Successive gas-solid reaction model for the hydrogen reduction of cuprous sulfide in the presence of lime

As an alternative to conventional smelting processes for producing metals from sulfide ores, which suffer from SO₂ emission problems, direct reduction in the presence of lime has in recent years attracted much attention. In this work, a mathematical model of successive gas-solid reactions in a porous pellet has been applied to the hydrogen reduction of cuprous sulfide (Cu₂S) in the presence of lime. The model has been formulated by incorporating the intrinsic kinetics of the individual reactions obtained from separate experiments, and compared with the experimental results on the hydrogen reduction of chalcocite mixed with lime particles. The model predictions were in good agreement with experimental measurements of the overall rate of reaction and the degree of sulfur fixation over a wide range of experimental conditions. The mathematical model not only can predict the performance of a given system but also enables one to design the optimum pellet properties and reaction conditions in terms of the reaction rate and sulfur fixation. Formerly Graduate Student in the Department of Metallurgy and Metallurgical Engineering, University of Utah.     

The selective oxidation of mixed metal sulfides with lime in the presence of steam without emitting sulfur-containing pollutants

The selective oxidation of mixed metal sulfides with lime in the presence of steam was studied as a function of the mixing ratio of the constituents, temperature, and steam concentration. Two combinations of samples were used in this study: ZnS/PbS/CaO and ZnS/FeS/CaO. The steam oxidizes one or both of the metal sulfides, and the hydrogen sulfide produced reacts with lime to form calcium sulfide and regenerate steam. There is no net consumption or generation of gaseous species; therefore, this process can be carried out in a closed system. The free energy of the reaction is negative only for certain metal sulfides, and thus selective oxidation for mixed sulfides can be achieved. An overall rate equation developed in this work satisfactorily predicted the experimental data obtained in the temperature range 823 to 1113 K. The potential implications of the results of this work in the treatment of complex sulfide ores are discussed. This paper is based on a presentation made in the T.B. King Memorial Symposium on “Physical Chemistry in Metals Processing” presented at the Annual Meeting of The Metallurgical Society, Denver, CO, February, 1987, under the auspices of the Physical Chemistry Committee and the PTD/ISS.     

Lime-enhanced carbon monoxide reduction of cuprous sulfide

Kinetic studies were conducted on the carbon monoxide reduction of cuprous sulfide powder in the presence of lime as a function of quantity of lime in the charge, CO flowrate, temperature, and time of reduction and particle size of the sulfide. Lime was found to enhance drastically the rate of reduction as well as reduce the COS emission into the off-gas to negligible levels. Both temperature and flowrate of the reducing gas were found to influence the reduction rate, and best results were obtained at 1273 K and at a CO flowrate of 3.33 cm³ s⁻¹. The overall reaction seems to be governed by the intrinsic kinetics of the Cu₂S-CO reaction. Kinetic analysis reveals the observance of the Valensi’s equation, indicating diffusional control through the product layer formed over reacting Cu₂S particles. The calculated experimental activation energy of 169.6 kJ/mole in the termperature range of 1123 to 1273 K is in good agreement with that reported in the literature for sulfur diffusion in copper. A critical comparison has been made of the lime-scavenged reduction of Cu₂S by different reagents, namely, hydrogen, carbon monoxide, and carbon.     

Kinetics of zinc oxide formation from zinc sulfide by reaction with lime in the presence of water vapor

A novel reaction scheme for transforming certain metal sulfides to the corresponding oxides has been developed. In this process, steam oxidizes the sulfide into the oxide, and the hydrogen sulfide produced reacts with lime to form calcium sulfide and regenerate steam. There is no net consumption or generation of gaseous species. Thus, the overall reaction can be carried out in a closed system as far as the gas phase is concerned. This eliminates the possibility of emitting hydrogen sulfide out of the reactor. Only certain metal sulfides are thermodynamically amenable to this treatment. In this paper, the reaction of ZnS to ZnO by this scheme is described, together with a detailed formulation of the rate equation for the overall reaction based on the kinetics of the component gas-solid reactions. Although the present work was done with CaO, other suitable oxides may be used in its place. A further potential application of this process is to the selective oxidation of certain sulfide(s) from complex sulfide ores as a treatment prior to the separation of minerals.     

Kinetics and Sulfur fixation in the reduction or oxidation of metal Sulfides mixed with lime

A number of metallurgical processes involve roasting of metal sulfides with oxygen or reduction of metal sulfides with hydrogen. In each case sulfur-bearing gases are emitted. Lime can be used to capture these sulfur-bearing gases. A model of this reaction occurring in a pellet made up of grains of metal sulfide and lime is presented. Specifically, a pellet made up of a mixture of metal sulfide and lime surrounded by a lime layer is considered. The computational investigation shows the distribution of lime necessary to achieve the maximum fixation of sulfur-bearing gases in the shortest time.     

Rate controlling processes for crack growth in hydrogen sulfide for an alsl 4340 steel

Parallel fracture mechanics and surface chemistry studies were carried out to develop further understanding of environment assisted subcritical crack growth in high strength steels. The kinetics of crack growth for an AISI 4340 steel (tempered at 477 K) in high purity hydrogen sulfide have been determined as a function of pressure at room temperature and as a function of temperature at hydrogen sulfide pressures of 0.133 and 2.66 kPa. The kinetics for the reactions of hydrogen sulfide with this steel and the extent of reactions were also determined. Two rate controlling processes have been identified. At the lower pressure, the rate of crack growth varies according to T^1/2 and is controlled by the rate of transport of hydrogen sulfide to the crack tip. At the higher pressure, crack growth is controlled by the rate of diffusion of hydrogen into the steel ahead of the crack tip and exhibits an apparent activation energy of about 5 kJ/mol. Embrittlement results from hydrogen that is produced by the reactions of hydrogen sulfide with the steel. These reactions are extremely rapid and are limited in extent, leading to the formation of one to two layers of “sulfide” on the fracture surfaces. The crack growth results are discussed in terms of measured reaction kinetics and published data on diffusion, and in relation to models for transport- and diffusion-controlled crack growth. Formerly with Lehigh University, Bethlehem, PA     

The carbothermal reduction of nickel sulfide in the presence of lime

The chemical feasibility of reducing nickel sulfide with carbon and lime, without emitting sulfur-containing gases, has been investigated. A reaction mixture of nickel sulfide particles intimately mixed with carbon and lime (used as a sulfur scavenger) was prepared. The thermodynamics of reacting this mixture in an inert atmosphere, producing carbon dioxide and carbon monoxide, was examined and found favorable. The rate of this reaction was measured in the temperature range 800 to 1124 °C ( 1073 to 1397 K). The effects of particle size and relative amounts of solid reactants were determined. The possibility of recovering the product nickel by carbonylation was also investigated. Formarly Graduate Student in Metallurgy at the University of Utah,     

A novel cyclic process using CaSO<Subscript>4</Subscript>/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part I. Feasibility and kinetics of the reduction of sulfur dioxide with calcium-sulfide pellets

Certain new sulfide-smelting processes and coal-gasification processes generate high-strength sulfur dioxide streams, for which a new process for converting sulfur dioxide to elemental sulfur needs to be developed because no process exists that is generally and economically applicable to the treatment of such streams. A thermodynamic and experimental investigation to develop a new process for converting sulfur dioxide to elemental sulfur by a cyclic process involving calcium sulfide and calcium sulfate without generating secondary pollutants was carried out. In this process, the starting raw material, calcium sulfate, is reduced by a suitable reducing agent, such as hydrogen, to produce calcium sulfide, which is used to reduce sulfur dioxide to elemental sulfur vapor and calcium sulfate. The latter is, in turn, reduced to regenerate calcium sulfide. In this Part I, detailed experimental results are presented on the kinetics of the reaction between sulfur dioxide and calcium-sulfide pellets, which produces elemental sulfur and calcium sulfate. The experiments were carried out at temperatures between 1023 and 1088 K and sulfur-dioxide partial pressures between 9 and 60 kPa by the use of a thermogravimetric analysis (TGA) technique. The rate of this reaction was demonstrated by the conversion of 40 pct calcium-sulfide pellets obtained from the hydrogen reduction of fresh calcium sulfate in 10 minutes at 1073 K under a sulfur-dioxide partial pressure of 43 kPa. The reactivity decreased somewhat during the first three cycles but remained largely unchanged thereafter up to the tenth cycle. This characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. A pore-blocking model was found to fit the reaction rate. The reaction is first order with respect to sulfur-dioxide partial pressure and has an activation energy of 101 to 134 kJ/mol (24 to 32 kcal/mol) for calcium-sulfide pellets reacted and regenerated several different times. Sulfur dioxide-containing streams from certain sources, such as the regenerator off-gas from an integrated-gasification, combined-cycle, desulfurization unit and new sulfide-smelting plants, contain much higher partial pressures of SO₂. In these cases, the rate of the first reaction is expected to be proportionally higher than in the test conditions reported in this article. The reduction kinetics of calcium-sulfate pellets with hydrogen gas is reported in the accompanying Part II.     

Lime-enhanced reduction of sulfide concentrates: A thermodynamic discussion

The need to control or eliminate sulfur dioxide emissions from sulfide smelters has increased the drive to develop new processes for the extraction of metal from sulfide minerals. One such process currently gaining interest is the lime-enhanced reduction of metal sulfides. This paper discusses the thermodynamic aspects relevant to chalcopyrite, chalcocite, and pyrrhotite reduction with hydrogen, carbon monoxide, or carbon in the presence of lime. The effects of temperature and gas composition on sulfide reduction are also discussed. ΔG°vs T diagrams for lime-enhanced sulfide reductions with hydrogen, carbon monoxide, and carbon are constructed and discussed together with some experimental results produced by the authors.     

A novel cyclic process using CaSO4/CaS pellets for converting sulfur dioxide to elemental sulfur without generating secondary pollutants: Part II. Hydrogen reduction of calcium-sulfate pellets to calcium sulfide

The reduction of calcium sulfate to produce calcium sulfide is a part of the cyclic process for converting sulfur dioxide to elemental sulfur that is described in Part I. The kinetics of the hydrogen reduction of nickel-catalyzed calcium-sulfate pellets were investigated using a thermogravimetric analysis (TGA) technique at reaction temperatures between 1023 and 1088 K and hydrogen partial pressures between 12.9 and 86.1 kPa. The reactivity of nickel-catalyzed calcium-sulfate pellets was demonstrated by the conversion of 70 pct fresh nickel-catalyzed calcium sulfate to calcium sulfide in 20 minutes at 1073 K under a hydrogen partial pressure of 86.1 kPa. Furthermore, the reactivity remained relatively intact after ten cycles of reactions and regenerations. This observed characteristic of the pellets is important because the solids must be reusable for repeated cycles to avoid generating secondary pollutants. The nucleation and growth rate expression was found to be useful in describing the kinetics of the reaction, which had an activation energy of about 167 kJ/mol (∼40 kcal/mol) in all reaction cycles except for the first regenerated samples that were lower at 146 kJ/mol (35 kcal/mol). The reaction order with respect to hydrogen partial pressure was 0.22 in all cycles with the exception of the first regenerated sample for which it was 0.37.     

Lime-enhanced hydrogen reduction of molybdenite

Kinetics of the direct hydrogen reduction of a high-grade (59 pct Mo) molybdenite (MoS₂) concentrate was investigated in the presence of lime as a function of the quantity of lime in the charge, hydrogen flow rate, temperature, and time of reduction. Lime was found to enhance tremendously the reduction rate of MoS₂ and drastically reduce H₂S emission into the off gas to negligible levels. Successful application of the lime-hydrogen reduction technique was found to depend on the employment of low hydrogen flow rate and moderate temperatures of reduction. In these laboratory studies, best results were obtained with a lime addition ≥ three times the theoretical requirement and at 1173 K in 3.6 ks employing a hydrogen flow rate of 3.33 cm³s^-1. The results were tested for the treatment of a low-grade (41 pct Mo) molybdenite concentrate. In this latter case, the procedure consisted of upgrading the concentrate by acid leaching (with dil HC1+HF) followed by lime-hydrogen reduction. The influence of quantity of acids, temperature, and time of leaching were investigated to optimize the conditions required for upgrading the MoS2 concentrate. The molybdenum powders obtained from the highgrade as well as upgraded molybdenite concentrates had 96 to 97 pct purity and could be further refined to 99.9 pct by electron-beam melting. Based on this lime-enhanced hydrogen reduction concept, a new ‘Leach-Reduction-Melting’ approach has been suggested as an alternative to the traditional methods of molybdenum extraction.     

Surface Effects in Sulfidation Reactions

Abstract

Pure iron and an Fe–41 wt% Ni alloy are reacted at temperatures in the range 793–1073 K with H₂–H₂S–N₂ atmospheres corresponding to equilibrium P _S2 levels from 6.5 × 10^?5 to 0.65 Pat The kinetics of iron sulfidation are intermediate in form to linear and parabolic rate laws. The instantaneous parabolic rate constant is found to increase with extent of reaction until a constant value is reached. For fixed equilibrium sulfur pressures, the instantaneous rate increases with hydrogen sulfide partial pressure; for fixed hydrogen sulfide partial pressure, the instantaneous rate decreases as the equilibrium sulfur pressure is increased. It is demonstrated that hydrogen sulfide is the reactant species. A Langmuir-Hinshelwood kinetic model based on the slow dissociation of adsorbed hydrogen sulfide accounts satisfactorily for the unusual gas-phase compositional effects, and also for the rate at which the reacting system approaches steady state. Similar effects are found for the Fe–41%Ni alloy, where nickel sulfide whisker formation results from localized catalysis of the hydrogen sulfide dissociation reaction.     

Crack paths and hydrogen-Afinssisted crack growth response in AlSi 4340 steel

A study of the correlation between crack paths and crack growth response was undertaken to define better the elemental processes involved in gaseous hydrogen embrittlement. AISI 4340 steel fractured under sustained load in hydrogen and in hydrogen sulfide over a range of temperatures and pressures, whose crack growth kinetics have been well characterized previously, was chosen for study. Fractographic results showed that crack growth followed predominantly along prior-austenite grain boundaries, with a small amount of quasi-cleavage, at low temperatures. At high temperatures, crack growth occurred primarily by microvoid coalescence. The fracture surface morphology, which is indicative of the micromechanisms for crack growth, was essentially the same for hydrogen and hydrogen sulfide. Changes in fracture morphology,i.e., crack paths, corresponded to changes in crack growth kinetics, both of which depended on pressure and temperature. There was no evidence for crack nucleation in advance of the main crack, and this suggests that the fracture process zone is located within one prior-austenite grain diameter from the crack tip. The experimental results indicate that microstructure plays an important role in determining crack growth response. The prior-austenite grain boundaries are seen to be most susceptible to hydrogen embrittlement, followed by the (110)_α’ and (112)_α’ cleavage planes. The martensite matrix, on the other hand, is relatively immune. The observed changes in crack growth rate with temperature and pressure in the higher temperature region are explained in terms of the partitioning of hydrogen into the different microstructural elements and the consequent changes in the micromechanisms for fracture. Leave from the Department of Materials Science, Shanghai Jaio Tong University, Shanghai, People’s Republic of China. Formerly Research Associate, Department of Mechanical Engineering and Mechanics.     

Kinetics of cobalt sulfide reduction in the presence of calcium oxide

Kinetic measurements have been made on the hydrogen reduction of solid cobalt sulfide in the presence of calcium oxide. The cobalt metal yield was compared with that of the direct reduction reaction over the temperature range 600 to 800°C at various hydrogen flow rates, and calcium oxde to cobalt sulfide mixing ratios. It was found that the presence of calcium oxide caused a sharp increase in the reaction rate—for example a 15 fold increase in conversion was achieved at 700°C after 24 min of reaction. Low hydrogen flow rates were found to be desirable, and an optimum mixing ratio of 3.0 established.     

Influence of Wastewater Constituents on Hydrogen Sulfide Emission in Sewer Networks

Transport of wastewater in sewer networks causes potential problems associated with hydrogen sulfide in regard to odor nuisance, health risk, and microbially induced corrosion. To what extent these problems occur depends not only on the rate of sulfide formation but also on the rate of hydrogen sulfide emission into the sewer atmosphere. To gain understanding of the influence of wastewater constituents on the emission process, a number of batch experiments were conducted on domestic wastewater collected from sewer networks. The emission rate of hydrogen sulfide in the wastewater investigated was found to be approximately 60% of that in de-ionized water in terms of the overall mass-transfer coefficient, resulting in a correction factor (alpha) of 0.6. The alpha factor did not change significantly within the turbulence range studied (Froude numbers of 0.04–0.23). The Henry’s law constant for hydrogen sulfide in wastewater was observed to be close to that in de-ionized water, reflecting a correction factor (beta) of 1.0. By taking these results into account, modeling aspects of hydrogen sulfide emission in sewer networks are presented in this paper.     

The influence of the ferrite to austenite transformation on the formation of sulfidesx

Steel solidifies either by a primary precipitation of δ-Fe or by a primary precipitation of γ-Fe. In the former case the steel can either go through a peritectic reaction or a solid state transformation to form y-Fe during cooling. The influence of the rate of solidification and/or the transformation sequence on the sulfide precipitation in steels was studied in unidirectionally solidified Fe-Ni-S and Fe-Ni-Mn-S alloys. Nickel was used to govern the solidification sequence. It was shown that the solid state transformation could give rise to iron sulfide films according to a metatectic reaction. It was also shown that the peritectic reaction favored the formation of iron sulfide films. These films solidified at a very low temperature. During cooling the films contracted and small sulfide particles were formed. If the alloy contained manganese the composition of the films was changed during cooling from nearly pure iron sulfide to nearly pure manganese sulfide due to diffusion of manganese from the matrix.     

Hydrogen reduction kinetics of nickel sulfide in the presence of calcium oxide

Recovery of pure nickel from nickel sulfide (Ni₃S₂) was studied by following to completion the hydrogen reduction reaction in the presence of calcium oxide. The effects of reaction temperature, molar ratio of calcium oxide to nickel sulfide, bed depth, and particle size of the nickel sulfide powder on the reaction were experimentally investigated. A simple empirical integrated rate equation describing the relationship among these variables over the temperature range 773 to 973 K was derived. The activation energy for the scavenged reaction was found to be 101.9 kJ from the experimental data. Over the range of experimental conditions, both globular and fibrous forms of metallic nickel were observed.     

Kinetics of Lime-Enhanced Hydrogen Reduction of Solid Nickel Sulphide

Investigations have been carried out on the hydrogen reduction of solid nickel sulphide (β-NI₃S₂) in the presence of lime. The effects of the charge composition, temperature (500-700°C). hydrogen flow rate, time of reduction and particle size of the sulphide have been studied. Lime was found to tremendously enhance the reduction process and drastically stifle H₂S emission into the off-gas. Temperature as well as hydrogen flow rate were found to affect the reduction process and best results were achieved (in static bed experiments) with 200% CaO addition at 630°C in 2 hr employing a hydrogen flow rate of 0.2 l/min. Thermodynamic considerations and several experimental findings indicate that the progress of the Ni₃S₂-CaO-H₂ reaction is governed by the intrinsic kinetics of the Ni₃S₂-H₂ reaction. Kinetic analysis reveals the observance of Jander's linear rate equation indicative of phase boundary control at the sulphide/gas interface. Scanning electron microscopic studies on the reduced nickel sulphide pellets show that like in solid state transformations, discontinuous precipitation (cellular morphology) is exhibited.     

A kinetic study on the pressure leaching of sphalerite

The dissolution of sphalerite (ZnS) in sulfuric acid solution under oxygen pressure was investigated. Effects of temperature, percent solids, agitation, sample size, oxygen partial pressure and foreign ions were evaluated. The effect of hydrogen pretreatment on sphalerite leaching rate was also examined. Leaching of sphalerite at 90°C and 150 psi oxygen pressure was found to occur at a constant rate. This rate was determined from the experimental data observed under the different leaching conditions mentioned above. The constant leaching rate was attributed to the chemical reaction occurring on the surface of the flat-plate type sphalerite sample. The rate-controlling step of the reaction was determined to be the oxidation of hydrogen sulfide to elemental sulfur. Oxidation of hydrogen sulfide was studied through the addition of iron and through the observation of the change in iron concentration during leaching. The oxidation was concluded to be by reaction with ferric ion rather than by direct oxygen oxidation. Leaching tests run with samples pretreated with hydrogen do not show any increase in the rate of zinc extraction. M. T. HEPWORTH, formerly with University of Denver.     

Intrinsic kinetics of the reaction between zinc sulfide and water vapor

The reaction between zinc sulfide and water vapor is a component reaction in a new reaction scheme recently developed to transform zinc sulfide to zinc oxide through the use of lime and water vapor. The intrinsic kinetics of this reaction for ultrafinely ground (<1 μm) ZnS particles was determined by carrying out measurements in the absence of heat- and mass-transfer effects. The reaction products were identified to be ZnO and H₂S. The kinetics of the reaction can be represented by and 3.94<C _H2_O <9.84 mol/m³ withn=1.28 andk ₁=45.3 exp(−14600/T) m³·mol⁻¹·s⁻¹, whereX _B is the fractional conversion. DAESOO KIM, formerly Granduate Student at the University of Utah