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By Charles R. Fettke

The Bradford and Richburg oil fields are the only pools where artificially conducted water drives on an extensive scale have been economically successful. Field practice has progressed from the original accidental or intentional circle flood, through the line flood development plan, to the intensive complete development plan, which is the most-recent and generally considered to be the most successful. Of the intensive development plan the five-spot arrangement of wells is the one that has been used most extensively. A further development associated with the latter method is the application of additional hydraulic pressure to that of the hydrostatic head of the column of water in the intake well. In conjunction with this method is the practice of delayed drilling of the oil wells until the water from the intake wells has entered even the less permeable portions of the sand and developed a "bank" of oil at which time all oil wells are drilled as nearly simultaneously as possible. The five-spot pressurc flood with delayed drilling gives more rapid return on investment than any other method. The seven-spot and nine-spot patterns are rarely used. No chemicals, such as sodium carbonate and other so-called flooding agents, are being added to the water at present since the field tests carried on in 1926 gave no positive results. All air and gas drives have been discontinued.

Jan 1, 1930

By Frederick Clapp

ALTHOUGH many oil fields have been, and still are being, discovered in Oklahoma, the geology and structure of most of them have not become familiar to the general public because of the delay in securing government geological surveys and the reluctance of oil companies and other interested parties to give out their "inside information." Therefore, until official surveys are available, it behooves us to publish geological results as soon as possible. Fortunately the writer has been authorized by the Cement Field Oil Co. to publish his data on the Cement field, Caddo County at this time. LOCALITY AND DESCRIPTION The Cement field is situated in the part of Oklahoma known generally, until recently, as "Healdton fields," and lies 60 mi. (96 km.) northwest of the Healdton field proper. Like the Healdton field, it forms an approximate ellipse, trending northwest and southeast through the village of Cement on the St. Louis-San Francisco Railroad, on which it is reached in 2 ½ hours from Oklahoma City. In its geological structure, the field constitutes an anticline over 13 mi. (21 km.) long and from 1 to 3 mi. wide; the point of greatest width being not far from its intersection by the above-named railroad. The major axis trends north 75° west from the village of Cement; but eastward appears deflected (if field interpretations are correct) to about south. 45° east. About 5 mi. south lies an approximately parallel syncline, which may be conveniently called the Cyril syncline, the south and west boundaries of which may be distant many miles, but forming a closed basin', south of the Cement anticline. The position of the offsetting synclinal axis, which is believed to lie north and east of Cement, has not been discovered.

Jan 2, 1920

By A. H. Daane, W. J. Wunderlin, B. J. Beaudry

The solid solubility of holmium in copper, silver, and gold, determined using metallographic techniques, was found to be a maximum of 0.06, 2.4, and 3.2 wt pct, respectively, nt the eutectic temperatures. The temperatures of these eutectic horizontals, determined by differential thermal analysis, were found to be 868", 787", and 778"C, respectively. The first compound on the silver-rich side of the Ag-Ho system was found to be A&Ho2. In a study by Gold et al.,' on the effect of small amounts of soluble impurities on the electrical resistance and thermoelectrical properties of copper, traces of iron were shown to have drastic effects on the thermoelectric power due to the magnetic scattering of the conduction electrons. Since little is known about the state of the iron ion when dissolved in copper, Gold had hoped to repeat these experiments using certain rare earths as the magnetic scattering centers; because of the tightly bound 4f electrons it is not expected that their spectroscopic state would be affected by alloying. In such an experiment the sole role of the trace rare-earth impurity would be to magnetically scatter the copper conduction electrons without producing appreciable distortions in the otherwise pure copper matrix. Since holmium was chosen for such a study because of its high magnetic moment, it was necessary to establish precisely its solid solubility in copper. The study was extended to include the solvents silver and gold, so that an evaluation of the data using classical solubility parameters could be made. No previously reported work on the systems of holmium with copper, silver, or gold was found in the literature. Information on the solubility of other rare earths in these three metals is also very meager. The solubility limit of yttrium in copper was reported as less than 1 wt pct2 and the solubility of praseodymium in gold as 0.35 wt pct,3 while no references were found on solubility studies of rare earths in silver. EXPERIMENTAL Materials. The materials used in this investigation were distilled holmium prepared in this Laboratory, OFHC* copper, electrorefined silver (99.9 *OFHC = oxygen-free high conductivity. pct), and gold with the analyses given in Table I. Sample Preparation. Samples weighing 1 to 2 g were prepared by arc-melting the components together on a water-cooled copper plate under purified argon atmosphere. The samples, turned and remelted at least five times to ensure homogeneity, showed weight changes of less than 0.1 wt pct after melting. Samples containing less than 0.7 wt pct Ho were prepared by diluting 1 to 2 wt pct Ho alloys with the pure solvent, while samples with concentrations greater than 0.7 wt pct Ho were prepared directly from the metals. The samples were wrapped in tantalum foil, sealed in outgassed Vycor tubing under helium, annealed at the desired temperature for at least 24 hr, and then quenched by shattering the Vycor tube in cold water. Metallographic Methods. Standard mechanical polishing methods were used in preparing the silver and gold alloys for examination, while the copper alloys were electropolished using a 40 pct solution

Jan 1, 1963

By M. D. Arnold, P. B. Crawford, P. C. Hall

An experimental study has been made to determine the optimum flooding pressures for four different oils. The oil formation volume factors ranged from 1.08 to 2.13, and solution gas-oil ratios ranged from about 200 cu ft/bbl to 2,250 cu ft/bbl. Viscosities ranged from 0.38 to 0.95 cp at the respective bubble points of the fluids and from 0.7 to 20 cp at atmospheric pressure. Water floods were conducted at various pressure levels from run to run. The recovery as a function of flooding pressure was found to be different for each fluid, with optimum gas saturations ranging from 7 up to 35 per cent. The data indicate that substantially higher recoveries may be obtained if water floods are conducted at an optimum pressure and that this optimum pressure is a function of fluid properties. The same core was used for all tests, and the reproduction of saturations for various runs indicates that wettability in the predominantly water-wet core did not change. INTRODUCTION A paper was presented by Bass and Crawford' which described an experimental study of the effects of flooding pressure and rate on oil recovery by water flooding. This work was conducted using high-pressure models operated in a manner similar to that of an actual reservoir, with gas saturations being obtained by a solution-gas-drive mechanism. They found that the greatest oil recovery was obtained for the system studied by flooding in the presence of a 5 to 7 per cent gas saturation. Another experimental study simulating field conditions was presented by Richardson and Perkins.' They used an unconsolidated sand pack containing kerosene-natural gas fluid and interstitial water. They flooded at various pressures and flooding rates. For their system it was found that the recovery was independent of the pressure level at which the water flood was performed. Kyte, et al," found that oil recovery by water flooding was increased as the free gas saturation at waterflood initiation was increased. However, after the initial gas saturation was increased above 15 per cent, the increase in oil recovery tended to level off. All of their runs were made at the same pressure using a light oil saturated with helium. The desired gas saturation was obtained by injecting helium into the core. Dyes' made calculations which showed that an optimum gas saturation of 12 to 14 per cent may result in an increase in oil recovery of 7 to 12 per cent over that obtained by flooding at the bubble-point pressure. Others have also found that the presence of a free gas saturation may increase the waterflood oil recovery. In each case shrinkage was small and changes in fluid properties with respect to pressure were small. A careful review of the literature reveals that at the present time there is a wide difference of opinion on the factors affecting waterflood recoveries. This diversity of opinion is probably due to the fact that very little research has been done which has taken into account the many variables existing in an actual field being water flooded. Since the literature contains little information on high-pressure waterflooding studies using various types of reservoir fluids, it was believed appropriate that such a study should be made. EQUIPMENT AND PROCEDURE All tests were made using the same consolidated sandstone core. Torpedo sandstone was used to turn a cylindrical core 13.5-in. long and with a 2.92-in. average diameter. The core had a porosity of 28 per cent and a permeability to brine of 146 md. This brine was made up by adding 20,000-ppm sodium chloride and 30,000-ppm sodium nitrite to distilled water. This was used as connate water and flooding water. No fresh water was ever brought in contact with the core, as tests showed the sandstone contained argillaceous material which swelled in the presence of fresh water and plugged the stone. The core was sealed in a section of 6-in. N-80 tubing with Woods metal filling the annulus. The core was mounted horizontally; an injection well was placed in the center of one end and a production well in the center of the other. Pressure control was maintained by placing a back-pressure regulator (upstream control) on the producing well. The "live" oil was stored in a separate bottle and water was injected into this bottle to displace the oil for saturating the core using a two-cylinder standard-proportioning pump. This same pump was used for water flooding the core at a constant rate. This system was enclosed in water jackets and the temperature was automatically main-

By Chung Yu Wang

DURING the time I was in charge, of this mine, from 1914 to 1915, I had occasion to read the interesting papers by T. T. Read and C. M. Weld about these deposits, to find how far their observations corroborated mine. To quote from the paper on "The Mineral Production and Resources of China" by T. T. Read:' "The iron ores at Tayeh lie along the contact between a marble and an intrusive body of a dark gray syenitic rock. * * * * At one place it is slightly magnetic, apparently having been partly reduced to the magnetic oxide by the action of reducing solutions, which have deposited small amounts of copper and iron sulphides along the foot wall." To quote from the paper on "The Tayeh Iron Ore Deposits"2 by C. M. Weld: "I find the orebodies described as occurring along an approximately E-W contact between horn-blende-granite and limestone. * * * * The granite is a granitoid rock consisting essentially of quartz, potash-feldspar and hornblende." These quotations show the differences of opinion entertained by two observers. My own study of these interesting deposits has been intermittent amid the manifold duties devolving upon a superintendent. General Description of the Deposits The deposits are situated to the west of the Yangtse River, being con¬nected with the river by a standard-gage railroad of 56 li (16.16 miles, 26 km.) in length, as shown in Fig. 1. The general topography of the region is of mature age, showing broad valleys with sluggishly meandering streams. These deposits are worked as two mines, named the Tieh Shan Mining Department and the Teh Tao Wan Mining Department; the former consisting of three orebodies more or less connected, named Tieh Man Kan, Sha Mau Tze and Lung Tung, and the latter consisting of Chang Pei Shan, Sze Tze Shan, Ta Shih Men, Yeh Chih Ping and Tsin Shan, also more or less connected, as shown in Fig. 2.

Jan 3, 1917

IN A broad sense, the subject of slag control includes not only the adjustment of the composition of the slag but also of its relative weight in terms of percentage of the metal-bath weight. The slag is made up essentially of (1) oxides formed by oxidation of silicon, manganese, phosphorus, and iron in the charge, (2) SiO2, MnO, and other oxides charged as such, and (3) lime charged or fed to the heat to neutralize the “acidic”: oxides present (Si02 and P2O5). Obviously, if practically perfect control were possible over the composition of the charge as well as over the oxidation process during the melting period, both slag weight and composition would be very nearly predetermined, and the control problem would be solved. Unfortunately, we have only a somewhat. imperfect control over these factors, so that beginning at about the lime-boil period in the heat, and later in the early refining period, it becomes necessary for the first helper, as the heat progresses, to make quick estimates of the composition and physical state of development of the slag (as well as of the amounts of phosphorus, sulphur, and carbon in the metal) from which he can judge how much extra lime, roll scale, fluorspar, and other additions will be needed not only to give the desired final slag composition, but also to hasten the complete fusion or shaping to a desired viscosity in the liquid state. The discussion in this chapter is limited essentially to those more or less practical rapid methods of slag estimation that have been used, or at least tried, for these purposes under actual open-hearth shop conditions. Another aspect of importance here is the extent to which the freedom of choice to the operator is limited by available charge materials, product specifications, and the oxidation and other chemical- reaction effects which inevitably occur under the conditions of this furnace process. For a better understanding of these control limitations and of the chemical and physical background of the subject, the reader is urged to read at least part of the discussion in Chapters XVII and XIX. Charge materials are discussed in Chapter IV, and many of the details of charging, melting, and refining practice closely related to slag control are given in Chapters VI and VII.

Jan 1, 1944

By E. F. Koppe

The Upper Freeport coal in the Freeport and New Kensington quadrangles, Pennsylvania, varies from a bony streak to a thick coal deposit often exceeding ninety inches, the "Double" or "Thick Freeport". Distinctive basal partings, a central bone layer, and a canneloid top bench may be present. The appearance of a sandstone roof, sandstone rolls, and bony coal at the top of the main coal bench can be anticipated in thin Freeport areas when basal partings are absent. When the two basal partings are present, a shale roof is normal. These effects are correlated with the original topography upon which the coal was deposited. The original depositional high areas tend to coincide with present structural highs. Preliminary data indicate that coal quality, in part, is affected by the deposi-tional setting. In "high" areas, a tendency exists for the main coal bench to contain higher percentages of fusain and mineral matter. Within limits, some-what higher ash fusion temperatures appear to correlate with paleotopographic highs. As a result of these findings, critical examination of the paleotopography and related sediments is indicated in other areas and other coals. The Upper Freeport coal is quite variable both in thickness and composition in the Freeport and New Kensington quadrangles of Pennsylvania (Figure 1). The coal horizon in these quadrangles is marked either by a thin carbonaceous shale bed or by a single bed containing a variable number of partings (binders). The complex coal zone known locally as the "Double" or "Thick Freeport" contains the Upper Freeport Coal Bed at the base; but in addition, it has an overlying bone layer and an upper coal bed occasionally capped with a canneloid layer. The "Thick Freeport" often exceeds 90 inches in thickness, whereas the normal Upper Freeport coal usually varies between 34 and 50 inches.

Jan 1, 1961

By H. W. McCue, Henry Rogatz

Oil.—During the year 1939, there were 365 oil wells drilled in the Texas Panhandle, with a total daily initial production of 130,968 bb1.— that is, 69 fewer oil wells drilled than in the previous year, with a decrease. in total daily initial production of 61,738 bbl. The total daily potential of the field on Dec. 5, 1939, as determined by the Texas Railroad Commission, was 1,344,677 bbl., an increase of 94,032 bbl. over the previous year. On Dee. 5, 1939, a daily allowable of 130,527 bbl., which was an

Jan 1, 1940

By Henry Rogatz, H. W. McCue

Oil.—During the year 1939, there were 365 oil wells drilled in the Texas Panhandle, with a total daily initial production of 130,968 bb1.— that is, 69 fewer oil wells drilled than in the previous year, with a decrease. in total daily initial production of 61,738 bbl. The total daily potential of the field on Dec. 5, 1939, as determined by the Texas Railroad Commission, was 1,344,677 bbl., an increase of 94,032 bbl. over the previous year. On Dee. 5, 1939, a daily allowable of 130,527 bbl., which was an

Jan 1, 1940

By J. C. Smock

The magnetic and polaric properties of magnetite, or magnetic iron ore: are fundamental facts in magnetism. The disturbing erect of this mineral upon the magnettic needle in land surveying must have been very early observed. The difficulties arising from this source are still almost insurmountable in making accurate surveys in districts where this ore occurs to any extent, either as a rock

By G. D. Cremer, J. J. Cordiano

ALUMINUM powder is a well-known article of commerce and in various forms has been marketed widely for use in paint, for pyrotechnic purposes and for exothermic mixtures. For a number of reasons, how- ever, aluminum powder has not been employed extensively in powder metallurgy, although a great many proposals along this line have been offered. Aluminum and aluminum-alloy powders oxidize readily upon exposure to air and the thin film of oxide (or hydroxide) thus formed is highly refractory, in that ordinary gaseous reducing agents such as hydrogen or carbon monoxide do not reduce the oxide to metal at temperatures below the melting point of aluminum. It has been thought that the presence of these films of oxide on aluminum particles would interfere markedly in powder metallurgical work and a number of suggestions have been made, either for preventing the formation of the film through the production of the powders in inert or reducing atmospheres, or for the removal of the oxide by means of powerful reducing agents, including "nascent" or atomic hydrogen released from metal hydrides. 4 second and more serious difficulty in the use of aluminum and aluminum-alloy powders in powder metallurgy resides in the fact that during compression such powders tend to adhere or cold-weld to the die walls, thus interfering with the formation and ejection of a compact. A third difficulty, which has been encountered only with aluminum-alloy powders, is their hardness when compared with elemental aluminum. Certain of these powders are susceptible to age- hardening, which further hinders the formation of strong green compacts. These conditions are particularly true of atomized aluminum-alloy powders. Even in the annealed condition, plastic deformation of alloy powders under pressure is low when compared with unalloyed powders. This fact, coupled with the lower corrosion resistance of the alloy powders, is probably the significant factor in our failure to obtain strong sintered pieces. METHODS OF PRODUCING THE POWER Many methods have been proposed for manufacture of aluminum powder, only a few of which are used commercially. Several of the more important processes include: (I) atomization of the molten metal; (2) mechanical pulverization and other types of comminution; and (3) graining, in which molten aluminum is stirred during freezing. For pigment and certain pyrotechnic uses aluminum flake powder is desirable, because of its greater proportion of surface to volume; and large quantities of such material are made by a procedure that involves stamping or ball milling. In making flake intended for use as pigment,

Jan 1, 1943

By Howard L. Hartman, Burke O. Trafton

There is a fruitful area of computer competence which has gone virtually unnoticed by the mining industry. This is in the solution of its numerous fluid-flow distribution problems, involving the circulation of air, water and other fluids in conduits through mines. Typical of these is the mine ventilation system, which circulates air through mine openings to the working faces. The networks of interconnected airways in large mines-often resembling a tortuous maze or labyrinth defying representation by schematic, let alone solution-must somehow be resolved and analyzed, if effective and safe control of the ventilation is to be maintained. These are admirably suited to programming for solution by high-speed electronic computer. Not only can direction of flow be determined but quantity and head loss as well. EARLIER EFFORTS AT NETWORK SOLUTION The only prior attempt to solve mine ventilation networks by digital computer methods was made by a Japanese investigator1 in 1958 whose work went unpublished. Unfortunately, he employed a method of network analysis little used in the United States and one which could accommodate a maximum of only 30 airways. While his analysis seems unnecessarily cumbersome and involved, it did suggest that a digital computer approach was feasible.

Jan 9, 1963

By P. Hadzeriga

There are two places in the world where potash, trade name for potassium chloride, is economically recovered from naturally occurring brines by solar evaporation. One is at the Dead Sea and the other at Wendover, Utah. American Potash and Chemical at Trona, Calif. recovers potash from natural brines, but uses fuel to accomplish evaporation. Solar evaporation is always desirable, because of low costs, however artificial evaporation may be economical if a group of very valuable salts are recovered. This is the case for the American Potash operations at Trona. Solar evaporation is limited by low working temperatures, which in most areas of the world is between 18 and 45°C. In many cases the average working temperature is about 25°C. However, solar evaporation will have to accommodate itself to the highs and lows of each 24 hour period, and to the different average temperatures during the months of the year. Therefore, solar evaporation, although more economical than artificial evaporation, has a tem- perature limit which greatly reduces the chances of its application. The feasibility of solar evaporation as a means of recovery of values from a particular brine, may be evaluated by the use of phase diagrams showing the several components present. This paper is restricted to the five component system: C1-, SO4=, Na+, K+, Mg++, and H2O, which correspond to brines found at Wendover, Utah, the Great Salt Lake, and sea water bitterns. THE BONNEVILLE OPERATION AT WENDOVER, UTAH For more than 25 years Bonneville, Ltd., now a division of Standard Magnesium and Chemical Co. (recently acquired by Kaiser Aluminum and Chemical Corp.), has been recovering potassium chloride from the brines found in the desert area just east of Wendover, Utah. Solar evaporation of the brines is possible as a consequence of relatively low precipitations (year average: 4.8 in.), and of dry and hot summer months. The brine, collected by a series of approximately 67 mi. of ditches crossing the desert, is fed into solar evaporation ponds. Evaporation which takes place from around the middle of May to about the end of September, permits the crystallization of approximately 90% of the originally present NaCl on what is called the "General Pond Area". Further evaporation,

Jan 1, 1964

By C. A. Allen

For over three years we have been endeavoring to reduce the number of fatalitics and minor accidents in Utah. The physical condition of the FIG: 1.—Number kiLlEd per million short tons of coal produced in ColoraI)o, New Mexico, utah, Wyoming, and bituminous mines of the United States 1014 to 1920. mines, concentrators, and smelters is good, yet the number of accidents,

Jan 1, 1923

By C. A. Allen

For over three years we have been endeavoring to reduce the number of fatalitics and minor accidents in Utah. The physical condition of the FIG: 1.—Number kiLlEd per million short tons of coal produced in ColoraI)o, New Mexico, utah, Wyoming, and bituminous mines of the United States 1014 to 1920. mines, concentrators, and smelters is good, yet the number of accidents,

Jan 1, 1923

New Device Eliminates Blasting in Coal A non-explosive device developed by duPont utilizes the high pressure of a gas generated inside a steel tube which is inserted in a hole drilled in a coal seam to break down the face of coal. Chemical reaction is started by an electric current which produces heat to initiate the action. The same heat destroys the starter wire as soon as electric current is no longer needed. The tube containing the chemical is closed at the outer end by a plug with electrical connections, and at the other with a disk that is ruptured by the compressed gases formed. When the gas has been liberated in sufficient quantities to create a desired pressure the disk breaks and the released gas breaks down the coal face. The new device is called a Chemechol.

Jan 10, 1951

By C. B. Manula, H. Gezik

In planning modem-day mining operations, management needs to pass from the area of subjective decision-making to an area of objective decision-makirlg. Planning procedures currently being practiced by many mine managers depend primarily on common sense and trial-and-error methods which oftentimes never reach optimum solutions. For this reason, an attempt is made to provide an understanding of linear programming to solve production planning problems. More specifically, a linear programming model is proposed to solve the production scheduling problem as it was found to exist in the crushed stone industry. Optimal production scheduling is of prime concern here, since the industry has to cope with seasonal demands for its products. The solution, as determined through the application of the model, provides management not only with an optimal production schedule but also with the following information regarding the improvement of existing facilities: (I) the location of bottlenecks which limit production and profit; (2) the directions in which the company i fixed equipment should be expanded or modified; and (3) the evaluation of unused resources. Future trends in stone production will quite likely parallel those in the construction industry. Continued record expenditures for structures such as dams, highways, and buildings are the reasons for this accelerated growth. Production forecasts for the next decade are predicted to be around one billion tons with an approximate 7% annual increase. The problem of increasing production from 570 million tons in 1966 to 1 billion tons by 1976 offers no small challenge. This situation is further compounded by other problems and economic factors. Population expansion, government regulation, labor agreement, and changes in technology wd cause managers and operators to be confronted by many more complexities than characterize present-day operations. Some of these. problems and economic factors are: (1) In some metropolitan and other urban areas, easily accessible sources of stone are almost depleted. Transportation costs will be a prime concern of the industry. (2) Population growth has forced residential expansion to a point where many quarry operators must conform to urban and suburban regulations. (3) Government regulation in regard to air and water pollution, noise, and reclamation as well as zoning developments necessitate that crushed stone producers keep abreast of changing conditions and requirements. (4) The crushed stone industry operates under pressure of a highly competitive situation. Every company's objective is to retain a favorable marketing position by exercising great attention to production and marketing costs. This is rather difficult, since the crushed stone industry is one segment of modern mining which has to cope with a seasonal demand for its products. Among the problems posed here, the one of exercising great attention to production and marketing costs is of current interest to management. Under seasonal demand conditions, this problem creates further difficulties for managers who need to plan and forecast. STATEMENT OF THE PROBLEM Various methods of Operations Research have been developed to handle a problem whose genesis is explained above. It is very seldom, however, that these quantitative means are used in practice by the mining industry. This paper describes the use of Operations Research methods to solve a production planning problem when demand is seasonal. The seasonal production planning problem is an important one because of the substantial costs associated with changing production, employment, and inventory levels to adjust to seasonal sales patterns. Most companies try to operate within reasonable levels of employment changes and hold inventories within storage capacities. In general, little or no attempts were made to develop minimum cosl schedules or to provide objective means to compare various production policies. When demand varies within a fixed time period, 11:-oduction requirements may be met by following one

Jan 1, 1970

By Avnulf Muan, Egil Aukrust

Activity-composition curves jor cobalt oxide and manganese oxide in solid solutions with spinel-type structure have been determined by studying the equilibrium between the spinel phase and a coexisting solid-solution phase in the tewzperature range 1100" to 1400"C. Within limits of experimental error, the system displays the behavior of a regular solution. The excess integral free energy of mixing is represented by the equation . The standard free energy of formation of cobalt manganite, CoMn,O,, from the oxide components COO mzd Mn2OS at 1200°C is calculated to be -8.6 kcal. AMONG the technologically and theoretically most important oxide phases are those which crystallize with the same structure type as the mineral MgO . A120,. Although the name spinel originally was used only for this mineral, the term is generally used today to designate the whole group of oxide phases with this same structure type. It is in this wider meaning that the term is being used in the present paper. The previous literature on spinels is very extensive. There are two aspects of spinels which have attracted particular attention: the structure, including the nature and distribution of the cations present, and the physical properties (electric, magnetic). The status of knowledge in these fields has been well-summarized in recent review articles.1'2 By contrast, thermodynamic properties of spinels are virtually unknown. Delineation of the activity-composition curve over the whole composition range of a solid-solution series with spinel-type structure is the objective of the present work. The system at elevated temperatures (>1000"C) constitutes such a series. The activity-composition curves for this system can be calculated from a study of the equilibrium between the above spinel solid solution and a solid solution (Co,Mn)O with sodium chloride-type structure. Data for the latter solid solution have become available recently.3 The system, in contact with metallic CO at 1200°C, obeys Raoult's law. The determination of the activity-composition curve for the spinel phase is based on the following relations. Consider the reduction-oxidation equilibrium for cobalt ions according to the equation: Because it is impossible in practice to measure single activities of electrically charged constituents, we will treat the equilibria in terms of electrically neutral components. Eq. [I] can then formally be written as follows: where and the activities of cobalt oxide in the (Co,Mn)O and the spinel solid-solution phases, respectively, K is a constant at constant temperature, and Pa is the oxygen pressure of the gas phase. The numerical value of K can be determined from a determination of the oxygen pressure P& for the equilibrium coexistence of Cos04 and COO in the binary system Co-0. Under these circumstances be set equal to 1, and hence K = [Po Eq. [3] can therefore be written

Jan 1, 1964

By J. C. Melrose, W. R. Foster, J. G. Savins, E. R. Parish

Many differences can be imagined between gas-oil flow in which the gas is supplied at the face of the core and gas-oil flow in which the flowing gas was originally dissolved in the oil. If capillary pressure characteristics and flow requirements control gas saturation distribution, the gas would be expected to be located at preferred sites within the porous medium as determined by pore sizes. On the other hand, during solution gas drive the gas first appears as bubbles through a nuclea-tion process. Nothing in self-nucleation theory specifies at which sites the first bubbles should be formed. In all probability they will be randomly distributed throughout the porous medium. Furthermore, it is not at all certain that even at low rates of production the gas will redistribute itself after nucleation to the channels normally occupied by gas in simple gas flow. Stewart, et at, have shown that at least for some limestone samples, oil recoveries could not be predicted for all rates of production using any one set of relative gas and oil permeabilities. An important factor in controlling recoveries during solution gas drive was the rate of bubble formation, higher rates giving higher recoveries. Stewart, et al, attributed the increase in recovery to a better distribution of the gas phase in heterogeneous limestone samples than is obtained by simple external gas drive. Differences in recovery from these causes were not reported for sandstone cores. In the experiments to be reported here, oil recovery, pressure and producing GOR history were measured during solution gas drive for a 5-ft sandstone core. The results were compared with predictions from the Muskat method for computing solution gas-drive behavior using external gas-drive relative permeability. The effects of changing the rate of production and oil viscosity were studied. At high laboratory rates of average pressure decline, two observations were made which would not have been predicted by Muskat's depletion theory: (1) oil recovery increased with increasing rate of production for a given viscosity oil, and (2) oil recovery increased with increasing oil viscosity for a given high rate of production. Both of these observations are explained as consequences of diffusion control of gas saturations superimposed on the normal gas-oil flow requirements, Fur- thermore, discontinuous gas phase flow appears to be significant during solution gas drive. The laboratory tests were performed at rates of average pressure decline many times greater than the maximum possible rate of average pressure decline in an actual oil field. It is, therefore, not possible to draw any direct conclusions regarding the effect of rate on recovery for the solution gas-drive mechanism under actual field conditions. However, at the lower laboratory rates, recoveries were nearly independent of rate and could be predicted by the Muskat method, using external gas-drive relative permeability data. These results suggest that at normal oilfield rates the effect of rate on recovery for the solution gas-drive mechanism is negligible. EXPERIMENTAL PROCEDURES The core material for the pressure depletion studies was Bandera sandstone from an outcrop in the Mid-Continent. This sandstone was selected because of its low permeability (about 10 md), which would permit the development of substantial pressure gradients in the corn at moderate flow rates. The core was 5-ft long and 2-in. in diameter. Its properties are listed in Table 1. Relative gas-to-oil permeability ratios were measured by an external gas-drive method2. The results are shown for a short 2-in. core and for the 5-ft core in Fig. 8. Oils used in the pressure depletion experiments were kerosene and a highly refined white oil (standard white oil No. 3) with gas-free viscosities of 1.8 and 25 cp, respectively. The gas was a naturally occurring methane from Gough field, Inglewood, Calif. The oil viscosities, gas solubilities and formation volume factors are plotted as functions of pressure at 75°F in Figs. 1 and 2. Methane viscosities and compressibilities were obtained from the literature"'. A core mounting was required which could withstand up to 2,500 psi internal pressure. This was obtained by first encasing the core completely in a plastic resin (Scotch Cast, manufactured by Minnesota Mining & Manufacturing Co.) The plastic covered core was then inserted into a steel pipe equipped with screw caps so that the plastic coating could be pressured from

By Laurance S. Reid, Joe A. Porter

Gas dehydration plays an important part in the production of natural gas. Effective dehydration prevents formation of gas hydrates and the accumulation of water in transmission Systems,2,6,7 insuring uninterrupted gas deliveries at maximum efficiency under the most adverse weather conditions. At the present time, most gas companies require a maximum water vapor content of seven lb per million standard cu ft of gas. so that virtually all gas tendered for sale must he dehydrated to meet this specification. For a number of years it has been common practice to produce gas and gather it at a common point for dehydration prior to discharge into the transmission system.1,3,11,16,17 However, higher transmission line pressures, long gathering lines and relatively low ground temperatures have made it necessary to dehydrate gas at. or near. individual. wells in order to gather gas from a number of newly developed fields without unusual difficulty. Where gas has been dehydrated at pressures ranging from 300 to 800 psi in the past. future trends indicate that these processes may be operated at pressures as high as 2,000 psi. Economics of gas dehydration are of great importance, partitularly where facilities must he provided to process relatively small quantities of gas, such as the production from an individual well. Although the adsorption of water vapor from gas on a granular sorbent material such as activated bauxite, activated alumina, or one of the alumina-silica gels is highly effective and produces virtually "bone dry" gas, the cost of a small unit of this type is substantially greater than that of an absorption process which, through proper selection of the absorbing liquid, will dehydrate the gas sufficiently to meet pipe line specifications. For this reason, a great deal of emphacis has been placed on the development of small, inexpensive dehydration units8,24 and the search for more effective absorb. ent liquids has been intensified. A wide variety of methods for dehydrating gas are known' and many of these have been used in industry. Earlier applications of the absorption process employed concentrated solutions of calcium and lithium chlorides as the absorbent. The severe corrosion problems inherent in handling these solutions and the relatively small dew point depressions obtained caused early abandonment in favor of, or conversion to. diethylene glycol when it was found that aqueous solutions of this organic liquid were more hygroscopic than the brines and were non-corrosive. Processes employing diethylene glycol-water solutions are widely used for gas dehydration at pressures ranging as high as 1,200 psi.13,14,15 At nominal pressures a dew point depression of 45° to 50°F may be be and the data of Russell et al." indicate that a minimum dew point is obtained from the effluent gas at a pressure of approximately 1,200 psi when the gas is in equilibrium contact with a 95 per cent by weight diethylene glycol solution. In a number of instances the dew point depression obtained with diethylene glycol-water solutions is not sufficient to produce a specification product without cooling the inlet gas. In a recent search for a better absorhent, triethylene glycol was used in a small commercial dehydration unit and subjected to rather exhaustive field tests.' The data obtained were encouraging and indicated that, at pressures ranging from 300 to 500 psi, triethylene glycol porduced a substantially greater dew point depression than diethylene glycol. These results led to an investigation of the system natural gas-water-triethylene glycol in an effort to obtain vapor-liquid equilibrium data, to determine pressure limitations, and to develop other data pertinent to the design of gas dehydration processes. A review of the literature has failed to reveal any data which permit reasonably accurate calculation of the vapor-liquid equilibrium conditions for a solution of water and triethylene glycol in contact with natural gas at high pressure. Since these constituents form a non-ideal system, the Poynting equation18,21 or the usual combination of Raoult's and Dalton's laws19,20,22 would not be valid. Correction of Raoult's and Dalton's laws by the use of activity coefficients2' is not feasible for available data are insufficient for the prediction of the actual increase in the ratio of the activity of one component in the vapor phase to its activity in the liquid. Therefore. experi-

Jan 1, 1950