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By Byung-Su Kim

The reaction between calcium sulfate and hydrogen is of interest both as a means of regenerating calcium sulfide as a reductant of sulhr dioxide to elemental sulhr and for producing elemental sulhr from gypsum. This reaction was investigated using a thermogravimetric analysis technique in the absence and presence of nickel catalyst. The reaction temperature was varied between 973 and 1153 K, while the hydrogen partial pressures of 12.9 - 86.1 kPa were utilized. At 1073 K and a hydrogen partial pressure of 86.1 kPa, 60 % of the original calcium sulfate in the absence, and 95 % in the presence, of the nickel catalyst was converted to calcium sulfide in one hour.

Jan 1, 1999

By H. O. Hofman

(Canal Zone Meeting, November, 1910.) I. INTRODUCTION. IN a previous paper,1 The Behavior of Calcium Sulphate at Elevated Temperatures with Some Fluxes, we published the results of our investigation, into the behavior of calcium sul-phate in air; that, is, under oxidizing conditions. The results as a whole hold good for a neutral atmosphere, or one which has no chemical effect upon calcium sulphate. The present paper deals with the behavior of calcium sulphate under reducing conditions, the reducing-agents employed being carbon monoxide and carbon, and the changes the calcium sulphide formed undergoes when it is subjected to an oxidizing-roast. Technical literature deals very sparingly with the subject. The information furnished by the recent leading chemical manuals is general. Thus Dammer,2 Moissan,3 and Abbegg,4 quote Berthier as having reduced, in 1823, calcium sulphate with carbon, and Stammer as having done the same in 1851 with carbon monoxide; Gmelin Kraut 5 add Leplay and Laurent (1848) as third investigators. Metallurgical authorities confine their statements to the known fact of reduction by carbon. II. PREPARATION OF RAW MATERIALS. 1. Calcium Sulphate.-This salt was prepared in the same manner as described in our previous paper,6 and was found to be chemically pure. * Professor of Metallurgy, Massachusetts Institute of Technology. + Metallurgical Instructor, Imperial Technological Institute. 1 Trans, xxxix., 628 to 653 (1909). 2 Handbuch der anorganischen. Chemie, vol. ii., part 2, p. 309 (1894). 3 Traité de Chimic Minérale, 1904, vol. iii., p. 543. 4 Handbuch der anorganischen Chemie, vol. ii., part ii., p. 116 (1905). 5 Handbuch der anorganischen Chemie, vol. ii., part 2, p. 233 (1909). 6 Trans., xxxix., 630 (1909).

Nov 1, 1910

By E. Uslu

The kinetics of the reduction of chromite from the LG-6 layer of the Bushveld Complex in Fe-Cr-C alloys were studied in the temperature range 15OO°C to 1680°C under an inert argon atmosphere. The rotating cylinder technique was used, and the rotational speed of the chromite cylinder ranged from 0 to 1000 r/min. The melt consisted of 30 to 80 per cent chromium and 2 to 8 per cent carbon. The initial chromium-te-iron ratios of the melts varied between 0,42 and 4,95. The reduction of chromite spinel was analysed in terms of the decarburization of the metal. It was found that decarburization increased with an increase in the temperature, the carbon content of the bath, and the rotational speed of the cylinder up to 400 r/min, after which it remained almost constant. Decarburization also increased with an increase in the chromium content up to about 50 per cent chromium but, at higher chromium contents, it decreased. In the early stage of the reduction, up to about 30 minutes of reaction time, the liquid-state mass transfer of oxygen was found to be the most likely rate-determining step. The apparent activation energy was calculated to be 84,864 kJ per mole of oxygen. In the later stage, diffusion of iron and/or chromium in the solid state is the most likely rate-determining step. The apparent activation energy for the diffusion was calculated to be 471,18 kJ/mol.

Jan 1, 1991

By J. Engesser

A research project supported by the Minnesota Department of Natural Resources and the Iron Ore Cooperative Research Committee was undertaken to reduce the dissolution of fluoride into process water during taconite processing. Leach tests were conducted using rod mill feed samples and water containing varying concentrations of calcium and sodium. Laboratory liberation grinds were performed to evaluate fluoride rejection during grinding and magnetic separation. Tube furnace tests were conducted to evaluate fluoride volatilization during pellet induration. The results indicate that fluoride concentration of process water is a function of both calcium and sodium concentration in process water. It appears that less than 1 percent of the fluoride present in rod mill feed will dissolve in process water during grinding. More than 90 percent of the fluoride present in rod mill feed is rejected with tailings during size reduction and magnetic separation. The furnace tests demonstrate that bentonite and fluxstone (calcite and dolomite) addition to taconite concentrate during pellet production increases the amount of fluoride that volatilizes during induration. Lime hydrate addition to pellets decreases the amount of fluoride that volatilizes during pellet induration. During acid pellet production approximately three times more fluoride enters the water during induration-off-gas scrubbing than during grinding. When fluxed pellets are produced three to eight times more fluoride enters the water during off-gas scrubbing than during taconite grinding.

Jan 1, 2004

By W. P. Channon, J. B. See

The reduction of fluxed and non-fluxed manganese, ores by ferromanganese silicide by W. P. CHANNON, B.Se. (Eng.), M.Sce. (Eng.) Wits. (Visitor) and J. B. SEE, B.Sce. Hons., Ph.D. (New South Wales), M.I.M., M.I.M.M. (Member) In South Africa, medium-carbonferromanganese is produced by the silicothermic reduction of slags containing MnO. Because of its importance in the production of refined ferromanganese, a study was made of the reaction between a premelted South African Mamatwan manganese ore and various ferromanganese silicide reducing alloys, with and without fluxing agents. Because the reaction is highly exothermic, temperature appeared to have little effect on the rates of manganese transfer to the metal and silicon transfer to the slag, and an apparent equilibrium was rapidly approached. Limits were determined for the favourable effects of fluxing additions, and manganese recoveries were found to decline as the ratio of CaO to MgO decreased as a result of the addition of basic flux. The recovery of manganese passed through a maximum, and subsequently decreased for variations in the ratio of alloy to ore. The results obtained, when used in conjunction with other physicochemical data related to this slag-metal system, suggest optimum slag compositions for the efficient manufacture of medium-carbon ferromanganese from Mamatwan ore.

Jan 3, 1977

The reduction in man's contribution to the Greenhouse effect will only be achieved by a number of small steps. Some steps will absorb carbon dioxide (CO2) from the atmosphere in slightly greater quantities, others will reduce the amount of carbon dioxide generated. This paper deals with the reduction of carbon dioxide by improving the combustion efficiency of petroleum fuels. Until recently most reductions in fuel consumption and air pollution have been brought about through mechanical adjustments to combustion equipment. Since the development of tetraethyl lead, little has been done to chemically modify combustion reactions to improve fuel efficiency or reduce emissions. During the past five years Australian laboratory and field trials with ferrous picrate treatment have demonstrated significant and economic gains in the combustion efficiency of diesel fuels. These studies have revealed that even under ideal conditions in diesel engines, carbon monoxide (CO) momentarily saturates the combustion chamber. This state reduces combustion rates, peak pressure and power and increases the risk of pollution. Theoretical, laboratory and field data are presented which support the mechanism by which the ferrous catalyst accelerates the oxidation of CO to the terminal CO2 thus reducing fuel consumption and the undesirable combustion products accompanying the CO saturation of combustion environments. While this paper deals principally with diesel fuels commonly used in mining operations, the catalytic effect of the ferrous ion is also shown to significantly reduce fuel consumption by petrol engines thereby promising a means to reduce the much larger contributions to the Greenhouse gases by automobiles.

Jan 1, 1989

The laboratory-scale reduction of fixed beds of iron ore pellets has been investigated over a range of experimental conditions. The effects of reduction temperatures, gas compos- itions and flowrates on 1) the rate of reduction and 2) the physical properties of the metallized products after reduction are being studied as part of a general programme aimed at the evaluation of the use of gaseous reductants for the direct reduction of Australian iron ores. This paper deals primar- ily with the effects of temperature on the rate of reduction using a H2/CO gas mixture. The physical properties of the metallized products such as strength after reduction, abrasion resistance and porosity are presented as functions of the reducing temperature.

Jan 1, 1974

By R. A. Lowe

The low-shear viscosity of kaolin slurries is one of the principal characteristics that determines whether the clay can be utilized for paper and ceramic applications. In this work, causes of poor low-shear viscosity and methods of improving rheology have been investigated. The presence of fine-grained smectite impurities within the kaolin was shown to detrimentally affect the low-shear rheology of slurries produced from these clays. It was also shown that mechanically working (i.e., pugging) a crude kaolin followed by desliming to remove these impurities can reduce the low-shear viscosity.

Jan 1, 1998

By Turnbull A. G

Thermodynamic calculations based on the ideal system NiO - Fe203 - H2(g) - CO(g) - H2O(g) - CO2(g) show that it is not possible to selectively reduce nickel oxide in the presence of hematite because ferronickel is the zero-valent nickel-containing product. The calculations show that temperature, reducing atmosphere composition and oxide to reductant ratio have a marked effect on the nickel content of the ferronickel alloy and the amount of nickel reporting jn the alloy. The general trends based on the calculations correlltte well with experimental observations.

Jan 1, 1980

By Hayes P. C

The kinetics of reduction of PbO-silicate melts in CO-N gas mixtures at 900¦C have been studied. Rea~tion rates were measured by moni- toring the CO2 content of the product gas. A wide range of gas and melt compositions and gas flowrates have been investigated. The overall reaction rates in heterogen- eous systems are typically characterised by a steady increase as the gas flowrate is in- creased. At low flowrates the processes are limited by gas film mass transfer. At high flowrates it is expected that the rates will tend to maximum values determined by either the rate limiting chemical reaction or diffusion in the condensed phase. In the present series of experiments it has been found that for any given gas composition the overall reduction rate goes through a maximum with increasing gas flow. The maxima, which occur at relatively low gas flows, are more than an order of magni- tude greater than those observed at high gas flowrates. The results of these and other experiments are presented and analysed. Possible rate limiting mechanisms in the reaction system and their implications regarding commercial reactors are discussed.

Jan 1, 1987

By M. E. Charles

The use of water flowing as a lower layer to reduce pressure gradients in petroleum pipelines was investigated using 17.5 deg. A.P.I. Lloydminster crude oil in a 1-inch laboratory pipe-line and a 21h-inch field pipeline. The method was found to be very effective in reducing the pressure gradient below that for the oil flowing alone. The factor by which the pres-sure gradient was reduced varied with the percentage of water added, and in general exceeded 10 for water contents ranging from 40 to 60 per cent. Within this range of water content the pressure gradient reduction factor was independent of the oil flow rate.

Jan 1, 1960

By Byung-Su Kim

The recovery of elemental sulfur from sulfur dioxide has important implications for coal- burning power plants and nonferrous metal smelters. The thermodynamic analyses showed calcium sulfide to be suitable for recovering elemental sulfur from sulfur dioxide. At the temperatures of 1023 to 1153 K under the sulfur dioxide partial pressures of 5.0 - 60.1 kPa, elemental sulfur from sulfur dioxide was recovered by its reaction with calcium sulfide. The kinetics of this reaction were measured at the same conditions using a thermogravimetric analysis technique. This reaction scheme would be attractive if the coproduct calcium sulfate can be reduced to regenerate calcium sulfide. This is the topic of another paper. At 1073 K under the sulfur dioxide partial pressure of 25.8 kPa, 48 % of the original calcium sulfide was converted to calcium sulfate in an hour. Under the same conditions, 55 % of the regenerated calcium sulfide were converted to calcium sulfate in an hour even after third regeneration.

Jan 1, 1999

By I. H. Warren

The high temperature lubricant molybdenite, MoS2, is usually produced by a complex sequence of processes involving mineral dressing of molybdenite concentrates followed by leaching with hydrofluoric acid to remove abrasive impurities such as silica (1). Many attempts have been made, mostly by techniques involving, direct fusion of molybdenum compounds with sulphur, to produce synthetic molybdenite. However, apart from some experiments of geochemical interest (2) in which aqueous solutions of sodium sulphomolybdate, Nat MoS4, were decomposed under pressure at temperatures between 300°C and 700°C, no attempts to produce the mineral by hydrometallurgical procedures have been reported. Since molybdenite is nominally a compound of tetravalent molybdenum with sulphur, and the most common state of molybdenum is +6, production of molybdenite is likely to involve reduction and sulphidization. The present study, therefore, describes the reduction, with hydrogen and carbon monoxide, of molybdenum in the hexavalent state in alkaline aqueous solutions containing sulphide ion. In these

Jan 1, 1972

By Hayes P. C

The reduction of small, dense zinc oxide (ZnO) samples in CO/CO2, and CO/N2 gas mixtures has been investigated at temperatures between 900 and 1100¦C. The microstructural characterisation of the reacted and partially reduced samples was complemented with measurements of the rates of the reactions. The mechanisms and kinetics of reduction of zinc oxide were found to be dependent upon the CO partial pressure, the oxygen potential of the gas mixtures, temperature and degree of reduction.

Jan 1, 1991

By E. A. van Dijk

Dusts from steel-making processes contain substantial amounts of zinc. Such dusts are also a hazardous waste and dumping them becomes unacceptable from environmental point of view. Therefore processes that can recover zinc and possibly other metals from steel-making dusts are being investigated. The aim of this paper is a contribution to the more fundamental kinetic aspects of zinc reduction from silica free calcium ferrite slags. The effects of alumina, lime and magnesium oxide contents of the slag, the COICO, ratio and the effect of initial Fe2O3/CaO ratio were studied experimentally at 1400°C The results indicated that the reduction of zinc from molten slag was possibly a first order reaction. As expected higher COICO, ratios increased both the extent and the rate of reduction. It was also observed that a higher iron content of slag improved the reduction of zinc from calcium ferrite slags. This fact seems to support the proposed mechanism that zinc is partly reduced by ferrous iron to zinc vapour and that ferric iron is reduced by carbon monoxide. The reduction rate of zinc in these slags was decreased by increasing alumina content of the slag. Alumina decreased the calculated optical basicity of the slag showing the fact that reduction of zinc oxide was more favorable in more basic slags. Probably the formation of complex ions by alumina and zinc oxide such as ZnAl2O32+ lowers the activity of Zn2+ ions in the slag and hence render them more difficult to reduce.

Jan 1, 1999

Iron(II), sulphur dioxide and sugars such as lactose are potential reducing agents for manganese dioxide to produce manganese(II) for subsequent hydrometallurgical treatment. The leaching of limonitic laterite and manganiferrous ores with sulphur dioxide produces iron(II) which in turn can catalyse the leaching of manganese dioxide in acid media. This paper presents a critical analysis of the kinetics of reductive dissolution of synthetic manganese dioxide and manganese ore to compare and contrast the effect of sulphur dioxide and iron(II) in acid media containing sulphate or perchlorate anions. Both one-electron and two-electron mechanisms are considered in the case of sulphur dioxide. The current knowledge on chemical speciation is used to construct an Eh-pH diagram to show the effect of complexation of Mn(II), Fe(II) and Fe(III) with sulphate. Heterogeneous and electrochemical reaction kinetic models are combined to propose reaction mechanisms which rationalize the dissolution kinetics.

Jan 1, 2003

By Briggs D

Comparing the results of a plant trial by averaging performance measures collected during the trial with measures collected before and after the trial is often quite subjective because of the impact of natural variation on the process. This is

Jan 1, 1997

By F. J. Bruey

Refdist is a simple but valid approach to planning or analyzing a test-vs-control plant trial that uses accumulated plant performance data to calculate objective criteria for judging the trial outcome. Refdist calculations and results are explained and illustrated with data typical of the mining industry. Findings from a simulation study of Refdist statistical properties are reported. Suggestions for dealing with messy data situations are offered.

Jan 1, 1999

By HORACE H. EJIRICH

(New York Meeting, February, 1912.) PREFATORY NOTE.-The first part of this paper was sent to me by Mr. Emrich nearly nine months ago ; and. I held it, waiting for the second part, which he had promised to forward soon, so that I might submit the whole to some of his former professional associates, and advise him of their criticisms and suggestions before offering his work to the Institute. But, five days before the second part reached me, I received by telegraph the news of Mr. Emrich's sudden death. The paper has therefore not had the benefit of such a revision by the author as might have made it in some respects clearer and more complete. Nevertheless, I believe that experts in the branch of metallurgy with which it deals will find it both original and suggestive.-A. EILERS. I. PARTIAL REFINING IN THE ANODE-FURNACE. During my connection with one of the large New Jersey copper-refineries, and probably before that period, from 15 to 20 per cent. of the copper-bullion received was the very foul, leady blister-copper produced from lead blast-furnace matte. It had been customary to mix a small part of this blister with each charge of purer pig-copper, in the effort to dilute it as much as possible before casting into anodes; but tank-house conditions were such that I was led to try making entire furnace-charges of this blister, and refining it as much as possible in the furnace-afterwards casting to anodes and refining electrolytically, in tanks and solution separate from the main bulk of the purer copper. In making this experiment, notes were made, for several furnace-charges, of everything thought to have a bearing on the question, and some interesting facts were brought out, both in the furnace-working and afterwards in the tanks.

Jun 1, 1912

By E. G. De Coriolis

THE development of huge production facilities and of new or improved processes for manufacturing magnesium from its raw sources has been an outstanding achievement of this war. Furthermore, at least one new method has reached a stage of pilot production that offers promise. Its potentialities seem to indicate that a reduction in cost and simplification or elimination of problems incident to the use of at least one of the present processes are quite within the realm of possibility. Although magnesium of very high purity (99.9 per cent and higher) is obtained, and the rate of recovery reasonable (60 to 70 per cent), the ferrosilicon reduction process is open to a serious objection, which at the time its use was proposed was thought to be sufficient to raise some doubts as to its success, at least on a high production basis. The temperature range at which the reaction is carried out-namely, 2100° to 2150°F.-is very close to the failure temperature of the material of which the retort is made. It is so close that for a time it was assumed it might make commercial use of the process an impossibility. However, at the time under discussion, the demand for magnesium was so great that it was felt by those who had to go ahead and produce this essential metal that the emergency warranted their taking a chance on this process. Subsequent developments have fully justified the soundness of their decision. Fortunately for the war effort, when the plants were put into operation it was discovered that although the retorts did collapse in rather short periods of time, as predicted, they could be blown back into operable shape by application of high-pressure air. This practical method of operation so relieved the situation that the problem disappeared. Nevertheless, if the process had not been successful, or the production of magnesium by the electrolytic process had not been able to keep pace with demands, our war program would have been seriously impaired. "FIRELESS COOKER" PROCESS For this reason a program was set up and assigned for the development of a new method that had been suggested to the War Production Board in 1941. It is believed justifiable in terming the method "new" for several reasons: (1) while utilizing the same (ferrosilicon) process as the Pidgeon, hence involving similar reactions, the type of retort or furnace is essentially different, (2) the method of operation, reaction temperatures, etc., differ materially, and, most important of all, (3) the problems to be overcome in making the process successful were not and could not have been anticipated by anything previously known about the Pidgeon process. As will be shown later, the briquetting process, the condenser, the furnace lining

Jan 1, 1945