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By D. W. Breck

Zeolites were first recognized as a new group of minerals by Cronstedt with the discovery of stilbite in 1756. The word zeolite was coined from the two Greek words meaning "to boil" and "a stone" because of the loss of water when heated in the mineralogist's blowpipe (Breck, 1974). In 1845 it was discovered that certain soils lave the power of retaining ammonium salts Way, 1850). These were the first ion exchange experiments. Later it was discovered that it was the hydrated silicates in the soil that produced this phenomenon. Several years later a paper was published dealing with the action of dilute salt solutions on silicates which showed that this base-exchange principle, which we now call cation exchange, is reversible. The quantitative cation exchange behavior of zeolite minerals, such as chabazite, was studied. As a result any aluminosilicate which exhibited the property of ion exchange was referred to as a "zeolite," even today the term has been applied to clay minerals as well as synthetic organic ion exchange resins.

Jan 1, 1975

By P. Sanchez-Mejorada

GEOLOGISTS who are acquainted with the mines of northeastern Mexico realize that the most important lead-silver replacement deposits of the province are confined to a single formation. But since the formation is several hundred meters thick, the author has determined the relative position of the lead mantos in the belief that this information will prove useful in the search for new mines. This article describes the stratigraphic location of lead-silver replacement deposits known in several mines situated in a region comprising part of the states of Coahuila and Nuevo Leon. The area studied extends for 200 km* (125 miles) from east to west and 70 km (45 miles) north to south. Metallogenic Province: The most important metallic deposits of the region have the following common characteristics: 1) The orebodies occur as manto replacements of calcareous sediments. 2) The horizons that have contributed large tonnages of ore are in similar positions in the corresponding stratigraphic columns (as it will be shown later on). 3) Lead is the most important metal in the ores. Silver is commonly present in small amounts. Occurrence of zinc is dependent on the degree of oxidation of the primary sulfides. 4) A large proportion of the total production has been in the form of oxidized ores. 5) The deposits are located on anticlines. Rocks of Cretaceous age crop out over large areas of the states of Nuevo Leon and Coahuila. forming part of a belt that extends to the south along the eastern Sierra Madre. The sediments are cut by a small number of intrusive stocks ranging in characteristics from rhyolite to diorite. The most prominent structural feature of the region is a series of folds trending northwest-southeast. Faulting is not conspicuous in the region, although a major fault zone is found farther East.' The physiography closely reflects structural features, with mountains formed by anticlines and valleys conforming with intermediate synclines. Narrow valleys have also been developed along the axes of many anticlines, where solution of limy sedi- ments and erosion have proceeded along axial tension fractures. Stratigraphy: Rocks of the Upper Cretaceous are exposed in only a small percentage of the total area. Generally they have been eroded away from the mountains and are covered by recent talus and alluvium in the valleys. Humphrey' has published an excellent paper describing the Cretaceous formations of the Sierra de los Muertos, a short distance west of Monterrey. A brief summary of these formations is given below to convey an overall picture of the stratigraphic sequence that prevails just south of the area under consideration. Upper Cretaceous Indidura: Essentially thin shaly sediments. Cuesta del Cura: Limestone in thin wavy beds

Jan 1, 1959

By M. Prats

Most of the information available on the heat efficiency of hot fluid injection processes, both water and steam, has been obtained from calculated temperature distributions in the pay zone and adjacent formations. The usual approach has been to write the heat balance equations in terms of the temperatures, and then to introduce whatever simplifications are necessary to help obtain an analytical or a numerical solution. In either case, the assumption has often been made that the vertical thermal conductivity in the flooded interval is infinite, so that the temperatures within the flooded interval are then independent of vertical position. Because it was first made by Lauwerier,l and has been used extensively since, this assumption will be referred to as the Lauwerier assumption. Excellent reviews of the literature on the heat efficiency of hot fluid injection processes have been given by Spillette,2 Flock et al.,3 and Ramney.4 Of course, the most significant contributions take into account the effect of a finite vertical thermal conductivity on the vertical temperature profile. The most general analytic expression for the heat efficiency of a hot fluid injection process is that of Antimirov5 who considers injection of a heated incompressible fluid into a reservoir through an arbitrary number of wells. The rate of heat injection into the reservoir, as well as the injection temperature, is an arbitrary function of time. The geometry of the horizontal flow is arbitrary, although the reservoir is considered to be of uniform thickness and properties and to be of infinite areal extent. Heat transfer within the reservoir is by horizontal convection and conduc- tion, and by vertical conduction. In the formations adjacent to the flooded interval, heat transfer is by conduction in any direction. Thus, the available expression for the heat efficiency due to hot water injection has been developed for rather general conditions. This degree of applicability has not been obtained for other thermal recovery processes. By making the Lauwerier assumption we have been able to obtain expressions for the heat efficiency that are essentially independent of the thermal recovery process, be it steam, hot-water, or underground combustion. Clearly, then, the approach followed here is more restrictive than that of Antimirov5 in that it uses the Lauwerier assumption. At the same time less restrictive assumptions are made about the horizontal heat transfer mechanisms, either in the flooded interval or in the formations adjacent to it. The main difference between our approach and that of other investigators is that the heat balance in the pay zone is expressed for the pay zone as a whole rather than for a volume element within it. The Lauwerier assumption is introduced after the problem is developed along these lines as far as possible. The details of the development of the heat efficiency are given in the Appendix, while the main features of the model are discussed in the next section. Results and their implications are discussed later in a separate section. The Model Certain assumptions have been made to determine

Jan 1, 1970

By A. G. Rozner

TRANSVERSE rupture tests have been commonly used in mechanical investigations of brittle materials. The specimens are simple, easy to prepare, and loading presents no difficulty. Owing to the complexity of stress distribution in bending1 one can determine stresses rigorously only for the elastic range. The bend-test results, however, are at times converted into tensile-strength data, determined as maximum fiber stress. The assumption is made that for small plastic deformations the linear stress-strain relation applies. This problem was experimentally investigated by Bach3 who tested cast iron in bending and in tension and found that the maximum fiber strength obtained in bending exceeded the experimental tensile strength by a factor depending on the geometry of the tested piece. The factor varied from 1.57 for a rectangular cross section to 2.12 for a circular cross section of the tested beam. Since this work was carried out 60 years ago, the cast iron used could be expected to have been highly brittle, thus the extent of plastic deformation prior to fracture very small. We have therefore carried out a number of tests on magnesium-modified cast iron with an average elongation of -5 pct. It was hoped that the data obtained from the tests would serve as a guideline for comparing data obtained in tension and bending for brittle materials. Mechanical properties were measured at room temperature on an Instron tensile machine at a crosshead speed of 0.05 in. per min. The three-point bend test employed cylindrical bars 0.20 in. in diameter with a 1.0-in. span. For the tensile test, cylindrical tensile specimens with a gage length of 0.85 in. and a diameter of 0.160 in. were used. Results are summarized in Table I. From Table I one can see that fracture strength

Jan 1, 1965

Jan 1, 1885

By K. E. Manchester, C. B. Sibley

The feasibility of doping silicon to produce device structres by directly implanting impurity atoms has been demonstrated. Both phosphors and boron ions have been successfully implanted in silicon to produce electrical junctions. Junctions as deep as 1.2 p have been produced by phosphorus ions having energies the order of 80 kev. An electromagnetic separator has been used to controllably produce uniform, large-area implantations for evaluation experimentation. Correlations between junclion depths and ion energies huve been obtained. Orientation effects have been observed and it has been found that the (110) direction is the easy direction for implanting. Monitoring of thermal treatments oj implanted substrates by sheet-resistance measurement indicates a very mild thermal anneal removes most of the damage done during the implantation. These indications are further substantiated by reverse-current measurements of j,inctions Produced by implantation. Electrical characteristics of implanted junctions are compared with those of diffused junctions. We have been interi n the interaction of energetic ions in the III-V groups, in particular boron and phosphorus, with single-crystal silicon to produce type conversion for possible device use. A number of investigators, a few of whom are avies, Kornelson,3 and so forth, have reported on penetration of energetic ions into both amorphous and crystalline solids. While most work has been done with ions of the rare gas and alkali metal groups, some work has been reported by ing, erber,' and others6 in which ions of the 111-V groups have been implanted in single-crystal silicon. A large amount of this work has been done with ion energies in the 100-kev to 1.5-Mev range. An excellent review article has been written by caldin. We have concentrated on ion energies which are in the 10 to 80 kev range, with which over 1500 implanted junctions such as the one shown in Fig. 1 have been produced in silicon substrates with both phosphorus and boron ions. Fig. 1 is a 3-deg angle lap in which the n type area produced by 66 kev P is delineated and the junction is 9500A below the surface. EXPERIMENTAL Implantations reported in this paper were made with the ion source adjusted to produce ion currents in the range of 1 to 2 pa with accelerating voltages varied from 10 to 40 kv. When using doubly charged ions this produced 10 to 80 kev ions. This allowed substrate temperatures to remain below 100°C. Sam- ple movement resulted in beam impingement angle variation of 7 deg from the normal to the substrate surface. Substrate resistivities have been varied through the range of 0.001 to 500 ohm-cm and specimens oriented in three directions, (110), (Ill), and (loo), within 12 deg. RESULTS For the purpose of this paper, discussion of results will be limited to phosphorus implantations with mention of results for boron-implanted silicon. Similar results have been obtained for boron and will be reported at a later date. In Figs. 2, 3, and 4 depth penetration is shown

Jan 1, 1967

By S. R. B. Cooke, H. S. Choi, I. Iwasaki

In a previous article1 the function of various fatty acids as collectors for iron ores was reported for the two alternate processes; (a) the flotation of iron-oxide minerals, and (b) the flotation of calcium-activated siliceous gangue. The selectivity of separation was shown to be markedly dependent not only on such common parameters as pH and the levels of collector and activator addition, but also on the structure and the degree of unsaturation of the acids used. The iron ores employed consisted primarily of hematite, goethite, and quartz and as the effectiveness of any one acid on the separation depends on the individual response of each constituent mineral toward the given collector, a comprehensive knowledge of the floatability of the individual minerals is desirable for the interpretation of the results obtained. The mechanism by which a collector ion becomes attached to a mineral-solution interface has been a subject of much investigation. From quantitative studies of the properties of the electrical double layer on mercury2 and on several solid surfaces3,4,5,6 , the adsorption of some flotation reagents at the mineral-solution interface is beginning to be understood. For example, it has been demonstrated from streaming potential measurements made on quartz5 and corundum6 that the interfacial electrical condition is strongly dependent on the pH. Thisoccurs presumably through the following electrolytic reaction at the interface, and in the presence of a flotation collector, controls the floatability of the solids. A concurrent investigation of the flotation behavior of goethite and of quartz carried out at the School of Mines and Metallurgy7 has shown a positive correlation with the electrokinetic behavior of these minerals. The purpose of the present investigation was to collect general information on the floatability of hematite, and to investigate the function of various 18-carbon aliphatic acids on the floatability of hematite, goethite, and of activated quartz. Electrophoretic mobility measurements, simplified flotation tests using a modified Hallimond tube, and contact angle and frothability measurements were employed. The results are of direct application in the interpretation of the batch flotation results on natural ores as

Jan 1, 1961

By H. A. Domian, H. Biloni, G. F. Bolling

Jan 1, 1965

By R. A. Wattenbarger, H. J. Ramey

The trend in gas well testing has been to rely more on the early-time flow data of drawdown and buildup tests than on stabilized flow tests. The stabilized testing methods often are not adequate for complicated modern gas reservoirs because many of these reservoirs have extremely low permeabilities and the transient flow period of a well test can last for days or weeks. It has become common to augment the flow capacity of gas wells by hydraulically fracturing their producing formations. In deep reservoirs the induced fractures are generally vertical and tend to follow a single plane of weakness. The presence of a vertical fracture at the wellbore complicates the transient flow behavior of a low permeability gas well. The flow is further complicated when turbulence occurs near the wellbore. Russell and Truittl published transient drawdown solutions for vertically-fractured liquid wells. They developed methods of drawdown and buildup testing utilizing these solutions, which were based on numerical simulation. Clark2 applied the basic Russell-Truitt solutions to analyze fractured water injection wells by falloff tests. Field examples were given to substantiate the method of analysis. The Russell-Truitt solutions and well testing methods can be extended to gas well flow. Millheim and Cichowicz3 presented the drawdown equations for *Now with Scientific Software Corp., Denver. ideal gas flow, including the effects of formation damage and turbulence. Two actual field cases were presented, both of which exhibited extensive fractures and turbulent flow. For the pressure range of these well tests, the use of ideal gas equations was acceptable. These field cases were significant in being the first published data showing the occurrence of turbulence in fractured gas wells. We, also, observed such cases in practice. Our purpose here is to extend the theory of fractured gas well testing to the flow of real gases. To determine the effects of wellbore storage and turbulence on well test interpretation, we developed a finite-difference model to simulate well test conditions. Since gas wells usually are widely spaced and have high compressibility, the emphasis has been put on the early transient behavior before the effects of the outer boundary are noticeable at the wellbore. The Mathematical Model The geometry of our mathematical model is similar to that used by Prats.4 The well is centered in a circular uniform reservoir. A vertical fracture of infinite flow capacity penetrates the formation and passes through the wellbore. The wellbore itself is not important. Fig. 1 shows a sketch of the problem. Fig. 2 shows the idealized model. The equation for the flow of real gas in a porous medium with uniform porosity, permeability and thickness is5-7

Jan 1, 1970

By J. H. Swisher

An experimental study has been made of the possible mechanisms for foam stability in the system CaO-SiO2-Cr2O3, where Cr2O3is the foaming agent. The degree of lowering of surface tension by Cr2O3 was determined at 1600 "C for high -silica melts. Measurements were also made of foam stability under standardized conditions. The results of the two sets of measurements then were correlated by applying the Gibbs and Marangoni theories of film elasticity. It was demonstrated that the Marangoni elasticity effect is probably the largest single contributor to foam stability, although the high uiscosity of' silicate melts makes some contribution in controlling the rate of drainage of liquid from bubble lamellae. ThE tendency of metallurgical slags to foam has frequently been observed during steel-refining operations. In the open-hearth furnace,this tendency is considered undesirable because it slows down the rate of heat transfer from the burners to the molten-metal bath. On the other hand, it is sometimes desirable to have a "foamy" slag in the basic oxygen converter.' A more effective blanket over the steel bath is made by a "foamy" slag, and loss in yield of metal due to splashing is minimized. In addition, a flush slag can be removed more easily in this condition. Since slag-foaming problems in the field have been attacked largely on an empirical basis, it appeared desirable to obtain a better basic understanding of the mechanism of foam stability. The experimental work was directed almost entirely toward the behavior of Cr2O3 as the foaming agent in CaO-SiO,-Cr2O3 melts. In the first stage of the investigation, the degree of lowering of surface tension by Cr2O3 was determined at 1600°C. The second stage consisted of measuring foam stabilities under standardized conditions. The two sets of experimental results then were correlated by applying various theories of foam stability. For convenience in interpreting the surface-tension and foam-stability results reported here, a portion of the CaO-SiO2-Cr2O3 phase diagram2 is reproduced in Fig. 1. EXPERIMENTAL 1) Surface-Tension Measurements. Very little information is available in the literature on the lowering of surface tension of slags by foaming agents. Kozakevitch 3 mentioned that the addition of 1.5 pct Cr2O3 lowered the surface tension of FeO slightly. In another system, some data on the lowering of surface tension of foaming slags by P2O5 were reported by Cooper and Kitchener.4 The technique used for the surface-tension measurements was the maximum bubble-pressure method,' using a single tube immersed to various depths in the melt. This method has been used extensively in high-temperature systems, such as in liquid metals, slags, and glasses.6,7 It has the advantage that the contact angle between the liquid and the tube material need not be known. The equation used for calculating surface-tension values from maximum bubble-pressure measurements is the Schroedinger equatioq5 which can be written as follows:

Jan 1, 1964

By George F. Kunz

Jan 1, 1902

By R. W. Heins, N. Street

An investigation was made of the Rehbinder-Kuznetsov pendulum as an instrument to aid in the study of rock drillability and of the effect of surface active agents on rock drillability. The "critical weight", i.e., the pendulum weight at greatest sensitivity, was determined for several solids and it was shown that a change in surface environment changed the maximum value of the apparent hardness but not the critical weight, and the critical weight increased with increase of hardness of the solid used. Using silver halides as the solid material, and solutions of either silver nitrate or the appropriate alkali halide, it was shown that there is a hardness maximum at the zero point of charge of the particular silver halide. INTRODUCTION The development of relative hardness measurement by the method of damped oscillations, or what has been called the pendulum sclerometer, is due largely to the Russian workers P. A. Rehbinder and V. D. Kuznetsov and their co-workers.1,2 The apparent simplicity of the method has led to its use in a number of fields, particularly those where relative hardness has to be determined on a brittle solid. As will be shown, the simplicity of the method belies its complexities. THEORY OF THE PENDULUM SCLEROMETER The operation of the pendulum is quite simple. Make a sharp point such as a diamond, hardened steel or tungsten carbide, as the fulcrum of a pendulum, with the center of gravity of the system below the point of support. The attenuation of this pendulum is a function only of air friction, provided no fragmentation, breakage or other work is performed by the point. However, when the solid surface breaks or disintegrates under the point, and the latter penetrates the solid, part of the energy of oscillation is absorbed in the work of creating new surface, and the rate of attenuation increases. In the case of brittle solids, the point of the pendulum produces fragmentary particles, whereas the point produces plastic deformation in a plastic solid; but in both cases damping occurs. This pendulum damping is a function of the hardness or strength of the solid. Whereas a pendulum oscillating on a hard material attenuates primarily by air friction, in the case of a soft material, the points penetrate the surface of the solid, producing new surface, and the pendulum damps much faster. Thus the attenuation rate is a function of the hardness or strength of a material in both plastic and brittle substances. Russian workers initially used a single support for the pendulum, but this created many problems because of oscillation of the pendulum in more than one plane. A revised version used two points, or sometimes a prism as support, successfully confining oscillation to one plane. The version using two points was constructed and used throughout this investigation, making the recording of the attenuation as a function of time relatively easy. That both points should be in contact with the solid during the damping is implied. Rehbinder (c.f. Kuznetsov2) proposed that the hardness H as measured by this method could be expressed by a quantity which is inversely proportional to the relative initial rate of attenuation of amplitude. where H = hardness parameter (arbitrary units) a, = initial amplitude da/dt = rate of attenuation of amplitude with time. In the simplest case of damping with a constant logarithmic decrement, H can be regarded as a constant for the duration of the whole damped oscillation process. That is

Jan 1, 1966

By A. B. Parsons

Jan 1, 1971

By N. R. Morrow, C. C. Harris

The experimental points which describe capillary pressure curves are determined at apparent equilibria which are observed after bydrodynamic flow has ceased. For most systems, the time required to obtain equalization of pressure throughout the discontinuous part of a phase is prohibitive. To permit experimental points to be described as equilibria, a model of capillary behavior is proposed where mass transfer is restricted to bulk fluid flow. Model capillary pressure curves follow if the path described by such points is independent of the rate at which the saturation was changed to attain a capillary pressure point. Aemodified suction potential technique is used to study cyclic relationships between capillary pressure and moisture content for a porous mass. The time taken to complete an experiment was greatly reduced by using small samples. INTRODUCTION Capillary retention of liquid by porous materials has been investigated in the fields of hydrology,l soil science,2 oil reservoir engineering,3 chemical engineering," soil mechanics,5 textiles: paper making: and building materials In studies of the immiscible displacement of one fluid by another within a porous bed, drainage columnsl and suction potential techniques2 have been used to obtain relationships between pressure deficiency and saturation (Fig. 1). Except where there is no hysteresis of contact angle and the solid is of simple geometry, such as a tube of uniform cross section, there is hysteresis in the relationship between capillary pressure and saturation.2 The relationship which has received most attention is displacement of fluid from an initially saturated bed (Fig. 1, Curve R2), the final condition being an irreducible minimum fluid saturation Swr. Imbibition (Fig. 1, Curve A), further desaturation (Fig. 1, Curve R), and intermediate scanning curves have been studied to a lesser but increasing extent.2 ,3,9-12 This paper first considers the nature of the experimental points tracing the capillary pressure curves with respect to the modes and rates of mass transfer which are operative during the course of measurement. There are clear indications that the experimental points which describe these curves are obtained at apparent equilibria which are observed when viscous fluid flow has ceased; and any further changes in the fluid distribution are the result of much slower mass transfer processes, such as diffusion. Unless stated otherwise, this discussion applies to a stable packing of equal, smooth, hydrophilic spheres supported by a suction plate5 with water as the wetting phase and air as the nonwetting phase. The discussion can also be applied, in many

Jan 1, 1966

By Frederick Laist

AFTER a series of experiments covering a period of about three years, ending from the spring of 19iJ.2 to the spring of 1915, a 2,000-ton leaching plant for the treatment of the accumulated copper concentrator tailing was built and put into operation. During the experimental period, the first step was that of laboratory experiments or beaker leaches. The results on this small scale were so satisfactory that a small operating plant, capable of handling 5 tons of roasted tailing per day, was installed. Again, the results proved satisfactory and an 80­ton plant was built and operated continuously from August until February, 1913. In this plant, full-sized roasting and leaching units were

Jan 8, 1916

By L. F. Elkins

Water coming into wells with bottom water present in the Fosterton field, when their oil recovery was only 0.1 to 1.5 per cent of oil in place below the lowest perforation, confirms lack of shale barriers to vertical flow which also are not apparent in cores and electric logy. Low contrast of vertical and horizontal permeability, high mobility ratio betweerz oil and water zone and pos.rible rate effects due to gravity Combine to prevent easy analysis of water invasion pattern and efficiency by analogy or intuition. Theoretical analysis of performance including these factors using a new direct nurnerical .solution of potential distribution in a network led to unanticapted indications that water would under-run the entire oil reservoir with low volumetric coverage if supplied through natural influx or peripheral water injecfion below the oil-water contact. An unusual pattern of water injection is to he adopted in this recently unitized pool to provide more uniform water flooding in that two-thirds of the oil reservoir not underlain by bottom wafer. INTRODUCTION The Fosterton field, Southwestern Saskatchewan, Canada, was discovered in Jan., 1952. It produces at a depth of 3,100 ft from a pinch-out of the Roseray sand at the Lower Cretaceous-Jurassic unconformity. The field, covering 2,500 acres, contains 54 wells on 40-acre spacing. Development was essentially complete in June, 1954, but significant production did not start until May, 1955, when a pipeline outlet became available. Within one year rapid in- creases in gas-oil ratio and early encroachment of water created operating problems in the down-structure eastern half of the field and raised serious questions about reservoir performance and ultimate recovery. This paper describes the unusual behavior of water encroachment—on both well and reservoir bases—and the analyses made to interpret it. The field was unitized July 1, 1958, for water flooding. A somewhat unconventional

By Thomas C. Wilder

Jan 1, 1965

By M. A. Elliott

The technology of gasifying coal to produce synthesis and pipeline gas has advanced significantly in the Past 20 to 30 years. This period has seen the extensive use of oxygen in coal gasification, the development of suspension gasification processes and fluidized-bed gasifiers, the operation of various gasification processes at elevated pressures, and operation of gasifiers under slagging conditions. These developments are discussed, and their application to commercial and pilot plant gasifiers is reviewed. Typical processes for synthesis gas production are described, and operating results are compared. Pipeline or high-Btu gas may be produced from coal either by catalytic conversion of synthesis gas to methane, or by the direct reaction of coal with hydrogen (hydrogasification) to produce a methane-rich gas. Neither of these methods has been applied commercially, but developments pertaining to each of them are reviewed, and general processing schemes are discussed. The use of coal as a raw material for manufacturing gas has a long and distinguished history. In fact, the gas industry began in the early 1800's when William Murdock demonstrated that it was feasible to produce and distribute gas made by retorting coal. Coal was used exclusively for gas manufacture until the middle of the 19th centruy, when Lowe invented the carbureted water gas process. In that process, coke was one of the raw materials used, so coal was still an important factor in gas manufacture. However the availability and relatively low cost of natural gas in the United States, and its widespread distribution by long-distance pipelines in recent years, has virtually eliminated the use of coal as a raw material for gas manufacture in this country. It should not be inferred from the foregoing that the technology of coal gasification has remained static in the United States and abroad. In fact, in the past two decades many new concepts have been developed in both the science and the technology of gasification. This progress has been a result of the considerable expansion in research on the fundamental chemistry and physics of gasification reactions, and in development work on gasification processes. This expansion in effort stems in part from increased interest in the use of gas as a raw material for the synthesis of chemicals and liquid fuels, and in part from the need to develop methods for gasifying coal and other solid fossil fuels to ensure a long-range supply of energy in the form of gaseous fuel. In these uses of gas, synthesis gas, a mixture of hydrogen and carbon monoxide in various proportions, is the starting material. It may be converted catalytically to gaseous and liquid hydrocarbons and other chemicals, or to hydrogen for use in hydrogenation or reduction reactions. Since coal is our most abundant fossil fuel, it is inevitable that one day it will regain its prominence as a raw material for gas manufacture. It is of interest, therefore, to consider the present status of gasification technology, directing attention particularly to advances made in recent years. Inasmuch as many comprehensive treatises l-3 and review4-7 of gasification technology are available, no attempt will be made in the present review to cover all processes in detail. Instead, the discussion will be concerned chiefly with typical processes embodying the advances that are most likely to be generally applied. ADVANCES IN GASIFICATION TECHNOLOGY For purposes of this discussion the starting point will be the conventional processes that were used for many years for the complete gasification of coal. These were: 1) carbonization in coke ovens followed by gasification of coke with air and steam in cyclic water-gas generators, and 2) fixed-bed air-blown producers. Both of these methods have obvious deficiencies when we consider that the ideal complete gasification process would be a single-stage, continuous

Jan 1, 1961

By S. A. Hovanessian

The method of characteristics which reduces the Buckley-Leverett mnlineur, partial differential equation to two first-order, linear differential equations is applied to the solution of a waterffood recovery problem for multiple lines of producing wells and one line of injection wells. The application of the method is described by a numerical example, and a brief theoretical background is given. From the results of this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple sets of producing wells. INTRODUCTION In this paper, the method of characteristics is applied to the solution of a waterflood recovery problem with multiple lines of producing wells and one line of injection wells. The application of the method to this type of recovery problem considerably simplifies the procedure of obtaining a numerical solution. It differs from the method described by Kern1 because it eliminates the need for integration in obtaining saturation fronts. In addition, the saturation history at any location within the field is obtained from a single diagram (time vs distance with saturation as a parameter)'. The paper includes a brief theory of the method of characteristics and its application to the solution of oil recovery problems. A numerical example is worked out, and the cumulative oil recovery-vs-time curve for a system with multiple sets of producing wells is obtained. This curve is then compared with the recovery curve of a system with only one set of producing wells. From this study, it is concluded that the cumulative water injected and oil produced are the same for single and multiple lines of producing wells. However, the recovery time is considerably longer for multiple sets of producing wells.

By H. D. Outmans

A method has been developed for determining the relative water wet-tability (fraction of the surface wet by water) of porous media. This method involves the adsorption of methylene blue dye from an aqueous solution onto the solid surfaces of rock contacted by the injected dye solution. Experiments on Berea snndstone cores have shown that water-wet cores adsorb a large amount of dye from solution. In oil-wet cores, however, the injected aqueous dye solution is prevented from contacting the adsorptive surfuces by a film of oil and virtually no dye is adsorbed. This method was tested by experiments on mixtures of water-wet and oil-wet sand. Using the dye adsorption method, it was possible to determine quantitatively the fraction of water-wet and oil-wet sarzd in such mixtures. The dye adsorption test is readily applied to determinitrg the relative water wettability of fresh oilfield cores. The cores are not extracted before testing. Observed values of the wettability of field cores tested to date have varied from 100 to 6 per cent water wet. INTR OD UCTIO N Recent articles1 ' have emphasized the important role that wettability plays in almost all phases of reservoir rock behavior. It has been shown that wettability has a profound effect on the interstitial water saturation, residual oil saturation, capillary pressure, relative permeability, waterflood behavior, and resistivity index of oilfield cores. A quantitative investiga- tion of the effect of wettability on these core properties is severely handicapped by the lack of a simple technique for measuring the wettability of a porous medium. If such a technique were available, it would provide investigators with a means of gaining insight into the distribution of phases within a core. A number of qualitative methods of estimating wettability are known. These include contact angle measurements, flotation tests and studies of displacement pressure: imbibition7 and relative permeability data.' Using these tests, it is usually possible to classify a core as water-wet, oil-wet, or some intermediate degree of wettability. One recently proposed method involving measurement of nuclear magnetic relaxatione offers promise of determining quantitatively the fractional wettability of cores. The equipment is rather elaborate and necessary treatment of the cores before testing probably alters the natural wettability. This latter point also applies to most of the cited qualitative methods. This paper presents a new technique for determining water wettability of cores; it is based on measurements of the dye adsorption capacity of the core. This method has the advantage of requiring relatively simple equipment and involves minimum handling of the core before testing. It is important to distinguish between the various concepts of wettability referred to in the literature. The term "wetting" is defined by Bartell as that phenomenon which occurs when a solid and liquid phase come in contact in any manner so as to form a solid-liquid interface. A preferentially water-wet solid is defined by Jennings in terms of the advancing contact angle in the solid water-oil systems. Brown and Fatt regard fractional wettability as the fraction of the total surface area that is preferentially oil-wet or water-wet. However, none of these definitions adequately describes the type wettability measured by the dye test. This calls for the introduction of a new term, "relative water wettability", which we define as the fraction of the total surface area of a core contacted by injected water. DESCRIPTION OF METHOD The ability of a porous medium (especially the clays) to adsorb large quantities of surfactants, dyes, etc., is well known. It is reasonable to assume that a substance can be adsorbed from solution onto a solid surface only if the solution contacts the surface. In this connection Shapiro" has shown by experiments on silica gel that completely dry gel will adsorb methyl red dye from a benzene solution. On the other hand, if a film of water more than several molecules thick is present on the silica gel, the adsorption capacity of the gel for the dye is drastically reduced. Thus, a study of the dye adsorption capacity of cores should give some clue as to the fluid distribution on the surface of the core. TEST OF METHOD As a qualitative check on this theory, dye adsorption tests were run on similar Berea sandstone cores (Table 1, Cores 1-5). Cores saturated initially with water and flooded with 0.01 per cent aqueous methylene blue adsorbed 0.58 mg dye/gm of core. Similar cores saturated initially with water, driven to irreducible water with oil, and then flooded with the same dye solution also adsorbed 0.58 mg dye/gm of core. Another core, treated with a 5 per cent Dri-Film solution, dried and saturated with oil (Soltrol) adsorbed no dye when the dye solution was injected. These tests confirm