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By Frank G. Miller

This report presents developments of fundamental equations for describing the flow and thermodynamic behavior of two-phase single-component fluids moving under steady conditions through porous media. Many of the theoretical considerations upon which these equations are premised have received little or no attention in oil-reservoir fluid-flow research. The significance of the underlying flow theory in oil-producing operations is indicated. In particular, the theoretical analysis pertains to the steady, adiabatic, macroscopically linear, two-phase flow of a single-component fluid through a horizontal column of porous medium. It is considered that the test fluid enters the upstream end of the column while entirely in the liquid state, moves downstream an appreciable distance, begins to vaporize, and then moves through the remainder of the column as a gas-liquid mixture. The problem posed is to find the total weight rate of flow and the pressure distribution along the column for a given inlet pressure and temperature, a given exit pres5ure or temperature and given characteristics of the test fluid and porous medium. In developing the theory, gas-liquid interfacial phenomena are treated. phase equilibrium is assumed and previous theoretical work of other investigators of the problem is modified. Laboratory experiments performed with specially designed apparatus. in which propane is used as the test fluid, substantiate the theory. The apparatus. materials and experimental procedure are described. Comparative experimental and theoretical results are presented and discussed. It is believed that the research findings contributed in this * paper should not only lead to a better understanding of oil-reservoir behavior, but also should be suggective in regard to future research in this field of study. INTRODUCTION In recent years much time and effort has been consumed in both theoretical and experimental studies of the static and . dvnamic behavior of oil-reservoir fluids in porous rocks. Although lack of sufficient basic oil-field data, principally concerning the properties and characteristics of reservoir rocks and fluids, largely precludes quantitative application of research results to oil-field problems, qualitative application has become common practice. In effect. oil-reservoir engineering research is serving as a firm foundation for oil-field development and production practices leading to increased economic recoveries of petroleum. This province of research. however, still poses many perplexing problems. The thermodynamic behavior of two-phase fluids moving through porous media constitutes one facet of reservoir-fluid-flow research that has not received the attention it deserves. This report embodies a theoretical discussion of this subject and a description of a series of related laboratory experiments. The significance of the problem to oil field operations is indicated but in articular the report centers around a theory and method for analyzing the steady. macroscopically linear, two-phase flow of a fluid (a single molecular species) through a horizontal column of porous medium. For simplicity in showing how the thermodynamic behavior of two-phase fluids moving through porous media affects oil-reservoir performance problems, attention is focused temporarily on a particular well producing petroleum from an idealized water-free solution-gas drive reservoir, the reservoir rock being a horizontal, thin, fairly homogeneous sandstone of large areal extent confined between two impermeable strata. The flowing hydrocarbon fluid is considered to exist entirely as a Iiquid at points in the reservoir remote from the well; however. the decline in fluid pressure in the direction of the well causes vaporization of the hydrocarbon to begin at a radial distance r from the well. Upstream from r the fluid moves entirely as a liquid and downstream from r it moves either entirely as a gas or as a gas-liquid mixture depending on the properties of the hydrocarbon and on the thermodynamic process it follows during flow. The distance r would be variable under transient flow conditions. but for purposes of analysis the flow is considered to l~e steady at the particular instant of observation during the flowing life of the well of interest. If the flow were isothermal and the hydrocarbon a pure substance, the fluid would be entirely gaseous downstream from r. Thus, this isothermal flow process for a pure substance would require that the heat of vaporization be supplied at r. over zero length of porous medium, at the precise rate necessary to maintain the constant temperature. This means that the solid matrix of the porous medium (reservoir rock) and the surroundings (impermeable strata confining the reservoir rock) would have to serve as infinite heat sources. Heat-transfer requirements would be somewhat less severe for the isothermal flow of a multicorn-ponent hydrocarbon as bubble and dew points at the same temperature correspond to different pressures. In this instance isothermal conditions would be sustained without complete vaporization of the fluid over zero length of porous medium. Nevertheless. as the flow is in the direction of decreasing

Jan 1, 1951

By M. Metzger, T. A. Read

The strengthening effects of hydroxide and synthetic plastic films in the creep of cadmium crystals were studied. The results were broadly consistent with the naive mechanical model. The dislocation-film reactions and the significance of the macroscopic stresses associated with certain films are discussed in the paper. ALTHOUGH a number of studies have been made of the strengthening of metal single crystals produced by surface films usually less than Ir in thickness, the mechanisms underlying this phenomenon are still not well established. Roscoe' first noted the critical shear stress and the stress-strain curve of cadmium-crystal wires to be raised markedly by the presence of oxide films. Subsequent investigators2-' have confirmed the effect for several metals and films including a number of plated poly-crystalline metal films. Harper and Cottrel1" with a thin film on zinc presumed to have formed as a result of etching and washing treatments) did not detect a strengthening at a rate of extension of 10 ' sec-' although at lo-' sec-' the film raised the flow stress by 7 pct at 0.0005 extension and by 22 pct at 0.01. The marked strengthening at moderate strains thus appeared to be the result of a dynamical effect dependent on the rate and amount of plastic flow. Other observations'. " are consistent with this view. The large effects of films on the tensile creep rate of single crystals were demonstrated when the observation of Andrade and Randall," that the creep rate of cadmium crystals increased on immersion in aaueous solutions of certain cadmium salts. was shown' * to hold only when a film was present initially and was explained by the attack of the solution on the film and the removal of its strengthening effect. Changes in the creep rate interpretable in terms of the removal or formation of various films have been observed by other investigators.3,8,10,31 Certain other experiments have been reported in which surface films or liquid environments have affected the plastic behavior of metals, but these are not within the scope of the present work which deals with the effect of solid films on single-crystal slip. Possible Mechanisms—The film does not significantly reduce the load on the crystal in the elastic range (the elastic moduli of film and crystal are not too greatly different and the area of the film is so small that its share of the load is negligible) so that the initial operation of internal Frank-Read sources is not affected. However, as Fisher" has pointed out, a source terminating on the crystal surface requires only half the critical stress for activation as an internal source of the same length and a relatively strong film (even a very thin one) would pin the free ends of the surface sources so that, if surface sources are responsible for plastic flow in a clean crystal. such a film would increase by roughly a factor of 2 the stress necessary for generation of dislocation loops at a given rate. The other general possibility is that the film resists the passage to the crystal surface of internally generated dislocations. If the film is adherent and if the specimen is to exhibit slip of the same general character as a film-free specimen, the film must deform or fail in shear at the active slip planes. The naive mechanical model, where shear-stress relaxation across the active slip plane in the metal transfers load to the film until it deforms and slip can

Jan 1, 1959

By Douglas W. Fuerstenau, Kalanadh V. S. Sastry

Based on an analysis of green pellet size distributions and kinetic data on ball growth with taconite concentrates, a ballability index has been developed to quantify ball growth behavior as a function of moisture and bentonite additions. The applicability of the ballability index to such other particulate materials as pulverized limestone and ground magnesite is shown.

Jan 1, 1973

By F. Louis Grammer

THE difference between blast-furnace gas and ordinary producer-gas is chiefly that blast-furnace gas is richer in CO, and poorer in hydrocarbons and hydrogen, as is shown in Table I. TABLE I.-Volume-Composition of Producer-Gas and Blast-Furnace Gas.. Producer-Gas. Blast-Furnace Gas. Per Cent. Per Cent. (Volume.) (Volume.) CO . 22 to 33 25.5 00., . 6 to 3 13.0 H . . 13 to 7 1.5 CH, 3 to 1.5 0.0 N . 54 to 60 60.0 If natural gas, water-gas, or by-product coke-oven gas be available, blast-furnace gas can be made to resemble very closely in calorific value the average producer-gas by merely mixing in one of these products, which are richer in hydro-carbons and, hydrogen. Blast-furnace gas, however, possesses a virtue which is sometimes absent in producer-gas, especially with coals very high in sulphur-namely, that blast-furnace gas is relatively free from sulphur. In some regions the sulphur in coal is an acute problem, and it is highly desirable to find uses for the products which are specially high in sulphur-content. An advantage would be gained if coal was coked before charging into the gas-producers, but this adds to the expense. Sulphur may be partly eliminated from coal by washing it, the success depending upon the form in which the sulphur occurs, and upon the efficiency of the washer, but it cannot always be removed to the extent desired at most American plants. It is not practicable to remove all the sulphur from producer-gas by washing it, though Mr. Reinhardt, of Germany,

Sep 1, 1908

By Robert L. Akright

LOCATION AND HISTORY The Candelaria silver mine is located in an arid, isolated desert setting in Sections 3 and 4, T.3N., R.35E., and Section 33, T.4N., R.35E., Mineral County, Nevada (Fig. 1). Silver was discovered in 1863 by Mexican explorers, and high grade silver veins were mined from the early 1870s through the 1880s. Essentially all mining had ended by 1890. The veins were mined by underground methods typical of the period. As is the case in many mining districts, Candelaria was studied and explored by a number of companies. All these efforts were terminated short of mine development because of low silver prices and difficult metallurgy. On March 1, 1976, Occidental Minerals (Oxymin) entered into a Limited Partnership agreement, known as Candelaria Partners, as General Partner with Congdon and Carey Ltd. No. 4. Prior to the agreement, Congdon and Carey had acquired the candelaria properties as part of a bullish silver program and did considerable exploration which indicated the possibility of a large reserve of shallow silver mineralization. GEOLOGY AND ORE DEPOSITS Silver and gold mineralization in the Candelaria district occurs in high-grade fissure veins with silver values ranging from 0.6 to 7.8 kg/t (20 to 250 oz per st). These veins, combined with the low grade disseminated mineralization in the intervening material between the veins, form Manto- like deposits 15 to 46 m (50 to 150 ft) thick. Three such deposits are found in the Candelaria district: the Lucky Hill, Mount Diablo, and Northern Belle deposits (Figs. 2 and 3). The average ore grade of the Lucky Hill and Mount Diablo [ ]

Jan 1, 1985

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By Cleveland Meeting

Jan 1, 1945

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,' for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.' They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By W. S. Gatley, F. C. Appl

This paper presents a combined analytical and experimental study of chisel penetration vs time during chisel impact on rock, a problem of fundamental importance in improving the performance of roller-cone bits or percussion drilling toots. For a given force-time relationship between chisel and rock, the problem of determining the penetration (displacement) vs time of the chisel is formidable. This is so because the rock is a nonlinear system with distributed mass and distributed damping (friction, dissipation of energy due to rupture, etc.). Since the literature does not contain adaptable solutions, the rock behavior to impact was simulated approximately by an "equivalent" lumped system, that is, an "equivalent" mass, spring, dashpot system. With this assumption, an analytical solution was found for chisel penetration vs time due to a sinusoidal load between chisel and rock. From this solution were found curves, in terms of dimension-less variables, for the maximum depth of penetration vs the frequency of the sinusoidal loading and for the energy transfer vs frequency. The results of this analysis were used to predict the penetration rate of rotary rock bits us rotary speed. The curve indicated that an optimum speed exists. To verify this analysis, an experimental apparatus was constructed and used to apply a sinusoidal pulse to a chisel penetrating a rock specimen under atmospheric conditions. Strain gauges were mounted on the chisel shank and a velocity transducer was mounted between the chisel and the rock surface. The velocity was integrated electrically and picked up simultaneously with the strain gauge signal on an oscilloscope. Permanent records were made photographically to provide simultaneous records of force us time and penetration us time. In comparing the experimental results for limestone and dolomite with the theoretical results, good agreement was found in the frequency range of the experiments. Unfortunately, the inertia effect (peak penetration) indicated by the theory occurs at a frequency much higher than could be obtained experimentally with the apparatus constructed. A "rate-of-loading" effect is indicated theoretically, but has not yet been verified experimentally. INTRODUCTION The process of drilling with percussion tools or rotary rock bits is basically related to the transient response of rock to surface impact. Each time a bit tooth contacts the rock, high stresses are developed which result in penetration and rock removal. As the tooth moves on, stresses are relieved and a new cycle begins as the next tooth contacts the rock. Thus the drilling process, which consists of an endless succession of these cycles, can be studied in terms of a single cycle. It is apparent, therefore, that the study of single-chisel impact on rock is fundamentally important in improving the performance of roller-cone and percussive-type drills. Previous studies in this area have been conducted by Simon1 and Hartman2 by means of drop tests. In these tests a chisel was attached to a weight and allowed to fall, due to the force of gravity, so that the chisel was driven into a rock specimen upon impact. Strain gauges were attached to the chisel shank and the resulting force-vs-time curves were recorded photographically from an oscilloscope screen. The depth of penetration and crater dimensions were also measured. These tests have provided much valuable information but, as mentioned by the investigators, have not provided complete information on the effect of "rate of loading'! This is partly due to the fact that the chisel motion during drop tests is not a controlled motion which can be varied in form and frequency. Therefore, it seemed that additional information could be obtained by studying chisel impact under conditions where both the motion and the frequency of loading could be controlled. This paper presents a combined analytical and exper-

By William P. Blake

THE use of diamonds upon a large scale in drilling rocks, and the substitution to a certain degree of rotary diamond drills for the ordinary steel percussion drills, marks a new era in the art of mining. Since the invention by Leschot of the diamond drill, it has steadily advanced in its utility and range of application, and in the appreciation of miners and engineers. I t must be claimed as one of the many gifts of science to the arts ; and it is, in particular, one of the fruits of the scientific education given at the Ecole Centrale, at Paris. Members are all, doubtless, more or less familiar with the construction of the drill and of the machinery by which it is applied in boring. I t is, therefore, my present purpose only to direct your attention to some recent marked improvements, made by the American Diamond Drill Company, by which the economy and efficiency of the machines have been increased. Form of Bit.-The annular or ring form of the drill-head or bit was, I believe, the earliest; and it is still in use, without essential modification, wherever it is desired to obtain a sample " core" or specimen of the rock traversed. But for mere drilling, regardless ~f the preservation of a test-core, a solid-head bit is preferred, except for very large holes. Until recently, these solid-head bits were made with a pointed cutting face shaped like an obtuse cone. This form was assumed to be the best, being most in accordance with the experience obtained with percussion drills. I t is found, however, that the exact reverse

By J. T. Cherry

A fundamental goal of the Plowshare Program is to predict crater dimensions when an explosive of known yield is buried at a given depth in a given medium. In this paper a technique is presented that seems to calculate adequately, from first principles, the mound and cavity growth that occur during nuclear and high-explosive cratering events. The technique features a standard, numerical approach to high- intensity stress-wave propagation coupled with a unique model of material behavior in brittle failure. A schematic of stress-wave propagation is presented in Fig. 1. The equation of motion provides a functional relation between the applied stress field and the resulting acceleration of each point in the medium. Accelerations, when allowed to act over a small time increment [A]t, produce new velocities, velocities produce displacements, displacements produce strains, and strains produce a new stress field. Time is incremented by [A]t, and the cycle is repeated. The time increment [A]t is determined by an independent stability condition which requires the increment to be smaller than the time necessary far a compressional wave to travel across the smallest zone. We assume that failure occurs in a brittle material when either the tensile strength or the maximum allowable strain energy of distortion is exceeded. When either of these two conditions is violated, the code uses the cracked equation of state to determine the stress. A preshot testing program is used to determine the consolidated and cracked equations of state. In situ properties to be determined by field logging are density and elastic velocity (compressional and shear ve-

Jan 1, 1967

By E. P. Pfleider, O. Rellensmann

For many years mine surveyors and exploration engineers have sought an accurate means of transferring meridian underground by using the gyro-compass. These efforts have generally failed, either because they were inaccurate or because the size and cost of the unit were prohibitive. During the past ten years, however, great strides have been made. Autonetics in California has developed a comparatively light-weight (100-lb) gyro-theodolite, and the Institute for Mine Surveying at Clausthal Mining Academy in Germany has developed an instrument that is accurate to within 20" to 30" of arc. Concurrently, Minneapolis-Honeywell has produced an astounding gyro, the size of a salt shaker, that weighs less than 0.5 lb and compares favorably in performance with the 50-lb gyros of conventional design. This unit, designed for missile guidance, should be adaptable for surveying small boreholes. Given the proper interest and approach from the engineering fraternity, excellent gyrocompasses could probably be available for accurate underground survey work at nominal cost within the next three years. Principles of the Gyro-Compass: The gyrocompass, used for 50 years as a navigational instrument in ships and aircraft, senses the turning axis of the earth and points out true polar north. It does this by employing the earth's rotation, the force of gravity, and the precession characteristics of a gyro. For further details the reader is referred to several excellent publications'"3 covering the principles and application of the gyroscope. The heart of the gyro-compass is the gyroscope, or rapidly spinning wheel, which rigidly maintains its angular orientation in inertial space. Free gyros employ universal joints to allow the wheel axle to maintain its rigid spatial orientation independent of base motion disturbances. Free gyros are independent of the earth's turning and are not north-seeking. Only as they might be initially oriented parallel to the earth's turning axis could any north indication be obtained. In practice, the free gyro tends to drift off its set position and lose its accuracy. The Sperry-Sun Well Surveying Co. instrument (5M in O. D.) is of this free gyro type. It is counterbalanced, however, against the rotational effects of the earth, so that orientation of the spinning axis will be maintained throughout the survey.

Jan 1, 1960

By C. E. Wood, T. L. Joseph

This paper is a brief report of experimental work undertaken determine whether barium oxide in any quantity increases the desulfur ing action of blast-furnace slags. Industrial furnace operation wi slag containing small quantities of barium oxide, referred to later, intc ested S. A. Sanford of the Commercial Chemical Co., Youngstown, Oh to conduct experiments to furnish comparative results on desulfurizati with normal slag and slag containing small quantities of barium oxic The U. S. Bureau of Mines agreed to assist on the problem because the possible saving in fuel if the desulfurizing action of blast-furna slag can be substantially increased, also because the experiments woi yield new information on sulfur elimination in general, a matter economic importance in furnace practice. A more complete and func mental study of desulfurization of iron by slag is in progress. Distribution of Sulfur iN the Blast Furnace More than 90 per cent. of the total sulfur entering the blast furnz is in the coke. Sponge iron formed by reduction of iron oxides absor part of the sulfur as ferrous sulfide. Kinney's examination of sample taken from various levels of a 3004,011 furnace, shows that the me continues to take up sulfur until it reaches a level near the tuyer Desulfurization must therefore take place as the metal falls through t slag and as the slag and metal exist as layers in the crucible. The relative amounts of sulfur removed while the metal falls throu the slag and while the slag and metal exist as layers in t crucible are not definitely known. Preliminary experiments by t

Jan 1, 1929

[*E. O'C. Acker '86 Jinzoc Adachl '88 T. H. Aldrich '96 *Truman H. Aldrich '78 Walter H. Aldridge '89 *Anson W. Allen '87 John H. Allen '84 *Thomas Andrews '94 *William R. Analeby '90]

Jan 1, 1946

By G. E. Karantzavelos

Anew flotation process to recover alunite from low-grade alunite ores is described. The process begins with run-of-mine ore, reduced to less than 5 mm (0.2 in.), being preconditioned with the reagents before grinding and alunite flotation. From the preconditioning step, ore particles, impregnated with reagents, form pellets that subsequently disintegrate into the pulp during grinding. The second step is basically a standard alunite flotation step. Pilot plant test results show that an alunite concentrate assaying at least 85% alunite and less than 5% silica can be produced. Laboratory and pilot plant results were in excellent agreement, indicating that the new process is a viable means of alunite beneficiation. Plant results, using the new process, were superior to results from conventional alunite flotation procedure.

Jan 1, 1986

By J. O. Betterton, D. S. Easton

A detailed investigation was made of the phase diagram of silver-zirconium, particularly in the region 0 to 36 at. pct Ag. The system was found to be characterized by two intermediate phases Zr2Ag and ZrAg and a eutectoid reaction in which the -zirconium solid solution decomposes into a-zirconium and Zr2Ag. It was found that impurities in the range 0.05 pct from the iodide-type zirconium were sufficient to introduce deviations from binary behavior, and that with partial removal of these impurities an increase in the a-phase solid solubility limit from 0.1 to 1.1 at. pct Ag was observed. The phase diagram of the silver-zirconium system is of interest as an example of alloying a transition metal from the left side of the Periodic Table with a Group IB element. Silver would normally act as a univalent metal, its filled 4d-shell remaining undisturbed during the alloying. However, there is a possibility that some of the 4d electrons might transfer to the zirconium. An insight into such a question can occasionally be obtained by comparison of phase diagrams. The silver-zirconium system forms part of a more complete review of various solutes in zirconium in which these valency effects were studied.' Earlier work on the silver-zirconium system was done by Raub and Enge1,2 who investigated the silver-rich alloys. After the start of the present experhents, work on this system was reported by Kemper3 and by Karlsson4 which for the most part agrees with the phase diagram presented here. EXPERIMENTAL PROCEDURE The alloys were prepared by arc casting on a water-cooled, copper hearth with a tungsten electrode and in a pure argon atmosphere. Uniform solute composition was attained by multiple melting on alternate sides of the same ingot. Progressive improvements in the vacuum conditions inside the apparatus during the course of the experiments reduced the Vickers hardness increase of the pure zirconium control ingot from 10 to 20 points, observed initially, to negligible amounts at the end of the experiments. Such hardness changes in zirconium are a well known indication of purity. For example, -01 wt pct additions of oxygen, nitrogen, and carbon increase hardness by 6, 10, and 3 VPN respectively. '9' Further verification that the final casting technique did not add a significant quantity of impurities was obtained when pure zirconium was arc cast and then isothermally annealed in the vicinity of the allotropic transition. The transition was always observed to take place over the same temperature range as in the original crystal bar. The alloy ingots were annealed in sealed silica capsules for times and temperatures which varied between 1 day at 1300°C and 60 days at 700°C. The best method found to prevent the reaction of the zirconium with the silica was foil wrapping of molybdenum or tantalum. With this method, samples of pure zirconium were found to be unchanged in hardness after annealing for 3 days at 1200°C. In most of the experiments the protection of these foils was supplemented by an additional layer of zirconium foil inside the molybdenum or tantalum foil. The alloys, foil, and the capsule were outgassed at pressures in the range 10 to l0-7mm Hg in the temperature range 800" to 1100°C before each anneal in order to remove hydrogen and other impurities, and to provide a suitable container for the high purity, inert atmosphere, which is essential in the annealing of zirconium. The temperature measurements were made with Pt/Pt + 10 pct Rh thermocouples calibrated frequently during the experiments against the melting points of zinc, aluminum, silver, gold, and palladium. For the longer anneals the sum of various temperature errors was generally well within ± 2°C. For short-time anneals and during thermal analysis the overall temperature error is considered to be within ± 0.5°C. The compositions of the alloys from the quenching experiments were determined by chemical analysis at Johnson Matthey and Company, Ltd., under the direction of Mr. F. M. Lever. The actual metallo-graphic samples were individually analyzed in every case, and prior to the analyses two or more sides of each specimen were examined to insure that the specimen was not segregated. The sum of the solute and solvent analyses was in each case within the range 99.9 to 100.1 pct. In the course of the experiments, minor impurities in the range 0 to 500 ppm were found to have significant effects on the zirconium-rich portion of the phase diagram. Similar effects had been encountered previously in other zirconium phase-

Jan 1, 1959

By J. A. Eisele, D. J. Bauer, L. E. Schultze

Approximately 100 million mt of magnetic reject tailings, which contain apatite and about 1% yttrium and rare-earth elements, exist in the eastern U.S. as a result of iron ore mining operations. At the present time, no economic process is available for recovering yttrium from this material. The U.S. Bureau of Mines (USBM) studied the problem to determine if an effective low-cost method could be found, thereby increasing our domestic yttrium reserves. [Fig. 1] is a line drawing of a photograph taken during microprobe analysis of a sample of the tailings, and shows the distribution of yttrium. Typical analysis of this material is 0.14% yttrium and 1.1% rare-earth elements (mainly lanthanum through neodymium). Over half of the yttrium is present as a hydrated Ca-Y silicate deposited along interfaces in the grain structure; whereas, the remainder of the rare-earth elements occur as Ca-Fe-RE silicates. The remaining yttrium and rare-earth elements are in solid solution with the

Jan 1, 1977

By H. S. Choi, I. Iwasaki

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer' stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,2 Mitchell et aL.,3 and particularly Hamilton et al.' have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski's French Patent No. 847,-215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores. The present article describes comparative results obtained at room temperature and at elevated temperatures by otherwise conventional flotation of iron ores, by single-mineral flotation in the Hallimond tube, and by contact-angle measurements. It is not the purpose of this article to evaluate the commercial feasibility of high-temperature flotation of iron ores, although preliminary calculations show that the cost should not be excessive and that the gains to be realized may well outweigh the extra cost of heating the pulp. LABORATORY FLOTATION TESTS Experimental: All flotation tests reported in this article that use a laboratory Fagergren cell were made on ore A (either containing the primary slimes or deslimed at 20µ as specified) following the preparatory procedures described elsewhere- or this particular ore. Ore A contained hematite, goethite (limonite), quartz, chert, and minor quantities of magnetite. Confirmatory tests made on other ores show that the same general principles apply to ores of similar mineralogy and structure. Conditioning was performed by adding the collector, as a soap, to the vigorously stirred and heated pulp. Conditioning time was 5 min, the pulp contained 60 pct solids, and the equivalent of 0.5 Ib of fatty acid was added per ton of original (unde-slimed) ore. The pH of the pulps ranged from 6.8 to 7.1 (25°C measurement) during conditioning. The pH was adjusted in the flotation cell by addition of either NaOH or H2SO4, the values reported being those of the pulp cooled to 25°C. During conditioning and flotation the pulp temperatures were controlled within l° to 2° by immersion of Variac-controlled Calrod elements in the conditioning beaker and in the cell, and by the use of water, heated to the appropriate temperature, for transferring pulp, adjusting pulp volume, and washing. Selectivity indexes have been calculated on the same basis as those reported in the article by Cooke, Iwasaki, and Choi." Results: Table I gives the results obtained by floating deslimed ore A with pure oleic acid at 25" and 50°C, and Fig. 1 shows the selectivity indexes plotted against pH of flotation. Inspection of Table I

Jan 1, 1961

H. M. BOYLSTON E. B. YOUNG SECRETARY-TREASURER OF SECRETARY-TREASURER OF BOSTON SECTION MONTANA SECTION R. M. KEENEY F. G. MOSES SECRETARY-TREASURER OF SECRETARY-TREASURER OF COLORADO SECTION UTAH SECTION

Jan 7, 1919

By J. L. Lehman, J. D. Sudbury, J. E. Landers, W. D. Greathouse

A full scale field experiment on cathodic protection of casing answers questions concerning (1) the proper criteria for determining current requirments, (2) the amount of protection provided by different currents, and (3) the transfer of current at the base of the surface pipe. Three dry holes in the Trico pool in Rooks County, Kans., were selected for cathodic protection tests. The three holes were in an area where casing failures opposite the Dakota water sand often accur in less than a year. Examination of the electric togs showed the wells to be similar to other wells in the field where casing in four of seven producing wells has failed. The three holes were cleaned out and cased with 75 joints of new 51/2-in. 14-tb J-55. Each joint was visually inspected and marked before it as run. The casing was bull plugged and floated in the hole 50 that the inside might remain dry and free of excessive attack. Also, if a leak occurred, a pressure increase could be observed on gawge at the surface. Extensive testing was done, including potential profiles, log current-potentid curves and electrode measurements from both surface and downhole connections. Based on these data, a current of 12 amps was applied to one well and 4 amps to mother. The third well was left to corrode. During the two-year period when the casing was in the ground, [he applied current was checked weekly, and reference electrode measurements were made about every two months. Three sets of casing potential profi1e.c were run. When the three strings were pulled, each joint was examined for type of scale formed, presence of sulfate-reducing bacteria, extent of corrosion nttnck and pit depth. Since the pipe was new when run, quantitative determination of the protection provided by current was possible. This is the first concrete field evidence to help resolve the many arguments about the proper method for selecting adequate current for cathodic protection of oilwell (-using. INTRODUCTION A casing string is run when a well is drilled. This pipe is supposed to protect this valuable "hole in the ground" for the life of the well. Often the casing does not last the life of the well; it is with these casing failures that this work is concerned. The cost of repairing a casing failure varies from field to field—from as much as a $30,000 per leak average in California to $5,000 per leak in Kansas. Additional costs other than actual repairs are also important. These include formation damage, lost production, etc. Casing damage caused by internal corrosion is important in some areas. Treatment normally consists of flushing inhibitor down the annulus, but further research is being done on control measures. The test described in this paper is concerned only with external corrosion. The problem of casing failure from external attack has appeared in several areas including western Kansas, California, Montana, Wyoming, Texas, Arkansas and Mississippi. Cathodic protection is currently being used in an attempt to control external corrosion. From reports in the NACE there are thousands of wells currently under cathodic protection. The quantity of current being applied ranges from 27 amps on some deep California wells to a few tenths of an amp being supplied from magnesium anodes on wells in Texas and Kansas. Considerable field and laboratory effort1,9,5,6 was exented on the problem of cathodic prctection of casing, and it became fairly obvious that this method could be used to protect wells. Early workers showed that current applied to a well distributed itself over the length of the casing and was not concentrated on the upper few hundred feet. Basic cathodic protection theory had shown that corrosion attack could be stopped by applying sufficient current. The problem resolved itself, then, into one of trying to decide just how much current was necessary. Various criteria were utilized in installing the many existing cathodic protection installations. These methods included the following. 1. Applying sufficient current to remove the anodic slope as shown by the potential profile." 7. Applying enough current to maintain all areas of the casing at a pipe-to-soil potential of .85 v.' 3. Applying the current indicated by a log current-potential (or E log I) curve." 4. Supplying the current necessary to shift the pipe to-soil potential .3 v." 5. Applying 2 or 3 milliamps of current per sq ft of casing."