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By Jeffrey W. Braithwaite

The laboratory characterization of the oxidation of chalcopyrite under conditions of deep solution mining is presented in this paper. A salient feature of this system is the pH buffering effect resulting from simultaneous acid producing and acid consuming oxidation reactions. The solution chemistry and related sulfur partitioning of the oxidation reactions are detailed. The contribution of temperature, acid concentration, oxygen pressure, particle size, and solution additions to the kinetics of copper extraction are presented. A mixed kinetic model was used to describe the kinetics of oxidation.

Jan 1, 1976

By I. S. Blair

The Mufulira smelter (1, 2,' 3, 4,) is one of three smelters situated on the Zambian Copperbelt to treat concentrates and other intermediate products produced in the area. Two mining companies, Roan Consolidated Mines Limited (RCM) and Nchanga Consolidated Copper Mines Limited (NCCM) each have 51% Zambia Government participation. RCM operates two smelters, one at its Mufulira Division and the other at its Luanshya Dl vision. NCCM operates one smelter at its Rokana Division (5). The Mufulira smelter was commissioned in 1937 with two reverberatory furnaces and four converters. The final product, blister copper, was cast from a holding furnace. In 1952 two anode furnaces and a common casting wheel were installed to feed a new and adjacent electrolytic refinery. In 1956 the smelter was extended to accommodate increasing production from the new Chibuluma mine and expansion at Mufulira mine. A third reverberatory furnace, a fifth converter and duplicate anode processing and casting facility were added. The Copperbelt smelters suffered a loss of production potential when higher ash content coals were used in reverberatory smelting furnaces from 1966 onwards. This, and the planned production increases from Mufulira and other RCM mines, indicated a smelting shortfall of 55,000 tonnes of copper a year in the combined capacity of the RCM smelters.

Jan 1, 1976

By L. W. Beckstead

The use of acid ferric sulfate solution as a lixiviant for chalcopyrite concentrates has been of little interest from a practical standpoint due to the formation of a tenacious layer of elemental sulfur which severely impedes the reaction progress. CuFeS2 + 4Fe+3 ?Cu+2 + 5Fe+2 +2s° For example, an acid ferric sulfate leach of chalcopyrite concentrate results in only 12% copper extraction in a three hour leach at 93°C. Experimental results suggest that particle size is the only controllable variable which has a significant effect on the rate of acid ferric sulfate leaching at ambient pressure. Size reduction of the concentrate prior to leaching was exam¬ined using various methods of grinding. Of the grinding methods considered, attrition grinding was found to be the most effective. Leaching of an attritor-ground product (median particle size 0.5 microns) resulted in approximately 90% copper extraction in a three hour leach at 93°C. Energy measurements suggest that the costs associated with attrition mill¬ing are not unreasonable. Evidence indicates that "activation" or stored strain energy is not responsibile for the enhanced reaction kinetics of the finely ground concentrate, but rather the experimental results can be explained simply in terms of the increased surface area due to size reduction. Leaching reaction mech¬anisms operative in the acid ferric sulfate system are discussed and the application of ultra-fine grinding technology to other systems is considered.

Jan 1, 1976

By Roger Altman

The solubility of copper in primary spinel crystals encountered in reverberatory slag samples has been determined by electron microprobe analysis. These spinels, which ranged in composition from 22% A12O3 to pure magnetite, contained small quantities of dissolved copper (0-0.4%). Based on literature data it was estimated that the solubility limit of copper in solid magnetite is no greater than about 1% at 1200°C and about 2% at 1250°C. However, it was found that practically every spinel crystal examined contained significant amounts of matte inclusions. Further examination of converter slag revealed large quantities of irregularly shaped precipitated magnetite crystals which contained a large proportion of copper inclusions. Additional experimentation showed that the total copper content in reverberatory slag samples was greater than the sum of the estimated en- trained plus dissolved matte in the slag. This difference is believed to be significant and is due to the presence of matte inclusions in the spinel crystals. In the present reverberatory slag samples these inclusions accounted for about 1/2 of the amount of sulfide directly entrained in the slag.

Jan 1, 1976

By Antonio Luraschi

The constituents iron, oxygen, silica and cop- per are of principal interest in slags utilized in pyrornetallurgical processes for producing copper. Accordingly, phase relationships in the.Cu-Fe-0-SiO2 system are important when one considers the physico- chemical behavior of slags. These phase relation- ships for the quaternary and constituent ternary systems are developed from available information. Isothermal composition and composition-oxygen potential diagrams, and oxygen potential-temperature diagrams are utilized to describe the' important relationships.

Jan 1, 1976

By B. Yawney

A copper-nickel sulfide concentrate was leached in water at about 2000C under oxygen pressures of about 0.35 MPa. Oxidation of sulfide to sulfate was virtually complete in about 30 minutes, resulting in greater than 95% copper and 98% nickel extractions. Leaching temperature was shown to be the most important factor affecting metal extractions. Measured rates of oxygen consumption were used to develop batch kinetic data. Mini-plant continuous pressure leaching tests agreed with batch leach results. A proposed overall flowsheet is briefly examined.

Jan 1, 1976

By P .. R. Ammann

A two-stage pyrometallurgical process has been developed for the recovery of copper (and other non-ferrous metals) from copper smelter slags. All types of slags, including highly oxidized, converter-type slags, are cleaned in an electric furnace which employs mechanical mixers to promote magnetite reduction and copper extraction at high rates. In a 10-ton pilot furnace, it has been demonstrated that slags can be cleaned to 0.2-0.3 per cent copper with economically acceptable usage of raw materials and energy; copper is recovered as a high-grade matte. Pilot plant data have been scaled up to a commercial furnace and engineering designs have been made for a furnace to treat 60 tons per hour of slag from a Noranda Reactor and the associated converters. Plans are being formulated for the construction of a prototype slag cleaning furnace.

Jan 1, 1976

By C. Palacios

The Plant, which was started up in April 1970, was originally designed for a capacity of 40.000 ton of cathodes per annum, using 12 sections, containing 408 cells. Since then the addition of another 8 sections containing 280 cells and using the Reverse Current System has made possible the increased output of 109.000 ton. The quality of the cathodes produced is excellent. The extension of the Electrolytic Refinery, by the introduction of the Reverse Current System, has been a great success and no problem has arisen in the new equipment or in the modifications carried out in the plant. The operation of the plant has improved due to better control procedures.

Jan 1, 1976

The merging of flash smelting with spray converting in one single furnace is proposed as a continuous copper making process. The proposed process is expected to produce blister copper, clean slag and gas with high sulfur dioxide concentration. Some high grade matte is an intermediate product recycled within the proposed furnace, spray-atomized and converted. The thermodynamic equilibria of the simultaneous oxidations which take place during copper smelting and converting are discussed in order to establish the gradient of oxygen potential along the furnace required for smooth operation. The proposed process is a dynamic system designed to reach equilibrium only close to the slag skimming end of the furnace. The process feasibility is based on the predesigned significant difference between the rates of converting reactions in a finely dispersed system and the rates of deconverting reactions between immiscible liquid phases of restricted interface area. The converting of small stationary droplets of matte, in a silica saturated system, was studied in the laboratory for extremely short oxidation times (10 to 120 seconds). These experiments led to some interesting observations on reaction mechanisms and kinetic trends. The droplet size and the matte grade affected very strongly the oxidation rate and the proportion of the different products obtained.

Jan 1, 1976

By H. Ikeda

The new Onahama N0.3 tankhouse was put into operation early in 1973. This new tankhouse, which has a capacity of 90,000 metric ton cathode per year, is distinct in many important respects from conventional tankhouses. The major objectives in design were to simplify the construction and ope- ration for reduction of the costs for labor, interest and depreciation and also to reduce the copper inventory in the tankhouse by the use of conti- nuously-cast anodes. As a result, the investment cost was decreased by approximately 30% and the inventory cost by approximately 600, while the production per unit area of the tankhouse was increased by 80 - 100% as compared with the existing conventional-type tankhouses at Onahama. By abolition of cell inspection and maximum mechanization of materials handling the labor cost was decreased by as much as 80%. On the other hand, the new system has some disadvantages, such as increase in anode scrap ratio and increased cost of anode casting. The No.3 tankhouse system is, however, still at its starting point, while conventional methods have been continuously improved over the past years of operation. It is expected that the innovational ideas behind this system will serve as bases for a more efficient electrolytic refining system in future.

Jan 1, 1976

By J. J. Kim

In a study of buildup in a green-feed reverberatory furnace, it was determined that approximately half of the crucible area has a moderate buildup of 25 in. or less, and that the area extending 45 f t from the burner end of the furnace has only a slight buildup. The false bottom, averaging 6 in. in thickness, was found to cover the entire crucible area. The stratification of Cr2O3, A12O3, and SiO2 occurs throughout the slag layer; this phenomenon is the principal reason for the formation of the false bottom in the green-feed reverberatory furnace. The false bottom is caused primarily by the settling of FeO*(A1,Cr),03 aggregates, which are derived mainly from returned converter slag. The false bottom can be transformed to a solid permanent buildup in the furnace, particularly when the matte is completely withdrawn. From the material balance of Al2O3 and Cr2O3 around the furnace, It is estimated that the average rate of aluminum chromite accumulation is approximately 0.3 ton per day or less.

Jan 1, 1976

By A. J. van der Zeeuw

The use of SME 529 in the extraction of copper from acidic liquors and of copper and nickel from ammoniacal solutions, is illustrated with results of laboratory and bench scale mixer/settler experiments. Special features of SME 529 are its high loading capacity and the ability to keep the complexes dissolved in the organic phase up to quite high concentrations.

Jan 1, 1976

By John C. Carpenter

Solvent extraction is used to selectively recover copper from iron containing sulphate solutions. As chloride ions, which form series of complexes with transition metals, are now being used for leaching. Little is known of the effects of these ions, on solvent extraction behavior. It has been shown that commercial extractants of the L1X and Kelex series extract copper from chloride media: (1) at a lower pH than from sulphate solutions, (2) to similar loadings, and (3) except for L1X 63, without transferring chloride to the organic phase. A process for selective extraction of copper from chloride solutions should thus be compatible with standard stripping and electrowinning practice. Of several diluents, differing in aromaticity, kerosene gave enhanced extraction only with L1X reagents. A change in operating temperature had little effect on equilibrium metal distribution. All the extractants examined gave adequate separation of copper from iron. L1X 63 was found to extract chloro-complexes of copper and of iron and thus transfer chloride to the organic solution. Consequently this extractant and its mixtures are not preferred for use with chloride leaching systems.

Jan 1, 1976

By P. Blazy

A hydrometallurgical procedure for the recovery of metal from ore, particularly of copper from sulphide materials is described. In the course of this procedure, the raw material is first of all submitted to the action of an appropriate reducing system and then treated with a ferric salt solution which brings about the selective solubilisation of the elements to be recovered with respect to those constituting the pyritic phase. This procedure is investigated using two ore samples proceeding from massive sulphide deposits, presenting different chemical and mine- ralogical characteristics. The results of this investigation are compared with those obtained by a classical process employing a ferric salt solution. It appears that one solubilisation of copper takes place under particularly advantageous conditions when our procedure is used. The principal parameters affecting leaching of zinc, lead and copper are examined. The selectivity of this treatment is evaluated by following the change during the treatment in the pyritic phase.

Jan 1, 1976

By Sepp Härkki

The energy crisis in Finland after World War I1 together with a sharp rise in the price of energy caused Outokumpu Oy to consider replacing the electric furnace smelting of copper concentrates by some other method. The flash smelting method developed under these circumstances offered a considerable saving of fuel through the utilization of the reaction heat of sulphides and yielded a high recovery of sulphur in the form of acid. The pilot plant testing of the new process was carried out in the years 1947 - 1948. The process was adopted for the smelting of copper concentrates (1) (2) (3) on a commercial scale in 1949 and applied successfullv to the smelting of -nickel concentrates' at the Harjavalta Works in 1959 (4) (5) (6). In 1962 Outokumpu adopted another type of flash smelting where elemental sulphur is recovered from the gases after the thermal decomposition of pyrite in the flash smelting furnace (7) (8): In recent years, the copper-nickel flash smelter and pyrite process have been combined to produce elemental sulphur instead of SO2 from the smelter gases (9) (10). The basic idea of the Outokumpu flash smelting process for sulphidic ores is that the conventional methods with separate roasting and smelting operations are replaced by a combined roasting, smelting and part-converting process carried out in one unit. The heat generated from the exothermic reactions can thus be used for smelting the ore so that only a small amount of additional fuel is needed. The characteristic of the method is also that the dried, fine-grained concentrate is smelted in suspension, which offers the best conditions for rapid reactions. The recovery of waste heat from the furnace off-gases had been considered already in the original flash smelting system. A

Jan 1, 1976

By J. C. Agarwal

Slags produced by modern smelting furnaces contain copper values which are unacceptably high for discard. The electric arc furnace is employed commercially to clean copper from flash furnace slags but the addition of highly oxidized converter slags to an electric furnace has created operational problems. Highly oxidized Noranda Reactor slags have not been processed successfully in a pyrometallurgical process. These slags, which contain large concentrations of copper (5 to 10 per cent), are treated in slag concentrators (controlled cooling, crushing and milling, and flotation) which produce a copper concentrate that must be resmelted. Though commercially operable, it will be shown that the slag concentrator has important process and cost disadvantages as compared to a pyrometallurgical process. In this paper an economic comparison is made between a pyrometallurgical process and the slag concentrator. For the analysis, five hypothetical smelting plants are considered. Each plant treats 1200 tons of copper concentrate per day and produces 109,000 tons of copper annually. The plant configurations used in this study are:

Jan 1, 1976

By R. Schuhmann

The thermodynamic data and calculations which underlie the design of the Q-S process for coppermaking are summarized. The efficient production of crude copper and slag of low copper content in a single con¬tinuous converter requires the establishment and control of gradients in oxygen activity and other physico-chemical variables throughout the reactor. These gradients are established by stagewise introduction of oxygen and solid feed materials to provide: (a) flash oxidation of sulfides above the bath, utilizing the great bulk of the oxygen, (b) conversion of high grade matte or white metal to crude copper by bottom blowing with restricted bath turbulence, (c) close approach to equilibrium staging of converting and deconverting reactions along the length of the slag layer, from a maximum oxygen activity near the metal discharge end to a minimum at the slag discharge end, and (d) completion of slag cleansing by deconverting. In terms of the Phase Rule, the Q-S process involves a system with a minimum of 5 components (Cu, Fe, S, O, and SiO2) and several liquid, solid, and gaseous phases. Accordingly, basic data from previously reported studies on simpler systems are utilized to prepare an equilibrium diagram for the 5-component system and to generate a quantitative thermodynamic model for the Q-S process. This model shows in particular the ranges of oxygen activities (measured by equivalent CO2/CO ratios) involved in the Q-S process and the relations of oxygen activity to temperature and other important physico-chemical variables of coppermaking.

Jan 1, 1976

By T. B. Braun

Cathode contamination is the principal factor affecting the quality of electrorefined copper. It is commonly accepted that annealability is unfavorably affected by the following elements, in decreasing order of adverse effect: tellurium, selenium, bismuth, antimony, and arsenic. Silver in cathodes has importance as it represents a nonrecoverable loss of silver to the refinery. Mechanisms for the contamination of cathodes by these elements are examined and the effect of operating variables on contamination, including anode composition, electrolyte composition, electrolyte temperature, addition agent practice, and electrolyte discard rate, are discussed.

Jan 1, 1976

By J. A. Holmes

Due to varying and complex mineralogy, the flotation tailings from the Chingola Concentrator have, for some years, contained upwards of 0.4% acid soluble copper. In 1968, an investigation was initiated, to determine a method for recovering this acid soluble copper. This initial investigation concluded with a recommendation to install a leach-solvent extraction-electrowinning plant at Chingola, to treat up to 900 000 tonnes of material per month, for an additional copper production of some 4 500 tonnes per month. The process consists basically of six stages :- Materials reclamation handling and preparation, acid leaching in air agitated pachucas, solid-liquid separation by countercurrent washing in thickeners, solution concentration and purification by solvent extraction, copper recovery by electrowinning, and residue neutralisation and disposal. This paper describes the development of the main parameters for design of each of the six sections, and gives details of the final plant design. Problems encountered in commissioning and initial operations are commented on, particularly insofar as they indicated any errors or misjudgements in the design. The choice of materials of construction is commented on in some detail.

Jan 1, 1976

By S. L. Kher

The Singhbhum Copper Belt located in the state of Bihar in Eastern India bears evidence of ancient workings and indicates the existence of a civilized habitation in this region in the past. It was in 1833. how- ever, that the first official announcement of the occurrence of copper in the district was made. Although the occurrence was confirmed in 1847, it was not until 1857 that the first company was formed to exploit the deposits. This Company was dissolved in 1859 and from then until 1920, there were many unsuccessful attempts to develop and exploit the copper deposits in the Singhbhum area. In 1920. the Cordoba Copper Co. took an option on the Mosaboni area, which is nearly 10 km away from the present works located at Moubhandar, Ghatsila and exercising the option in 1924, purchased the mining rights from the Cape Copper Company. The Cordoba Copper Co. was then converted into Indian Copper Corporation Ltd. This was subsequently taken over by the Government of India in March 1972 and is now known as Indian Copper Complex (ICC), forming one of the two smelting units of Hindustan Copper Ltd.

Jan 1, 1976