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By John V. Beall

There were no easily identifiable tourists. Everybody carried attaché cases and sported the buttoned-down look in dress. They were all there at the Hotel Indonesia to make a deal. But deals don't come quickly over there and those that staved and persevered became bored. They clung to the air conditioning of the Hotel and sought hobbies to while away the weeks-and even months. It is not an easy life but it can pay off fog sonic company. The government officials are neither stupid nor lazy. They are new at their jobs. Many are ex-army men and they know they must learn before they can enter into a contract with confidence. So they take time, and time is on their side.

Jan 1, 1970

By F. Hulsmeir

The increase in drilling activities in Venezuela noted during the latter half of 1932 continued, and 132 wells were completed in 1933 as compared to only 60 completed during 1932. Notwithstanding these new wells, 114 of which were producers, and also the appreciable increase in artificial lifting installations during the year, Venezuelan production was maintained at only a slightly higher level than in 1932, amounting to 120,356,000 bbl. in 1933 as compared to 118,167,000 bbl. in 1932. However, at the end of the year the daily average production of 358,-860 bbl. was 16 per cent higher than that at the end of 1932. Exports from Venezuela recorded an increase of approximately 4 per cent, totaling

Jan 1, 1934

By H. Leslie Bullock

From aluminum to zirconium, the quantitative preponderance of quartz as a gangue material is well recognized. lf this material is to be efficiently removed, its variations must be understood. Variations with temperature are especially important. Too little attention has been given to the thermal polarization of quartz. Under closely controlled conditions, electrostatic upgrading is very reliable. For efficient separation, contact charges must be fostered and charges due to radiation, surface coatings, or thermal polarization avoided. This paper lists thermal transition points of quartz and shows their effect on actual separations. Simple separation tests with all factors except temperature held constant are recommended for determining transition points. With silica making up more than 27% of the earth's crust, its oxides comprising more than 59% of all igneous rocks, and quartz accounting for most of the main free oxides, the mining engineer is in constant contact with quartz, which may occur as a valuable mineral to be purified or, far more frequently, as a gangue material to be removed as completely and economically as possible. As a means of effecting such purification or removal, dry beneficiation is becoming more and more desirable owing to local water scarcities, wet waste disposal problems, or freezing conditions. One method that has been gaining particularly rapid acceptance is electrostatic beneficiation, or the separation of dry free-flowing materials by means of opposite surface charges, differences in potential, or differences in conductivity. Electrostatic beneficiation dates back to the 1870's, but only in recent years have newly developed methods and apparatus and a growing knowledge of solid-state physics widened the field for its economical application. Because the term "electrostatic beneficiation" has been rather loosely used in the literature, it has come to include both electrostatic and electrodynamic procedures. Attracting type separators, however, in which oper- ation is based on differences of surface charge or potential, are truly electrostatic, because the separation occurs in a substantially static field set up between oppositely charged surfaces. Separations with this type of equipment may occur at potentials as low as 1000 v and seldom require potentials as high as 30,000 v. In the new contact charge dielectric separators1 the variation in charge is produced by continuous contact and separation of the particles in the moving feed stream and these charges are fostered by the use of non-conducting support and feed surfaces and by handling the feed in the form of streams of appreciable depth. This favors uniformity of feed and allows higher production rates. The distinctive surface charge differences are set up on the separation of the particles according to Coehn's Law,2 which states that equal and opposite charges are generated on the separation of any two materials in contact and that the substance having the highest dielectric constant will be positively charged. The basic contact charge concept is reliable, but all electrical charges are transient and modified by the electrical conditions of the surroundings. Pyro-electric, photoelectric and radiant effects may modify or totally destroy the contact charges necessary for efficient separation, or contact with conducting surfaces may neutralize them. Such hostile conditions must be carefully guarded against, since they have led to many costly failures in the past. The most consistent difference in surface charges to insure good separation is produced by repeated uniform contact and separation of particles in the moving stream. The thickness of the feed stream possible with this method reduces the effect of contact with the supporting surfaces, but as some contact is inevitable, the best results may be assured by having the dielectric constants of the supporting surfaces between the dielectric constants of the substances to be separated. In general, the hard smooth surface of quartz makes it an ideal substance for electrostatic separation from most minerals. For instance, with calcite, starting with a feed containing 1.9% acid insolubles, one can produce a concentrate containing 0.30% acid insolubles with a tailings containing 21.7% acid insolubles and a yield of 92.8%. The color can be held at 92 or above and the tint at 1.7 or lower. Working with specularite iron ore, laboratory work has given a concentrate of 68.8% Fe., with an iron unit recovery of 96.7%. Excellent results are also in pros-

Jan 1, 1969

By Fred C. Bond

MANY grindability tests have been made in the Allis-Chalmers laboratory since the tabulated results were last published.1 The lists of standard ball-mill and standard rod-mill grindability tests are brought up to date in this paper, and considerable new material is added. This includes a tabulation of open-circuit grinding tests, with impact and compression-crushing tests. The standard ball-mill grindability tests (Table I) were made in a standard laboratory ball mill, 12 by 12 in. inside, running at 70 rpm, with a charge of 285 iron balls ranging from 1 1/2 to 3/4 in. in diameter and weighing 20,125 grams. Seven hundred cubic centimeters of minus 6-mesh stage-crushed dry feed was used, and the circulating load was maintained constant at 250 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 28 to 200, and the grindability is the number of net grams of screen undersize produced per revolution. The table includes 479 tests. It has been calculated that the ball mill does 52.3 joules of useful work on the ore per revolution2 with 93 joules input to the mill. The standard rod-mill grindability tests (Table 2) were made in a laboratory tilting rod mill, 12 in. in diameter by 24 in. long inside, with a wave-type lining, running at 46 rpm. The grinding charge consisted of six 1 1/4-in. diameter and two 1 3/4-in. diameter steel rods, all 21 in. long and weighing 33,380 grams. The mill was rotated level for eight revolutions, then tilted up 5° for one revolution, down 5° for one revolution, and returned to level for eight revolutions. It was discharged by tilting downward at 45° for 30 revolutions. Feed consisted of 1250 cc of minus 1/2-in. stone and the circulating load was maintained constant at 100 pct by adjusting the number of mill revolutions for each grinding period. Tests were made at all mesh sizes from 3 to 65, and the rod-mill grindability is the number of net grams of screen undersize produced per revolution. The table includes 105 tests. The impact and compression-crushing tests (Table 3) are given in a table that is an extension of a previous publication3 in which the method of testing was described in detail. Two equal hammers weighing about 30 lb each were arranged to strike simultaneous blows on opposite sides of the test specimen. Broken pieces of rock passing a 3-in. square and retained on a 2-in. square were set up with the smallest dimension between the hammers, and this distance was measured. The height of the hammers was increased slightly before each blow until the specimen broke, and the foot-pounds per inch of thickness was calculated. Ten pieces

Jan 1, 1947

Since production curtailment for other than engineering reasons is gradually disappearing, and more and more wells are now producing at capacity and showing declining production rates, it was considered timely to present a brief review of the development of decline-curve analysis during the past three or four decades. Several of the commoner types of decline curves were discussed in detail and the mathematical relationships between production rate, time, cumulative production and decline percentage for each case were studied. The well-known loss-ratio method was found to be an extremely valuable tool for statistical analysis and extrapolation of various types of curves. A tentative classification of decline curves, based on their loss ratios, was suggested. Some new graphical methods were introduced to facilitate estimation of the future life and the future production of producing properties where curves are plotted on semilogarithmic paper. To facilitate graphical extrapolation of hyperbolic-type decline curves, a series of decline charts was proposed, which will make straight-line extrapolation of both rate-time and rate-cumulative curves possible. Introduction During the period of severe production curtailment, which is now behind us, production-decline curves lost most of their usefulness and popularity in prorated areas because the production rates of all wells, except those in the stripper class, were constant or almost constant. While production-decline curves were thus losing in importance for estimating reserves, an increasing reservoir consciousness and a better understanding of reservoir performance developed among petroleum engineers. This fact, together with intelligent interpretation and use of electric logs, core-analysis data, bottom-hole pressure behavior and physical characteristics of reservoir fluids, eliminated a considerable part of the guesswork in previous volumetric methods and put reserve estimates, based on this method, on a sound scientific basis' At the same time, a number of ingenious substitutes were developed for the regular production-decline curve, which made it possible to obtain an independent check on volumetric estimates in appraisal work, even though the production rates were constant. with the now steadily increasing demand for oil to supply the huge requirements of this global war, proration for reasons of than prevention of underground waste is gradually disappearing. More and more wells are, or will be, producing at capacity or at their optimum rates, as determined by sound engineering practice. With this trend, the character of producing wells seems to regain, more or less, its "individuality," and the old and familiar decline curve appears to have had a comeback as a valuable tool in the hands of the petroleum engineer. It may be timely, therefore, to retrace the development of decline-curve analysis in the past by presenting a brief chronological review of bulletins and papers published during the past three or four decades, which have

Jan 1, 1945

By H. W. Meyer, H. N. Lander, F. D. Delve

A method of calculating the changes in blast-furnace performance brought about by burden and/or blast modifications is presented. Essentially the method consists of three simultaneous equutions derived from materials and heat balances. These equations can be used not only to evaluate quantitatively the effect of changes in process operating variables on furnace performance, but also to provide a useful means of evaluating changes in process variables which cannot be measured directly. It has been customary for a number of years to use simple heat and materials balances as a basis for assessing blast-furnace practice. A good example of the method used to set up these balances is that proposed by Joseph and Neustatter.1 This approach to process assessment has limited utility, however, in that it cannot be used to predict the furnace coke rate or production under new operating conditions. Using an approach based on multiple correlation of blast-furnace variables, R V. Flint2 has developed an equation which may be used to predict the change in coke rate that will result from some changes in operating conditions with a reasonable degree of accuracy. Although this equation has useful applications in production planning, it cannot be used to study the relationships between the operating variables and the fundamental thermochemi-cal characteristics of the process. In attempting to analyze the blast-furnace process quantitatively, the idea of dividing the furnace into zones3 may at first appear attractive. In our present state of knowledge, however, it is not possible to define with any accuracy the physical limits of such zones in relationship to their temperatures or to the reactions which may occur in them. Although its application is restricted, the zonal approach to blast-furnace analysis is useful in some instances. For example, the change in the calculated flame temperature in the "combustion zone" caused by injecting steam constitutes information which is helpful in understanding why the addition of steam to the blast is best accompanied by an increase in blast temperature. The zonal approach cannot, at the present time, be used to establish the relationships between process variables and process performance if the whole process rather than part of it is to be considered. One of the earliest approaches to the problem of relating blast-furnace operating variables to pro- duction and coke rate was that developed by Marshall.4 Essentially Marshall's work showed that it was possible to estimate the performance of a furnace by solving three simultaneous equations which consisted of rudimentary carbon and heat balances plus a further equation relating the production, wind rate, and the carbon burned at the tuyeres. Although these equations did not include all of the chemical and thermal variables of the process, their derivation and application seems to be the earliest attempt which achieved any success in relating prior furnace operating data to the calculation of furnace performance under different blast conditions. Work carried out in Germany has been directed mainly towards prediction of coke rates using material and thermal balances rather than statistical methods. wesemann5 used prior furnace operating data as part of the basis for predicting the change in coke rate accompanying a change in burden composition. This author employed a method of successive approximations to estimate the secondary changes in slag volume and stone rate brought about by the change in coke rate. The most recent analysis, which seems to have been developed concurrently with the thermochemical model presented in this paper, has been described by Georgen.6 This author has succeeded in improving on Wesemann's approach by expressing the total changes in the slag volume and stone rate in terms of the change in coke rate itself. This is accomplished in a manner similar to that used in the thermochemical model described in this paper. Although Georgen makes use of a calculated furnace heat loss, he does not relate the heat loss per unit of hot metal to the production rate as is done in the present work. Georgen's approach may be used to calculate the changes in materials requirements accompanying changes in furnace operation; it cannot be used to assess the resulting changes in production. The fact that blast-furnace behavior can be interpreted by consideration of the heat requirements of the process was demonstrated by Dancy, Sadler, and Lander.7 In the analysis of blast-furnace operation with oxygen and steam injection these authors showed that it was possible to account for the changes in production and coke rate

Jan 1, 1962

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944

By J. T. Mackenzie

Henry Marion Howe, in whose memory we are gathered together, was one of the great thinkers who develop from time to time to whom is given the rare gift of synthesis. Analysis is given to few, but synthesis, the ability to show the relation of all parts to each other and thus to give a clear picture of the whole, is reserved for the very few. Analysis can be achieved by honesty, intelligence, and industry, but synthesis is only given to genius. Professor Howe's crowning achievement is the picture of the whole iron-carbon series shown in Fig. I, which places steel, malleable, gray iron, mottled and chilled irons in their proper relation to each other and shows the essential unity of the series. Perhaps his best statement of the case is found on page go of the Metallography of Steel and Cast Iron in these words: " Each member of the gray cast-iron series consists of the metallic matrix approximately equivalent to that member of the steel-white-cast-iron series to which it corresponds in percentage of combined carbon with its continuity broken up—by masses of graphite ..." Apparently he had taken considerable interest in this idea around the turn of the century, for he refers to a discussion at the Franklin Institute in I900 in which he said: "Though many others had probably conceived this relation between the steels and cast irons, it was here enunciated for the first time, so far as I know. It was received with great incredulity." The concept was explained in some detail in a paper on "The Constitution of Cast Iron" presented before the A.S.T.M. in 1902 when Professor Howe was retiring president of that young society. In the discussion Dr. Sauveur stated that he was "very well acquainted with Professor Howe's theory of the constitution of cast iron," and went on to say that while he "shared it to the fullest extent, some foundrymen . . . claim cast iron is a metal entirely different from steel . . . that steel and cast iron have very little in common, and that therefore the knowledge gained in the study of steel is of little or no value in the study of cast iron." Dr. Moldenke, in discussing the same paper, said he had been working on the same theory for 12 years but he laid no claim to publication. Discussing the difference in the micro-structure of the metallic matrix, Professor Howe pointed out that "such minor structural differences are indeed to be expected, because of the difference in the conditions under which these constituents are generated. "One difference in these conditions is that the steel of most micrographs has been either forged or at least treated thermally in such a way as to give a new structure radically different from that which formed during the initial solidification, whereas the cast irons have not. Hence what we see in the steels is a transformation structure, but in the cast irons a solidification structure. By giving the cast

Jan 1, 1944

By A. H. Daane, J. F. Haefling

The limits of miscibility in some of the uranium rare-earth alloy systems have been determined in the temperature range 1000°to 1250°C. The solubilities of lanthanum and cerium in uranium are greater than those of the remaining rare earths by a factor of more than two. The solubility of uranium is greater in cerium, braseodymium, and neodymium than in the other rare-earth metals studied. The values found in this study are in qualitative agreement with those which might be expected if the solubility rules of Hildebrand and Scott are applicable. AS interest in nuclear reactors intensifies, many new types of fuels are being suggested in attempts to improve the economics of some of the proposed reactor schemes. To remove some of the difficulties inherent in the use of solid-fuel elements and their reprocessing, many types of liquid-metal reactors have been suggested. One of the more attractive features of several of these reactor concepts is that they include a continuous or semicontinuous process for the extraction of fission products and "bred" fissionable materials from the fuel, utilizing immiscible metal extractants. This would enable a much higher burn-up of fissionable material to be achieved and would present a very attractive economic picture. Several studies have been reported on equilibrium systems in which there exists a high degree of immiscibility between uranium and another metal that might be used as an extractant in such a processing scheme.' Two of these systems in which a high degree of immiscibility exists are those of uranium with the two rare-earth metals, lanthanum, and cerium. Since the rare earths constitute a significant fraction of the fission products, their removal is of prime importance. It is reasonable to believe that this might be accomplished by equilibrating a rare-earth phase with the contaminated uranium fuel in the liquid state. In order to make a more complete study of those systems which would be of interest either as extractants in a liquid-liquid extraction process, or as fission products formed in the fuel, the alloy systems of uranium with lanthanum, cerium, praseodymium, neodymium, and samarium were studied in some detail in the temperature range 1000" to 1250°C; less detailed studies were made with the other rare earths. In addition to being of value to the reactor program, the data obtained in this study should be of help in making a study of the role played by the electronic structures of metals in determining the nature of metallic solutions. The unique electronic structures of the rare-earth elements make them particularly interesting in this respect. EXPERIMENTAL The usual procedure for a solubility determination was to seal equal volumes of uranium and the particular rare earth in a tantalum crucible under an atmosphere of helium; this crucible was then sealed in a stainless steel jacket in an atmosphere of helium. These samples were equilibrated by repeated inverting of the crucibles in a furnace for 15 min at the desired temperature, left in an upright position for 15 min to permit separation of the two phases, and then quenched under a stream of water. In some runs the temperature of the furnace was held 50' to 100°C above the desired quenching temperature while inverting in order to insure good mixing. However, it was found that above 1200°C the crucibles were subject to failure and for these runs the furnace temperature was not raised above the desired quenching temperature. A small amount of tantalum was dissolved in the uranium and the rare earths in these runs, a maximum of 3 wt pct in the uranium phase at 1250°C and up to 1 wt pct in the rare-earth phase at this temperature. On cooling, the major portion of this tantalum precipitated as primary tantalum crystals. Any residual tantalum would probably have a negligible effect on the mutual solubility of uranium and the rare earths in each other. Samples for analysis were cut from each phase with an abrasive cutting wheel; the region near the interface between the two metals was carefully avoided. In the case of the rare earths with melting points above 1250°C no solubility data were taken on the rare-earth phase since this phase could not have achieved equilibrium in a reasonable length of time. (For the same reason no data were taken on the uranium phase below its melting point of 1132°C.) Equilibrium appeared to have been reached in the uranium phase in these cases although the rare-earth phase had not melted. To verify this, samples were melted together in an arc furnace similar to that described by Kroll.2 These samples were sub-

Jan 1, 1960

By A. R. Gregory

A shear wave velocity laboratory apparatus and techniques for testing rock samples under simulated subsurface conditions have been developed. In the apparatus, two electromechanical transducers operating in the frequency range 0.5 to 5.0 megahertz (MHz: megacycles per second) are mounted in contact with each end of the sample. Liquid-solid interfaces of Drakeol-aluminum are used as mode converters. In the generator transducer, there is total mode conversion from P-wave energy to plain S-wave energy. S-wave energy is converted back to P-wave energy in the motor transducer. Similar transducers without mode converters are used to measure P-wave velocities. The apparatus is designed for testing rock samples under axial or uniform loading in the pressure range 0 to 12,000 psi. The transducers have certain advantages over those used by King, 1 and the measurement techniques are influenced less by subjective elements than other methods previously reported. An electronic counter-timer having a resolution of 10 nanoseconds measures the transit time of ultrasonic pulses through the sample; elastic wave velocities of most homogeneous materials can be measured with errors of less than 1 percent. 5- and P-wave velocity measurements on Bandera sandstone and Solenholen limestone are reported for the axial pressure range 0 to 6,000 psi and for the uniform pressure range 0 to 10,000 psi. The influence of liquid pore saturants on P- and S-wave velocity is investigated and found to be in broad agreement with Biot's theory. In specific areas, the measurements do not conform to theory. Velocities of samples measured under axial and uniform loading are compared and, in general, velocities measured under uniform stress are higher than those measured under axial stress. Liquid pore fluids cause increases in Poisson's ratio and the bulk modulus but reduce the rigidity modulus, Young's modulus and the bulk compressibility. INTRODUCTION Ultrasonic pulse methods for measuring the shear wave velocity of rock samples in the laboratory have been gradually improved during the last few years. Early experimental pulse techniques reported by Hughes et al.2 and by Gregory 3 were beset by uncertainties in determining the first arrival of the shear wave (S-wave) energy. Much of this ambiguity was caused by the multiple modes propagated by piezoelectric crystals and by boundary conversions in the rock specimens. Shear wave velocity data obtained from the critical angle method, described by Schneider and Burton4 and used later by King and Fate sand by Gregory, 3,6 are of limited accuracy, and interpreting results is too complicated for routine laboratory work. The mode conversion method described by Jamieson and Hoskins7 was recently used by King 1 for measuring the S-wave velocities of dry and liquid-saturated rock samples. Glass-air interfaces acted as mode converters in the apparatus, and much of the compressional (P-wave) energy apparently was eliminated from the desired pure shear mode. A more detailed discussion of the current status of laboratory pulse methods applied to geological specimens is given in a review by Simmons.8 A new shear wave velocity laboratory apparatus has been developed for testing rock samples under elevated pressures. This apparatus employs liquid-solid interfaces as mode converters. The technique for generating pure shear waves at liquid-solid interfaces was developed from studies of critical angle methods.6 Two identical transducers are placed in contact with opposite ends of the rock sample, one transducer acting as an ultrasonic energy emitter or generator and the other acting as an ultrasonic energy receiver or motor. The P-wave energy emitted from the piezoelectric crystal in the generator transducer is converted into pure S-wave energy at the Drakeol-aluminum

By L. F. Mondolfo

R301 is a clad aluminum alloy, composed of a core of a duralumin-type alloy clad with a magnesium silicide alloy. It differs from other well-known clad alloys in that the cladding and the core respond to the same heat-treatments, and therefore the cladding contributes appreciably to the mechanical properties of the material. In Table 1 are reported the compositions of the core and cladding alloy for the material used for the experiments. [ ] In clad aluminum alloys where the core contains copper and the cladding does not, at elevated temperatures the copper tends to diffuse from the core through the cladding. This fact is well known and many investigations have been conducted to determine the features of this diffusion.1-7 Most of those investigations cover materials clad with pure aluminum; the present investigation covers a material clad with an alloy. Since the cladding thickness on R301 varies with the gauge, as shown in Table 2, several gauges were investigated. [ ] MATERIAL AND PROCEDURE The material used was sheet of the following gauges: 0.025, 0.040, 0.064, 0.102, 0.170. Cut in pieces approximately 3 by 5 in., it was in the cold-rolled state and was soaked for increasing times at the following temperatures: 910°F., 940°F., 970°F. A Lindberg cyclone furnace was used for the experiments. The procedure was as follows: The furnace was started empty with controlling pyrometer set at the determined temperature. After the furnace had reached that temperature, it was run for some 20 to 30 min. empty, in order to allow the temperature inside to become stabilized. Then the first samples were introduced. A load thermocouple, with recording pyrometer, was connected with the sample of the heaviest gauge. About 10 min. was required for the material to reach temperature and the soaking time was counted from that point. After 200 min. soaking, the second group of samples was introduced without stopping the furnace. After 200 min. more, the third group of samples was introduced, and so on, until the last sample had been introduced. Every time the furnace was opened and new samples were added, a drop of temperature was registered by the thermocouple connected with the material

Jan 1, 1945

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By J. E. Pollock, W. R. Hicks, E. Camp

IN the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. TEST METHODS Either one Of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

By Alfred Weiss

When I first received the announcement of this meeting I was pleased to see that this 14th APCOM Symposium had expanded its range of interest. One new topic to be considered this year is long range or strategic planning--the continuous process by which current risk taking decisions are made systematically, and with the greatest knowledge of future impact. Long range planning should receive our attention. It is the first step in the management process and the foundation of many--if not all --key managerial decisions. Improvements made at this stage of managing are almost certain to be of benefit in later stages of decision making. It is obvious to many of us that in a physical process such as mineral beneficiation, one does not concentrate all of one's attention on the flotation design without also considering the grinding, cycloning, and desliming stages of the process. Taking this a step further it would be equally erroneous to find a mineral engineer designing a mill without due consideration for mine, smelter and refinery and beyond that the sales goals, growth and profit objectives of the firm itself. And yet, how many times have we seen organizations staff and reorganize without consideration of an overall plan; without adherence to the management process which by its definition, calls for a plan first, followed by the appropriate organization and staff. The computer applications traditionally discussed at APCOM meetings have concentrated on areas dealing with things and people-- the implementation of the plan, rather than with concepts and ideas, the formulation of the plan.

Jan 1, 1977

By H. A. Jr. Koch, C. A. Hutchinson

Miscible phase displacement of oil from reservoirs has been emphasized in the past few years. The reason for this emphasis lies in the high oil recovery attainable by this process. Removal of capillary effects in the reservoir leads to recoveries approaching 100 per cent in the area contacted by the miscible phase. The miscible slug process is one means of obtaining a miscible displacement. Here a band or slug of I,PG is injected into the reservoir prior to gas injection. The idea is to maintain the band of LPG "wedged" between the gas and oil phases and thus achieve a miscible phase displacement. A second method lor achieving miscibility is through the injection of a gas which is not miscible with the reservoir fluid but which develops a zone of miscibility in [he reservoir through mass trans-ier with the reservoir oil.' This mass transfer results in either an enrichment of the lean injected gas by intermediates from the oil or an enrichment of the oil by intermediates from a rich injection gas or one that has been enriched on the surface by LPG addition. We are interested here in discussing the process in which miscibility is developed at the displacement front by the evaporation of interrnediatcs from the oil phase into the gas phase. This process "builds up" its own slug of miscible material at the displacement front and therefore does not require the injection of LPG to obtain miscibil-ily. Each process has its own area of applicability. Generally, the high pressure gas process is applicable only with reservoir fluids which con-!ain a high concentration of inter- mediates. If the high pressure gas process is technically feasible at pressures less than 4,500 psi, it is probably more desirable economically than the slug process. The slug process has broad applicability in the shallower reservoirs and with reservoir fluids which contain a relatively low concentration of LPG and natural gasoline constituents. This paper deals with some new concepts of the high pressure gas injection process where it is proposed that flue gas can be substituted for hydrocarbon gas without sacrificing our goal of miscibility. MECHANISM Introduction Considerable effort has been devoted to study of the mechanics ot the high pressure gas injection proc-one generalization result-ing from some of these studies was that the composition of the injected gas is relatively unimportant in establishing the miscibility pressure* for a given reservoir fluid. This generalization is correct for the composition range of gases typically encountered in the field. Two such gases are a gasoline plant tail gas containing 85 per cent methane and 15 per cent ethane, and a field separator gas containing 70 per cent methane and 30 per cent heavier components. The most important factor which sets the miscibility pressure in the operation is the reservoir fluid composition, particularly the concentration of LPG-natural gasoline constituents. The injected gas is the agent by which the LPG-natural gasoline constituents are concentrated at the displacing front to create a miscible displacement. Based on these results, it appeared feasible that some inexpensive gas, such as flue gas, might be substituted for hydrocarbon gas for use in the high pressure gas process. A re-examination of the phase relations of the high pressure gas injection process should clarify the principle behind using flue gas (essentially nitrogen) as an injection gas. Three Component Diagram The phase relations of the high pressure gas injection process have been illustrated by the use of the three component diagrams.'," In Fig. 1 we have arbitrarily represented the multi-component reservoir system by three components; methane, ethane through hexane, and heptanes plus. The solid curve ABC is the phase boundary curve. It represents the locus of compositions which have fixed saturation pressure at a fixed temperature; the lower branch AB shows bubble point compositions, the upper branch BC, the dew point compositions. Point B is the coniposition of the critical mixture at this temperature and pressure. The dashed lines (tie lines) connect vapor and liquid compositions which are in equilibrium. Let us consider Reservoir Fluid D which we wish to displace in 21 miscible manner by gas injection. Let us further restrict the discussion to the case where miscibility between an injection gas and the reservoir fluid at the displacement front is developed by gas enrichment in the reservoir. For this case, any gas whose composition lies between Points C and E on the right side of the three component diagram can be used to give a miscible displacement of Reservoir Fluid D. This is true because the more mobile injected gas moves faster than the displaced oil and is in continuous contact with virgin oil at the displacement front. This leads to a continuing enrichment 01' the gas at the displacement front by evaporation of the C, - C,

By MAGNE MORTENSON

IN laboratory work and industrial tests it is important to set forth the results of research, clearly. This is generally achieved by means of some form of diagram or graphical illustration. The most common form for such graphs of flotation research is a simple chart with two curves for percentage and recovery of the concentrate. This may be quite useful, especially for minerals which may be floated: by means of one reagent in variable and another in constant amounts. If both reagents are used in variable quantities the process may be illustrated by means of several diagrams, .keeping one reagent constant in each series of tests. A more useful form of diagram for a. system with two variable - components (reagents) may be established by drawing a chart with the weights of the two reagents as .abscissas and ordinates. Every test is marked down -in the diagram with an indication of the extraction and concentration gained. In this diagram there are drawn lines for equi-extraction and equi-concentration of the mineral that is floated out in the - concentrate. The contour of these lines gives a relatively clear impression of the conditions for flotation by means of .the chemicals used. The best conditions are of course found in diagrams where the 'areas for maximum extraction and high conntration are coincident

Jan 1, 1931

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By W. R. Hicks, J. E. Pollock, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935

By J. E. Pollock, W. R. Hicks, E. Camp

In the oil-refining industry, steel comprises by far the greatest proportion of the materials used in construction work, but with an enormous number of alloy steels and nonferrous alloys available, and a greater knowledge of their properties and corrosion resistance, a substitution first in the "hot spots" and then in locations of moderately severe corrosive conditions will be made as the greater expense can be justified. In new construction work, advantage is taken of the experience already gained and appropriate materials used, whether for high temperatures and pressures demanding additional strength or for corrosive conditions. The locations, however, where equipment in operation constantly requires replacement will soon become evident, as will the necessity for replacement in more resistant materials, if considerable down-time is to be avoided. In what direction and how far to go in the matter of alloys then becomes a question of the highest importance. Obviously, any replacement with more costly material must be justified economically by the promise of longer life, thereby saving both material and installation costs besides the reduction of loss of production. Where the equipment is overcapacity and a regular schedule of cleaning periods is in force, the last item frequently must be ruled out and justification made on the basis of the first two only. Installation of material that will outlast the remainder of the equipment and have no recovery value must also be avoided; this is particularly important in temporary construction or in old equipment that will soon become obsolete. Test Methods Either one of two methods or a combination of both, in the absence of reliable data in similar services, may be adopted to determine to what extent replacement with other, and perhaps more expensive, materials is justified. A unit may be constructed incorporating different metals or alloys so that comparative service may be obtained under the same service conditions; this has been applied in many instances, such as condenser and tank construction, but the opportunities for inspection may be few and

Jan 1, 1935