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By R. A. Pyper, J. L. Hendrix

Laboratory leaching experiments were conducted to ascertain the effectiveness of acidic solutions of thiourea, CS(NH2)2, for dissolving gold from finely disseminated gold ores. The ore tested was from the Chipmunk ore body of the Northumberland mining district in Nye County, Nevada, USA. Extractions of up to 90% were attained from the ore. Extraction was shown to be dependent on thiourea concentration, ferric sulfate oxidant concentration, acid concentration, and leaching time. Optimum conditions were an ambient temperature leach near pH 1.0 utilizing 100 to 200 kg/ton thiourea and 50 kg/ton ferric sulfate for 8 to 24 hours.

Jan 1, 1981

By G. Adachi, K. Machida, T. Ozaki, K. Murase

The chlorination rate with CCl4 was unexpectedly slower than carbochlorination using chlorine under the same reaction conditions. Chlorination with CCl4 was topochemical and the amount of monazite reacted after different periods suggested that the kinetic control step was the reaction between CCl4 and the monazite core at the interface. The kinetic order of the reaction was 0.5. The presence of a complex former, AlCl3, promoted the chemical vapour transport of rare-earth chlorides as complexes

Jun 18, 1905

By Kelly E. G

NZ Steel's flushing slag typically contains 1.2 per cent V203. Extraction of vanadium from powdered slag using a salt (NaCI or Na2CO3) roast/leach process was investigated. With NaCl, optimum extraction conditions were a charge containing 10 per cent NaCI, roasting in air at 875°C for 4 hours, followed by leaching in dilute H2SO4. Extractions were typically 30-50 per cent. NaCI roasting did not chemically attack the slag; the phase transformations that occurred were due to high temperature oxidation. Slag particle size had a significant effect on extraction.Optimum conditions for extracting vanadium by Na2C03 roasting were 20 per cent Na2CO3 in the charge and roasting in air for 3-4 hours at 850-875°C followed by water leaching.Na2CO3 roasting involved chemical attack that resulted in the formation of perovskite (CaTiO3) and carnegieite (NaAISiO4).The extent of vanadium extraction depended on the amount of Na2CO3 added and the original slag SiO2 content.Compared to the separate roasting treatments, simultaneous treatment with NaCI and Na2CO3 gave lower vanadium extraction, while requiring considerably higher roasting times and temperatures.

Jan 1, 1982

By John Chipman, Wayne L. Worrell

Using recent thermodynamic data for the carbides and oxides of tantalum, columbium, and vanadium, the stable solid phases aboue 1300°K and at 1 atm CO(g) pressure in each M-C-O system have been determined. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures necessary to obtain these metals by carbothermic reduction under reduced pressures. TANTALUM, columbium, and vanadium react with carbon to form the M,C and MC carbide phases. The M,C carbides have narrow homogeneity ranges, but the MC phases possess considerable ranges of homogeneity.' The free energies of formation of the MC carbides were recently measured, and those of MC and M2Ccarbides have been estimated., (The notations MC and MC denote, respectively, the carbide compositions at the carbon-rich and at the metal-rich boundaries of the homogeneous MC phase.) In this paper, these carbide data are combined with thermodynamic data for the oxides to predict the stable phases in the Ta-C-O, Cb-C-O, and V-C-O systems at specified temperatures and oxygen pressures. M-C-O PHASE DIAGRAMS The solid phases in equilibrium above 1300°K for each M-C-0 system are shown in Figs. 1, 2, and 3. Above 1300°K, the vapor would consist entirely of carbon monoxide; and these phase diagrams were obtained by specifying the vapor pressure of CO(g) to be 1 atm. The temperature at which any two solid phases become unstable is specified along the two-phase equilibrium lines in each diagram. To simplify the diagrams, all solid phases in the Ta-C-O and Cb-C-O systems are represented as stoichiometric compounds. However, the homogeneity ranges of VO and VC are indicated, because they form a complete series of solid solutions.3 It also should be noted that the homogeneity range of

Jan 1, 1964

By A. W. Schlechten, R. P. Abendroth

Jan 1, 1960

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

By W. A. Krivsky, R. Schuhmann

Jan 1, 1962

By Edna A. Dancy, Gerhard J. Derge

Jan 1, 1963

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2&apos;3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By D. H. Gurinsky, D. G. Schweitzer

The empirical equilibrium constantsd the heat of reaction for the reduction have been determined from 300° to 500°C. The mechanisms of the oxidation of uranium and magnesium from dilute bismuth solutions have been investigated. The kinetics of some of the reactions were affected by air adsorbed on the uranium oxides. THE Liquid Metal Fuel Reactor studied at Brook-haven National Laboratory uses a solution of uranium in bismuth as the fuel. Corrosion and stability problems require that the fuel solution contain corrosion inhibitors and deoxidants. Of the additives tested, magnesium has been found to be the best deoxidant and zirconium the best corrosion inhibitor in bismuth. Some experiments1 indicate that magnesium may play a secondary role in increasing the effectiveness of zirconium in inhibiting corrosion. The work reported here was intended to determine the relative concentrations of Mg and U required to prevent oxidation of the uranium fuel in the event of an air leak. In addition, an attempt was made to identify some of the mechanisms of the oxidation and reduction reactions occurring in the liquid bismuth solutions. EXPERIMENTAL Apparatus and Procedure—The equipment shown in Fig. 1 was designed so that the reaction kinetics could be studied as functions of temperature, melt composition, pressure, and flow rate. At the start of a run, the 10-liter bell jar (F) is removed by opening the bottom Dresser fitting (L), and the bismuth and additives are placed in a pyrex crystallizing dish (I). The bell jar is replaced, the system is evacuated to 10-5 to 10-6 mm Hg and then the heater (J) is turned on. When the selected temperature is reached, the oxidizing gas is admitted to the system to the desired pressure as read on the manometer (D). Gas is introduced through the slide tube (Q) which has a pyrex frit (R) sealed to its bottom. Stirring is accomplished by immersing the end of the tube in the melt. To maintain a constant pressure under flow the input and evacuation rates must be equalized. To obtain this condition stopcock (C) is closed and flowmeters (B) are matched. The reaction is "stopped" by closing the inlet flowmeter and quickly evacuating the system. To obtain a liquid metal sample, the system is evacuated with the sampler positioned near the surface of the liquid. The sampler, Fig. 2, is then immersed until its thermocouple reading matches thermocouple (G) Fig. 1. The system is then pressurized with helium which forces the solution through the frit. Twenty to 30 min elapsed between the time the system was evacuated and sampled. During evacuation and pressurization of the system, the temperature variations did not exceed ± 5°C. While bubbling occurred the temperature remained constant to within 1/2 oC. The volume of the equipment was determined by adding a known volume of air at atmospheric pressure to the evacuated system and noting the resulting pressure.

Jan 1, 1962

By C. S. Samis, D. P. Seraphim

In the presence of oxygen, galena is oxidized in an aqueous medium containing ammonium acetate in accordance with the following reaction: PbS + 1/2 0, + 2 NH~Ac -» PbAc, + So + 2 NH: + H2O. This reaction was studied in an autoclave under oxygen pressure by polarographic measurement of the concentration of lead ion in solution. Oxidation rate is parabolic. The reaction products are lead acetote and elemental sulfur, the latter forming a film on the galena crystal. Reaction kinetics appear to be determined by the diffusion of lead from the galena phase to the solution interface through the film of sulfur. RECENT applications of pressure leaching on a commercial scale have emphasized the metallurgical importance of the oxidation of sulfide minerals in aqueous media by oxygen under pressure. Research experience has shown that sulfates, thio-nates, and metal oxides are the products of humid oxidation of sulfide minerals in basic solutions. The metal oxides may be solubilized in the presence of a complexing ion.&apos; Certain oxide minerals are also amenable to treatment by this type of oxidation.&apos; Several kinetic studies have been made of reactions of this type. Stenhouse&apos; found that pyrite (FeS?) oxidized in a sodium hydroxide solution to produce a soluble sulfate and an insoluble layer of iron oxide and that the kinetics of the reaction were controlled by oxygen diffusion through the oxide layer. Andersen&apos; studied the oxidation of galena (PbS) in a sodium hydroxide solution under oxygen pressure. He found the lead and sulfur to be simultaneously oxidized to produce plum bite ions and sulfate ions, and that the reaction rate was proportional to the surface area of the galena. The kinetics appeared to be determined by the reaction of oxygen and water with the galena surface. In each of the above reactions the metal and sulfur components of the mineral were oxidized simultaneously and at equal rates. In the present study the alkaline medium has been replaced by an approximately neutral solution of ammonium acetate in which lead sulfate is soluble. Under the conditions no sulfate was produced and no sulfur could be detected in the solution. The metal component of the mineral was solubilized and the liberated sulfur remained as a film of elemental sulfur on the surface of the galena crystal. A kinetic study of this reaction was undertaken to establish the kinetic mechanism and to determine the rate controlling step. Specific reaction rates were determined by oxidizing crystals of galena of measured surface areas in an autoclave maintained at the desired temperature and oxygen pressure. The rate of reaction was followed by measuring the concentration of lead in the ammonium acetate solution with a cathode ray polarograph, employing stationary platinum electrodes incorporated in the autoclave. Experimental Materials and Equipment Crystals of galena obtained from Violamac Mines, Retallack, B. C., were selected for oxidation because

Jan 1, 1957

By W. A. Tiller, J. D. Harrison

HOT pressing of powder particles has gained importance recently, since it affords a method in which high densities are rapidly attained. In a recent study on hot pressing of alumina powders, Mangsen, Lam-bertson, and Best1 have shown within the limits of their experiment, the validity the rate equation for densification in hot pressing, originally proposed by Murray, Livey, and Williams.2 i.e., where D = fraction of theoretical density, t = time, P = pressure and 77 is the viscosity, all in appropriate units. This equation was derived from earlier work of Shuttleworth and Mackenzie3 which is based on the closing of spherical pores under the action of surface tension. The integrated form of this equation yields a straight-line relation between log (1 - D) and t. Such conditions were found by Felten4 to be true only after extended periods of pressing. In an endeavor to quantitatively evaluate the exactitude of this equation in the initial sintering stage, i.e., prior to sealing of the pores, spherical anti-

Jan 1, 1962

By J. H. Bain, D. C. Haigh, L. C. Parsons

Jan 1, 1964

By Ling Yang, John Henderson

Self-diffusion coefficients of copper in molten copper have been measured by the capillary reservoir method in the temperature range 1140o to 1260°C. The results can be represented by the equation D = [(1.46 * 0.01) x 10-3) exp [(-9710 * 710)/RT] cm2/sec. The energy of activation agrees within the limit of experimental uncertainty with that for viscous flow. The relationship between the diffusivity and coefficient of viscosity is best described by the equation D = kT/4pnr cm2/sec. MEASUREMENT was made of the self-diffusion coefficient of copper in molten copper in the temperature range 1413º to 1533ºK, using the capillary reservoir technique and CU64 as the radioactive tracer.The procedures for filling the capillaries, making the diffusion run and evaluating Dcu from the counting results were the same as described previously.1,2 All experimental operations involving the melt were carried out in a purified argon atmosphere. A graphite crucible, enclosed in a McDanel tube, was used as a container for the melt because of its satisfactory nature as a refractory material and the low solubility of carbon in copper. Graphite was also used for the capillary material. A McDanel thermocouple sheath, to which graphite radiation shields were affixed, was used to hold the capillaries. By moving this sheath through a rubber seal at the top of the McDanel tube, the capillaries could be lowered into or raised out of the melt. A Globar furnace with a constant temperature zone (± 2°C) of 2 in. was used to heat the assembly. The temperature of the furnace was the equilibrium value corresponding to a given setting of the transformer. Temperature was measured with a Pt-10 pct Rh/Pt thermocouple and varied during a run

Jan 1, 1962

By G. T. Engel, W. G. Gruzensky

Jan 1, 1960

By I. Cadoff, E. Miller, K. Komarek

Jan 1, 1960

By W. J. Kroll

Jan 1, 1960

By Frank E. Woolley, Robert D. Pehlke

Jan 1, 1965