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By MCA Woolsey

(Butte. Meeting, August, 1913.). IN metallurgical circles it is known widely, but somewhat vaguely, that the ease of: reduction of metallic oxides depends largely on the way they have been prepared. It is likewise known that different forms of carbon have different and greatly varying reducing powers. It is the purpose of this paper to show somewhat more definitely and scientifically these facts. Some years ago the writer published an account of pyrometric determinations of the reduction- temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature it which zinc oxide evolves zinc according to the equation Zn0. +' C = Zn + CO depends upon the ;nature of:., the.' two reacting bodies. The determinations bad a range of accuracy of from 2° to. 6° C.,whereas differences were found to. amount to an extreme. of 90° C. :.86 the differences are real ones and must have, definite cause. The equation of boiling water, (H20)4 = 4 (H2O) has a fixed temperature for equilibrium of 100° C. at 760 mm. pressure. , In general, all equations. reacting e in .the liquid or the gaseous phase have-well-defined constant physical conditions which govern the equilibrium point and reaction velocities. In a reaction where we have one or more solid phases, the temperature conditions requisite for the unbalancing of the stable system are found to vary. These variations are due to the fact that in a solid there is a very complex molecule and it is not, a question solely of the tearing away of two interlocked atoms, but also of the destruction of a complex molecule containing hundreds, or possibly thousands, of smaller molecules.

Jan 7, 1913

(Butte Meeting, August, 1913.) IN metallurgical circle it is. known widely, but somewhat vaguely, that the ease of reduction of metallic .oxides. depends largely on the way they have been prepared. It is likewise known that. different forms of carbon have different and greatly varying reducing powers. It is the purpose of, this paper to show somewhat more definitely and scientifically these facts. Sonic years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equation, ZnO+C? Zn+CO depends upon the nature of -the two reacting bodies. The determinations bad a range of accuracy of from 2°to 6°C.,whereas differences were found to, amount to an extreme of 90° C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2 O)4 = 4 (H20) has a fixed temperature for? equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities.

Jan 7, 1913

Discussion of the paper of Woolsey McA. Johnson, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1137 to 1145. F. L. GRAMMER, Leesburg, Va. (communication to the Secretary *):-Mr. Johnson's paper must interest by suggestion those connected with the " burning " of lime, the production of cement, and the smelting of iron. All iron men know how quickly the impalpable purple ore of wet origin reduces compared to finely ground red hematites of approximately identical composition obtained from Lake lump ores. Most housekeepers appreciate that the several forms of carbon-charcoal, coke, and anthracite, not to include graphite and diamond -have different temperatures of ignition. The temperature usually rises with the density and hardness. Some of the scientific bureaus of the government might appropriately conduct some tests along lines suggested by Mr. Johnson's article. We are unable to say whether the topic lies within the spheres of activity of the Bureau of Mines, the Bureau of Soils (Agricultural Department), the Geological Survey, or the Bureau of Standards. The calcining qualities of limestone is a topic too wide for individual effort and is of wide enough interest to merit government or State activity. It is of interest, as aforesaid, to burners of lime, cement manufacturers, and smelters. The chemical composition of a limestone does not tell all the story -if over 1-in. size lumps. The limestones of Annville and Myerstown, Pa., break at a tap; those on the Hudson above Poughkeepsie .act like "nigger heads." The manager of lime kilns near Lake Champlain told me his fuel consumption was high compared to that at other points. Yet the Hudson and Annville stones were both of greatest purity, being rivaled by only the marble at Rutland, Vt., or some stones near Martinsburg, W. Va. A local kiln operator says the conglomerate or pudding limestones of Loudoun county, Va., act very differently in the kiln from the more normal limestone deposits nearby. The tilted and twisted bedding in the anthracite region tells the story of hard coal origin. We might therefore expect that the limestones of greater geological age or depth or metamorphism

Jan 11, 1913

By I. J. Moon

The reduction behavior of hematite by H2 and H2-CO gas mixtures was investigated to elucidate the reduction mechanism at 800-950 °C. The hematite compacts were made by Cold Isostatic Pressing to produce compacts of uniform shape and size. The compacts were sintered at 1000° C for 30min, and showed a contraction of 29%. Mercury pressure porosimeter was used for measuring the total porosity, pore size distribution and pore surface area of the compacts. Reduction was measured by means of weight-loss technique using Cahn Balance (Model : TG-171, capacity log, accuracy f 10pg). Microscopic examination and X-ray analysis were used to correlate the structure of reduced compacts with the mechanisms of reduction. Neither chemical reaction control nor diffusion control is adequate in describing the complete course of reduction of the hematite compact. The reduction of hematite compacts was initially controlled by the chemical reaction at oxidelmetal interface. The reaction goes through a transition phase .where it is undergoing a mixed control, followed by the diffusion control towards the end of the reduction. The values of apparent activation energies for chemical reaction control were 3.48-8.43 kcal/mol depending on the gas compositions.

Jan 1, 1997

By K. R. Vost

Calculations are given for the reduction in amplitude and change in phase of the diurnal variation in air temperature as the air flows through a mine. The concrete lining of a typical shaft was found to have a much greater effect than the steelwork. An increase in the conductivity of the concrete, or filling of the steelwork with water, did not have enough effect on the rise in air temperatures underground during the day to justify the costs involved. The steel temperature followed the air temperature much more closely than the concrete temperature did. Calculations are given for the heat stored in steel and concrete during the day.

Jan 1, 1980

By Richard C. Corson

Modern microprocessor systems make it possible to use several variables to anticipate changes in the process and to react with responses before upsets can be magnified by the process or by control action. Through tighter control, "insurance" can be eliminated from process set points without affecting product quality. In actual operation with a traveling grate furnace this control philosophy has produced savings of up to 20% in fuel consumption and 8% in fan power usage while producing a more consistent quality product.

Jan 1, 1982

By Kun Wang, Weipeng Luan, Qingbo Yu, Qin Qin

The oxygen uncoupling property of the oxygen carrier is essential for the chemical looping gasification process. In this paper,the combined Cu-based oxygen carrier were prepared by mechanical mixing method. XRD and SEM were used to characterize the oxygen carrier prepared. TG experiments were performed in a thermal analyzer to investigate the oxygen uncoupling property. The XRD pattern of the fresh oxygen carriers showed that the phases of the oxygen carriers were stable.The active phase of oxygen carrier was CuMnO. With the increasing of x 3-x 4 heating rate, the starting and ending temperatures of the reduction reaction increased. However, the reaction time decreased and the reduction rate increased. With the increasing of oxygen concentration, the starting temperatures of the reduction reaction shifted to high level. Temperature had great effect on the reduction rate and the reduction rate increased with increasing of the reduction temperatures.

Mar 1, 2018

By R. L. Nyirenda

An investigation of the reducibility of a cassiterite concentrate with charcoal was made in the temperature range of 1123-1373 K. The course of the reaction was monitored by a combination of sample weight loss measurements, product gas analysis, and chemical analysis of the reaction product. It was found that the cassiterite could be best reduced by a combination? of high temperature, reasonably high charcoal proportions, high charge poroslty, and the addition of a small percentage of lime. Analysis of kinetic data obtained from isothermal experiments using theory from the oxidation of carbon by carbon dioxide gave an activation energy value of 255 lci/mole for the consumption of carbon by reaction with cassiterite.

Jan 1, 1990

By A. F. Saavedra, N. E. Richards, C. J. McMinn

"The aluminum industry in general and Reynolds Metals Company in particular have continued to support development work for improvement of the Hall cell design and for alternative processes for the reduction of alumina. The evolution of the Hall cell design will continue into the next century as a result of further development of mathematical models, sophisticated control systems and new materials for cell components. This paper discusses the areas in which the new generation cell advances will differ from the present day design. Additionally, Reynolds Metal s has supported work for the development of a carbo thermic process to reduce alumina. Theoretical work has indicated that this process could possibly have economic advantage over the Hall process. Several complicated furnace configurations have been proposed to provide the conditions for successfully reducing alumina. The results of small pilot scale operation and most promising furnace design are discussed. For comparison, projected capital investment costs and operation costs are discussed. IntroductionThe evolution of the Hall-Heroult process will continue into the next century. This evolution will be influenced by economics, more .restrictive environment and worker protection requirements, and technological development. These factors will also cause changes in the competitive position of alternate processes for aluminum production.Several aluminum producers have made major investments in alternate processes for aluminum production in the past three decades and there is continued support in some companies for improvements in the Hall-Heroult process and for alternate processes. The more visible development work in reduction technology, not aimed at significant process changes, is in the areas of higher amperage cells with bus bar designs to reduce harmful magnetic effects, more advanced and automated feed, voltage and electrolyte composition control, improved energy efficiency and sol id waste disposal . Efforts to bring significant change to the reduction process are being made in development of materials that can function as inert anodes and cathodes. These materials could lead to the development of reduction cells with multiple bipolar electrodes operating on oxide feed and fluoride electrolytes. Development work on new processes was reduced in the last decade by several companies because of economic and technological realities. Reynolds Metals supported work on a carbothermic process to reduce alumina and produce commercial pure aluminum. This work progressed through small pilot plant operation, and resulted in development of furnace designs and operation regimes. This paper reviews how this and other technologies could influence the reduction of alumina beyond the year 2000."

Jan 1, 1988

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 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

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 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 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

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