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

846 . . . Metals Transactions, Vol. 185 T. J. WOODSIDE*—In the paper it was stated that many of the A. S. and R. plants probably used a process patented by Roscoe Teats in 1930. I might describe

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' 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' 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 H. A. Wriedt

A method of calculating activities in binary systems having miscibility gaps is described. The method, which applies only to the phase in which the gap occurs, is exact when the function defined by the equation varies linearly with composition. Analytical and numerical solutions (as a function of the conjugate phase compositions) are presented for two coefficients A and B from which the thermodynamic activities can be calculated. Deviations from Henry's law, calculable by the method presented, are shown graphically for the particula~ case of the component i at the edge of the miscibility gap more remote .from pure component i. For symmetrical gaps, the deviation from Henry's law at this gap edge becomes smaller as the gap becomes wider, The interrelation of gap location, the direction of departures from Henry's law and the occurrence of maxima and minzma in these departures is discussed in some detail. Values for a and for activity calculated from phase diagrams show fair to excellent agreement with corresponding experimental values in the Al-Zn and CaO-SiO2 systems. WHEN structurally similar phases, B and 6, lie at the sides of a two-phase region in a constitution diagram, it can be assumed that, stably or metast-ably, they will become completely miscible at a higher temperature. The B and 6 phases are particular composition ranges of a single B6 phase region with a miscibility gap. Below, as above, the critical solution temperature, the free energy of formation of the 06 phase is a continuous function of composition through the range of the miscibility gap. It is the purpose of this paper to use this continuous free-energy function in order to develop a simple method for computing the thermodynamic activities in the B6 solution of a binary system. To make these calculations it is assumed that the function ai, familiar from Gibbs-Duhem integrations and defined by the equation

Jan 1, 1962

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' 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 '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 W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.' Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.' The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company's mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

Jan 1, 1962

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'.' 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'" 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.'.' 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.' 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 R. C. Ruder, C. E. Birchenall

The method of decrease in surface activity was used to determine the rates of diffusion of Co" into cobalt and into nickel. Since the absorption curves for cobalt radiation were quite complex under the conditions of these experiments, the effects of geometry and surface preparation on the diffusion results were investigated. The cobalt self-diffusion coefficients obey the equation DCoco = e-61100/RT cm2 per sec. For dilute cobalt diffusing in nickel, DConi, == 1.46 e-/R' cm2 er sec. AS part of the general program to measure the self-diffusion and dilute-solution diffusion rates of the iron-group metals, the diffusion coefficients of cobalt into cobalt and nickel have been measured using the radioactive isotope Co"'. Self-diffusion studies in iron have been previously reported by Birchenall and Mehl.' The technique of measurement used was the decrease in surface activity method described by Steigman, Shockley, and Nix.' It has been determined that scattering of the measured beta radiation by the specimen matrix is significantly influenced by the condition of the surface and the counting geometry. Accurate diffusion coefficients can be calculated from the activity data provided that the specimens have plane diffusion surfaces and that the absorption properties of the emitted radiation are determined under geometrical conditions duplicating with external absorbers the absorption and scattering in a thin film at the specimen surface as nearly as possible. The cobalt used in this research was originally in the form of hydrogen reduced rondels 99.9+ pct pure. The nickel had been prepared by the carbonyl process and was found by spectrographic analysis to contain 0.03 pct Fe, 0.04 pct Co and smaller traces of other metallic elements for a balance purity of 99.9+ pet Ni. Both materials were vacuum melted and cast in rectangular ingots. Specimens 7/8x7/8x1/4 in. were machined from these ingots. The specimens were then ground to 4-0 emery paper and annealed in hydrogen for at least a day at 1200°C. Some of the specimens were used in preliminary experimentation after which their diffusion faces were machined to remove the radioactive material from the previous diffusion experiments. After grinding, the specimens were polished using an electrolytic lapping technique described by Mazia." This lapping was continued until at least 0.005 in. was removed from the diffusion surface. The final surfaces were metallographically smooth except for a few fine scratches caused by the glass cloth. A large percentage of the area was undisturbed as determined by microscopic examination. The grain diameters of the diffusion specimens varied from 0.1 to 5 mm. There were no effects due to grain boundary diffusion in the experiments

Jan 1, 1952

By W. S. Reid

In March, 1938, E. P. Fleming, metallurgist for the American Smelting and Refining Co. inaugurated an investigation into the possibilities of recirculating the gases from Dwight-Lloyd sintering machines operating on lead charge, with the twofold object of concentration of the SO2 content and reduction in volume of total gas produced. The possibility of recovering a commercial grade of SO2 gas from D & L machines operating on lead charge had previously been considered by several investigators. Early History of Recirculation The Selby Smelter Commission Report, published by the Bureau of Mines in 1914, contains a chapter by A. E. Wells regarding results obtained at Selby, wherein some of the richer gas was recirculated through a hood over the pallets. Oldright and Miller of the U. S. Bureau of Mines had also made tests at Trail, B.C., and at Kellogg, Idaho. R. C. Rutherford, while at the Chihuahua, Mexico, Smelter of the American Smelting and Refining Co., in May, 1937, proposed recirculation of D & L gases to decrease the volume of gas handled by the baghouse. At none of these plants, however, was the operation commercialized. In July, 1938, Mr. Fleming, in correspondence with the Selby Plant, inquired regarding the possibility of obtaining 6 pct SO2 gas from the Selby D & L machines. At that time, the writer advised that there was slight possibility of obtaining 6 pct SO2 gas without re- circulation, but believed that it was possible with recirculation, and that experimental work toward that end should be tried at some plant where spare D & L machines were available. The foregoing statement was based on the following information then available— 1. Tests on Selby first-over machines showed 2.28 pct SO2 from first windbox and 1.03 pct SO2 from second windbox, and corresponding figures for second-over charge of 0.81 pct SO2 for first windbox and 0.08 pct SO2 for second windbox. 2. Oldright and Miller (US. Bureau of Mines) in 1932 at Bunker Hill, on 42 in. X 22 ft machines found: a. First-over charge—Maximum SO2 concentration (leaving cake) of 9.5 pct. b. First-over charge—SO2 concentration of over 8 pct from the 4 ft to the 12 ft points beyond the front dead-plate and that the concentration then dropped rapidly. c. That approximately 80 pct of the total sulphur eliminated on the second-over machines occurred during the travel of the pallets from the 1 ft to the 6 ft distances from the dead-plate. d. That approximately 94 pct of the total sulphur eliminated on the second-over machines occurred over the first windox. 3. Oldright and Miller (US. Bureau of Mines) in 1932, at Trail, on 42 in. X 50 ft machines found: a. First-over charge—SO2 varied from 2.0 pct to 5.5 pct (leaving cake) from the 12 ft to 28 ft points from the deadplate. b. That the average SO2 increased from 1.0 pct at 7 ft from dead-plate to maximum of 3.3 pct at 20 ft, then dropped to 1.5 pct at 40 ft. c. That on a 22 ft, second-over machine with an 11 in. bed the SO2 varied from 4.5 pct to 6.5 pct from the 2 ft to the 8 ft points from the dead-plate. d. That on the final roast, the SO2 concentration also varied across the pallets; that is, 2 1/2 pct at the side, increasing to 6.0 pct, 5 in. in, and to 7.0 pct at 10 in. to 20 in. in, then decreased vice versa at the opposite side. e. Concluded that most of the sulphur on a 22 ft machine was removed over the first 7 ft of the first windbox; therefore, they partitioned the first windbox so that the exit gas from the second 4 ft section was returned to the surface of the pallets over the fist 7 ft section, and during a seven-day trial the gas from the 4 ft section averaged 2.4 pct SO2, while the recirculated gas from the first 7 ft section only increased to 3.8 pct SO2. (Excess suction over the 7 ft section to prevent escape of SO2 laden gas from the 4 ft section caused dilution by air.)

Jan 1, 1950

By W. S. Reid

R. H. McNAUGHTON*—The Smelt- ing Co. and Mr. Reid and his men at Selby are to be congratulated on the job they have done on sinter gas recircula-

Jan 1, 1950

By Margaret G. Scroger, Luke L. Y. Chang, Bert Phillips

Using the sealed-system technique, isothermal sections at 1000°, 1400°, and 1700°C for the system Co-W-O hare been determined. The equilibrium data were obtained by microscopic and X-ray diffraction examination of samples winch had been equilibrated in pellet form fit sealed capsules and subsequcelly quenched. The only ternary phase in the system is CoWO, which mells congruentlly at approximately 1280°C. At 1000°C, this ternary phase exists in equilihrinm with all the allows and oxide compounds in the hounding binary systems. At 1400°C, liquid forms in thin oxygen-rick region near the CoWO4 composition and only one phase assemblage in the system (W + WO2 + H'5CV7) contains no In order for tungsten to be used to its full potential as a refractory metal. it is necessary that coatings be developed which will preclude oxidation of the metal. It is true that coatings now in use do protect tungsten for short periods at temperatures near 1700 °C. but no coating has been developed which protects adequately at or above this temperature where the use of tungsten is most required. This situation exists despite the great effort in recent years to develop such coatings. and it has become evident that success in this area can be achieved only after a more fundamental knowledge of the thermochemical and therrnophysical propertics of tungsten oxidation and tungsten -metal oxidation is obtained. In our 1aboratories. a project liclrriel. At 1700°C, tungsten is the ouly solid phase which is stctble, and a large range of compositions melt to two liquids, one metallic and one oxidie. The sealed-system method of etjuilibra lion prevents the determination of the partial pressure of oxygen and the total gas pressure orer the condensed phases at equilibrium. This data is not available and can be obtained only by some other method. We can generalize on these unknowns and indicate that both partial pressure of oxygen and total pressure of the gas phase must increase as compositions change from the W-Co binary toward the oxygen apex and as temperatures increase. has been initiated which is directed at providing some of this fundamental information through a study of metal-tungsten-oxygen reactions and equilibria and the properties of any intermediate phases which result. This paper is based on a part of this program in which the system Co-W-O was studied between 1000° and 1700°C. I) RELEVANT INFORMATION FROM THE LITERATURE A) The Notable Lack of High-Temperature Work on Metal-Tungsten-Oxygen Systems. It should be pointed out that there has been no published report (of which we are aware) which deals with the study of a metal-metal-oxygen system at 1700°C. Also, there has been no report on a complete metal-luugsten-oxgen system at any temperature. As a matter of fact. before this program started. The

Jan 1, 1965

By R. E. Shinkosk

This paper outlines the development of a program for increasing the life of woolen bags used for filtering Dwight-Lloyd gases by treating the bags and gases with hydrated lime. Methods and apparatus are described for determining alkalinity of dusts, acidity and breaking strength of bag cloth. Procedure and results, based on several years of operation, are presented. DURING 1939, additional facilities were constructed in the Dwight-Lloyd Blast Furnace and Baghouse departments at the Selby, California, Plant of the American Smelting and Refining Co. In order to handle adequately the increased volume of gases from the resultant increase in production, it was necessary to increase gradually the amount of water used for cooling gases ahead of the sinter machine baghouse. As a result of this increased water cooling, the average bag life dropped from 27 months in 1939 to 14 months in 1941. (Table I). This drop in life meant an increased. bag cost, as well as lower recovery of dust and some curtailment of operation. During 1941, it was found new bags showed as high as 0.3 pct acidity* after two weeks of opera- tion and as much as 2.0 pct acidity after some months of operation. This high acidity was present in spite of the fact that free oxide or relative alkalinity of the unburned dust ran from 5 to 6 pct. In view of these circumstances, a twofold program was started in Nov. 1941.t Part one of this program consisted of vigorously dipping all new bags in a weak lime solution, containing 50 lb of hydrated lime per 50 gal of water. Part two consisted of feeding fine, dry, hydrated lime into the gas stream intake of the sinter baghouse fan. Apparatus for feeding this lime is shown in fig. 1. All baghouse chambers are shaken in rotation about once each hour. On alternate hours, the baghouse operator places 50 lb of hydrated lime (one sack) into the lime feeder, starts feeder and immediately starts the bag shaking machinery. The rate at which lime is fed is set to coincide with the approximate time necessary to shake all sinter bag-house chambers, or about 15 min. It is felt this method of lime addition is most effective for getting lime into the woolen bag fabric. The amount of lime so fed averages about 600 lb per day. The amount of lime fed per day is varied to keep a minimum relative alkalinity of 9 pct in the unburned sinter dust. A daily dust sample is taken for alkalinity by allowing dust to accumulate in a sample pipe over a 24-hr period. This sample pipe, placed in any chamber cellar, is 2 in. in diam, 4 ft long, is sealed on the inner end, and capped on the outer end. It has a 1/2 in. slot cut for 18 in. along the tip end. This slot faces upward and allows the pipe to fill gradually with dust as bags are shaken. Breaking strength of bags has, in most cases, been the deciding factor in bag replacement. Bags that normally test 100 psi breaking strength when new are replaced when they test under 35 lb. The method for determining breaking strength is shown in the description accompanying fig. 2. Since the start of the liming program in 1941, bag life has increased from 14 months to an average of over 23 months, with a consequent material decrease in bag cost per year. Acidity, as per cent sulphuric acid, may be determined by means of a Beckman pH meter as follows: From a piece of bag cloth. which has been thoroughly cleaned of dust, a 5 g sample is weighed on a balance. Cut the sample into fine pieces and place in a 400 cc beaker. Add 100 cc (measured) of distilled water and stir vigorously. Filter on suction funnel, holding cloth pulp in beaker with a stirring rod. Wash cloth sample and filter wash water four additional times, each time with 20 cc distilled water, the last time squeezing cloth pulp over funnel. Discard pulp and rinse funnel and filter paper. Pour wash solution jnto measuring graduate and make up to exactly 300 cc with distilled water. Place into clean 600 cc beaker and measure the pH on meter. The per cent acid in bag cloth is read from the following table:—

Jan 1, 1951

By R. G. Powell, R. Schuhmann, E. J. Michal

Liquidus surfaces in the ternary system FeO-Fe2O3-SiO2, were determined from 1250' to 1450°C by the procedure of equilibrating small samples in platinum crucibles, quenching, and microscopic examination. The experimental results were combined with previously published information to construct a ternary diagram for the system showing the entire temperature-composition range of stability of iron silicate slags. Metallurgical applications of the diagram, especially in copper smelting, are discussed briefly. IRON oxides are almost unique among the common oxide constituents of metallurgical slags in that the iron occurs in two different states of oxidation, ferrous and ferric. Moreover, in liquid slags the degree of oxidation of the iron is readily changed by reactions of the slags with oxidizing agents or reducing agents. This behavior of iron oxides in slags accounts, for example, for the effective transfer of large quantities of oxygen through slag layers in open hearth steelmaking. In this process, oxygen supplied by reactions at the gas-slag interface is dissolved in the slag with the oxidation of ferrous iron to ferric. Ferric oxide is transported across the slag layer by convection, and at the slag-metal interface the oxygen reacts with liquid metal while the ferric iron is reduced back to the ferrous state. Another group of processes in which variation in degree of oxidation of iron has great practical importance is in copper smelting. In matte smelting and converting, such large proportions of the iron are oxidized to the ferric state that problems are encountered in preventing or controlling the formation of solid magnetite. The ferrous-ferric relationship also affects the attack of iron oxides on high-SiO2 refractories, which appears to be most severe under reducing conditions for which ferrous iron predominates. Darken and Gurry' determined the chemical properties and phase equilibria of pure iron oxide slags. Their data show that iron oxide melts can have compositions ranging almost all the way from FeO to Fe2O3. The melts of lowest oxygen contents, which exist in equilibrium with metallic iron, approach ferrous oxide in composition but still have a small percentage of ferric oxide. The melts of highest oxygen contents, which have oxygen dissociation pressures of 1 atm, are above magnetite in oxygen content, with over two-thirds of the iron in the ferric state. The previously established phase diagrams for silicate slag systems all show FeO as the iron oxide component. However, Bowen and Schairer? who determined the FeO-SiO2 diagram and many of the other diagrams used by slag chemists, have been careful to point out that their systems always contained both ferrous and ferric iron. Thus, their data are for limiting mixtures with minimum contents of ferric iron, obtained by melting and equilibration in iron crucibles. Under these conditions, the Fe2O3 percentages found by analysis were small enough to justify simplification of the published phase diagrams by calculating the Fe2O3 to equivalent FeO and ignoring Fe2O3 as an additional component. On the basis of experimental measurements of melting points of iron oxides on silica in the presence of various gas mixtures, Darken3 worked out phase diagrams for the Fe-Si-0 system which show the important phase equilibria in terms of temperature and gas composition. This study clarified many aspects of the application of the phase rule to the FeO-Fe2Oa-SiO2 system and was an important basing

Jan 1, 1954

By R. McNeill, D. E. Weiss, E. A. Swinton

In a continuous countercurrent exchange process, an alteration in any one of the operating conditions has a complex effect on the others, which can only be predicted by employing the transfer unit or the theoretical stage theory on a basis of trial and error. A simple method is described for illustrating diagrammatically the behavior of a counter-current system, the equations being simplified by means of a concept the maximum hypothetical exchange performance. An example based on a typical metallurgical system is given, in which a divalent metal is recovered from a dilute solution, the resin being regenerated continuously by a monovalent ion. Useful conclusions are drawn from a study of the theory. Practical methods for performing continuous ion exchange are discussed, and the development of equipment based on modified ore dressing jigs is described. A swinging sieve jig contactor is evaluated experimentally. DURING the last decade, the new synthetic ion exchange resins have been applied extensively in industries outside the field of water treatment, but there is no record of a continuous counter-current process operating on an industrial scale. Attempts have been made to devise a satisfactory process but many problems remain to be solved. The basic principles of continuous processes will be outlined, as well as the major problems in their operation and the progress made in the CSIRO laboratories toward the development of satisfactory industrial techniques. In the metallurgical field ion exchange resins can be used for various applications such as the recovery and concentration of valuable metals from mine waters,' the regeneration of pickling and plating liquors," the prevention of pollution by waste effluents and the recovery of the constituents from them," and the purification of valuable metals such as the rare earths by chromatographic fractionation on columns of ion exchange resins.7,8 . Turther applications undoubtedly will be found in the field of hydrometallurgy where the use of ion exchange resins would enable direct extraction of the desired metal ion from the filtered leach liquor or the leach pulp. For example, an ion exchange process has been described recently for the extraction of gold from a cyanide leach pulp." A continuous process would have advantages in many applications over the usual process employing a fixed bed and intermittent cycle. In a recovery process, it would yield a product stream of steady purity and concentration, it would waste less water in rinsing, and if the contacting apparatus were efficient less resin would be used, since each portion of the resin would be cycled as soon as it was loaded instead of lying idle until the whole bed was ready for regeneration. A very major advantage is that it would be simpler to control automatically. It is probable that continuous operation will be the key for really large scale applications of ion exchange. The flow sheet of a continuous ion exchange recovery-concentration process is illustrated diagrammatically in Fig. 1. Dilute liquor containing the valuable ion flows through the stripping section countercurrently to a moving bed of resin and leaves after a final contact with freshly regenerated resin. The resin leaves the unit almost in equilibrium with the incoming liquor and then flows to the regenerating unit where it is treated by a slow countercurrent flow of concentrated regenerant solution. The adsorbed ion is displaced from the resin and appears in the concentrated product stream. The resin then must pass through a rinse unit or section where regenerant entrained by the resin is washed back into the regeneration section by water. The regenerated and washed resin is then recycled back to the stripping section. I. Theoretical Operating Behavior of Continuous Ion Exchange Stripping System The simple theory of continuous ion exchange is analogous to that of solvent extraction and other diffusional transfer operations and is governed by the equilibrium relationship, the mass balance, the rates of mass transfer, and the contacting efficiency of the unit. Equilibrium Relationship—The relative affinity of two ions A and B, for a particular resin immersed in their solution, can be expressed by plotting compositions of the solution against compositions which exist in resin in equilibrium with those solutions, i.e. C/Co vs q/a where C, is the total normality of the solution, C is the normality of ion A in the solution, a is the total exchange capacity of the resin in gram equivalents

Jan 1, 1956

By J. R. Stone, J. T. Roy

ASARC09s continuous tapper for lead blast furnace is described. Its use throughout the company's plants has resulted in higher production rates, lower labor costs, and better working conditions. It has also permitted wide latitude in blast pressures, as well as in charge and slag compositions. The practice of tapping a lead blast furnace has remained essentially unchanged for many years. In principle, it is a batch operation discharging the products from the continuous smelting of lead-bearing materials. As such, it imposes certain restrictions on the proper functioning of the smelting operation. First, it calls for a highly developed sense of timing, and a considerable amount of physical effort on the part of the operator. Dirty and hot working conditions, as well as the hazards of flying metal and slag, usually prevail. These conditions have resulted in higher labor costs, both in rate and in amount. Labor turnover has also been high. Secondly, rigid control of mechanical and metallurgical factors must be maintained. Frequent oxygen lancing of the tap hole is needed to permit tapping, thereby increasing operating costs. Rapid increases in smelting rate, plugged tap holes, or forgetfulness on the part of the operator may permit the molten material to rise above the tuyeies and freeze the furnace. Also, the operator will often blow out the tap hole after draining, filling the area with fume. Composition of charge also vitally affects the tapping. The type of lead-bearing material being smelted will naturally affect the smelting rate, and thus the frequency of tapping. The amounts and types of fluxing materials, which determine the ultimate fluidity of the slag, must be regidly controlled. Finally, the batch tapping of a continuous smelting operation of this type appears to be wrong in principle. The molten material drains into the crucible at the bottom of the furnace where it starts cooling immediately and continues to cool until tapped out. While keeping the lead molten is no particular problem, maintaining a fluid slag at all times is often difficult, and sometimes impossible. These factors all point to the desirability of a method for the continuous tapping of a lead blast furnace. The expected advantages would be more desirable working conditions, lower labor costs, increased production, and a much wider latitude in both blast pressure and charge composition. CONTINUOUS TAPPING Historical. A number of devices, e.g., mechanical tappers, siphons, and lead wells, have been tried in the past in attempting to effect continuous tapping. None proved to be entirely satisfactory for tapping lead and slag simultaneously. It was not until 1955, however, that ASARCO designed and put into operation a successful tapping unit at its East Helena, Mont. lead smelter. This unit is described in detail in U.S. Patent NO. 2,890,951. Continuous Tapping Unit—See Figs. 1 and 2. Fig. 1 is a schematic drawing of the unit in place, showing front and side views. The component parts are identified in the caption. Fig. 2 is an actual photograph, front view, of the tapping unit attached to the base of the blast furnace. Operation. The operation of the tapping unit is quite simple. Essentially it consists of a narrow tapping bay surrounding the furnace tap hole, with a deep notch in the front wall. When the blast furnace is started this notch is open down to the level of the tap hole. Starting the furnace may be accomplished in several ways but the most satisfactory method is to plug the tap hole with clay, permitting metal and slag to build up inside the furnace. Before the liquid reaches the tuyeres, the plug is removed and the furnace is drained to the settler. The blast is then stopped momentarily while the notch in the front wall of the tapping bay is dammed with chrome brick and plastic chrome ore. The blast is again started, and the height of the dam is adjusted so that the liquid in the bay will counterbalance the internal pressure of the furnace. When the desired level is reached the slag and metal will overflow to the settler. It should be noted that the molten material ,is not siphoned from the furnace and that the metal 'acts as a liquid valve controlling the flow of slag through the tap hole. During normal operations the tapping bay is filled primarily with lead, covered with a thin layer of slag. Thus, the heavier lead plays the major role in compensating for variations in furnace pressures. Due to the high specific gravity of lead, changes in the liquid level in the tapping bay will never exceed a few inches. For this reason it is seldom necessary to change the height of the dam due to minor variations in operating conditions. Some turbulence of the liquid in the bay is essential at all times. This indicates that the level of the

Jan 1, 1963

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

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