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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

Jan 1, 1930

By W. A. Clark

THE production of sand in an oil well increases operating costs because of abnormal wear in subsurface equipment, the necessity for frequent cleanouts, and the need for a means of disposing of the sand. Moreover, removal of sand from the zone can bring about the creation of cavities from which bodies of formation, sand or shale, may slough into the hole, endangering the shutoff, impeding production or collapsing the liner. The procedure known as gravel packing is attracting attention as a means of controlling these factors and contributing to the productive life of a well. That gravel packing is now substantially beyond the preliminary stage on the Pacific Coast is reflected in the 191,000 bbl, of oil produced monthly by the 66 gravel-packed wells in 11 different producing sectors. REASONS FOR GRAVEL-PACKING Gravel packing, if properly carried out, can be expected to provide the following benefits: 1. Prevent the movement of sand and thus eliminate sand production and sand fills, and prevent the formation of cavities. 2. Provide a practical, relatively inexpensive, large-diameter hole, which will provide well-known theoretical advantages. 3. Support the walls of the hole by completely filling the space between the liner and the formation, regardless of its irregularities, and afford a support for liners. 4. Provide for more efficient pumping operations in wells by: (a) possibly utilizing the gravel as a gas trap in pumping gaseous fluids, (b). allowing deep submergence of the pump into the oil zone.

Jan 1, 1939

Jan 1, 1935

By G. L. Chierici

Starting from Muskat's theory of water and gas coning, maximum permissible oil production rates without water and/or free-gas production have been determined, in a broad range of reservoir and well parameters, using the potentiometric model technique. The main assumptions made are as follows: (1) the reservoir rock is homogeneeous (either isotropic or anisotropic); (2) the volume of the aquifer underlying the oil zone is very small, so that it does not contribute to reservoir energy; and (3) the gas cap expands at a very low rate, so that it can be assumed to be in quasi-static conditions. The results obtained are presented in the form of diagrams which can be used for solving two types of problems: (1) given the reservoir and fluids characteristics, as well as the position and length of the perforated interval, determine the maximum oil production rate without water and/or free-gas production; and (2) given the reservoir and fluids characteristics only, determine the position and length of the perforated interval which optimize the maximum permissible oil production rate, without water and/or free-gas production. INTRODUCTION In oil reservoirs where the oil-bearing formation is underlain by an aquifer which does not participate in the production mechanism, water-coning is a limiting factor to the flow rates of producing wells. Production rates are usually kept to a value that will prevent the water from entering the wells. The entry of water into a well lowers its productivity by increasing the weigbt of the fluid column; moreover, the separation of water from the effluent, at the surface, may constitute a very difficult problem in cases of heavy viscous oils. A similar situation is encountered in oil reservoirs with a gas cap overlying the oil-saturated zone; here a downward gas cone is induced by the flow of oil towards the producing wells. Production rates must be low enough to prevent the gas from being produced; producing gas from the gas cap would be a waste of energy. Of course, water-coning and gas-coning phenomena can occur at the same time in the same reservoir if the oil-producing formation is both overlain by a gas zone and underlain by a water zone. Due to its relevant practical importance, the mechanism of coning was studied by many people.2,3,5-8 Defining the conditions for getting the maximum water-free and/or gas-free oil production rate is a difficult problem, often encountered under one of the following aspects: 1. Predict the maximum flow rate that can be assigned to a completed well without the simultaneous production of water and/or free-gas. 2. Define the optimum length and position of the interval to be perforated in a well, in order to obtain the maximum water and gas-free production rate. A systematic study of these problems was made by means of the electrical analog technique. The results of this study are presented here, under the form of a set of curves providing solutions for the above stated problems. These curves are valid only for homogeneous forrnations, either isotropic or anisotropic. Should the formation be non-homogeneous (by horizontal or vertical variation of permeability, shale diaphragms, fractures, etc.), a specific potentiometric study would be required for each specific case. Especially when shale diaphragms of some radial extension are present, the critical rates observed are much larger than would be expected from the diagrams. STATEMENT OF THE PROBLEM In the present study the aquifer is supposed to be of such limited volume that it does not contribute to the energy of the reservoir. Moreover, the gas cap is supposed to expand at such a low rate that the potential gradient in the gas cap is negligible. Under static conditions water-oil and gas-oil interfaces (T1 and T2) are both horizontal. When the reservoir production starts, below each well these interfaces take a cone-like shape (Fig. 1) having as an axis the axis of the well. This shape results from the equilibrium between potential gradients in the oil zone and gravitational forces due to density differences between oil and water and between oil and gas. Assuming the oil-bearing formation to be homogeneous and the oil to be incompressible, the analysis of the problem (see Appendix) shows that the oil-water and gas-oil interfaces are stable only if the oil production rate of the well is not higher than the following values.

Jan 1, 1965

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Jan 1, 1938

Jan 1, 1933

For the year ending February, 1918 PRESIDENT PHILIP N. MOORE ST. Louis, Mo. PAST PRESIDENTS WILLIAM L. SAUNDERS NEW YORK, N. Y. L. D. RICKETTS, NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS, NEW YORK, N. Y. TREASURER GEORGE C. STONE, NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND,.. NEW YORK, N. Y. SECRETARY BRADLEY STOUGHTON NEW YORK, N. Y.

Jan 3, 1917

Jan 1, 1890

Jan 1, 1902

By Arthur Knapp

NO oil territory in the world has been so rich in large producing wells, in a comparatively small area, as the Baku field. Particularly is this true of the Bibi Eibat field, which formerly produced millions of "poods " of " gusher," or as it is called in Russia, "fountain" oil. The Bibi Eibat and Balachany fields have been exhausted of gas and ruined by water, but ' the Surachany and Benegadi fields are still fountain territories and: many outlying districts that have only been prospected produce rich fountains. The method of controlling fountains, or gushers, is the result of growth, along with the Russian system of drilling, where large diameters and riveted casing have been in vogue. The screw casing is seldom used except to exclude water. Formerly the method of finishing wells and the condition of the casing at the top of the well would not permit the use of gates, manifolds, and connections as is standard elsewhere. The life of the flowing wells is very short, particularly those 10 in. (25 cm.) or more in diameter, which produce large quantities of sand and often flow for but a few days and are then a complete loss. More than 1,000,000 poods in 24 hr. have been claimed in several instances, but in no case was the flow for more than a few days. The oil sands of this district are free uncemented sands and vary in thickness from paper thin to a maximum of 10 ft. (3 m.). The sands are interlaid with strata of soft clay. In spite of this, the practice has been to drill into such sands and produce from the open hole without screen or liners. Sometimes the casing is set below the oil sand but in this case holes from 21/2 to 3 in. in diameter are drilled opposite the oil sand, which would not have the effect of a screen. Fig. 1 is an outline of the fountain shield ready for the control of a fountain. It is composed of an inner and an outer covering made from rough boards. The framework is made of rough round poles. When a light flow is expected, only the inner lining is built; and when the fountain comes in unexpectedly, it is often possible to build only the outer cover. The bridge is for the purpose of renewing the blocks as they become worn by the flow. The lower block, as here shown, is made of hardwood and is bolted to the crossbeams with brass bolts. The grain end is toward the flow. The upper block, as shown here, is made of cast steel and is also bolted to the crossbeam with brass bolts.

Jan 1, 1921

By Ursula E. Wolff

Il.lechanica1 twins have been observed in brigsten single crystals of a variety of axial orientations defornzed at room temperature in tension or bending. The twins formed near the final fracture and were up to 3 p thick. The twinning plane was always of the type (113). Twinning at room ternperature occurred only after considerable prior slip. Twins usually preceded fracture and nucleated cracks. The crack surfaces often alternated between a (001) plane and the twin interfaces. Secondary twins could also nucleate from cracks. In the absence of twinning tensile samples failed by shear; twinned samples failed by cleavage. On the assumption that observed sudden load drops in the stress-strain curves are associated with twinning, a critical resolved stress for twinning of 60, 000 to 65, 000 psi was calculated. MeCHANICAL twinning has been observed in iron and iron alloys at low temperature by a number of investigators.'-7 Similarly, for high-purity tungsten, twinning has been reported for deformation temperatures below 211°K.8-10 In W-Re and Mo-Re alloys, 20 pct Re was determined as the lower limit for twin formation at room temperature." Since the twins are generally very narrow, they are usually identified only by etching techniques. The expected (112) habit plane has always been confirmed by angular analysis of the surface traces. Recently, however, a complete identification by X-ray analysis has been performed on twins in a Mo-35 pct Re alloy.12 During an investigation of the deformation charac- teristics of tungsten single crystals, twins were revealed in tensile and bend samples deformed at room temperature. This paper deals with the conditions for such twinning and the relation of twinning to fracture. EXPERIMENTAL PROCEDURE Tungsten single crystals, 1/8 in. in diam, of a variety of axial orientations were grown from un-doped material by four-pass electron-beam zone melting. A representative analysis is given in the following table: From these crqstals, tensile samples with 1 in. gage lengths were made by surface grinding, leaving shoulders for gripping. The diameter after grinding was 0.082 in. The distorted surface layer was then removed by ele1:trolytic polishing which reduced the diameter of the gage length to 0.080 in. Tensile tests were carried out at room temperature in an Instron machine under two different sets of conditions: a) Rigid mounting; strain rate 0.02 in. per in. per min. b) Gimbal mounting; strain rate 0.002 in. per in. per min up to a total strain of approximately 0.2 pct, then 0.01 in. per in. per min to fracture. Stress axis and growth direction coincided in all samples and are subsequently called orientation.

Jan 1, 1962

By R. J. Fruehan

The oxygen activity and concentration were measured in Fe-Cr-0 melts in equilibrium with an oxide phase at 1600°C (2912°F). The activity was determined by ,use of the following solid oxide -electrolyte galvanic cell CY-Cr8,(s) I ZrOz(CaO) I Fe-CY-G(saturated)(l) The oxygen concentration decreases with increasing Cr concentration to about 270 ppm 0 at about 7pct CY and then increases gradually. The activity coefficient of oxygen (fo) decreases with increasing Cr. In melts containing up to about 20 pct Cr, log f is approximately a linear function of wt pct Cr with a slope (e q 2) of —0.037. The activity of chromium was calculated and found to exhibit a small negative deviation from Raoult's law. From the activity and solubility data for low chromium melts, the free energy of formation of chromite, FeCr204, was found to be -79.8kcal per mole where pure liquid chromium and oxygen at I wt pct in Fe are the standard states. ThE effect of chromium on the chemical behavior of dissolved oxygen in liquid iron is of great importance in controlling the deoxidation of steels containing a significant amount of chromium. Chen and chipman' equilibrated Fe-Cr melts in the presence and absence of slag with hydrogen-water vapor mixtures. They concluded that at 1595°C chromite was the oxide phase in equilibrium with Fe-Cr alloys containing less than 5.5 pct Cr while at higher chromium concentration Cr,O, was the stable phase. In the composition range 0 to 10 pct Cr they found that the interaction coefficient, was equal to -0.041. Turk-dogan,' Schenck and Steinmetz,, and pargeter4 measured egr) in a similar manner and found the value to be -0.064,-0.04, and -0.052, respectively. McLean and Be11 evaluated egr) from their data on the equilibrium of Fe-Cr-Al-0 alloys with H2/H20 mixtures and found it to be -0.058. However, McLean and Bell's value should only be considered an estimate because the effect of aluminum on the activity coefficient of oxygen is about a hundred times greater than that of chromium. Consequently, an error in the value of egl) used, which at the present time is not well-known, or an error in aluminum analysis, which is present in very small quantities, will result in a significant error in egr). Fischer et a1.6 determined the interaction coefficient (eEr) in Fe-Cr-0 melts not in equilibrium with an oxide phase and containing less than 18 wt pct Cr at 1600°C electrochemically. They determined a value of -0.031 for egr). Hilty et aL7 measured the oxygen content of Fe-Cr melts in equilibrium with an oxide phase containing up to 50 pct Cr. They found that the solubility of oxygen decreased as the chromium content increased to about 6 pct Cr and then increased gradually. They concluded that the equilibrium oxide phase was chromite below 3 pct Cr, distorted spinel from 3 to 9 pct Cr, and Cr,04 above 9 pct Cr. Adachi and lwamotoa also investigated this system, but did not find Cr30,. They X-rayed the equilibrium oxide phases and did not find the presence of Cr,O,. They also X-rayed the oxide phase extracted from a 65 pct Cr melt which was heat treated and did not find metallic chromium as would be expected if Cr3O4 were the equilibrium oxide phase as indicated by the reaction : 3Cr3O4 — 4Cr2O:, + Cr [lj It was the purpose of the present investigation to determine the effect of chromium on the activity coefficient of oxygen in Fe-Cr melts by measuring the activity and solubility of oxygen equilibrated with an oxide phase in the composition range 0.18 to 50.5 wt pct Cr at 1600°C (2912°F). The activity of oxygen in the melts was determined by use of the following galvanic cell: The relationship between the partial pressure of oxygen in equilibrium with the melt and the reversible electromotive force of the cell (E) is where 11 = 4, F is the Faraday constant, pb, is the oxygen pressure in equilibrium with the meit and is the oxygen pressure in equilibrium with Cr203 as determined from the free energy data compiled by Elliott et al? The oxide phase in equilibrium with pure chromium was assumed to be Cr If Cr30, were the equilibrium phase the activities derived would be approximately the same, since the best estimated free energy of formation of Cr,O,, if it does exist, is approximately % the free energy of formation of The activity of chromium in Fe-Cr alloys at 1600° C was also determined from the measured electromotive force. The activity of chromium (aCr) is related to the electromotive force as follows: , The oxide phase in equilibrium with pure chromium and Fe-Cr melts from 10 to 52 pct is assumed to be Cr203 so that n equals three. If future work proves the existence of Crs04 in equilibrium with Fe-Cr melts and pure chromium, the experimental results can be reevaluated using a value of $ for n in Eq. 141. A value of ^ for n will make the activities about 10 pct higher. In order for Eqs. 131 and [4J to be valid the electrolyte, ZrOa(CaO), must exhibit predominantly ionic conduction at the temperature and oxygen partial pressure of its use. Previous work1' has demonstrated that ZrOz(Ca0) is predonlinantly an ionic conductor

Jan 1, 1970

By C. E. Lundin, M. Hansen, D. J. McPherson

PRIOR work on the Zr-Cu phase diagram by Alli-bone and Sykes,' Pogodin, Shumova, and KUGU cheva,' and Raub and EngeL3 as confined largely to copper-rich alloys. The investigations of Raub and Engel were the most recent and seemingly the most complete of these. Alloys from 0 to 68.3 pct Zr were studied principally by thermal analysis and microscopic examination. These authors reported an inter metallic compound ZrCu, (1116°C melting point) and two eutectics, one at 86.3 pct Cu (977°C mp) and the other at 49 pct Cu (877°C mp). The solubility of zirconium in copper was reported to be less than 0.1 pct at 940°C. The zirconium melting stock consisted of Westing-house "Grade 3" iodide crystal bar (nominally 99.8 pct pure). It was treated by sand blasting and pickling (HF-HNO, solution) to remove the surface film of corrosion product, resulting from grade designation tests. The crystal bar was cold rolled to strip, lightly pickled again, and cut into pieces approximately 1/32 in. thick and 1/4 in. square. These were cleaned in acetone, dried, and stored for charging. The high-purity copper (spectrographic grade) was supplied by the American Smelting and Refining Co. with a nominal purity of 99.99 pct. These copper rods were rolled to strip, cut into squares the same size as the zirconium platelets, cleaned in acetone, dried, and stored. Equipment and Procedures The equipment used for melting and annealing the zirconium binary alloys and for the determination of solidus curves has been described in connection with previous work on the Ti-Si system' and in recent papers in this series describing the studies on eight binary zirconium systems.5-' Techniques employed for preparing and processing the alloys were also similar to those used in the above references. Ingots of 20 g were melted under a protective atmosphere of helium on water-cooled copper blocks in a nonconsumable electrode (tungsten) arc furnace. The ingots were homogenized and cold-worked prior to isothermal annealing to aid in the attainment of equilibrium. The specimens were heat-treated in Vycor bulbs sealed in vacuo or under argon, depending on the temperature of the anneal. Quenching was accomplished by breaking the Vycor bulbs under cold water. Temperature control was within ±3OC of reported temperatures. Thermal analysis was primarily relied on to determine eutectic levels, peritectic levels, and compound melting points. The induction furnace incipient melting technique was also used but did not provide the accuracy obtained by thermal analysis in this system, which involves much lower solidus temperatures than the other zirconium systems. A special technique for the determination of characteristic temperatures was employed in the case of several intermediate phases and their eutectics which displayed very small differences in melting temperatures. Specimens were sealed in Vycor bulbs and annealed at a series of very accurately controlled temperatures. Metallographic examination was then employed to reveal incipient melting. Furnaces and techniques in general were described previously.' The echant used was 20 pct HF plus 20 pct HNO3 in glycerine unless otherwise stated. Results and Discussion The chemical analyses of the majority of alloys prepared for the determination of phase relationships in this system are given in Table I and a brief summary of the equilibrium anneals employed is given in Table 11. In a preliminary program, alloys containing 1, 4, and 7 pct Cu were annealed for three different times at each of the temperatures 700°, 800°, and 900°C. No change in the relative amounts of phases present was detected after 350, 150, and 75 hr at the above temperatures, respectively. The times listed in Table II were accordingly chosen as a result of these preliminary tests. Zirconium-rich alloys containing from 0.1 to 10 pct CU were reduced by cold pressing from 58 to 8 pct, depending upon thk alloy content, homogenized for 7 hr at 900°C, and then reduced 80 to 13 pct by cold rolling, again depending upon copper content. Other alloys were studied in the cast, or cast and annealed conditions. The contracted scope of investigation for this system included the range 0 to 50 atomic pct Cu. This approximate region is shown in Fig. 1. Due to evidence of phase relationships departing considerably from those proposed by Raub and Engel" in the 50 to 100 atomic pct range, the investigation was extended to cover this composition area rather thoroughly also. Fig. 2 is a drawing of the entire diagram. The labeling of some phase fields was omitted in Fig. 2 for the sake of clarity. An expanded view of the zirconium-rich region, with the experimental points necessary for its construction, is given in Fig. 3. The generally accepted value of Vogel and Tonn8 or the allotropic transformation a + 862' ±5OC, was employed in the construction of these diagrams. A careful study revealed that the "Grade 3" crystal bar used in this investigation actually transforms over the approximate range 850" to 870°C, due to impurities. It must be expected that this two-phase field in unalloyed zirconium will cause some departures from binary ideality in the very dilute alloys. Zirconium-rich Alloys: The a + ß transformation temperature is decreased from 862" to about 822°C by increasing amounts of copper. Thus, a eutectoid reaction, fi ß a+ Zr,Cu, occurs at a composition of about 1.6 pct Cu. The eutectoid level was determined to lie between the alloy series annealed at 815" and 830°C. The placement of this eutectoid temperature

Jan 1, 1954

The Institute has no available copies of Bulletin No. 7, January, 1906, and Bulletin No. 105, September, 191.5. The sum of 30.50 per copy will be paid for these Bulletins.

Jan 6, 1917

For the year ending February, 1917 PRESIDENT L. D. RICKETTS, 1............... NEW YORK, N. Y. PAST PRESIDENTS BENJAIMN B. THAYER.1 ............... NEW YORK, N. Y. WILLIAM L. SAUNDERS,P ................ NEW YORK, N. Y. FIRST VICE-PRESIDENT SIDNEY J. JENNINGS,1 .....,...... ., .... NEW YORK, N. Y. TREASURER GEORGE C. STONE,l. ................ NEW YORK, N. Y. SECRETARY EMERITUS ROSSITER W. RAYMOND, .... .,. .......... NEW YORK, N. Y

Jan 9, 1916

By J. D. Alexander, W. L. Martin, J. N. Dew

This paper presents data obtained using a flood-pot technique to determine the fuel available and the corresponding theoretical air requirements for in situ combustion of crude oils. Since the technique is relatively quick and easy, it is a practical and convenient tool for evaluating reservoirs as fireflood prospects. It is also a research tool which facilitates systematic study of the variables affecting fuel availability and corresponding air requirements. The understanding of these variables is of prime importance to those concerned with the technical and economic development of in situ combustion as an oil-recovery process. The experimental results show conclusively that the fuel available for in situ combustion is not a constant but, rather, varies with crude-oil characteristics, porous-medium type, oil saturation, air flux and time-temperature relationships. Thus, the fuel availability for specified field applications should be determined using actual reservoir crude and core material and the process conditions expected during in situ combustion in the reservoir. INTRODUCTION In situ combustion is a thermal process for recovering crude oil from reservoirs. The thermal energy released during the combustion of a small amount of the oil in place aids in the displacement of the remaining oil. Numerous articles have been published describing the in situ combustion process giving detailed results of laboratory and field experiments.10 In order to engineer an in situ combustion project, a number of important factors must be considered and determined. These factors include: (1) the amount of fuel consumed per unit of reservoir volume swept by the combustion zone, (2) the composition of the fuel consumed, (3) the amount of air required to consume this fuel, (4) the portion of the reservoir swept by the combustion zone, (5) the appropriate air-injection rates and pressures, (6) the amount of oil that will be recovered, (7) the rate of oil production and (8) the operating costs. Nelson and McNiell1 recently have described a procedure which utilizes laboratory combustion-tube data as a basis for the calculation of some of these design factors. Various authors have attempted to describe the in situ combustion process mathematically, and considerable progress has been made. Analytical solutions to the problem of heat transfer from a moving combustion front have been obtained for linear and radial systems."-' All of the published results involve the assumptions that: (1) fuel concentration is constant throughout the reservoir, or that fuel concentration is inversely proportional to the velocity of the front for a given rate of oxygen consumption; and (2) the fuel reacts instantaneously with injected oxygen, while liberating a constant amount of heat per unit weight of fuel at all temperatures. It seems both desirable and reasonable to test the validity of these assumptions experimentally. This paper presents laboratory data which were obtained by means of a "fire flood-pot" method for determining fuel availability and composition, and the corresponding theoretical air requirements for in situ combustion of crude oils under variable conditions. The mechanics of the method are similar to a conventional tube-run experiment.' The important differences involve the size of the reservoir model used and the method for providing the experimental environment. The new method subjects conventionally-sized core samples or unconsolidated sands to a programmed environmental sequence similar to that experienced by a similar volume of rock during the approach and passage of a combustion front in a long tube or in an oil reservoir undergoing in situ combustion. Restored-state samples can also be used. The small samples and relatively simple techniques involved allow an experiment to be set up, run and calculated in about three 8-hour days. This is a considerable improvement over long-combustion-tube techniques which can require several days to run and several more work days to set up and calculate. All the runs presented were run at 40-psig injection pressure. Pressure was not considered as a variable for these experiments, since we previously had found that it had only a small effect on fuel availability up to 600 psig.APPARATUS AND MATERIALS APPARATUS The fire flood-pot apparatus consists of a consolidated

By D. W. White

The kinetics of isothermal transformation of ß-to-u uranium have been studied over a broad temperature range in alloys containing from 0.3 to 4.0 atomic pct Cr. Two modes of transformation are indicated by the existence of two C-curves in the TTT diagram. The upper temperature mode is regarded as a nucleation and growth mechanism, whose rate is controlled by diffusion of chromium in the ß phase matrix. The lower temperature mode is martensitic in nature. The M, temperature increases with decreasing chromium content, suggesting that the two transformation processes become synonymous in unalloyed uranium. URANIUM metal undergoes two allotropic transformations in the solid state. The a phase, orthorhombic in crystal structure,' is stable from room temperature up to about 665°C. The ß phase, characterized by a complex tetragonal structure,' prevails from 665" to about 770°C. The y phase is body-centered-cubic3 and is the stable modification from 770°C up to the melting point (about 1130"). In uranium of reasonable purity, neither of the two high temperature phases can be retained by quenching. However, the addition of certain alloying elements to uranium makes it possible to retain either the y-uranium phase or the ß-uranium phase at room temperature. Chromium alloyed in small amounts with uranium will permit retention of the ß-uranium phase in a metastable state at room temperature upon quenching from a ß-phase temperature.' From available information' on the equilibrium phase diagram for the U-Cr alloy system (Fig. I), it is to be expected that, however sluggish in its rate, the ß phase in such alloys should decompose eutectoidally to a phase and elemental chromium. It was the aim of this investigation to measure the rate and study the nature of this decomposition as a function of temperature and of chromium content. The investigation was reported in classified literature about five years ago and has recently been declassified for publication. In the meantime, there have appeared the papers of Holden,5 Mott and Haines,".' and Butcher and Rowe8 ealing with the metallography and the crystallography of the ß-to-a transformation in U-Cr alloys. These investigators have confirmed several of the phenomenological observations that will be described in the present paper and have examined in considerable detail certain aspects of the transformation and its mechanism. Although all of these investigations have concerned themselves experimentally with U-Cr alloys for the most part, an important consequence has been a clearer understanding of the nature of the ß-to-a transformation in uranium metal itself. Experimental Procedure This investigation dealt with a series of uranium alloys varying in chromium content from 0.3 to 4.0 atomic pct (0.066 to 0.90 weight pct). On five of the alloys, rates of isothermal transformation from the ß to the a phase were measured over a wide temperature range, leading to the development of TTT (time-temperature-transformation) diagrams. Transformation rates were measured over certain narrow temperature ranges on additional alloys. The alloys were prepared by vacuum melting and casting, using zircon or magnesia crucibles and graphite molds. Electrolytic chromium was used as the alloying addition, and the uranium was Mallin-ckrodt biscuit metal that had been vacuum remelted and cropped to remove many of the nonmetallic impurities that had floated to the top of the ingot. The ingots, 3/4 or 1 in. diam, were reduced in size by swaging. Alloys containing less than about 2 atomic pct Cr were swaged at 250° to 275°C, with initial and intermediate anneals at 550°C after every 75 pct reduction in area. Alloys with higher amounts of chromium were swaged at 550" to 600°C, although at the smaller sizes some of them were reduced by the procedure used on the more dilute alloys. Before use as test specimens, the swaged rods were annealed at 700" to 720°C for several hours, followed by slow furnace-cooling. The purpose of the anneal was to achieve the maximum amount of solution of the available chromium into the ß phase, as well as to remove extensive preferred orientation. The isothermal transformation rates were measured dilatometrically, using a quenching dilatometer and an experimental technique similar to those employed by Davenport and Bain in their original work on the transformation kinetics of austenite in

Jan 1, 1956

By D. W. Reed, R. L. Reed, Tracht

Laboratory experiments on the reverse combustion of tar sands in a linear adiabatic system have shown that a highly upgraded oil can be produced from an exceedingly viscous, immobile oil. The dependence on the air-injection rate of peak temperature, combustion-zone velocity, oil recovery, air-oil ratio, residual coke and oil, fuel burned and distribution of product gases is shown graphically. Eflects of initial temperature, oxygen concentration, oil saturation and heat loss are discussed. Experiments bearing on the coking properties of heavy oils are mentioned and some results exhibited. Field application of the process hinges on the existence of adequate air permeability and the rate of reaction under reservoir conditions. INTRODUCTION It has been established that oil can be recovered from underground reservoirs by means of at least two fundamentally distinct methods involving in situ combustion of a certain fraction of the oil. Characteristic of both of these known methods is the production of oil from one or more wells by means of hot gases formed when a high-temperature reaction zone is advanced through the reservoir. In both cases, the reaction zone is created by heating certain of the wells to a sufficiently high temperature prior to the introduction of air, and the zone is maintained and advanced through the reservoir by appropriate control of the air-injection rate. In the first of these methods, which is called "forward combustion",' the combustion zone advances in a direction which is generally the same as that of the air flow; whereas in the second method, "reverse combustion",' the combustion zone moves in a direction generally opposite to that of the air flow. Forward combustion, on the one hand, is an ideal combustion process in the sense that a minimum of the most undesirable fraction of the oil is consumed as fuel in the form of coke, a clean sand is left behind and generated heat is used as efficiently as possible. However, the applicability of forward combustion is limited. Since the products of combustion, vaporized oil and connate water must flow into relatively cold regions of the reservoir, there is an upper limit on the viscosity of oil which can be moved by this process in a practical and economical fashion.' On the other hand, it is characteristic of reverse combustion that the vaporized oil and water together with the products of combustion are produced through sand which is already hot and has had its mobile liquid content eliminated. This means there is no upper limit on oil viscosity; indeed, the oil may be an entirely immobile semi-solid. However, fuel for the process is an intermediate fraction of the original oil, and the most undesirable fraction remains on the sand surface as a substantial deposit of coke. Since this coked material is not burned during reverse combustion, it represents energy which is available for the production of oil but is not used for this purpose. It follows that one can expect economics to be somewhat less attractive with reverse combustion than with forward combustion. Nevertheless, it is a process which is designed for reservoirs where forward combustion is impossible and, as such, has become a subject of experimental and theoretical investigation. In this paper, only experiments made with tar sands are discussed. DESCRIPTION OF THE PROCESS We proceed, then, to consider the process of reverse combustion in greater detail. Fig. 1 illustrates a temperature profile defining a combustion zone which moves from right to left when air flows from left to right. In Zone 1, the temperature is the initial reservoir temperature, and the tar sand is as yet unaltered. This statement must be modified to the extent that physical properties of the oil may be changed by low-temperature oxidation at reservoir temperature. As air passes into Zone 2, which has been warmed by conduction, it assists in vaporization of the very light ends (if there are any), and oxidation occurs at a significant rate. In this region, there is almost no production of carbon monoxide or carbon dioxide because predominantly addition-type reactions take place with the formation of oxygenated compounds such as aldehydes and acids together with water. The hydrocarbon-enriched and slightly oxygen-depleted gas stream enters Zone 3 where

By F. B. Speaker

MUCH of White Pine's success is due to the mechanization of mining operations and the development of an efficient beneficiation process to extract usable copper from the low-grade ore (averaging slightly more than 1 pct copper content). When the mine was first opened, all ore was trucked to a conveyor system installed in the slope leading out of the mine. But as new mining areas have been opened up at increasing distances from the slope, conveyors have replaced the trucks for much of the haulage. This conveyor program is expected to continue as mining progresses. Here is how the present underground system functions: Run-of-mine ore is dumped into two truck hoppers and withdrawn from the bottom of each hopper by a 60-in. apron feeder 22 ft long (see diagram). Collecting conveyors 54 in. wide and 44 ft long receive the material from the apron feeders and discharge to two main-line 54-in. conveyors, one 2000 ft and the other 2600 ft long. Operating at 312 fpm and handling 1200 tph, the main-line conveyors converge near the bottom of the tunnel leading out of the mine and discharge into two 72x168-in. Vibrex screens. Ore under 8 in. goes directly to the bin beneath. The oversize is fed to two 32x40-in. jaw crushers and after crushing joins the 8-in. material in the bin.

Jan 12, 1957