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By Holbrook G. Botset

Experiments performed in this laboratory on the flow of gas-liquid mixtures through unconsolidated sands have been described and discussed in an earlier paper.4 In these earlier experiments a definite relationship was found between the liquid saturation of a sand and its permeability to the liquid or gas phase. Furthermore, the nature of the sand, the permeabilities of the sands over a range between 17 and 260 darcies, appeared to have a negligible effect upon the saturation-permeability relation. Likewise experiments indicated that the viscosity of the liquid, or the substitution of an immiscible liquid for the gas phase, had only a very slight effect on the permeability-saturation relation. This conclusion has since been definitely confirmed by the experiments of M. C. Leverett3 on the flow of oil and water through unconsolidated sands. The sands used by Leverett were of very low permeability (between 6.8 and 1.04 darcies), while the oil-water viscosity ratio varied between 90 and 0.057. Since the sands that constitute petroleum reservoirs are largely consolidated, although of widely varying degrees of consolidation, it was desirable to extend the experiments on gas-liquid mixtures to consolidated sand. In the study of consolidated sands additional variables are involved, but for the initial experiments the only new variable to be introduced was the cementing material. Experimental Procedure A comparatively limited assortment of sandstones was available for the selection of the experimental material. Of these, the Nichols buff sandstone appeared to be most suitable. It gives no visual evidence of any bedding planes, it has a firm structure, permitting easy handling, and its permeability is about 0.5 darcy. Its only disadvantage is the fact that it contains an appreciable amount of ferric oxide which, for experiments involving water, will hydrate and reduce the permeability. This

Jan 1, 1940

By M. C. Leverett

The behavior of mixtures of immiscible liquids in porous solids is of rapidly increasing interest to those engaged in the production of petroleum. The operation of artificial water-floods and the control of natural ones immediately raise questions concerning the fundamental nature of such processes. Moreover, it is now recognized that often water occurs dispersed throughout the rock from which the oil issues into the well,' and thus tends to move toward the well simultaneously with the oil. The work reported here is a laboratory investigation of the simultaneous, steady-state flow of oil and water through the same column of uncon-solidated sand. It is thus directly related to the situation in which water occurs in oil-producing sands; it may have less direct implications for the displacement of oil from sands by water. However, it is to be clearly understood that the experiments to be described were performed primarily to obtain information of a more or less fundamental nature, and are not an attempt to reproduce, on laboratory scale, any part of an oil field. The dynamic behavior of a system in which oil and water are flowing simultaneously through sand is best described in terms of its "effective permeability" to either phase. For incompressible fluids flowing through a system of uniform cross section, the effective permeabilities to the two phases, in darcys, may be defined by the equations: Ko = PA6A [la] and Ku = Q [lb] In order to put the results obtained on a comparable basis for different sands, the effective permeabilities will be stated as fractions of the normal permeability of the sand; i.e., fractions of its permeability to a homogeneous fluid. Algebraically, these fractions are: KO' = Ko/K, and KWr = K,/X [2a] and [Zb]

Jan 1, 1939

By M. C. Leverett

The behavior of mixtures of immiscible liquids in porous solids is of rapidly increasing interest to those engaged in the production of petroleum. The operation of artificial water-floods and the control of natural ones immediately raise questions concerning the fundamental nature of such processes. Moreover, it is now recognized that often water occurs dispersed throughout the rock from which the oil issues into the well,' and thus tends to move toward the well simultaneously with the oil. The work reported here is a laboratory investigation of the simultaneous, steady-state flow of oil and water through the same column of uncon-solidated sand. It is thus directly related to the situation in which water occurs in oil-producing sands; it may have less direct implications for the displacement of oil from sands by water. However, it is to be clearly understood that the experiments to be described were performed primarily to obtain information of a more or less fundamental nature, and are not an attempt to reproduce, on laboratory scale, any part of an oil field. The dynamic behavior of a system in which oil and water are flowing simultaneously through sand is best described in terms of its "effective permeability" to either phase. For incompressible fluids flowing through a system of uniform cross section, the effective permeabilities to the two phases, in darcys, may be defined by the equations: Ko = PA6A [la] and Ku = Q [lb] In order to put the results obtained on a comparable basis for different sands, the effective permeabilities will be stated as fractions of the normal permeability of the sand; i.e., fractions of its permeability to a homogeneous fluid. Algebraically, these fractions are: KO' = Ko/K, and KWr = K,/X [2a] and [Zb]

Jan 1, 1939

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

By John E. Sherborne

Much valuable scientific research has been performed in recent years on the subject of phase behavior of hydrocarbons.l-11 Engineers employed in petroleum production are interesting themselves in this work as well as in methods of applying the fundamental data available to the solution of their various problems. Recently a number of papers have been published in which applications of phase behavior have been made to specific cases pertaining to critical phenomena.l2-16 Little effort, however, has been made in the literature to show the relation between changes occurring in the critical region and the more common phase behavior, therefore it is believed that a presentation of the fundamentals of phase behavior with reference to hydrocarbons is timely. Study of phase behavior is not new. In the metallurgical field, knowledge of heterogeneous equilibria has advanced tremendously, particularly with reference to solid-solid and solid-liquid behavior. Much is known about vapor-liquid equilibria too, but few engineers are familiar with this subject. Definition of Terms In a discussion of this sort, a definition of terms used is most important. Such terms as "pressure," "temperature" and "volume" need little definition other than mention of the units in which they are considered. Pressure is expressed in pounds per square inch absolute. Temperature is usually expressed as degrees Fahrenheit or degrees Rankine. In considering thermodynamic and phase behavior, the use of the absolute, Rankine, scale is desirable. Volume is expressed as specific volume, such as cubic feet per pound. This will be recognized as the reciprocal of the specific weight. In considering systems composed of more than one component, it is sometimes desirable to consider molal

Jan 1, 1940

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