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By T. S. Fuller

The tensile properties of steels at elevated temperatures have been studied by numerous investigatorsll primarily for the purpose of determining their suitability for structural uses. Tests with this objective have been confined largely to the temperature range of approximately 20" to 500' C., because of the rapidly decreasing tensile strength at the latter temperature. Tests have also been extended to higher temperatures2 for the purpose of determining the most suitable forging range. This temperature range is also of theoretical interest. The phenomenon if increased tensile strength and decreased ductility .in the so-called "blue-heat" range, approximately 200" to 300" C., is well known. It was suggested to the Bureau early in 1926 that a study of the properties of rail steels in this temperature range might prove of interest in relation to the studies of transverse-fissure failures in rails. There were available from another investigation3 several new rails from several different heats made to approximately the same specification requirements, the complete manufacturing histories of which were known. It was decided to determine, at least in the preliminary series of tests, only the ultimate tensile strength, elongation and reduction of area, because of the difficulty, time and cost involved in determining the proportional limit and yield point at elevated temperatures.

Jan 1, 1930

By Herbert Hoover, Harlod Washburn

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By Harlod Washburn, Herbert Hoover

This paper is in the nature of a rough preliminary report on the progress that has been made in the application of the mass spectrometer to various problems arising in the petroleum industry. A few years ago the authors considered a number of the problems that were arising in the qualitative and quantitative measurement of small amounts of hydrocarbons. The methods available of making analyses by chemical techniques appeared to leave much room for improvement. Without going into the reasons at this point, attention was turned to the possibility of employing physical instead of chemical methods of accomplishing the desired results. A preliminary investigation disclosed that the mass spectrometer presented a possibility of solving many problems which could not easily be accomplished by other methods. Work was begun in developing the necessary apparatus and technique. A great deal of encouragement and many valuable suggestions were received from Dr. Robert A. Millikan, Dr. W. R. Smythe, and Dr. W. N. Lacey, of the California Institute of Technology, and from Dr. E. 0. Lawrence, who recently received the Nobel Prize, of the University of California. The authors particularly wish to acknowledge the very great willingness of these outstanding scientists to be helpful in solving many of the problems that were involved. So far as the authors are aware, this was the first application of the mass spectrometer to commercial work. The results were considerably better than had at first been anticipated. Briefly, it is possible to run a qualitative and quantitative analysis of an unknown mixture of hydrocarbon gases, with an accuracy of better than plus or minus 5 per cent of each of the various constituents. An exceedingly high degree of sensitivity has been obtained, and a relatively short time is required to complete an analysis. Furthermore, it is unnecessary to separate a mixture of gases into its various components in order to complete the analysis. The Mass Spectrometer The mass spectrometer should not be confused in any way with the optical 01 grating type of spectrograph now in general use. The operation of the mass spectrometer is entirely different in principle and bears practically no resemblance to the optical or grating instruments. The original conception and development of the mass spectrometer dates from and is generally credited to Aston, of Cambridge, England. An early accomplishment of his research, about 20 years ago, was the discovery that the inert gas neon was actually a mixture of two kinds of atoms, one of the atomic weight 20 and the other of atomic weight 22. These two components occurred mixed in such proportion as to yield the usual atomic weight of 20.2. The study was continued and most of the elements were shown to be mixtures of components whose atomic weights can, to in

Jan 1, 1941

By Donald L. Katz

The equilibrium constants developed by Souders, Selheimer and Brown1' have been very useful tools in predicting vapor-liquid equilibria during the past five years. Their equilibrium constants were computed by assuming ideal solutions and recognizing the deviations of vapors from ideal gas laws. The same fundamental concepts were used by Lewis and co-workers8 for predicting vaporization phenomena by means of fugacities. The equilibrium constant is defined by equation 1: y\x =K [1] in which K = equilibrium constant, y = mol fraction of a constituent in the vapor phase, x = mol fraction of the constituent in the equilibrium liquid phase. The equilibrium constants are a function of temperature and pressure and might be considered as replacing the ratio of the vapor pressure to the total pressure of Raoult's law. They may be used to compute the vapor or saturation pressure of a liquid or the dew point of a vapor for any pressure or temperature from the analysis of the mixture much as Raoult's law is used. Likewise, the quantity of a mixture that will vaporize at any equilibrium temperature and pressure and the composition of the vapor and liquid may be calculated. The purpose of this paper is to review the available equilibrium data of interest in petroleum production, to discuss the auxiliary physical properties of the hydrocarbons, and to present typical uses of the equilibrium constants. The particular applications chosen are the computation of the results of stage separation of crude oil and natural gas, the calcula: tion of a pressure-volume curve of a crude oil-natural gas mixture, and information gleaned from a consideration of reservoir equilibria.

Jan 1, 1938

By Eugene A. Stephenson

In most instances the fluids produced from underground reservoirs have been described as they appear at the surface, and usually it has not been necessary to distinguish between surface and reservoir phases. More recently it has become imperative to recognize the fact that changes in phase may occur between the reservoir and the receiving unit. The simple terminology of "wet" and "dry" gases and "crude petroleum oil" served our needs fairly well in the shallow, low-temperature and low-pressure fields. It has been left to the legislatures, regulatory commissions, and courts to decide whether a field is or was a gas field, an oil field, or both. This they have done by direct definition and also by implication. For example, in Texas:' (d) The term "gas well" is any well (a) which produces natural gas not associated or blended with crude petroleum oil at the time of production, or (b) which produces more than one hundred thousand (100,000) cubic feet of natural gas to each barrel of crude petroleum oil from the same producing horizon, or (c) which produces natural gas from a formation or producing horizon productive of gas only encountered in a well bore through which crude petroleum oil is also produced through the inside of another string of casing. (e) The term "oil well" is any well which produces one (1) barrel or more of crude petroleum oil to each one hundred thousand (100,000) cubic feet of natural gas. In the state of Louisiana, the same general result is achieved largely by the following paragraph :* Wells producing both oil and gas shall not waste or blow into the air an amount of gas of more value at three cents per thousand cubic feet, than the market value of the oil recovered. The Commissioner of Conservation shall allow a reasonable time to determine the status of any well. This means that for wells making both oil and gas, if n represents the price of oil in dollars, and x the allowable gas waste expressed in M cu. ft. Per day,

Jan 1, 1938

By Stuart E. Buckley

The application of hydrocarbon equilibrium data to various problems encountered in refining and in natural gasoline recovery is an old and well established practice. Both generalized data and data on specific hydrocarbon systems have been made available by a number of investigators. More recently such data have been applied to the relations governing the separation of oil and gas both in the reservoir and at the surface. Most of the applications to production problems, however, have been based upon examinations of surface samples of oil and gas. This paper describes a technique that has been used satisfactorily in a number of cases to calculate directly from the hydrocarbon analysis of and auxiliary laboratory data on a subsurface sample of the reservoir fluid the behavior of the oil and gas during the various stages of separation at the surface incident to production. Types of Information Calculated The system of calculations is not designed to supplant field data, but rather to correlate with them laboratory data obtained under controlled conditions in order to obtain a more complete and exact picture than usually is possible through the use of field data alone. The chief advantage of the calculations is the possibility of their use at a minimum of both time and expense to determine completely the effect of any possible operating technique upon each of the following: (1) The gas-oil ratio resulting from liberation of the dissolved gas; (2) the composition and gasoline content of the liberated gas; (3) the composition and gravity of the residual oil; (4) the amount and composition of the gas liberated upon flashing the oil from the separator to the stock tank; (5) the shrinkage of the oil in passing from the reservoir to the stock tank. This information is frequently essential to the correct determination of the advisability of installing a natural gasoline plant, to design such a plant to take care of seasonal production, and to determine the optimum separator pressures to carry in various parts of a field.

Jan 1, 1938

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By M. C. Leverett

Knowledge of the theory underlying the behavior of mixtures of fluids in reservoir rocks is essential to the proper solution of certain types of problems in petroleum production, but is as yet incompletely developed. The object of this paper is to show the application of well established thermody-namic and physical principles to these problems, and thus to assist in the development of the basic theory. For convenience the problems to be considered here may be divided into two groups: 1. Static problems, involving only the static balance between capillary forces and those due to the difference in densities of the fluids; i.e., gravitational forces. 2. Dynamic problems, involving analysis of the motion oi mixtures of immiscible fluids in porous media under the influence of forces due to gravity, capillarity, and an impressed external pressure differential. Capillary Equilbrium in Sands Under this heading the static type of problem will be discussed and the results of experimental investigations on the capillary properties of unconsolidated sands will be presented. Although the discussion of this section is, in a sense, prefatory to the treatment of problems of mixture flow, the concepts developed here have considerable intrinsic importance apart from their ap-plication to flow problems. For, it is reason-able to postulate that the reservoir fluids are, owing to their long existence in undis- turbed mutual contact prior to exploitation, in substantial equilibrium. It follows that their distribution in the reservoir at the time of tapping should be entirely predictable from the theory of capillary equi librium, provided certain experimentally measurable properties of the reservoir rock are known. Knowledge of the distribution of the several fluids in the reservoir is, ol course, helpful in the estimation of reserves and in other problems. It is to be emphasized that throughout the discussion of capillary statics it is assumed that the fluids are in equilibrium from the capillary standpoint. Thus, water, where it is referred to as being in a reservoir, will be understood to be interstitial water, present at the time of drilling the reservoir, commonly termed "connate" water. The theory developed here is perfectly general for any porous solid, whether a carefully prepared unconsolidated sand or a natural sandstone from an oil reservoir. At present, however, only problems involving clean, unconsolidated sands can be made to yield numerical solutions, since only such sands have been adequately investigated experimentally. Experimental evaluation of the pertinent properties 01 natural reservoir rocks will permit the extension of the numerical treatment to problems involving these materials. We shall now consider in some detail the static equilibrium of fluid mixtures in porous solids: that is, the manner in which the reservoir fluids are distributed vertically whell the Forces due to capillarity are just balanccd by those due to gravitation.

Jan 1, 1941

By J. F. Fidiam, T. F. Ford, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By T. F. Ford, J. F. Fidiam, A. G. Loomis

It is only within the past 10 years that serious attempt appears to have been made to improve rotary drilling fluids by the application of the principles of colloid chemistry, although the use of chemicals to control the rheological properties of clay slips has long been known in the ceramic industry. The main difficulty apparently lay in the lack of a complete analysis of all of the functions of a drilling fluid in the drilling of the well, together with the lack of adequate consideration of how colloid science could be applied to secure these ends, and particularly how apparent antithetical properties of the fluid could be compromised. Thus one analvsisl of the many requirements of a drilling fluid proved conclusively that the viscosity should be low, in order that cuttings and entrained gas might be eliminated effi-ciently in the settling ditch, while the loss in carrying capacity accompanying low viscosity could be regained by increasing either the density of the mud or the upward velocity of the mud stream in the annular space of the well, and the danger of sticking of the drill stem due to rapid settling in case of enforced suspension of drilling operations could be eliminated by enhancing the thixotropic properties of the fluid. The desired properties of the drilling fluid having thus been established, it was a natural step to treat the fluid with vis-cosity-reducing chemicals, such as salts of weak organic acidsl for example, sodium tannate or gallate—and to adjust the pH to the alkaline side to such a degree of thixo-tropy as would give low viscosity and low yield point under the conditions of flow prevailing in the settling ditch, but rapid gelation and high yield point when quiescent in the annular space during shutdowns. In fact, flow in the settling ditch should be just short of turbulent while flow in the well, together with the flow of mud past the cuttings, is practically always turbulent. The use of chemicals other than those mentioned, such as Calgon (sodium hexametaphosphate) and certain other phosphates together with sodium tannate, has now become standard practice and it is the consensus that this method of treatment has proved to be an important step in the development of the art of drilling oil wells. It is safe to assume that the application of colloid chemical principles can also help in solving other outstanding problems of drilling fluids, such as the development of cheaper and more efficient viscosity reducers ; the development of chemicals that do not lose their effectiveness in a short time during drilling operations; the finding of chemicals to preserve the plastering properties of muds when concentrated brines are encountered or in drilling through salt beds; improvement in the plastering properties of poor muds by further defloc-culation, and, conversely, the prevention of excessive deflocculation of certain marine shales sometimes encountered; the preparation of muds suitable for the successful drilling of heaving shale formations; the finding 0f chemicals to treat the mud to prevent or to diminish lost circulation; the development 0f muds that will not impair 6

Jan 1, 1941

By Ralph J. Schilthis

Several investigators1-8 have reported evidence of the existence of native or connate water in oil-and-gas-bearing strata. Both water and salt have been detected in cores of oil sands that yielded oil and gas exclusively when produced. Electrical logs often reveal unexpectedly low resistivity through oil and gas sands, indicating the presence of some material that is a considerably better conductor of current than oil and gas. Furthermore, calculationsg of the oil and gas content of reservoirs based upon production and reservoir-pressure decline data indicate appreciably lower values than are arrived at under the assumption that the pore space is occupied completely by oil and gas. Origin and Occurrence of Connate Water in Oil-and-gas-bearing Formations The view has been expressed, 10-15 and is generally agreed upon, that the expulsion of oil and gas material from source beds and the subsequent migration and accumulation occurred in the presence of salt water. As the strata that usually form reservoirs for oil and gas were laid down by, or in the presence of, ancient seas, the pore space within the strata must have been saturated with salt water before the entrance of the oil and/or gas. Thus, the accumulation of oil and/or gas in the upper regions of structures suitable for reservoirs must have required displacement of the connate water therefrom. In the absence of any forces other than gravitational, it would be expected that the displacement of the connate water out of the zones finally occupied by gas and oil would be complete, and that the vertical distribution of gas, oil, and water in a reservoir would be strictly in the order of their densities. Apparently, however, surface and interfacial forces that will not permit complete segregation of the fluids are active within the capillary spaces comprising a reservoir. The effects of these forces on both accumulation and production of oil and gas have been the subject of study by a number of investigators.16-37 In general, the view is held that the character of most materials that make up the reservoir rock leads to preferential wetting of the rock by

Jan 1, 1938

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

In recent years there has been an increase of interest in the flow of gases at relatively high pressures. Hydrodynamic calculation of the energy losses in the flow of gases in conduits, as well as through the porous solid materials constituting natural petroleum reservoirs, requires a knowledge of the viscosity of the fluid at the pressure and temperature involved. Although there are numerous publications concerning the absolute viscosity † of hydrocarbon gases at atmospheric pressure, there appears to be little information available relating to the effect of pressure upon the viscosity of these gases. Voge133 determined the viscosity of methane at 32° F. and atmospheric pressure. His measurements at 32° F. were later substantiated by the measurements of Rankine and Smith20 at 63° and 212° F. Ishida14 also reported values for the viscosity of methane at atmospheric pressure. Trautz and Kurz30 measured the viscosity of propane at atmospheric pressure, from 83° to 530°F., by the use of a short capillary tube. Rap-penecker2' determined the viscosity of gaseous isopentane at elevated temperatures. Day6 made an accurate investigation of the effect of pressure upon the viscosity of n-pentane and isopentane at pressures from 2 lb. per sq. in.‡ to the vapor pressure at 77° F. (approximately 9.8 and 13.3 lb. per sq. in., respectively). Earhart7 reported data upon the viscosity of several natural gases measured by the long capillary-tube method. The viscosity of air, at atmospheric pressure and 73.4° F., was measured by Harrington9 by the rotating-cylinder method. Kellstrom15 has rec,ently made an elaborate investigation of the viscosity of air at atmospheric pressure. The latter work is perhaps the most accurate investigation of the viscosity of a gas that has been made.

Jan 1, 1938

By J. H Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By J. H. Lightfoot, Stuart E. Buckley

Deep drilling has led to the development of numerous pools which yield products consisting predominantly of natural gas accompanied by high-gravity water-white or slightly straw-colored liquid. Yields of this "condensate" or "distillate," as it is commonly called, vary from traces to over a hundred barrels per million cubic feet of gas. The fact that this liquid exists in the reservoir as an integral part of the gas phase and is formed by condensation attending simultaneous reduction of pressure and temperature after its entry into the well was apparently first recognized about 1932.l The nature of the physical phenomena involved in this condensation was clarified for the petroleum industry in 1933 by a report by Sage, Schaafsma, and Lacey2 of the results of an experimental investigation of the behavior of mixtures of methane and propane. Search of the literature has revealed that the condensation of liquid from gaseous mixtures by isothermal pressure reduction is not a new discovery. Kuenen was led by theoretical considerations to expect such a phenomenon, and in 1892 reported3 the results of experimental verification of his deductions. This was followed by a considerable amount of work on the phase relations of mixtures by Kuenen 4,5,6 and by 0thers,7,8 mostly in European universities. Since 1930 investigators in this country have reported experimental data on the properties and behavior of a number of hydrocarbon systems."' It is now generally known that in the presence of natural gas the solubility in the gas phase of the heavier and normally liquid hydrocarbons increases rapidly with increasing pressure above 500 to 1000 Ib. per sq. in. Thus, at pressures of 2500 Ib. per sq. in. or higher a gas may contain appreciable quantities of hydrocarbons with normal boiling points as high as 6o0°F., which in turn may be condensed from the gas phase by the reduction of their solubility therein attending pressure reduc-tion. The combined effects of pressure and temperature on condensation and vaporiza-tioi of mixtures are most readily visualized by the study of phase diagrams. Since the construction, application, and interpreta-tion of such diagrams have been described fully in readily available literature, 18-20 this paper will not review the theoretical aspects of this subject. While the behavior of gas-distillate sys tems is now clearly understood, at least in a qualitative way, most of the published work deals with the results of laboratory studies of binary systems or of synthetic mixtures of hydrocarbons, and although several systematic investigations of the effects of separator pressure and temperature on the yields of liquid product from gas-distillate wells have been made21,12z it appears that in all cases the limitations have precluded the construction of even approximately complete phase diagrams for naturally occurring systems. There has 2

Jan 1, 1941

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By C. E. Webber

The economical recovery of the valuable constituents from the effluent of gas-con-densate wells has developed into a problem of balancing the cost of recovery against the cost of compressing the residual gas back into the formation. A possible method of extracting the gasoline and distillate from the natural gas is by oil absorption at high pressures. In order to design and evaluate an absorption plant, fundamental data on the composition of the coexisting hydro- carbon vapor and liquid phases at various temperatures and pressures are essential. A review of the literature indicated that the necessary data for the design of such plants are lacking. The nearest approach to desired published data is that of Katz and Hackmuth,~ who experimentally deter-mined the composition of the coexisting vapor and liquid phases in a natural gas-crude oil system at pressures up to 3000 lb. per sq. in. and at temperatures from 40' to zoo°F. This paper presents the results of the experimental determination of the equilib-rium distribution of the hydrocarbons methane through hexane between natural gas and a typical absorber oil. The ranges of temperature and pressure chosen were from 33' to r8oUF. and from 100 to 5000 lb. per sq. inch. Materials The absorber oil was a typical naturally occurring, Straw-colored distillate that had previously been steam-distilled to an initial boiling point of 300 F. The physical and chemical properties, including the results of an Engler distillation, are presented in Table I. A large volume of this oil was obtained and it was used throughout the complete set of experiments. Table i.—Properties of the Absorption Oil Gravity .......................... . . 32.5' A.P.1. Molecular weight by benzene freezing- point depression.................. 183 Viscosity, poises; at 100°F........... 0.0a80 At 200°F...................... 0.0102 Composition, PeR Cent Aromatics........ 24.0 Naphthenes..... 36.7 unsaturates,Aromatics...... .I24.00.3 1 Parafins Naphthenes.....36.7 39.o EngLeR Distillation Per Cent /ncg. F. Per Cent Dez. P. Initial boilins rmint.. 300 I 60....... 523 5.................. 402 I 70....... 538 10.................. 421 180....... 557 20.................. 462 90....... 570 30.................. 480 1 95....... 623 40.................. 49 .................1 511 Residue, z .o per cent; loss, 0.3 per cent. See refrence I. The n-hexane was obtained from the Ohio Chemical and Manufacturing Co., Cleveland, Ohio. This liquid had a boiling range of from 149" to 152.6'F., with a density of 0.667 at 60°F. and a molecular weight of 85 by benzene freezing-point depression. The propane, isobutane, wbu-tane, isopentane and n-pentane were ob-ta,ined from the Philgas Department of the Phillips Petroleum Co. Certified analyses of these compounds showed their purity to be in excess of 99.5 per cent and they were riot further purified.

Jan 1, 1941

By J. R. Coleman, G. L. Corrigan

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941

By G. L. Corrigan, J. R. Coleman

FOUR factors that largely determine the end product obtained when cement and water are mixed are the chemical composi-tion of the cement, the fineness to which the cement is ground, the amount of mixing water used, and the procedure used in mixing the slurry. In order to study the effect of two of these factors, the other two, the chemical composition and method of mixing, are kept constant, leaving as variables fineness and water-cement ratio. Through years of experimentation and usage it has been well established that the reduction of cement clinker to a very fine state by grinding improves its cementing value, principally because the reaction between cement and water takes place only at the surface of the cement particle, further action being hindered by the accumulation of reaction products that tend to coat the unreacted material. Therefore, the moE finety-ground %cement, and the greater the surface exposed in propor-tion to its mass, the more rapid is the The work covered by this paper was done by the authors in pursuance of graduate studies in the ~epartment of petroleum Engineering at The University of Texas. The present paper is a condensation of a more detailed DaDer from which, for brevity, information such as the procedure for determining permeability and some of the discussion and procedure relevant to slurry volumes and fineness of cement have bsen deleted. It was felt that this information would not be of interest to most readers and should be outside the scope of this paper. Manuscript received at the office of the Institute Aug. 16, 1940. Issued as T.P. 1266 in Petroleum Technology. January 1941. hydration rate. Similarly, the greater the surface exposed, the greater the proportion of the cement that reacts, and the lower the amount of residue that is unreacted and so remains inert and unable to make any contribution to cementing properties.] Although it is more expensive to manufacture a finely ground cement than a coarser cement, the advantages of fine grinding of construction cements were so marked that the fineness of cement has increased considerably in past years. When the manufacture of special oil-well cements was begun, it was necessary to consider properties of cement that previously were considered of minor importance, foremost of these being pumpability. Since, with the water-cement ratio constant, a finely ground cement will produce a neat slurry of higher consistency and shorter time of pumpability than will a coarser cement, there is a tendency to grind oil-well cements to a lower degree of fineness. Therefore, in order to produce oil-well cements that will make a slurry having a long time of pumpability, cements are manufactured that because of their coarseness generally are Poorer cementing materials than some of the more finely ground construction and on the other hand, often it is necessary to Pump oil-well cements for long periods of time to place them properly behind a string of casing in a deep well, and since high strength is not of foremost importance for such cement, there is room for considerable controversy concening the proper fineness range.

Jan 1, 1941