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By E. A. H. Tays, F. A. Schiertz

In 1893 the Anglo-Mexican Mining Company, Limited, purchased the Guadalupe and adjoining mines, and, after opening up the Guadalupe, constructed a 20-stamp mill, which was started in August, 1894. Although the results were extremely profitable (the ore being very rich and carrying much free gold) they were not satisfactory, because the tailings were found to average about $20 per ton in gold. Early in 1895 the late Mr. James E. Mills made for the company a very thorough study of the subject, and decided that the tailings could be treated most advantageously by the cyanide process. In view of this opinion, Mr. Henry R. Batcheller, of Boston, was sent down in the winter of 1895-96 to experiment on a working scale. Mr. Batcheller was successful; and, during 1896-97, built a cyanide-plant with a capacity for treating 1500 tons per month. This was run until May, 1899, when all the sands suitable for the process had been treated. The mill was stopped about the same time for lack of ore; but no tailings from the mill had gone to the dump since October, 1897, as the values they contained after that date were far too low to warrant further treatment. When the cyanide-plant was stopped there still remained on the dump about 16,000 tons of slimes, consisting of about 75 per cent. of clay-slimes and 25 of sand-slimes. The successful treatment of this very unfavorable material is the theme of this paper. Fig. 1 is a view of the hacienda, taken in 1897.

Jan 1, 1902

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

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

By John Mullen

Impingers TWO types of midget impinger apparatus are used at Climax. The Mine Safety Appliances Company's midget impinger (MSA) and the Climax Molybdenum Company's midget impinger (CMC) (Fig. I). The Leiman Brother's No. 25, positive displacement pump is used in the CMC impinger instead of the four-cylinder radial pump that is used in the MSA impinger. With the MSA apparatus it is possible to obtain the proper vacuum by adjusting the needle valve on the vacuum chamber, while with the CMC impinger the proper vacuum is obtained by varying the rate at which the pump is cranked. The Leiman Brother's No. 25 pump is built to displace 0.1 cu. ft. of air per min. when operated at 145 r.p.m. In the CMC impinger this pump is so geared that the required crank speed is approximately 59 r.p.m. Both types of impinger apparatus are equipped with a water gauge mounted on top of the case and they are calibrated and operated in reference to the gauge. The MSA impinger flasks and nozzles are used with both types. Calibrating Impingers A calibrated precision Sargent wet-test meter (Fig. 2) is used in calibrating the impinger apparatus. The apparatus is set up as for taking a sample in the field, except that the hose from the outlet side of the meter is attached to the impinger nozzle. One revolution of the large hand of the meter indicates 0.1 cu. ft. of air displaced. The impinger pump is cranked for one minute, therefore, at a rate that will cause the large hand of the meter to make one revolution. The gauge reading is noted, then the impinger is cranked at this rate for 10 min. and is checked for error. If the meter indicates that more or less than I cu. ft. of air has been displaced, the impinger must be cranked—ither slower or faster according to the error—for another 10 min. and again checked for error. This operation is repeated until the proper gauge reading for a sampling rate of 0.1 cu. ft. per min. has been determined. This gauge reading is used in all sampling operations until the impinger is again calibrated. An impinger is calibrated at least twice each week. MlCROPROJECTOR A Bausch and Lomb model B micro-projector is used (Fig. 3). It consists of a substantial metal base supporting the light source and a microscope. Illumination is provided by a Bausch and Lomb 4.5-amp. arc lamp with mechanical feed. A glass water cell filled with a heat-absorbing and color-filter solution is placed between the arc lamp and the microscope. Two types of solution have been found satisfactory— a 2 per cent solution of copper sulphate or a 2 per cent solution of picric acid and distilled water. This percentage may be varied to give the desired color to the light reflected upon the screen. Any standard microscope may be used. A Bausch and Lomb microscope with

Jan 1, 1946

By W. W. Odell

Once it was believed that anthracite or coke were the only fuels generally available and suitable for the generation of water gas, particularly so when this gas was made in the generators of standard carburetted water-gas sets such as are commonly used in the manufacture of city gas. During the past 8 years, practice has changed considerably and it is now common to find gas plants operating without anthracite or coke and using bituminous coal in the generator. This change in fuel has appreciably increased the marketability and sales of certain coal producers' products; accordingly it is of interest to coal operators and others to know the reason for this change, the present trend in practice and the adaptability of various coals for generation of water gas. This paper briefly discusses these conditions and some of the factors relating thereto. Bituminous Coal not Ideal but Cheaper than Coke In spite of many changes which have been made in both process and generating apparatus for using bituminous coal as generator fuel more efficiently, in general it is not an ideal fuel for this purpose. It is supplanting coke because it costs less; it is so much cheaper per ton delivered at the gas works that water gas made therefrom costs less per unit-volume than that made from coke, even though the quantity of generator fuel consumed per therm (100,000 B. t. u.) of gas made is greater with coal. This is the reason why so many city gas plants, as well as others, are using bituminous coal instead of coke. Conditions Favoring Change from Coke to Coal The conditions which have made it possible and feasible, as well as economical, to supplant coke with coal may be summarized as follows: (1) Changes in methods of operating and alteration in generating apparatus; (2) lowering of the calorific standards for city gas, and (3) availability

Jan 1, 1927

By John D. Sullivan, Chester R. Austin, Edwin J. Rogers

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

The problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce lightweight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough qo that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an - outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, partitularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating."² The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the Purpose Of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By Robert J. Hite, Samuel S. Adams

Potash, the generic term for a variety of potassium-bearing minerals, ores, and refined products (Table 1), owes its importance as an industrial mineral to the potassium requirement of growing plants. The term potash originally referred to potassium carbonate produced by the leaching of wood ashes. This process, for which the first US patent was issued in 1790, was the basis for the largest United States chemical industry in the early nineteenth century. The agricultural use of potash soon eclipsed the chemical applications following the German discovery in 1840 that potassium is essential to plant growth. The initial discoveries of large deposits of soluble potassium minerals, essential for agriculture applications, were made in 1857 in Germany and in 1914 in the United States. More than 90% of the 27.5 Mt K20 produced in the world in 1980 (Searls, 1981) was derived from marine evaporite deposits and approximately 90% was used in fertilizers. The potassium content of an ore, mineral, or product is customarily expressed as % K20, a unit of measure which is neither a natural nor synthetic compound of potassium (1.0% K is equivalent to 1.2046% K2O). Geology Potassium, the seventh most abundant element in the earth's crust, is present in silicate minerals in igneous, sedimentary and metamorphic rocks. Potassium is also a major constituent of many surface and subsurface brines (Table 2). Economic potash deposits are essentially restricted, however, to widespread, thick accumulations of marine chloride evaporite deposits. These deposits yield high grade, large tonnage ore bodies, many of which are amenable to low cost mining and beneficiation. The products from these deposits are, moreover, ideal for use in fertilizer because of the high relative solubility of the potassium chloride and sulfate evaporite minerals. World potash production and reserves for such deposits so vastly overshadow other sources of potassium that the following discussion will be limited largely to potash deposits in marine evaporites with brief reference to certain potash-rich brines. Approximately 85% of current domestic production is from bedded salt deposits and much of the balance is from brines. Marine evaporite deposits are accumulations of salt minerals deposited in structural sedimentary basins through the evaporation of seawater or mixtures of seawater and other brines. The salt minerals are precipitated in assemblages and sequences of assemblages as determined by the compositions of the brines and the solubility relations in the salt systems (D'Ans, 1933). The evaporation of seawater normally yields carbonate minerals as the first precipitates (Table 3). Further evaporation and concentration of the brine leads to the precipitation, in succession, of sulfate, chloride, and supersaline mineral assemblages including the salts of potassium and magnesium. The common minerals, ores, and products of potassium deposits are listed in Table 1. Many potash deposits contain accessory evaporite minerals together with a variety of detrital and authigenic silicates (Braitsch, 1971). The structural basins within which marine evaporites occur are of two main types: (a) cratonic basins formed by broad epirogenic movements (for example, the Michigan Basin of the midwestern United States and the Permian Zechstein Basin of eastern Europe), and (b) grabens, commonly related to continental

Jan 1, 1983

By Neil H. Bostick

A specialized electronic data system processes data taken from normal gologic maps and stratigraphic tables to yield predictions of uranium resource location for an area such as much of the United States. Strata underlying specific quadrangle cells of the earth are evaluated for uranium favorability on the basis of selected criteria of lithology, structure, and stratigraphy but not specific past production in the area. Stored data are computer processed to yield volume of likely host rock beneath each cell to a given depth and at a given favorobility level. Results are plotted by machine directly as maps. A specialized and simplified procedure for predicting approximate uranium resources has been devised at Stanford Research Institute (SRI). The prediction is based on general geology beneath specific area cells of the earth in order to provide complete volume coverage; the strata underlying these areas are evaluated for uranium mineral favorability on the basis of a few selected geologic criteria in order to allow rapid data input. In order that the predictions be generally applicable, they are based on geological factors only, not past ore production of a given cell. Since the bulk of U.S. resources are in elastic host rocks, only such strata are considered in this work. This paper describes the structure and some details of the resource system and how it was tested in an area of the western United States.

Jan 1, 1971

By B. M. Larsen

ATTEMPTING to review the fundamental aspects of segregation in steel ingots of all types in a paper of reasonable length, we encounter two difficulties: (I) the fact that a large number of different physical and chemical effects are involved, and (2) rather incomplete and confusing evidence on certain aspects of detail and mechanism in the freezing process in which the segregation effect is involved. The best solution seemed to be to link together most of the underlying factors into a simplified theoretical picture that appears to the writer to explain most of the observed data, in the hope that this will serve as a reasonably good target for discussion and criticism. Segregation effects, especially in steel ingots or castings, are often divided into " microscopic " and " macroscopic," depending on whether the variations in concentration of solutes? or dissolved elements in the iron occur as: (I) a periodic variation over the small distances between the nuclei and the surfaces of the primary grains, or (2) as a larger scale effect involving concentration gradients over distances of the order of several inches, more or less. The reason for this somewhat artificial division is, of course, that it is only the macroscopic scale effect that has much practical importance. About the only effect of practical importance that results from microscopic segregation is the banded structure often left in rolled sections, and even this is relatively harmless in most cases. However, the causes of microscopic segregation also underly the larger scale effect, so we must first consider matters such as the formation and growth of crystal nuclei, selective freezing and diffusion, and others that are fundamental to all segregation effects. UNDERCOOLING AND NUCLEI FORMATION It is probable that although the degree of undercooling is small in iron, as in metals in general, a certain amount of it takes place, and also that the number of crystal nuclei increases very rapidly with increased undercooling below the liquidus tempera¬ture. In practical terms this means that the nuclei number increases very rapidly with increased cooling or freezing rate, thus being dependent on the rate of heat flow out from the zone of crystallization. TEMPERATURE GRADIENTS AND HEAT DISSIPATION DURING FREEZING Each pound of steel evolves about 100 B.t.u. when freezing. In addition to this, the temperature gradient in the solidified portion (required to dissipate the heat as freezing progresses into the axis) necessitates a loss of heat required to cool the solid metal below its freezing range, which is equivalent to an amount of not so much less in magnitude. In a 5-ton ingot, the total would include about one million B.t.u. for freezing alone and about 0.4 to 0.5 million B.t.u. for the gradient, up to the end of the freezing period: Thus the rate of freezing depends primarily on the rate of heat dissipation. In the ordinary ingot shapes, the axial rate of growth of the solid

Jan 1, 1944

By D. Silverman, A. R. Brown

EquipmENT and methods for locating the points of entry of salt water into oil wells are described. These techniques make it possible to delineate accurately the top and bottom boundaries of water zones whether bottom water or intermediate zones of production, Data are given on tests by this survey method on a number of producing wells, Complete results were obtained on wells shelving water percentages ranging from high values to as Little as 10 pct salt water. A number of the wells tested were plugged back and the results are reported in detail. While not all the work-overs were successful, evidence, including the results of reruns by this survey method, points to failure of the plugback operations. The data provided in the tests discussed show, contrary to general opinion, that a large percentage approaching 50 pct of the wells showed intermediate water instead of bottom water. Furthermore, approximately a third of the wells tested showed multiple zones of water production. The equipment comprises a long pipelike assembly carrying 10 pairs of electrodes spaced apart a distance of 4 ft. A surface-controlled solenoid-operated switch is provided to connect each of the individual pairs of electrodes in turn to a single-conductor steel-armored cable by means of which the conductivity of the fluid in the vicinity of each of the electrode pairs can be continuously recorded at the surface. Any number of electrode pairs and any spacing can be used. This assembly is lowered on tubing and placed in position opposite the section of the well to be studied. A conventional rod pump is used to produce the well for the survey. The pump inlet is placed below the lowest electrode pair. The well is conditioned by pumping Out the salt water normally standing in the well and introducing fresh water into the annulus at the surface. When the resistivity of the water standing in the well has been increased to a sufficiently high value, the inflowing fresh water is stopped and the drawdown operation of the survey is started. As the fluid head is lowered by pumping, fluids flow into the well and the entry Of salt water is indicated by the change in resistivity of the fresh water opposite the 'Ones Of water entry, The process can be repeated as Often as necessary with little effort and without moving any well equipment to be sure that the fluids produced from each zone are representative Of the true reservoir content. Introduction The oil industry has been concerned from its inception with the control of fluids entering its wells. In order to effect the greatest economy of operation and to get the greatest total production of petroleum liquids out of the ground, the flow of gas and water must be controlled and often extensive workovers are planned and carried Out for this purpose. This has become even more important in recent Years because of the need for the conservation of natural resources. Whereas producing operations concerned with the original completion of a well are assisted to a great extent by a wide variety of instruments developed and perfected for that purpose, workover operations on oil wells have been greatly hindered by a lack of suitable instrumentation. The industry has searched for many years for a satisfactory instrument and process that

Jan 1, 1948

By A. R. Brown, D. Silverman

EquipmENT and methods for locating the points of entry of salt water into oil wells are described. These techniques make it possible to delineate accurately the top and bottom boundaries of water zones whether bottom water or intermediate zones of production, Data are given on tests by this survey method on a number of producing wells, Complete results were obtained on wells shelving water percentages ranging from high values to as Little as 10 pct salt water. A number of the wells tested were plugged back and the results are reported in detail. While not all the work-overs were successful, evidence, including the results of reruns by this survey method, points to failure of the plugback operations. The data provided in the tests discussed show, contrary to general opinion, that a large percentage approaching 50 pct of the wells showed intermediate water instead of bottom water. Furthermore, approximately a third of the wells tested showed multiple zones of water production. The equipment comprises a long pipelike assembly carrying 10 pairs of electrodes spaced apart a distance of 4 ft. A surface-controlled solenoid-operated switch is provided to connect each of the individual pairs of electrodes in turn to a single-conductor steel-armored cable by means of which the conductivity of the fluid in the vicinity of each of the electrode pairs can be continuously recorded at the surface. Any number of electrode pairs and any spacing can be used. This assembly is lowered on tubing and placed in position opposite the section of the well to be studied. A conventional rod pump is used to produce the well for the survey. The pump inlet is placed below the lowest electrode pair. The well is conditioned by pumping Out the salt water normally standing in the well and introducing fresh water into the annulus at the surface. When the resistivity of the water standing in the well has been increased to a sufficiently high value, the inflowing fresh water is stopped and the drawdown operation of the survey is started. As the fluid head is lowered by pumping, fluids flow into the well and the entry Of salt water is indicated by the change in resistivity of the fresh water opposite the 'Ones Of water entry, The process can be repeated as Often as necessary with little effort and without moving any well equipment to be sure that the fluids produced from each zone are representative Of the true reservoir content. Introduction The oil industry has been concerned from its inception with the control of fluids entering its wells. In order to effect the greatest economy of operation and to get the greatest total production of petroleum liquids out of the ground, the flow of gas and water must be controlled and often extensive workovers are planned and carried Out for this purpose. This has become even more important in recent Years because of the need for the conservation of natural resources. Whereas producing operations concerned with the original completion of a well are assisted to a great extent by a wide variety of instruments developed and perfected for that purpose, workover operations on oil wells have been greatly hindered by a lack of suitable instrumentation. The industry has searched for many years for a satisfactory instrument and process that

Jan 1, 1948

By M. B. Bever, A. K. Jena

Equations for the heat effects of additions of mixtures of multicomponent phases to a solution have been derived in terms of the enthalpy interaction coefficients. By these equations and the measured composition dependence of the heat effects on addition of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions, values of the enthalpy in-teraction coefficients in tin-rich solutions at 541°K have been obtained. Analysis of these results in terms of the regular solution theory and the quasichemical theory suggests that near the melting point of the solvent association in the solution becomes important. SEVERAL recent papers have discussed the nature of dilute solutions on the basis of measured enthalpy interaction coefficients. l-3 These coefficients contribute to the understanding of the constitution of solutions and can be used for the evaluation of thermo-dynamic data of multicomponent systems. Their experimental determination, however, is laborious. This communication reports values of the enthalpy interaction coefficients of silver, cadmium, and gold in liquid tin-rich solutions obtained from the measured heat effects of additions of mixtures of Ag-Cd solid solutions and elemental gold to liquid tin-rich solutions. These measurements were made in the course of the determination of the heats of formation of Ag-Cd solid solutions reported in a concurrent publication.4 THE HEAT EFFECT OF AN ADDITION TO A SOLVENT This analysis is concerned with the addition of a mixture of multicomponent phases from the temperature To to a solvent of known composition at temperature T. If Nmixture << Nsolvent, where N designates the gram-atoms involved, the heat effect per g-atom of mixture added can be expressed as (HT - HT )i = difference in heat contents of component element i in the mixture at T and To Q = heat effect on solution of the mixture at temperature T Also1 Q = S Xi [2] where ?Hi ,T,x = relative partial enthalpy per g-atom of i in solution at temperature T and composition of the solution x x = average of the atom fractions of the added material in solution before and after the addition The relative partial enthalpy ?Hi per g-atom of an element i in a dilute solution composed of a solvent 1 and the solutes j = 2, ... m is related to the interaction coefficients by the following equation5 ?Hi - ?Hi-?Hi,x1-1 + S n1ixj+ . . . +S...S...S nrixn2... Xnji...Xnmm+... [3] vhere Xj = atom fraction of solute j in the solution nri = the rth order enthalpy interaction coefficients, which can also be represented by the more general designation5 L(i)n2,n3...nm and nj may have any positive integral value or zero. For identification of various rth order interaction coefficients, nri is written as nn2i2,...nij,...nmm. Eqs. [1], [2], and [3] combine to give the following general equation for the heat effect on addition of a small quantity of a mixture to a large quantity of a dilute solution n = _?ga ?Ha,To + ? Xi(HT - HT o)i a. i + ?xi?Hi,X,i?1 + ??xnjixj + . . . + ???. . .?. . .?xinrix2n2. . . xnji. . . xnmm+ . . . [4] The first term on the right-hand side of this equation is the heat of decomposition at the addition temperature of the phases present in the mixture, the second term is the heat required to raise the temperature of

Jan 1, 1970

By A. W. Jenike

A theory of gravity flow of bulk solids like ores, concentrates, coal is outlined and an example of design for unobstructed flow is given. Mass-flow and plug-flow patterns are defined and related to the geometry of the bin. The effect of these patterns on segregation, first in-first out flow, and caking is described. This paper is a report on the results from the AIME sponsored project "Flow of Bulk Solids" which was carried out under the author&apos;s direction at the Utah Engineering Experiment Station, University of Utah, during the period 1956-1962. The theory has been applied to the design of numerous industrial storage plants. A QUANTITATIVE METHOD OF DESIGN FOR FLOW There is hardly an industry which does not store and handle solid materials in bulk form. When the volume of the solids is large, gravity is invariably relied upon to cause the solids to flow out of storage, through channels and chemical reactors. Such materials as ore, coal, cement, flour, plastics, clay, soil, to which a general term of bulk solids is applied, flow by gravity or are expected to flow by gravity in thousands of installations and by billions of tons annually. The chemical and process industry depends on gravity flow of solids in process and out of storage. Mining relies on gravity flow in block-caving, in ore passes, as well as in storage and loading bins. Agriculture uses gravity flow in elevators, in feed plants, and in farm silos. In practice, satisfactory gravity flow is seldom attained. Such problems as doming, piping (rat-holing), lack of live capacity, segregation, deterioration in storage, harass industry. In spite of the universality of these problems, until recently, there has been no theory of solids flow, no method of predicting how a solid would behave, and how the channel, bin, or hopper should be designed. In the late nineteen forties and early fifties, the theory of plasticity came of age and simultaneously the computer became widely available. These two factors permitted the development of a theory of flow of bulk solids. The work was conducted during the years 1953-1961. In conjunction with the development of the theory a method to measure the flowability of solids was also developed1-7 and the theory was ap-plied to the design of ore pockets, storage plants,16 chemical reactors and adsorption columns. A comprehensive report of this work is given in a previous work." THEORY OF FLOW The most important question which a theory of flow has to answer is: what conditions need to be satisfied for a given solid to flow uniformly and without obstructions through a channel? First of all, the following observations are made:

Jan 1, 1967

By M. F. Williams, L. G. Hendrickson

IN classification of pulps bearing magnetized ferromagnetic particles, depolarizing is of great importance. If size separation is to be effective, particles must be individual rather than in floes. Depolarizing is also practiced in heavy medium separations in which ferrosilicon or magnetite is the medium. When particles of ferromagnetic material have been removed from a magnetic field, residual magnetism causes agglomeration. The term depolarizing refers to the operation of reducing or eliminating this residual magnetism and may thus be considered magnetic deflocculation. The terms demagnetizing and randomizing are also used. At the Research Laboratory of Oliver Iron Mining Div. in Duluth a method was developed for measuring depolarization of the pulp of ferromagnetic material. Experiments were made with Mesabi taconite,&apos; a natural magnetite of low coercive force. Ferromagnetic materials of higher coercive force, such as lodestone or the artificial magnetite produced by reduction roasting of hematite, present a more difficult problem, which was not within the scope of this investigation. It is possible, however, that some of the techniques evolved for measuring and calculating electrical characteristics of alternating current coils would be of use in depolarizing high coercive force material, particularly in conjunction with high-frequency alternating current, as proposed by Hartig and others.&apos;," Properties of Ferromagnetic Materials:&apos;7 Experimental work, described below, has shown that if a sample in the magnetized state is heated above the Curie point and cooled, much of the preferred orientation is destroyed and the sample is substantially depolarized. It has been thought that when the sample cools below the Curie point the domains cancel each other, leaving a zero net moment. However, such particles still exhibit a tendency to cohere, and undoubtedly this is caused by the forces of residual magnetism. -AS measured by the percent depolarization, this tendency is reproducible for any sample upon repeated heating above the Curie point and subsequent cooling and is independent of the initial state of magnetization. It is postulated, therefore, that as the material is cooled below the Curie point the domains in any particle do not completely cancel each other, but rather are preferentially oriented to some extent. Mechanism of Depolarizing with Alternating Current Magnetic Fields: It is believed that when ferromagnetic material is passed through an alternating magnetic field, depolarizing occurs in the decaying portion of the field. As the particles pass through the portion of highest intensity they become magne- tized. If the particles are not free to move, the polarities of the particles will be reversed (by a mechanism similar to that described above for magnetism) at a frequency equal to that of the applied field. As the material moves through the decaying field, intensity levels become such that a domain does not completely reverse, but stops on an axis of easy magnetization. By the time the material reaches the point of zero field intensity, a state of fairly random orientation of domains is achieved. If conditions are such as to give a completely random orientation, the particle will have little or no external magnetic field, and a pulp of such particles will be depolarized. Previous Work In 1918 E. W. Davis was granted a patent for demagnetization of magnetite pulps.&apos; His method consisted of passing the pulp through a tapered coil, activated by alternating current of normal frequency (60 cycle). This method, with minor modifications, has been used almost universally in all pilot plants and commercial installations in which depolarization of low coercive force materials has been required. Hartig, Onstad and Foot2,3 avd made a detailed study of the factors involved in depolarizing both low (below 100 oersteds) and high (above 100 oersteds) coercive force material. They developed a method for evaluating the relative degree of depolarization of any pulp based on the settling characteristics of the pulp. Their standard of comparison was a sample heated to above the Curie point and cooled in a zero field, all in a neutral atmosphere.* For low coercive force material they found treatment.Thisprocedure is subsequently called, in this report,theCurie that results equivalent to Curie treatment could be

Jan 1, 1957

By J. S. Pascover, S. V. Radcliffe

The structures and transformation temperatures of high-purity Fe-Cr alloys have been investigated as functions of composition (0 to 10 wt pct Cr) and rate of quenching from the high-temperature Y phase field (up to 40,000°C sec-1). The structures were chmacterized by transmission electron microscopy. The transformation temperatures for each alloy exhibited the progressive decrease to a constant value with increasing cooling rate which has been shown to be characteristic of several iron binary systems. The corresponding structures were found to become increasingly finer in scale with increasing cooling rate and solute content, but to remain essentially equiaxed in character. In all the materials except the high-purity iron and one of the alloys, an additional and lower transformation temperature than the constant value for the equiaxed structures was observed. The structures of specimens which transformed at these lower temperatures (only single thermal wrests were observed in any given run) were martensitic and consisted of arrays of fine ferrite laths which varied in size and morphology with changing solute content. The factors controlling the nature of these transformations are discussed. The composition dependence of the martensitic transformation temperature, ME, in Fe-Cr alloys together with those reported for other iron binary systems indicate that MB for pure iron is some 700°c, rather than the values of 550° and 760°C reported previously. This conclusion is further supported by the results of a compmison of the thermodynamics of mmtensite formation in several systems. ThE extensive investigations of the structures formed on athermal transformation in iron and its alloys have led to the characterization of several forms of martensitic or "military"1,2 transformations and, in addition, a "civilian7&apos; transformation to ferrite or "equiaxed a"* which occurs athermally and at a very high rate.374

Jan 1, 1969

By David Baker

Our large modern blast-furnaces, equipped with ore-bins, larries and mechanical means for putting stock into storage, withdrawing it therefrom, and charging it at the tunnel-head, are indeed wonderful in capacity; yet, it is admitted that, with some notable exceptions, they have disappointed us in economy—that is, in the items of low fuel-consumption, uniformity of product, freedom from slips, and reduced cost of repairs and relining. The manager who estimated the cost of pig-iron to be made in a modern plant, by taking the costs of the hand-filled furnace and deducting the amount to be saved by the mechanical appliances, has been surprised, in many cases, to find that unfavorable results in these items of economy have greatly reduced his expected gains. Is there any reason why the fuel-consumption should be greater for a modern furnace than for an older stack using the same mixture ? Certainly the equipment is much more complete, and the trouble, therefore, must lie in the management or in the character of that equipment. Everybody knows that intelligent and vigilant management is a prime requisite: that any neglect of a detail, though it may not be felt that day or week, will surely sooner or later make its appearance as an increased item of cost. But to hold the furnace-maaager responsible for the relatively poor work of the modern blast-furnace would be, I am convinced, a great injustice. For its management has received much more study and care than was given to the older types. Many furnace-managers have lost their health through worrying over this problem, and some hare lost their positions, being held responsible for results made inevitable, as I believe, by the equipment provided for them.

Jan 1, 1905

By d&apos, D. L. Guernsey, J. C. Entremont, John Chipman

The reaction of aluminum with oxygen in liquid iron has been studied at 1740° and 1910°C. Interaction coefficients are very much smaller than those previously published. The equilibrium constant falls within the approximate range of earlier experiments and calculations. It is now well established that the "deoxidation constant" for aluminum in liquid steel at normal steelmaking temperatures is extremely srnall. Thus at 1600 the product [% Al] is of the order of 10- 14. At this temperature, therefore, great experimental difficulties are encountered in any attempt to obtain a direct measure of the constant. If the aluminum content of the metal is high enough to permit accurate analytical determination, that of the oxygen is too low. If the oxygen content is high, the aluminum is below the limits of detection. Our best values of the constant have come, therefore, from indirect calculations or by extrapolation downward from observations at higher temperatures.. For their studies in the range 1695° to 1866°C, Gokcen and chipman&apos; restricted their aluminum concentrations to less than 0.06 pct. Oxygen analyses were made by the vacuum fusion method which appears to be dependable at these low aluminum concentrations. Experimental results, even at the highest temperature employed, are extremely sensitive to small errors in the analysis of either element. The slight change in the equilibrium constant with aluminum and oxygen concentration was utilized in the calculation of interaction coefficients expressing the effect of aluminum on the activity coefficient of oxygen and the reciprocal effect of oxygen on the activity coefficient of aluminum. The range of concentration, however, was so limited that only a rough value for the interaction coefficient could be obtained. This value was much more negative than that found for any other pair of reactants. In view of the very limited range of concentration employed, the reported values have always been regarded as very questionable. A redetermination was the object of the work reported here. EXPERIMENTAL METHOD At high aluminum concentrations, the vacuum fusion method is susceptible to grave error due to absorption of gas by aluminum distilled from the sample. Since it was desirable to extend the study to at least as much as 1 pct Al, another method for analysis was sought. In steels containing more than a few hundredths of a percent aluminum and no other deoxidizing element, it is safe to assume that

Jan 1, 1963

By R. J. Wysor

SINCE the outbreak of the European war, few problems of raw-material supply have commanded more nation-wide attention than potash. It is well known that before the war the domestic production of potash was an insignificant percentage of the imports. The average annual importation of raw potash salts for several years prior to 1914 was slightly over 300,000 net tons, and f other potash manure salts about 700,0000 tons. The sudden and almost total cessation f these imports created a unique and stringent situation. Methods of recovering potash from feldspar and other native mineral sources, and reclamation from hitherto waste products, have received a marked impetus. Soaring prices have been a keen-incentive to research and industrial development. Although several brief articles concerning the possibilities of potash recovery have appeared in recent trade journals, it still may be a matter of some surprise to the average technical mind that potash might be reclaimed as a profitable byproduct in the manufacture of pig iron. At the present time it may be of special interest to present some data, largely of a technical nature, on this subject. A fairly thorough search of the literature reveals a number of articles concerning salts of the alkali metals in the blast furnace. Many of them deal with the-theoretical role f alkali cyanides in the furnace. Several discuss the, probable effect of the alkalies on the furnace brickwork. Two or three ambitious patents have been granted for reclaiming potash or other products from blast-furnace gas. However, we have heard nothing further as to the practical application of these patents. Little literature of importance has appeared during the last 10 years concerning alkalies in blast-furnace practice, and I have discovered no record whatsoever as to the actual sale or commercial disposal f flue dust for its , potash content until this was inaugurated in our plant at Bethlehem. A bibliography of the most important articles discovered is appended.

Jan 1, 1917

OF THE many categories into which scientific knowledge has been arbitrarily divided, the one which has proved most applicable in our attempts to gain an insight into the details of steelmaking processes is physical chemistry. To the young metallurgist who has only recently survived a college course in this subject, the application of its principles to reactions in liquid steel should not be difficult. To one who has had no such course or whose auld acquaintance with the subject has all but been forgot, such application is all too often thwarted by the abstruse presentations of the subject found in many of the available textbooks. AS a tool for the control of a complex process involving many chemical reactions, physical chemistry can become very valuable. The specialist who is using this tool for many purposes and perhaps contributing to its development will want to know a great deal more about it than can be included in this book. He will be interested in its history, its accomplishments and limitations, and its applications to many and varied problems. To the steelmaker or metallurgist, however, it is only one of a number of tools that he must use. He is willing to forego the detailed study of its inner workings in order to concentrate upon the development of skill in its application. It is the purpose of this chapter to present a simplified view of physical chemistry as a tool of great potential usefulness. This purpose and the desire for brevity have required the elimination of many of the gadgets with which the tool is usually adorned. It is hoped that this simplification will be conducive to clear understanding. The beginner is urged not to overlook the more extended treatments of the standard textbooks.* He is assured at the same time that the basic tool is sound and serviceable and is guaranteed to give satisfaction if regularly lubricated with common sense. Certain parts of physical chemistry require rather formidable mathematics for their complete development, but in the main those applications in which we are here interested can be expressed in fairly

Jan 1, 1944

By K. H. Coats

This paper describes an approximate technique for handling the problem of percolation of evolved gas upwards through the oil column in computer simulation of natural depletion. This technique has been incorporated into a general model for simulating three-phase flow in one, two or three dimensions. The mathematical model for perfonning these calculations is described in detail in a separate article. 1 While vertical gas percolation occurs during natural depletion in a reservoir of any configuration, it is especially pronounced in the pinnacle reel or bioherm. The reel may have an areal extent less than one section with a thickness of up to 800 It. The upward percolation of evolved gas often limits the time step in calculations as little as one day. Using this small time step, computer expense for a single 30- to 40-year simulation on even a one-dimensional basis has exceeded 92,000. The method described here for handling the percolation allows time steps of 60 days or more (depending on reservoir size and production rate), resulting in a considerable reduction in computing expense. The method also allows calculations in which secondary gas caps build up in tight zones of the oil column below the main gas cap. The validity of the method is indicated in connection with an example pinnacle reef field. Calculated results using a 2-day time step (where the method in question is not needed and not invoked) are compared with results using the method and a 60-day time step. The comparison shows good agreement. Results from one- and two-dimensional simulations of the reef are presented along with the corresponding computing times on the CDC 6600 computer. A three-dimensional simulation was also performed and the required computing time is given. INTRODUCTION A general analysis for simulating three-dimensional, three-phase flow in reservoirs has been developed. 1 In applying this model to reservoirs undergoing natural depletion, a time-step restriction was encountered due to the flow of evolved gas upwards through the oil column and toward the gas cap. A remedy for this problem has been incorporated in the analysis and is described here. The time-step restriction is encountered only in calculations which include flow in the vertical or near vertical direction. The restriction occurs to some extent in reservoirs of any geometrical configuration, but it is especially pronounced in the pinnacle reef or bioherm where the ratio of thickness to areal extent is unusually large. This paper describes the problem, a method of handling it, incorporation of the method in the three-dimensional, three-phase model, and, finally, a test of the method&apos;s validity in an application to an example pinnacle reef reservoir. THE PROBLEM During the early stages of reservoir depletion, pressure falls below bubble point in progressively lower regions of the oil column. Continuing production results in evolution of dissoived gas throughout the oil column. This gas then percolates upwards toward the top of the reservoir. If the gas encounters a sufficiently low permeability zone in its travel upward, then it can accumulate and form a secondary gas cap. If no zones are encountered which are tight enough to hold gas against the gravity forces, then the gas travels on until it reaches the top of the sand or the main gas cap. Numerical simulation of multiphase flow in reservoirs is generally performed with time steps such that the flow of a fluid into or out of a block in one time step is a fraction (considerably less than one) of the total amount of that fluid present in the block. Use of a time step where the time step&apos;s

Jan 1, 1969