Specimen 17-A, whose orientation is given in Fig. 1, was compressed to a total of 19 pct. As observed before,' increasing deformation took place by increasing density of slip lines in initially formed clusters, with little if any formation of new slip clusters in unslipped areas. The specimen was then etched in nitric acid until its length had been reduced from 0.766 to 0.735 in. It was annealed at 1000°C, in increments of a few minutes. After 63 min, two small grains had appeared in the center, Fig. 2. They were found to be twinned with respect to each other (AB, Fig. 4). After 30 min more, the specimen was completely recrystallized. A typical view of it is given in Fig. 3. A summary of all orientations found is given in Fig. 4, in which the prominent grain G is in (001) standard projection, and the poles of the active slip planes after deformation are indicated by SP (primary slip plane), CrSP (cross-slip plane), and CnSP (conjugate slip plane). All the orientations found were related through seven orders of twinning. A "family tree" of these twins is given in Fig. 5. Furthermore, the BG twin composition plane lies close to the cross-slip plane

Jan 1, 1954

By Shiou-Chuan Sun, R. E. Zimmerman

An evaluation of the mechanism surrounding the froth flotation of coarse coal and mineral particles as a result of experiments conducted at The Pennsylvania State College. Maximum size ranges for both bituminous and anthracite coals were established as well as the factors affecting the floating of coarse particles. CONSIDERABLE interest is developing in the froth flotation of coal and the maximum particle sizes which can be treated by such method. The economic necessity of recovering extreme coal fines and slurries plus the restrictions being placed upon stream pollution have brought about many new and prospective installations of flotation plants. Most coal slurries or silts have a wide size range, some sizes of which may be unsuitable for effective froth flotation. This fact also enters into the froth flotation of other minerals and the principles that SHIOU-CHUAN SUN and R. E. ZIMMERMAN, Members AIME, are Assistant Professor and Division Chief, respectively, Division of Mineral Preparation, The Pennsylvania State College, State College, Pa. Joint AIME-ASME Fuels Conference, French Lick, October 1949. TP 2843 F. Disccussion (2 copies) may be sent to Transactions AIME before June 30, 1950. Manuscript received Sept. 12, 1949. apply to coal would also apply to minerals in general. A series of experiments were made by the authors for the purpose of investigating factors influencing the froth flotation of coarse mineral particles and an attempt has been made to evaluate those factors. This paper presents the results of a study of the froth flotation of coal particles in the size range greater than 35 mesh. During the study a "multi-bubble" hypothesis has been developed to explain the various phenomena observed in the behavior of coarse particles in froth flotation of coal. The terms coarse, intermediate, and fine particles as used in this paper are arbitrary and differ for various minerals. For coal alone the term intermediate particles means that the particle size is within the range of 35 and 200 mesh of Tyler sieve sizes. Sizes of coal particles coarser and finer than this size range are termed respectively as coarse and fine particles. Methods of Conducting Flotation Experiments: All of the flotation tests, except those shown in table 1, were carried out in a laboratory Fagergren flotation machine, using 300-a samples of solids for each test. All mineral samples we; prepared from selected lumps of high purity by crushing, grinding, and screening to the desired sizes. Except coals, all the other samples were cleaned through magnetic

Jan 1, 1951

By K. L. Clark, Nicholas Kowall

MAXIMUM furnace efficiency and close control of final steel composition demand that the steel melter be able to follow closely the variations in the carbon content of the bath. For many years, the fracture test has been used by melters for estimating carbon, because it requires only a very short time to pour a sample into a chill mold, cool it in water, break it with a sledge hammer, and observe the fracture. After long experience gained from the observation of such fractures, most melters are able to estimate the carbon content of steel with amazing accuracy, particularly in the lower carbon ranges. Notwithstanding the utility of the fracture test, there has been widespread interest in other methods for rapid carbon determination to supplement it and to ensure against possible errors in human judgment. Several methods, based upon measurement of magnetic properties as functions of carbon content, have been described in the literature1-6 and have been found to give reasonably reliable results in plant practice when scrap composition is known and controlled. A difficulty encountered in the use of analyzers of the magnetic type is that alloying elements do change the relationship between carbon content and magnetic properties and it becomes necessary to establish calibration curves for all the expected combinations of alloy residuals that are not oxidized in the bath. The work reported here is of an investigation of a method that is independent of alloying elements normally present in constructional steels, being based upon the relatively well-known fact that in plain carbon and low-alloy steels martensitic hardness is a function of carbon content alone. WORK OF OTHER INVESTIGATORS In 1938, Burns, Moore and Archer published a curve7 that showed that the hardness of martensite is a function of carbon from 0.10 to 0.50 per cent and is independent of grain size or alloy content, at least within the range found in constructional S.A.E. compositions. Some of the deeper hardening types investigated, however, contained carbon to a maximum of only 0.20 per cent. Using this principle, Kern8 developed a method of rapid carbon determination for S.A.E. 43xx steels. His procedure consisted of chill-casting a test bar that was large enough to give a surface that could be prepared for Brinell indentations. The test piece was quenched immediately after solidification was complete and hardness readings were taken, so that the carbon content could be read from an experimentally determined curve giving the relationship between as-quenched hardness and carbon. EXPERIMENTAL WORK Although Kern's work had been done with a relatively deep-hardening steel, it

Jan 1, 1944