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By A. W. Schlechten, A. H. Larson

Equilibrium H2S/H2 ratios were determined as functions of temperature (500o to 900°C) and composition in a hydrogen-circulation apparatus. Within the composition range studied there exists a two-phase region of "Zr3S4" and "ZrS2". The upper composition limit of this two-phase region is hounded by a disulfide phase and is practically constant over the temperature range investigated. The lower composition limit of this two-phase region is bounded a "Zr3S4 " phase and varies appreciably with tem- perature. The upper composition limit of the homogeneous region of the disulfide phase is not definitely determined, but it appears to he bounded by the stoichiometric composition of ZrS2. The lower composition limit of the homogeneous region of the Zr3S4 phase could not he determined due to the extremely low values of the equilibrium H2S/H2 ratios. Various thermodynamic quantities are evaluated from the data. PUBLISHED free-energy data for the Zr-S system are practically nonexistent. Strotzer, Biltz, and Meisel1 measured the sulfur pressures for the reaction 2ZrS2(s) + S2(g) = ZrS3(s) in the temperature range 783" to 874°C. The average heat of reaction calculated from the temperature dependence of the sulfur pressure is -47 keal. It should be noted, however, that according to these investigators, the two-phase region as determined by sulfur pressure constancy under isothermal conditions extended from approximately ZrS2, 3 to ZrS2.7. From consideration of X-ray data they concluded that the homogeneous regions of the disulfide and trisulfide phases are ZrS1.8-2.0 and ZrS2.8-3.2, respectively. Hahn and coworkers2 have made a structure study of the zirconium sulfide phases. They summarized the zirconium sulfide phases as follows: the compounds ZrS3 and ZrS2 with narrow homogeneous regions, a "Zr3S4" phase with a homogeneous region roughly within the limits of ZrSl.5 and ZrSo.9, the compounds ZrS and Zr4S3, and a "Zr3S2" phase with a homogeneous region within the limits ZrSo.8 and ZrSo.5. It is noted that the compounds ZrS and Zr4S3 are only formed in the gaseous state through sublimation of a phase which has the approximate composition of the compound. This paper describes the determination of the stability of the zirconium sulfide phases by a hydrogen-reduction method in which hydrogen is circulated over the heated sulfide until equilibrium is attained. The resulting H2S-H2 mixture is then analyzed. Partial molar free energies, enthalpies,

Jan 1, 1964

By A. L. Labbe

SOON after the Cottrell treater was placed in operation in the Murray plant in 1918 to treat combined lead sinter and Wedge roaster smoke, it was noticed that the power flowing through the treater did not remain constant. This was indicated by the varying milliamperes and also by the total amount of power consumed by the rectifiers. At times, for then unknown reasons, the treater current fluctuated through a wide range of from 40 to 300 milliamperes. Fortunately, these variations in power did not affect the treater's overall recovery, as this installation consisted of three independent units in series, a feature which made the Murray Cottrell an outstanding installation over many years of operation. Water conditioning of the smoke as a means of improving recovery was already known, but was not adaptable to this installation for reasons of excessive corrosion, which had been the case with other treaters using water as a conditioner exclusively. Tests conducted on the smoke had proved conclusively that water vapor played no part in the fluctuation of power, and the same was true of the SO2 contents and dust burden of the smoke. Neither did temperature variations of from 150 to 400°F have any effect on the power. Finally it was noticed that the variation in power taken by the treater, and the efficiency of recovery, had some definite relation to the number of Wedge roasters operating, and particularly to the sulphur contents of the charge. This observation soon led to the discovery that free sulphuric acid was the conditioner for Murray smoke and that variations in acid contents of smoke accounted for fluctuations of treater power. Analysis of recovered dust revealed that only a few hundredths of a per cent free acid was necessary to maintain a very efficient recovery. Once this knowledge was available, the roaster charge was adjusted as to sulphur contents to produce the necessary acid conditioner. For a number of years this practice was followed, but with improvements in the field of flotation, excess pyrites were eliminated from the smelting picture, so with a change in metallurgical practice we were confronted with the problem of providing the deficiency in acid by some other means. The situation was aggravated and our problem of acid conditioning made more difficult by the increase in the lead contents of concentrates roasted resulting from better flotation methods. The first step towards introducing acid vapors into the smoke stream by accessory means was accomplished by boiling sulphuric acid in cast iron pots placed in an open fire box. Acid fumes evaporated from the pots together with the combustion gases from the fire box were discharged into the flue through a cast iron pipe. Capacity of the iron pots was quite limited because of the comparatively slow rate of evaporation and the use of lump coal as a fuel, which did not lend itself to practical temperature control. This method of firing resulted in frequent pot failures due to overheating. In spite of these incidental difficulties, encountered in any new venture, the pot evaporator demonstrated the practicability of fuming sufficient acid to make up the deficiency in that naturally evolved in the Wedge furnace operation. As time progressed, less and less high sulphur material was available for Wedge roasting, and the necessity for accessory acid conditioning reached a climax when the supply of this material was entirely eliminated. Since the cast iron pots could only evaporate a few hundred pounds of acid per day, and were costly to replace, the logical thought presented itself of spraying the acid in a heated chamber. This new type of acid evaporator was simpler and more economical to operate and had sufficient capacity to fume several thousand pounds per day. The attached fig. 1 presents the outstanding features of the new furnace. A is the vaporizing drum, which is heated by the combustion gases of coal stoker fire box, B. Acid is sprayed into the hot gas stream within the drum through a number of air-acid atomizers, C, and the acid vapor, together with combustion gases, is introduced into the smoke stream through two cast iron pipes extending to different points in the flue. The operation of this type of furnace requires control of temperature inside the drum to prevent overheating, which dissociates the acid vapor to SO, and eventually to SO2, with resulting loss of acid. The dissociation to SO, at elevated temperatures is comparatively high, and in some cases accounts for as much as 60 pct of the acid sprayed into the drum. To reduce the loss of acid, through dissociation, some Cottrell plants, where the rate of acid sprayed reaches at times 9 ppm, use two evaporating units. Fuming the acid into the smoke stream is only

Jan 1, 1951

By J. F. Elliott

PRESENT knowledge of the usual metallurgical slags indicates that they are, for the most part, rather complex in behavior and as yet there is no ready means for describing, in a simple manner, the behavior of any one of them. One of the best known slag systems is the iron oxide-silica-lime ternary which is the basic "solvent" in a number of important metallurgical refining operations, the basic open hearth being one of the most important. In this operation, the slag dissolves such components as sulphur, phosphorus, manganese oxide, and magnesia. Considerable study of this slag system and the behavior of these additions has been carried out in the past by a number of authors, as has been summarized in several critical reviews.','2 However, except for determination of the activity of iron oxide, only a limited amount of effort has been directed towards developing, from these data, an understanding of the general behavior of the basic solvent. Reported here are the results from a series of calculations based on data from the literature which permit a semiquantitative evaluation of the activities of iron oxide, silica, and lime (plus magnesia) in the ternary system at 1600°C. The preliminary results, which were reported briefly at a symposium held by AIME in 1953, have been revised and are completed. The steps in the calculation are as follows:* I—establish the activity curves and the curve of the excess molar free energy of mixing at 1600°C for each of the binary systems, 2—construct the activity surface of iron oxide for the ternary from the data on the binary systems and information available in the literature for the ternary area, 3—determine the surface of excess molar free energy of mixing for the ternary system from the activity surface of iron oxide and from the molar curves obtained for the binary system, and 4—differentiate the ternary surface of the molar excess free energy of mixing to obtain the ternary surfaces for the logarithm of the activity coefficients for silica and lime (log rslo, and log rc.~). Si0,-Fe,O: Schuhmann and Ensio have measured the activity of iron oxide in simple iron oxide-silica slags when in equilibrium with y iron. Their data recalculated to 1600°C are shown in Fig. 1. Also included is a point representing a measurement by Gokcen and Chipmana of the activity of iron oxide at 1600°C at the point of saturation with solid silica. For convenience and in accordance with other treatments,' the calculations are based on the hypothetical component, FelO, which is obtained by converting all the analyzed iron in the slag to FeO. In spite of Schuhmann and Ensio's conclusion that the activity of iron oxide in the system does not vary with temperature over the experimental range of 1258" to 1407"C, the data are corrected to 1600°C assuming that temperature does have an effect. It was felt to be most reasonable to assume that the term log rr.10 is a linear function of the reciprocal of the temperature. Reyu has indicated that an effect of temperature on the activities in this system is to be expected from the Schuhmann and Ensio data. In essence, the correction consists of multiplying the experimental value of log rf,,o by the ratio of the experimental temperature in Kelvin to 1873°K. The magnitude of the correction is not large, being approximately 11.5 pct of the experimental value of log rve10. A very minor correction was necessary to compensate for the fact that the slags were in equilibrium with y iron in the experiment, while at steel-making temperatures they would be in equilibrium with liquid iron. Data for the correction were obtained from Darken and Gurry. The standard states established are pure liquid iron oxide (FelO) in equilibrium with pure liquid iron (with the appropriate amount of oxygen in solution) and pure liquid silica. The method of plotting in Fig. 1 is convenient for the calculation of the activity of liquid silica and permits a reasonable extrapolation for the activity of Fe,O in the ranges where no experimental data are available. The uncertainty in the extrapolation to infinity at one terminal where Nvelo = 1 for the usual Gibbs-Duhem integration is reduced considerably by this method. The region of two coexisting liquid phases is estimated to range from 1.8 to 41.7 mol pct Fe,O. The nature of the activity curve for the single-phase region indicates that the activity of iron oxide across the two-phase region is very close to 0.39. Computation of the function log ~F,,o/(1— NF,,o)' for this region (dashed line) in conjunction with the curve through the adjusted experimental data indicate the best probable value of 0.382 for alPe,o in the two-phase area. The line from 0 to 0.018 Nf~~o is obtained by assuming that the component follows Henry's law. In this range, the value for log rveto is 2.59. Appropriate mathematical manipulation of the plotted linet yields the activity curves for the The curve AF", the excess molar free energy of mixing (actual minus ideal), as shown in Fig. 3 is also computed from Fig. 1. This curve is required for subsequent calculations. CaO-Fe,O: The phase diagram for the lime-iron oxide system when in equilibrium with liquid iron is not well known but there appears to be no intermediate compound present. This fact as well as the activity values for Fe,O extrapolated to the CaO-Fe,O binary from Taylor and Chipman' tend to indicate somewhat negative deviations from ideality for the activity curves for the two components. Strong indication of this is evident in Fig. 1 where are plotted the points computed from the estimated activities of Fe,O for the binary system.' It appears that the best line through the data is a horizontal straight line. Because of the general indication of the slight negative departure from ideality, the line is extrapolated horizontally to NF~,o = 0. It is con-

Jan 1, 1956

By Klaus Schwerdtfeger, Hans-Jürgen Engell

Activities of silicon in Ni-Si melts have beelz determined in the temperature range 1480° to 1610°C from electromotive-force measurements involving the cells The data obtained are used to derive the activities of nickel and the integal free energies of mixing. Entropies of mixing are calculated from the free energies of mixing as obtained in the present study and the heats of mixing as available in the literature. ACTIVITIES in Fe-Si and Co-Si melts have been determined recently by the authors&apos; using galvanic cells consisting of alloy, an oxygen electrode, and an oxide melt as electrolyte. The present paper deals with activities in Ni-Si melts as measured with the same technique. A schematic diagram of the cell is shown in Fig. 1. The alloy and the electrolyte consisting of CaO and SiO2 are contained together in a silica-glass crucible. During the experiment the silica glass crystallizes to cristobalite on the surface of the crucible. Nickel contents of the electrolyte are very small (<0.1 pct as checked with chemical analysis), because of the noble character of nickel in comparison with silicon. A tapered silica tube is connected to the crucible through which a platinum or molybdenum wire is inserted, as shown in Fig. 1. A platinum tube reaches the surface of the CaO-SiO2 electrolyte from above. The platinum tube is provided with four holes on its side, through which oxygen of 1 atm pressure is blown over the electrolyte. The cell reaction is given by the equation Si(metal) + O2(gas) = SiO2(electrolyte) [3] and the galvanic electromotive force of the cell is given by the formula

Jan 1, 1965

By J. F. Pierce, S. M. Enterline

Since January 1959 a zinc refiner of novel design has been in operation at Blackwell, Okla., producing 99.995+ zinc from the output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyro-metallurgical unit with principal dimensions horizonhl permitting one floor operation. It is very ruggedly constructed. Furthermore it is not subjected to deterioration from high concentrations of iron in the feed metal because the boiling units are separate from the rectification columns and constructed with silicon carbide brick arches through which the heat is transferred radiantly to the zinc. A zinc refiner of novel design has been in operation since January 1959 at the Blackwell, Okla. plant of the Blackwell Zinc Co., Inc., a wholly owned subsidiary of American Metal Climax, Inc. Developed by the company&apos;s technical and operating staffs, the new refiner produces special high-grade zinc (nominally 99.995+ pct Zn) from the prime western1 slab output of the Blackwell horizontal retort smelter. The refiner is a continuously operated, pyromet-allurgical, high-capacity unit employing fractional distillation to separate zinc from its impurities, consisting principally of lead, cadmium, and iron. In prime western slab, these elements may vary in concentration from 0.005 to 1.6 pct. Table I shows the impurities usually encountered in the Blackwell prime western metal fed to the refiner together with their boiling points and vapor pressures at 907oC. The commercial pyrometallurgical smelting processes for extracting zinc from ore include distillation from retorts and a limited degree of refining can be accomplished by redistillation in similar retorts. To achieve special high-grade purity, an impractical number of batch redistillations would be required, however, with an accompanying loss of much metal. A continuously operated and integrated unit is required in which fractional vaporization and condensation can take place in a large number of stages. The first commercial continuously operated unit was developed by the New Jersey Zinc Co.4 In the separation of any two substances the degree of separation is limited if a mixture exists having a constant boiling point. The Zn-cd5 and Zn-pb6 systems contain no constant boiling points and hence these metals may be separated to any degree of purity. Basically, the pyrometallurgical refining of zinc involves three steps: a) iron, copper, and other metals having no appreciable vapor pressures at 907ºC concentrate in the bath when the impure zinc is boiled, b) lead, bismuth, antimony, and other metals having boiling points above but closer to that of zinc are selectively condensed from the vapor boiled from the bath, and c) cadmium and other metals having lower boiling points than zinc are fractionally distilled by reboiling and subsequent condensation of the zinc from the vapor. The boiling and condensation of zinc must be conducted in vessels constructed of materials which are refractory at the temperature involved (907 ºC) and it is highly desirable that they also be resistant to attack by the various metals. This requirement dictates construction from relatively small, simply shaped pieces which limits the pressures which may be employed to avoid leakage through the numerous joints. Stresses induced must be limited essentially to compressive ones and suitable provision must be made to permit thermal expansion of the components in order to minimize these stresses. Where heat is to be added for boiling or removed for condensation, refractory material through which the heat flows must have a high thermal conductivity. Silicon carbide is highly conductive but is subject to attack by iron and is expensive compared to other commonly employed refractories. A hard, dense aluminous fireclay is well suited to contain these metals where high thermal conductivity is not required. Zinc will penetrate the pores of fireclay brick but only to a limited depth in an exterior wall and has little effect other than an increase in weight and conductivity. The design objectives of the Amax refiner were: a) to achieve a long life by heavy, rugged construction and by employing silicon carbide refractories only where required for heat conductivity and not in contact with liquids of high iron concentrations, b) to simplify operation, manning and control by essentially horizontal construction, and c) to obtain high capacity in a single unit. DESCRIPTION Flow of metal through the Amax refiner is shown diagrammatically in Fig. 1 and schematically in Fig. 2.

Jan 1, 1963

By J. Nutting, D. H. Kirkwood

The oxidation of lead sulfide in air between 200° and 350°C has been investigated by electron diffraction from thick sulfide films and from galena surfnces. It has been demonstrated that sulfate is the stable reaction product up to 570°C. Sulfate is HAGIHARA has investigated&apos; single crystals of galena roasted in air by the reflection electron-diffraction technique, which owing to the very limited penetration of the beam into the crystal gives information of the nature of the surface only. He has shown that up to 280°C the first oxidation product is lead sulfate, followed by lead mono-oxysulfate (PbO . PbS04). At longer times and higher temperatures more complex patterns appeared which could not be analyzed. All of these patterns were of streaks or spots arising from crystals oriented on the galena surface, and it is probable that these crystals are lead compounds whose structures have not been determined, such as the other oxysulfates (2Pb0 • PbS04 and 4Pb0 . PbS04) or a number of oxides. Certain lead sulfide films, formed chemically, give ring patterns in transmission electron diffraction2 because they are polycrystalline, and should also give ring patterns of the products after oxidation. It was thought that a diffraction study would reveal the sequence of phases produced in the reactions at different temperatures, since X-ray powder patterns are available for many lead compounds. PREPARATION OF FILMS The films were prepared by passing H2S over a saturated solution of lead nitrate in water. Once a silvery film had formed on the solution surface, no further thickening was apparent. The films were transferred by a gauze to a bath of distilled water for washing and pieces of film were caught on small discs on which they were dried. The discs were formed initially on galena up to temperatures of 300°C, followed by oxide and oxysulfates in turn at longer times. The appearance of- these phases is believed to result from an inadequate rate of supply of sulfur to the top surface 01. the crystal. standard Siemens mounts, made of platinum alloy, and had seven 20-p apertures drilled through them. The parts of the film which had dried onto the disc surface were light blue in color, which is the interference color of a film about 600A in thickness. A strong pattern of lead sulfide was obtained in transmission electron diffraction through the apertures but slight broadening indicated a crystallite size of around 200A. Tilting a sulfide film in the beam produced arcing of the rings, increasing the intensities of the (Ill), (3111, and (222) rings and reducing (200) and (220). This arises from preferred orientation in the film, a [loo] direction of the crystallites being normal to the plane of the film. These specimens were oxidized in an oven maintained at the required temperature. The reported times include that taken to heat the film to the reaction temperature. STABLE PHASES FORMED IN OXIDATION The conditions in which various oxidation products of lead sulfide are stable have been considered by the authors in a previous paper.3 It was shown that in a normal atmosphere, taken as containing lo-&apos; atm of SOs, lead sulfate would be stable up lo about 570°C. This was confirmed by oxidizing thin films of sulfide for several days, and the analysis of the transmission-diffraction pattern is given in Table 1. The fit with the patt$rn from X-rays is good, except for the missing 3.62A ring. Some disagreement in intensities of reflections given by X-rays and electrons is to be expected. Up to 570°C a spotty pattern of sulfate was still obtained, indicating grain growth, but above this temperature the film disintegrated. Probably this is associated with the decomposition to PbO . PbS04. It needs to be emphasized that the atmosphere

Jan 1, 1965

By F. Forward, H. Veltman, A. Vizsolyi

Activities of oxides in the ternary FeO-MnO-SiO system are calculated from data on the binaries, using the Gibbs -Schuhmann method. These activity data are used, together with thermodynamic relations, to calculate the contents of oxygen, silicon, and manganese in liquid iron, and the composition of the corresponding oxide phases in equilibrium with it. Excellent agreement was found between calculated and experimental metal compositions, indicating that thermodynamic methods, such as those presented, can supply useful data on slag-metal equilibria, and are therefore capable of wider application. When molten steel containing oxygen is treated with a deoxidizer, the product of the reaction is composed of the oxides of the deoxidizing elements together with more or less iron oxide. This assemblage of oxides is presumably very close to equilibrium with the melt since it is formed directly from elements dissolved in it. Therefore, it is likely that metal analyses corresponding to a given oxide phase composition are calculable with considerable precision where sufficient information is available on activities in both phases. The present study was made to test this hypothesis in the case of deoxidation by silicon and manganese. Here experimental data on the relationship among oxygen, silicon, and manganese in the metal phase are available, as are activity data for the MnO-SiO2, FeO-SiO2, and FeO-MnO binary systems. A further objective was to demonstrate in a specific example how gaps in the data may be filled by judicious interpolation, and how the Gibbs-Schuhmann method is applied to obtain activities in ternary systems. The rigorous derivation of the latter, requiring considerable facility in handling partial differential equations, tends to mask the real simplicity of the method, and repel the very engineers and experimenters who would benefit the most from its use. I) GENERAL PROCEDURE Deoxidation of steel with silicon and manganese results in the formation of two phases, metal and oxide. The number of components is four—Fe, Mn, Si, and 0. The phase rule then gives the number of degrees of freedom: If temperature and pressure are fixed, 2 deg of freedom remain. Consequently, it suffices to fix the concentration of two of the components of the system for all the concentrations to be determined and, at least in principle, calculable. The practical problem is then to discover a straightforward method of calculation with a minimum of trial and error solutions. The type of reactions to be dealt with are like the following: Si (in steel) + 2 O(in steel) = SiO2(in oxide phase) The standard free energy of this reaction is readily obtained from the literature, so that the equilibrium constant can be calculated by the expression: Since the metallurgist is concerned with percentages rather than activities, a real solution requires information that will permit activities to be converted to concentrations. This information is fairly adequate for the elements dissolved in molten steel, but is not available for the FeO-MnO-SiO2 oxide system. Therefore, the first step in this study was to find the relation between activity and concentration for the three oxides making up the system. The next step was the calculation of slag and metal compositions that are in equilibrium with one another. As shown by the phase rule, it is sufficient to assume the values of two composition variables in order to calculate the rest. But which two are picked makes a vast difference in how difficult the calculation turns out to be, so that it is necessary to make preliminary trial of several routes to find the easiest one. A convenient method is to begin with the slag, and to pick FeO concentration and that of one of the other oxides. Starting with the relation between oxygen dissolved in the liquid steel and FeO in the slag permits a good first estimate to be made of the oxygen content of the steel in equilibrium with FeO, because the iron content being fairly close to 100 pct, Fe has an activity close to unity. Using this first estimate of oxygen activity, approximate values of the manganese and silicon contents of the melt are readily calculated from the appropriate equilibrium constants. A minor correction for the depar-

Jan 1, 1963

By S. F. Radtke, J. A. Snyder, R. M. Scriver

An automatic, continuous casting arc furnace employing a nonconsum-able electrode and a direct current arc has been constructed and operated successfully for titanium. A comparison of the properties of arc and induction-melted titanium indicates that where high ductility, formability, and toughness are required, arc-melted metal is preferable. BECAUSE of the reactivity of titanium metal with all known refractories and the common atmospheric gases, melting of the metal presents numerous problems. It is necessary to provide an inert atmosphere in the furnace as well as a crucible material that will not react with the molten metal, if a ductile ingot is to be produced. Two special furnaces have been developed that meet the requirements and one, the induction heated graphite furnace, has been described in some detail.&apos; Little information is available for sizable units wherein power is applied to the melt through an arc, and the dearth of technical information on such a furnace prompted this report. It has been demonstrated clearly that arc melting produces titanium metal with superior toughness, ductility, and formability. To produce titanium ingots with these properties, an automatic, continuous casting arc furnace has been developed and is described herein. The history of arc melting may be traced to 1800, when Sir Humphrey Davy2 first experimented with Volta&apos;s electric battery and found that light could be produced and an arc formed between two carbon points attached to the cell. The discovery of the arc was followed by the design and construction of an arc furnace by Napier," in 1845, for the reduction of metal oxides. In 1853, Pichou&apos; described a similar furnace, although it was not until the discovery of the dynamo in 1867 that the arc furnace could achieve commercial significance. In 1878, Siemens- esigned the first arc furnace intended for the melting of metals and by 1882 had melted steel and platinum successfully. . This was followed by Moissan&apos;s" classical work with the arc furnace in 1892. W. von Bolton,&apos; in 1905, found that the arc furnace was suited admirably for melting refractory metals. In his work with tantalum, no suitable refractories for retaining the molten metal were found to exist. Together with Otto Simpson, he developed an arc furnace with a water-cooled copper crucible in which tantalum could be melted without contamination. This technique proved eminently successful. In his paper on the preparation of ductile titanium, Krolle first described an application of the von Bolton furnace to the melting of this metal. The

Jan 1, 1952

By H. A. Shaw, H. G. G. Whitton

This paper describes the use of the electric-arc furnace for the production of tough-pitch, horizontal cast copper shapes and the production of copper anodes from tank house anode scrap. This installation is the only one of its kind in the United States. SINCE the initial use of electric-arc furnaces for refined copper melting on a commercial scale at Copper Cliff in 1936, this type of melting has been of extreme interest to everyone in any way connected with copper casting and fabricating. Early in 1948, Kennecott Copper Corp. decided to build an electrolytic copper refinery at Garfield, Utah. One of the major decisions to be made at that time was the type of furnace to be used for melting cathodes for casting into refined copper shapes and for melting anode scrap for the production of anodes. Based on the results obtained from arc furnaces by the Tnternational Nickel Co. of Canada, at Copper Cliff, and by the American Smelting and Refining Co., at Baltimore, coupled with certain important economic factors such as having an adequate amount of relatively cheap power available at the Magna Central Power Plant, high cost of poles and oil in the Salt Lake District, and the lack of natural gas at that time, the final decision was to install electric-arc furnaces rather than the standard type of rever-beratory furnaces. Experience has shown certain parts of the original installation to have been inadequate or in need of modification. Although the present status of arc-furnace melting at the Utah Refinery is far from perfect, nevertheless substantial progress has been made. At the Utah refinery, copper is melted in three 15-ft diam, size "M" Lectromelt furnaces, two of which are used for melting cathodes and one for remelting anode scrap. Each furnace is energized from a 13,800-225 v, 3-phase, 60-cycle, 6000-kva (at 40°C rise) oil-immersed water-cooled transformer. Auxiliary equipment for each refined copper furnace includes a charging machine, launders, ladle, 40 ft diam Walker-type casting wheel, bosh, and inspection conveyor. The anode furnace differs in that it is charged by hand from an elevated platform and the anodes are picked off the 24-ft diam casting wheel by a takeoff hoist and loaded directly into specially designed trailers, Figs. 1 and 2. Electrical Equipment Electric power to operate the arc furnaces is generated at the Kennecott-owned Magna Central Power Station two miles distant and transmitted to the Refinery outdoor substation at 44,000 v. At this point it is stepped down to 13,800 v and carried through concrete-lined underground tunnels to the switchgear and then to the primary side of the furnace transformers. The power is conducted from the Y-connected secondary bus bars of the transformer to the electrode arms by means of 22 flexible copper cable conductors per phase. Each cable has a cross-sectional area of 1,750,000 circular mils, giving a total area of 38,500,000 circular mils per phase. The power is carried from these cables to the three individual electrode holders by means of water-cooled copper bus tubing. The electrode clamps are incorporated in the electrode holders and are released by air pressure working against a spring in the clamp control cylinder. The movement of the electrode arms is either automatic or manual. The automatic control is used during melting and is regulated by three Westing-

Jan 1, 1954

By J. A. B. Forster

W. G. WOOLF*—The paper has a wealth of data that take careful, detailed study. As has been indicated the highlights can be only touched in the paper. The design and the arrangement of the rabble teeth as well as some of the other details of operation show a very careful study and a scientific approach to the problem which in most plants using hearth roasters are matters of trial and error with empirical conclusions and, perhaps too often, just arbitrary supervisory preferences which may be erroneous. Here the problem has been approached from a scientific angle which think well merits careful study. The ability to treat the tonnages they get through these furnaces think is made easier by reason of the high sulphide sulphur in the resulting calcines which the balance of the plant—the leaching and so on—can cope with. As indicated by Mr. Weldon in his dis- cussion earlier this morning, in most zinc plants an attempt is made to have as low a sulphide sulphur content in the roaster calcine as possible. But in the operation of the Risdon plants, they are able to cope with sulphide sulphur content up to 5 pct which is far beyond the amount of sulphide sulphur that can be handled elsewhere. I think the autogenous roasting is made easier because driving out the last percentages of sulphide sulphur brings on the necessity for extraneous heat, and that is further exemplified because even at Risdon the author shows the desirability of using some oil to better the operation, particularly for uniformity of roasting results and to obtain more regularity of furnace operation. A. A. CENTER*—Regarding the hard crusts in the beds of the furnace and autogenous roasting, the paper speaks of the former being due, at least to a considerable extent, to lead sulphide in the crusts. I wonder if the author has considered the hard crusts as being due in large part to zinc sulphate. While I was developing large zinc operations we ran into hard crusts which had to be dug up. I took several lumps which were so hard they showed the marks of the rabble teeth very plainly and kept them in my office for some weeks. A visitor came along one day, and as he was having similar troubles, I told him what we were doing about ours. I started to pick up one of these lumps and to my amazement the thing crumbled in my hands whereas originally it had been so hard it wore the rabbles down very rapidly in the furnace. I sent the sample to the laboratory and found that it analyzed very high in water-soluble zinc and sulphate-sulphur. The crumbling of the lumps was evidently due to the anhydrous zinc sulphate gradually taking on moisture from the air and forming crystalline zinc sulphate seven parts water. The increase in volume would, of course, result in disintegration of the lumps. As to getting a high tonnage in the autogenous roast, that is partly because of finishing at about 5 pct sulphide sulphur. It is a real job to get down to, say, ½ pct sulphide sulphur, which is what is usually desired, and still put through a good tonnage.

Jan 1, 1950

By H. E. Lee, P. C. Feddersen

Greenockite is the only known cadmium mineral of importance. It occurs rather universally, in minor concentrations, as a secondary mineral in sphalerite deposits. The world&apos;s cadmium output is obtained through the processing of metallurgical by-products, largely from the treatment of residues from electrolytic zinc, retort zinc and lithopone plants. These sources are supplemented by the processing of fumes from lead and copper smelting operations. The development of modern selective flotation practice in the decade 1920-1930, which permitted the economical mining of complex lead-zinc ores, resulted in significant increases in the quantities of cadmium entering lead smelting systems. Being closely related to zinc as to occurrence, properties and production, most detailed description of cadmium recovery methods are to be found recorded in connection with zinc metallurgy. Other than occasional articles pertaining to particular operational procedures, literature offers but little in the nature of a balanced survey of lead smelter cadmium recovery practices. While many of the basic operations described for the recovery of cadmium from zinc by-products are applicable to the treatment of lead plant products, the inherent problems involved differ widely. In general the cadmium content of related by-products from routine lead smelting operations is present in lower concentrations, exists in a less soluble state and is associated with both a greater quantity and a greater variety of detrimental impurities. To cope with these problems, lead smelter practices are found to follow the general outline: Preparatory Processing 1. Concentration operations 2. Sulphation operations Cadmium Plant Processing 1. Leaching operations 2. Purification operations 3. Sponge precipitation operations 4. Metal recovery operations 5. Refining and casting operations As in the case of related zinc plant operations, cadmium recovery practices at lead smelters are not standardized. They not only vary as to type, but also extent. Depending upon prevailing conditions, lead smelter cadmium operations range from simple concentration campaigns, for the purpose of sufficiently "up-grading" products for shipment elsewhere, to complete processing steps for the production of refined metal. Preparatory Processing The cadmium content of lead smelter receipts is low and, as a rule, proportionate to the zinc content; the usual range of cadmium contained being of the order of 0.01-0.05 pct. Were it not for the low boiling point of cadmium, such small concentrations would, no doubt, be lost in the large tonnages of slag, metal and other smelter end products. However, the ready volatility of cadmium and its compounds at prevailing lead smelting temperatures results in its concentration in fractional portions of fume collected. This collected fume comprises a circulating load within the smelter system. Thus, the cadmium content of blast furnace fume* increases with each successive circulation until an equilibrium value is reached when the sum of the cadmium losses, due to handling and in slag, waste gases and other end products, becomes equal to the intake as ore. With ore receipts averaging, say 0.03 pct cadmium, the concentration value obtainable, through fume circulation in a routine manner, approaches 10-12 pct. In such operations, cadmium concentrations in blast furnace fume of from 3-5 pct are readily .attainable. However, the concentration gain beyond this range, with each additional circulation, is progressively decreased as a result of mounting losses occurring through handling and in end products. Therefore, to avoid excessive cadmium loss and to enhance the ultimate concentration anttainable, it is customary practice to isolate blast furnace fume at some intermediate cadmium content for special concentration procedure. The most common type cadmium concentration "campaign" involves special smelting operations wherein a relatively high portion of blast furnace fume at 3—6 pct cadmium is incorporated into the sinter charge. This type practice is roughly illustrated by the diagram on p. 111. Cadmium fume collected from lead blast furnace operations is not amen-

Jan 1, 1950

By C. K. Gupta, P. K. Jena

Niobium (columbium) metal in the form of a button has been produced by calciothermic reduction of niobium pentoxide using sulfur as the heat booster. In these experiments with 50 g of niobium pentoxide per batch, the influence of percentage of calcium in excess of the stoichiometric, the percentage of sulfur by weight of the niobium oxide, and the outer-wall temperature of the bomb on the quality and yield of the metal has been studied. The maximum yield on this scale was 78 pct using 50 pct excess Ca and 20 pct of S and at a bomb-wall temperature of 600°C. In experiments conducted on 500 g of niobium pentoxide, reduction with 40 pct excess Ca and 20 pct of S, and at a bomb-wall temperature of 500°C, the.yield of the metal improved to 82 to 84 pct. Some of the reduced-metal samples have been electron-beam melted and the button melts thus obtained have been observed to be extremely ductile and capable of cold reduction to 98 pct without intermediate annealing. NIOBIUM, because of its high melting point (2468oC), its ductility, its resistance to corrosion especially in liquid metals, its high-temperature mechanical properties, and its relatively low capture cross section (1.1 barns) for thermal neutrons, has potentialities as a structural material in the field of nuclear engineering. Niobium and its alloys are also gaining importance in high-temperature technology as components in aircrafts, jet engines, and missiles, electronics, chemical engineering, and surgery. In 1904 Weiss and Aichel 1 produced niobium by reduction of its pentoxide by misch-metal. Since then a large number of investigations have been carried out for the extraction of niobium from its compounds. The various routes through which the metal niobium has been extracted from its compounds can broadely be classified into the following groups: a) reduction of its halides, oxides, and fluo-salts with metals like calcium, magnesium, sodium, and aluminum;2-10 b) reduction of its halides with hydrogen and oxides with carbon or carbides;11-18 c) electrolytic winning from its halides and fluo salts;19-25 and d) thermal decomposition and disproportion ion of its halides26-30 Among the processes in commercial use at present are sodium reduction or fused-salt electrolysis of potassium niobium fluoride, carbide or carbon reduction of the oxide, and hydrogen or metallothermic reduction of the chlorides. In 1907 Von Bolton2 prepared niobium by reducing niobium pentoxide with aluminum. Dennis and Adam-sona attempted reducing the oxide with magnesium powder in argon atmosphere and the resulting metal contained as much as 5 pct O. Mondolfo8 claimed a method for the reduction of the oxides with aluminum. In the case of both magnesium and aluminum reduction, it has been stated31 that by-product oxides such as MgO or A12O3 would involve a major separation problem. Further, in the case of alumino-thermic reduction, the solubility of aluminum in niobium and intermetallic formation have to be reckoned with. In 1922 Bridge3 produced niobium by calcium reduction of niobium pentoxide. Dennis and pdamson&apos; obtained the metal by a similar method with an oxygen content of 0.2 pct. In most of the cases of metallothermic reduction of niobium oxides mentioned above, the metal niobium is obtained in the form of powder. In an attempt to produce massive niobium metal, lock&apos; used iodine as the thermal booster in the bomb reduction of niobium pentoxide by calcium. Massive niobium metal was obtained with a maximum yield of 75 pct containing 0.1 pct 0. Joly32 carried out experiments on calcium reduction of niobium pentoxide on a 2-kg scale using sulfur as the heat booster in a sealed bomb filled with argon. In his experiments, the reaction was initiated by passing a current through niobium spiral wire embedded in the charge. In a typical run consisting of 2000 g of niobium pentoxide, 3100 g of calcium, and 800 g of sulfur (S/Nb2O5 = 3.3), he obtained massive metal in the form of a very uneven mass with a yield of -57 pct. With lower amounts of sulfur and calcium, powder niobium mixed with small metal globules was obtained and the yield was also poor. From these experiments he concluded that this method is not a suitable one for industrial development considering the quality and yield of metal obtainable and the possible hazards with higher ratios of sulfur to niobium pentoxide in the -~charere. In the present work, a detailed investigation on the calciothermic reduction of niobium pentoxide in a stainless-steel bomb in presence of sulfur as the heat booster was undertaken on a laboratory scale.

Jan 1, 1964

By R. N. Dokken, J. F. Elliott

A high-temperature solution calorimeter was used to measure directly the partial molar heat of mixing of nickel in the Cu-Ni system, 0 to 15 at. pct Ni and 1200°C; of silver in the Cu-Ag system, 0 to 50 at. pct Ag and 1100°C; and of cobalt in the Cu-Co system, 0 to 6 at. pct Co and 1200°C. The heats of fusion of copper and silver were also detervnined directly. The results of these investigations are as follows: Cu-Ni: HM = [2.64 + 0.25Xm JXNiXCy kcal/g-U~OI Cu-Ag: HM =[4.00 + 0.31XAglXAgXCu kcal/g-atom Cu-Co: HF~ = [8- 5X~,]X& kcal/g-atotn Cu, AH, = 3290 * 275 cal/g-atom Ag, AH, = 2890 * 250 cal/g-atom The performance of the calorimeter was enhanced by improving the operational and control procedures, particularly the temperature-wieasuren~ent method and the solute-addition practice. The interpretation of the experimental data was improved by developing machine computational techniques that increased the speed, flexibility, and accuracy of the treatment of the data. THIS paper reports further measurements of the heats of solution of liquid metals with the high-tem- perature solution ca1orimeter.l Measurements were made of the partial molar heats of mixing in the following liquid alloys: Cu-Ni, Cu-Ag, and Cu-Co. In addition the heats of fusion of copper and silver were also determined. The apparatus and the experimental procedure were essentially those of Benz and Elliott.2 Several modifications in the experimental method and the means for interpreting the data were incorporated in this study to improve the results. The operation of the calorimeter and its characteristics will be described only briefly here. The

Jan 1, 1965

By W. A. Sheaffer

Electric furnace installation and tough-pitch copper-casting operation at Canadian Copper Refiners Ltd. are described. General layout, power supply and control, refractories, induction pour hearth, casting equipment, metal temperature control, and oxygen-content control are discussed. E LECTRIC furnace at Canadian Copper Refiners Ltd. was put into operation in August 1949. The installation was designed primarily to melt electrolytic copper cathodes and to produce vertically cast tough-pitch shapes. To meet emergencies during reverberatory furnace shut-downs, provision was made for casting horizontal tough-pitch wire bars. Due to the ease with which metal temperatures, melting rates, oxygen content, and casting hours can be altered to suit production demands, the electric furnace has met the requirements admirably. General Layout The plant has been described by H. S. McKnight&apos; and by J. H. Schloen and E. M. Elkin.2 Since these papers were written, the electric furnace has been installed in a 140 ft extension of the original casting building. The extension, 264 ft in width, is divided into one 24 ft and four 60 ft bays, each a continuation of similar bays in the older building. Fig. l, a partial floor plan of the extension, shows the location of major equipment. Power Supply and Control Power for the electric furnace and its auxiliary equipment is delivered by Quebec Hydro over two 12 kv three-phase, 60 cycle pole lines. One line is in use, while the second serves as an emergency standby. Connections for the electric furnace from these lines, which also feed the refinery power house, are made to a substation on Canadian Copper Refiners Ltd. property. Connections between this substation and the furnace transformer room are in underground conduit. The are-furnace transformer, 550 v auxiliary-equipment transformer, and 12 kv switchgear are in the transformer room near the furnace. Stepdown from 12 kv to are-furnace voltages is done by a 7500 kva oil-immersed water-cooled three-phase 60 cycle transformer. This unusually high kva rating is available because the arc furnace and transformer were adapted from a steel-melting unit. Secondary voltages are available in 16 steps between 251 and 95 v (across phases). A four-position tap changer, operated from the furnace switchboard is connected to taps yielding 199, 164.5, 127, and 115 v, respectively. The transformer primary feeder is equipped with a General Electric Magne-Blast circuit breaker. The pour hearth, casting wheel, bosh conveyor, and other auxiliary equipment are fed by a 12 kv to 550 v, 750 kva three-phase 60 cycle transformer. Graphite electrodes, 14 in., with tapered nipples are held in the are-furnace electrode arms with steel wedges. The arms, fed from the transformer secondary busbars by flexible cable bundles, are actuated by winch cables. Direct-current motors operating the winches are supplied by a 250 v motor-generator set. Power input to the furnace is controlled from the furnace switchboard. The board has the usual combination of remote controls for the 12 kv breaker and transformer tap changer, meters, overload relays, automatic and manual electrode motion controls, switchgear, etc. When power is on the furnace, automatic electrode feed is used; the power draw on a given voltage tap then is governed by current-limiting rheostats. The rheostats work through a Westinghouse bal-lanced-beam control circuit which, in turn, operates reversing contactors in the winch motor circuits. Arc Furnace The arc furnace is a standard-type NT Pittsburgh &apos;Lectromelt with inside shell diameter 12 ft 3¾ in. By hydraulic-lift cylinders, the furnace can be tilted forward to 39 ½ ° and backward to 5" from horizontal. A roof-swing cylinder is also installed but not used. Fig. 2 shows refractory-lining details. With the lining as shown, operating life between repairs is 6 to 9 months of two-shift casting operation. Charge slot, skim door, and roof refractories then are replaced completely, and any necessary repairs made to side walls. Bottom life is longer and the original under courses are still in service, while the top course was replaced in October 1951. The launder is lined with high chrome-magnesite trough brick backed by fireclay and insulating brick. The trough is covered with fireclay brick and asbestos sheet. At intervals, openings 12x6 in. are left in the permanent covering. These are covered with

Jan 1, 1956

By F. A. Forward, V. N. Mackiw

The paper relates to the laboratory and pilot plant studies that have been carried out by Sherritt Gordon Mines Ltd., Metallurgical Research Div., in developing the ammonia pressure leach process for extracting copper, nickel, cobalt, and sulphur from high grade nickel concentrate produced from Lynn Lake ores, and describes in some detail the chemistry of the process. IT is well known&apos;.&apos; 2 that copper, nickel, cobalt, zinc, ferrous iron, and a number of other metals combine with ammonia in aqueous solution to form complex ions of the form [Me(NH,)x]"+. The stability and solubility of these ions depend on the concentration of the metal ion in solution, on the amount of NH, present, and on the amount and type of anions present, e.g., OH-, C0;-, NO,, C1-, SO;-. If ammonia is partially or completely removed from such solutions, for example by boiling, the soluble ammines tend to decompose and the metals precipitate as basic salts. These properties of metal ammines have found practical application in the commercial recovery of copper, nickel, and cobalt from a variety of ores. In an operation formerly conducted at Kennecott"" the mill tailing containing 0.80 pct Cu as copper carbonate was leached by percolation with an ammonia-ammonium carbonate solution to dissolve the copper as the ammine. At Calumet and Hecla0-" With a mill tailing containing about 0.4 pct Cu as metallic copper, it has been found necessary to aerate the ammonia-ammonium carbonate leach solutions between stages to oxidize the solubilized copper. At Nicarol"-" where nickel and cobalt occur as oxides and silicates which are not soluble in ammonia, the ore is heated to decompose silicates and to selectively reduce the nickel and cobalt to metal, leaving the iron as Fe,O,, and is then leached with ammonia-ammonium carbonate solution accompanied by aeration to dissolve nickel and cobalt as ammines. In each of these leaching operations, the anion present is CO, and the metals can be precipitated from the leach solution as oxide (copper) or hydroxide and carbonate (nickel and cobalt) by boil- ing off NH, and C02 both of which are recycled to treat a subsequent ore charge. The products-—oxide, hydroxide, or carbonate—can be treated by conventional smelting, calcining, or electrolytic methods to convert them to refined metals. Thus the procedures mentioned utilize the properties of the ammines to extract copper, nickel, and cobalt from nonsulphide ores and separate them from the leach solutions. These processes have the advantage that they can be carried out in closed vessels at atmospheric pressure, that the leaching solutions are specific for the desired metals, that the metals can be recovered as relatively pure compounds by the boiling operation, and that the NH, and CO, can be recycled. Also, as the leach solutions after boiling and filtration are substantially free of metals, NH,, and CO,, they can be discarded, thus facilitating the control of the water balance in the leaching circuit. When, as is the case with Sherritt Gordon concentrates, sulphides are treated with ammonia solution in the presence of oxygen, the leach solution contains SO,--, and an entirely different set of conditions is encountered. The ammine sulphates (of nickel, for example) are more soluble than the carbonates and can be only partially decomposed by boiling. The SO, and NH, in the solutions can not be recovered by boiling. Thus, despite the more favorable leaching conditions resulting from high solubility of the ammine sulphates, the recovery of metals, NH,, and SO, from the solutions must be effected by other means. Sherritt Gordon Nickel Concentrate Treatment The Ni-Cu-Co flotation concentrate produced at Lynn Lake&apos;" contains 12 to 16 pct Ni, 1 to 2 pct Cu, 0.2 to 0.5 pct Co, 33 to 40 pct Fe, 28 to 34 pct S, 8 to 20 pct insoluble, and less than 0.02 oz per ton precious metals. The nickel is present chiefly as pentlandite, the copper as chalcopyrite, and the iron as pyrrhotite and pyrite. Most of the cobalt is thought to be present in pentlandite, although it is known that a small amount occurs as Co-Ni-pyrite.

Jan 1, 1956

By Arne Bergholm

Australian rutile was chlorinated in the presence of CO or carbon. The chlorination velocity in CO was found to be strongly influenced by temperature and proportional to the CO concentration, but independent of the Cl, concentration. In the presence of carbon, the reaction velocity is much higher. The reactivity of the carbon and the distance between the carbon and the rutile surfaces are important variables. The reaction velocity is approximately proportional to the Cl, concentration and independent of the CO concentration of the surrounding atmosphere. Experiments with fluidized-bed chlorination of carbon-rutile mixtures indicate that the motion of the bed has little influence on the reaction velocity. At low temperatures, the chlorination velocity of dense tablets is much greater than that of TiO, coke mixtures suitable for fluidization. The reaction mechanism is discussed. In the industrial production of TiCl, rutile is chlorinated in the presence of carbon. Disregarding intermediate steps, the reaction may be expressed by the following equations: The ultimate object of this study was to find out whether the reaction velocity was higher in fluidized bed operation compared with chlorination of pelle-tized carbon-rutile mixtures. From a literature survey and preliminary experiments it was learned that some basic knowledge about the reaction mechanism was needed for a good experimental design. Therefore the following sets of experiments were carried out: 1) Studies on the reaction velocity in the chlorination of rutile with CO as the only reducing agent. 2) Chlorination of separate rutile-carbon tablets. 3) Chlorination of rutile-carbon tablets at different temperatures with various kinds of carbon, various grain sizes, and various tablet-making techniques. This series of experiments was carried out not only with pure chlorine but also with mixtures of chlorine with argon, CO and CO,. 4) Chlorination of rutile-carbon tablets made in a strictly standardized manner. 5) Chlorination of static-bed rutile-carbon mixtures. 6) Fluidized-bed chlorination of the same mixture. The experiments 4 to 6 formed the final and direct test of the main question: Static bed vs fluidized bedo. Although there are many patents and papers dealing with the general aspects of chlorination, only few experiments from which detailed information can be obtained have been reported in the literature. Pamfilov and coworkersl3 have studied chlorination of TiO, with CO or carbon as the reducing agent. They found that the weight decrease per hour at 600o to 800°C amounted to 11 to 14 pct with CO and 45 to 51 pct with carbon. They suggest that phosgene might be an intermediate in the chlorination of TiO,. Takimoto and Hattori have chlorinated reduced titanium oxide (TiO) and found a very high rate of TiC1, -production. They proved that the composition of the gas from the chlorination of rutile-carbon mixtures contained mainly CO. They reported for instance 74.7 pct CO, and 5.6 pct CO at 800°C at which temperature the Boudouard equilibrium composition is 12 pct CO and 88 pct CO. Seligman and Segerchano6 have studied the chlorination of TiO. They proved that Ti0 and chlorine react rather rapidly at temperatures as low as 300°C. Above 400°C, the reaction was complete. At 500°C the velocity of this reaction was much higher than was chlorination of TiO, + C. McTaggart,7 Nishimura, et al. and Wilskam have chlorinated mixtures of carbon and various kinds of rutile or beneficated ilmenite. Nishimura, et al. also report the results from reduction of TiO, with H2, CO, or carbon. At 900°C only 1 pct Ti O is formed in 2 hrs. At 1100°C 23.1 pct Ti, 0, was formed if elementary carbon was present. No carbide formation occurred below 1400°C. McIntosh and Cofferll have observed that the CO, content of the exit gases from chlorination of rutile and calcined petroleum coke is appreciably higher than found in the Boudouard equilibrium. At 900°C the ratio (CO, /CO + CO) is about 80 pct, whereas the equilibrium value is about 2 pct. W. E. Dunn12 has studied the chlorination rates of several TiO,-bearing minerals with CO + Cl, or COCl . Chlorinations were carried out either in a fluidized reactor or a fixed-bed reactor, both having a 30-mm diameter. The results obtained in both reactors were comparable. It was proved that benefi-ciated ilmenite (i.e., ilmenite from which the iron oxide had been removed by chlorination) was chlorinated 10 times faster thanrutile. Sore1 slag showed an intermediate rate. When phosgene is used, the

Jan 1, 1962

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.&apos;.&apos; It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.&apos; Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By D. H. Wertz, R. R. Furlong

Dry room equipment at Donora Zinc Works is of the design which prevailed at the time the plant was built in 1915. It consists of 11 adjoining rooms, each being 99 ft long, 11 ft wide, and 7 ft high and having a capacity for 1040 retorts. Heat is supplied by steam coils beneath the slatted wood floor and by warm air ducts at the ceiling. Drying practice is about the same as that generally followed in the industry except that, under normal zinc furnace operations, the maximum drying time is 45 days. During certain seasons of the year the drying process was seriously affected by varying weather conditions which frequently resulted in a scrap loss of 5 to 7 pct. Because of these unfavorable conditions, which caused uneven drying and strains in the retorts, increased retort failures in the zinc furnaces were recorded. Regulation of temperature and humidity under all conditions appeared to be the logical solution of this problem. Controlled drying had been developed for a number of ceramic products and investigation of several such drying processes in this area revealed favorable results. Along with control of drying conditions and the attendant decrease in scrap losses, plant operators also reported a material reduction in drying time. Another factor affecting the decision to proceed with this development was the drastic change in market conditions for retort clay. Curtailment of shipments from the chief source of supply made it necessary to proceed with blending of other available clays, but quality of these clays was questionable for adequate retort life in the 24 hr furnace cycle. Rapid furnace testing of new mixtures was desirable but impossible with the prolonged drying schedule. Therefore development of a controlled drying process for zinc re- torts offered the solution to the problem of rapid testing of retort mixtures. Description of Process and Equipment The freshly extruded retort is cylindrical in shape, 58 in. long, 9 in. id and has 1 1/8 in. side walls. One end is closed and approximately 2 in. thick. The moisture content of this "green" retort is about 17 pct which means a necessary removal of 30 lb of water per retort. Retorts are set on the slatted floor of the dry room with the closed end down. The controlled drying process depends upon the circulation of a large volume of conditioned air at low velocity. To provide for uniform distribu-

Jan 1, 1950

By F. W. Archibald

The American Smelting and Refining Co. has standardized its copper converting practice to attain a maximum unit blister production with a minimum of refractory consumption by careful location of the tuyeres and by applying magnetite coatings on the hard-burned magnesite brick linings. THE American Smelting and Refining Co. operates four primary copper smelters in the United States with a total of 17 Peirce-Smith type converters; 15 of them are 13 ft in diameter by 30 ft long, and two are smaller. Some details of operations vary with locale; however, fundamentals of design, operation, and maintenance are common to all plants. All converter shells are l-in. thick except for one new converter with riding rings on the ends which has a shell thickness of 1 1/2 in. More tuyeres can be installed with rings on the ends and hence more air can be used. Welded construction is replacing riveted. Minor shell repairs are made after each campaign. Principal causes of complete shell replacement are warpage and cracking resulting from localized over-heating. A 13x30 ft shell is being replaced after 34 years of operation and a total production of approximately 750,000 tons of blister. Converters are driven by 80 hp DC motors through company-designed worm gear reducers. Rotation is 0.38 rpm which permits the skimmer to spot the converter quite accurately for skimming slag. At three of the plants, protection against unscheduled air or power failures is afforded by the installation of emergency drives, consisting of auxiliary air motors or storage batteries. In order to avoid excessive splash out of the converters, the converter mouths are located as far back on the shells as existing flue facilities will permit. At one plant, the back of the mouth is only 13" to the rear of the vertical center line of the converter,. whereas it is 28" at another plant. Newly-lined mouth areas vary from 36 to 44 sq ft with effective operating areas about 25 pct less. It is important to keep the converter mouths as clean as possible. Dirty mouths create back pressures in the converters and as a consequence the tuyere air volumes are reduced. Mouths are generally cleaned by bumping with an empty ladle. Small mouth-cleaning rams have been used but unless extreme care is exercised the brickwork may be damaged. After considerable experimentation, the plants standardized tuyere elevations at 4 to 4% in. below horizontal center line at the shell with a downward pitch of about 13/16 in. per ft of length. Tuyeres are spaced at 6 in. centers except at the riding rings where there are no tuyeres. With this tuyere location, several of the plants now freeze magnetite slag in the bottoms, fronts, and backs up to the bottom of the tuyeres to control the internal shape of the converter. This has the effect of improving the agitation and mixing so that there is a marked increase in converting speed besides affording protection to the brick lining. Currently, the trend is to increase tuyere diameters from 1% to 2 in. to increase the air flow. At present, all converters are hand-punched but one converter is being equipped with a set of mechanical tuyere punchers. Rods for punching are % in. hexagonal smelter bar upset to ll/s in. and rods for cleaning tuyeres are upset to about 1% in., or larger, depending upon the tuyere diameter. Two of the plants use pneumatic reamers for cleaning the tuyeres between charges to minimize disturbing the coating on the inside of the refractory lining. Most of the puncher&apos;s platforms are pneumatically or hydraulically mounted so that a convenient punching position can be maintained regardless of tuyere position. For normal operations, tuyere air pressures vary from 15 to 13.5 psi, although some cycles such as magnetiting require pressures down to 8 psi. Air requirements vary from an average of 25,000 cfm on the newer installations down to 12,000 cfm on the older ones. Converter hoods are designed to protect the punchers from sparks, splash or hood accretions as well as to prevent the escape of objectionable

Jan 1, 1955

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957