Search Documents

By E. T. Turkdogan, P. Grieveson, J. F. Beisler

Jan 1, 1963

By James C. M. Li, J. Weertman

James C. M. Li (United States Steel Covp.)—The author has discovered a single analytical relation between the minimum, or the steady-state, creep rate and the applied stress confirming a statement made earlier by orn" that such relation should exist and should reduce to the power law at low-stress levels and to the exponential law at high-stress levels. However, as pointed out by the author, all the available theories of creep are not adequate to explain such a single relation. Inspired by such a statement, I have made a suggestion concerning a possible explanation13 of the new relation. This is based on the concept that the rate-controlling step is the cooperative motion of a short dislocation segment. The nature of and the reason for the cooperation have been discussed13 as well as the reason why the motion of the dislocation could be controlled by the mobility of the short segments. A natural short segment has been proposed13 to be the node formed at the intersection of two dislocations. The reason why the node may contain only a few atoms has not been discussed and the application of the proposed model to all the metals and alloys reported in this paper has not been attempted. It seems appropriate to include these in this discussion. The model was partly inspired by the substructure recently observed in the electron microscope on creep specimens. One such example is shown in Fig. 48 in Darken's Campbell Memorial Lecture. The substructure is a collection of dislocation intersections and irregular networks. No pileups have ever been observed in such specimens. A closer look at the network indicates that one set of dislocations is more straight than the other set sug- gesting that the other set may be mobile in the plane of the net. Since, for the network to survive the creep deformation, some dislocation reaction has to take place at the intersection of the two sets of dislocations, the mobile dislocation, even if it can slip in the plane of the net, will have difficulty in moving at these intersections. To illustrate, an idealized network is shown in Fig. 9. The thin lines represent the set of dislocations which are mobile and can slip in the plane of the net except at the nodes which are formed at the intersection of the two sets of dislocations. The other set of dislocations, represented by the thick lines, may have a Burgers vector which is not parallel to the plane of the net, and therefore may be immobile. Because of this nonparallel Burgers vector, the Burgers vector of the node, which is avectorial sum of the Burgers vectors of the two sets of dislocations, will also be nonparallel to the plane of the net. Therefore, the node cannot slip in the plane of the net and the set of mobile dislocations will have to drag the node along as indicated in Fig. 9. Now the problem is how many atoms could be involved in the nodes. Exact calculation of the length of the node is a difficult task especially since the length should be a steady-state length and not an equilibrium length. An estimate of the equilibrium length can be made by balancing the line tension of all the dislocations. The results would be a small fraction of the length 1 between nodes as shown in Fig. 10. In some instances such a calculation shows that the node will not be formed. But, since the calculation is only approximate, it does not rule out the possibility of the formation of a short node. In other instances the equilibrium length of the node is an appreciable fraction of I. Such a node would

Jan 1, 1963

By H. J. de Haan, L. Schenk

Scope for Thermal Recovery in Shell's Heavy Oil Fields in Venezuela The main heavy oil reservoirs on the East coast of Lake Maracaibo (Fig. I), known as "Bolivar Coast", initially contained some 20 billion bbl of oil in place with gravities in the range of 10 to 15° API. The current total production rate is about 400,000 B/D. Since the recovery to date is on an average only 12.5 percent of the initial oil in place, these fields offer a vast potential for secondary recovery methods. The reservoirs are characterized by moderate depth (generally 1,000 to 3,000 ft; maximum 5,000 ft), good formation properties such as net oil sand thickness (50 to 300 ft), high porosity (30 to 40 percent) permeability (1 to 3 darcies) and oil saturation (initially about 80 percent) and high oil viscosity (100 to 10,000 cp in situ), all of which are favorable for the application of thermal recovery processes. Since 1957, steam drive, steam "soak" and underground combustion have been tested or are being tested in this area.1-3 This paper deals with a major steam drive test in the Tia Juana field. The test was commenced in Sept., 1961, on the basis of encouraging results of laboratory experiments and pilot field tests, which will be discussed briefly. Early Laboratory Investigation of the Steam Drive Process In 1956 a series of model experiments was carried out in the Koninklijke/Shell Laboratorium, Amster- dam, to investigate the displacement of heavy oil by steam.' The prototype studied was a horizontal, un-consolidated heavy oil reservoir, subjected to a linear steam drive. The model, representing a slab from this reservoir along the main flow direction, consisted of a steel tube filled with oil-saturated sand, provided with layers of rock at the top and bottom to simulate conductive heat losses to cap and base rock. Lateral heat losses, perpendicular to the main flow direction, were minimized by insulating the sides of the model. Heat flow and viscosity and gravity forces were scaled by taking the steam injection rate and sand permeability inversely proportional to the geometric reduction factor of the model, and using materials (oil, steam, cap rock, etc.) identical with those of the prototype. The main feature of the process was a frontal displacement mechanism that was observed within wide ranges of injection pressure and rate, oil viscosity, initial oil saturation and sand permeability. The high stability of this front can be attributed to the high volumetric steam flow rates, combined with the reduction in oil viscosity. High recoveries were obtained due to the low residual oil saturation of about 15 percent in the zone swept by steam. The latter value pertains to the specific test conditions (heavy oil, uncon-solidated sand) and may be lower for light oil, due to the effects of steam distillation. The applicability of this experimental approach is limited, as it does not take into account the fact that

Jan 1, 1970

By J. L. Gregg, J. L.

RECENTLY there has been considerable interest in the production and use of extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wire-drawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names. No performance data are given and no inference as to the inferiority of one alloy as against any other is made. K. Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification.

Jan 1, 1929

By Richard Miller

RECENT studies of creep have made it apparent that plastic deforma-tion may occur in metals under stresses less than the elastic limit as deter-mined from short-time tests. In summarizing conclusions drawn from creep tests by various investigators, Tapsell1 said: "It is evident that if a material has a true elastic range, the elastic limit must represent the maximum stress for no creep." The presence of a. definite elastic limit, represented in single crystals by a critical or threshold shearing stress, is claimed by Schmid2, Elam3 and others who have investigated the plastic deformation of single crystals. However, this "law of critical shearing stress" was deter-mined2 from short-time tests, and the measurement of the deformation was made with apparatus primarily designed to observe large amounts of plastic deformation, not to detect elastic changes. Experimental data recently obtained with highly sensitive instru-ments by A. W. Hanson4 on zinc and by Podaschowsky5 on rock salt indicate that the elastic range in single crystals is considerably narrower than formerly was supposed. Moreover, a theoretical possibility of permanent deformation, under the influence of even the smallest shear stress in single crystals above a certain temperature (Td), has been developed by G. I. Taylor6. This evidence seemed to warrant an examination of the elastic limit in large single crystals by means of creep tests. The first metal chosen for examination was zinc.

Jan 1, 1936

By E. T. Turkdogan

Jan 1, 1962

By P. T. Allsman

INTRODUCTION The honor of being the recipient of the Mining Society's Daniel C. Jackling Award for 1966 imposes on me the responsibility to search for the subject that I would be best qualified to discuss. It seems that my experience in the mineral industry — nearly 15 years in private and 30 years in public employment — should uniquely qualify me to comment upon the relationships between the mining industry, mineral engineering as a profession, and government, and the changing economic, technologic, political and social changes that dictate their relationships. Such conditions, the increasing knowledge of the world mineral resource base, the greater demands of an expanding population with a rising standard of living, shall be evaluated with respect to our profession — mineral engineering. In all of these forty or so years, I have been in close touch with many phases of the mineral and energy resource industries, especially those of the United States. Particularly during the past 10 years, I have had a ringside seat at the "goings on" in Washington. During all of this period I have observed and analyzed many of the problems of the industry and its relations with the government. During the past few years, I have had increased opportunity for doing research and have found a need to learn something about the mathematical techniques that are undergoing such a revival since electronic computers were developed. One of these techniques is multivariate analysis, which is a system for correlating a large number of complex variables. By applying this technique to the seemingly chaotic present-day situation, there emerges a course of steady improvement in the minerals resource industries that wars, depressions, and political strife have failed to obstruct for long. In short, I advocate a need for new concepts in mineral engineering to cope with the changes, pos- sibly adding many more specialized areas on one end of the spectrum, and broad engineer-generalist approaches at the other. The meeting place shall be where the intricate mineral resource problems at the frontier of knowledge merge into the socio-techno-logical problems of the world. HISTORICAL INVOLVEMENT OF GOVERNMENT IN MINERAL RESOURCE PROBLEMS Involvement of government in mineral resource problems undoubtedly is as old as government itself. But passage of the Mining Act of 1866, superseded by the Act of 1872, was the first major entry of our Federal Government into the problems of mining. Passage of the law was necessary to resolve many conflicting claims and disputes in mining. The General Mining Law of 1872 and the Mineral Leasing Laws of 1920 apply to millions of acres of public lands and to certain privately owned land on which the mineral rights have been reserved to the Federal Government. The extensive involvement of government in the mineral industry business today often comes as a shock to the mineral engineer who has begun to climb the ladder to the top in his company. He is often poorly prepared to cope with the situation and becomes frustrated and even hostile. Better knowledge of the role of government perhaps would ease his situation. In our political system, private industry is responsible for producing minerals. To make certain that the production is adequate for a peace-time economy, and to guarantee the Nation's security in an emergency, the Federal Government finds it expedient to develop policy and engage in regulatory, educational, and research activities. A few examples will illustrate the varied role of government in relation to mineral problems. In varying degrees many agencies of the Executive Branch of Government have responsibilities that influence the functioning of the mineral and energy industries. In addition, of course, Congress, the Judiciary, and State and local governments exercise great influence. The Department of the Interior is primarily responsible for activities to promote the development and conservation of mineral and fuel resources, and the

Jan 1, 1967

By C. H. Mathewson

CONSIDERABLE progress has been made during the last few years in analyzing the action of plastic deformation in metallic crystals. This is due largely to the development of X-ray spectrographic methods for studying changes in the orientation of single crystals, or of conglomerates, as they occur during the process of plastic deformation, but partly to the widespread knowledge of suitable technique for preparing large (single or variously combined) crystals for direct crystallographic observation under stress or in various conditions of strain. These two methods of studying changes in the crystalline structure of metals may of course be used in conjunction with features of mutual support, but unfortunately the advantage of direct crystallographic observation is lost when we proceed to the study of severely cold-worked structures, owing to the occurrence of real or apparent crystalline discontinuities which become more and more complicated as the amount of plastic action increases. Furthermore, the X-ray methods do not appear to be adequate, at least in their present stage of development, to fix definitely the character of structural alteration in the parent crystal lattice by plastic deformation. The principal question at issue concerns the nature of the crystalline particles that remain after plastic deformation. These are generally known in our American metallurgical literature as crystalline fragments,' and they seem, indeed, to diffract as individuals causing the Hull pattern of a severely cold-worked metal to resemble the pattern of a fine powder,2 with certain features of preferred orientation among the particles deter- mined by the manner and intensity of cold working. We must freely concede that there are conceptions of lattice alteration, apart from that of simple fragmentation, which would account for an increasing number of lattice positions according to X-ray spectrographic observation as the degree of deformation increased.

Jan 1, 1927

By E. C. Stephens

The eastern Washington— Idaho clay region stretches along the northeast margin of the Columbia basin for 150 mil es. The three better known and developed clay areas are Clayton, Wash., (2 miles north of Spokane); Mica, Wash., (10 miles southeast of Spokane); and Moscow-Deary-Bovill, Latah County, Idaho (about 80 to 90 miles southeast of Spokane) see Fig. 1. Clays from the eastern Washington— Idaho clay area have been mined for more than 50 years. At present Mica, Washington deposits are used by the Gladding—McBean & Co. to make a variety of bricks and ceramic products and Latah County, Idaho clays are used by the A. P. Green Fire Brick Co. to make refractories. The Anaconda Co. made an intensive investigation of the clay deposits in the northeastern Washington-!daho area in 1919 to determine the existence of a supply of raw materials from which alumina could be made. The greater part of the work, which included systematic drilling and shaft sinking, was concentrated at Mica, Wash. This was part of a research project carrted on by the Anaconda Metallurgical Research Dept. under the direction of Frederick Laist and F. Frick and it was terminated in 4920. V. D. Perry, Vice President and Chief Geologist for The Anaconda Co., in 1952 assigned the writer to make a preliminary study of clay and other potential sources of alumina ore in the Pacific Northwest with particular emphasis on those deposits which might be of future importance to The Anaconda Co9s. then new aluminurri plant at Columbia Falls, Mont.

Jan 1, 1961

By P. van Meurs, C. van der Poel

From observations of the linear displacement of oil by water from a porous medium as visualized in transparent models, new insight into the mechanism of vircous fingering, as occurring in the case of unfavorable oil-water viscosity ratios, has been obtained. A mathematical description of the observed phenomena leads to formulas. expressing both oil production and pressure drop across the formation as a func-tion of cumulative water injection with the oil-water viscosity ratio as a parameter. Theoretical results are compared with those obtained from scaled laboratory experiments in sand-filled rubes in which water was injected at the one end and production was obtained from the other end. In the second part of the paper the same principles are used to calculate a more realistic production scheme in which production of oil and water is obtained from wells regularly distributed over the field. Results show satisfactory agreement with production data of an actual oil field. Application of the theory is extremely simple as only a limited number of readily available parameters have to be known and results are presented in an analytical form. INTRODUCTION When oil is displaced from a porous medium by water having a viscosity lower than the oil. the oil-water interface is essentially unstable and has the tendency to break up into what are called "fingers" or "streamers". This Viscous fingering has been noted before by Engelberts and Klinkenberg' and has recently been demonstrated in transparent models by van Meurs-. It is highly questionable whether it is at all possible to perform relative permeability measurements In the laboratory reproducing the same distribution of water and oil in the cores as Present in practice. Therefore, we based our descriptive theory on an idealized model which was "tailored" to the fingering mechanism as observed in transparent models under scaled conditions. This approach was the more attractive, as a highly simplified model had already yielded an adequate description of the process. Though we are aware our theoretical approach can be extended in several ways, it is given here in its simplest form to explain the fundamental principles and to avoid complicated formulas. SIMPLEST CASE OF A LINEAR DRIVE Observations and Theoretical Model In Fig. 1 a series of photographs shows how water penetrates into a formation saturated with an oil which is considerably more viscous than the water. The technique for obtaining these photographs, using transparent models, has already been described?. The fingers can be clearly observed and are seen to be mainly parallel to the flow direction. Note that the contours of these fingers are not smooth but show protrusions of water enclosing oil pockets.

By Ernst M. Cohn

The demonstrations of the "Silent Sentry" by Union Carbide Corp. in 1957 and of a special tractor-plow by Allis-Chalmers in 1959 ushered in the technology era of fuel cells. The idea for direct conversion of chemical to electrical energy, first published in 1801 by Davy in England and Ritter in Germany, has been kept alive by a few people through 150 years: Grove built the first hydrogen-oxygen fuel cell in 1839; Mond and Langer made electrolyte contributions around 1890 that are still used today; Baur worked on coal-based cells from 1900; Bacon started his work in the '30's, which resulted in the first multi-kilowatt unit in the '50's; Davtyan studied molten-salt electrolytes in the '40's, followed by Ketelaar in the '50's; and Justi developed highly active electrodes in the '50's, to name only some of the pioneers. Despite the tremendous increase in research and development of fuel cells, these direct energy converters are still in their infancy. They will find their functional application in space, where power density must be maximized and product water utilized. These early systems will provide valuable experience in system engineering and reliability.

Jan 9, 1964

Jan 1, 1967

By Edward Capillon

THE problem of scrap is probably of greater importance inn the production of gold, silver and other precious metal alloys than is the case for base metals and alloys. Remelting of gold and silver scrap in the shop is always a costly process because it involves losses by oxidation of the base metals in the alloy with a consequent increase in the percentage of precious metal. This is most marked in the case of alloys containing the low-boiling and easily oxidized metals zinc and cadmium. Since it is. not generally feasible to assay every shop remelt it follows that the possibilities of lost values are large. So-called rolled gold and silver plate is made by soldering or welding the precious metal alloys onto base, metal. Such plate when defective must be sent to the refinery to recover the gold and silver values, thereby involving additional expense in the form of refining charges. It is obvious therefore that gold and silver alloy scrap is an important item in manufacturing cost and must be reduced to a minimum. The amount of scrap resulting from poor metal will depend on a number of factors in the manufacturing operations, not least among which is the melting and casting practice. The notes which follow are a summary of experiments performed at various times to determine what variables in melting and casting are influential in the production of sound alloys.

Jan 1, 1930

A regular general meeting of the Canadian Mining Institute will be held in Vancouver, B. C., on Nov. 26-28. The Council extends a cordial invitation to all members of the American Institute of Mining and Metallurgical Engineers to attend.

Jan 11, 1919

By Roger L. Beals, George A. Tweedy

I. INTRODUCTION. THE results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time, hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data Pan- Amalgamation. Cyanidation. 1905. 1907. 1903. Tons treated, . . 51,387 53,983 69,300 Value per ton (U. S. currency),. $10.75 $8.39 $8.28 Extraction, per cent., 65.00 88.50 S7.45 Extraction, per ton. .- $7.00 $7.4.; $7.24 Total cost, per ton treated, 6.50 4.311 4.01 Profit, per ton treated, . . 0.50 3.07 3.23.;

Feb 1, 1910

By R. W. Smith

Many industries such as the cement industry handle large quantities of limestone and clay slurries. However, at present very little is known about the flow properties, such as friction loss due to flow of slurries in pipelines. This lack of knowledge has made it often very difficult to calculate the total dynamic head of a proposed slurry handling system, and therefore has often made the selection of correct size slurry handling equipment difficult. Because of lack of knowledge about slurry flow a study of slurry flow theory has been made at the Portland Cement Association's Research and Development Laboratory with the idea of developing a method whereby friction losses due to slurry flow may be predicted for any size pipeline. The flow equations developed have been checked by pilot plant size equipment. DERIVATION OF FLOW EQUATIONS It has been known for some time that limestone and clay slurries handled in cement plants do not flow in the same manner as a Newtonian fluid such as water. When a Newtonian fluid flows the shear stress at any flow velocity is proportional to the rate of shear. This phenomenon can be illustrated by a line (Figure 1). The viscosity of the fluid is the slope of the curve. Thus, the flow properties of the material may be characterized by a single materials constant: viscosity. When a non-Newtonian fluid with the type of characteristics exhibited by limestone and clay slurr-ries flow, a similar curve can be constructed (Figure 2). This graph is a shear diagram of a Bingham plastic non-Newtonian fluid. It should be noted that with the Bingham(1) plastic type of flow viscosity, the slope of the curve, is still an important materials constant. In addition, however, there is another materials constant, namely the yield stress of the material. One way to visualize this constant is to consider it as the amount of energy that must be put into a Bingham plastic material to start it flowing.

Jan 1, 1961

By D. M. Davidson, P. F. Kerr

The Permian Cutler Formation in Kane Creek, Utah bears uranium ore in fissure-type vertical veins. This fissure vein formation and its associated host rock bleaching, weak argillic alteration, and base-metal sulfide mineralization along with the development of hydrothermal minerals, a 60 m.y. isotopic Pb/U age, and well-crystallized uraninite's structural control, give evidence of ore deposition in a hydrothermal environment consistent with Laramide mineralization. Mica polymorph studies indicate first, that temperature during the hydrothermal alteration or subsequent ore deposition did not exceed 200°; hence Cutler deposits are classified telethermal; and secondly, that rock alteration and ore deposition are closely related both in time and space, as is seen in argillic alteration sequence. Ore deposition in an alkaline to slightly acid reducing environment is postulated. Ore textures and mineral associations and distributions also indicate that carbonate complexes may have been transported with the deposing ores. Bleached rock formations are not primary strati-graphic phenomena. Bleaching, or changes in ferric iron content, results from a chemical process involving reduction and conversion of hematite to a soluble aqueous ion. Nearby Chinle bedded deposits (Moss Rack sandstone), containing shale lenses, fossil wood, organic debris and minor fractures, overly the Cutler formation. Chinle ores have a single reported isotopic age of approximately 200 m.y. Their chemical environment is assumed similar to that of the Cutler ores, though slightly more acidic. Two genetic, paradoxically divergent interpretations of the bedded deposits are derived from available spectrographic, petrographic, X-ray and chemical analyses. Kane Springs canyon is located southwest of Moab, Utah, south of the Colorado River and northwest of the Lisbon Valley mining district (Fig. 1). Uranium deposits occur along the northeast flank of a Kane Creek salt anticline where two geologic formations bear ore, the Permian Cutler and the Triassic Chinle. The Cutler deposits' fissure vein formation is an unusual occurrence in the Colorado Plateau. The Chinle deposits appear to be of the normal sedimentary type. Associated with the vein deposits are a number of features, including argillic alteration of sedimentary strata. The minerals of these deposits and their associated features have been studied in detail in a two year program entailing both field and laboratory techniques. STRATIGRAPHY A stratigraphic section of the lithologic units in the Kane Creek area is given in Table I.

Jan 1, 1967

By Lucien Eaton

THE use of filling in mines is less common in the United States than it is in Europe, where in some places it is required by law. In most cases the filling is placed by hand, and the material used for this purpose is the waste from development and that sorted from the ore in the stopes. When these sources provide an insufficient supply, additional rock must be quarried on surface or mined underground, or some other material :st be used. In different parts of the world sand, clay, gravel, culm, nulated slag, mill tailings, and even ashes, have been used as filling material in place of or in conjunction with rock. Of all the materials used for filling the best is probably clean sand. Gravel, finely crushed rock, granulated slag and coarse mill tailings are almost as good, and the methods used for placing and confining sand will apply equally well to any of these. The advantages of sand are its comparatively slight compressibility and the ease, economy and convenience with which it may be placed. On account of the voids, which necessarily occur in fills made of coarse waste, such fills will compress 10 to 25 per cent before they develop their full strength, whereas clean sand seldom compresses more than 5 per cent. Sand is especially desirable when practically complete filling is required, and sand derived from mill tailings, especially when not thoroughly cleaned, has been remarkably effective in sealing off and extinguishing mine fires. When natural sand is available on surface, or when it can be obtained from the mill tailings or tailings dump, the cost of using this material for fill will probably be considerably less than that of rock. In this paper it is not proposed to discuss all methods of filling, butt to describe some of the methods used for placing sand fill and to make a brief comparison of their merits.

Jan 1, 1932

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By H. T. Kennedy, S. G. Dardaganian, J. L. Clanton

This paper presents equilibrium ratios measured on oil and gas samples taken from the Kelly-Snyder field at the reservoir temperature of 128°F. From these data smoothed curves were constructed for the reservoir fluid up to the bubble-point, 1,874 psia. A material balance calculation, based on the use of equilibrium ratios instead of the usual solubility and shrinkage meayr~rements is made on the field and compared to the con\.entional method. DETERMINATION OF EQUILIBRIUM RATIOS The equilibrium ratios, or K values were obtained by recombining separator samples of oil and gas taken when the reservoir was above its bubble point, and thus represented the reservoir fluid before any change had occurred due to the evolution of gas. The well sampled had a gas-oil ratio of 617 cu ft of high pressure sepalator gas per barrel of separator oil. and a bottom-hole temperature of 128°F. Samples were brought to equilibrium by agitating for 24 hours in a thermostat, maintained at the proper temperature within 0.2ºF, mercury being added when necessary to maintain the pressure constant. Samples of oil and gas were then taken by constant pressure displacement, and analyzed by low temperature frac-tionation. Equilibrium ratios were determined at 128°F and 500, 800, 1,000 and 1,400 psig. At the latter pressure, there were indications that the gas samples were contaminated with small quantities of oil, and only data taken at the first three pressures were included in Fig. I. This figure has been extended to higher and lower pressures by the use of the Fluor charts for 3,000 psi convergence pressure, on which the experimental points fit well. MATERIAL BALANCE EQUATIONS The possible errors involved in conventional material balance equations have been analyzed by Muskat1. Where the errors occur in field measurements, or in obtaining effective averages from variables such as gas-oil ratio and pressure, they will evidently be involved in any attempt to estimate the content of the reservoir. On the other hand, substantial errors may be introduced in conventional material balance calculations by: (1) the neglect of the amount of oil dissolved in gas at high pressures and temperatures in the reservoir, but which condenses under separator conditions; (2) the assumption that the separation of oil and gas in the reservoir may be duplicated by a differential liberation in the