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By M. J. Adam

The U.S. Bureau of Mines is investigating the partitioning of selected complex minerals into simple phases using sulfidation reactions. Successful partitioning of complex mineralogy to simple phases may afford an opportunity to improve selective extraction of mineral constituents of economic value. The research has shown that complex minerals, such as chalcopyrite (CuFeS2) and pentlandite [(Fe,Ni)9Se]' may be partitioned to the simpler phases covellite (CuS) plus pyrite (FeS2) and vaesite (NiS2) plus pyrite (FeS2), respectively. Demonstrations of these reactions were verified through long-react ion-time (24 h or more) experiments, but basic rate investigations and modeling were not included in the previous research. This report describes research aimed at determining the rate at which the complex mineral CuFeS2 converts to the simple sulfides CuS plus FeS2. Small samples of CuFeS2 were blended with elemental S prior to thermal treating under an He atmosphere for time periods up to 4 h. Products from each treatment period were characterized using metallography, chemical analysis, X-ray diffraction (XRD), and scanning electron microscopy (SEM). Results of the investigation revealed a rapid conversion of CuFeS2 to CuS plus FeS2 early in thermal treatment periods. As the reaction occurred, a CuS rimming of particles was observed which separated the reacting species (CuFeS2 and S) and caused a considerable decrease in transformation rate.

Jan 1, 1991

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander model for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2, MgO-SiO2, FeO-CaO-SiO2, FeO-FeO1.5-CuOo.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-MgO and FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte (L s/m as), and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5-CaO-MgO slag and liquid copper (L s/Cu as) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte-metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for prediction in multi-component slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes.

Jan 1, 2003

By George Kazonich

The high costs and environmental problems associated with making iron and steel in the United States is driving the development of new technologies to replace the blast furnace. A prototype reactor incorporating rocket technology was designed and built. This rapid rate reactor was operated successfully and consistently made iron metal. Minus 325-mesh magnetite particles could be reduced to iron metal in less than 50 ms in a high temperature flow through reactor. Iron product was recovered inside the reactor and in a downstream cyclonic separator. The results of typical operation and how parametric changes affected the reduction of iron ore concentrates are discussed.

Jan 1, 1993

Achieving continued economic growth with social equity within the natural limits of the Earth's 'eco-systems is the major issue facing the world today. The material and energy needs of the world cannot be met with the current ways of addressing this issue. The need for metals, an important class of materials, will continue into the future because their unique properties make substitution by other materials impossible in many applications and this need will continue to be met from primary metal production and recycling. However, the recycling rate will increase and the usage pattern of metals will change to reflect the environmental impact of their production and use. Pyrometallurgy has an important role in meeting the metal needs of the future since some metals can only be produced pyrometallurgically; the energy required to produce some metals pyrometallurgically is significantly less than by other methods; most metals are most efficiently recycled pyrometallurgically; and the release of harmful and toxic elements into the biosphere can sometimes best be controlled through pyrometallurgical processing. The development of strategies for pyrometallurgical processing for the future lies in the recognition that sustainable development calls for large step improvements in value delivered per unit of environmental impact over the entire supply chain. Pyrometallurgists can respond to this challenge by contributing to reducing the environmental impact of meeting metal needs using three broad strategies: "end-of-pipe" approaches to convert emissions into benign materials for storage or disposal; flowsheet redesign to limit or eliminate emission production; and improved recycling technologies. A number of examples are discussed to illustrate how the sustainability driver is already influencing the technological development of pyrometallurgical processes, and how these will develop further as the sustainability driver strengthens.

Jan 1, 2003

By Christopher B. Vierrether

Reflected light microscopy, scanning electron microscopy, and electron microprobe analysis have been used to determine the mineralogy, phase percentages, grain sizes, textures, and partitioning of cobalt and nickel in two cobalt-nickel rich mattes. These mattes were prepared by submerged bath smelting from a flotation cobalt-nickel concentrate containing 4.8% cobalt and 5.1% nickel. The concentrate was derived from lead-zinc-copper ores of the Viburnum Trend, southeast Missouri. Eleven discrete phases have been distinguished in the matte samples, three of which contain significant cobalt and nickel. The phases are cobaltpentlandite ((Co,Ni,Fe)9S8), cobalt-bearing marmatite ((Co,Fe,Zn)S), shandite (Ni3Pb2S2), bornite (Cu5FeS4), galena (PbS), magnetite (Fe3O4), pyrrhotite ((Co,Ni,Cu,Fe)1_xS), chalcocite (Cu2S), CuPbS phase, metallic copper, and metallic silver. Cobaltpentlandite and cobalt-bearing marmatite- occur in coarse grains (50 µm) that would separate readily during grinding, but shandite contains small (5 - 10um), abundant inclusions of pyrrhotite and bornite.. Some mineralogical variations between the two matte samples were due to differing degrees of oxidation during smelting,

Jan 1, 1988

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of873 OK is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composItion formed under roasting of concentrates with particle sizes less than 0.02 J..lm (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CufeSz) each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forehamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By William Petrul

Image analysis studies were performed on mill products from laboratory flotation tests of the Zn-Pb ore from the Faro deposit in Yukon, Canada, to determine mineral liberations at specific grinds and to predict recoveries at optimum flotation conditions. The minimum and optimum grinds for liberating sphalerite and galena were predicted from size analysis data for the minerals in large ore pieces, and determined by image analysis studies of the mill products. The determined optimum grinds are about 2 Tyler mesh sizes larger than predicted because sane of the fine grained sphalerite and galena occurs in interstices between coarser grained pyrite and is liberated when the pyrite grains are broken apart. Materials balance calculations were performed on the analyzed values for the liberated and unliberated sphalerite and galenaa to determine their distributions in the mill products. The laboratory flotation tests recovered 74% of the sphalerite and 83% of the galena in Zn and Pb concentrates respectively. The mineral evaluation study indicates that the optimum recovery for sphalerite and galena are 85 and 83% respectively. The company is currently recovering 80% 'of the sphalerite and 82% of the galena.

Jan 1, 1989

By John R. Goode

The fist part of this paper comprises a general discussion on refractory gold ores and their mineralogy. Processing methods now in use are reviewed and test procedures for the important methods are discussed. Factors determining the selection of a process are outlined. The paper includes a survey of production plants using pressure oxidation, roasting and biological oxidation to process refractory ore. The status of processes under development is briefly reviewed.

Jan 1, 1993

By D. McConchie

Management of caustic red mud wastes at the QAL bauxite refinery uses an innovative approach . involving neutralising the red mud with seawater; solids settle in a Red Mud Dam and residual water (pH = 8.6) is discharged to a tidal inlet. A survey of 18 trace elements in sediment, water, mangroves and molluscs, and an ecological survey of benthic fauna in the inlet, and at near-pristine control sites, revealed no significant trends that were linked to the discharge, except for the concentration of Al which was slightly elevated within 100m of the outfall. Trace element concentrations in water samples were close to, or below, world average seawater values and oysters collected near the outfall were acceptable for human consumption. The impact of discharges is minimised by a high tidal range, >60% flushing of the inlet in each tidal cycle, and the very high trace element binding capacity of sediment in the dam (> 100meq/ 100g dry mud).

Jan 1, 1996

By J. M. Demarthe

MINEMET RECHERCHE (IMETAL Group, formerly Le Nickel-Penarroya-Mokta) has studied on a laboratory scale and patented a new process to recover metal values -copper- from sulphide ores and concentrates. It combines a cupric leaching, solvent extraction and copper sulphate electrowinning according to the main following steps - A direct and selective leaching of copper sulphide ores or concentrates at atmospheric pressure with cupric chloride to form cuprous and ferrous chlorides and elemental sulphur. Pyrite remains in the sulphur residue. - The leach solution is separated into two parts -In the first one, air is injected to precipitate iron as goethite. The oxidation step can be easily realized at atmospheric pressure by maintaining an excess of cuprous and-ferrous chlorides in the liquor. Copper is extracted from the second part as cupric ion by an LIX reagent. Direct injection or air in the mixing chamber maintains good extraction conditions, so that only one mixer settler is required. - Iron, in the form of ferrous ion, is not coextracted. - Copper is stripped from the organic phase, transferred into a sulfuric phase and sent to sulphate electrowinning cells, which are now conventional in copper metallurgy. - Only electricity and air are required. After a feasibility study, the next step will be to develop it on a pilot and commercial scale.

Jan 1, 1976

By E. vanHuyssteen

A method of establishing the relationship between the mineralogy of a sinter and its subsequent processing behaviour in a lead blast furnace is demonstrated. It involves: 1) analyzing the Zn-spinels, hardystonite, larsenite, Pb-silicates, Pb-arsenates, Pb-(Ca)-sulphates and other femtes with an electron microprobe; 2) determining the extent of elemental substitutions in various mineral structures; 3) establishing a sequence in which the various phases formed during sintering. In this manner the relationship between the bulk chemistry of a sinter formulation and the speciation of elements into various phases in the sinter can be established. Specifically, the-substitution of Mg for Zn in hardystonite significantly influences sinter production. Mg substitution releases Zn into the surrounding matrix. This Zn reacts with the Pb-silicate to form larsenite thereby reducing the amount of Pb-silicate available for anhydrite digestion. Excessive amounts of residual anhydrite thus result if the sinter formulation is based solely on the CaO/Si& ratio.

Jan 1, 1993

By Liu bing-guo, Peng Jin-hui, Guo Sheng-hui, Kong dong-cheng, Hu jin-ming, Zhang Li-bo

The novel technology of calcination to prepare triuranium octaoxide（U3O8）from ammonium uranyl carbonate in microwave fields was investigated on the basis of the temperature rising characteristics of ammonium uranyl carbonate, triuranium octaoxide (U3O8), and their mixture. The result of experiments show that ammonium uranyl carbonate had weak capability to absorb microwave energy, while triuranium octaoxide has the very strong capability to absorb microwave energy and the sample temperature increased rapidly with an increase mixture ratio of triuranium octaoxide. The optimal calcination conditions were as follows: microwave power 700 W, calcination time 10 min and 60 g in this experiments range, respectively. Under these conditions the value of total uranium and 4 U of triuranium octaoxide was 84.28% and 31.02%, respectively. It is feasible to prepare triuranium octaoxide by calcination from ammonium uranyl carbonate, which mixed with small amounts of triuranium octaoxide under microwave fields.

Jan 1, 2015

By Frame Ritzert, Dennis Keller, Vijay Vasudevan, David Arenas

"An investigation was conducted to describe topologically close packed (TCP) phase instability as' a function of composition in the advanced ·Ni-base superalloy Rene N6. TCP phases are detrimental to overfill high-temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements. Thirty-four variations of polycrystalline .Rene N6 determined from a design-of-experiments approach were cast and homogenized at 13 l5°C for 80 hours followed by exposure at 1093°C for 400 hours to promote TCP formation. The alloys had the following composition ranges in atomic percent: cobalt 10.61 to 16.73, Mo 0.32 to 1.34%, W 1.85 to 2.52%, Re 1.80 to 2.11%, Ta 2.36 to 3.02%, Al 11.90 to 14.75%, and Cr 3.57 to 6.23%. Physical and chemical characteristics of all microstructures obtained were described using various analytical techniques. From these observations, a mathematical description of TCP occurrence (s and P phase) was generated for polycrystalline Rene N6.IntroductionNi-base superalloy single crystals represent the state-of-the-art for turbine engine airfoil application as they offer the best balance of properties to allow for the high operating temperatures required: for efficient engine operation.1 Current trends in alloy design take advantage of improved creep rupture strength with the addition .of higher levels of refractory elements. 2 In .particular, the addition of significantly higher levels of Re in third generation superalloys is key for both microstructural stability and creep rupture strength. 3 While the presence of the refractories is thought to provide strength benefits from solid solution hardening, a tendency for alloy instability in the form of topologically-close-packed (TCP) phases or secondary reaction· zone (SRZ) ·phenomena accompanies the high refractory content. 3 The formation of these phases in sufficient amount is detrimental to the overall high temperature performance of Ni-base superalloys because of their brittle nature and because they deplete the Ni-rich matrix of potent solid solution strengthening elements.4 The tendency for a particular composition to form TCP may not be immediately known since the precipitation of TCP phases in Ni-base superalloys is nucleation controlled, thereby requiring long times at elevated temperatures to precipitate. 5 They preferentially nucleate along the octahedral planes of the Ni-base superalloys, usually in areas of refractory metal enrichment at grain boundaries or inside dendrites.5-6 In Rene N6, two closely related TCP phases, a and P, have been observed.2"

Jan 1, 1998

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By Salustio s. Guzman

The standard .free energies of formation of tin chlorides were estimated with reviewed and estimated basic thermodynamic data, and measured reversible potentials for the disproportionation of tin dichloride into metallic tin and tin tetrachloride. Values for cºp, Sº, Hº?-Hº 298, -(Gº - Hº298) /T,.Hºf, Gºf, and log Kp are given in tabular form, these estimations are compared with estimations reported in the literature.

Jan 1, 1985

By H. Y. Sohn, S. PalDey

"A new chemical synthesis process for the preparation of intermetallic compounds has been developed. It involves the vapor-phase reduction of mixtures of constituent metal chlorides by magnesium vapor to produce intermetallic compounds in the form of fine powder. The advantages of the process include (a) the use of inexpensive raw materials, (b) low reaction temperatures, and (c) products in the form of fine particles. Titanium and nickel aluminides were prepared by this method. The effect of AlCl/TiCl3 partial pressure ratio on the formation of different titanium aluminides was studied. A two-phase mixture containing 80 mol % of TiAl and 20 mol % of TiA13 formed at an AlC13/TiC13 ratio of 10. The amount of TiA13 was maximized to 72 mol% at an AlC13/TiC13 ratio of 16. The maximum conversion of the limiting chloride TiCl3 was 94 % . In the case of nickel aluminides, NiAI, NiAl3, and Ni2Al3 were formed by reducing mixtures of NiC12 and A1Cl3 vapors. The effect of the partial pressure ratios AlCl3/NiC12 and Mg/NiC12 on the formation of nickel aluminides was studied. The maximum content of NiAl obtained was 98 mol % . At the AlC13/NiC12 ratio of 19, a two-phase mixture of 17 mol% of NiAl and 83 mol% of NiA13 was produced. The product particles were very fine in the size range of 0.05 to 0.2 µm.A. IntroductionIntermetallic compounds are attracting much attention [1]. Titanium and nickel aluminides have attracted a great deal of attention from the aerospace as well as automobile industries because of their potential for high-temperature application (e.g., low density, good oxidation resistance, and high-temperature strength retention [2, 3]). Gamma TiAl and two-phase (TiAl and Ti3Al) alloys [4] are used for gas turbine engine rotational components as well as automobile exhaust valves. TiAl3 is one of the most extensively investigated aluminum-rich intermetallics. Nickel aluminides are attractive because of their low densities, relatively high melting point and good high-temperature strength properties. For example, Ni3Al shows increasing rather than decreasing yield strength with increasing temperature [5]."

Jan 1, 1998

By Roy J. M. van Lier

In industrial aqueous solutions, germanium generally occurs in trace amounts amid high concentrations of other metals, such as zinc, copper and iron. Separation of germanium from these metals as well as its isolation from gallium and indium pose a real challenge to the hydrometallurgist. After a brief discussion of the aqueous chemistry of germanium, this paper reviews the flowsheet of the Apex Mine in Utah. The Apex property was the only mine in the world to be operated primarily for production of gallium and germanium, but apparently closed due to great operating difficulties. Several process variants proposed for the treatment of the Apex ore, including bioleaching methods, are addressed. Following a more general description of the behavior of germanium in hydrometallurgical zinc processing streams, available technology for its recovery from aqueous solutions is summarized. Precipitation, solvent extraction, ion exchange, electrowinning, ion flotation and liquid-membrane separation are all outlined in terms of the aqueous chemistry of germanium. Finally, the production of high purity germanium dioxide and metal is briefly discussed

Jan 1, 1995

By Y. A. Chang

The objective of the present study is to evaluate and compile the relevant phase equilibria and thermodynamic data reported in the literature for the ternary system Cu-Fe-S. It is hoped that the results presented here will be useful to practising engineers and scientists in industry who are attempting to improve continually the existing processes of copper extraction and refining. At the same time, the present work will undoubtedly reveal the lack of some basic data which are important for the improvement of our existing extractive processes. Lastly, this work will also show that the development of theoretical models for the alloy phases in the Cu-Fe-S system is essential before complete consistency between the phase equilibria and the thermodynamic data can be achieved.

Jan 1, 1976

By J. E. Dutrizac

A mineralogical study of a weak acid leach residue from the Clarksville zinc plant of Savage Zinc Inc. was carried out. The study focused on Pb and Cd as these elements most significantly impact on the environmentally acceptable disposal of the residue. The residue consists of major amounts of bassanite, zinc ferrite and various Zn-Pb-Fe-Cd silicate species. Also present are lesser quantities of PbSO4, sphalerite, Fe2O3 quartz, Mn-Pb-Fe oxides, SrS04, (Pb,Sr)SO4 iron gel-silica gel, jarosite and Ti oxide. The principal Cd carriers are the zinc ferrite, which contains up to 9.00% Cd and likely accounts for -45% of the total Cd content of the residue, and the various silicate species which contain up to 6.97% Cd and account for about 45 % of the total Cd. The sphalerite is a minor Cd carrier containing an average of 0.35 % Cd and accounting for -5 % of the total Cd; the other carriers contribute only trace amounts to the total Cd content. The major Pb carriers are PbS04, Pb-bearing silicates and Mn-Pb-Fe oxides. Minor proportions of the total 1.09% Pb content of the residue are carried by SrS04 and (pb,Sr)S04' Trace Ph carriers include the iron gel-silica gel, Fe-Zn-AI oxide and bassanite. The residue after the toxicity characteristic leaching procedure (TCLP) is mineralogically very similar to the initial weak acid leach residue; the amounts of calcium sulphate are approximately the same in the two products. The principal Cd and Pb carriers are also the same as those noted in the initial residue, except that some dissolution and reprecipitation of Pb-Sr sulphate takes place. That the residue fails the TCLP test is likely a consequence of the superficial dissolution of Pb and Cd from species such as PbS04 or Zn-Pb-Fe-Cd silicate.

Jan 1, 1995