Search Documents

By H. G. Turner

The coals mined in the area known as the anthracite fields of Pennsylvania have always been recognized commercially as anthracites. In the literature, however, some of these anthracites have been called semi-anthracites by various writers. The coals mined in Sullivan County, especially those from the Bernice field, have been recognized commercially both as anthracites and semi-anthracites. In the literature they have almost always been referred to as typical semianthracites, although Franklin Platt,1 in his report to the Pennsylvania Geological Survey, uses the terms semibituminous, semianthracite, and anthracite in describing them. The purpose of this paper is to endeavor to dispel the confusion of names used to describe these coals and to supply further information that will permit a logical and definite classification. Most of the confusion of the past has been due to the impossibility of securing enough fresh face samples from which to draw sound conclusions; some of it was due, no doubt, to lack of standard methods of analysis, and of course, to the ever-present lack of definition of boundaries from the standpoint of classification. Map Showing Lines of Equal Volatile Matter and Lines of Equal Specific Gravity As a foundation for this work the writer constructed a map showing lines of equal volatile matter and lines of equal specific gravity throughout the anthracite and semianthracite regions. The points on these lines were determined from a study of analyses of 214 face samples from 28 mines and composite analyses from 18 different breakers. These samples were collected through the joint efforts of the U. S. Bureau of Mines and the Anthracite Institute. The Bureau of Mines standard method of sampling was used in all cases. All analyses were made by the Bureau of Mines and are used here with its permission. The

Jan 1, 1934

By V. E. McKelvey

The Phosphoria formation of the northwestern states presents a stimulating challenge to workers in every field of mineral technology. In addition to its large reserves of phosphate, the formation has been found to contain important amounts of fluorine and several metals, such as vanadium, nickel, and molybdenum. Because these minor metals in the Phosphoria do not have their usual glitter, concentrations of them are not easily discovered nor appraised. Like the phosphate itself, production of these metals very likely can be achieved only through use of costly chemical methods, for their mineralogy precludes treatment by the usual methods. In addition, in much of the area the containing rocks lie in complexly folded and faulted structures, which complicate mining and increase its cost. Yet the chain of research necessary to establish what elements are present; their geographic and stratigraphic distribution and reserves; the most suitable methods for recovering them; the combination of beds which, when ruined and processed, will yield the greatest recovery of the most valuable elements; and the methods most adaptable to their profitable extraction may well lead to the development of an important mineral industry and may make possible a significaut reduction in the cost of fertilizer this in itself would be an achievement of momentous importance—and at the same time make the nation more self-sustaining in critical materials. Although this research has great

Jan 1, 1950

By B. H. Dunshee

THIS paper is not intended to be a technical discussion of square-set framing as used in mines, but merely a short description of the different kinds of framing that have been used in the Butte mines, and what has been decided upon, after years of practical experience, as being the best, taking into consideration the physical condition of the veins and country rock, and. also the supply of timber available for mining purposes. Butte is, essentially, a square-set district. Virginia City, Nev., was the first mining camp to use this method of timbering, and to Philip Deidesheimer, who went to the Ophir mine in 1860, is given the credit of solving the problem of square-set framing, where large bodies of ore were stoped and the timbers were supposed to hold the ground from caving without any filling. That he did his work well is shown by the fact that the main features of his framing are in use to-day. In the Butte mines the conditions are such that this method of timbering is generally used. We do not, of course, depend upon the timbers any more than is necessary. The worked-out stopes are filled with waste rock as close behind the miners as possible and not interfere with mining operations. The waste rock is obtained from development work on the different levels or from the surface. In the earlier days of mining in Butte there were numerous independent companies and naturally there were different ideas as to the best way to frame the square sets, although the general features were the same.

Jan 8, 1913

By H. L. Shergold, O. Mellgren

Concentration of fine quartz particles at the iso-octane/water interface has been investigated under different conditions of pH and dodecylamine concentration. The results obtained from the related studies on the effect of amine concentration and pH on the interfacial tension, adsorption density, electrokinetic potential, contact angle, and concentration of the various amine species in the system are presented. A good correlation was obtained between these different variables. It is well-known that very fine mineral particles are difficult to float in conventional flotation machines. Flotation rate studies have revealed that the rate of flotation of fine mineral particles is much smaller than that of coarser size fractions. The theories accounting for this behavior have been discussed by Arbiter and Harris1 and also Meloy.2 Theoretically, a hydrophobic fine particle might never make contact with a bubble because of the presence of an energy barrier in the vicinity of the air/water interface.' This energy barrier will have electrostatic, hydrodynamic, and Van der Waals force components. It was thought that by using an oil phase instead of air the energy barrier would be decreased so that fine particles could be concentrated at the oil/water interface more readily than at the air/water interface. The technique used involves dispersing the fine particles in water, containing the appropriate chemical reagents, and injecting a fine dispersion of iso-octane oil droplets into the pulp. After vigorous conditioning, the pulp is passed into a separating column where the oil droplets coated with a layer of mineral particles rise to the surface to form a separate layer. Air is introduced into the base of the separating column to ensure that heavy agglomerates of oil and particles report with the organic layer. This technique has been described previously4 and adopted by Lai and Fuerstenau5 who studied the alumina-dodecyl sulfonate system. The interfacial phenomena in the system composed of hematite, water, and iso-octane in the presence of sodium dodecyl sulfate have been studied and the results reported" earlier. This paper describes the results obtained from investigations into the interfacial phenomena in the quartz/water/iso-octane system in the presence of dodecylamine. The technique used in measuring the interfacial tension, electrokinetic potential, contact angle, and adsorption density were similar to those described previously? Materials Selected pieces of a high purity natural quartz, from the Isle of Man, were crushed in a laboratory jaw crusher and pulverizer. The — 52+72 mesh size fraction was retained and leached with successive washes of hot concentrated hydrochloric acid to remove iron impurities. When no iron was detected in the solution by ammonium thiocyanate, the quartz was washed thoroughly with distilled water until the conductivity of the wash water assumed that of the distilled water. Samples of 25 g of the —52+72 mesh quartz were ground for 5.25 min in an agate vibratory mill. The ground product was 100% —44 m and 57% —10 am, as determined by the Andreasen pipette. The specific surface area of the sample used for the adsorption and flotation tests was 0.94 sq m g-l. This corresponds to a mean particle diameter of 2.4 am. The —44 am quartz sample was stored under vacuum in the presence of silica gel crystals. For the contact angle determination between the three phases, quartz, iso-octane, and water, a piece of the natural quartz was ground into a block about 15 mm long, 15 mm wide, and 5 mm thick. One surface of the block was then polished by successively finer grades of silicon carbide "paper." The final polishing was conducted with alumina on a "hyprocel" paper. The polished quartz specimen was cleaned using nitric acid and ethyl alcohol followed by a wash with distilled water and then stored under distilled water. This pro-

Jan 1, 1971

By A. B. Kinzel

PRECISE knowledge regarding the effect of heat treatment on the properties of steel has made possible the detailed specifications and instructions covering optimum heat-treating temperatures and practices that are in current use. A distinct contrast is presented by the metal-lurgical treatment of steel adjacent to a fusion weld, as such steel is subjected to each, temperature from room temperature to fusion tempera-ture, and cooled at a rate that is not generally controllable but is pre-determined by the nature of the assembly to be welded, the kind of welding used, and the surrounding conditions. This is true regardless of the type of fusion welding: oxyacetylene, electric arc, thermit or flash resistance. Therefore it seemed desirable to investigate the effect of this metallurgical treatment on the characteristics of carbon steels commonly used for welding, by a detailed study of metal subjected to each temperature range; i.e., each heat-affected zone. Oxyacetylene welding was chosen for the investigation because of the experimental facility of accurately segregating and studying each tem-perature zone. The nature of the zones produced by other types of welding is the same. The difference is primarily a matter of dimensions of each of the temperature zones involved. The advantages and dis-advantages of the extent of the zone are of prime moment, and are dis-cussed after the presentation of the detailed zone study. No mention is made of the fused metal proper, as this has been the subject of much published research and the nature of the solidified metal is fairly well known.

Jan 1, 1935

By Thomas O. Ziebold, Robert E. Ogilvie

Experimental analysis of diffusion samples covering the entire Cu-Ag-Au system at 725°C has been carried out. Experimental coefficients are computed at twenty-eight points in the lermary system. It is found that the direct coefficienl for copper is nearly independent of the silver, content for 1ow-silver alloys and that the cross coefficient for silver correlates with the ther-nzodynatnic properlies. This lalter observalion leads to the conclusion that the mobililies of copper and gold are nearly equal. Thermodynarmic actiuilies for Cu-Ag-Au were computed from binary data and adjusted to be consistent with neasured tie lines across the two-phase region which extends into the ternary diagram at 725°C. Application of these therknodynarnic calculaliorls to the dijftcsion data terifies the Onsager reciprocal relations to the extent that experimental uncertainlies will allow. It is jound that diffusion neav the critical point of the 1200-phase field in the isothermal section at 725°C causes the composition gradients for copper and silver to approach infinity while the direct and cross coeficients become equal. From the standpoint of experimental Procedures, it has been shown that microanalysis of ternary samples may be carried out using a simple expression for the conversion of X-ray zntensily to composilion. The accuracy of' this method has been demonstrated by the analysis of standard alloys and by the reproducibility of composition determinations using differed X-ray lines. DIFFUSION in a ternary alloy system is basically and significantly different from diffusion in binary alloys. When only two elements are present there is just one independent composition variable, and the diffusion profile of composition vs distance across a sample must change monotonically through all solid solutions bracketed by the terminal alloys. If two-phase regions are stable for compositions between the terminal values, these must appear as planar interfaces in the diffused sample, with the composition profile exhibiting sharp discontinuities. Adding a third element may alter this picture completely. Because of the additional degree of freedom in the composition, we may see composition profiles which do not change monotonically through solid-solution ranges, and stable, nonplanar phase interfaces. Even though two-phase regions may lie between the terminal compositions of a diffusion sample on the constitution diagram, they will not necessarily appear in the diffusion profiles. In binary diffusion only one coefficient is needed to describe the interdiffusion process. From Fick's law this coefficient relates the diffusive flux of one component to its own composition gradient. In ternary diffusion we must allow for cross interaction between the two independent species. By a linear extension of Fick's law we introduce "cross" or "off-diagonal" diffusion coefficients which relate the flux of one component to the composition gradient of the other independent constituent. Thus, we require four interdiffusion coefficients to describe the transport process in a ternary system. In its most general form,1,2 the rate equation for mass transport by isothermal diffusion in a system of s components states that the diffusive flux of component i, Ji, is a linear summation of all driving forces, Xk, each force being multiplied by an appropriate compliance coefficient:

Jan 1, 1968

By B. S. Gottfried

A generalized mathematical model is presented, which describes the thermal recovery of oil in linear systems with convective external heat loss. Three-phase fluid flow, conduction-convection heat transfer, chemical reaction between oxygen and oil and aqueous phase change are included, making the model applicable to a variety of thermal recovery processes. The complexity of the model requires that numerical solutions be obtained with a digital computer. The numerical approximations of the partial differential equations are presented and the algorithm is discussed in detail. The analysis is applied to the detailed simulation of a forward-combustion laboratory tube experiment. The results of the simulation exhibit with reasonable accuracy all of the principal thermal and bydrodynamic characteristics observed in the laboratory (i.e., the propagation of a combustion zone, a steam plateau, and oil and water banks). Numerical variations in the parameters appearing in the external heat-loss term, the aqueous phase-change term, and the Arrhenius combustion term are examined, and their effects on the predicted temperature profiles, oil and water production histories, and the air-oil ratio are presented. In spite of an oversimplification in the chemical reaction mechanism and the considerable computer time required to obtain solutions, the model represents a major advance in the ability to simulate the phenomena observed in thermal recovery experiments. INTRODUCTION Thermal oil recovery refers to a class of recovery processes where heat is supplied to a reservoir to provide the necessary expulsive energy. This thermal energy can be supplied externally as steam or hot water, or it can be generated in situ by forward or reverse combustion. In either case, however, thermal recovery processes are charac- terized by the simultaneous flow of two or three fluid phases in a variable - temperature field, accompanied by possible chemical reaction or phase-change effects.2-5, 7- 10, 14,16-18,20-22 Although a physical understanding of the thermal recovery processes is far from complete, it is possible to construct mathematical models which describe approximately all of the principal physical and chemical phenomena. However, attempts to solve such models, even with high-speed computers, involve formidable mathematical difficulties. Consequently, theoretical solutions have been obtained only for idealized cases in which important physical phenomena are neglected. For example, consider the process of forward in situ combustion. All such theories which have been developed consider only certain aspects of the process, such as heat transfer, 2-4,8,9,l6,l8 heat transfer with phase change,10 heat transfer with chemical reaction,7 or the hydrodynamics of three-phase flow.21 A general theory including all of the above phenomena has not been developed to date. This paper presents a unified theory of thermal recovery processes in linear systems. A mathematical model is developed which explicitly includes conduction-convection heat transfer with convective external heat loss, chemical reaction between air and oil, aqueous phase change, and the hydrodynamics of three-phase flow. A system of equations is developed which can be solved numerically on a high-speed digital computer, resulting in predicted temperature, pressure, and saturation histories in space and time. The model allows a more detailed simulation of thermal recovery tube experiments than had previously been possible. THEORETICAL DEVELOPMENT Consider the linear flow of gas, water and oil in a homogeneous porous medium. Assume that the oil will react with gaseous oxygen, and that mass is transferred between the water and gas phase by evaporation or condensation. In the absence of hydrocarbon phase change, intraphase diffusion,

Jan 1, 1966

By M. Cohen

THERE seems to be a natural urge for the human mind to wonder about the beginning of things. When an explosion occurs, we immediately inquire "what set it off?" If a person contracts a disease, we are likely to ask "how did it happen?" On a much loftier plane, when we reflect about the universe, there is the inevitable question "what, or rather Who, started it all?" In principle, these varied queries have at least one attribute in common: they are attempts, whether earnest or casual, to search out the origin of events in nature. Accordingly, they involve not only scientific, but philosophical and even re1igious matters of deep concern. It is evident that, in a broad sense, the phenomenon of nucleation is enmeshed in this enticing concept of "the beginning", but we must extract the scientific component of the problem for our present purposes. Nucleation, as in the case of phase transformations, is best regarded from the standpoint of kinetics. There are then two main steps, which may come in either order: (a) Experimentally, one attempts to measure the frequency with which transformation centers spring into existence; and (b) theoretically, one seeks a model that will account for this observed birth-rate. Temperature, composition, strain, and prior history are some of the important variables that must be considered both experimentally and theoretically when dealing with nucleation in the solid state. Such interaction of theory and observation is an integral part of science in general, but it is particularly significant in the nucleation problem because the very beginning of a phenomenon invariably occurs on too localized a scale in both space and time to be detected with available techniques. Thus, there is little hope of making direct measurements on the nucleus during its birth or to ascertain the exact nature of the process; one can only infer the details of nucleation from the model whose predicted behavior seems to harmonize best with the measured rate of nucleation and its dependence on known parameters. In the field of solid-state nucleation, both theory and experiment call for much ingenuity, but somehow the conceptual schemes have spawned faster than they can be tested by observation. This is not to say that there are many basically new ideas in modern nucleation theory; rather, as we shall see, it is because the required fine-scale measurements are of immense technical difficulty. Quite likely, some of the nucleation models existent today have survived only because of the latitude permitted by meager data. There is great need to bring theory and experiment into better balance in this important area of physical metallurgy. Although one can

Jan 1, 1959

By Richard A. Conkling

A shale layer, buried beneath two or three thousand feet of strata, in some instances, will upon folding become thicker in the synelines and thinner on top of the anticlines. This can be accounted for, in part, by the stretching on the crests of the fold and the compressing in the troughs; but this will by no means account for all of it, as is shown in the example herein set forth. It is my firm belief that the rest of the thickness is due to flow. What causes the movement, however, does not concern us here, SO long as there is movement, for this article purposes to show its effect upon the producing area of different sands. It is the author's hope, in this way, to drop a hint or two that may be valuable to the oil geologist, in making estimates of future productions and values of oil properties. An example will be given from property in the famous Gushing Pool in northeastern Oklahoma, where the author has had occasion to make a detailed study before recommending some property to his company, and has then been able to watch the results of this work. The author never mapped the surface structure in this pool, as this had been done by Frank Buttram when he was with the Oklahoma Geological Survey. We are using, therefore, a section of his map in this article for our surface contours. The main east dip comes farther east than this section shows. From the 10-ft. contours in Fig. 1, it will be seen that the surface folding is very slight, but in the contour map of the Bartlesville sand (Fig. 2), which was the greatest producing sand, we see much more complex folding. It seems that the folding becomes greater with the depth. Folding may have started in Middle Pennsylvanian times and continued through the Upper Pennsylvanian which is found at the surface. This may, or may not, have been the cause of the increase of folding with depth. However, the fact that mostly concerns us is the interval of shale between the Bartlesville sand and the Tucker sand. The Tucker is the next productive sand below the Bartlesville. Not enough wells have been drilled to the Tucker sand to make a contour map of it, but

Jan 1, 1917

By Ira B. Joralemon

The sampling of disseminated copper deposits has been describeu often but the method of combining assays to give the true shape and value of the orebody as it will be mined has received less attention. As the ore mined during five or ten years at several of the great disseminated properties has averaged materially lower in grade than the published estimates, the question of the sampling and estimating of these orebodies seems timely. In this paper, attention is given particularly to factors that may cause errors in the final estimate. Sampling of diamond-drill holes, churn-drill holes, and underground workings is briefly described in the first part of the paper; then the method of combining assays to give the average grade and tonnage that will be mined is taken up in some detail. The necessity of study of the geology of the deposit and of probable costs is emphasized. Finally, the methods of calculating tonnages are outlined. DlAMOND-DRILL SAMPLING There are three main requisites for accurate diamond-drill sampling. First, the core should be removed and the hole cleaned out at the beginning of every sampling interval, usually 5 ft. (1.5 m.). After the rods are let down, water should be run through them until it becomes clear. The water must be clear before drilling starts. 'In this way the material knocked down from the sides of the hole by the descending rods is washed away, instead of being left to salt the sludge sample. The second requisite is to save all the sludge and all the core from every sampling interval. Where the material is uniformly heavy, the cuttings will settle suffciently in a box, through which the sludge flows s1owly.l Where part of the material is too light to settle readily, the sludge should be run into barrels, and allowed to settle until the water becomes clear. Then the clear water is siphoned off, and the sludge evaporated to dryness over a slow fire, sacked, and assayed.2 To obtain

Jan 1, 1925

By Morgan Walker

ONE of the most serious problems in the produc- tion of natural gas is the removal of water from the wells. As a gas well approaches its period of exhaustion, the removal of water by properly de-signed devices becomes increasingly important. Sev-eral methods are used for dewatering gas wells. If the .gas velocity and pressure are high enough, the water in the well will be carried out by the gas on opening the well to atmospheric pressure and allowing the gas to flow unrestricted except for the resistance of the casing. This method of dewatering a gas well is detri-mental to the producing sand, and very wasteful if used frequently. When the well has declined in production a string of tubing is often run in the well, with a packer set at the top or bottom of the well. If the top of the tubing is opened to atmospheric pressure and the gas is allowed to flow unrestricted as in the above method, the water can be discharged at the top of the well, provided the velocity of the gas is high enough. However, if the water has accumulated in the well until the water pres-sure is equal to or greater than the gas pressure, the ,water cannot be brought to the surface. In dewatering :a gas well by this method the operator sometimes finds -that if the packer is set near the top of the well and -the casing is tight, the water can be blown out when .it is impossible to blow it out with the packer set at the top of the sand. This is largely due to some gas leaking into the tubing through the collars. This method of dewatering gas wells is also wasteful. Water can be pumped out of a gas well with virtually the same equipment, as used for pumping oil, but the method involves installing a separate pump for each well, and difficulties are encountered in attempting to pump water under high gas pressure.

Jan 3, 1927

By Hugh Spence

THE use of natural feldspathic rocks, as opposed to straight feldspar, for ceramic purposes is not new. "Cornwall stone," a semi-kaolinized granite containing fluorite, has long been used by the English pottery trade instead of feldspar, and "Carolina stone," a similar rock, is now being offered to the American trade. A recent report of the U. S. Bureau of Mines states that trachyte, a glassy volcanic rock, is being used in California instead of feldspar in ceramic bodies. In Germany, phonolite and basalt have been investigated, and possibly also used, as ceramic raw materials, and extensive research has been conducted in Russia in recent years looking to the utilization of the immense bodies of nepheline syenite of the Kola Peninsula, which is the host rock of the apatite deposits now being exploited on a large scale in the Murmansk region; the nepheline is recovered as a by-product of the concentration of the apatite. Long used principally as a raw material for the pottery and allied industries, where, in bodies, glazes, enamels, etc., it serves as a fluxing ingredient and forms, on firing, a glassy bond with the more refractory clay, flint and coloring particles, feldspar has been finding ever increasing employment in glass. In 1936, over half of the nearly quarter of a million tons of feldspar sold in the United States went to the glass trade. Its usefulness for this purpose is due to the resistance to thermal shock which it imparts to glass products, particularly bottles, containers and tableware, because of its alumina content, which averages from 16 to 20 per cent. Active search has been made on the American continent during the past few years for other minerals of feldspathoid type, with comparable or higher alumina content, that may be suitable for glass and other ceramic purposes. One of the most important results of this work has been the delimiting in central Ontario of large bodies of nepheline syenite of excellent ceramic grade.

Jan 1, 1938

By John P. Hager, Adolfo R. Zambrano

The thermodynamics properties of the liquid Pb-Ag-Au system have been determined from galvanic cell measurments five pseudobinary systems of fixed XAg/XAu ratio. The galvanic cell employed a molten PbO-SiO2 electrolyte and was operated between 775" and 1030°C. The thermodynamics properties of lead were obtained directly from the experimental data, whereas the excess integral molar properties and the activities of silver and gold were obtained by means of the Gibbs-Duhem equation. The calculated proper -ties of the Ag-Au system agree well with the published properties. The liquidus surface of the Pb-Ag-Au system has been determined at 1200°K. In Parts I' and 11' the galvanic cell Mo,Pb(l)|(PbO-SiO2)(l) SiO2(s) |Pb(alloy)(l), Mo [I] was used to determine the thermodynamics properties of the Pb-Ag and Pb-Au systems, respectively. The use of cell I, in which a molten oxide electrolyte is employed rather than the classical fused-salt electrolyte, was shown to result in more accurate ther-modynamic measurements in that the displacement reaction at the alloy-electrolyte interface (l/Zb)B(alloy) + (I/za)A+Za = (1/Za)A(alloy) + (1/Zb)B+zb [1] was minimized. For the Pb-Ag system, where B = Ag(l), the error in the activity of lead (aPd) re-sulting from Reaction [I] was calculated to be less than 1 pct.l For the Pb-Au system the error in aPb was calculated to be less than 0.5 pct.2 Also, electro-transport measurements on the PbO-SiO2 electro-lyte1,2 established that the conduction was entirely ionic and that lead was present only in the divalent state. In the present study the experimental technique is extended to an investigation of the thermodynamic properties of the liquid Pb-Ag-Au system. Five pseudobinary systems of fixed X Ag/XAu ratio were selected. The experimental results were then combined with the previous measurements on the component binary systems Pb-Ag1 and Pb-AU2 to calculate, by means of the Gibbs-Duhem equation, the molar and partial molar mixing properties for the liquid ternary solutions.

Jan 1, 1970

By W. A. Lang, K. C. Gilbart, E. Stansfield

It has long been known that coal is unstable and oxidizes in air, even at ordinary atmospheric temperatures; also, that such oxidation affects the analysis of coal. Nevertheless little or no precaution is taken to prevent oxidation in the ordinary methods of analysis, and the possibility of error due to oxidation is sometimes ignored even in researches on coal. Although the general nature of coal oxidation is well known, and many workers have made careful studies of the rate of oxidation of different types of coal exposed to oxygen at different temperatures, yet the amount of oxidation coals undergo in the ordinary process of analysis, and its influence on the determined analysis, is not well known, and the published data are widely scattered through the literature. This paper is a collection, from this laboratory, of data that bear on the subject, together with a brief summary of three methods employed here to evaluate the oxidizabil-ity of coal. The post-Carboniferous coals of Alberta range all the way from anthracite down to lignite. As some of them are notably susceptible to oxidation, the necessity for care was early forced upon our attention, and oxidation has been reduced either by the removal of air with a vacuum pump or by the displacement of air with natural gas (methane). The two routine analytical operations most liable to involve oxidation are the preliminary, partial drying of the crushed coal (called air-drying) and the determination of moisture. The first is a prolonged operation on coarse coal at ordinary temperatures, and the second a short treatment on powdered coal at higher temperatures. Oxidation also occurs in coal samples stored in ordinary sample bottles. In order to gain information for this study, determinations were recently carried out on the same samples in air, in natural gas, and in vacuo. Sixteen coals were tested; three would be classed in the United States as coking bituminous coals, two as noncoking, nonslacking, bituminous coals, and the rest as subbituminous. Table 1 gives typical analyses of these coals as mined.

Jan 1, 1934

By Joseph Hartshorne

The attention which this process has attracted, especially in Europe, has led me to believe that members of the Institute would be interested in a report of the progress which has been made in the year and a half that has elapsed since my paper on the subject was read at the Colorado Meeting of this Institute. As already described in that paper (Duns., xxvi., 380), this process is a modificatioii of the open-hearth steel manufacture, whether acid or basic, collsistillg essentially in the division of the charge between two furnaces, one of which is charged about two hours earlier than the other, and tapped into the other after the charge in the latter has become fluid, the slag of the first bath being removed from it during the transfer. This description still remains true as far as it goes, but further experience has demonstrated that circumstances will very materially modify the relation of the two furnaces to each other, and the character of the work done in each of them. The function of the primary furnace has become more clearly and entirely that of doing the rough work of desiliconiziug and dephosphorizing, while that of the second or finishing-furnace has become almost entirely that of decarburizing and finighing the heat. To indicate these developments and their results is the object of this paper. In order to avoid needless repetition, I shall try to accomplish part of this object by giving a short resume' of what has been published elsewhere on this subject since my former paper was read. This will at least enable those interested to study the matter for themselves from original sources. Since that time the following papers have been read and published: " The Bertrand-Thiel Process of Making Steel," by Percy C. Gilchrist (Cleveland Institution of Engineers, Session of 1896-

Jan 1, 1899

By H. N. Mead

In a reservoir when gas comes out of solution and rises, additional pressure is created because of the change in position of this gar in the bounded volume. If this pressure effect is not taken into account as a pseudo-influx ill mate rial balance calculations on reservoirs in which there is evolving gas, an error is introduced that is directly proportional to the length of oil column and amount of gas evolved and inversely proportional to the reservoir pressure. In reservoirs with small oil column this pseudo-influx is of little importance. The larger the oil column the more important the effect becomes. The most important application, however, will be for reservoirs with declining pressure in which increasing water entry has been indicated by material balance calculations. It could be that this indication is the result of the cited pseudo-influx and not water entry at all. This paper attempts to explain this phenomenon in relation to material balance calculations and prevents an approximate method of determining tile pseudo-influx. INTRODUCTION Only recently has the pressure-volume relationship of gas rising in a liquid appeared in engineering literature, although its effect has been discussed for several years—especially among engineers engaged in drilling operations. The writer published a paper in 1957 in which this phenomenon was examined in relation to blowouts in drilling wells.' Also, in 1957 Stegemeier and Matthews' authored a paper in which the relationship was presented with respect to pressure build-up tests when shutting in producing wells. In this paper the effect will be called "pressure inversion" which is descriptive of the phenomenon. Fundamentally, the effect just mentioned is the result of changing the position of a quantity of energy contained within the gas itself (as a result of its compression) within the bounded volume in which the gas exists. If the gas were allowed to expand "beyond all bounds" there could be no pressure inversion effect. This is because all of the energy contained within the gas as a result of compression would have been re- PRESSURE INVERSION A phase that has not been discussed in the literature is the effect of pressure inversion upon material balance calculations in reservoirs in which the reservoir pressure drops with reservoir withdrawal and is below the bubble point. This action releases solution gas which, after the critical gas saturation has been reached, will tend to rise and collect at the top of the reservoir. The pseudo-influx caused by this effect could be great enough in reservoirs of large oil column and high permeability to render invalid any analyzer studies made on them — if pressure inversion has not been taken into account. Most suspect would be those reservoirs with large oil column in which increasing water entry has been predicted but the bottom wells have not yet produced water. Example 1 Simply stated, this phenomenon exists in oil reservoirs because of the difference in density and expansibility between gas and oil. For example, if a bubble of gas exists at the bottom of a 1,000-ft column of oil having a gradient of 0.30 psi/ft with the pressure at the top of the column zero, the bubble of gas will be compressed to a pressure of 300 psi. If temperature and the combined volume of the oil column and the gas bubble remain constant, as the gas bubble rises in the oil column it will have the same volume and consequently the same pressure at any point. Under these conditions when thc bubble reaches the top of the oil column, the pressure will be approximately 300 psi at the surface and approximately 600 psi at the bottom of the oil column. If it is assumed that the oil is incompressible the pressures will be exactly 300 and 600 psi, respectively.

By J. S. Ll. Leach, L. R. Rubin, M. B. Bever

The energies of formation of ordered and disordered solid solutions of composition CusAu and the energy of ordering in this alloy were determined by tin solution calorimetry. The degree of order was measured by X-ray diffraction and electrical resistance and microhardness measurements were made on ordered and disordered specimens. AMONG the phenomena associated with the order-disorder transformation of a solid solution, the change in internal energy is of special interest because of the part it plays in the various theories of ordering. Published values for the decrease in internal energy accompanying the formation of a superlattice from a disordered solid solution of composition CuAu range from —370 to —2260 cal per gram-atom. Some of these values represent calculations based on theory and others are the results of experimental measurements. The distinction between the change in internal energy, AE, and the change in enthalpy, AH, can here be neglected, because they are approximately equal for solid-state reactions at normal pressure. An analysis of ordering by Bragg and Williams' predicts an energy change of —605 cal per gram-atom for the formation of a superlattice in the alloy Cuau from a completely random solution. Peierls" application to Cuau of Bethe'sb earest-neighbor theory yields —560 cal per gram-atom for the formation of a superlattice from a matrix which initially contains short-range order. Cowley' extended the nearest-neighbor approach to include as many as five shells of neighbors; on this basis a change in energy of —500 cal per gram-atom is expected. Eguchi," using a quantum-mechanical treatment, calculated a value of —2260 cal per gram-atom for the difference in the energy of completely disordered and completely ordered Cu,Au. Sykes and Jones- eated a completely ordered alloy and measured its heat capacity as a function of temperature. This measured heat capacity agrees closely with the corresponding value found by the Kopp-Neumann (or mixture) rule up to about 250°C and above this temperature exceeds it, especially near the critical temperature for ordering. The difference between the integrals with respect to temperature of the observed and the Kopp-Neumann heat capacities was considered to be the energy of ordering. By this method Sykes and Jones found a value of —530 cal per gram-atom. This value is not adjusted for the short-range order remaining above the critical temperature. The pres- ence of such short-range order is suggested by the difference between the measured heat capacity and the extrapolated Kopp-Neumann heat capacity immediately above the critical temperature. Values reported by Weibke and von Quadt' and by Hirabayashi, Nagasaki, and Maniwaa were obtained in the course of investigations primarily aimed at other objectives. Weibke and von Quadt measured the temperature coefficient of the electromotive force of a Cu-CuAu cell. They obtained a value of —1010 cal per gram-atom for the heat of formation of the alloy at 500°C, at which temperature there is no long-range order. They also obtained —1380 cal per gram-atom as the heat of formation of the ordered alloy at 370°C. Considering the heat of formation of the disordered alloy to be independent of temperature, they estimated the energy of ordering at 370°C as —370 cal per gram-atom. At this temperature long-range order is incomplete and the degree of order changes rapidly with temperature. Hirabayashi, Nagasaki, and Maniwa," using an annealing calorimeter, investigated an alloy containing 23.4 rather than 25.0 atomic pct Au and thus could not obtain complete order. Thelr value of the energy of ordering was —490 cal per gram-atom. Orianis has recently investigated the Au-Cu system by the galvanic emf technique. He reports values for the heats of formation of Cu-Au alloys, from which the heat of formation at 427 OC of an alloy of composition CuAu may be found by interpolation. This value is —1080 cal per gram-atom. In the work here reported, disordered and ordered alloys of composition CuAu and corresponding mixtures of gold and copper were dissolved in liquid tin and the heat effects measured. These heat effects are small, since the dissolution of gold in tin is exothermic and the dissolution of copper is endothermic. The method, therefore, yields fairly precise values of the heats of formation of disordered and ordered alloys and of the energy of ordering. Experimental Procedure The calorimeter consisted of a long-necked Dewar flask immersed in a constant temperature salt bath and has been described by Ticknor and Bever." The chief changes in this equipment were an improvement in vacuum and the replacement of the mercury thermoregulator by a resistance thermometer control circuit. The solvent, which was maintained at a constant temperature near 350°C, consisted of 500 grams of 99.99 pct pure tin. The solute samples were mixtures of gold and copper in the proportion corresponding to the composition Cu,Au or solid solutions

Jan 1, 1956

By Leendert de Witte

Conventional resistivity logs consisting of a short normal, a long normal, and one or more long lateral curves do not give data that allow a complete quantitative interpretation in beds thinner than 20 ft. Reservoir rocks usually exhibit zones of continuous homogeneity of quite limited thickness where the long lateral curves become useless because of adjacent bed effects and boundary phenomena. If the beds are 12 ft or thicker, the short and long normals may be used for qualitative interpretation, which can be streamlined by the application of simplified departure curves. For beds of a thickness less than twice the long normal spacing, this procedure breaks down. The combination of the limestone curve, the later-olog or guard electrode log, and the microlaterolog permit quantitative interpretation for beds that are at least 10 ft thick, provided the mud resistivity and the hole diameter are known with sufficient accuracy. For beds thinner than 10 ft, combinations of the microlaterolog with short spaced laterologs and pseudo laterologs appear to be promising. Interpretation of these curves again requires the application of simplified departure curves. Resolution of various possible combinations was analyzed using departure curve data calculated on the Whirlwind I computer at the Massachusetts Institute of Technology. A field example is shown using the microlaterolog-microlog combination, and the combination of a 6-in. modified laterolog plus a 6-in. pseudo laterolog. INTRODUCTION For the purpose of quantitative interpretation of resistivity logs in porous formations, we want to obtain two essential quantities from the logs, namely, the true resistivity of the undisturbed formation, Rt, and the resistivity of the part of the formation invaded by mud filtrate, Rt. The apparent resistivities of all conventional logging devices are functions of these two parameters and are also influenced by a third unknown parameter, the diameter of the invaded zone, d. It has been shown' that from the normal curves alone it is impossible to arrive at a unique solution for the three unknowns, Rt, R1, and d1. In very thick homogeneous beds, if invasion is not too deep, we can obtain a fair approximation to Rt from the long lateral curves and then use the two normal curves to find Rt and d1 Even under the most favorable conditions, the resolution of this system is not very good. The short normal does not give a reasonable approximation to R1 unless invasion is very deep (dl>16 hole diameters). For very deep invasion, however, the long laterals no longer approximate Rt. For bed thickness between 20 and 40 ft, the long laterals are affected appreciably by the adjacent beds; and the curves are distorted by boundary anomalies to the extent that they lose their quantitative usefulness in most cases. For the same bed thicknesses, the normal curves still function reasonably well. Although it is impossible to find unique solutions Lor R1 and Rt using the normal curves alone, we can obtain a reasonable approximation for the ratio R1/Rt through the use of simplified departure curves. This fact was brought to our attention by A. J. de Witte, geologist with Continental Oil Co. As the magnitude of Rl/Rt is a major clue to the presence of oil in formations, this method can be used to good advantage for qualitative analysis and will be discussed in somewhat greater detail. With the aid of suitable bed thickness corrections, the analysis of the normal curves may be used for bed thicknesses larger than 12 ft. For thinner beds, the method rapidly loses its resolution; and we have to resort to different types of resistivity logs if we want to attempt to analyze the curves quantitatively. The inadequacy of conventional resistivity curves in thin beds is far more serious than generally realized. Fig. 1 shows a conventional E. S. with a 16-in. and 64-in. normal and a 16-ft lateral through a section of Lansing-Kansas City lime, in comparison to a guard electrode survey through the same section in a neighboring well. The porous zones, which show up as low resistivity breaks on the guard electrode log, are completely masked by adjacent bed effects and boundary anomalies on the conventional curves. Even the short normal shows most of the porous Zones only as Vague deflections and in many cases fails to register Their

Jan 1, 1955

By D. R. Wieland, A. N. Barron, A. R. Hendrickson

A definite relationship has been found between the reactivity of flowing hydrochloric acid and its shear rate in a carbonate fracture. Both flow velocity and fracture width affect the acid reaction rate. Laboratory studies were conducted on acid reactivity at different flow velocities through horizontal-linear fractures, using 15 per cent hydrochloric acid at 80' F and approximately 1,100 psi. Fracture width varied from 0.02 to 0.20 in. These data provide a new basis from which the spending time and penetration of the acid can be estimated. Equations were derived expressing the relationship between injection rate, fracture width, acid concentration, time and fracture height, for linear and radial fracture systems. Because the penetration of the acid before spending is closely related to the extent of productivity increase resulting from an acidizing treatment, these data provide a valuable insight into some of the controlling factors that must be taken into consideration during treatment preplanning. INTRODUCTION Acidizing of carbonate reservoirs to improve production characteristics has been widely practiced since 1932. Originally, it was assumed that the acid uniformly penetrated natural formation pores and flow channels, enlarging them and thereby increasing their flow capacity. Little consideration was given to the reaction rate of the acid, or how far it would penetrate away from the wellbore into the formation, before spending. It has been shown recently' that, unless fractures are present in the rock, very little penetration is attained before spending, and the benefits of the acidizing treatment are largely confined to the immediate vicinity of the well-bore. Therefore, acid treatments may be classified into two categories: (1) matrix acidizing, in which the acid flows through multiple: formation pores; and (2) fracture acidizing, in which the bulk of the acid travels through fractures in the rock, whether natural or induced. When acidizing treatments are conducted at pressures of sufficient magnitude to open and extend such fractures, it is often desirable to inject a propping agent to hold the fracture open after the treating pressure has been released, thus providing a highly conductive flow channel through the rock. In some cases where acid attack produces surface irregularities, the resulting flow passages can be sufficient to provide high conductivity without use of a propping agent. During injection, the acid dissolves the carbonate rock with which it comes in contact until it is spent. Deeper penetration of the spent acid into the formation produces no appreciable benefit (if no propping agent is used) because the unetched fracture faces will rejoin when treating pressures are released and the fracture will "heal", with negligible resultant conductivity. The spending time of the acid thus becomes important in determining how far from the wellbore the improved-conductivity zone extends. The spending time of acid after injection into carbonate rock depends on the rate at which the acid reacts with the rock. This in turn is controlled by a number of factors, as previously reported. 2-4 These include temperature, pressure, acid concentration, rock composition, injection rate and the area-volume relationship between the acid solution volume and the surface area of the formation flow channels through which it penetrates. Thus, in matrix acidizing, where an extremely large area is exposed to the acid, spending is rapid. In contrast, spending time is prolonged in open fractures, where the area-volume ratio is much lower. Thus, greatest penetration of the acid before spending will be achieved in acid-fracturing treatments where fractures are held open by hydraulic pressure. Perkins and Kern5 have presented equations for fracture-width determinations which, for hard formations such as limestone or dolomite, indicate that high injection rates and viscous fluids are required to create wide fractures. Increasing the injection rate will, in itself, produce faster reaction rates. Because this type of reaction can be considered to be first-order diffusion-controlled, '-' the rate of movement of fluid past the rock surface affects the thickness of the diffusion layer, in turn affecting the reaction rate. Staudt, et al,10 report the results of tests in which a rotating marble cylinder was immersed in acid, and the weight loss at different speeds determined. Such test conditions, however, are not truly indicative of the situation in a formation during an acid-fracturing treatment. This paper reports reaction-rate data obtained under

By M. Prats

The effect of a sand-filled vertical fracture of limited radial extent and finite capacity (fracture capacity is the product of the permeability and width of the fracture) on the flow behavior of a cylindrical reservoir producing an incompressible fluid through a centrally located well has been investigated mathematically. The shape of the lines of equal pressure near the fracture is essentially independent of the size of the reservoir, provided that the field radius is of the order of the fracture length or larger. For reasonable values of production rates and of fluid, reservoir and fracture properties, the total pressure drop between the end of the fracture and the well is gelrerally negligible compared with the pressure drop in the reservoir. With regard to production response, the effect of vertical fractures can be represented by the production response of an equivalent or effective well radius. For a high-capacity fracture, the effective well radius is a quarter of the total fracture length, decreasing with the fracture capacity. When invasion effects are simulated by decreasing the width of the damaged zone with distance from the well, the effect of formation damage around a fracture on the production response is not so seriolls as indicated by the literature. This suggests that frac fluids with a conventional filter-loss response are better than high-spurt-loss frac fluids, provided the effective permeability of the damaged zone is the same. INTRODUCTION This paper considers the effect of the fracture capacity, as well as the formation damage which can result from fracture treatments, on the productive capacity of vertically fractured wells. Other publications, notably those of van Poollen,l,2 consider these same effects. In addition to providing more general results for vertical fractures than are available from the liter- ature, the present paper gives the equivalent well radius of fractures having different lengths and capacities and, also, includes pressure distributions in and around the fractures. The effect of a damaged zone around a fracture on the production response was not found to be so great as that reported by van Poollen. 2 This difference probably stems from the fact that we consider a damaged zone which is widest (but is still small) near the well and thins out toward the extremities of the fracture, whereas van Poollen considers a damaged zone having a uniform width for the entire fracture length. Simple, but adequate, equations which describe the effect of these variables on production response are presented (in Appendixes A and B). Thus, results can easily be extended to values of the variables not specifically considered here. IDEALIZATION AND DESCRIPTION OF THE FRACTURED SYSTEM It is assumed that a horizontal oil-producing layer of constant thickness and of uniform porosity and permeability is bounded above and below by impermeable strata. The liquid is incompressible. It is assumed that, after the well is fractured, the cylindrical outer "boundary" is at a uniform potential, provided that it is not too near the fracture. The fracture system is represented by a single, plane, vertical fracture of limited radial extent, bounded by the impermeable matrix above and below the producing layer (reservoir).3 Fig. 1 indicates the general three-dimensional geometry of the fractured reservoir described above. If gravity effects are neglected, the flaw behavior in the reservoir will be independent of the vertical position ill the oil sand. This means that the flow behavior in the fractured reservoir can be described by the two-dimensional flow behavior shown in the horizontal cross section of the reservoir, Fig. 2. PARAMETERS The effect of a fracture on the pressure distribution in the fracture itself and in an otherwise undamaged (no skin) reservoir indicates that the pressure distribution is a function of three parameters.