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By P. Datta, L. L. Handy

For a wetting phase displacing a nonwetting phase from a porous medium the distribution of the residual fluid may depend on displacement conditions. Although this subject has been debated in the literature, only a few experiments have been cited to support the various conclusions. Experimental results presented in this paper show that fluid distributions are dependent on imbibition pmcedures. Results agree qualitatively with predictions from the pore doublet model. If the rate of water imbibition is restricted, the nonwetting phase is trapped preferentially in .the larger pores as expected. But if the rate of water imbibition is unrestricted, trapping occurs somewhat more in the smaller pores. These conclusions were deduced primarily from relative permeability measurements. INTRODUCTION Relative permeabilities are known to depend on the saturation history of the porous medium. For either continuously increasing or continuously decreasing wetting phase saturations, however, they have normally been assumed to be single-valued functions of saturation. Severat investigators have compared relative permeabilities measured by different methods and have reported acceptable agreement.1-5 Studies of simple models of the displacement process suggest that the distribution of residual fluids can be influenced by the displacement method. If this is so, relative permeabilities also should depend on the method of displacement. These predictions have not been supported by experimental data. The object of this paper is to investigate experimentally some of the predictions of these model studies. The particular question of importance is whether steady-state and unsteady-state methods should be expected to give the same values of relative permeability. Much of the reported data showing agreement between steady-state and unsteady-state methods have been obtained on un consolidated sand. Johnson, Bossler and Naumann, however, compared steady-state and unsteady-state results for Weiler sandstone and found no significant differences.5 Levine made a detailed study of pressure and saturation distributions for a laboratory waterflood in a consolidated system but made no attempt to calculate performance from steady-state relative permeability data Bail and Marsden in a somewhat similar set of experiments did attempt a comparison of observations with predictions but the results were inconclusive.7 Excluding gravity, two forces affect the distribution of wetting and nonwetting phases during an unsteady-state, immiscible displacement: viscous and capillary forces. If relative permeabilities are indeed the same when measured by steady- or unsteady-state methods, the fluid distributions at the same fluid saturations must be similar for both methods. Furthermore, the implication is that the relation between capillary and viscous forces is the same for both methods insofar as the effect on microscopic fluid distributions is concerned. Unsteady-state displacements are normally run at high rates to maximize the ratio of the viscous to capillary forces. The objective is to reduce the effect of capillary forces on macroscopic fluid distributions. For floods in which the phase which wets the porous medium displaces the nonwetting phase, capillary forces compete with viscous forces in determining fluid distributions.8 The residual nonwetting phase is discontinuous. Competitive aspects of viscous and capillary forces and the resulting effect on water-oil distribution in porous media have been illustrated in an elementary way using a pore doublet model. This model and predictions from it have been discussed at considerable length by Rose and Witherspoon, Rose and Cleary and by Moore and Slobod.9-13 Rose and Witherspoon show that so long as water invades the model at a rate equal to or greater than the free imbibition rate, the water will move through the larger capillary of a doublet first and trap oil in the smaller capillary. On the other hand, if a negative pressure is applied to the water

Jan 1, 1967

By G. M. Ritcey, A. W. Ashbrook, E. G. Joe

Solvent-in-pulp extraction of uranium from acid leach slurries of flotation concentrates is described. Solvent extraction was carried out in a 10 in. diam pulsed-plate column. The extractant was a 0.1 M tertiary amine (General Mills Alamine 336) in a kerosene diluent containing isodecanol as an emulsion suppressor and third phase inhibitor. In pilot plant operation at the Beaverlodge mill of Eldorado Mining and Refining, Ltd., slurry feeds containing up to 35% solids were processed at a throughput rate of 13.5 tpd of dry feed. Uranium extraction obtained was as high as 98%. Amine losses to the raffinate were approximately 0.07 lb amine per ton of original dry feed. The Beaverlodge Mill of Eldorado Mining and Refining employs a carbonate leach for the extraction of uranium from the ore.',' Prior to carbonate leaching sulphides are removed by flotation to reduce reagent consumption. This flotation concentrate containing some uranium is then leached with sulfuric acid, filtered, and the uranium precipitated with magnesium hydroxide. The precipitate is then returned to the carbonate leach circuit. Although the tonnage of flotation concentrate treated by acid leaching is low, reagent costs are relatively high. Also maintenance costs on the acid leach filtration circuit were beginning to show significant increases. The choice of solvent extraction-in-pulp as an alternative to the present circuit was influenced by the following factors: 1) elimination of acid pulp filtration, 2) increase in overall recovery because of soluble loss elimination, 3) reduction of reagent cost (mill sodium carbonate solutions are used as strip), and 4) production of higher purity precipitate at the mill site. Because a solvent-in-pulp process would be difficult to test on a bench-scale, the Eldorado experience in the use of pulse columns,3-5 mixer-settlers,6 and solvent-in-pulp operations in particular7 was applied directly to the initial pilot plant carried out during the summer of 1965 and followed by the second pilot plant in 1966. The latter work, which is presented in this paper, determined the following factors for anticipated scale-up to plant production: 1) overall uranium recovery by this process, 2) tonnage throughput expected, and 3) solvent losses anticipated for the full-scale plant. The equipment used consisted of a 10 in. diam extraction pulse column and three mixer-settlers for scrubbing, stripping, and acid equilibration. All equipment was designed by Eldorado and much of the pilot plant was built at the mill site. PROCESS CHEMISTRY Feed to the acid leach plant consists of a sulphide flotation1,2 concentrate containing mainly pyrite, uranium and graphite, with a particle size of 90%

Jan 1, 1968

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4'5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,' then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By H. De Cizancourt

Peche1bronn.—So far Pechelbronn is the only producing district. Figures are given in Table 2 covering the main features of the field, but these figures call for the following remarks: First, Pechelbronn should not' be considered as a single unit, it appears, but as a succession of small oil fields, each of which is affected by very variable conditions. Consequently, certain figures concerning production per acre, production per acre-foot, pressure conditions and thicknesses of oil sands would be so misleading that they have been omitted here. Second, as regards production methods, attention is drawn especially to the fact that 42 per cent of the oil is extracted by the use of shafts and galleries and the remainder by pumping wells. Exploitation, formerly confined to Oligocene sands, has been extended recently to Jurassic and Triassic oil-bearing formations. Gabian.—This small oil field, discovered in 1924, is almost exhausted. Exploitation to date is restricted to three wells. There were no drilling activities in 1933. Exploration.—During 1933, two exploration holes have been started in France. The first, in the vicinity of Lavelanet (Ariége) on the Dreuille anticline, has reached the depth of 2400 ft,.; the second, in the Autun Permian Basin, is drilling at 1300 feet. Northern Africa Morocco.—Drilling operations have been on a large scale in Morocco. In the Gharb district (Souk el Arba area), the deepest well was abandoned in 1933 at 7014 ft. Small irregular productive horizons were encountered in the Miocene at shallow depth, oil and gas showing in the Eocene, but no commercial oil field has been discovered. In the Djebel Tselfat, near Petitjean, a small production of oil was obtained from a Jurassic horizon. In the meantime deeper formations are being explored and a new structure in the vicinity is being tested. In Eastern Morocco, a well is drilling near Taza. Production in Morocco, about 2400 bbl., has not been listed on Table 2, owing to its origin—exploration wells.

Jan 1, 1934

By T. Federighi, S. Ceresara, C. Panseri

The results of an exploratory investigation by means of resistivity measurements at -195ºC, on the aging characteristics of a set of Al-Mg alloys with a maximum content of 7 pct Mg, are reported. Whereas for dilute alloys (Mg < 1.5 pct) only a decrease in resistivity is observed at about 100°C (due to the elimination of quenched-in vacancies), for more concentrated alloys such a decrease is preceded by an increase in resistivity in the range between -60ºand +40°C. Following some previous suggestions, this increase is considered as good evidence for clustering of solute atoms @reprecipi-tation process). From the analysis of the results it appears that, although the process is substantially similar to that observed in other Al-rich alloys, it is characterized by a strong interaction between vacancies and zones. THE process of formation of Guinier-Preston zones, i.e., preprecipitation,1&apos;2 which occurs during the aging at about room temperature in many supersaturated aluminum-rich alloys, has been extensively investigated in the past few years by several workers.2,3 owever, a very interesting question arises when the case of Al-Mg alloys is considered: although it is very easy to supersaturate Al-Mg alloys, just in the same way as for many other aluminum alloys showing preprecipitation, only very little experimental evidence was available until a short time ago in the literature supporting the existence of "natural" aging in supersaturated Al-Mg alloys (see, for example, Refs. 4 to 6). On the other hand, as is well known, the X-ray method is not useful in this case because the X-ray scattering factors of magnesium and aluminum atoms are about the same. Recently, however, Cordier and Detert7 have stressed that during the aging at about room temperature of a supersaturated Al-Mg 10 pct alloy it is possible to detect an increase in resistivity; since, as is well known, such an increase is observed also in most alloys showing preprecipitation, the above authors have interpreted their results as evidence for the formation of magnesium-rich clusters (or Guinier-Preston zones) during the aging. In the course of or ientative investigations on preprecipitation in several aluminum-rich alloys, we also could detect a similar phenomenon in more dilute Al-Mg alloys, see Instituto Sperimentale Metalli Leggeri, Annual Report, 1959, and also Ref. 8. Since the details of our observations, although of a preliminary nature, differ from those of Cordier and Detert and allow one to draw a more advanced picture of the preprecipitation process in Al-Mg alloys, we have thought it useful to report our results in this paper and to comment on them briefly.

Jan 1, 1963

By D. W. Fuerstenau

Recently R. J. Charles1 showed that comminution of brittle or semi-brittle materials in batch operations is described more appropriately by a variable energy relationship than by the specific relationships proposed by Rittinger,2 Kick,3 and Bond.&apos; That is, the value of n in the empirical differential operation which applies to crushing and grinding (Eq. 1) is variable. Independently, Holmes&apos; developed an identical generalized equaton for size reduction. The experimental data of Charles and Holmes show that the value of n is determined by the material and the comminuting machine and is constant for a given combination of these two conditions. The general objective of the present article is to extend the Charles-Holmes concepts to continuous ball milling. The specific objective is to analyze the operation of a vibratory ball mill dry-grinding chromite in a continuous open circuit and to develop an equation for the comminution of chromite in this mill. Basic Principles: In a batch mill the length of time during which the material is ground is a direct measure of the energy expended on the material, except possibly for exceedingly fine grinding. However, in a continuous operation, the fraction of the total expended energy which is useful for grinding will vary according to feed rate and amount of material in the mill. If the amount of material within a continuously operating vibratory mill is low enough so that only part of the expended energy is used for grinding, the extent of size reduction at constant power input must depend upon the length of time the material is retained within the mill, namely, upon retention time. The following analysis pertains to a continuous mill operating under these conditions. The empirical differential equation that applies to the comminution of brittle materials is:" dE = -Cdx/x" [1] where dE is an infinitesimal energy expenditure, C a constant, dx an infinitesimal size change, x the particle size, and n a constant. For continuous grinding in an open circuit at constant power input, P, Eq. 1 must be written as (dtr)P = -C dx/x" [la] where dt, is an infinitesimal time during which a particle of size x is in the mill, and C&apos; is a constant. A ground product never consists of particles of single size but always comprises a distribution of sizes. In comminution, the expenditure of energy causes a lateral shift in the size distribution.&apos;, &apos; " The general objective of any engineering study of comminution is to correlate the magnitude of this size distribution shift with the energy expended, the ultimate aim being to cause the greatest shift with the least amount of expended energy. Although a number of criteria can be used to measure this shift, Schuhmann&apos;s size modulus has been found convenient.&apos; Mathematically, the Schuhmann size distribution can be expressed as follows:" y = l00(x/k) [2] or in differential form: dy = [F- xa-&apos; dx ] K, where y is percentage of material finer than size x, a is a constant that determines weight distribution among particles of various sizes, and k the size modulus that denotes the theoretically maximum-sized particle in any size distribution. By considering the energy required to reduce an element of weight of material, dy, from size x, to size x, the element of time during which the material must remain in the mill at at power will be (dt..).= J&apos;-Cax!(dy) [3] Summing up all the elements of weight from zero to 100 for a product that conforms to the Schuhmann size distribution yields C C f Cdx,\( 100«x°-&apos;dx\

Jan 1, 1960

By R. V. Norris

The removal of mine-water by hoisting in tanks instead of pumping, while somewhat a reversion to the methods of the ancients, has come very rapidly into favor in the anthracite region of Pennsylvania during the past few years. In fact, so much so, that at the present time there are at least eight large collieries at which all the water is hoisted, and six more plants are in preparation. The particulars of the plants in operation and under construction, as far as decided on, are given in the tables on pages 107 and 108. Besides these, the Delaware, Lackawanna and Western R.R. Co. is constructing a hoist of large capacity for a depth approximating 500 feet, to be located in the Keyser Valley, near Scranton. The hoists will be driven by electric motors, geared directly to the sheaves. The Lehigh Valley Coal Company is planning a large hoist for the Packer collieries in the Shenandoah district, but no work has been done on this as yet. The earliest regular hoisting, I believe, mas done by means of semi-cylindrical tanks (Fig. 1) at the Nanticoke collieries of the Susquehanna Coal Company. These tanks were attached under the regular shaft-carriages, taking in water through six large clack-valves in the bottom, and discharging through an endgate opened by a lever which was operated by a guide-piece on the shaft head-frame. These tanks were designed July, 1880, by the late J. H. Bowden, one of the very early members of the Institute. Similar tanks are still used in emergencies at the Nos. 1, 2, 3 and 6 shafts of the company. The objections to. their use were: that water could only be hoisted during the night-shift, or when the shafts were not in use for hoisting coal, thus requiring a very large sump, and greatly limiting the water capacity of the plants; that the alternate wetting and drying

Jan 1, 1904

By C. A. Wright

The average lead and zinc content of the ores mined and milled in the Joplin district is low as compared with that of other lead and zinc deposits throughout the United States. Because of this fact and of the high grade of the concentrates, the ratio of concentration is unusually high. Most of the operating companies have aimed to produce as high a grade of concentrate as possible in order to obtain the highest price for their product. They have done this at the sacrifice of the percentage of zinc recovered. The average percentage of zinc recovery is from 60 to 70 per cent. For percentage of recoveries from actual mill tests, see tables. The concentration is commonly effected by crushing the ore to ½-in. (12.7 mm.) size and subjecting it to a roughing and cleaning over two or more large Cooley jigs, of the Harz type, the finer sands being treated on the usual types of sand and slime tables. The treatment of slimes by flotation is being tested at several of the larger mills. Coarse Concentration When the ore has been hoisted from the mine it is dumped onto a chute leading to a grizzly made of iron bars, usually heavy rails, spaced 4 to 5 in. (101 to 127 mm.) apart. The oversize is caught on the grizzly, the mineralized pieces are broken with sledge hammers so as to pass through, and the boulders that are practically barren are sorted out by hand and trammed to the waste-rock pile. The proportion of waste rock thus sorted out varies from a fraction of 1 per cent. to 15 per cent., depending on the nature of the rock. Crushing The undersize material, 5 in. (127 mm.) or less in diameter, passes through the openings of the grizzly into the mill hopper below. From

Jan 1, 1918

By J. E. Clennell

It is a common observation that the improvements introduced in practice since the first announcement of the cyanide process have been almost entirely mechanical. Although .a good deal of study land research has been devoted to the chemical problems [involved, the results obtained appear trifling in comparison. Few of the suggested modifications in the chemical treatment have come into practical use and those only in limited fields. Nevertheless, if we study the recent history of the cyanogen compounds from a somewhat broader standpoint, we shall find that considerable additions have been made, not only to our knowledge of their chemical properties, but also to their applications for industrial purposes. The present review of these advances naturally falls into two divisions: (1) processes involved in the treatment of ores; (2) manufacture of cyanides and other related compounds. Part I. Advances in the Chemistry of Ore Treatment by Cyanide In the attempt to extend the scope of the process, various ores have been encountered which contain gold and silver in such forms that they will not yield satisfactorily to ordinary methods of cyanide treatment. In some cases the difficulty is due to the excessive action on the solution of base metals present in the ore; in others, to the occurrence of minerals such as dyscrasite (the native alloy of antimony and silver), or a supposed oxidized manganese compound containing silver, which are either altogether insoluble in or very slightly attacked by cyanide. A particularly troublesome case is that of the so-called "graphitic" ores, containing carbon in some form which has the property of precipitating gold and silver already dissolved. Other efforts have been directed to improving extraction by electrolysis of working solutions, and by addition of various chemicals with or without electrolysis; to the diminution of cyanide consumption by "re-

Jan 1, 1916

By Morris Muskat

A theory is presented for calculating the performance history of complete water-drive systems producing from idealized stratified formations. The general equations are applied to systems where the permeability stratification is either of the exponential or linear type. Calculations were carried through for different degrees of permeability stratification, but with special emphasis on the effect of the mobility ratio between the produced oil and the invading water on the resultant performance. These results are also expressed graphically as curves for the initial water breakthrough recovery, for the different degrees of stratification, as a function of the mobility ratio, and of the composition of the produced fluid stream as a function of the cumulative oil recovery. For several typical cases the latter has also been plotted as a function of the cumulative oil and water throughflow. The general result is that when the mobility of the oil is lower than that of the invading water the channelling tendency resulting from the permeability stratification becomes aggravated as the higher permeability zones become flooded out. Situations of this type would obtain when producing low gravity or highly viscous oils. Conversely, if the mobility of the oil is high compared to that of the invading water, the flooding of the high permeability zones will lead to a retarding and choking effect, and the gross bypassing phenomena will be partially suppressed. These conditions would correspond to those of flooding high gravity or low viscosity oils. A discussion is given of the various basic assumptions made in the analysis, including that of ignoring the stripping phase of the production history as implied by relative permeability concepts. INTRODUCTION The physical ultimate recoveries from oil reservoirs are basically determined and limited by the physical oil displacement processes associated with the reservoir producing mechanism. In practice, however, the economic ultimate recoveries are further limited by the mobility of the reservoir fluids and the uniformity and continuity of the producing formation. In fact, it is the differential depletion between the component parts of the composite reservoir which ultimately determines the total recovery at the time of field abandonment. While this observation applies to both the solution gas drive and gravity drainage mechanisms, in which use is made only of the energy contained within the original oil-bearing reservoir, it is of even more paramount importance under operations wherein the energy associated with extraneous fluids provides the ultimate oil expulsion mechanism. Whether the invading fluid is the water from an edgewater drive, water injected for pressure maintenance, gas injected for pressure maintenance, or gas returned to the formation in a cycling program, it is often the continuity and uniformity of the producing section which will control the economic efficiency of the operations. The importance of the problem of reservoir non-uniformity does not, of course, lessen its complexity or the difficulties of its solution. In fact, these are inherently such that the concept of a "general" solution is virtually meaningless. About all that can be reasonably hoped for is the analysis of specific and well-defined types of non-uniformity which may give some degree of approximation to actual reservoir conditions. Since variations in the nature of the reservoir which depend only on the position along the streamlines will not lead directly to major differential depletion development within the reservoir, the types of non-uniformity considered thus far have involved stratification assumptions. That is, the producing section has been replaced by a multi-layer "sandwich," each uniform areally, and differing from the others only in its basic physical constants as to thickness, porosity and permeability. The fluid motion in the composite system is thus approximated by a parallel superposition of the independent fluid movements in the individual strata. For the specific application to cycling operations the theory of the effect of permeability stratification has been developed for both discontinuous&apos; and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear&apos; or probability3 functions. In all these studies complete dynamical equivalence was assumed between the injected dry gas and the displaced wet gas. The overall effective permeability of each stratum was therefore considered as constant and independent of the degree of invasion of the injected fluid. In the case of the displacement of oil by water, the assumption of dynamical equivalence between the water and oil will be strictly valid only by accident. Even if the oil viscosity should be the same as that of the water, the effective permeability to the oil in the presence of the connate water will in general be quite different from that of the water behind the water-oil interface flowing past the trapped residual oil. As a result the effective permeability for the stratum as a whole and rate of water invasion will change with time as the intrusion continues. The differential fluid motion in the individual strata will thus also vary with time. Qualitatively, it is easy to predict the resultant effects. If the permeability to viscosity ratio of the invading fluid exceeds that of the fluid displaced, the stratification and bypassing effect of the perme-

Jan 1, 1950

By C. Gutiérrez

Flotation and adsorption studies of ilmenite with technical oleic acid, pure oleic acid, and mixtures of each of them with n-hexadecane have been conducted. From them it is concluded that the depression of ilmenite caused by a too long conditioning time is due to adsorption of the collector onto the fines produced by attrition in the conditioning cell, and that fuel oil is necessary for economic flotation of non-deslimed ilmenite ore. This beneficial effect of fuel oil is attributed to van der Waals forces, of the hydro-carbon chains.

Jan 1, 1978

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

A generalized mathematical model has been developed to describe the kinetics of gas-solid reactions with special attention given to the hydrogen reduction oj dense spheres of hematite. This reduction process must pvoceed through a sequence of transport and chemical .reaction steps acting in series. Under typical experimental conditions, none oj the individual transport and reaction resistances may be neglected in the development of a physically significant model. A linear vate of thickening oj the product layer, usually taken as evidence of interface-controlled .reuction, may be observed even though transport resistances play a dominant role in the over-all kinetics. The temperature and pressure dependencies of all terms have been carefully evaluated in order to .make fill use oj arailable expe-inzental data in evaluation oj the model. FOR obvious technological reasons, the kinetics of reduction of iron oxides has become the subject of intensive experimental and theoretical investigation during recent years. Continuing efforts to construct mathematical models to describe the kinetics of reaction between a gas stream and a granular bed of solid particles have demonstrated the necessity of a thorough understanding of the reaction kinetics of a single particle within the system as a prerequisite to the construction of physically significant models of complex, reacting systems. This paper presents a critical examination of the transport and chemical-reaction processes involved in single-particle oxide reduction and develops the mathematical expressions necessary to evaluate their importance. Comparison of theoretical predictions with experimental results contributes important new understanding of the complex nature of this process. The reduction process has been studied under a wide range of experimental variables, and it is not surprising that apparent conflicts in observation and interpretation appear in the literature. The interested reader is referred to the reviews of Themelis and auvin"? and Manning and philbrook3 for a description of much of this work. The course of reaction commonly has been followed by measuring the oxygen weight loss from the particle as a function of time. A number of authors have suc- cessfully correlated their data in terms of a model which assumes that the reduction process is controlled by the rate of reaction at a single, sharply defined, advancing interface. According to this model, the interface will advance linearly with time. A mathematical model for gaseous reduction in a packed bed developed by the present authors in an earlier paper4 recognized that reduction must proceed through the series hematite (Fe203), magnetite (Fe30,), wiistite (Fe,O), and finally metallic iron. The reduction scheme permitted a stepwise topochemical reduction of the individual particles to metal or to the lowest oxide thermodynamically possible for the local gas composition in the bed. The limiting situations of theoretically dense and very porous oxide structures were considered. On the basis of available experimental evidence, the simplifying assumption was made in each case that all product layers would thicken linearly with time. A generalized single-particle model has now been developed to determine the significance of transport resistances in the product layers and in the gas film surrounding the particle. The analysis shows that the interplay of transport and chemical resistances is such that an apparently linearly advancing interface may be observed despite the fact that the reaction may be under significant transport control. Attention thus far has been focused on the development of a model for the topochemical behavior of dense spheres of hematite in atmospheres capable of reducing them completely to metal. The formation of successive product layers of iron, Fe,O, and Fe304 is assumed to follow the mechanism originally described by dstrijm.&apos; All oxygen removal from the core occurs at the iron/Fe,O interface, intermediate oxide layers being propagated by sol id-state diffusion without change in the oxygen density of the core. Since fractional reduction is operationally defined in terms of oxygen weight loss, the kinetics of the over-all reduction of FeZ03 to iron is properly studied in terms of the gas-solid reaction occurring at the iron-wiistite interface. The fractional reduction of a partially reduced oxide sphere is given by: here refers to the radial position of the iron/Fe,O interface. This model is not universally applicable because, as explained in the earlier paper,4 a consideration of porous particles or of dense particles in atmospheres not capable of reducing wiistite must allow for the possibility of gaseous reduction at interfaces other than the one between iron and Fe,O. However, evidence that certain hematite specimens actually do follow the dense-pellet mechanism developed here is provided by the data of cewan&apos; and of Bogdandy and

Jan 1, 1967

By Ralph J. Schilthis

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

Jan 1, 1938

By Graham P. Crutchfield

The W. I. Cook pool in Shackelford County, Texas, has been the subject of a number of papers and articles. Its unique position both as to operation and development has made it an ideal location for unit repressuring. The major portion of the pool is located on the W. I. Cook ranch and most of the oil leases are owned by Roeser & Pendleton, Inc. and the Continental Oil Co. and operated by Roeser & Pendleton, Inc. The Humble Oil & Refining Co. and Tom James operate producing leases which have a vital bearing on the unity of the pool. Both have cooperated in the repressuring project. Practically the entire royalty is owned by Mrs. W. I. Cook and she has given the operators her entire cooperation in all phases of unit repressuring.

Jan 1, 1931

By P. W. Bridgman

It is a commonplace that experimental physics in the last few decades has discovered manifold complexities in the atomic and subatomic levels, where it was thought for hundreds of years that no structure existed, as is witnessed by the derivation of the word "atom" itself. The field of exploration opened by the discovery of the electrical structure of the atom was so fundamental, rich and stimulating, that it has been almost exclusively cultivated by physicists since they obtained their first intimations as to the nature of the basic facts. Only within the last few years has it begun to dawn on us that we have overshot an enormous domain in which are situated many phenomena of fundamental importance for all the practical uses to which we put matter in our daily lives; the domain, that is, of most of the phenomena of interest to the biologist and the metallurgist. Furthermore, we are beginning to find that this intermediate domain is not entirely simple, but that it contains unsuspected complexities, some of them derived from the complexities of structure on the atomic and subatomic levels, and some of them emergent as matter collects itself into large aggregates, which often offer the key to the explanation of hitherto baffling large-scale properties of matter. Today I want to describe and consider some of these newly discovered complexities in the behavior of matter in bulk. The application to metallurgical problems is not always direct, but I hope to be able to suggest that such general notions as to structure as those here discussed must have important reactions on our attitude toward the problems of metallurgy. Three different sorts of phenomena of this kind to which I shall direct your attention are (1) the so-called structure sensitive phenomena, (2) complexities of such a nature that they are masked by the presence of extraordinarily small amounts of impurities, and (3) complexities depending on internal molecular rearrangements which can be understood only from the point of view of the quantum theory.

Jan 1, 1931

By Francis R. Conley, John A. Sievert, John N. Dew

A brief review is presented of the past performance of a number of large, thin, highly permeable reservoirs with low dips in the Bolivar Coastal fields of Venezuela. The performance of these reservoirs indicates that the fluids are segregated vertically within the sand section by gravity. With this assumption, equations are developed which describe the performance under pressure maintenance operations. Methods of solving these equations and results of simple example calculations are presented. Example calculations indicate that under pressure maintenance conditions injected gas tends to {tow preferentially along the top of the sands and that encroaching water has a tendency to flow preferentially along the bottom. The expected performance of segregated fluids is discussed and compared with that of fluids which are uniformly distributed in any sand section. INTRODUCTION The field performance of a number of reservoirs described herein indicates that the fluids are segregated vertically within the sand section by the force of gravity. Thus, it was felt that any method used to predict the future performance of these reservoirs should consider the effects of segregation in the sand sections. A study of the available information on some of the reservoirs suggests that increased recoveries may be expected if the reservoir pressure is maintained by either crestal gas injection or flank water injection. To predict future performance of reservoirs under pressure maintenance operations, a method of analysis was needed which would account for segregation of fluids in the sand sections. Several methods of analysis have been developed to take into account the segregation of fluids in the reservoir as a whole1,3 To our knowledge no method considers segregation of the fluids within sand sections in the manner indicated by the past performance of several reservoirs in the Mara-caibo Basin. This paper outlines part of the work done in studying some of these reservoirs and contains a description of their performance characteristics. The analysis presented is restricted to pressure maintenance conditions, since space limitations prevent a full discus- sion of the development of the mathematical relations and the various methods of solving them. Only a sketch of the development of the mathematical relations is given. The various methods of solving these relations are pointed out, but the actual determination of solutions to various problems are omitted except for one example. It is felt that these results may aid in the study of reservoirs outside the Maracaibo Basin. Some concepts on which the present analysis is based are outlined by D. N. Dietz. However, the analysis presented herein includes several factors not considered by Dietz: (1) variations in permeability and in the cross section, (2) various shapes of the cross section, and (3) the production of fluids. Also, the mathematical development presented by Dietz differs considerably from our corresponding analysis. RESERVOIR CHARACTERISTICS The reservoirs under consideration, large and thin, with low dip and high permeability, are large to the extent that they contain from 0.5 to over four billion bbl of oil initially in place. The section thicknesses vary from 100 to 400 ft and the lengths from 10,000 to 40,000 ft. Thus, a length-wise cross section of the producing formation appears to be long and thin. The dip angles vary from 0 to 6 degrees and the average permeabilities vary from 0.5 to over three darcies. The reservoirs contain from 20 to 50 per cent shale inter-laminated with the productive sands. Most shale breaks within the major sands do not correlate from one well to the next, and correlation is often difficult, even between wells drilled from the same location. However, it is often possible to correlate the shale breaks between major sands for some distance. Herein we are concerned with the performance of reservoirs containing oil of gravities over 20" API. Past reservoir performance indicates good pressure communication and, in cases where pressure sinks have developed, large amounts of fluid migration have occurred. Few of the reservoirs have had initial gas caps, but also, few have been found to be highly under-saturated. Due to gravity segregation, secondary gas caps usually form before the pressure has been reduced more than 25 per cent of its initial value. The effect of gravity has not only been apparent on a reservoir-wide basis, but has also caused segregation of the reservoir fluids in productive sections. Proof of this is found from the results of selective well tests, workovers, and electric and various other types of logs. Evidence that

By Thomas M. Drown

The process for determining phosphorus in iron now in most general use in the laboratories of iron and steel works, is, I think, the one proposed bv Mr. Emmerton." In this process the solution of the iron for precipitation by ammonium molybdate is effected by treating the iron with nitric acid, evaporating to hard dryness in a dish, taking up with hydrochloric acid and driving off the greater portion of the hydrochloric by nitric acid. This procedure accomplishes, first, the destruction of all the carbonaceous matters; and, second; it renders all the silica insoluble. Experience has proved the former—the complete oxidation of the carbon—to be absolutely essential; but the explanation usually given, namely, that unless the carbon compounds are destroyed they will have a solvent action on the yellow precipitate, I am inclined to

Jan 1, 1890

By L. C. Brown, A. J. Stewart

Phase transformations have been studied in Ag-Zn alloys quenched from the high-temperature bcc 0 phase and lying in the composition range 37.4 to 50.0 at. pct Zn. On quenching, the alloy with the lowest zinc content transformed to massive a (fcc); all other alloys formed the ordered (3&apos; phase. On deformation, a martensitic reaction took place forming a close-packed structure. At Lou&apos; zinc contents transformation to this structure was complete. However, above 43 at. pct Zn a p.rogressively increasing amount of ß&apos; was retained following deformation. The close-packed structure was fcc at lower zinc contents (under 47 at. pct Zn) and either hcp or a mixture of fcc and hcp at high zinc concentrations. The structures produced by cold working were unstable and on aging transformed to the ß&apos; phase or the complex hexagonal to phase. For low zinc contents (under 43 at. pct) the fcc st-ructure transformed directly to the equilibrium To phase. With higher zinc contents, some 13&apos; was retained following defownation, and on aging the amount of this phase relative to the close-packed structure increased. On further aging both structures transformed cornpletely to PO. Metallographic examination indicated that the nature of the deformation product depended very markedly on the mode of deformation. Tensile deformation gave a microstructure characteristic of thermal martensite. KING and Massalski1 have shown that an alloy of Ag-50 at. pct Zn quenched from the high-temperature bcc ß phase undergoes a low-temperature ordering reaction forming ß&apos; which can be retained to room temperature. On deformation an hcp phase is produced, although this is unstable and the structure reverts completely to ß&apos; on aging. In the present paper, the work of King and Massalski is extended to cover a wide composition range in the p phase, observations being made of the structure of the quenched 13 and of the effects of deformation and aging. The relevant portion of the Ag-Zn phase diagram is shown in Fig. 1. King and Massalski have shown that close to stoichiometry the ß&apos; phase is the equilibrium structure at low temperatures. The approximate composition range of this phase, taken from a recent paper by Pops and Massalski,3 is shown on the phase diagram. The locations of atom sites are very similar in the ß&apos; and to structures, and the 4, structure can be derived from the 0&apos; structure by a small movement of atoms mainly in the direction of the cube diagonal.4&apos;5 However, the probability of filling any particular atom site by a silver or a zinc atom is markedly different in the two structures. The structure can be considered partly ordered but the arrangement of the ordered atoms is completely different from that in the p&apos; structure and transformation from ß&apos; to requires a large fraction of the atoms to change position. It has been shown that the ß&apos; transformation is thermally activated involving normal nucleation and growth processes.5,8 Massalski and Barrett7 have shown that in the Cu-Zn binary the (3 phase can be retained in the ordered state to room temperature over a wide composition range. On deformation a new close-packed phase is produced, the structure varying from fcc to a mixture of fcc + hcp to hcp alone with increasing zinc concentration. It appears that an ordering reaction is necessary to retain the bcc phase to room temperature. In CU-Ga,8 the bcc phase cannot be retained to low temperatures as it transforms by a massive reaction above the ordering temperature of the ß phase. The structure of the massive phase is very similar to that in Cu-Zn, varying from fcc to fcc + hcp to hcp with increasing zinc concentration. Similar structures have also been observed in CU-A1,9 Ag-Cd,10,11 and Ag-Al.12 EXPERIMENTAL The alloys were prepared by melting fine silver (99.99 pct purity) and electrolytic zinc (99.999 pct

Jan 1, 1969

By M. J. Bradley, P. H. Dike

THE art of melting nonferrous metals, in smelting, casting, and in compounding of alloys, is highly dependent on a knowledge of the temperature of the metal. This knowledge may reside in the experience and judgment of the melter, or it may be based on measurement by suitable instruments. It-is our purpose to discuss briefly the instruments available for such measurements, and more at length the present, practice in molten metals, without recommendation. In the limits of time and space allotted, we can do little more than mention the available methods of measurement that are directly applicable in this field. In the 1939 edition of the Metals Handbook, issued by the American Society for Metals, pages 285-310, there is a more extensive discussion of pyrometry than can be attempted here, which should be referred to for details we must omit. For reasons that will appear, thermoelectric pyrometry will constitute the major portion of our discussion of the subject, only limited attention being given to radiation or optical pyrometry. METHODS OF MEASUREMENT THERMOELECTRIC PYROMETRY A thermocouple consists of two dissimilar wires, or a wire inside a tube of a dissimilar material, joined together at one end, which is placed in the region or medium where the temperature is to be measured, while the other ends are connected through suitable lead wires to a voltage-measuring device, which may be a millivoltmeter or a potentiometer. An electromotive force is generated in the circuit, which is proportional to the difference in temperature between the hot junction and the junctions of the lead wires to the measuring instrument. If this latter temperature is maintained constant, the e.m.f. measured varies only with the temperature of the hot junction. Every thermoelectric pyrometer is calibrated for a particular cold-junction temperature such as 0°F., 32°F. or 75°F., but usually it is more practical to compensate instrumentally over the probable range of cold-junction temperatures than to maintain the junction at the particular temperature for which the instrument was calibrated. Thermocouple Materials Only a very few pairs of metals are in frequent use for pyrometric measurements. The most generally used are iron-constantan for temperatures up to 1500°F. in oxidizing and up to 1800°F. in reducing atmospheres and chromel-alumel, which may be used in oxidizing atmospheres at temperatures up to 2400°F. for intermittent service. The accuracy of the latter deteriorates rapidly at temperatures above 2200°F. Platinum vs. platinum-rhodium thermocouples may be used up to a temperature of 3000°F , but they are easily contaminated by slow absorption of

Jan 1, 1946

By Jacob T. Wainwright

The object of this paper is to describe some efforts and observations by the writer relating to this subject. Althongh the usual type of&apos; blast-furnace is a most efficient device for smelting and melting purposes, it is not suitable for utilizing the cheaper grades of fuel, such as coal-slack and certain gaseous fuels. This problem not only involves the consideration of the furnace as a suitable apparatus, but also embraces the consideration of the chemical and calorific properties of the proposed fuel. In the hearth of the ordinary blast-furnace an extremely high temperature is maintained. This extreme temperature is due to the complete combustion of the fuel in the hearth, and before the gases reach the zone of fusion their temperature is reduced, by the absorption of carbon, 2300 degrees Fat). In a smelting-furnace, the maintenance of this extreme temperature at the hearth becomes useless when it can be reduced without

Jan 1, 1889