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By Ralph J. Schilthuis, William Hurst

The nature of the forces that are important in producing the oil in the East Texas field and the manner in which these forces are affected by the rate of production have always been problems of outstanding interest. These questions are of great interest to the industry as a whole on account of the economic importance of the East Texas field and to the engineers in particular on account of the unique character and behavior of the field. Subsurface pressure data throughout the field have been collected systematically, so that a quite complete history of the reservoir pressures has been kept as the field has been developed and produced. Subsurface samples of the oil and gas have been taken and these have been examined to obtain data on the physical properties of the reservoir fluids under the actual conditions of temperature and pressure. All of these data have been valuable because they have afforded the basis for a careful study of the means by which the oil is produced. It is the purpose of this discussion first to point out several of the important facts revealed by the data mentioned and then to describe studies that have been made concerning the interpretation of these facts. Reservoir Pressure Data and Properties of Oil The reservoir pressure data on the East Texas field have shown conclusively that the pressures are readily affected by changes in the rate at which the field is produced. This can well be seen in Fig. 1, where the average reservoir pressures obtained from time to time are plotted with the daily production rates and the cumulative production of the field. It is noted that the average reservoir pressure has declined irregularly, depending upon the rate of production, from the estimated original value of 1625 Ib. per sq. in. to the value of 1228 lb. per sq. in. observed for Aug. 11,1934. The decline in pressure has been more rapid at the higher rates of production than at the lower rates. In contrast, the average reservoir pressure has increased, on several occasions, upon reduction of the withdrawal rate from a high value to a lower value. The reservoir pressure data have also shown that a definite gradient in pressure has existed across the field from west to east since the begin-

Jan 1, 1935

By Walter Miller

The broad picture of petroleum refining engineering during 1934 continued to show a tendency in the direction of highly specialized processing improvements, particularly in manufacture of lubricating oil. The slowing up of the trend toward higher octane products in non-premium gasoline noticed in 1933 was definitely established as a fact by 1934 development, with just a slight indication of recession. No outstanding engineering achievements can be credited to 1934 in refinery cracking, unless the completion and successful operation of the 30,000-bbl. crude capacity combination cracking and skimming unit at Texas City, Texas, and a 20,000-bbl. similar unit in the East can be listed as such. Development and improvement was largely a continuation of previous lines of endeavor. Such trend as there is shows a continnation in the direction of very large integrated skimming and cracking units. A lessening of the cost of ethyl lead, coupled with the reaching of the octane number "ceiling," kept the subject of "reforming" low-octane gasoline into high-octane products pretty well in the background. Considerable interest, however, was shown during the year in cracking and polymerizing of refinery gases into high-octane motor fuel. The commercial development and application of this activity was greater in 1934 than during any previous year. Fair yields of gasoline of satisfactory stability and high antiknock value were reported, ranging from 2 to 8 gal. per 1000 cu. ft. of fixed refinery gas, yields varying with both the nature of refinery gas treated and processing methods. Assuming economic feasibility, regarding which there is still difference of opinion, gas polymerization offers the industry a possible outlet for its gases more in keeping with its basic chemical composition and value. The increased interest of railroads and heavy-duty truck and tractor manufacturers served to focus more attention on diesel fuels. The publicity given the Union Pacific diesel train, the Burlington "Zephyr" and others operated on special diesel fuels served to revive the intimations and fears of several years ago as to the ultimate replacement of the gasoline motor by diesel engines in even the passenger car field. How-

Jan 1, 1935

By Walter Miller

Advancement in engineering in the refining industry during 1933 might be likened to the jagged flame of a poor wick-test kerosene—a few outstanding high spots, but not broadly spectacular. Economic conditions were unsatisfactory for the first six or eight months, but the improvement in the latter part of the year had some immediate effect in stimulating new designing and building. The national legislative program involving the industry drew the attention of executives away from petroleum technology to some extent. The National Recovery Act, and its offspring, the Petroleum Code, demanded deep and continued study to put the machinery into smooth motion. From a purely technical engineering stand, therefore, the emergency measures might be considered a temporary brake on progress. The ultimate effect, if the whole industry can get back "out of the red," may well be a more than expected advance. Of course, petroleum technologists and engineers, including both those engaged within and those busy in designing and building for the industry, continued their efforts, and much of the results of their work will undoubtedly see the light of day under the improved economic conditions, which bid fair to stay with us. There was little improvement during 1933 in atmospheric distillation, sweetening processes, or furnace design, but experimentation during the year on these subjects may materialize into distinct advances. The trend toward compact distilling and fractionating equipment, especially in the Appalachian district, deserves noting. A number of refineries in that district replaced obsolete shell still units with up-to-date tube stills and efficient fractionating towers, both for the better separation of lubricating fractions from the crude and for improving the boiling range of the gasoline. A number of small skimming and topping plants in flush fields, such as East Texas, which felt the pinch of production control, were forced to shut down, but the stronger among them are consolidating their positions by installing cracking equipment and in some cases more modern crude-distillation units. Motor Fuel For the first time in many years a reviewer is able to point to at least a temporary cessation in the competitive race in the manufacturing

Jan 1, 1934

By Walter Miller

Any annual review of engineering progress in petroleum refining must of necessity include many features mentioned in earlier reviews. Advances do not spring mushroom fashion to wide acceptance overnight, but rather resemble rolling snowballs, gathering size and velocity as they progress. The new ideas of one year develop through the course of scattered adoption and testing during following years, to be ultimately discarded or to become an integral part of refinery engineering and operation. Polymerization and Cracking As an illustration, the publicity given to the polymerization and cracking of petroleum gases during the year has given many the impression that this is a new art. But patent and technical literature have disclosed active work on the problem dating back a decade or more and a unit capable of making 100 bbl. a day of polymer gasoline was constructed as early as 1930. Important strides have been made during 1935 looking to the more general commercialization of available processes, and some four important groups are furthering this work. In addition to the production of liquid products for inclusion as a constituent of commercial motor fuel, polymerization has also been a factor leading to the installation of a plant at the Houston refinery of The Shell Petroleum Corporation for manufacturing isooctane for aviation use, by making available dibutylene for catalytic hydrogenation Polymerization is not confined to unsaturated hydrocarbon gases as a source of raw material, and has been extended to include a preliminary decomposition of normal saturated gases under suitable heat and pressure conditions into the unsaturated types, which can then be used as raw material for the polymerization process. Thus there is opened up the possibility of eventually using large quantities of natural gas in the manufacture of high-grade motor fuels, although the early commercial growth will be largely on cracking still gases for economic reasons. Such utilization will result in a somewhat lowered drain on crude-oil reserves and a partial elimination of the

Jan 1, 1936

By Walter Miller

Any annual review of engineering progress in petroleum refining must of necessity include many features mentioned in earlier reviews. Advances do not spring mushroom fashion to wide acceptance overnight, but rather resemble rolling snowballs, gathering size and velocity as they progress. The new ideas of one year develop through the course of scattered adoption and testing during following years, to be ultimately discarded or to become an integral part of refinery engineering and operation. Polymerization and Cracking As an illustration, the publicity given to the polymerization and cracking of petroleum gases during the year has given many the impression that this is a new art. But patent and technical literature have disclosed active work on the problem dating back a decade or more and a unit capable of making 100 bbl. a day of polymer gasoline was constructed as early as 1930. Important strides have been made during 1935 looking to the more general commercialization of available processes, and some four important groups are furthering this work. In addition to the production of liquid products for inclusion as a constituent of commercial motor fuel, polymerization has also been a factor leading to the installation of a plant at the Houston refinery of The Shell Petroleum Corporation for manufacturing isooctane for aviation use, by making available dibutylene for catalytic hydrogenation Polymerization is not confined to unsaturated hydrocarbon gases as a source of raw material, and has been extended to include a preliminary decomposition of normal saturated gases under suitable heat and pressure conditions into the unsaturated types, which can then be used as raw material for the polymerization process. Thus there is opened up the possibility of eventually using large quantities of natural gas in the manufacture of high-grade motor fuels, although the early commercial growth will be largely on cracking still gases for economic reasons. Such utilization will result in a somewhat lowered drain on crude-oil reserves and a partial elimination of the

Jan 1, 1936

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government's hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Walter Miller

BY the beginning of 1945 the output of petroleum products for war had reached a volume and a rate of growth which practically assured all requirements so long as war continued. The programs for making gasoline, lubricating oils of required quality, toluene for T.N.T., and chemicals for manufacture of synthetic rubber, as well as numerous other lesser petroleum products, were all well in hand, and unless catastrophic developments occurred there was no doubt of the ability of the industry to meet all demands. The end of the fighting found the refining industry working at top capacity on war commodities, but also in position to convert quickly into peacetime civilian production. 100-octane Aviation Gasoline Production of the vital 100-octane aviation gasoline, starting with approximately 44,000- bbl. daily capacity at our entry into the war, reached a top of 525,000 bbl. a day in the United States by the end of hostilities. With 75,- bbl. from other Allied sources, the grand total was 600,000 bbl., or 25,000,000 gal. each 24 hr. available to the armed forces had fighting continued. At times it was a close race between requirements and production, but never were any important military operations involving the use of high-octane aviation gasoline held up or delayed for lack of sufficient output of such material. The undivided effort of the entire refining industry in full cooperation with the Government made this record possible. Little diminution in output followed the German surrender on May 7. Plans called for a correspondingly greater activity for the Japanese war and possibly for well into 1946. But when the Japanese sued for peace on Aug. 10 most contracts were quickly canceled. Substantial stocks, reputed to be somewhere between 20,000,000 to 30,000,000 bbl., built up largely between V-E and V-J day pending organization of the larger Japanese war program envisaged after Germany gave up, were in the Government's hands in this country, in addition to working stocks in the war areas. Toluene and Lubricating Oil Requirements for toluene for T.N.T. increased rapidly as bombing speeded UP with increasing control of the air by the Allies in Europe and Asia. Production in excess of T.N.T. requirements which had been going into 1000-Octane aviation fuel blending during 1943 and 1944 was again drawn into explosive manufacture early in 1945. In anticipation of the war continuing into 1946, two new plants were ordered constructed, the decision being announced in April, plans calling for one of them to get into production about the end of 1945, the other in the first quarter of 1946. Both of these projects were later canceled as victory made it evident that the additional supplies would not be needed. Production was

Jan 1, 1946

By Walter Miller

A surprising development during the year was the continued high demand for petroleum products and the high level of crude oil charges to the stills. Generally speaking, the petroleum industry during 1946 succeeded in producing a greater quantity of crude oil and petroleum products than in any of the war years, and considerably exceeded the production of any prewar year. Daily crude still charges averaged between 4,700,000 and 4,800,000 bbl per day for 1946 and about equaled the 1945 record, although most pessimistic 1945 guesses, predictions, or fears ranged, for 1946, from only 3,900,000 to 4,400,000 bbl per day. In spite of the high crude charge to the stills, total stock of crude oil was higher at the end of the year by some 7,000,000 to 8,000,000 bbl. A similar story holds regarding stocks of the principal refined products. Gasoline on hand at year's end was two to three million barrels lower, and was considered low for the expected demand during the coming high consuming season, while stocks of light and heavy fuel oils, although some higher than a year previous, hardly reached a comfortable level. The trend in gasoline of high octane number, which has resulted in a marked rise in. the antiknock quality by the end of 1945 (five or six numbers higher than during the war and one number higher than the prewar quality of civilian motor gasoline of 1941) was abruptly arrested by an acute shortage of metallic lead for manufacturing tetraethyl lead. Government action in the form of lead price control, rationing, and the setting of octane ceiling specifications to conform to the reduced ethyl lead compound available were enforced until abrogated at the end of the year. It will be interesting to see how rapidly the octane levels will resume the rising trend, as more metallic lead slowly becomes available for making greater quantities of ethyl lead compound. As octane quality rises over present levels the disadvantage of the refiner without catalytic cracking equipment will increase. Gasoline made by catalytic cracking, without addition of ethyl lead, approximates 77 octane by the official ASTM Motor Method test, compared with 66 for gasoline generally similar in volatility made by the older thermal cracking operation. Catalytic gasoline shows an even greater improvement in the Research octane number, the comparison being roughly 86 Research versus 71 Research octane for the thermal cracked product. This higher differential in Research octane is credited by many, although not universally so, as contributing to better road performance, and consequently resulting in a more desirable product marketwise. In some parts of the country a premium of roughly one fourth cent per gallon is now being paid for gasoline with higher Research octane made possible by including catalytic cracked product in the final blends. If such price differentials in favor of catalytic gaso-

Jan 1, 1947

By Walter Miller

A surprising development during the year was the continued high demand for petroleum products and the high level of crude oil charges to the stills. Generally speaking, the petroleum industry during 1946 succeeded in producing a greater quantity of crude oil and petroleum products than in any of the war years, and considerably exceeded the production of any prewar year. Daily crude still charges averaged between 4,700,000 and 4,800,000 bbl per day for 1946 and about equaled the 1945 record, although most pessimistic 1945 guesses, predictions, or fears ranged, for 1946, from only 3,900,000 to 4,400,000 bbl per day. In spite of the high crude charge to the stills, total stock of crude oil was higher at the end of the year by some 7,000,000 to 8,000,000 bbl. A similar story holds regarding stocks of the principal refined products. Gasoline on hand at year's end was two to three million barrels lower, and was considered low for the expected demand during the coming high consuming season, while stocks of light and heavy fuel oils, although some higher than a year previous, hardly reached a comfortable level. The trend in gasoline of high octane number, which has resulted in a marked rise in. the antiknock quality by the end of 1945 (five or six numbers higher than during the war and one number higher than the prewar quality of civilian motor gasoline of 1941) was abruptly arrested by an acute shortage of metallic lead for manufacturing tetraethyl lead. Government action in the form of lead price control, rationing, and the setting of octane ceiling specifications to conform to the reduced ethyl lead compound available were enforced until abrogated at the end of the year. It will be interesting to see how rapidly the octane levels will resume the rising trend, as more metallic lead slowly becomes available for making greater quantities of ethyl lead compound. As octane quality rises over present levels the disadvantage of the refiner without catalytic cracking equipment will increase. Gasoline made by catalytic cracking, without addition of ethyl lead, approximates 77 octane by the official ASTM Motor Method test, compared with 66 for gasoline generally similar in volatility made by the older thermal cracking operation. Catalytic gasoline shows an even greater improvement in the Research octane number, the comparison being roughly 86 Research versus 71 Research octane for the thermal cracked product. This higher differential in Research octane is credited by many, although not universally so, as contributing to better road performance, and consequently resulting in a more desirable product marketwise. In some parts of the country a premium of roughly one fourth cent per gallon is now being paid for gasoline with higher Research octane made possible by including catalytic cracked product in the final blends. If such price differentials in favor of catalytic gaso-

Jan 1, 1947

By E. Brunner, E. S. Mardock

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By E. S. Mardock, E. Brunner

A method of measuring oil saturations in cores or sand packs by neutron scattering is described. This method permits local SatUrations to be measured in a core enclosed in a steel pressure vessel without interrupting the flow. calibration data and a saturation distribution measurement obtained with the apparatus are included by way of illustration. Introduction In laboratory flow experiments designed to study the mechanism of oil production it is frequently necessary to measure the oil saturation in a core or sand pack containing Oil, gas, and perhaps brine. It is sometimes desirable that the saturation measurement refer to a relatively small portion of the core, so as to eliminate end effects; that it be made without interrupting the flow, and that it be applicable to a core enclosed in a steel Pressure vessel capable Of withstanding the Pressures encountered in petroleum reservoirs. None of the usual methods of measuring saturation meets all Of these requirements. To measure the gas saturation by observing the apparent compressibility of the gaseous Phase1 would require the interruption of the flow and would give an average saturation for the whole core. An electrical conductivity method is available for measuring brine saturations,2,3 but it is not applicable to oil. A radioactive tracer might be used if a suitable substance could be found that would dissolve in the oil, emit gamma radiation, and not be adsorbed on the sand, the steel core holder, or in an aqueous- phase. The large gamma-ray background from the mass of radioactive oil in other parts of the apparatus might, however, be undesirable. There remain for the saturation measurement methods involving the absorption or scattering of some penetrating radiation produced outside the apparatus. It might be possible to use X-rays or gamma rays; but these radiations would be so much less strongly absorbed and scattered by the oil than by the steel walls of the core holder and by the sand that it seems doubtful that much precision could be attained. In a beam of neutrons, however, there is a radiation that is very penetrating and, moreover, its scattering by substances containing hydrogen, such as oil, is qualitatively different from that occasioned by other materials. It would seem possible, and has proved to be quite practicable, to measure oil saturations accurately under the required conditions by means of neutron scattering. The first, to our knowledge, to suggest neutron scattering as a means of measuring oil saturation were F. Brans and ,. A. Bottema,4 of the Amsterdam laboratories of the Bataafache Petroleum Maatschappij, who made a few preliminary experiments to test the method while they were engaged in exploring the possibilities of neutrons for well-logging purposes. A comprehensive account of neutrons and their behavior will be found, together

Jan 1, 1946

By R. L. Boyer, F. Morgan, M. Muskat

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-' In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By M. Muskat, R. L. Boyer, F. Morgan

In the last several years a type of application of the fundamental permeability-saturation relationships has been developed which offers great promise in the interpretation of general reservoir performance.l-' In these developments no attempt is made to solve the detailed flow dynamics in actual oil and gas-producing systems. That problem still remains unsolved. But the permeability-saturation phenomena are incorporated in the analysis of oil-producing reservoirs in a manner such as to reflect the true role they play in controlling the gross reservoir behavior. In particular, they are introduced in such a manner as to determine the gas-oil ratio of the production at any stage of depletion, and, when combined explicitly with the so-called material-balance principles in differential form, one can obtain a differential equation describing completely the average pressure and gas-oil-ratio history of oil-producing reservoirs. While thus far they have been applied directly only to gas-drive reservoirs, they are susceptible of extension to partial water-drive systems, and qualitatively the same principles are of value in the study Of complete water-drive reservoirs. Moreover, in addition to giving a means for computing the variation of the reservoir pressure and gas-oil ratios vs. the cumulative production, they automatically lead to predictions of the gross ultimate recovery under natural depletion—and when properly extended they provide means for predicting the ultimate recovery under gas or water injection. The data required for such applications are the initial fluid distribution in the producing section, the pressure-volume-temperature data on the gas and liquid phases, and the permeability-saturation relationship for the oil-satuiated zone. The former can be obtained with reasonable accuracy by methods that are well established and available throughout the industry. The permeability-saturation data, however, involve techniques that are not at all standardized. In fact, only

Jan 1, 1947

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By Norris Johnston, Carrol M. Beeson

The gravimetric-vacuum distillation method was developed to permit rapid and accurate determinations of the oil-water ratios of small samples or sands containing little oil. In addition, the samples usually are so well cleaned and so little altered by the distillation at reduced pressure that rapid estimations of other physical properties may be made with the evacuated cores. Requiring only elementary glass-blowing technique, the distilling tubes and traps used in determining oil-water ratios were easily fashioned from the usual glassware. A sketch and description are given of the necessary apparatus, including the cylindrical electrical heaters. The procedure, requiring about 40 min., consists in raising the temperature and maintaining it between 675' and 725°F. for at least 10 min. while the pressure is held between I and 2 mm. Hg. The fluids condensed in the trap (cooled by a mixture of kerosine and solid carbon dioxide) are separated in a centrifuge and the volume of water is recorded. Determination of changes in weight with an analytical balance of all parts of the apparatus permits computation of weight of oil distilled and total weight of oil recovered. Introduction In determining the oil-water ratios of core samples, distillation at atmospheric pressurel-5 has proved to be sufficiently reliable for samples containing moderate quantities of oil. Since small samples and sands with little oil are encountered, how- ever, it appeared advisable to develop a method that would be applicable under these circumstances. Thegravimetric-extraction procedure1,6-9 undoubtedly is very reliable and could be used in all tests, but the time consumed in the determination would often delay field operations. This would be especially true when dealing with tight sands or viscous oils, both of which retard the extraction process. Accordingly, the gravimetric-vacuum distillation method was developed in order to combine the good features of both of the older methods; that is, accuracy and speed. By reducing the pressure, it was found possible to perform the distillation at a temperature that permits the use of glass apparatus, all parts of which can be weighed on an analytical balance. Thus, the fluids may be removed quickly from the core, the water is readily trapped and measured, and the loss in weight of the core is easily determined. In addition, the total weight of material condensed in the distilling tube and in the trap provides a method of determining the oil-water ratio that is practically independent of the one involving the loss in weight of the sample. The use of vacuum not only permits as much accuracy as does the gravimetric-extraction process, but it actually allows an increase in speed over the atmospheric-distillation method, because of the time required to cool the metal pots from about 1200°F. between runs. More important yet, the innovation makes possible the almost immediate reporting of permeability, and saturation, which is impossible

Jan 1, 1946

By C. M. Moncrief, B C. Craft

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By C. M. Moncrief

A bentonite-clay drilling mud when treated with tetrasodium pyroarsenate underwent substantially the same reduction in viscosity and water loss as when treated with the complex phosphates. The complex arsenate showed a slightly higher reversion after heating; the other arsenates showed poor viscosity-reducing properties. Introduction During the past 10 years the chemical control of drilling mud has become of major importance in affecting the successful drilling and working over of wells. The desired properties of drilling mud have been well established, and in obtaining these characteristics there has developed a large market for viscosity-reducing chemicals. Viscosity reduction produced by humic acid, tannic acid, sodium silicate, sodium tannate, Calgon, and the complex phosphates has been described by Loomis, Ford, and Fidiam.l The effects Of treatment with complex phosphates and ammonium PolyPhosPhates on the rheological properties of muds were investigated by Fancher2 and the alkali vanadates have been described by Williams.3 Laboratory Investigations It is the purpose of this paper to point out the effects of arsenates in controlling the viscosity and gelling characteristics of a drilling mud. Viscosities and gel strengths were measured at room temperatures with a Stormer viscosimeter calibrated in centipoises and operated at 600 r.p.m. Water loss was determined at 80°F. with the Baroid low-pressure wall-building tester at a pressure of I00 lb. per sq. in. for 30 min. The hydrogen-ion concentration was measured with a glass electrode. The bentonite-clay suspensions were prepared in the laboratory and allowed to age several days before testing. Members of the Arsenic Group in the periodic Table include arsenic, antimony and bismuth, but this investigation was limited to arsenic. Phosphorus also occurs in Group V of the Periodic system and phosphorus and arsenic form many closely related compounds such as pH3 and AsH3, P2O5 and As2O5, H3PO4 and H3AS04 Samples of tetrasodium pyroarsenate were prepared by fusing c.p. disodium arsenate (Na2HA5O4.7H2O). According to Friend,' this re-forms the ortho-arsenate on dissolution in water. Sodium trihydrodiorthoarsenate was prepared as described by Mellor,5 from arsenic pen-toxide as follows: As2O5 + 3H20 -> 2H3AsO4 2H3AS04 + 3NaOH Na3H3(AsO4)2 .3H20 Sodium dihydrogen orthoarsenateWaHz-As04) was obtained by fusing together equivalent quantities of arsenious Oxide and sodium nitrate, dissolving the residue in water and allowing it to crystallize.

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By M. Muskat, M. O. Taylor

Theoretical calculations have been made on the performance to be expected of gas-drive reservoirs for various characteristics of the oil and gas and the producing rock. Such performante has been expressed graphically as curves for the reservoir pressure and gas-oil ratios of the production as functions of the cumulative oil recovery. The latter has been expressed in terms of percentage of pore space of the reservoir rock. Such curves automatically give values for the ultimate physical recovery, if the latter is interpreted as the recovery obtained when the reservoir pressure has declined to atmospheric, or to any other pressure chosen as defining the state of practical complete depletion. Calculations of these pressure and gas-oil ratio histories have been made for conditions in which the oil viscosity, the gas solubility and shrinkage, the size of an overlying gas cap, if present, the permeability-saturation characteristics of the rock, and the amount of connate water, have been individually varied, The results serve to show the extent to which the ultimate recoveries are sensitive to the important physical parameters characterizing the oil reservoir. As is to be expected, the ultimate recoveries are found to decrease with increasing oil viscosity. Because of the predominant effect of the oil shrinkage associated with the liberation of the gas in solution, the ultimate recovery will decrease with increasing gas solubility. Increasing gas-cap volumes lead to higher recoveries, although the contribution made by the gas-cap gas is small as compared with the oil expulsion by the equivalent amount of solution gas. As a whole, the oil recovery when expressed in percentage of the pore space is not very sensitive to the details of the permeability-saturation relationship. However, if the rocks possess an equilibrium free-gas saturation, the rise in gas-oil ratio will be retarded, and the 'ultimate recovery somewhat increased' The oil shrinkage associated with the liberation of the dissolved gas also leads to the result that as long as the connate water is immobile and the permeability ratio curve for the rock is a function only of the total liquid saturation, the stock-tank oil recovery will be less for a sand containing no connate water than for One with an Original water content as high as 3' per cent. The space voidage in the former case will be somewhat greater, but the effect of oil shrinkage will lead to smaller values for the equivalent stock-tank recovery. These calculations also give data showing how the productivity indexes for the producing wells will vary during the reservoir history. Because of decreasing Permeability to the oil and increasing oil viscosity, the productivity index will fall continuously as Production proceeds, and may finally reach values as low as 10 per cent of the initial productivity index. Introduction In a previous paper1 was developed the basic theory for the prediction of the production histories of gas-drive reservoirs. The data required for the application of this theory included the characteristics of the petroleum fluids, such as the viscosity of the Oil and gas phases, the solubility of the gas in the oil, and the oil shrinkage— all expressed as functions of the reservoir pressure—and the permeability-saturation characteristics of the producing rock, as

Jan 1, 1946

By O. F. Thornton, D. L. Marshall

Results of the determination of the inter stitial water content of several core samples from oil reservoirs are presented. Data obtained by the capillary pressure method, which has recently been developed, are compared with water saturations measured in cores cut with oil-base mud and with values calculated from the electrical resistivity of the formation. The agreement between the capillary pressure and other methods, combined with the fact that similar agreement has been obtained by others, indicates that the capillary method properly applied yields results sufficiently accurate for most engineering purposes. In some cases, it may be possible to extend the utility of data obtained with the capillary pressure method by correlation of interstitial water saturation with more easily measured physical properties of the media. Introduction Several methods are in use for determining or for estimating the interstitial water saturation at given points within oil and gas reservoirs. The direct measurement of the water content of cores obtained with nonaqueous fluid in the hole is believed to be an accurate method under most conditions. The water saturation may be calculated by use of the resistivity curves of the electric log,' although this method is not applicable under conditions that exist in some reservoirs. Recently, a method has been developed and described3.' wherein the interstitial water saturation of cores is measured at a capillary pressure such that conditions existing in the reservoir are simulated. The purpose of this paper is to present data obtained by use of this latter method, and to compare the results obtained with determinations made by other means. Method The theory underlying the capillary pressure method applied to petroleum reservoirs has been discussed adequately in the literature by Garrison,2 Leverett,5 and Others.3,6,7 Briefly, and simply, capillary pressure is defined as the difference in pressure between two contacting fluid phases, such as oil and water. For the simplified sand, water and oil system illustrated in Fig I, the pressure difference can be stated as follows:6 where Pc is the capillary pressure in pounds per square inch, ? is the interfacial tension between oil and water in pounds per inch, r1 and r2 are the radii of curvature of the interface between oil and water in inches. Capillary pressure varies in a given reservoir with depth because of the greater density of the water phase as compared with oil or gas. The following equation expresses the difference in pressure between two points: p1- p2 - h?p/144 [2] where p1 — p2 is the capillary pressure difference in pounds per square inch, h is

Jan 1, 1947