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By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By W. N. Poundstone, G. R. Spindler

A comprehensive report on extensive experimentation in degasification of the Pittsburgh Coal seam is presented. Detailed accounts of the procedures and results are given for permeability tests, vertical bore hole tests, measurement of gas flow from sealed drainage areas, horizontal rib hole tests, and water infusion tests. The removal of methane gas from coal seams in advance of mining is not a new idea with mining men—much attention has been given to the possibility for many years. In other parts of the world, a principal concern has been in the recovery and utilization of the gas and a number of successful projects have been developed in Europe and elsewhere. In this country, the principal motivation has been related to the safety aspect with some possible side benefits concerning costs and efficiency in mining as secondary objectives. To date, experimental work in this country has been largely or entirely exploratory to determine bed characteristics with respect to the liberation of combustible gases to investigate or establish the possibility of degasification in advance of mining and as an aid in projecting mine ventilation systems to provide for safe, effective and economical handling of combustible gases liberated during mining. With these objectives in mind, the School of Mines and Engineering Experiment Station at West Virginia University, in cooperation with the Christopher Coal Co. of Osage, W. Va., initiated some experimental work in May 1952 and the project has been more or less continuous since that time. The work has been centered entirely in mines of the cooperating company in Monongalia County, W. Va., and Greene County, Pa. LOCATION AND GENERAL CONDITIONS OF THE AREA The principal mining in the area involved is in the Pittsburgh coal seam which lies at the bottom of the Monongahela series of the Pennsylvanian. The Pittsburgh coal in the area is generally uniform in its structure and physical characteristics. The bed thickness averages about 7 to 8 ft and the coal has a characteristic blocky structure as the result of pronounced face cleats and definite, but somewhat less pronounced, butt cleavage. It is a medium volatile coal, averaging about 37 pct, and is marketed principally as a steam fuel and for metallurgical purposes. The Pittsburgh coal outcrops along the Monongahela River and dips gradually, but not uniformly, slightly north of west (about N75°W). The westward extensions of the bed, from the areas contiguous to the Monongahela River which have been heavily mined, constitute the principal reserves and are all well below drainage with the depth of cover increasing with the distance from the river. In general, with deeper cover, it may be expected that methane liberation will be more of a problem in future mining as compared to areas mined previously; therein lies the interest in possible de-gasification in advance of mining. Fig. 1 shows the Pittsburgh coal area in the vicinity of Morgantown in Monongalia County, W. Va., and Greene County, Pa., in which the experimental work discussed is located. Fig. 2 shows the contours on the Pittsburgh coal in the test area. It will be noted that the first two bore holes for the experiments were at the edge of a bench or terrace with considerable change in the gradient in the immediate vicinity of the test holes and that the same general condition applies to later test areas. Mining is intensively mechanized in the area and in the mines involved in the experimental work with corresponding rapid advance of working faces a typical characteristic. In the areas now mined the total methane liberation ranges from moderate to relatively heavy, but the actual face liberation is extremely variable and may range from practically

Jan 1, 1961

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By Charles W. Dickson

CONTENTS. [ ] I.THE RELATION OF NICKEL TO PYRRHOTITE. Introduction. The Sudbury district is to-day one of the two great sources of nickel in the world. The peculiar geological relations of

Jan 1, 1913

By E. T. Turkdogan, M. T. Hepworth, R. P. Smith

The permeability of oxygen in 0 iron in the tempera-ture range 700" to 900 C and in 6 iron at 1450°C was determined by the rate of internal oxidation of iron, containing -0.1 pct Al. The solubility of oxygen in zone-refined iron was determined by equilibration with hydrogen-water vapor gas mixtures at 1450" and 1510°C; oxygen solubilities , for iron in equi1ibriu.rn with molten oxide, are found to be 66 and 83 ppm for these two temperatures, respectively. The diffusivity of oxygen in iron at 14500C3 as calculated from the permeability and solubility data, is (4.1 * 0.6) x 10 "B sq cm per sec. OXYGEN is one of the most common impurities present in iron or steel, mainly in the form of oxide inclusions. In the study of many metallurgical problems concerning solid iron, it is often desirable to know with a reasonable accuracy the solubility and diffusivity of oxygen over a wide temperature range. The solubility of oxygen in solid iron has been the subject of numerous studies yielding highly discordant results as seen for example from the literature surveys made by Meijering &apos; and Schenck et a1.&apos; As shown by Kitchener et aL3 and by Sifferlen, the high oxygen solubilities reported by many investigators are the result of oxidizable impurities which are often present in iron. In addition, there have been experimental problems associated with icaccuracy of oxygen analysis of iron containing less than 100 ppm 0. A number of studies have been made on the permeability of oxygen in a and y iron using Fe-Si, Fe-Mn, and Fe-A1 alloys in the internal-oxidation experiments.1&apos;2&apos;5&apos;6 However, no direct measurements have been made of the diffusivity of oxygen in iron. In the present work two sets of experimental measurements were made: permeability and solubility studies at 1450" and 1510°C and permeability studies only in the range 700 to 900°C. In both sets of permeability measurements slab-shaped specimens containing small predetermined amounts of aluminum in solution were exposed at constant temperature to gas mixtures of hydrogen, water vapor, and argon for varying times. These specimens were quenched, sectioned, and examined for oxygen penetration by metallographic observation of aluminum oxide particles which formed. From these data, it is possible to calculate the ratio of the diffusivity of oxygen in iron, D, to the equilibrium constant K for the reaction Hz(g) * O (dissolved in iron) = H,O(g). EXPERIMENTAL Permeability Measurements at 1450°C. An ingot of vacuum-carbon deoxidized iron containing 0.086 pct A1 was prepared, using commercial "Type lO4A Plas-tiron"; after hot rolling, specimens were machined into slabs a by 2 by 2 in. The impurity contents were: S, P < 0.002 pct; C, Mn < 0.01 pct; each of all other Usual impurities < 0.004 pet. The amount of oxide inclusions in this material, determined by a bromine-methyl acetate extraction, corresponded to about 20 ppm 0 in the iron which agreed well with the results of vacuum-fusion analysis. Each specimen was annealed at 1450°C for 1 hr in purified hydrogen, polished to a smooth surface, and then introduced into a controlled oxidizing atmosphere in a recrystallized alumina tube at 1450°C. The constant temperature zone (*3"C) was about 3 in. in length. The gas composition was controlled by mixing argon with hydrogen (using calibrated constant-head flow meters) and passing the mixture through a column of a mixture of oxalic acid dihydrate and 10 pct anhydrous oxalic acid, to establish a required water-vapor content in the gas mixture. The temperature of the oxalic acid dihydrate column was controlled by a thermostat. The total gas flow was in the range 800 to 1000 cu cm per min. The exit gas from the reaction tube was passed through a weighing bottle containing a desiccant, to cross-check the degree of water-vapor saturation, which for all experiments was about 97 pct of those derived from the data of Baxter and Lansing.1 For a typical experiment, a specimen was introduced into the furnace in a stream of dry argon and hydrogen. The specimen was then rapidly raised by a Pt-Rh alloy wire into the hot zone and allowed to reach the reaction temperature, at which time the oxidizing gas mixture was introduced. The oxygen potentials employed were sufficient to oxidize aluminum but not to cause liquid iron oxide to form. After a specified time, the experiment was ended by dropping the specimen onto a water-cooled copper block at the bottom of the reaction tube. The depth of the internally oxidized zone, hereafter called the "case", was determined by sectioning the specimen at right angles to the long direction. The section was then examined under a microscope equipped with a micrometer stage. In general, the oxide particles were fairly uniform in size and distribution, forming a reasonably well-defined interface between the oxidized and unoxidized region. A typical cross section as observed at X30 is shown in Fig. 1. A thermal macroetch was used in one selected specimen to delineate the case. A cross section of a previously oxidized slab was polished and reheated at 1450°C in a hydrogen atmosphere for about 10 min. Upon quenching, the surface relief shown in Fig. 2 was produced; causes of this effect are unknown. Permeability Measurements Below 900°C. A slightly

Jan 1, 1967

[ ] DISCUSSION F A LORIA*-The method of testing gun steel for resistance to surface cracking described in this paper was restricted to the examination of small, rod-shaped specimens The writer would like to point out the importance of other factors in producing defects in forged and bored gun tubes which would not be apparent in this investigation because of the nature of )he test Actual section size would accentuate the possibility of internal wall (bore) defects arising from unequal expansion between the internal and external wall surfaces on firing, resulting in internal tearing Checks and tears on the inside walls arise from internal tensions and nonuniformity on cooling, but the internal tearing can be reduced by using alloys of low expansion and of good thermal conductivity so as to reduce the difference between the outer and inner wall surfaces Also, the possibility of the location of inclusion segregates within a machined gun tube becomes more likely than in a small test specimen The effect of these nonmetallics on gun life and performance is evident when one realizes that the inclusions are soft yet brittle They reduce the amount of plastic deformation which can take place before cohesive failure occurs Once localized fracture has occurred at the position of a chain of these inclusions, a sharp notch (crack) is formed which produces stress conditions more favorable to cohesive failure than to plastic deformation These cracks aid erosion by providing channelways for the explosive gases, eventually leading to the tearing out or spalling of blocks of metal Oxidation of the surface may be partly responsible for the change in the surface of gun steel during firing observed by the author The appearance of burn on the surface is an indication that high temperatures were reached on firing, resulting in a slight oxidation of the surface Since the color of the oxidized film depends on both temperature and time, a higher temperature is required for a given color to form when it is caused by explosive heat, which acts for only an extremely short time at a given spot, than when it is caused by ordinary tempering The cross section of the gun steel specimen, Fig 16, illustrates that the repeated firing temperatures were high enough to cause

Jan 1, 1948

By Chas. Y. Clayton, Francis B. Foley, W. E. Remmers

DuRing the summer of 1919, the late Dr. Henry M. Howe, then Chairman of the Division of Engineering of the National Research Council, organized a committee to obtain a better insight into the behavior of carbon steels under the influence of various treatments by a proper control of the time and temperature factors. During part of 1919 and 1920, work in connection with this investigation was carried on at Dr. Howe&apos;s laboratory at Bedford Hills, N. Y. During 1921 there was an enforced hiatus in the work, occasioned by the illness which resulted in Dr. Howe&apos;s death in 1922. At that time one of the present authors compiled the results of the work which had been done and this was published in 1923.&apos; Following the publication of this work, it seemed desirable to carry on in the same manner an investigation of steel of C 0.75 per cent., which steel had not been as fully treated as had the other steels of C 0.34 and 0.52 per cent., used in the published work. Furthermore, certain unusual results have been obtained in the treatment of C 0.52 per cent. steel by quenching and drawing, and repetition of this part of the work seemed advisable. This has been done during the past year at the School of Mines and Metallurgy of the University of Missouri at Rolla, Mo., by a cooperative undertaking of the School and the Bureau of Mines, working in conjunction with the Committee on Heat Treatment of Carbon Steels of the National Research Council. The present paper is a report of the results obtained in this work.

Jan 1, 1926

By N. Schapiro, R. J. Gray, G. D. Coe

A petrographic and chemical investigation was conducted to determine the occurrence and distribution of the organic and inorganic forms of sulfur in various size and specific gravity fractions of a high volatile, A-rank, Pittsburgh seam coal. The investigation was conducted to aid in the resolution of the problem of how metallurgical coke of lower sulfur content can be produced from high sulfur coals. The Pittsburgh raw coal contains about 2.4% S in two dominant forms: pyritic and organic. Pyritic sulfur constitutes about 57% of the total sulfur in the raw coal and occurs in macroscopic and microscopic-size particles. A plant cleaning process mechanically separates between 50 and 60% of the pyritic sulfur, mainly the macroscopic particles. The organic sulfur constitutes 41% of the total sulfur in the raw coal and 55% of the sulfur in the washed coal. Thus, organic sulfur is not reduced by physical methods of separation. Organic sulfur occurs in all the coal entities, but in general, increases as the exinoid content of the coal increases. In this study, it was found that carbonizing certain selected low gravity coal fractions containing an average of 0.45% pyritic sulfur and 1.01% organic sulfur produced cokes containing an average of 0.22% pyritic sulfur and 0.91% organic sulfur. However, the organic sulfur in the coke is probably derived in part from the heating of pyrite in the presence of carbon. Thus, the total sulfur in the coal carbonized is the most important factor affecting the sulfur content of the coke produced. Concentration of microscopic pyritic and organic sulfur in the middling-type coal indicates the necessity for rejecting as much of this material as is economically feasible. Most of the sulfur introduced into the blast furnace originates from the coke. Although the sulfur content of the hot metal can be controlled by the addition of flux, the flux used restricts the productivity of the furnace by displacing ore and requires first to be smelted; therefore, low sulfur coke is highly desirable. Since the sulfur content of coke is dependent upon the sulfur content of the coals from which the coke is produced, low sulfur coals are required to produce low sulfur coke. In the western Pennsylvania area, large quantities of good coking coal are available from the Pittsburgh seam, but this coal unfortunately contains relatively large quantities of sulfur. To provide information that might be useful in reducing the sulfur content of this coal in the cleaning process, an investigation was conducted to determine the physical and chemical forms in which this sulfur occurs and with what petrographic components it might be associated. The Pittsburgh seam coal, like most other coals, contains two dominant forms of sulfur: one occurs as the minerals pyrite and/or marcasite and is referred to as pyritic sulfur; the other is combined with the coal substance and is called organic sulfur. Pyritic sulfur is amenable to physical methods of separation, whereas organic sulfur is not. Pyritic sulfur particles must be freed from the surrounding coal if they are to be removed in the washing process. Generally, this requires crushing; the required degree of crushing being a function of the size and distribution of the pyrite. The present investigation was conducted to 1) determine the size, distribution and association of sulfur-bearing minerals in the coal and 2) to determine whether the organic sulfur has a preferential association with specific coal entities. If a preferential association exists, this knowledge may be useful in devising a method for organic sulfur reduction. In addition, a study was made to determine the extent to which pyritic and organic forms of sulfur in the coal contribute to the sulfur in the coke produced from this coal. A representative 3%-ton sample of raw coal was crushed to —3 in. and screened into square-mesh sizes: 3 to 1 in., 1 to % in., % to % in., % in. to 10 mesh, 10 to 35 mesh, and 35 to 200 mesh. Separate samples of the -200-mesh fraction and the all-size composite were also collected. Each size fraction (except the -200 mesh) was fractionated on heavy liquids of the following specific gravities: 1.280, 1.300, 1.325, 1.350, 1.375, 1.400, 1.425, 1.450,

Jan 1, 1963

By A. A. Blow

The productive area of the Leadville mining district immediately adjoining the city of Leadville, which, by its wonderful richness, has attracted the attention of the mining world for the past twelve years, may, with a few exceptions, he considered as divided into seven local mining centers, separated one from another by the topographical features of the country, and designated by common consent as Fryer Hill, Yankee Hill, Breece Hill, Rock Mill, Printer-Boy Hill, Iron Hill, and Carbonate Hill. Of these seven distinot mining localities, or groups of mines, the central one, Iron Hill, is the one of greatest importance and interest. It was the scene of the earliest discovery of carbonates, as far back as 1875, and since that time has always maintained its position

Jan 1, 1890

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,&apos; however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki&apos;s method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B&apos;, it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By R. G. Hudson, L. Yang

In electrochemical separation of metals, it is necessary to control the potential applied between the electrodes so that only the desired electrode reactions can occur. A knowledge of the minimum potential needed for a given electrode reaction to take place continuously is therefore pertinent to the success of the process. In molten chloride systems at high temperatures, activation polarization is believed to be small,1,2 so the minimum potential needed for the electrolytic decomposition of a molten metal chloride MC1n (n = valence of the metal ion) is therefore essentially the equilibrium electrode potential E of the metal-chlorine galvanic cell in the solution. If the decomposition products are pure M and chlorine at a pressure of p atm, E*Eo-rt/nf in [i] Since EO (the standard electrode potential of MCln) is a constant at a given temperature and R (the gas constant), and F (the Faraday&apos;s constant) are all constants, the variation of E with the electrolytic bath conditions is largely determined by the effect of the latter on the activity of the metal chloride amcln (standard state = pure MC1,). Measurement of E and study of how amCin varies with temperature and concentration, the nature of the solvent, and that of the coexisting solutes are therefore pertinent in the selection of optimum operating conditions for the electrochemical separation of metals. Because of its low melting point, high decomposition potentials of its components, and the low solubility of heavier metals in it, the LiC1-KC1 eutectic melt is a useful solvent and has been used in the electrodeposition of Mo,3Ce,4 and u5 metals. Senderoff and Brenner3 measured the potentials of Zn/Zn++, Fe/Fe++, Cu/Cu+, Mo/Mo+++, and Ag/Ag+ against an Ag/AgCl (pure) reference electrode at 600°C and a concentration of 4.1 mole pct of each chloride and came to the conclusion that complex ion formation occurred in some of the melts. Laitinen and LiUe gave an electromotive force series at 450°C for a number of {Metal/Metal ions (unit activity)) electrodes in LiC1-KC1 eutectic melt, the {pt/pt++ (unit activity)) electrode being chosen as the reference. Walker and Danly7 studied the ther-modynamic properties of NiC12 in LiC1-KC1 eutectic melt over a wide range of temperatures and concentrations by measuring the electrode potential between a nickel electrode and a chlorine electrode in the melt. Since potential measurements made by using the chlorine reference electrode are of more direct significance both in the study of electrochemical separation and in the evaluation of the thermodynamic properties of the melt, it is therefore decided to measure the electrode potentials of cells of the type {M/MCin (mole fraction = N) in LiC1-KC1 eutectic melt/Cl2 over a range of N values and temperature for a number of metal chlorides. The results should indicate the order by which the various metals plate out on the cathode and how this order is affected by temperature and the concentration of the metal chloride in the solu-

Jan 1, 1960

By R. B. Snow

THIS paper describes a technique of polishing and etching specimens of open-hearth furnace slags or hearth aggregates for identification of the crystalline constituents-lime (CaO), tricalcium silicate (3CaO•SiO2), dicalcium silicate (2CaO-SiO2), monticellite (CaO•MgO-SiO2), or forsterite (2MgO•SiO2), with especial emphasis on the mineral merwinite (3CaO-MgO.2SiO2). With proper standardization, this identification does not require the use of the petrographic microscope. The composition of basic open-hearth slags and furnace bottoms falls, almost without exception, within systems containing CaO, MgO, "FeO," MnO and SiO2, in which the number of basic molecules so greatly exceeds the orthosilicate ratio (two molecules of base to one of silica) that free basic oxides, and combinations between them such as aluminates or ferrites, are present in cooled specimens. Orthosilicates of (CaO + MgO) are the most common in such specimens, since in nearly all cases, except premelt slags, the molecular ratio of (CaO + MgO) to SiO2 is more than 2 to r. When sufficient lime is available it combines with the silica to form dicalcium silicate (2CaO•SiO2), which contains little, if any, MgO, FeO or MnO in solid solution whereas the latter oxides combine to form the oxide solid solution known as periclase. If the lime present is insufficient to form dicalcium silicate (2CaO•SiO2) it combines with MgO to form either merwinite (3CaO•MgO.2SiO2) or monticellite (CaO-MgO•SiO2); these minerals take little if any FeO or MnO into solid solution and the remaining MgO, FeO and MnO combine as periclase. This generalization seems to be valid for basic slags and furnace bottoms, since minerals such as CaO-MnO•SiO2 and CaO-FeO-SiO2 are found only in slags in which the lime-silica ratio is less than 2 and are not observed in specimens from furnace bottoms. The identification of crystalline constituents in such materials, especially of fine crystals in the groundmass, is difficult under the petrographic microscope. They are often masked by their neighbors because of their small size in relation to the thickness of the thin section and because of the presence of opaque or colored constituents. The indices of retraction and the optical sign of the mineral are sometimes difficult to determine because of the small size or because of twinning or of inclusions within the crystal. Moreover, the positive identification of merwinite (3CaO•MgO.2SiO2) from its optical properties is usually difficult in the presence of dicalcium silicate (2CaO•SiO2). CaO, MgO, 3CaO•SiO2 and 2CaO•SiO2 in open-hearth slags have been identified for a number of years in the U.S. Steel Corporation Laboratory by the usual

Jan 1, 1947

By E. H. Dix

All commercial aluminum contains small percentages of copper, iron, and silicon as unavoidable impurities. The purest metal obtainable commercially, special grade high purity ingot, contains a maximum of 0.50 per cent. impurities of which the usual minimum amount of copper is 0.01 per cent.; silicon, 0.12 per cent.; and iron, 0.20 per cent. This grade is too costly for most purposes. The two standard grades, Nos. 1 and 2, containing a minimum of 99.0 and 98.0 per cent. aluminum, respectively, are more generally used. Other grades of secondary aluminum often contain as high as 3 or 4 per cent. of impurities, which include 1 per cent., or more, of zinc. Specifications for high-grade aluminum-casting alloys generally allow a maximum of 1.7 per cent. for total impurities. The S. A. E. Specification No. 33, which is intended to cover alloys made from secondary aluminum ingot, gives the iron maximum as 1.5 per cent. and the maximum for silicon (including manganese and tin) as 0.75 per cent. The effect of even relatively small amounts of impurities on the physical properties of ingot aluminum is shown by the following cornparison of two lots of aluminum, which may be taken as representative of special grade and grade No. 2 ingot, respectively. AnalysEs Special Grade, Gbade No. 2, Per Cent. PeR CBnt. Copper................................. 0.01 0.32 Silicon................................. 0.12 0.32 Iron................................... 0.42 0.82 Aluminum.............................. 99.45 98.54

Jan 1, 1923

By Milton H. Fies

Although pig iron from iron ore and red cedar charcoal preceded the mining of coal by many years, for tradition says that Alabama iron was used to shoe the horses of Andrew Jackson&apos;s soldiers, coal was not produced until 1830. In that year, coal was mined in Tuscaloosa County, in the vicinity of what is now the University of Alabama, and shipped on flat boats (obviously during the wet season, for there were many shoals) down the Warrior River to Mobile. About that time, the first railroad, the Decatur & Tecumseh, was being constructed in northern Alabama to overcome the obstructions to freight traffic caused by the now well-known Muscle Shoals in the Tennessee River. This railroad was patterned after a railroad at Mauch Chunk, Pa., which was used for hauling anthracite from the Panther Creek valley. The Alabama railroad, which required about four years to complete, was 46 miles long and was used solely for the transportation of cotton. Although it was a failure, it demonstrated the practicability of the undertaking, and the succeeding railroads, which were begun in 1834, 1848, 1852, and 1853, added immeasurably to the development of the coal resources of the state. Between the years 1830 and 1860, practically all the coal mined in the state was dug from the outcrop near the river or from the river beds, and shipped by boat to Mobile. Transporting coal down the Warrior River was an undertaking of great risk, required much skill, and frequently had heavy losses. It is recorded that this coal was sold to the gas company in Mobile in 1844; it was most likely mined from the Black Creek Seam. In 1914, on the completion of Lock 17, the Warrior River became a navigable stream from 9 miles above Cordova, Ala., to Mobile and offers a great opportunity for the future development of the coal resources of the state. Coke for foundry use was first made in Alabama in 1855. It was 21 years later, however, in 1876, that pig iron was made from Alabama ore with Alabama coal.

Jan 1, 1925

By Charles T. Malcomson

In the United States, improvements in methods of combustion have made possible the use of the smaller sizes of anthracite. This coal is now being reclaimed from the culm banks accumulated by the miners in the more prodigal years. To-day the freshly mined "slush" is segrega,ted and stored against the time when, through briquetting or some other means, it may be utilized as a commercial fuel. For many years Europe has achieved enviable results in the conservation of her small coal by briquetting. This profitable industry, first placed on a commercial basis in France in 1842, has grown to such magnitude that the production during 1913 exceeded 36,000,000 short tons. Briquets produced in Great Britain are used principally for steam purposes and the greater part of the output is either exported or taken by the Admiralty. On the Continent the briquets are sold in all branches of the coal trade. The French railways consume from 16 to 40 per cent. of their fuel in briquet form, and in Germany the lignite briquets (of which 20,000,000 tons were produced in 1913) are as familiar and interesting to the American traveler as the huge porcelain stoves in which they are burned. It is not strange, therefore, that aggressive and far-sighted promoters heralded this means of converting our ubiquitous coal waste into revenue. To the superficial student the briquetting process seemed so simple as to make success easy. It is for this reason principally that the path of the industry in America has been strewn with failures. The rash enthusiast had either not worked out the mechanical problems involved or had failed to grasp the local conditions under which the briquets must be made and sold. It may be confidently stated, however, that in spite of the many vicissitudes through which it has passed, coal briquetting is now an accomplished economic success in this country, and as a profitable adjunct to the coal industry it has come to stay. Several valuable contributions relating to coal briquetting are found in the Transactions. Charles Dorrance, Jr., has sketched briefly the history of the anthracite briquetting plants from the time of Loiseau&apos;s pioneer plant down to that of the Lehigh Coal & Navigation Co. at Lans-ford. Since then this phase of the industry has remained practically at

Jan 1, 1915

By Keijiro Nishio

At a time of great antiquity when our Yomato tribe had not yet found its way throughout the country, there lived in Japan barbarous tribes of the stone age, whose dwellings were vertical caves covered with roof&apos;s of twigs and weeds. In a cave lately discovered at the village of Morita, 10 miles west from the port of Aomori, there were found pieces of micaceous iron-ore and psilomelane, with oval holes pierced from both sides. Apparently these objects were regarded as ornaments or curios, without being applied to any practical use. Among the traditions given in the Nihonshoki, an ancient history of Japan, there is one relating to the mining industry. According to this tradition, in the mythological age Izanami-no-Mikoto gave birth to Kanayamahiko-no-Mikoto, god of mines, and Amaterasu-Okami (the sun-goddess) was armed with swords. It came to pass at one time that she concealed herself in Ama-no-Iwato ("Heavenly Cave"), and several gods made contrivances to entice her out. Among them, Ishikori-dome, a smith, made a mirror with copper obtained from the Ama-no-Kagoyama, by means of a pair of bellows known as the Ama-no-habuki, which was made of a deer-skin. It is recorded also that Susanb-no-Mikoto, her younger brother, observed the abundance of gold and silver in Korea, where his descendants were to reign, and urged them to provide themselves with boats to convey them across the Sea of Japan. In the course of time he accomplished his object, proceeding to Korea with his son, Isotakeru-no-Mikoto. These accounts

Jan 1, 1913

By Russell W. Dayton

The metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger,"&apos; i in 1909, was the first to apply polarized light to the microscopic study of opaque substances; Endell and Hanemann(2) were the next, in 1913. In 1919 and 1920, Wright(3,4) prepared two papers on the subject. In the first he developed the detailed mathematical theory from the viewpoint of the electromagnetic theory of light, and in the second described the various methods in use, giving improvements of his own. Schwarz(5)

Jan 1, 1935

By J. F. Lewis

Much has been written on this great engineering work, principally from the civil engineer&apos;s stand-point. In presenting the subject to the Institute, it seems necessary to include something of geology as well as engineering. In this case, it is particularly the glacial and post-glacial periods with which we are concerned; for it has been clearly proved that the canal recently excavated has not for the first time opened the Des Plaines valley for drainage away from Lake Michigan, and that this valley, as well as the site of this city, is very closely connected with the processes and effects of the ice period. We have simply renewed a channel and a drainage direction which formerly existed. As the days of deep water-ways for commercial purposes are fast approaching, engineers may find the consideration of ancient topography and geologic changes highly useful. For what I may say on this subject I am greatly indebted to Mr. Ossian Guthrie, who has made an earnest study of glacial geology and labored especially to decipher the records of its history in this region. * Chicago is situated in the track of one of four great glacial ice-streams that swept down from the North: one moving due South from Marquette and entering the Illinois valley at Ottawa; one through the Lake Michigan valley, entering the Illinois valley near Lemont; one from Saginaw Bay diagonally across the States of Michigan and Iadiana, entering through

Jan 1, 1898

By Nathaniel Arbiter, Norman L. Weiss

Factors now accelerating the trend to larger concentrators and larger equipment units are reviewed. After almost 40 years of stability with unit sizes less than 100 cu ft, 200 and 300-cu-ft flotation-cell units are now operating and a 500-cu-ft machine is being built. The design of these cells is considered, as is the design and operation of flotation circuits against the background of the need to achieve greater process efficiency while holding down operating and investment costs. Particular attention is paid to the scale-up problem. With the newer cells having five to ten times higher unit capacities, the advantages resulting from this in sampling, mill operation nnd control, testing and plant layout are indicated, as well as the broad direction for changes in the overall design of 50,000 to 100,000-tpd concentrators. A comparison is given of the available larger cells of U.S. manufacture with analysis of differences and similarities. After almost 60 years of application in this country, froth flotation is still by far the most important process for concentrating metallic ores as well as a number of nonmetallic ores including fluorspar, phosphate rock, and potash. Its use on iron ores and coal is increasing. In the metals groups, the largest plants and the greatest progress are found in copper and molybdenum mills, and the section of this paper that deals with applications will be found most pertinent to that field. During its long reign, the flotation process has passed through several phases of evolution and has achieved progress in economy, efficiency. and simplicity of operation. Much of today&apos;s success in the flotation of low-grade ores can be attributed to that progress. Even more important to us than our ability to cope with today&apos;s conditions are tomorrow&apos;s problems, which we can contemplate with some prescience and confidence. Our annual production of copper, lead, zinc, and molybdenum—to mention only the most important metals occurring in the U.S. as sulfides- must be held at a high level in the face of a declining grade of ore. It is probable that the tonnage of such ores mined and processed will double in this country before the turn of the century. Not only will many of the existing flotation mills be enlarged again and again, but larger mills will be built here and abroad to meet our needs. At this moment, in fact, there are at least three proposed new foreign mills or expansions that envision 100,000-tpd milling rate on copper ores. Table 1&apos; shows the trend in copper ore grades in U.S. in recent years. Table 2&apos; shows the projected annual growth rate of consumption 1966-1985. A study by one of the authors 25 years ago showed that of 32 copper mills in North America with more than 100-tpd capacity, only eight had capacities exceeding 10,000 tpd. The average for these eight was 25,000 tpd. These included the three giants of that day, Magna, Arthur, and Morenci; the other five averaged a little over 10,000 tpd. Today instead of the eight mills with capacities exceeding 10,000-tpd capacity we have 25, and the mill with less than 1000-tpd capacity is fast becoming extinct. Much less range is found in lead and zinc mills, which are still generally small except for the few with over 1000-tpd capacity in Missouri, Utah, and Idaho, and a few zinc ore mills in the same size category. Molybdenum and potash operations are the fastest growers in North America today, but when one considers the projected increase in consumption of copper together with the projected decrease in grade of ore (3% annually), he can foresee that copper ore milling will soon lead the list. Technological improvements to meet the challenge of lower-grade ores have taken the wholly predictable path toward bigger equipment. In mining, shovels, draglines, scrapers, and trucks have led the way; in ore processing, we have seen a rapid increase in size of grinding mills, flotation cells, and pumps. Twenty-five years ago, for example, the 10-ft-diam ball mills treating 2000 tpd at Morenci were considered the giants, but today some grinding mills in similar service have five times that capacity. The specific matters to be dealt with in this paper are 1) the underlying principles that affect flotation-machine design, and the conditions required to produce

Jan 1, 1971

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,&apos; or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967