Search Documents

By Terkel Rosenqvist

THE desulphurization of molten iron and steel is a very complicated process. One way to arrive at a better understanding of this process is to break it down into several simpler chemical processes that can be studied individually in the laboratory. For a study of the different factors that influence the equilibrium distribution of sulphur between liquid metals and slags, several simpler equilibria may be investigated. One very important subject is the determination of the escaping tendency of sulphur in the liquid metal and its dependency on temperature and composition of the melt. Several papers in this field have recently been published.', ' Another subject is the study of the sulphur capacity of the slag. A molten slag is indeed complex, and even if sulphur distribution data for a large variety of molten slags may give empirical data about their desulphurizing power, the importance of the individual components is still not quite clear. It is accepted generally that lime is the most important desulphurizing component in the slag. The present investigation has as its purpose to study the desulphurizing power of lime in its standard state, and to provide a basis for thermodynamic calculations of the desulphurizing power of various lime-containing slags. The standard state of lime at steelmaking temperatures is solid calcium oxide, CaO. It can react with sulphur to form solid calcium sulphide, CaS. The relative stability of calcium oxide and calcium sulphide is expressed by the free energy of the reaction: 2Ca0 (s) + S1 (g) = 2CaS (s) + O2 (g) The existing free energy data for this reaction, listed by Kelley5 nd Osborn,' are uncertain to about 10 kcal and are of limited value for a calculation of equilibrium constants. Under the conditions prevailing in a melting furnace, the sulphur pressure may be expressed conveniently by the ratio H,S/H2 and the oxygen pressure by the ratio H,O/H, (or CO,/CO). The desulphurizing power of calcium oxide may, therefore, be studied by the reaction CaO + HIS = CaS + H2O. A study of this reaction may be complicated by certain side reactions: Water vapor and hydrogen sulphide may react. to form sulphur dioxide, and calcium sulphide may be oxidized to calcium sulphate. A thermodynamic calculation shows that these side reactions will be suppressed to insignificance if the equilibrium is studied in the presence of an excess of hydrogen. The apparatus used is shown in Fig. 1. About 10 g calcium oxide and 20 g calcium sulphide (laboratory qualities) were intimately mixed, and some water was added to make a thick paste. The paste was put into a thimble of zirconium silicate, which was placed within the constant temperature zone of a furnace, and capillary refractory tubes were attached in both ends. After the mixture had been heated in dry hydrogen at 1000°C for several hours all Ca(OH), and CaCO, had decomposed and CaSO, was reduced, so only CaO and CaS remained in the thimble forming a porous plug. The mixture was examined by X-ray diffraction after the initial reduction in dry hydrogen as well as after the subsequent experimental runs up to 1425 °C. It was shown that crystalline calcium oxide and calcium sulphide were always present together in about equal amounts. The unit cell edges were found to be 4.80A for CaO and 5.68A for CaS in good agreement with existing literature values." This shows that the mutual solid solubility is very small, and that the compounds are present in their standard states. Purified hydrogen was passed through water sat-urators kept at constant temperature in a thermostat bath. The amount of water vapor saturation was checked by means of a dew point method, not shown on Fig. 1. The gas mixture was passed through the capillary inlet into the furnace, where it was sifted through the porous plug of calcium oxide and calcium sulphide. The hydrogen sulphide present in the outgoing gas was absorbed in a zinc acetate solution and the hydrogen was collected over water. When one liter of hydrogen had been collected, the amount of hydrogen sulphide was determined by iodometric titration. As one molecule of H,O is used for the formation of each molecule of H,S, the equilibrium ratio H,S/H,O would be , where (H,O) is the molar concentration in the ingoing gas, and (H,S) the molar concentration in the outgoing gas. In the present work (H,S) was always very small compared to (H20). In order for the observed H,S/H20 ratio to represent the true equilibrium ratio the gas flow has to be: 1—Sufficiently slow to give a complete establishment of equilibrium, and 2—sufficiently fast to counteract thermal diffusion. Incomplete reaction would give a value decreasing with increasing flow rate, and thermal diffusion would give a value increasing with decreasing flow rate. When inlet and outlet tubes of about 2 sq mm cross-section were used, the observed gas ratio was independent of the flow rate between 15 and 125 cc per min, Fig. 2. In this range, therefore, the observed gas ratio represents true equilibrium.* For the rest of the in-

Jan 1, 1952

Jan 1, 1929

By J. Halpern, D. R. McKay

SOME of the most important hydrometallurgical developments in recent years relate to processes involving the oxidation of sulfide minerals in aque- ous suspension at elevated temperatures by air or oxygen under pressure. Among these is the acid pressure-leach process which has been developed, particularly for the treatment of pyritic uranium ores.1-5 In this process, an aqueous suspension of the ore is digested in an autoclave, in which an overpressure of air or oxygen is maintained, at temperatures above 100°C. Oxidation of the pyrite (FeS,)

Jan 1, 1959

By Roger M. Nendick

The recovery of precious metals from heap leach solutions can be accomplished by two processes: 1. The Carbon Adsorption Process 2. The Merrill-Crowe Zinc Precipitation Process A brief review of the relative process economics is made. Each process presents certain design considerations that must be addressed during the evaluation and engineering design for the project. Discussion is presented on the design criteria for each process.

Jan 1, 1984

By Archer E. Wheeler

IN the copper industry, the year 1942 was one of striving for larger tonnage and increased production. The demands of the war program placed copper high in the list of strategic metals and the Government encouraged production by offering a premium of 5c. per pound for copper output in excess of the 1941 quotas. This had the effect of increasing the tempo of existing operations and also of initiating a number of projects which will eventually result in production from sources not hitherto exploited. No radically new methods of copper reduction were reported.

Jan 1, 1943

November 21st, 1871. THE first session of this meeting was held Tuesday evening, in the chamber of the Common Council, the President, Mr. David Thomas, in the chair. Mayor Carroll, of Troy, gave a cordial welcome to the Institute, which was responded to, on behalf of the Institute, by the first Vice-President, Mr. R. W. Raymond. The Council reported the names proposed for membership with recommendation for election. The following named gentlemen were duly elected Anthony, J., - Williamstown, Pa. Babcock, George, - Troy, N. Y. Blake, Theo. A., - San Francisco, Cal. Blossom, T. M., - New York. Boalt, James A., - San Francisco, Cal. Bowman, Amos, - San Francisco, Cal. Chester, Prof. A. H., - Clinton, N. Y. Dewey, C., - Pittsfield, Mass. Dock, Gilliard, - Shamokin, Pa. Emerson, G. D., - New York. Endres, John J., - Pittsburgh, Pa. Firmstone, Frank, - Easton, Pa. Fowle, W. B., - Philadelphia, Pa. Frazier, Prof. B. W., - Bethlehem, Pa. Gardner, George A., - New York. Goodyear, Watson A., - San Francisco, Cal. Griswold, Chester, - Troy, N. Y. Griswold, J. A.,* - Troy, N. Y. Hague, J. D., - San Francisco, Cal. Hahn, O. H., - Eureka, Nev. Harkness, T. C., - Wilkes-Barre, Pa. Harris, Samuel, - Hudson, N. Y. Henry, E. T., - Oxford, N. J. Holley, A. L., - Brooklyn, N. Y. Howe, H. W., - Troy, N. Y. Hunt, Dr. T. Sterry, - Boston, Mass. Jannet, J., - Troy, N. Y. Knapp, John A., - New York. Laughlin, Henry A., - Pittsburgh, Pa. * Since deceased.

Jan 1, 1873

By Fred W. Gordon

It is my purpose to call attention to the close approximate correctness of certain coefficients and formulas concerning the flow of gases, and their applicability to the practical construction of flues and

Jan 1, 1886

“The mining industry can do more to alleviate world poverty, hunger and human misery, more to close the widening gap between advanced and developing nations and more to achieve international peace and understanding than any other single force in the world," Charles W. Court, Minister for Industrial Development, Western Australia, told the American Mining Congress audience at the opening session of the 1969 Mining Convention, October 19-22, San Francisco. Australia, he pointed out, is a shining example. In 1971, 60% of U.S. mining investment overseas will go to Australia and other parts of Oceania, an increase of 42% over a year ago. Australia has capitalized on world needs, its own rich resources and good investment climate. Developing nations can and should do the same, but they mix emotion with nationalism, often frightening away foreign investment which could breathe life into dormant and backward areas, said Court.

Jan 12, 1969

By R. L. Tobie

Handling and storing ore at transfer points underground are encountered frequently. An ideal solution to these troubles is probably still to be found, but at the Mather mine "B" shaft a method incorporating scraping trenches has been developed giving better service, from the standpoint of safety and simplicity, than obtained from other schemes. When shaft pockets are used for storage, the size of the ground opening required to assure capacity is often prohibitive, and shaft depth below the last level can become excessive, particularly if a crushing station is used. Also, if the material being handled contains large amounts of wet fines, it is difficult, if not impossible, to hold the material with regular chute gates. In order to remedy these problems Cleveland-Cliffs' Mather "B" has utilized three types of trenches. Types I and I1 are now in service and the third is under construction.

Jan 4, 1955

By H. Engelmann

THE very extensive development of a brown coal formation, in the region of the Rocky Mountains, is well known to all of you. The existence of these coals was known years ago, but they were of no practical importance until within a few years, when the mineral wealth of that country began to be developed and railroads were built. As their qualities became better known, their adaptability to domestic manufacturing and metallurgical purposes was more appreciated. They are still much undervalued, although they are mined at some points on a very extensive scale. A large portion of this coal formation is of cretaceous age, while it appears to extend into the tertiary epoch; but whatever difference there may be in the ages of these coals of different localities, they all have some common characteristics which distinguish them from our Eastern stone coals of the

Jan 1, 1876

By H. Engelmann

The very extensive development of a brown coal formation, in the region of the Rocky Mountains, is well known to all of yon. The existence of these coals was known years ago, but they were of no practical importance until within a few years, when the mineral wealth of that country began to be developed and railroads were built. As their qualities became better known, their adaptability to domestic manufacturing and metallurgical purposes was more appreciated. They are still much undervalued, although they are mined at some points on a very extensive scale. A large portion of this coal formation is of cretaceous age, while it appears to extend into the tertiary epoch; but whatever difference there may be in the ages of these coals of different localities, they all have some common characteristics which distinguish them from our Eastern stone coals of the

By AIME AIME

H OWEVER extensively water-lines may be laid in the mine for fire fighting purposes, there are still, usually, points being worked temporarily, development, stoping or other work of a temporary or incidental nature where it is considered that the expense of laying fire-lines is not warranted. While the laying of water-lines in some sections of the mine may not be warranted, in most metal mines it is necessary to lay an air-line to all working places. In the mine of the United Verde Extension Mining Co., at Jerome, Ariz., advantage has been taken of this fact by providing a means of by-passing the water at the end of the water-line into the air-line in case an emergency arises. By this means the 2-in. air-line can be quickly converted into a water-line for fighting fire which might otherwise be beyond the reach of the water-lines.

Jan 1, 1930

By E. T. Turkdogan, P. Grieveson

Experimental results are given for the rate of oxidation of ferrous iron to ferric iron in pure molten iron oxide by carbon dioxide + carbon moloxide mixtures at 1550°C. It is shown that the rate-controlling process is the interdiffusion of iron and oxygen atoms within the melt. The inter-diffusivity of iron and oxygen in the melt is obtained from the results and the value of (5.0 * 1.0) x 10-5sq cm per sec is recommended for the temperature of 1550°C. Similarly, it is also found that the rate of reduction of molten iron oxide is con -trolled by diffusion in the melt; however, apparent interdiffusivity values from these experiments are 10 to 20 pct higher than those obtained in the oxidation experiments, by virtue of convection arising from density difference. The results of the oxidation experintents are used to calculate an estimated self-diffusivity of iron in molten iron oxide of (1.5 * 0.5) x sq cm per sec. BECAUSE of the industrial importance of iron oxides, the study of the kinetics of both the reduction and oxidation of the solid oxides has received a great deal of attention. However, knowledge of the kinetics of similar reactions in the liquid state is very meager. Dancy 1 studied the kinetics of reduction of molten iron oxide by carbon in pig iron and found that the reaction is very fast. It was concluded from the results that the reduction of molten ferrous oxide is a first-order reaction up to 80 pct reduction, while

Jan 1, 1964

By R. C. Croft

Chlorination is frequently employed as a method of chemical attack and separation of the constituents of minerals. Occasionally, bromination has been used similarly. Separation of metal halides resulting from the use of either of these halogens generally entails difficult fractional distillation of the halides. Recovery of the halogens for re-use has often been attempted in the case of chlorine by oxidation of chlorides. Though attractive thermodynamically, this method of recovery fails due to the formation of stable oxychlorides. Although a little less reactive than either chlorine or bromine, iodine offers advantages in the field of mineral treatment. It has been shown, for example, that iron may be removed completely from ilmenite by iodinating the latter in the presence of carbon or hydrogen at temperatures near 800°c where good reaction rates are obtained. Under these conditions titanium does not form an iodide and is not transported in the vapour phase as is the Fe12 formed. Other good separations obtained between zinc and iron in willemite and tin and tungsten in scheelite concentrates confirm that separations of metal iodides by sublimation are more specific than similar separations attempted by distillation of volatile chlorides. Readiness of iodides to form stable vapour-phase complexes appears to contribute to this specificity. The very low stabilities of most metal oxyiodides permit quantitative recovery of iodine by oxidation of metal iodides. In the case of Fe12 derived from iodination of ilmenite, full recovery of iodine can be achieved by air oxidation of this compound at temperatures ranging from 350 to 500° C.

Jan 1, 1973

By Strathmore R. B. Cooke, Iwao Iwasaki, Hyung Sup Choi

The effect of temperature as a parameter in ore flotation has not been systematically studied, although for some ores it has been known for many years that selectivity and grade of concentrates can be improved by conditioning or flotation at moderately or substantially elevated temperatures. In 1934 Coghill and Clemmer' stated that "elevated temperature seems to make hard water more tolerable" in soap flotation, and a cursory examination of the literature indicates that some earlier investigators were aware of beneficial results obtained by floating above room or mill-water temperatures. Tartaron,' Mitchell et al.,3 and particularly Hamilton et al." have shown that high pulp temperatures give high recovery and selectivity in soap flotation of fluorite from a variety of gangue minerals. As a result of the work of these and of other investigators, high-temperature flotation has been successfully applied to industrial flotation of fluorite. Falconer" stated: "The use of high temperature conditioning (above 35°C and preferably above 60°C) in connection with the soap flotation of nonsulphide ores, as covered in B. Kalinowski's French Patent No. 847,- 215, Dec. 7, 1938, is claimed to provide more intense activation, better separation of values from gangue, and reduction in quantity of reagents." The various investigations quoted above clearly demonstrate the improvements to be realized by increasing the temperature at which fluorite is floated, and it is surprising that little or no information has been published on systematic investigation of the same method as applied to other ores.

Jan 5, 1960

Discussion of the paper of BOYD DUDLEY, JR., presented at the New York meeting, February, 1915, and printed in Bulletin No. 96, December, 1914, pp. 2767 to 2782. H. 0. HOFMAN, Boston, Mass.-At the close of the paper Mr. Dudley said that his experiments in the laboratory had shown that it was possible to separate nickel from copper by means of a chloridizing roasting, but that in order to demonstrate a process of this kind, work upon a large scale would have to be carried out. I think it was in 1913, that experiments of this kind were carried out at the works of the Pennsylvania Salt Manufacturing Co., Philadelphia, in a Wedge furnace, and at Sault Ste. Marie in a Sjöstedt furnace. They showed a satisfactory separation of nickel and copper. The ore was first subjected to an oxidizing roast, then mixed with pyrite and salt, and given a chloridizing roast. A. H. Carpenter published in the Engineering and Mining Journal, vol. xcvii, p. 1085 (1914) the details of this work. The conclusion arrived at is, that if you subject sulphide ore to an oxidizing roast, finishing at the temperature at which all nickel sulphate is dissociated, i.e., 764° C., then mix it with pyrite and salt, and subject the mixture to a chloridizing roast between 600° and 700° C., you can chloridize a high percentage of the copper without chloridizing any of the nickel, and obtain thereby a satisfactory means of separating the two.

Jan 5, 1915

By Klaus Schwerdtfeger

In order to test the performance of ZrO, (CaO) and Tho,(Yz03) electrolytes in the electrochemical determination of oxygen activities in liquid metals at steel-rrzakitng temperatures , electromotive force measurements have been made with the following cells: The oxygen-- activities are calculated from the electmrnotive forces for the investigated systems. The standard free energy of- formation of MnO and the activity of manganese in Fe-Mn melts are derived. Indications are that the Zr 0z(Ca0) electrolyte exhibits little electronic conductivity at oxygen pressures as low as 10'a atnz at 1600°C; however, the partial electronic conductivity may become noticeable at lower oxygen activities. The Tho,(Yz03) electrolyte is found to be an ionic conductor at the oxygen pressure as low as that for the Mn + MnO equilibrium, but exhibits partial electronic conductivity at oxygen pressures higher than 10"1 atm (1500°C). fi. better control of oxidation and deoxidation reactions in steelmaking may be facilitated if the oxygen activity in the steel is known during various stages of the process. In the present work oxygen activities have been measured in liquid iron, manganese, and iron alloys with galvanic cells using ZrOz(CaO) and s solid electrolytes with the object of establishing the range of oxygen pressure in which these materials can be used as electrolytes at steelmaking temperatures. Calcia-stabilized zirconia and Tho2-Y203 solid solutions are oxygen ion conductors. Such electrolytes were first used by Kiukkola and Wagner1 and Peters and ~ann' in galvanic cells for the determination of thermodynamicquantities of oxide systems in the temperature range 700" to 1200°C. At these moderate temperatures calcia-stabilized zirconia has been found to exhibit predominantly ionic conductivity at oxygen pressures as low as those for the Cr + Crz03 equilibrium,394 but at lower oxygen pressures elec- tronic contribution to conductivity becomes significants4 The Th02-Y203 solid solutions are ionic conductors at oxygen pressures lower than those applicable to zirconia base electrolytes.5'6 At high oxygen pressures Thoz base electrolytes exhibit significant p-type semiconduction. At the time the present experiments were carried out several papers1'-* were published on the electrochemical determination of oxygen activities in liquid iron using the ZrOz(CaO) electrolyte. The results of different authors do not agree well. For instance, according to Fischer and ~ckermann" stabilized zirconia can be used to measure oxygen contents in liquid iron larger than 0.02 wt pct, but according to Baker and west1' ZrOz(CaO) cannot be used for the determination of oxygen content in liquid iron because of high electronic contribution to the conductivity. Fig. 1 is a schematic diagram of the apparatus used. About 500 g of liquid metal is contained in a crucible into which a stabilized zirconia or Th02(Y203) tube is immersed. A platinum contact wire is pressed (with a spring mechanism) against the inside bottom wall of the electrolyte tube. The tube is flushed continuously with a stream of air, CO-CO, (or Hz-C02) (at 0.96 atm and at a rate of about 300 cu cm per min), via an alumina tube inserted inside the electrolyte tube. This alumina tube also contains the Pt-Pt/10 pct Rh thermocouple. A capillary alumina tube shielding the other contact wire is immersed in the melt. The molybdenum contact wires were used mostly; in some cases platinum wire was employed. Molybdenum has the advantage that it dissolves more slowly in the melt than platinum. The whole cell was contained in the alumina reaction tube of a resistance furnace with molybdenum winding. The reaction tube was closed gas tight at both ends and flushed continuously with argon. Because of the poor thermal shock resistance of the electrolyte tubes the cell had to be assembled in the cold furnace. The electrolyte tube and alumina sheath

Jan 1, 1968

By C. J. Barber

This paper Donald describes how New Jersey Zinc Co. made surveys for a connection between the Ivanhoe and Van Mater shafts at Austinville, Va. Except to say that the two faces had to meet "accurately" on line and grade, Donald does not indicate the required precision. Assuming that there were 24 angles in the 1 ½ -mile traverse and 15 in the one-mile traverse, it can be shown that if the average error in plumbing each shaft was ±30" and the average error in measuring each traverse angle was ±10", then the average error at the point of connection would have been about ±1.9 ft normal to the line between the shafts. This calculation assumes that any errors in the triangulation would be negligible compared with the errors in the plumbings and traverses, and it also neglects taping errors. With no constant errors or blunders, the latter would be important only in lines normal to the line between the shafts.

Jan 7, 1959

By T. M. Olson, B. G. Lewis

The adsorption of selenite on bentonite, kaolinite, and an iron--coated illite was studied to determine the importance of several soil variables on selenite removal from uranium mill tailings pond seepage. Adsorption capacities of the clays of selenite varied by orders of magnitude and decreased in the following order: illite > kaolinite > bentonite. Maximum adsorption of selenite on the clays was observed between pH 2.5 and the clay's zero-point-of-charge. Substantially less selenite was adsorbed on these clays in actual mill tailings solutions than in model systems. Virtually all selenite was removed from the tailings at pH 7. The principal removal mechanism at this pH is suggested to be the adsorption of selenite on freshly precipitated metal hydroxides. It is concluded that selenite can be removed from tailings seepage in soil or in clay liners in the presence of kaolinitic clays and iron oxides. Selenite would also tend to be removed from tailings seepage in calcareous strata.

Jan 1, 1984

ALABAMA Altoona -Cain, J Anniston-Cowie, L K Hermrod, A A White, H E Bessemer -Abbott, C E Ball, E M Mitchell, F R Thompson, N E Birmingham -Adler, J E Aldrich, T H Aldrich, T H, Jr Blackburn, A R Bush, M W Clark, G H Cowrn, P G Crane, W R Crawford, G G Crockard. F H

Jan 1, 1923