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By Paul M. Tyler, Oliver Bowles

The extensive employment of nonmetallic minerals antedates the use of metals, but only within the last two decades has the production of nonmetals begun actually to keep pace with the complicated activities which characterize the so-called Machine Age. The economic changes ushered in by the Industrial Revolution were reflected first in an increased demand for metals and for fuels. In the modern sense, therefore, the nonmetallic mineral industries are new and afford new opportunities for engineer and economist alike. A certain amount of caution is indicated, therefore, before attempting to apply ready-made formulas to the problems of these industries. Economics is not an exact science. In the field of production technology where the number of variables is fairly well known, the principles of economics are readily applicable, but as the student proceeds through the province of marketing into the unexplored regions of psychology and sociology he must distinguish carefully between scientific reasoning and purely metaphysical speculation, even when the latter masquerades as economics. The present paper attempts to prove no preconceived theorems and is designed primarily to stimulate careful thinking on sundry neglected phases of these industries. An attempt is made to differentiate the general problems into single aspects which afford promise of being comprehended separately; also, some fundamental statistical data are presented, but merely to indicate a method of scientific approach applicable to more intensive studies. Definition Before discussing the economics of the nonmetallic mineral industries, it is appropriate to consider what we mean when we say "nonmetallic minerals." This term, inasmuch as it is merely a negative description, is somewhat loose and ambiguous and gives rise to questions in regard to minerals that, like chromite or bauxite, are alternatively classed either as nonmetallic or as metallic minerals (or ores). The chrome ore used to make ferrochrome for steel manufacture is undoubtedly metallic in character; similar material destined for use as a refractory in the same

Jan 1, 1934

By F. W. Schremp, V. L. Johnson

This paper discusses the results obtained from high temperature, high pressure filter loss studies in which field samples of clay-water, emulsion, and oil base fluids were used. High temperature, high pressure tests of some premium priced emrilsion and oil base drilling fluids show filter loss peculiarities that are not predicted by standard API tests. It is recommended that high temperature, high pressure filter loss tests be used to evaluate the performance of such fluids. Apparatus is described which proved to be satisfactory for evaluating filter loss behavior over a wide range of temperatures and pressures. INTRODUCTION The petroleum industry spends large sums of money each year on chemical treating agents for lowering filter loss and on premium-priced low filter loss drilling fluids. While it is an accepted fact that low filter loss is advantageous during drilling operations, it is questionable whether the present standard method of determining filter loss gives a reliable indication of the loss to he expected under bottom hole conditions. The purpose of this paper is to show that high temperature. high pressure filter loss tests Should be used to evaluate filter loss behavior of fluids for deep drilling. Concern over possible effects of filter loss on oil well drilling and well productivity dates back to the early 1920's. During the years 1922 to 1924, filtration studies were reported by Knapp,' Anderson2 and Kirwan." These studies were the first to be reported in the literature on this subject. No further information was published on the subject until 1932 when Rubel' presented a paper in which he discussed the effect of drilling fluids on oil well productivity. In 1935. .Jones and Babson constructed the first laboratory tester designed to study the effects of temperature and pressure on the filter loss behavior of clay-water drilling fluids. In a discussion of their investigations, Jones and Babsons stated, "Performance characteristics of a mud can he evaluated with considerable reliability by a single test at 2,000 psi and 200°F. Exact correlation between the results of performance test5 made under these conditions and the behavior of muds in actual drilling operations is of course impossible." Jones arid Babson apparently were well aware that at best laboratory tests can give only qualitative answers to the question of what is the actual behavior of a drilling fluid when subjected to deep drilling conditions. Jones' presented a paper in 1937 in which he described a static filter loss tester to be used for routine filter loss tests. This instrument subsequently was adopted as the standard APl filter loss tester. In 1938, Larsen7 developed a relationship between filtrate volume and filtrate time that is in general acceptance today. Larsen was cognizant of the danger of estimating bottom hole behavior from filter loss measurements at room temperature. He tried to predict the effect of temperature on filter loss by relating temperature effects through the temperature dependence of filtrate viscosity. This was undoubtedly an over-sirriplification of the temperature dependence of drilling fluid filter loss. In 1940, Byck" published a summary of experimental results of filter loss tests made on six representative California clsy-water drilling fluids. He concluded that "no existing method will permit even an approximate determination of the filtration rate at high temperature from data at room temperature. It is necessary to measure filtration at the temperature actually anticipated in the well, or to make a sufficient number of tests at various lower temperatures so that a small extrapolation of these data to the anticipated well temperature may be applied." Byck's findings were presuma1)ly well accepted and recognized by drilling Fluid technologists, and yet, they did not lead to wide adoption of high temperature drilling fluid filtration equipment. This is evidenced by the fact that no addition information has appeared in print on the subject since 194). Study of Byck's data shows that there was a useful consistency in them. The fluids did not show predictable losses at high temperatures, but they did line up at high temperatures in approximately the same order that they lined up at low temperatures. That is, if a fluid appeared to be a good fluid with relatively low loss at low temperatures, it would also be a good fluid with relatively low loss at high temperatures. In the last decade. the above situation has changed. The drilling fluid art is markedly different from what it was. The outstanding change, as far as the present discussion is concerned, has been the adoption of wholly new types of drilling fluids. Oil base and emulsion drilling fluids have come in to wide use. It is, therefore, necessary- to re-examine previously satisfactory generalizations to see if they are still valid. It turns out. as might have been expected. that Byck's explicit generalization. already quoted, is still true. Filter losses at high temperatures cannot be predicted from filter losses at low temperatures. However, no further generalizations are valid now. Fluids of different chemical types show different general behaviors. No longer do the fluids line up approximately the same at high temperatures as they do at low temperatures. They may line up entirely differently. Special fluids exhibiting very low loss at low temperatures may have losses as high as those of ordinary clay-water fluids at high temperatures. This fact is highly significant, because premium prices are being paid for the special fluids.

Jan 1, 1952

By W. B. Triplett, H. I. Aaronson, G. M. Andes

THE morphology and mechanism of the proeutectoid a and the eutectoid reactions have been recently investigated in some detail in an iodide-base Ti—7.22 pct Cr alloy.' These studies have now been extended to an iodide-base Ti—10.8 pct Cr alloy in order to evaluate the effects of composition on the proeutectoid and eutectoid transformations in titanium-chromium alloys. The alloy used in this investigation had the following composition: 10.8 Cr, 0.0327 0, 0.011 N, 0.0063 H, and 0.011 pct C. Specimens of this alloy were heat treated in evacuated and internally get-tered Vycor capsules. The specimens were solu-

Jan 1, 1959

By C. C. Harris

A critical literature review leads to a descriptive model of tumbling mill operation based upon energy partition concepts and the necessary requirements for particle fracture. As grinding proceeds into the ultra-fine region, conditions which are of little significance during normal operations gradually become controlling. These involve increasing resistance to fracture and an increasing tendency to aggregate as particles become smaller, and a growing fraction of the power input being consumed fruitlessly. The result is that fineness asymptotes to a maximum value as comminution proceeds indefinitely; thus where t is time, p and n are experimentally determined parameters, and Ø is a measure of fineness, which is presumed to be proportional to specific surface area, or proportional to the reciprocal of the size modulus (provided that the distribution modulus remains constant with time), or both. Ø, is the asymptotic value of Ø and is a measure of the grind limit. A method for its graphical determination is given. In a previous paper1 the physical and mathematical principles requisite to a study of the role of energy in comminution were reviewed. The micro-process of comminution — or the comminution event — can be investigated in terms of (a) the magnitude of the force-field localized around the individual particles which gives rise to the stresses generated in the particles, which in turn induces their fracture, and (b) the distribution of fragment sizes, should the event prove fruitful. The entire fragmentation operation can be considered to be the totality of its individual events, and in order to obtain a single independent variable of the process it is necessary to transform and sum the local stresses in terms of energy.1 This energy, however, will account for only a fraction of the energy input to the comminution process, the actual magnitude depending upon the kind of mill and several related factors. From the comminution viewpoint the primary function of a mill is that of stressing as many as possible of the individual particles of the charge to failure, with the maximum economy of energy expenditure. This is difficult indeed to achieve, for stressing a particle does not always break it, while the overwhelming portion of the energy input is involved with various internal mill processes which — almost incidentally — determine the magnitude, frequency, and manner in which the forces are applied to the particles. Essentially, these processes depend upon the mill dimensions, loading and speed, and they may be little affected whether fracture occurs or not. These processes must be delineated if a complete description of the role of energy in comminution is to be given; the energy account sheet1 (Fig. 1) in showing how the energy is partitioned for the requirements of the several functions it performs, provides a framework for the development of a model of the comminution process. Actual numerical values for the variables appearing in Fig. 1 will depend upon the mill, materials, and operating conditions. A possible general relationship between the variables will be suggested in this paper. Before proceeding further, a cautionary note must be issued. It was pointed out in an earlier paper' that while energy input is not changed by increasing the power and decreasing the time in the same proportion, and vice versa, the results of the process in terms of particle fineness may be different. Thus, although energy is chosen as the independent variable of a comminution process, it is not absolutely independent, and care must be exercised to ensure that it is used within its range of valid application. Time has the necessary independence, and it will be used in place of energy where it is appropriate. The residence time in a mill is usually of the order of minutes. Under these conditions the particles are subjected to "... a relatively constant fracture producing environment".2 However, under the more rigorous conditions of greatly extended time, which pertain in ultra-fine grinding, indications are that the fracture producing environment no longer remains constant; this is the major subject of this paper. At this extreme limit the mill is probably taxed to its utmost, and at the same time the bulk material properties are becoming closer to ideal, while the physico chemical effects associated with surfaces, edges and corners are multiplying. (The edge length per unit volume is proportional to the square of the specific

Jan 1, 1968

By R. H. Smith, A. C. Polk

The physical properties of the materials are listed, together with a short explanation of how this material binds the sand grains together without materially reducing the effective permeability of the sand. The chemical can be used in wells with bottom-hole temperatures ranging from 105°F to more than 350°F A description of the equipment required and the techniques used for applying these plastics to the wells is included. Introduction Recovering oil and gas from unconsoli-dated sand formations offers one of the most troublesome of all production problems. These sands generally present no particular trouble while drilling is in progress, but after the well has been completed and a pressure differential has been established across the face of the producing zone, the formation begins to L'slough," resulting in "sanding up" of the well. The term "sanding up" means that sufficient volumes of sand have moved into the well bore or casing to cause a serious reduction or complete halt of all flow of oil, water or gas. In rare cases a well may produce only a small amount of sand and still continue to flow or pump, the sand being carried to the surface in the fluid stream. However, in such instances, the result may be a costly repair bill due to the effect of the sand on surface and pumping equipment. The difficulty of producing petroleum from sands that are loosely cemented has long been recognized by petroleum engineers but only within the last few years has any new approach to the problem been undertaken. This involves the use of plastics that are capable of bonding the individual sand grains in place without materially reducing the effective permeability of a formation. The successful application of plastics for the consolidation of poorly cemented sands is relatively recent but now it is widely used in many of the more difficult areas on the Gulf Coast of Texas and Louisiana. This relatively new use of plastics1 in the oil fields has been preceded by much laboratory and field research on the use of various chemicals2,3 for solving numerous well-completion and work-over problems. Plastics now are being used successfully to control gas-oil and water-oil ratios,4'6 in zone isolation, the repair of casing leaks, the elimination of caving in cable-tool drilling wells6'7 and in the setting of linerss and casing.9 Sand-consolidating plastics, however, are basically different from all others in that they must not form an impervious seal. Field Practices The approach to the sanding-up problem usually has been the mechanical obstruction of the movement of the sand grains.

Jan 1, 1947

By A. C. Polk, R. H. Smith

The physical properties of the materials are listed, together with a short explanation of how this material binds the sand grains together without materially reducing the effective permeability of the sand. The chemical can be used in wells with bottom-hole temperatures ranging from 105°F to more than 350°F A description of the equipment required and the techniques used for applying these plastics to the wells is included. Introduction Recovering oil and gas from unconsoli-dated sand formations offers one of the most troublesome of all production problems. These sands generally present no particular trouble while drilling is in progress, but after the well has been completed and a pressure differential has been established across the face of the producing zone, the formation begins to L'slough," resulting in "sanding up" of the well. The term "sanding up" means that sufficient volumes of sand have moved into the well bore or casing to cause a serious reduction or complete halt of all flow of oil, water or gas. In rare cases a well may produce only a small amount of sand and still continue to flow or pump, the sand being carried to the surface in the fluid stream. However, in such instances, the result may be a costly repair bill due to the effect of the sand on surface and pumping equipment. The difficulty of producing petroleum from sands that are loosely cemented has long been recognized by petroleum engineers but only within the last few years has any new approach to the problem been undertaken. This involves the use of plastics that are capable of bonding the individual sand grains in place without materially reducing the effective permeability of a formation. The successful application of plastics for the consolidation of poorly cemented sands is relatively recent but now it is widely used in many of the more difficult areas on the Gulf Coast of Texas and Louisiana. This relatively new use of plastics1 in the oil fields has been preceded by much laboratory and field research on the use of various chemicals2,3 for solving numerous well-completion and work-over problems. Plastics now are being used successfully to control gas-oil and water-oil ratios,4'6 in zone isolation, the repair of casing leaks, the elimination of caving in cable-tool drilling wells6'7 and in the setting of linerss and casing.9 Sand-consolidating plastics, however, are basically different from all others in that they must not form an impervious seal. Field Practices The approach to the sanding-up problem usually has been the mechanical obstruction of the movement of the sand grains.

Jan 1, 1947

By E. J. Roberts, E. B. Fitch

Most classifiers in use today are, in function, settling pools. A fluid suspension of particles is passed through a pool at such a rate that only a fraction of the particles-the coarser fraction-has time to settle out of suspension. The rest are carried on out of the pool as overflow. The most fundamental way in which such classifiers differ is in the mechanism used to remove the settled particles from the pool. The particles may gravitate from the pool, as in the various sand cones, or they may be conveyed mechanically from the pool by drags, spirals, or reciprocating rakes. The mechanism of settling pool classification and its limitations are discussed. A method for calculating countercurrent classifications is presented. The practical validity of the calculation method has been confirmed through 20 years of use within The Dorr Co. During this time it has been used on diverse feeds and has been checked against many types of settling pool classifiers, with close agreement in nearly every case. Excellent elimination of third critical mesh particles and finer ones may be obtained in a countercurrent classifications series where all stages separate at the same mesh, but elimination of first and second criticals is inherently limited. Spectacular elimination of all criticals may be obtained by arranging successive stages to classify at successively coarser mesh. Improvement in elimination is obtained at the cost of an increased internal recirculation, but this may be tolerable in many cases.

Nov 1, 1956

By Charles H. Doolittle, Royal P. Jarvis

The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,' has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (W. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1803, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as 1885 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have

Jan 1, 1911

By LE B. GRAY

ALL meeting of the Chemical Section, National Safety Council, in Rochester, N. Y., put his hand on at least ten salient points that apply to safety in nearly any laboratory ; these are as follows : 1. Impress your laboratory worker at the start that he is dealing with powerful and dangerous-forces and that every experimental set-up must be studied from the stand- point of its fiber, electrical, explosive, and health hazards.

Jan 1, 1929

By Charles A. Anderson

THE Bagdad copper deposit is of the disseminated type (porphyry copper) occurring in a quartz monzonite stock of late Cretaceous or early Tertiary age. This stock, located essentially at the intersection of two dike swarms, is the only one of several stocks cropping out in the area which is appreciably fractured and mineralized. Most of the rocks in the area are of pre-Cambrian age, but their structures have had no discernible influence on the copper mineralization. Hypogene alteration of the quartz monzonite includes the addition of quartz, orthoclase, and sericite and recrystallization of biotite. The hypogene sulphides are pyrite, chalcopyrite, and molybdenite, the latter younger than the chalcopyrite. The late Cretaceous or early Tertiary igneous rocks, veins, and faults were controlled by northeast and northwest shear zones, the intersection of which marks the zone of appreciable copper mineralization. The minor mineralized fractures carrying the bulk of the copper have a preferred orientation parallel to the intersecting shears, and it is concluded that they are of tectonic origin rather than the result of shrinkage on cooling, crystallization, or mineralization. Supergene enrichment during late Tertiary or early Pleistocene time formed a chalcocite zone providing the minable copper ore. The enrichment was controlled in large part by northeast and northwest faults, particularly at their intersection or where the faults are closely spaced.

Jan 1, 1947

By S. Stutz

Coal, like most other minerals, only exceptionally occurs in a sufficiently pare state to he directly available for general manufacturing purposes. And even where this is the case, the small coal or slack is usually more impure than the lump coal, as the slate, clay, etc., from the roof and bottom of the vein become mixed with it in the handling it undergoes. These impurities often exceed ten or more per cent. in addition to the impurities of the coal itself. The most common impurities of the coal are slate, or shale, clay, and sulphur. The latter occurs in different forms, but moat frequently as bisulphide of iron, or iron pyrites, and as sulphate of lime, or gypum. In both cases the impnrities add greatly to the amount of ash, and where they are present in considerable quantities the raw coal, and still more the coke made from it, is unfit for the manufacture of iron. Coke will coutain on an average at least fifty per cent. more ash and sulphur than the ram coal from which it is made. To the manufacturer of iron every additional per cent. of ash which his coal or coke contains is a source of additional expense, seemingly small, and yet very important in the aggregate. In the blast-furnace, for instance, the ash must be heated up to the melting-point, and, since it is composed largely of refractory substances, the consumption of carbon in melting it will be equal to at least one-half of its weight; that is, a certain part of tile coke is consumed for the melting and fluxing of the ash and is lost. Besides this, it is well enough known to the iron-master that coke containing lees ash makes the &lag or cinder more liquid and less incliner1 to stick to the walls of the furnace. Fuel containing much sulphur produces generally a white iron, poor in carbon, while from the same ore arrd flux, with a pure fuel, a good foundry iron might be obtained. The work of separating slate, sulphur, etd, from the coal has as yet only been successfully accomplished by the washing process. This process depends for its success on the differences in the specific

Jan 1, 1881

By J. W. Furness

Before attempting any discussion of the importance of tariff enactments as applied to exhaustible resources, certain basic factors should be emphasized. First, it must be remembered that minerals differ from organic substances in that they are irreplaceable, and when once taken from the earth's crust enter into uses which ultimately dissipate them, so . that they cannot be recovered for future use. A second factor entering into the problem is the unequal distribution of the mineral deposits of the world. No industrial nation has within its political confines a sufficient quantity of all the minerals necessary for the maintenance and advancement of present civilization; hence international exchange of these commodities is inevitable. As minerals are essential to modern industry, the supply available to any given nation constitutes a factor which limits its ambition to advance industrially. A nation which has this ambition endeavors to secure not only a supply of minerals sufficient for its current needs, but also sources which will assure it expansion. Should mineral raw materials be withheld from such a nation by enactment, it seems inevitable that every effort will be made to obtain them, and that, should the nation deem itself sufficiently powerful, its ultimate recourse will be force. Thus the importance of tariff enactments, not only from the standpoint of industrial prosperity but from the standpoint of international peace, can be appreciated.

Jan 1, 1932

ALTHOUGH the open-hearth charge contributes CO, C02, H2, A and water vapor to the combustion gases and absorbs oxygen from them, in the main the thermal effects in the melting charge and molten bath can be considered independently of those in fuel combustion; the latter then is regarded simply as the source of the net heat required to finish a heat of steel. First of all, it should be remembered that a large percentage of the heat supplied to the bath is furnished by oxidation of the various elements in the charge itself. If this charge consisted of 80 to 100 per cent of hot metal and the oxidation were accomplished by blowing in air or oxygen, as in the bessemer converter, the net heat absorption would be negative; that is, the bath would contribute part of the heat required to keep the melting chamber hot, in addition to that contained in the finished steel and slag. In actual open-hearth practices, probably the nearest approach to this is in the duplex furnace, charged with bessemer-blown metal and some hot metal, where very little heat is required to complete the refining and nearly all the heat energy from fuel combustion is used to keep the roof and walls of the melting chamber up to around 2900 to 3000 F (1600 to 1650 C), so that the bath will not cool off during the refining. The other extreme is with all-cold charges containing around 80 per cent steel scrap and 20 per cent cast iron or cold pig iron, in which case a very large proportion of the heat in the bath at tap is supplied from the fuel combustion. THERMAL EFFECTS IN MELTING In a typical heat, the fuel furnishes about four million British thermal units per ton of steel produced. The heat required, for the metallurgical processes is not easily defined in useful manner but it ranges downward from about one million Btu, depending not only on the charge but on the manner of calculation. In, any event, this requirement appears. small in comparison with the

Jan 1, 1964

By John B. Goddard, David R. Brosnahan

Leaching of uranium in situ from sandstone deposits with ammonium carbonate solution containing dissolved oxygen occurs rapidly compared with the leaching of the bulk of the sulfur present as FeS2. However, because of their high reducing capacity and their relative abundance, the FeS2 minerals consume the bulk of the oxidant. A pressure leach apparatus was constructed that permitted measuring oxygen consumption by FeS2, best described by a first-order reaction. The experimental rate constants for various cores are roughly proportional to their FeS2 contents.

Jan 1, 1983

By William M. Courtis

Since many accounts of Silver Islet Mine, in Lake Superior, have already been published, it is supposed that the members of the Institute are familiar with the location and character of the mine. To many, however, a more detailed account of the ore and manner of treatment will, perhaps, not be without interest. The extraordinary richness of Silver Islet ores, and the difficulty of obtaining correct assays, induced the company to erect smelting works of its own. Accordingly, ground was broken at Wyandotte; Mich., early in the spring of 1871, and the work was pressed on with indomitable energy by Captain E. B. Ward of Detroit, as president, and Mr. Thomas MacFarlane, the discoverer of Silver Islet, as superintendent of the works, so that by July 1st the works were so far completed that smelting could be commenced. The intention was to work Western ores with those from Lake Superior, since the latter contain but a small amount of lead. Hence the capacity of the works is much larger than is needed for the present yield of the mine. The planned process for treatment was smelt-

By Duane N. Goens, Clifford R. Porter

A 91 kg/h (200 lb per hr) pilot plant was constructed according to "Magnex" design. A non-compliance eastern coal which would generate more than 0.85 kg of S02 per GJ (2.0 lb of SO2 per million Btu.) upon burning was brought into compliance less than 0.52 kg of SO2 per GJ (1.2 lb SO2 per million Btu) during continuous operation of the pilot plant. Approximately 85% of the pyritic sulfur was removed while recovering 90% of the Btu of the feed coal. Pilot plant operation is summarized and preliminary economics presented. Present status of the Magnex design program is reviewed.

Jan 2, 1979

By F. G. Miller, R. C. McFarlane, T. D. Mueller

During the process of gas storage in pressure-depleted oil reservoirs, it has been observed that in some instances additional liquid oil is recovered and that the composition of the storage gas is materially altered. A mathematical study was made of the dynamic behavior of such a depleted oil reservoir undergoing gas injection. The important variable considered in this study, not included in previously published work, was that of compositional effects on the phase behavior of two-phase flow. Pressure, saturation and component composition profiles were developed for a linear, horizontal and homogeneous porous medium containing oil and gas but undergoing dry gas injection. Special new techniques were developed to overcome the problems of numerical smoothing which arise in the solution of the equations representing such systems. The method of solution includes the development of partial differential equations describing the behavior of the system, representing these equations by finite difference approximations, making certain simplifying assumptions and, finally, applying methods of numerical analysis with the aid of a high-speed digital computer. In an example calculation, results using the mathematical model are compared with field observations made on a gas storage project in Clay County, Tex. This field project involved a depleted oil reservoir used 'for gas storage and gas cycling purposes. As a result of these processes, the reservoir yielded substantial amounts of secondary oil, both in the form of stock tank oil and as vaporized products in the produced gas. The methods derived in this study may be applied to a variety of oil reservoir problems which are dependent on compositional effects. In recent years the number of oil reservoirs being used for gas storage purposes has increased greatly, and there has been at least one published account of additional oil recovery resulting from gas cycling a depleted oil reservoir after repressur-ing with dry gas for storage purposes. Additional oil recovery from oil reservoirs resulting from gas storage operations could become an important secondary recovery process. This is especially true since the use of natural gas in large metropolitan areas continues to increase and more gas storage volume near these areas is needed. These facts provided the motivation for the work reported here. This paper reports on a study of the inter-relations of composition, saturation and pressure changes which occur when hydrocarbon gas is injected into an oil reservoir system. From an understanding of the process, prediction methods may be developed for use in forecasting the secondary recovery products from gas storage operations in oil reservoirs and, consequently, .the economics of such projects can be developed. The process of storing hydrocarbon gas in an oil reservoir and the cycling process both involve the transient multi-phase flow of oil reservoir fluids with changing fluid compositions. There is a scarcity of work published on the subject. One of the first laboratory models developed to study a problem similar to the one posed here was published in 1948 by Standing, Lindblad and Parsons. l They developed a model to study gas condensate recovery by gas cycling, including the effect of heterogeneous reservoir permeability. Their results showed the compositional effects of injecting a gas of known composition into a two-phase condensate reservoir of known composition. A major finding of their study indicated that maximum oil recoveries from gas cycling projects result when low cycling pressures are used. Previous to their work it was generally considered

By F. Morgan, M. Muskat, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.' Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

By M. Muskat, F. Morgan, R. G. Russell

Core experiments with radioactive tracers are reported in which an artificial radioactive material, radiovanadium, was used in aqueous solution in a study of the mobility of connate water. Sandstone cores saturated with active water were first oil-flooded to simulate virgin sand conditions in which the pores are filled with oil and connate water. They were then subjected to flooding with inactive water. Measurements were made of the activity of various portions of the effluent as well as the activity of the core after the flooding process was completed. In additional experiments the distribution of activity along the core was measured during the flooding process. In still other experiments direct flooding tests were made on cores fully saturated with active water. In all cases it was found that after injecting into the core a volume of inactive water equal to a pore volume, the effluent contained more than 80 per cent of the active content originally in the core. It is felt that these results imply a high degree of mobility of the connate water when subjected to flooding, although at least a partial contribution of the effect of tracer transfer within the core cannot be definitely excluded. The implications of this result with respect to water-flooding, core analysis and electric logging are discussed. A better approach to determining the connate water saturation of oil-producing rocks, by measuring the fluid content of core samples at the surface, is by the use of crude oil or oil-base muds as the coring fluid. Although water flooding is of considerable importance in the recovery of ail, comparatively little is known with certainty about the role played by the connate water during the operations. Two possibilities exist. Either the connate water is retained in the formation while the flood water sweeps past, or it is pushed along to a greater or lesser degree by the flood. Thus far no explicit recognition in terms of quantitative studies appears to have been given to the displacement of connate waters by the intruding extraneous waters, although such a possibility might be important in determining the efficiency of the oil -displacement process in water-flooding operations, especially in argillaceous rocks. On the other hand, it is a common observation that the first water produced with the oil as a result of water-flooding is definitely saline.*.' Similar questions regarding the mobility of the interstitial water arise in the quantitative description of the advance of edge-water drives. In the interpretation of the water saturations determined from core analyses, when coring with water-base muds, it is generally assumed that the drilling fluid merely adds to the connate water without displacing the

Jan 1, 1947

By J. B. Berkowitz-Mattuck, R. Hopper, L. Kaufman, E. V. Clougherty

MARNOCH has reported on the attractive high-temperature oxidation resistance of Hf-Ta alloys.' In view of current interest in these alloys, three Hf-Ta alloys were tested in the present study. These included a Hf-27Ta alloy and a Hf-20Ta-2Mo alloy which were supplied by Marquardt Corp. and a Hf-20Ta-Zr alloy provided by Illinois Institute of Technology Research Institute.' The microstructure of these alloys was heated inductively in a glass vacuum system; the oxidizing gas, helium carrier plus a known partial pressure of oxygen (35-102 Torr), was continually passed over the sample at temperature for a given time period. The concentration of oxygen in the gas stream was continuously measured by a differential thermal conductivity technique2 so that the rate of oxygen picked up by the sample could be obtained. The flow rates were 0.1 to 0.2 ft per sec in the vicinity of the specimen. The concentration of oxygen did not fall below 50 pct of the input level in any of the experiments. In several cases a single sample was exposed consecutively at a series of increasing temperature levels. In a second system at ManLabs, cylindrical specimens were exposed to flowing air in a z irconia tube which was heated by radiation from a carbon tube resistance furnace. The specimen was heated from room temperature to the test temperature in flowing argon, then oxidized in air flowing at 0.1 to 0.2 ft per sec. Following exposure, the air was displaced by argon and the specimen was cooled. Postoxidation metallography was performed on every sample. The depth of conversion of the metal matrix to oxide was measured as shown in Fig. 1. The conversion depth was obtained by measuring the oxygen-contaminated metallic zone (which is bounded by a dense outer oxide and a subscale oxide region), subtracting its dimensions from the original dimensions, and dividing by two. Preferential oxidation of

Jan 1, 1968