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By B. H. Sage, W. N. Lacey

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By W. N. Lacey, B. H. Sage

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By Nico Van Wingen

Experiments performed with distilled water, unconsolidated sand and dead oil for the purpose of determining the influence of oil flow on the water content of sands were described. While results found are not necessarily, therefore, identical with those that would be obtained under natural petroleum reservoir conditions, the following conclusions were drawn. 1. When oil under constant head is flowed through an unconsolidated sand, the amount of water retained in the core is inversely proportional to the specific permeability of the core. This corroborates the view that the degree to which oil displaces water out of the pore space is limited by the size of the pores. 2. For the range investigated, the displacing action of a more viscous oil of higher specific gravity was found to be the same as a less viscous oil, or lower specific gravity. 3. The amount of interstitial water retained in the sand bears an inverse relationship to the pressure head of the displacing liquid. 4. The degree of retained water saturation of the sand appears to approach 100 per cent as the specific permeability approaches zero. 5. For the higher values of specific permeability and for the pressure range investigated the remaining amount of water in the sand occupies approximately 10 per cent of the pore space. This, together with the fact that the limiting oil velocity curve approaches approximately 10 per cent water saturation as an asymptote, indicates that beyond this point removal of water is achieved only by a stripping of the grains requiring considerable pressure drops across the sands; or by a balancing of the molecular forces. 6. As the water saturation of the sand exceeds approximately 15 per cent of the pore volume, the permeability of the sand to oil decreases rapidly. 7. Sands with water saturations as high as 40 per cent were found to produce 100 per cent oil.

Jan 1, 1939

By Nico Van Wingen

Experiments performed with distilled water, unconsolidated sand and dead oil for the purpose of determining the influence of oil flow on the water content of sands were described. While results found are not necessarily, therefore, identical with those that would be obtained under natural petroleum reservoir conditions, the following conclusions were drawn. 1. When oil under constant head is flowed through an unconsolidated sand, the amount of water retained in the core is inversely proportional to the specific permeability of the core. This corroborates the view that the degree to which oil displaces water out of the pore space is limited by the size of the pores. 2. For the range investigated, the displacing action of a more viscous oil of higher specific gravity was found to be the same as a less viscous oil, or lower specific gravity. 3. The amount of interstitial water retained in the sand bears an inverse relationship to the pressure head of the displacing liquid. 4. The degree of retained water saturation of the sand appears to approach 100 per cent as the specific permeability approaches zero. 5. For the higher values of specific permeability and for the pressure range investigated the remaining amount of water in the sand occupies approximately 10 per cent of the pore space. This, together with the fact that the limiting oil velocity curve approaches approximately 10 per cent water saturation as an asymptote, indicates that beyond this point removal of water is achieved only by a stripping of the grains requiring considerable pressure drops across the sands; or by a balancing of the molecular forces. 6. As the water saturation of the sand exceeds approximately 15 per cent of the pore volume, the permeability of the sand to oil decreases rapidly. 7. Sands with water saturations as high as 40 per cent were found to produce 100 per cent oil.

Jan 1, 1939

By C. R. Hocott

The distribution and movement of fluids in oil reservoirs are influenced to a great extent by capillary forces, which depend upon the size and shape of the pores in the reservoir rock, the surface characteristics of the rock, and the interfacial tension between the fluid phases. This paper presents the results of an investigation of the interfacial tension between salt water and crude oil containing dissolved gas under reservoir conditions. Apparatus and Procedure In the preliminary phases of this investigation, it was found that a scum formed at the oil-water interface, which made measurement of interfacial tension by either the ring or capillary rise methods unreliable. Accordingly, the drop-weight method, in which a fresh interface is continuously formed, was selected. In this method, a tip through which drops of one fluid can be expelled is immersed in a second fluid. At the instant that the drop becomes large enough to fall, the gravitational force tending to pull away the drop exactly balances the interfacial force tending to hold it. From the size of the drop, the dimensions of the tip, and the density of the two fluid phases, the interfacial tension may be calculated. The apparatus consists of a circulating pump for bringing the oil to equilibrium with gas at the desired pressure, a displacement pump for forming the drops, an interfacial tension cell in which the drops are formed, and a density cell to determine the density of the oil. The density of the water is determined separately in another apparatus. A flow diagram of the assembled equipment is shown in Fig. 1. The interfacial tension cell contains a stainless-steel dropping tip suspended from the top and extending below the surface of the oil. The tip is a cylindrical rod with a small hole in the center through which the water was forced to form the drop on the lower face. The walls of the tip were highly polished, to prevent the water on the tip from creeping up the side and increasing the effective diameter. The face of the tip, how-

Jan 1, 1939

By C. R. Hocott

The distribution and movement of fluids in oil reservoirs are influenced to a great extent by capillary forces, which depend upon the size and shape of the pores in the reservoir rock, the surface characteristics of the rock, and the interfacial tension between the fluid phases. This paper presents the results of an investigation of the interfacial tension between salt water and crude oil containing dissolved gas under reservoir conditions. Apparatus and Procedure In the preliminary phases of this investigation, it was found that a scum formed at the oil-water interface, which made measurement of interfacial tension by either the ring or capillary rise methods unreliable. Accordingly, the drop-weight method, in which a fresh interface is continuously formed, was selected. In this method, a tip through which drops of one fluid can be expelled is immersed in a second fluid. At the instant that the drop becomes large enough to fall, the gravitational force tending to pull away the drop exactly balances the interfacial force tending to hold it. From the size of the drop, the dimensions of the tip, and the density of the two fluid phases, the interfacial tension may be calculated. The apparatus consists of a circulating pump for bringing the oil to equilibrium with gas at the desired pressure, a displacement pump for forming the drops, an interfacial tension cell in which the drops are formed, and a density cell to determine the density of the oil. The density of the water is determined separately in another apparatus. A flow diagram of the assembled equipment is shown in Fig. 1. The interfacial tension cell contains a stainless-steel dropping tip suspended from the top and extending below the surface of the oil. The tip is a cylindrical rod with a small hole in the center through which the water was forced to form the drop on the lower face. The walls of the tip were highly polished, to prevent the water on the tip from creeping up the side and increasing the effective diameter. The face of the tip, how-

Jan 1, 1939

By M. C. Leverett, S. E. Buckley

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By S. E. Buckley, M. C. Leverett

The production of oil is accomplished as a result of its displacement from the reservoir by either gas or water, and the amount of oil recovery is limited by the extent to which the displacing gas or water accumulates. This paper describes the mechanism by which the displacement is effected and the advantages of water over gas as a displacing agent. In the light of the results of experimental observations of the flow of mixtures of oil and/or gas and/or water through sands, certain conclusions are drawn relative to the changing character of the displacement as depletion proceeds, and on the effects of the properties of the fluids and of producing conditions on the ultimate oil recovery. Introduction Crude oil has no inherent ability to expel itself from the pores of the reservoir rocks in which it is found; rather, it must be forcibly ejected or displaced by the accumulation of other fluids. Accordingly, a knowledge of the mechanism by which one fluid is displaced by another is essential to an understanding of the fundamental process by which oil is recovered. The displacing fluids normally available are gas and water, either or both of which may exist originally associated with the oil in a potentially usable form or may be supplied to the reservoir from external sources. Gas is present in most oil reservoirs. If the quantity is relatively small, it may exist originally completely dissolved in the oil, but if the quantity exceeds that which may be held in solution by the oil at the prevailing pressure, the excess will be found in the free state. Most reservoir sands appear to contain some water,l and in the majority of fields the oil is trapped in the structure and held over water. In certain conditions the entrapping water may advance into the oil zone and displace the oil therefrom. This paper describes in a qualitative manner some of the characteristics of the displacement of oil by either gas or water, with an attempt to elucidate somewhat the mechanism by which such displacement is effected. Role of Dissolved Gas When the pressure on an oil containing dissolved gas is reduced to the saturation or bubble-point pressure, gas escapes from solution and expands, imparting to the oil-gas mixture a high degree of expansibility and causing it to flow in the direction of reduced pressure. This expansibility has frequently been attributed to the oil; closer analysis, however, reveals that as gas escapes from solution the oil phase actually. contracts. Hence, it is the accumulation and expansion of the liberated gas that supplies the propelling force for the oil. It has been shown experimentally2-5 that within certain limits a sand containing oil, gas and water will permit the simultaneous flow of all three; the readiness with which they may flow depends upon the characteristics of the sand, of each of the fluids, and upon the relative amounts of the fluids in the sand. Thus, in the initial stages of production by the mechanism of dissolved gas drive, the liberated gas is present in the sand in low concentration and is unable to

Jan 1, 1942

By Kenneth S. Ritchie

The natural emulsion samples used in this study were shipped directly from twelve California oil fields, through the courtesy of the superintendents of the main producing companies in those fields. Representative parts of each sample were chosen for the slides. Preparation of the slides was generally made in less than two minutes, including time of exposure; in a few cases, about five minutes was required. The short time was intended to minirmize the changes in conditions. Whenever comparison was of value, standard conditions were established. Spreading by gravity was adopted instead of smearing. Cover glasses were not allowed to rest on the films. General Characteristics of Emulsions The main purpose of the general views (Figs. 1-16) is to illustrate the general characteristics of the dispersed droplets together with any other constituent or impurity that may be found in each emulsion. The magnification is given so that dimensions could be measured from the plates. The slides used for these views had spherical recesses; they gave the best light. Where crystals were intended to be shown in the picture a filter (green was the best') was usually used. Emulsions that showed a tendency to move by concentrated light were pictured without a condenser.

Jan 1, 1931

By Harmon F. Fisher

In the course of a comprehensive investigation for the development of the electrical process for the dehydration of oil-field emulsions, the writer has had an unusual opportunity to direct and execute a number of related, parallel studies concerning crude oil emulsions and extending over a period of nearly six years. Among these was an investigation utilizing the microscope for studying both the general characteristics of crude oil emulsions, the nature of their electrical charge and the action of an alternating current field in causing coalescence of the finely dispersed, more or less permanently suspended, emulsion particles into larger droplets of such mass that subsequent dehydration would follow by the ordinary process of settling, further agglomeration of the water droplets and, finally, separation into commercially dry, pipe line oil and a clean water discharge. It is not the purpose of this paper to enter into a detailed discussion of the highly specialized subject of microscope technique, nor into a theoretical discussion concerning the origin of the electrical charge on the emulsion particle or concerning the mechanism of the electrical phenomena occurring during the electrical treatment of oil-field emulsions. In a short paper of this character one can hope to touch on only a very limited discussion of the theoretical aspects of crude oil emulsions. The subject of emulsions and colloids is comprised in a comparatively young science in which, however, very rapid progress is being made and consequently it is undergoing many changes; a tentative conclusion valid today may be overthrown tomorrow. Nor would it be a simple science even if it were no longer undergoing this rapid progress; a thorough study of emulsions is based upon a knowledge of such fundamental subjects as molecular structure, ionization and other electrical phenomena, surface chemistry, surface and interfacial tension phenomena, viscosity and other factors too numerous to discuss here and the fundamental theories of which are still undergoing more or less change. Therefore this paper will confine itself largely to a generally descriptive discussion, a sufficiently detailed outline of the microscope technique and a brief comment on

Jan 1, 1931

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By D. B. Carson, D. L. Katz

Natural gases under pressure form crystalline hydrates with water. Experimental data are reported on four-phase equilibrium for the methane-propane-water, methanc-pentane-water, and methane-hexane-water systems. Temperatures and pressures for equilibrium between gas, water-rich liquid, hydrocarbon-rich liquid, and hydrate were measured, as well as the percentages of methane and propane in the hydrate. The data indicate that natural gas hydrate behaves as a solid solution and that pentanes and heavier hydrocarbons do not enter into the solid phase. Vapor-solid equilibrium constants are presented that permit the approximation of the conditions for hydrate formation, from the composition of a gas. Introduction Natural gas hydrates have been the object of considerable research in recent years, because of the trouble they have caused in the natural-gas and natural-gasoline industries. Natural gas hydrates are white crystalline compounds of water and gas, which, under pressure, exist at temperatures considerably above the freezing point of water. Because of the relatively high temperatures at which the hydrates exist, they become a nuisance in high-pressure gas operations where water is present, since their formation causes partial or complete plugging of valves and pipes. From a practical standpoint, the trouble incident to hydrate formation has been solved by dehydration of the gas before it enters the plant or pipe line, or by other remedial measures. Extensive work on gas hydrates in the latter part of the nineteenth century, by Villardl and others, gave data on methane hydrate and on ethane hydrate. Schroeder summarized these theoretical studies2 Hammerschmidt3 introduced the information on gas hydrates to the gas industry and Dcaton and Frost4-6 gathered a considerable number of data on the behavior of natural gas hydrates. Recent papers7,8 have extended both the data and the theory of these hydrates. At present, data are available on tem-peraturcs and pressures of hydrate forma. tion for pure methane, ethane, propane, n-butane, methane-ethane mixtures, meth-ane-propane mixtures, methane-butane mixtures, and some Is natural gases, all- in the Presence of excess water. However, up to the Present time no method has been available for predicting the temperature at given pressures or the pressure at given at at which natural gases will form hydrates if hydrates with water. 'This Paper Presents data on the methane-propane-water, methane-pentane-water and methane-hex-""e water systems in four phases, one of which is the hydrate. he application of the phase rule to the methane-~ro~ane-water data Proves that hydrates behave as solid solutions. The data of this paper and those in the literature were used to develop vapor-solid. equilibrium constants,8 which permit prediction of conditions of hydrate formation from the analysis of a natural gas.

Jan 1, 1942

By Charles R. Fettke

The permeability of an oil or gas sand is its capacity for transmitting fluids, either liquids or gases, under pressure. The permeability of a sand depends upon the size and shape of the openings in it and the extent to which these communicate with one another, as well as upon the ratio of their volume to the total volume of the sand. The apparatus employed and the method of procedure used by the authors in conducting the permeability tests have been described in a previous pub1ication.l For the tests described here 1/2-in. cubes were used. They were set in the lower end of a 1-in. union, inserted in a square hole cut in a hard rubber stopper which fitted into the lower end of the union. In the tests with air, volumes were measured with a wet American gas meter of 100 cu. ft. capacity. In those with water, distilled water at room temperature was employed, unless otherwise noted. DescRiption of Sands Tested The tests described in this paper were performed upon 18 samples representing typical oil and gas sands from 7 localities in northwestern Pennsylvania. For purposes of identification, the cores from which the samples came have been designated by capital letters, the sequence of the samples in the cores by numerals, and the individual cubes by small letters. All cubes from the same samples came from adjacent portions parallel to the bedding. Core A of the Bradford sand came from the north central part of the Bradford field, from an area where water-flooding operations have proved highly successful. Core B of the same sand was obtained from the southern part of the field. This core contained a so-called "loose streak," 7.5 ft. thick, in the middle portion of which B2 is a representative sample. The "loose streak" has given trouble in water-flooding but responded favorably to an air-drive, using a pressure of 300 lb. The natural production was increased approximately five times over a period of three years in which the air-drive was in operation. Core C, also of the Brad-

Jan 1, 1931

By R. A. David, D. J. Vink, D. L. Katz

A phase diagram showing boundary curve and quantity of liquid in the two-phase region was determined for a mixture of natural gas and natural gasoline in the region of its critical conditions. The temperatures and pressures of phase measurements were in the range of 85 to 212 F. and 1300 to 2600 Ib. per sq. in., respectively, with the critical conditions at 169.5 F. and 2615 Ib. per sq. in. abs. Color phenomena were observed in the region of the boundary curve from 102' to 192 F. Approximate densities of the single-phase and two-phase regions and analysis of the system are included. Boundary curves between the single-phase and the two-phase regions have been determined for several binary mixtures containing hydrocarbons. 2,3,4.6,7,10,11,12,14 These investigators did not report the relative amounts of liquid and vapor within the two-phase region. The equilibrium values obtained from the dew-point and bubble-point data can be used to compute the lines showing percentage of liquid on the pressure-temperature phase diagram8 but the positions of the lines near the critical temperature and pressure are uncertain. Relative amounts of vapor and liquid were obtained for a gasoline and a naphtha1 within the two-phase area but not in the region of the critical temperature and pressure. The bubble-point and dew-point lines, as well as the percentage liquid lines within the two-phase region, were determined by visual observations in glass apparatus. Apparatus An arrangement of the apparatus is given in Fig. 1, showing the Jerguson gauge A with glass windows B. Pressure was supplied by the

Jan 1, 1940

By R. A. David, D. L. Katz, D. J. Vink

A phase diagram showing boundary curve and quantity of liquid in the two-phase region was determined for a mixture of natural gas and natural gasoline in the region of its critical conditions. The temperatures and pressures of phase measurements were in the range of 85 to 212 F. and 1300 to 2600 Ib. per sq. in., respectively, with the critical conditions at 169.5 F. and 2615 Ib. per sq. in. abs. Color phenomena were observed in the region of the boundary curve from 102' to 192 F. Approximate densities of the single-phase and two-phase regions and analysis of the system are included. Boundary curves between the single-phase and the two-phase regions have been determined for several binary mixtures containing hydrocarbons. 2,3,4.6,7,10,11,12,14 These investigators did not report the relative amounts of liquid and vapor within the two-phase region. The equilibrium values obtained from the dew-point and bubble-point data can be used to compute the lines showing percentage of liquid on the pressure-temperature phase diagram8 but the positions of the lines near the critical temperature and pressure are uncertain. Relative amounts of vapor and liquid were obtained for a gasoline and a naphtha1 within the two-phase area but not in the region of the critical temperature and pressure. The bubble-point and dew-point lines, as well as the percentage liquid lines within the two-phase region, were determined by visual observations in glass apparatus. Apparatus An arrangement of the apparatus is given in Fig. 1, showing the Jerguson gauge A with glass windows B. Pressure was supplied by the

Jan 1, 1940

By R. V. Lukes, H. W. Scheeline

Knowledge of a large number of the physical properties of the hydrocarbons is needed in the calculations and studies of the production engineer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and temperature,' enthalpy2 and vapor-liquid equilibria13 on the basis of reduced temperatures and pressures, are outstanding examples of this development. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been published by several authors4 and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter propertics are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are

Jan 1, 1939

By R. V. Lukes, H. W. Scheeline

Knowledge of a large number of the physical properties of the hydrocarbons is needed in the calculations and studies of the production engineer. Since experimental data on these properties of the individual hydrocarbons and their mixtures are available in only a relatively few cases, the use of generalized correlations has developed rapidly in the last decade. The generalized correlations of pressure, volume and temperature,' enthalpy2 and vapor-liquid equilibria13 on the basis of reduced temperatures and pressures, are outstanding examples of this development. These correlations are of particular value to the production engineer interested in the flow of oil and gas, since they can be used to estimate the conditions under which segregation of phase occurs as well as the composition, density, and relative amounts of the phases. The technique of using the correlations for such estimations has been published by several authors4 and will not be considered in this paper. A considerable number of data have been obtained to check the generalized pressure-volume-temperature correlations, and these data indicate that such relations hold for the hydrocarbons from methane to heptane. The accuracy is in general sufficient for most engineering pressure-volume-temperature calculations. However, the generalized correlations of enthalpy and vapor-liquid equilibria have in general been developed from the pressure-volume-temperature correlations by thermodynamic calculations and only a relatively few experimental data are available to check these calculated values. The calculations from pressure, volume and temperature are likely to lead to large errors in the calculated enthalpy and vapor-liquid equilibria. Thus, in the calculations of enthalpies, slopes of the pressure-volume-temperature data are employed, and determining these slopes can greatly amplify small errors in the original data. In the vapor-liquid equilibria calculations it is necessary to have the pressure-volume-temperature relations of the mixture, and the latter propertics are much more questionable than those of pure components, particularly in the critical region. A considerable number of experimental data are

Jan 1, 1939

By L. S. Panyity

The inception of this paper may be traced directly to the various discussions of another paper by the writer1 wherein certain indefinite beliefs and opinions were emphasized as to the relative importance of total sand porosity and the actual size of the openings between the grains. Since publication of that paper it has been possible to study various methods of sand analyses and results that have been obtained under different conditions and actual operations in the field. The purpose of this paper is to indicate the value of screen analysis, especially in areas where repressuring by means of water-flood, air or gas is being used in the partly depleted fields. Sand samples have been analyzed for porosity, saturation and grain size. They are mainly from the Bradford water-flood area, where a great reliance has been put upon such analyses, and where many data are available, A few sand studies are included from fields other than the water-flood area, in order to indicate the possibilities of screen analysis in any field. Examples of various conditions are given in Figs. 1 to 7, which show the porosity, saturation and grain-size analyses of submitted cores or drill cuttings. The generally accepted methods of delineating such sand studies on cross-section paper, known as "core charts" has been employed; with the exception that a method of representing grain size has been evolved which is believed to be the best adapted for this purpose. It differs from the block diagrams generally used, in the employment of a linear section. Percentage of grain-size is represented by the subdivision of a given distance, where the total length represents the whole sample of rock chunk, while the subdivisions indicate the percentages of grains of the different sizes that will pass through the various sieves, through which the samples of crushed sand are sorted to determine the size and amount of the components that make up the aggregate. Thus, on Fig. 1, under the heading of Grain Size, the first samples are composed of grains of the following sizes: 16 per cent. through 120-mesh sieve; 33 per cent. through 150-mesh; 25 per cent. through 180-mesh; 26 per cent, through 200 mesh; a total of 100 per cent. A minus sign is placed before

Jan 1, 1931

By Ben E. Lindsly

PetRoleum engineers generally are familiar with the investigations of Dow and Reistle,1 Beecher and Parkhurst,2 and Dow and Calkin3 relative to the solubility of natural gas in crude oil. Since the publication of the results of those investigations and the work of Mills and Heithecker,4 little additional knowledge on this interesting and important subject has appeared in the petroleum engineering literature. The reports of Beecher and Parkhurst and Dow and Calkin agree substantially. The data from both investigations showed that, under the conditions of the tests, the solubility of natural gas in crude oil increased in direct proportion to the pressure at which the gas was put into solution, and the solubility decreased to a considerable extent with increased temperature. These facts, and others relating to the changes in viscosity, surface tension and specific gravity of the crude caused by the solution of gas in the oil, have been given due consideration in the petroleum industry, and the recognition of these facts has resulted in a great improvement in the technique of producing oil. However, in these first experiments, various grades and types of weathered crude oil were contacted at various pressures up to 500 lb. per sq. in. gage with gases deficient to a considerable degree in the heavier hydrocarbons, as compared with the gas that was originally in solution in the oil in its natural underground reservoir. The amount of dissolved gas that was liberated upon reducing the pressure to 1 atm. was measured. For these reasons, the complete significance of the effect of dissolved gases in crude oil, as it occurs in nature, cannot be determined directly from the data obtained under the conditions of the tests as described.

Jan 1, 1931

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939