Search Documents

Discussion of the paper of G. K. Burgess and J. J. Crowe, presented at the New York Meeting, October, 1913, and printed in Bulletin No. 82, October, 1913, pp. 2537 to 2591. HENRY M. Howe, New York, N. Y. :-I think we can hardly rate the importance of the entry of the Bureau of Standards into our field. There is no body in the world that is better fitted to undertake this work than that Bureau, and it is work which really calls for the aid of some national organization. The skill and care with which this work has been done speaks for itself. It is very striking that within a very few months the distinguished English investigator, Professor Carpenter, of whom I spoke before, thought that he had disproved the existence of beta iron by proving that the A2 retardation which Professor Burgess has now demonstrated did not occur. Dr. Burgess's demonstration of the existence of. this retardation makes the existence of beta iron very probable, in my opinion. Osmond used to call beta iron " decipuum." You knew of its existence as you know of the existence of certain planets, only by the perturbation which it caused. Certain phenomena could not be explained, except by assuming the existence of a third allotropic form, beta iron. The evidence that you got was always evasive and susceptible of other explanations, except that which we have to-day, which it seems to me is not capable of other explanation. Professor Carpenter proceeded in the same way that Dr. Burgess has, by taking the heating and cooling curves of exceedingly pure iron, and thought that he had shown that there was no thermal change, no absorption or evolution of heat at the supposed A2 point, and hence that the A2 point did not exist. This he did by a piece of reasoning which I think seems to most of us rather surprising. That is to say, if of ten witnesses, three have seen a thing and seven have not, the evidence of the seven who have not is set aside, and that of the three who have seen stands. In Dr. Carpenter's own experiments under certain conditions he found the A2 change, the heat evolution., under certain others he did not. That is like the three witnesses who saw and the seven who did not see. You can arrange your test so that this change will not become visible or so that it is masked. But though an existent change can be masked a non-existent one cannot be shown. So that the reasoning seemed to me wholly fallacious.

Jan 12, 1913

J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—The fact that the experimental work has been applied to copper rather than iron and that the paper is presented to the Iron and Steel Division, I regard as rather significant. It shows the unity of metallurgy and the fallacy of trying to cut it up by metals. This result for the solubility of sulphur in molten copper correlates with Professor Schuhmann's finding that the published data on the other side of the copper-sulphur miscibility gap are also in error. I should like to ask the author to say a little bit more about the sulphur capacity of the slag. T. Rosenqvist (author's reply)-—I hope that Dr. Chipman will find the derivation of the expression for sulphur capacity more clearly explained in the printed version of the paper than in the oral discussion at the meeting. I feel that this quantity, which actually is the ratio of two activities, can be measured more easily than the individual activities. Even if the ratio CaO/CaS is chosen as the standard state, the expression can be used for any slag, even for slags completely free of lime, and it represents a way to put the desulphurizing power of all slag constituents into one bag. Some doubt has been expressed as to whether oxygen ions really exist in calcium oxide and in molten slags. From a thermodynamic view point that question is of minor importance. The term oxygen ion activity, or any activity for that matter, is defined rigorously by the equation: activity = exp u/RT, where u is the change in free energy connected with the transfer of one mol of ions from the standard state into the slag. Whatever happens to the ion in the slag is of no concern to the thermodynamicist. Regardless of whether the ion is "free" in the slag or not, or whether it is present in a very small amount, its activity can always be expressed, and for a thermo- dynamic calculation that is all we need. However, ionic activities will only be of some real value if they are simple functions of the slag composition, or can be measured easily. Concerning the real nature of the oxygen in the slag, my feeling is that the oxygen atom has a rather multiplex nature depending on how strongly it is tied by covalent forces or polarized by the other atoms or ions present. The oxides of iron, cobalt, and nickel differ from calcium oxide and blast furnace slags as to the amount of free electrons that can give rise to electronic conductivity. In slags we know that the conductivity is mostly ionic. The fact that reversible emf's can be obtained with oxygen electrodes in certain salt melts, indicates a significant amount of oxygen ions in these melts. But extended work, e.g. polaragraphic studies and measurements of transference number; are needed to obtain quantitative information about the real structure of the slags. D. E. Babcock (Republic Steel Corp., Youngstown, Ohio)—-With reference to the ion, it might be well to remember Dr. Moses Gomberg. All of his life he had no use for the ionization theory and he contributed greatly to the field of chemistry on the assumption there was no such thing as ions. I do not think we have to worry about whether the oxygen is ionic or not. I think one thing specifically should be brought to your attention and this I think is one of the important contributions of Dr. Rosenqvist. He pointed out what we know as oxygen potentials or what is described as oxygen potentials. I have used this concept for a long period of time and I want to state that if this concept is properly applied, it vitiates much of what we have in the literature, or makes our usual ideas regarding oxidation seem primitive. That one thing is more valuable than almost all the rest of the discussion as a fundamental basis on which to build a reasonable in-

Jan 1, 1952

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By L. L. Newman

As soon as the Congress recognized the alarming rate at which our domestic oil resources were being depleted during the war, it took action to step up the rate of research and development which the Bureau of Mines had been conducting for several years on the production of synthetic liquid fuels from coals. Under Public Law 290, approved April 5, 1944, funds were authorized for the Bureau to proceed with research, development, design and construction of demonstration plants for the hydrogenation of coal, the synthesis of oil from carbon monoxide and hydrogen, and the distillation of oil from shale. During the latter part of 1944, when it became evident that the collapse of Germany was near, a Technical Oil Mission was organized to study the German techniques of synthetic oil production. Since the cost of hydrogen or synthesis gas is one of the major factors of expense in the operation of hydrogenation or synthesis gas processes, the Bureau of Mines considered it of prime importance to include on the mission gas engineers whose instructions were to examine closely the methods employed by the Germans in solving the problem of providing low-cost hydrogen or synthesis gas for their very extensive operations on synthetic liquid fuels. The Solid Fuels Mission and the Utilities Mission, as well as the Army and Navy Missions, also included teams for the study of German gas production. Although their objectives naturally differed from those of the Technical Oil Mission and from each other, it was recognized that there was considerable overlapping of their fields of investigation. Duplication of effort, however, was largely avoided through the close cooperation between the group leaders of these missions. For example, although I went to Europe as a member of the Technical Oil Mission, my first Gcrman assignment was actually made by Dr. Harry F. Yancey, leader of the Solid Fuels Mission— to investigate the brown-coal gasification methods in central Germany. The art of gasification in the United States and England, and to a large extent in the proximity of the coking-coal regions of Germany and the rest of continental Europe, depends essentially on two stages of operation; namely, carbonization and intermittent water-gas generation. As far as the United States is concerned, complete gasification in a single stage of operation is rarely practiced, except in gas-producer operations where the product is a relatively lean gas consumed close to the point of manufacture, and for water-gas production with anthracite as a generator fuel. Complete gasification of bituminous coal has been the subject of numerous investigations. Many relatively simple modifications of the water-gas generator have been tried to permit the direct gasification of low-cost bituminous coal instead of high-cost coke and anthracite for the production of water gas. Although varying degrees of Success have been achieved and the water gas produced generally has been higher in

Jan 1, 1947

By F. W. Jessen, James N. Howell

The accumulation of paraffin deposits in tubular goods has been recognized as a major production problem since the inception of the petroleum industry. This problem is not limited to any particular geographical area nor is it limited to a specific type of crude oil.' Generally speaking, "paraffin" deposition pertains to the deposition of any predominately organic material in flow lines, and possibly even at the sand face, which would hamper the production of oil. In some fields, a continuous effort is required to remove deposits of paraffin and in order to accomplish this, many unique methods have been devised. The best solution to this problem, however, is to prevent the formation of such deposits. One method which has been tried in a number of fields is the use of plastic pipe. The purpose of this investigation is to compare the relative effectiveness of several plastic materials to aid in the reduction or prevention of paraffin accumulations in surface flow lines. COMPOSITlON OF PARAFFIN DEPOSITS By definition, paraffin deposits are those materials which are insoluble in crude oil at the prevailing producing conditions of temperature and pressure. Such deposits1 s usually consist of small particles of petroleum wax intermixed with resins, asphaltic material, and crude oil. They may also contain a variety of foreign materials such as sand, silt, water, various metal oxides, sulfates and carbonates of iron. barium, and calcium. The petroleum waxes deposited in flow strings usually consist of both a "hard" and a "soft" wax fraction. These waxes are largely aliphatic hydrocarbons with smaller amounts of aromatic and naphthenic compounds. Nathan' has classified the hard and soft wax fractions. The aliphatic hydrocarbons present are those of high molecular weight with high melting points. Reistle3 pointed out that these high molecular weight compounds first separate from the oil due to a sharp decrease in solubility as the melting point increases. The identification of the resins and asphaltic materials rests, at present, on an arbitrary solubility procedure. Under certain conditions, materials which are insoluble in pentane (ASTM D-893) are defined as resins and asphalts. Subgrouping of these materials is made on decreasing solubility in benzene and carbon disul-fide. Shock' found some correlation be-tween the solvent response and the pentane insoluble content of paraftins: higher pentane insoluble fractions are less soluble in any of the commonly used commercial solvents. PARAFFIN CONTROL METHODS The methods used in oil fields to prevent and remove paraffin accumulations can be grouped into four general classes: (1) operative methods, (2) physical methods, (3) chemical methods, and (4) combination of any of these. Operative methods attempt to prevent the formation of paraffin deposits while the other methods are concerned primarily with the removal of these deposits. Plastic coated pipe has been used for a number of years to prevent cor- rosion in wells, and in manv instances paraffin deposits have -been greatly reduced. Field observations have indicated that plastic coated pipe not only reduced paraffin accumulation but in some cases eliminated deposition completely; however, data are needed to demonstrate the relative effectiveness of plastic materials. Deposition Apparatus The pipe used to determine the effect of velocity on rates of deposition was %- and 2-in. nominal diameter, and 5 ft in length. Steel, butyrate, rigid PVC, kralastic resin-type plastic pipes, epoxy coated pipe, PVC lined glass fiber pipe, and aluminum pipe were tested. Steel pipe was used as a control. Fig. 1 is a schematic diagram of the apparatus showing the relative position of the separate units making up the equipment. In order to facilitate the installation and removal of the test pipes in the apparatus, O-ring seals capable of sustaining pressures of 50 psi were provided at each end. Test pipes were submerged in a cold water bath maintained at or below room temperature by circulating water through copper cooling coils packed in ice. A hot water bath equipped with immersion-type heaters, stirrers, and a thermoregulator was used to maintain the temperature of the oil prior to introduction into the piping manifold. The capacity of the oil reservoir was 30 gal. A 33-gal/min centrifugal pump, capable of producing turbulent flow velocities in the test pipes, was used to circulate the oil through the system when using %-in. pipe; and a 70-galjmin centrifugal pump was used in later tests using 2-in. pipe. A by-pass arrangement made it pos-

By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By James H. Boettcher

INTRODUCTION A complex interaction of worldwide economic and political forces is increasingly requiring 3 primary participants for the successful development of large natural resource projects in developing countries. They are the host government of the developing country (the "host government"), one or a consortium of international natural resource companies, (the "Resource Company") and one, or more likely, a syndicate of international lenders. The host government typically controls the rights to its country's natural resources and establishes the economic ground rules for their development. However, because of worldwide inflation and the depletion of easily accessible, high-grade resources, the nominal and real capital development and operating costs of projects have been spiraling. Moreover, the depletion of high-grade and mineralogically uncomplicated resources also raises the technical and operating risks associated with resource recovery. Thus, despite increasing political self-consciousness and economic nationalism in developing countries, international resource companies are still often necessary project sponsors since they can provide, among other things, the required technical and management expertise and equity capital. The presence of these factors, and often the addition of worldwide market access in a project, is often critical in determining whether or not the project will be considered creditworthy by international commercial lenders. The international commercial lender is often the critical third party in project development, due in a large part to the ever escalating-costs of project developments relative to the financial resources of many companies and even a growing number of countries. In addition, lenders have other reasons for taking more than a passive interest in all aspects of a project's development. These reasons include the following: 1. Projects are often financially structured such that the primary security for a loan, once completion and performance standards are met, is the cashflow of the project rather than recourse to its sponsors. 2. Lenders, in addition to the "project risk" just described, are frequently asked to assume various elements of "political" risk which nay put them in a sensitive economic position between the host government and international resource firms (This is discussed later). 3. International banks today have large loan portfolios of developing country debt with final maturities ranging from one to fifteen years. The various current projects undertaken are the building blocks of most developing country economies that will hopefully contribute to the long run economic development of a country as well as generate the foreign exchange necessary to repay foreign loans in the future. In this regard it is useful for lenders to realize whether a given project "makes sense" in terms of a country's natural resource endowments and competitive advantages over other countries. The type of framework discussed in this article would help lenders to better make such assessments. In order to facilitate the continued international flow of capital and technology to developing countries and of readily available supplies of raw materials from them, it is important for each of these three parties to increase its awareness of the goals and objectives of the other parties as well as the bargaining process that results in the legal, financial, credit and fiscal structures by which a joint venture project ultimately proceeds. Each of the parties faces increasingly complicated accept/reject decisions when they are faced with difficult choices among. a wide range of alternative structural combinations each of which has different implications for risk and reward to them. Therefore, by increasing the mutual, 3-way awareness of the decision processes of the other parties, it should be possible to: • provide better information and results in the formation of more rational expectations by all parties going into negotiations, • facilitate the project formulation process by allowing parties to focus more clearly on the areas of common interest and conflict, • result more frequently in final structures and agreements that better reflect the economic and political realities associated with a project and thus • result in more creative, innovative agreements that should reduce the need for changes to them and thus promote the kind of long run political stability conducive to attracting capital and further investment.

Jan 1, 1982

By H. L. Hazen

THIS is the story of the recent operations of the Standard Cyaniding Co., which owns the Standard mine, a low-grade gold property in sight of Highway 40 about thirty miles from Lovelock toward Winnemucca, Nev. The ore is mined by power shovel and cyanided after grinding to only 3/S in. A total direct cost of $1.24 was attained in 1941 on 600 tons a day. Mining operations ceased, under Government edict, in 1942, and only in recent months have been resumed. The operating difficulties of today are: (1) the high cost of supplies; (2) labor problems; and (3) Federal laws as interpreted and enforced by executive bureaus of the Government. Of these, the increased cost of supplies is the least important.

Jan 1, 1947

THROUGHOUT the Colonial era, Philadelphia was easily the leading city of North America, and it still held that position at the end of the period, with a population of about 25,000, though closely pressed by Boston, which had slightly over 20,000, and New York, which had nearly as many. It was the center of a region in which mineral industry was important. Thomas Rutter's bloomery, built in the Schuylkill valley in 1716, was quickly followed by many others, and during the Colonial period at least 20 blast furnaces, 45 forges, and iron- works of other types were built in eastern Pennsylvania, which easily led all the other colonies in iron manufacture. During the Revolutionary period others were erected as far west as Fort Loudon, in the Cumberland c alley.6 After 1800 the rapid development of the anthracite mining industry profoundly affected Philadelphia's development, since transportation of the coal was then necessarily by water,, and the streams of the anthracite regions mostly flowed into either the Schuylkill or the Delaware Rivers. With an abundant near-by supply of coal and iron, with the seat of government, which had been there since 1774, and with a national Bank established there in 1791, one would have seemed safe in prophesying, at the beginning of the nineteenth century, that Philadelphia would permanently remain the leading city of the United States. Education in Philadelphia was at first wholly in the hands of the Quakers, who had established a "Public School" there in 1689, but in November 1739 George Whitefield, who had created a sensation in England by his preaching, though only 24 years old, passed through Philadelphia on his way to Georgia to found an orphan school there. He preached a series of sermons in Christ Church that were so disturbing to the established church that on Nov. 25 the Rev. Richard Peters (who was also Provincial

Jan 1, 1941

IT will be recalled that when educational instruction for the mineral industry began at Freiberg, at the beginning of the eighteenth century, the original aim was to organize and systematize the procedures previously followed by young men in gaining familiarity with the technology then in use. There must have been many other ideas current, even then, as to just what a young man needed to learn in order to become capable of assuming responsibility for the supervision and direction of such technical work. The problem in Europe was decidedly different from that in nineteenth-century America, because some of the European mines were actually owned and operated by the governing authority and the others were supervised, regulated, and taxed by it. The American problem was the efficient performance of technical operations; the European one was regulatory supervision. It was natural, therefore, that in the development of educational processes in Europe stress was laid on those factors which conserved and protected the interests of the state. The study of mineralogy and geology, leading to correct judgments as to the workability and value of mineral deposits; assaying, which gave the means of quantitative measurements, as did surveying; chemistry, which furnished a better basis of understanding for assaying, mineralogy, and geology; and physics and mathematics, which are the bases for the understanding and efficient use of mechanical appliances, became the core of systematic instruction for the mineral industry. It was early recognized that men could learn more than was already known about all of these subjects and education took on that dichotomy which still characterizes it; the teaching of established knowledge to the unlearned, and that of extending of the bounds of knowledge, now loosely termed research, which after two and a half centuries of work still shows

Jan 1, 1941

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' and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear' 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 F. J. Norton

THE object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760° C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove.

Jan 1, 1932

By Morris Steinberg, John Wulff, Robert Kamm

IN powder metallurgy it has often been observed that shrinkage may occur in one direction and growth in another during sintering. Even in long-time sintering experiments the rate of shrinkage may be different in different parts of the compact. In the fabrication of some parts requiring a constant permeability it is even questionable in some cases whether pressing from one direction should be attempted. These observations require for their interpretation a more detailed study of green or pressed density than has heretofore been available. Usually average density measurements of the whole compact are made and in some cases carefully cut sections are measured. A different approach to the problem was first mentioned by Rakowski1 and also used by Balshin.2 Balshin's diagram is reproduced in Fig r and schematically shows the result of pressing three layers of metal powder with fine intervening layers of graphite. The retarding effect of the die walls and a qualitative example of the density distribution is evident. More quantitative information about the distribution of density within a cold-pressed powder compact would be useful in showing the variation in density in compacts as influenced by the type of powder, shape of die, lubrication during the process, and other variables. Furthermore, information about the cracking of cold-pressed compacts may be obtained from an analysis of the stress distribution within a powder compact, and some information about the stress distribution can be obtained in turn from the density and strain distributions. A more detailed report on some of the present experiments appears in reference 3. PRESENT INVESTIGATION In order to ascertain the density gradients in cold-pressed metal powders, a deformable lead grid within the powder was employed. After pressing in cylindrical dies the ejected compact was radiographed, giving a pattern of the deformed grid. From the radiograph density and deformation from point to point is readily measured. From the radiograph strain distribution and stress trajectories were also determined. The latter also permits the determination of the coefficient of friction at the die wall. This technique indicates that the densest part of a compact pressed from one side is at the top outer circumference and the least dense region at the bottom circumference near the stationary plunger. For some heights of compacts the density at the axis is such that the lower density is at the top rather than at the bottom. So irregular a density distribution is due primarily to die-wall friction. As the ratio of diameter to height of compact is increased the die walls play a correspond¬ingly smaller role. More uniform density

Jan 1, 1947

By A. McLean, D. W. Gomersall, R. G. Ward

An experimental study has been made of the solubility of nitrogen in liquid iron and liquid Fe-C alloys using levitation melting and a rapid quenching device. Iron alloy droplets were equilibrated with nitrogen gas at 1 atm pressure, quenched, and analyzed. Previous techniques for studying the Fe-C-N system have produced data which me in marked disagreement. This disagreement is due largely to errors caused by reaction between the molten alloy and the crucible material. With the levitation procedure, errors from this source have been eliminated and precise solubility data obtained for temperatures between 1450° and 1750°C. C-N interactions in molten iron have been expressed in terms of first- and second-order free energy, enthalpy, and entropy parameters. ALTHOUGH the solubility of nitrogen in iron base alloys is in general small, the effects of nitrogen on the properties of steel may be quite profound. For most purposes nitrogen in finished steels is undesirable, particularly in the low-carbon grades, since on cooling to room temperature the solubility limit of nitrogen in the steel may be exceeded and this can lead to embrittlement and loss of ductility on aging. On the other hand, nitrogen can improve the work-hardening properties and machinability of steels while in certain stainless grades nitrogen is important in order to stabilize the austenite phase. It is, therefore, desirable that one should be able to predict the solubility of nitrogen in liquid iron alloys. To do this, information is required concerning the interactions between nitrogen and the various alloying elements which may be present in liquid iron. There have been several investigations of these effects in recent years1"7 and the interactions between nitrogen and many elements dissolved in liquid iron are now known to a high degree of precision at steel-making temperatures. Unfortunately, a number of iron alloy systems which are of interest in steelmaking have been difficult to deal with by the experimental techniques generally used for this type of investigation. Among the most important of these are the Fe-C alloys. In the past, two methods have been widely used for determining nitrogen solubilities: the Sieverts' technique, in which the amount of nitrogen required to saturate a given mass of liquid metal at a particular temperature and pressure is measured volumetrically, and the sampled-bath technique in which liquid metal held in a crucible is equilibrated with a gas phase containing a known partial pressure of nitrogen, and samples drawn from the melt are quenched and analyzed. These two methods have been discussed in detail elsewhere.5,8 With the Sieverts' technique, errors may be introduced from the following sources: i) Gas adsorption on metal films which have condensed on the cooler parts of the reaction chamber. ii) Uncertainty in the determination of "hot volume" calibrations. iii) Crucible-melt interaction, particularly if a gaseous reaction product is formed or if the melt becomes contaminated with material from the crucible walls. The sampled-bath method may also suffer from errors due to reaction between the melt and the crucible material. In addition, there is the possibility that gas may be lost from the sample during solidification and cooling. In the present investigation, the solubility of nitrogen in liquid iron alloys has been studied by means of a new technique based on the use of levitation melting equipment and a rapid quenching device. In addition to the fact that problems of the type outlined above are avoided, this particular approach has the following advantages: i) The high-frequency current induces vigorous stirring within the levitated droplet so that gas-metal equilibration is rapidly attained. ii) The gas phase surrounding the melt can be changed very quickly and is easily controlled. For example, a droplet may be levitated in helium, deoxidized in hydrogen, equilibrated with nitrogen, and quenched, within a period of 15 min. ii) Melts can be readily under cooled or superheated, thus extending the effective temperature range of an investigation and allowing temperature-dependent data to be determined with a high degree of precision. Excellent reviews of levitation melting techniques and their application to physical-chemistry studies at high temperature have been published recently by Jenkins et al.,9 Peifer,10 and Rostron.11 In the present investigation a levitation melting technique has been used to obtain data for the solubility of nitrogen in pure liquid iron and liquid Fe-C alloys at temperatures between 1450° and 1750°C. The solution of nitrogen in liquid iron can be described by the reaction:

Jan 1, 1969

By R. Schuhmann

Available thermodynamic data applicable to copper smelting systems are collected and tabulated, and the important gaps are pointed out. A few examples are given of estimations which can be made from the available data. An experimental research program is proposed to supply the thermodynamic data that appear most essential to better quantitative understanding of the chemistry of copper smelting. The proposed program is designed also to shed specific light on the practical problems of slag losses and magnetite behavior. OPPER smelting, from flotation concentrates to V-/ blister copper, is conspicuous among the large scale chemical processes which are conducted with only relatively incomplete knowledge of the physical chemistry involved. For example, no common metallurgy text explains adequately why copper enters the matte phase while iron enters only to the extent that sulphur is left over after satisfying the copper. Explaining this important phenomenon as a manifestation of the greater affinity of sulphur for copper than for iron is unsound because the affinities of copper and iron for sulphur are about the same at smelting temperatures. As will be shown, other affinities are really decisive in the relatively clear-cut separation of copper in the matte. In contrast, thermodynamic studies have contributed much to our understanding of copper refining, zinc oxide reduction, magnesium production, steelmaking, etc. For each of these processes, the important reactions are clearly recognized, and fair to good quantitative values of the free-energy changes and equilibrium constants are available. Such data have proved to be of constantly increasing practical value in process development and improvement. Work in other fields has furnished much thermodynamic data applicable to copper smelting systems. In fact, several promising starts have been made in applying such data to specific smelting problems. Kelleyl made an appraisal of the possibilities of recovering elementary sulphur from low grade matte. His calculations and compilations of thermodynamic data have represented the starting point for much of the work in this field, including the present survey. Huang and Hayward2 nd Aksoy3 used thermodynamic methods in the study of copper losses in reverberatory slags. Peretti4 used thermodynamic data in explaining the chemistry of converting. The recent publications of Darken and Gurry"." and of Darken,' dealing with the iron-oxygen and iron-silicon-oxygen systems, respectively, present equilibrium data that are applicable to copper smelting systems. Also additional data were reported recently on the affinity of sulphur for copper, manganese, and iron8 and on the sulphur pressures of iron-sulphur melts." The survey presented in this paper was made as the basis for planning an experimental program on the thermodynamics of copper smelting. Few researches on the chemistry of copper smelting have been reported in recent years, so that a reappraisal and coordination of old and new data are essential if further work is to take the directions of maximum value. The experimental program is now in progress, and the plan of attack is outlined at the end of this paper. Progressive Oxidation and Desulphurization of Copper-bearing Liquid Phases: The chemical activities of sulphur and oxygen are two of the most important thermodynamic yardsticks to be applied to copper smelting processes. Virtually the entire smelting and refining sequence involves a series of systems characterized by decreasing sulphur activity and increasing oxygen activity. In this section, therefore, an attempt is made to define and explain these activities in terms of equilibrium partial pressures of SO2, s2, and O,. Also, estimates of these quantities are presented, the estimates being based largely on calculations presented in a later section of this paper. The sequence of steps from raw flotation concentrate to fully oxidized copper ready for poling involves progressive and controlled oxidation. Iron is oxidized and enters the slag. Sulphur is oxidized and leaves in the gas. Table I summarizes several important features of this oxidation and desulphurization sequence, starting at the beginning of the matte blow in the converter. The top line gives in order the principal smelting and refining stages up to fully oxidized copper, plus the additional step, not used commercially, of oxidizing all the way to Cu,O. In the second line are shown the principal copper-bearing liquid phases which characterize the process. Through most of the sequence the copper

Jan 1, 1951

By C. H. Gorski

A method for preparing titanium tetrachloride is described which consists of reducing rutile with coke and chlorinating the reduced product at 200° to 500°C. The crude distillate is purified by treatment with copper powder and distillation. Recoveries, exceeding 90 pct of the titanium in the rutile, were obtained. IN recent years considerable interest in metallic titanium has been aroused because of its outstanding physical and chemical properties. The present commercial processes for preparing titanium are modifications of the Kroll1 process and consist essentially of the reduction of titanium tetrachloride with magnesium in an inert atmosphere to produce metallic titanium with magnesium chloride as a byproduct. At present,' commercial titanium tetrachloride costs $0.32 a pound, which makes the price of the included titanium $1.28 a pound. As the titanium tetrachloride must be purified further before processing into metal, its ultimate cost obviously will be higher. Consequently, one of the prime requisites for the production of lower cost titanium metal is a source of low-cost titanium tetrachloride. Recently, Knickerbocker, Gorski, Kenworthy, and Starliper3 escribed a method for preparing titanium tetrachloride from low-grade Arkansas rutile by smelting the rutile with pyrite and coke to form a titanium matte and then chlorinating the titanium matte to prepare a crude titanium tetrachloride. This process had several inherent advantages. Low-grade rutile concentrates were utilized, the chlorination temperature was relatively low (approximately 200°C), and the reaction was strongly exothermic. However, this process had several disadvantages, chief of them being the rather low recoveries of titanium tetrachloride (65 to 81 pct) and the difficulty in purifying the crude titanium tetrachloride obtained. Because of the high-titanium and low-iron con- tents of rutile as compared to ilmenite, rutile should be of greater potential value as a source of titanium tetrachloride than ilmenite. Rutile, however, is not chlorinated directly in commercial practice, because reaction temperatures above 700 °C are required, at which point chlorine attacks most of the common materials of construction. The process now in use consists of converting the titanium in rutile to the cyanonitride by high-temperature reduction in an electric furnace, and then chlorinating this compound. The disadvantages of this process are the difficulty of producing the cyanonitride, the use of high-grade rutile concentrates in the charge, and the presence of several percent of silicon tetrachloride in the finished product. It would be of considerable interest to develop a new process for the preparation of titanium tetrachloride from rutile by chlorination at 200" to 500°C. Process Development Several investigators'-' have studied the reduction of titanium dioxide with carbon in an effort to prepare titanium monoxide. Invariably, the titanium monoxide formed in this manner was not pure, as it contained titanium carbide and one or more of the lower oxides of titanium. As these lower oxides of titanium are more reactive chemically than rutile, and as it is known that titanium carbide may be chlorinated readily, a study was made of the chlorination of carbon-reduced rutile. A sample of rutile concentrates from Hot Spring County, Ark., containing 76.19 pct TiO,, 5.65 pct Fe2O3, 4.18 pct SiO2, and 2.88 pct Al2O3, was used for this investigation. The experimental procedure consisted of making an intimate mixture of —100-mesh rutile and petroleum coke, adding water and molasses as a binder to foi-m a paste, charging into a graphite crucible that was covered, except for a vent to allow the

Jan 1, 1952

By H. W. Gudenau, R. S. Chatty, W. Wenzel, M. Ponthenkandath

During several experimental programs conducted at the Institute of Ferrous Metallurgy, Technical University, Aachen, whisker formation was observed when iron ores were reduced at low as well as at high temperatures. Thus, in an attempt to find the reason for the volume change taking place during reduction, iron whisker growth was observed. Whisker growth appears to be one of the important reasons for the swelling of pellets. One set of experimental observations determined that when iron forms as needles rather than as a crust on the surface of oxide, the pellets became very porous. In related experiments, the beneficiation of finely disseminated iron ores, in which the metallic iron is separated from the gangue in granular or nodular form, was achieved by a reduction-concentration method. In this process, which is conducted at sufficiently high temperatures, oxide whisker growth, resulting from the formation of volatile suboxides and a gas transport mechanism, plays a vital role in the joint deposition of SiO, and iron from the vapor stage.

Jan 1, 1973

By R. P. Aikman, F. G. Miller, J. M. Podgursky

As part of a larger study of the mechanism of froth flotation of coal, the rates at which coal particles of various size and specific gravity react to froth flotation were investigated. Results of this study show that in flotation: I) recovery rate increases, but selectivity decreases with a decrease in particle size down to 100 mesh, and 2) recovery rate is constant for all sizes between 100M and 325M. n response to the growing demand for low-sulfur coking coal for iron making, the coal industry is continually striving to perfect methods for cleaning coal to acceptable ash and sulfur levels while maintaining maximum product yield. By present standards the industry has adequate processes for cleaning coarse coal, i.e., + 28 mesh, at almost any desired specific gravity. However, in the case of fine coal, i.e., —28 mesh, neither of the two existing processes - froth flotation or hydrocycloning — in its present state of development yields products that are comparable in ash and/or sulfur content to products normally obtained from coarse coal processes. The work outlined in this paper is part of a larger study directed toward maximum exploitation of froth flotation for fine coal processing. The concepts and data presented are now serving as a basis for designing fine-coal circuits in which improved efficiency is obtained by optimum use of froth flotation with other fine-coal processing methods. The paper includes: 1) A discussion of the value of a detailed wash-ability study as a method of assessing the problems associated with fine coal processing, 2) A general discussion of hydrocyclone principles, included to serve as a basis for understanding the mechanism of coal flotation, and 3) A detailed discussion of the mechanism of coal flotation, as well as the research leading to the optimum use of froth flotation in combination with other fine-coal cleaning methods to provide efficient fine-coal processing. Our study of the rates at which coal particles of various size and specific gravity react to flotation shows that in flotation: 1) recovery rate increases but selectivity decreases with a decrease in particle size down to 100 mesh, 2) recovery rate is constant for all sizes between 100 mesh and 325 mesh, and 3) the flotation process effectively rejects only those extremely fine particles which do not contain surface carbon. (Because of this feature, froth flotation is an excellent method for rejecting clays - the only extreme fines in - 325-mesh coal that are always carbon free.) Washability studies of flotation products are used to assess flotation efficiency. These studies show that: 1) the increase in percent sulfur in flotation products above the theoretical sulfur content as defined by the washability study is due almost entirely to flotation of fine high-specific-gravity particles that are part coal and part pyrite, and 2) in a given size range particle floatability decreases with an increase in particle specific gravity. Error curves are explained and are used to compare the mechanisms of coal flotation and hydrocycloning. These comparisons show that hydrocyclone performance is affected primarily by particle mass, i.e., particle specific gravity and size, whereas coal flotation performance is dependent on both the particle mass and the coal surface available for bubble attachment. Since the error curve is a basic tool for rating the efficiency of any coal processing system, it will be useful to quickly review the principles of error curve construction. RATING COAL-PROCESSING EFFICIENCY BY THE ERROR CURVE The organic component of coal is of lower specific gravity than its impurities, and the most effective principle for coal concentration is therefore separation on the basis of specific gravity. However, since there is no sharp dividing line between pure coal and pure ash components, specific gravity must be closely controlled if the product is to have acceptable quality at maximum yields. In turn, the basis for close control in any coal processing system is the reference standard provided by precise laboratory washability studies. In these studies, coal is carefully separated into a series of progressively higher specific gravity fractions to establish a relationship

Jan 1, 1968

By W. J. O'CONNOR

THE production of lead in the United States for the period from 1720 to 1912 was 10,432,668 tons valued at $924,600,000. The average price during this period was 4.4c. a pound, although lead sold at times below 3 cents. We know that in the early days of lead smelting in Montana lead was deliberately lost in the slag and only enough reduced as bullion to collect the silver. This bullion was freighted by ox team to Corinne, Utah, the terminus of the railroad at that time, and shipped to Swansea or Omaha, Neb., for refining. The slag from some of the above mentioned operations contained as much as 15 per cent lead and has since been resmelted. Since 1921 the production of lead has increased each year and the price and tonnage have been as follows :

Jan 1, 1926

By W. J. Reagan

Many factors enter into the manufacture of basic open-hearth steel of high quality. Perhaps the two most important are temperature and the iron oxide content of the metal. If we can control these two factors we can essentially control basic open-hearth practice. SOURCE AND EFFECT OF IRON OXIDE Earlier investigators, especially Herty and his associates, have shown that iron oxide is introduced into the open-hearth furnace in four ways:' 1. By oxidation of the scrap by furnace gases. 2. By decomposition of the limestone. 3. By oxidation of the iron oxide in the slag by furnace gases. 4. By direct addition of iron ore to the charge. We also know that the speed of operation of an open-hearth furnace depends, for a given charge and given combustion conditions, on the rate at which iron oxide will diffuse from the slag into the metal. The rate of diffusion depends upon a number of variables, such as iron oxide content of the slag, slag viscosity, etc., which also depend upon the amount of iron oxide in the metal, amount of carbon present, temperature, and so forth. For a given carbon and a given temperature, the iron oxide content of the metal is in proportion to the iron oxide content of the slag. This fact can be easily verified by analysis of slag samples taken as described by Herty.2 It is preferable to take these samples just before deoxidetion. In killing the steel samples with aluminum it is desirable to use aluminum rod of 99 per cent purity; ordinary commercial aluminum rod with a purity of approximately 92 per cent is not satisfactory. In drilling these samples it is also essential to take the largest amount of drillings possible. This gives more accurate results because it eliminates spotty segregation of A12O3.

Jan 1, 1932