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By HOWARD I. OSHRY, James W. Ballard, H. H. Schrenk

Photometric instruments were designed and built for use with X- ray and spectrographic apparatus for the investigation and analysis of a variety of materials of hygienic interest . The instruments are simple in design , may be constructed economically , and have a number of features that make them stable and easy to operate . They are readily adaptable for measurement of either X - ray diffraction patterns or spectrographic films or plates . Because of these features and the interest shown in the instruments , they are described in detail , and reference is made to their application in the laboratory .

Apr 1, 1942

By Zhonglin Ye, Guangping Dai, Ba Zhang, Yonggang Wei, Shiwei Zhou, Bo Li, Hua Wang

Decreasing copper content in slag is critical for improving copper recovery, where apparent viscosity is the main factor affecting the separation of matte/copper from the slag. The viscous behavior of copper converter slag was investigated during reduction process in this paper, and its non-Newtonian viscous behavior and shear thickening characteristics were clarified. The effects of silicate structure and solid particles in the melt on the slag apparent viscosity were investigated. As slag cleaning proceeded in an electric furnace, the magnetite gradually transformed into ferrous oxide, increasing the FeO/SiO2 ratio. With this ratio increased from 1.2 to 2.0, the slag structure was simplified, and its apparent viscosity decreased from 0.26 to 0.12 Pa·s at 1523 K. The iron phase was excessively reduced to metallic state; the slag contained metallic copper-iron alloy particles, increasing apparent viscosity. The apparent viscosity and phase structure of the slag corresponding to the iron phase reduction process were analyzed in detail; the results obtained in the present study are of great significance to the reasonable control of the converter copper slag cleaning process.

Nov 7, 2022

By Oliver Bowles

Chalk is defined as a noncrystalline, soft, friable, fine-grained, light-colored type of limestone. It consists essentially of calcareous shells of minute organisms known as "foraminifera," although skeletal remains of molluscs, corals, and sponges are also present. Flint balls which are found so commonly in the chalk cliffs of Europe are regarded as segregations of the remains of certain organisms, such as radiolarians and sponges, that secrete siliceous shells or spicules. The famous chalk beds of northwestern Europe are of Upper Cretaceous age, a geological period that was particularly favorable for the develop- ment and multiplication of foraminifera. The distinguishing physical characteristics of true chalk never have been fully defined; probably its noncrystalline and colloidal properties are most important. The properties of chalk, whiting, and whiting substitutes are not well understood, and much re- search is necessary before definite reasons may be ascribed for the behavior of these materials under various conditions of use. The Bureau of Mines has undertaken a detailed study of chalk and similar materials to determine their exact properties and to establish a basis for classifying formations loosely designated as chalk occurring in various parts of the United States, but the results of this study will not be available for some months. Whiting is a pulverized, purified, and carefully sized chalk. Whiting substitutes consist of finely ground limestone or dolomite, ground marble (marble flour), white marl, and chemically precipitated calcium carbonate.

Jul 1, 1931

By Anand Kumar Agrawal, Kinzel Klaus Peter, Lorenzo Micheletti, Cristiano Castagnola, Horst Kappes, Andre Oliveira, Björn Rösner, Philippe Bermes

Blast furnaces are widely employed today for iron production all around the world, with a total production of around 1.2 billion tons per year. Its operating principle, which relies on usage of coke to reduce the ore, to ensure the permeability in the reaction vessel, to maintain its flexibility of operation and acceptability for varying qualities of iron ores. The blast furnace route is widely considered as the most economic and efficient route of iron production, however it is based on fossil energy carriers. The blast furnace route has undergone significant developments in terms of energy efficiency in the last decades, which led to a substantial reduction in the use of fossil reduction materials. Being an energy intensive process, competitiveness and cost saving in the blast furnace plant was always strongly related to the saving of energy and hence reduction of CO2 emissions. In addition to this, EU emissions trading system (EU ETS) as a cornerstone of the EU's policy in response to climate change has set new “challenges” for iron production in Europe. Paul Wurth has always been deeply involved in the development of energy saving technologies for blast furnaces. In the following a review of energy saving achievements developed in the last decades will be presented and the potential of available CO2 saving technologies will be summarized. Additionally, an outlook about the potential of future technologies, concepts and their impact on the blast furnace and the steel plant’s energy balance will be discussed. Finally, the replacement of carbon by hydrogen as reduction agent in the steel plant will be reviewed, with special focus on a comparison of costs and incentives.

Oct 1, 2019

By W. J. Fene, G. W. Grove

An important activity of the Safety Division of the Bureau of Mines , in its efforts to reduce accidents , is the safety inspection of mines . Inspections are made at the request of the operators and are not connected with the inspections by the various State departments of mines . The operating management is furnished with a confidential report of the results of the Bureau's inspections , with recommendations for elimination of the hazards found . These mine - safety inspections include a study of mining practices , conditions , and equipment and in some cases the sampling and analysis of mine air and coal dust . The Bureau of Mines has no regulatory powers , therefore the recommendations made in these reports are merely suggestions , and operators are not required to adopt them . Mine inspections are a check on safety standards , methods , and practices and are essential to any accident -prevention program . A foreman or superintendent may be sincere in his efforts to operate a mine safely and believe that he has done everything possible to attain this end . However , experience has shown that because of his familiarity with the mine and the consequent " nearness " of its various features many unsafe conditions may be , and in most cases are , overlooked ; an inspector , particularly an outsider who is trained to look for hazards , can point out the unsafe conditions overlooked by the foreman or superintendent . Some companies employ safety engineers who make regular inspections of their mines , report substandard conditions and hazards found , and make recommendations for correcting them . Unless these recommendations are carried out the inspections have little value . In making recommendations , due consideration should be given to the feasibility of carrying them out ; the management may and very often does consider a recommendation impracticable because of the

Mar 1, 1935

By Jie Long, Zijie Liu, Pu Liu, Bo Li, Menghua Li, Qiang Wu

During coal mine operations, roadways may be located close to faults. When designing these roadways, it is important to determine the width of the rock mass between a roadway and a fault area to prevent water inrush. In this paper, the Xintian Coal Mine in the northern Guizhou Province of China is selected as a typical case. Through numerical simulation based on orthogonal tests, range analysis, and multiple linear regression (MLR) analysis, the process of water inrush from faults in excavation roadways is studied. The results show that the influencing factors of the safe width of a rock mass preventing water inrush (RMPWI) can be ranked according to the degree of influence from large to small as follows: the hydraulic pressure of the fault, the surrounding rock grade, the overburden depth of the roadway, the cross-section height, and the dip angle of the fault. Among them, the dip angle of the fault, the cross-section height, and the surrounding rock grade are negatively correlated with the safe width, while hydraulic pressure of fault and overburden depth of roadway are positively correlated with safety width. The predicted value for the safe width based on MLR is greater than the measured value of the width of the RMPWI when water inrush occurs, but less than the calculated value based on the empirical formula in the standard, which proves the accuracy and practicability of the prediction method. This research provides a certain basis and reference for the prevention and control of water inrushes in mines.

Jul 5, 2023

By Yisa Liu, Lili Xu, Shina Li, Kang Li, Jiong Dong, Zichen Yin, Ruixin Ma

With the evolving landscape of gold mineral resource development and utilization, the easily treatable gold resources are continuously decreasing, while refractory gold minerals are becoming the most important resources in the field of gold extraction. In these original ores, most of the gold is encapsulated in the lattice of pyrite and arsenopyrite, resulting in difficulty of gold transfer into the solution during the leaching process. The most effective method to solve the problem of insufficient contact between gold particles and leaching reagent is oxidation pretreatment before leaching. Different from traditional high-temperature roasting, concentrated sulfuric acid was used as both an oxidant and leaching agent in a sulfideencapsulated refractory gold ore to decompose the pyrite in the curing environment to expose the gold and improve the leaching efficiency. The experimental results showed that under the conditions of liquid solid ratio 3:1, curing temperature 240 °C and the reaction time 1.5 h, the weight loss rate and iron removal rate of the ore sample reached the highest value of 60.01% and 99.68%, respectively. The main phase of curing residue was Fe2( SO4)3, and silica was nearly the only phase after washing. At the same time, by combining the sodium thiosulfate system gold leaching method, the gold leaching rate increased from 3.67% to 81.30% before and after pretreatment with concentrated sulfuric acid.

Feb 19, 2024

By K. Szafran, R. E. L. Seal, M. Tansey

Conversion of hydraulic equipment to fire resistant fluids has been hampered by less than satisfactory component performance and in some cases, catastrophic equipment failure. Concern over identifying possible causes to these problems led to a joint research project between the Potash Corporation of Saskatchewan Mining Limited and the University of Saskatchewan. This paper summarizes some of the results and conclusions derived from this joint project. In this study, the research was limited to evaluating the effects of potash contamination on the performance of hydraulic equipment. Two separate types of tests were conducted in order to provide a basis upon which trends could be established. This study concluded that the presence of potash dust in the hydraulic fluid can induce severe wear over relatively short periods of time. It was also deduced that a contaminant free fluid combined with proper fluid maintenance could extend the performance of hydraulic components using fire resistant fluids even under very severe operating conditions, such as elevated pressures and temperatures. Recommendations as to how to achieve this goal and the practicality of doing so are presented.

Jan 1, 1988

By J. H. Swisher

The solubility of graphite in CaO-S2O2-Al,O3 slags was measured by equilibrating slag samples with graphite crucibles and CO gas. Carbon contents as high as 2 ut pct were obtained in CaO-saturated, CaO-A1,O3 slags, and 1.3 wt pct in slags of the composition CaO.Si0,. Although the observed conditions for Sic formation were in agreement with those predicted from thermodynamic data, CaC, was found to form at a lower temperature than predicted frotn thermodynamic data. From measurements of the equilibrium carbon content as a function of CO Partial pressure, it was found that carbide ions dissolve in CaO-A12O3 melts with a valence of minus two. The carbon content increased with CaO concentration in Ca0-Al,O3 melts and increased with SiO, content along the CaO'AlO3-CaOSi0 join in the ternary system. When solid CaC2 was added to CaO-A12O3 and CaO-SiO2-A12O3 slags, it was found that one of the oxides in the slag was reduced by the carbide (Al2O3 in the forrner and SiOz in the latter). In electric furnace steelmaking, a double-slag practice is frequently used to meet alloy specifications. Initially a flush slag, which is oxidizing in nature, is used to remove phosphorus and carbon from the steel bath. Later in the refining period, the flush slag is replaced by a highly reducing carbidic slag. When calcium carbide is formed in or added to a finishing slag, the slag is effective as a desulfurizing agent and also permits alloying elements such as chromium, vanadium, and tungsten to be added to the slag in the form of oxides. The oxides are readily reduced by calcium carbide, thereby minimizing the use of expensive ferroalloys. More work has been done on the thermodynamics of silicon carbide in slags than on calcium carbide. Baird and alor' and Kay and alor' determined the free energy of formation of Sic by measuring the partial pressure of CO in equilibrium with solid silica, silicon carbide, and graphite. Using a similar technique, they determined SiOz activities in CaO-SiOz and Ca0-Si0,-A1203 slags. Rein and chipman3 also determined the free energy of formation of Sic using slag-metal equilibrium measurements. A literature survey has uncovered only one experimental study of the behavior of CaC, in slag systems. Shanahan and cooke4 report the results of some preliminary experiments on the solubility and stability of CaC, in a CaO-A1,03 and a Ca0-Si0-A1,03 slag at a temperature of about 1500". The carbon solubility as CaC, in a slag containing 50 pct CaO and 50 pct A1203 was reported to be 0.6 pct. They also review earlier work on the binary CaO-CaC, system. A eutectic exists in this system, but various investigators disagree on the eutectic temperature and composition. eal has given an explanation for carbide furnace erruptions in terms of the thermodynamic properties of CaC,; his analysis is not based on experimental data, but on compiled data for the free energies of formation of CaC, and CO.' , These data for steel-making temperatures are all extrapolated from the results of low-temperature measurements. In the experiments described in this paper, slag samples were equilibrated with graphite crucibles and with mixtures of CO and argon or with CO gas at 1 atm total pressure for measurement of the carbon solubility. Most of the work was done on Ca0-A1203 binary slags, although in some experiments CaO-SiO, and Ca0-Si0,-A1,03 slags were used. EXPERIMENTAL Slag samples of the desired composition for the solubility measurements were obtained by blending pre-fused master slags. The master slags were prepared by fusing mixtures of reagent-grade CaC03 with either A1,03 or Si0, in a graphite crucible. The master slags were crushed, then decarburized in air in a muffle furnace at 1200O C. A schematic diagram of the apparatus is shown in Fig. 1. The source of carbon for the solubility meas-

Jan 1, 1969

By James Westfield

Drilling for roof bolting has created a new dust problem for the coal-mining industry. Drilling is inherently dusty, and control of dust produced by drilling vertical or nearly vertical holes is much more difficult than control of that produced by drilling flat or down holes.4/ Also, the dust produced by roof drilling differs in composition from that produced by drill-fur, or cutting the coal face because it contains a significantly greater amount of free silica and therefore presents a greater potential hazard of silicosis. Roof bolting has been practiced successfully in the mines of the St. Joseph Lead Co. in southeastern Missouri for over 20 years, but it was not until 1947 and 1948 that large-scale roof-bolting experiments were conducted in coal mines.5/ Although the need for dust control in conjunction with roof drilling was recognized from the beginning, the development and acceptance of roof bolting progressed so rapidly during 1949 and 1950 that solution of the dust problem lagged behind other engineering phases of the technique.

Jan 1, 1951

By Joseph D. Davis, GEORGE S. POPE

This bulletin is the fourth of a series a showing the results of the purchase of coal by the Government under specifications. The work of inspecting and analyzing coal delivered on Government contracts was transferred to the Bureau of Mines by an act of Congress effective July 1, 1910. It had been carried on for several years before that date by the technologic branch of the United States Geological Survey. The purchase of coal on the dealer's statement as to quality or on the reputation of the mine or district producing the coal is gradually being discontinued. At present most coal-purchasing contracts make definite provision regarding the desired heating value of a coal and the composition as shown by analysis. The heating value is usually expressed in British thermal units" and the composition specified is that shown by proximate" analysis. The price to be paid for delivered coal is made to depend on whether the analyses and heating-value tests of samples representing the delivery show the quality to be above or below the quality set forth in the contract. Large coal consumers are beginning to appreciate more and more the importance of the cost of power as a factor in the cost of producing a finished article. The endeavor to increase the efficiency and the economical operation of a power plant calls for an intimate knowledge of the quality of the coal being used. The purchase of coal under specifications insures the purchaser getting what he pays for and the coal being of the quality guaranteed. In addition, the analyses and tests of the delivered coal furnish data whereby the power-plant results can be comprehensively studied and a continuous check maintained on the conditions of operation.

Jan 1, 1912

By N. A. Gokcen, J. Chipman

A revised treatment of the authors' published data eliminates the complex relation previously proposed between concentration of silicon and activity coefficient of oxygen in liquid iron. Revised values of the thermodynamic properties of the liquid solution are presented. IN a recent experimental study of the reaction SiO2 (s) = Si+ 2O; Kf, = [% Si] [% O]² [1] the authors' found a substantially constant equilibrium product in liquid iron at 1600°C of 2.8x10-5 They also reported extensive data on the reactions: SiO2 (s) + 2H2 (8) = Si- + 2H2O (g); K'2= [% Si] (H2O/H2 [2] and H, (g) + 0 = H2O (g); K'3 =( H2 O [31 (H2) [%O] From the results on reaction 3 and earlier data of Dastur² on this same reaction in the absence of silicon, they determined the activity coefficient of oxygen, f0, on the basis of the definition K3 = (H2O)/ (H2)f0 [% 0] where K, is the equilibrium constant and f0, is taken as unity in the pure Fe-0 system. Similarly values of fsi were deduced from results on reaction 2. In a more recent study" of analogous reactions in the system Fe-A1-0, it was found impossible to reconcile the results on reaction 3 with Dastur's data; accordingly the latter were ignored and the equilibrium results were extrapolated to find a value of K, at zero concentration of aluminum. This procedure failed to locate the cause of the discrepancy but it did yield reasonable values of activity coefficients. It also avoided introduction of the complex empirical relation between the oxygen activity coefficient and the concentration of the added element. The same type of discrepancy exists for system Fe-Si-0.' In the earlier paper an attempt was made to fit both sets of data by a single curved line (Fig. 6 of ref. l), the form of which is contrary to the theoretical requirement of a finite slope at infinite dilution. In the light of experience on the Fe-A1-0 system the discrepancy must be recognized as one which can be resolved only by more refined measurements. Accordingly Figs. 6 and 10 are retracted. It is pointed out also that until the discrepancy is resolved Figs. 7, 8, and 11 are subject to some uncertainty. Qualitatively the following conclusions still appear valid: 1—The activity coefficient of oxygen is reduced by addition of silicon. 2—In dilute solutions the activity coefficient of silicon increases with its concentration. 3—With respect to equilibrium in reaction 1, the above effects are approximately compensating. The discussion of K'1 in the previous paper requires no revision. It was pointed out that the constancy of the product [% Si] [% 0]² ndicated a compensating effect of the activity coefficients of silicon and oxygen. Therefore, as a very good approximation, K1 = K'1 and the following average values are suggested both for K, and K', at the temperatures 1550°, 1600°, and 1650", respectively, 1.0x10-", 2.8~10-" and 5.5 ~lo-'. Revision of the thermodynamic treatment is necessitated by the recent appearance of new data, based on a combination of combustion and solution calorimetry,' which yields for the heat of formation of low-cristobalite from the elements, the value —209,330 ±250 cal per mol at 25°C. This is about 4000 cal larger than the value previously accepted. The new value for cristobalite is used, together with Kelley's tables of high-temperature heat contents" and entropies and with Korber and Oelsen's' heat of fusion of silicon to obtain the following equation for the standard free energy of cristobalite in the temperature range 1700" to 2000°K: Si (1) + 02 (g) = Si02 (crist.); ?F° = -217,700 + 47.OT [4] The free energy of solution of 0, in liquid iron is:8 O2 (g) = 20 (in Fe); AF° = -55,860 - 1.14T [5] and these two equations are combined to give: Si (1) + 20 = SiO, (crist.); AF° = -161,840 + 48.14T [6] ?F°1873 = -71,700 cal. From the experimental value of K, = 2.8x10-5, Si + 20 = SiO2 (crist.); ?F°1873 = -39,000 cal. [7] The combination of Eqs. 6 and 7 yields the free energy change when liquid silicon dissolves in iron to form the dilute solution of unit activity (1 pct). Si (1) = Si; ?F°1873 = -32,700 cal. [8] The heat effect in this process according to Korber and Oelsen' is an evolution of 28,500 cal per gram

Jan 1, 1954

By D. E. Spiller

Introduction Precious metals recovery from ore can generally be accomplished using gravity concentration, flotation, and/or hydrometallurgical (leaching) techniques. The objective of this paper is to show why gravity concentration can be an important part of recovery systems that employ leaching as the primary unit operation. A brief discussion of modem gravity concentration equipment is also presented. Discussion Gravity concentration of ores has generated increasing interest in recent years. Reasons for this interest include: • Gravity concentration is environmentally attractive. There is little or no use of reagents. Hence, it is relatively nonpolluting. • The cost of cyanide has continued to increase. Therefore, cost savings may be realized whenever leaching feed tonnage can be reduced by preconcentration. • Compared to flotation and leaching, gravity equipment costs are low per processed ton. Field installation costs for gravity circuits usually are less because many' units are supplied as self-contained modules. Also, the cost required to supply services, particularly power, to a gravity plant site are also less. In situations where preconcentration at coarse particle size is applicable, significant grinding equipment savings may be possible. • Gravity circuit operating costs are also relatively low compared to typical flotation and leaching circuits. Reagents, power, maintenance, and manpower savings in a well-engineered gravity plant may be realized. Again, if grinding is reduced, significant power and steel (media and liners) savings are possible. •In recent years, more efficient gravity concentrating devices have been developed. Benefits to Precious Metal Leaching Gravity beneficiation can complement precious metal leaching in two ways. First, the recovery of coarse liberated values before leaching may reduce leach time requirements and may reduce reagent consumption. Second, gravity preconcentration can reduce the size of a leach plant by decreasing the quantity of material to be leached. Coarse gold and silver have been shown to leach rather slowly. Kameda (1949) and Habashi (1967) have investigated the kinetics of cyanide leaching systems. They concur that in a heterogeneous reaction, the rate of gold and silver dissolution is directly proportional to the surface area. Thus, the instantaneous rate of dissolution for spherical 0.37 mm (400 mesh) gold is theoretically -25 times faster than for the same amount of gold at .841 mm (20 mesh), based on data from Fuerstenau, Chander, and Abouzeid (1979). Conversely, coarse liberated, +.841 mm (20 mesh), gold is more readily recovered by gravity concentration than is fine, -.037 mm (400 mesh) gold. Therefore, it is apparent that the two recovery systems complement one another. Figure 1 data demonstrates the potential synergism. A sample of - 3.327 mm (6 mesh) Nevada gold-bearing ore was cyanide leached using conventional bottle-roll test procedures. Gold extraction was determined as a function of leaching time. A second sample split from the same leach feed material was hand jigged to remove a coarse heavy mineral fraction, including virtually all of the +.210 mm (65 mesh) liberated free gold. This second sample, with the coarse gold and heavy minerals removed, was subjected to an identical cyanide leach procedure. Figure 1 presents the resulting comparative extraction data. Note that the percent gold extraction for the sample containing no +.210 mm (65 mesh) free gold includes the coarse gold recovered by gravity. The data show that the sample containing coarse gold required about 72 hours of leaching time to achieve 80% extraction. This compared to about 22 hours of leaching time for 80% gold recovery from the sample that contained only -.210 mm (65 mesh) free gold. Thus, there was a 69% reduction in leaching time. The improved extraction data is not wholly attributable to coarse gold removal, but rather it was the combination of gold removal and rejection of other heavy mineral cyanide consumers or leach retardants. Further investigation was not warranted at this time. Preconcentration is the second manner in which leaching systems can benefit from gravity concentration. The premise is that preconcentration can reduce the quantity of leach feed, which, in turn, may reduce leaching costs. Figure 2 presents preliminary data developed by CSMRI for US Minerals Exploration (USMX). Centennial Exploration Inc., in agreement with USMX, is proceeding with evaluations to determine the suitability of various processing schemes for recovery of gold values from the Montana Tunnels property. The data shows how the ore can be preconcentrated by gravity techniques to result in a reduced feed tonnage to secondary extraction techniques, presumably flotation or cyanide leaching. Testing has shown that Reichert cones, followed by treating the cone concentrate on spirals, can deliver about 88% gold recovery in about 13% weight, that is, 87% weight rejection. Consequently, fine grinding and reagent costs are attributable to only 13% of the plant feed rate. Cost data is not yet available, but the potential exists for significant cost savings.

Jan 1, 1985

By G. F. Kuncir

This volume was prepared in support of an evaluation of the Advancing Oil Shale Mining Technology Program performed by The Aerospace Corporation under a Bureau of Mines contract. The evaluation is described in part within a companion volume entitled Benefit-Cost Analysis. The economic mine models outlined herein provide a quantitative basis for the assessment of program benefits. Reference is made to estimated oil shale mine costs to delineate the beneficial impacts that can be expected to accrue for the future implementation of program developed technology. Estimated mine cost data are provided for surface, underground, and modified in situ oil shale mining operations.

Jan 1, 1977

By M. G. Wallis

This report presents the results of a study to develop a detailed mining method design based on longwall mining with sublevel caving. The method is applicable to low-dipping coal seams 20 or more feet thick such as are found in the western United States. The report covers (1) the development and description of the mining method, (2) evaluation of the engineering feasibility of the design, (3) estimates of productivity and recovery, and (4) an engineering cost analysis and economic feasibility evaluation of the mining method design.

Jan 1, 1977

By Oliver C. Ralston, Dorsey A. Lyon

The data reported in this bulletin are largely the result of experiments conducted by the Salt Lake City station of the Bureau of Mines in cooperation with the department of metallurgical research of the University of Utah. The work on lead is only one of the phases of the investigations carried on at that station during the years 1914 to 1916. The results of similar work with zinc ores and with copper and other ores will be published in future reports of the bureau.

Jan 1, 1918

By Martin J. Gavin

The results of investigations of the oil-shale resources of the United States were first published by the United States Geological Survey in 1915.1 Other reports 2 have followed. These reports, investigations by private individuals and corporations, and the beginning of the development of an oil-shale industry in this country have aroused considerable interest in the possibilities of these shales as a commercial source of hydrocarbon oils. The Bu- . reau of Mines bas appreciated these possibilities, and since 1916 one or more of its engineers have given all or part of their time to investigations relating to the treatment of oil shales. A short pamphlet a containing general information on the possibilities of oil shale in this country, particularly the shales of the Rocky Mountain district, has already been published. This pamphlet gives methods for assaying the shales of oil and ammonia and contains a bibliography for the use of those desiring to search the literature.

Jan 1, 1924

By D. R. Irving

Prior to this time, ample supplies of high grade mineral fillers, such as clay, have been available close to consuming centers. Now depletion of these accessible deposits, coupled with other factors such as increasing demand due to population expansion and standard of living rise, has made development of upgrading techniques attractive to producers. Various investigations being carried out by the U.S. Bureau of Mines are described. Factors making the development of improved methods for upgrading clays attractive to producers include: depletion of accessible deposits of high-grade clays, rising transportation and labor costs, more exacting specifications, and increased demand resulting from an expanding population and a constantly rising standard of living. Industry recognizes the need for upgrading presently unusable materials and has cooperated with the U.S. Bureau of Mines by providing samples from submarginal deposits and by evaluating the products that USBM upgrades. Following are some examples of recent clay beneficiation work by the Bureau. FIRE CLAY BENEFICIATION At the Rolla Metallurgical Center, Rolla, Mo., the Bureau is conducting research to develop technically and economically feasible mineral-dressing methods to remove quartz, pyrite, and other impurities from submarginal fire clays. The research has been spurred by the growing shortage of high-grade bur-ley, flint, and plastic clays in the Missouri fire-clay district resulting from increased consumption and the low rate of discovery of new deposits of adequate quality. There apparently is ample tonnage of submarginal flint and plastic clays to maintain the industry for many years if such material can be upgraded to commercial quality. Samples have been submitted to USBM by several major producers of refractories, including A. P. Green Fire Brick Co.; Harbison-Walker Refractories Co.; Mexico Refractories Div., Kaiser Aluminum and Chemical Corp.; and Wellsville Fire Brick Co. Research on some samples has been completed and still is in progress on others. The Bureau has found that specimens containing quartz or pyrite in grains coarser than the accompanying clay generally can be upgraded either with a gravity table or hydraulic cyclone. The improvement in quality is notable not only in chemical analysis but in an increase in pyrometric cone equivalent (PCE) of one or more cones. As an example, consider the results attained on a sandy flint—a fine-grained mixture of kaolin and halloysite with quartz and minor quantities of iron and manganese oxides. Chemical analysis was: 35.4 pct alumina (A12O3) and 47.8 pct silica (SiO2). The sample contained 9.2 pct free silica as quartz. The PCE was 33. The sample was crushed to -10-mesh, blunged with water, and then stage-ground to -48-mesh. The ground sample was tabled to yield a clay fraction containing 37.6 pct A12O3, and 45.3 pct SiO2 of which 2.4 pct was free silica. The PCE was 34. Recovery of alumina by this process was 73.6 pct. Concentration of the same clay in the hydraulic cyclone was even more effective in respect to quartz removal. The clay fraction analyzed 38.6 pct A12O3, 45.0 pct SiO2 of which 0.5 pct was free silica as quartz, and had a PCE of 34. Recovery of alumina was 71.9 pct. The hydraulic cyclone was also effective in reducing the pyrite content of a plastic clay which likewise was a mixture of kaolin and halloysite, plus some pyrite, quartz, and carbonaceous material. It analyzed 30.6 pct Al2O3, 52.3 pct SiO2, 2.3 pct Fe2O3, and 0.76 pct S. The sample was blunged and screened through 10-mesh to remove some coarse pyrite, then ground to -65-mesh and cycloned to remove most of the remainder. The final product recovered 81.8 pct of the alumina at a grade of 32.3 pct A12O3, 50.9 pct SiO2, 1.4 pct Fe2O3, and 0.1 pct S. The PCE was 32-1/2, compared with a PCE of 31-1/2 for the crude clay. The fine beneficiated clays, of course, must be pelletized and dried or fired to meet commercial acceptance. This operation has already been solved by industry. Little progress has been made on two remaining problems. One is that of fine-grained impurities, not separable by table or cyclone. Flotation is being investigated to solve this. Although fine pyrite is readily rejected, a satisfactory quartz-clay separation has not been attained. The second problem, a stubborn one, is that of alkali. Samples containing as much as 5 pct potas-

Jan 1, 1961

By G. V. Jere, C. C. Patel

Chlorination of the various constituents of ilmenite by different chlorinating agents in presence of various reducing agents, have been considered on the basis of the standard free energy and standard enthalpy changes as a function of temperature. The standard free energy change considerations show that it is beneficial to chlorinate ilmenite by chlorine in the presence of carbon and also that iron constituent of ilmenite can be preferentially chlorinated by clzlorine, titanium tetrachloride or their mixture. These findilzgs have been corroborated from the published work. METALLURGICAL processes involving the use of titanium tetrachloride have gained in importance because of the use of the latter in the manufacture of titanium metal. Since ilmenite is more abundant in nature than any other titanium mineral, the future of the metallurgical processes depends on the utilization of ilmenite for the production of titanium tetrachloride. In these laboratories, investigations have been carried out on the chlorination of ilmenite under a variety of conditions.1'2 During these studies, it was noticed that 1) preferential chlorination of iron was effected at low temperatures (400° to 600°C) and at low carbon content (6 to 7 pct), 2) carbonyl chloride retarded the chlorination of iron oxides and titania perceptibly, while 3) carbon-tetrachloride, compounds of sulphur and some other catalysts favored the chlorination. Moles3 has found that oxides of iron are chlorinated in preference to titania at high temperatures, while wilcox4 has claimed the preferential chlorination of titania between 1200" and 1500°C. It has been shown in this paper that preferential chlorination of titania claimed by Wilcox is not likely to occur. Daubenspeck and coworkers5,6 have claimed the preferential chlorination of iron by chlorine or by a mixture of titanium tetrachloride and chlorine between 700° and 1050°C in the absence of carbon. Even when plain titanium tetrachloride is employed as the chlorinating agent, pascaud7 noticed the preferential chlorination of iron and other oxides. The purpose of this paper is to explain from thermodynamical considerations, the various chlorination reactions studied so far. ILMENITE CONSTITUENTS AND THEIR CHLORINATION PRODUCTS Although the general composition of the ilmenite mineral is represented as FeTiO,, most of the ilmenites found in nature have variable quantities of TiO2 (44.6 to 64 pct), FeO (4.7 to 36 pct) and Fe2O3 (6.9 to 28 pct).8 The higher content of ferric iron in ilmenites was attributed by Millerg to the presence of arizonite (Fe2O3.3TiO2). But the X-ray studies by Overholt, Vaw, and odd" have shown that arizonite is a mixture of haematite, ilmenite, anatase, and rutile. Except for the anatase, similar views have been advanced by Lynd, Sigurdson, North, and Anderson8 from magnetic, X-ray, and optical and electron microscope studies. The ilmenite ores can, therefore, be assumed to consist of mineral aggregates of ilmenite, rutile and haematite. From the free energy of formation of ilmenite (FeTiO3), it has been shown by Kelley, Todd, and King11 that ilmenite is stable even up to its melting point (1367°C) and would not undergo decomposition into its constituent oxides. Schomate, Naylor, and Boericke12 have found that in the presence of a reducing agent the iron constituent of ilmenite is selectively reduced. The reaction of chlorine with ilmenite in presence of a reducing agent can, therefore, be synonymous with that of the reaction of chlorine with the constituents of ilmenite, viz., TiO2, FeO, and Fe2O3. Most of the reaction products of chlorination of ilmenite in the presence of reducing agents will be in equilibrium with their dissociation products, depending on the temperature. The titanium tetrachloride is, however, quite stable up to 1500°C due to its covalent nature. The equilibrium for the ferric chloride system has been investigated by Kangro and Bernstorff, 13, schafer14 and Kangro and petersen,15 and the results are summarized in Fig. 1, curves a, b, and c respectively. From these results, it is clear that the ferric chloride disociates as follows: 324° to 700°C FeaCl6(g) ?2FeCl2(c) + Cl2(g) [1] 324°to 900°C Fe2Cl6(g) =2 Fe Cl2 Reaction [I] (curve a) occurs in the forward direction to about 6 pct at 400°C but falls off very rapidly with increase in temperature and beyond 600°C, it is practically negligible, perhaps due to the formation of the stable monomer, FeC13(g). As the temperature is further increased, the amount of FeCl,(g) in-

Jan 1, 1961

This briefing was sponsored by the Bureau of Mines to summarize ongoing and recently completed chromium-chromite research and resource assessment activities by the Bureau. Through the series of 18 presentations compiled herein, Bureau personnel covered a wide range of topics including U.S. chromite and chromium trends and usage patterns; foreign and domestic resources; and research activities on mineral characterization and beneficiation, chemical and pryometallurgical processing of chromite and chromium-bearing wastes, new low-chromium alloy and coating substitutes, corrosion- and oxidation-resistant stainless steels, and chromium-containing refractories.

Jan 1, 1986