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By R. G. Robins

Metal separations based on the selective precipitation of phosphates have a potential application in many hydrometallurgical processes. This paper reviews the literature on the solubility of a number of both divalent and trivalent metal phosphates and presents the result of some additional experimental measurements. The systems examined have been modelled to obtain free energy of formation data for the various species. Computer generated solubility diagrams which are described can be useful in predicting a variety of metal separations.

Jan 1, 1991

By Larry Southwick

This Peirce-Smith Converting Centennial symposium is celebrating the contributions of two men, William Peirce and E.A.C. Smith, in advancing technology allowing the copper industry to realize its full potential. However, theirs is representative of a larger story: New, simpler technology releasing the stranglehold of older, more complicated technology, new developments in vessel configuration and design finding alternate routes around dead ends in operability, advances in technique and concepts removing roadblocks of cycle time and capacity, and overall innovation opening up vast new reserves around the world to those companies willing to embrace those improvements. Our story is also one of personalities, stubborn smeltermen versus the innovators, those inside the industry versus those from outside. It is a story of an initial borrowing from the steel industry, but also Peirce and Smith, from the refining end of the copper business, taking the ideas of Baggaley from Pittsburgh’s steel and airbrake industry, who built on what Hollway, Manhès and David, Douglas, and others had done in smelter tests, further to compete with the previous primacy and closely held expertise of the copper smeltermen in Wales. These advances have been well recorded in photographs taken over the last 150 years. A number were submitted especially for this symposium. Many others were published in the mining and metallurgy press of the times. Several mining schools also retained copies of photos either taken during field trips, or donated to the school by alumni and operating companies. This presentation will provide a selection and discussion from these sources of “converters in action”, describing the various designs, operations and developments depicted. The focus here will be on the first roughly 60 years of copper converter development, from Bessemer’s days at the dawn of this new idea, up to and slightly past the time of initial adoption of Peirce and Smith’s designs.

Jan 1, 2009

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 Paul L. Wichlacz

A mathematical model of growth and ferrous iron oxidation for attached bacteria was applied to rotating biological contactor (RBC) units treating acidic mine drainage. The model describes attached bacterial growth as a saturation function, where the rate of substrate utilization is determined by a maximum substrate oxidation rate constant, a half saturation constant, and the concentration of substrate within the RBC. The maximum oxidation rate constant was proportional to flow rate and the substrate concentration in the reactor varied with influent substrate concentration. The model was tested at three separate sites and with three different size RBC units. The ability of the model to predict the rate of iron oxidation under all test conditions was significant. The accuracy of the model was found to be affected by unit size and vary with specific test site.

Jan 1, 1985

By William A. Hockings

This report describes the results of laboratory studies on leaching of copper ores.tlf These studies are the first step of a program for the investigation of in situ leaching of tabular, metalliferous ore bodies.(2) The basic steps required in the development of an in situ process are: 1. Leachability - the ability to dissolve the metal values from the ore under in situ conditions must be demonstrated. 2. Ore Preparation - the ore must be prepared so that sufficient contact with the solution can be attained. 3. System Design - integrated in situ systems must be designed and studied for engineering feasibility. 4. Economic Feasibility - the economics of the system must be shown to be economically feasible and competitive. 5. Environmental Feasibility - the loss of reagents into the environment must be investigated. 6. Pilot Scale Testing - the feasibility of the system must be demonstrated on a sufficiently large scale. The studies described in this report were concerned only with the first step of the program, viz., leachability. Native and sulfide copper ores from the Michigan copper district were selected as model ores for these studies. Aqueous amnonia solutions were chosen as the solvents to be investigated. In this study carbonate (CO3, HCO3, H2CO3) was used exclusively as the anion. In keeping with custom it is referred to as carbon dioxide and concentrations are ex- pressed in terms of CO2. When leaching native copper the reaction is

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 D. A. Milligan

Ammonia leaching of copper sulfide concentrates, matte, scrap or other sources of copper yields copper amnine sulfate solutions which are converted to metal in a two-stage process involving precipitation of inter- mediate sulfites and their thermal decomposition to copper powder of high purity. Processing details and results are given. Considerable simplification in circuitry and cost savings are indicated. Energy requirements are reduced by substitution of copper powder precipitation and ammonium sulfate crystallization for solvent extraction, electrowinning and lime boil.

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 Ruiqing Li

It is possible to purify some liquid metals by exploiting the difference between the vapour pressure of the bulk metal and the minor constituents or impurities. The rates of purification can be improved by carrying out the process under reduced pressure, that is, so called, vacuum. Some commercial examples of vacuum refining are the purification of molten tin to eliminate trace amounts of lead and the refining of cobalt, also to remove lead. The objective of this paper is to review the basic theory behind vacuum refining technology in order to show how the feasibility of vacuum refining can be determined simply for a particular system by evaluating Olette's Volatility Refining Criteriont.

Jan 1, 1991

By Rolando Campos

Until 1970, the Caletones Smelter of CODELCO-CHILE, División El Teniente, operated under the conventional pyrometallurgical process used by most of copper smelters. The annual copper production varied around 165.000 tons. The failure in the commissioning of the "oxygen smelting" technology in Peirce- Smith converters (1970-1972), forced further introduction of transcendental changes in the Caletones smelter operating scheme. Implemented technological innovations were based on wide studies and research works performed by División El Teniente. This paper presents a summary of technological modifications introduced, their impact on production and energetic performances, and short and medium terms improvement plans.

Jan 1, 1993

By Grant E. Casley

Since 1970 Mount Isa fines Limited has made a significant increase in blister copper production from approximately 100,000 to 155,000 mt per annum and in fact 161,040 mt were produced in the calendar year 1974. Flowsheet developments including fluidised bed roasting and converter slag flotation are discussed, particularly their contributions to minimising major equipment changes in smelting and converting. The use of model- ling and simulation techniques for such an exercise is mentioned. The paper reports the alterations made to both equipment and operating techniques in the reverberatory furnace and converter sections to achieve the regular production of 250 mt of blister per converter day from a 41% Cu matte grade. The effects of flux composition on converting performance are highlighted. The air quality control programme is discussed in relation to its restriction of blister copper production.

Jan 1, 1976

By S. L. Pohlman

Physical characteristics of possible importance in the acid leaching of Chrysocolla have been evaluated. Surface area studies and pore size distribution indicate: 1) a large surface area (350 m /gm); 2) an average pore size of 13 or 16 Å , depending upon use of the adsorption, or desorption, branch of the Type IV isotherm in the evaluation; ) the presence of a significant fraction of pores of size less than 15 Å determined by the accumulation surface area method. The initial structure is micro- crystalline on the basis of x-ray powder patterns; the silica leach residue is amorphous and has only 24 m2 /gm surface area, and loses integrity when dry. However, readsorption of copper onto the wet leach residue gives a product with integrity and 100 m2 /gm surface area. Visual observation of the leach residues supports evidence of a non-protective diffusion mechanism of leaching which is well correlated by the shrinking core model previously presented.

Jan 1, 1976

By Derk G. E. Kerfoot

The extractive metallurgy of nickel and cobalt has proved to be a particularly fruitful area for innovation in hydrometallurgy and electrometallurgy ever since the development of the Hybinette process for nickel in the early 1900's. In current practice, nickel concentrates are generally smelted to high grade mattes which are then refined to metal by a combination of hydrometallurgy and electrometallurgy, although low grade copper-nickel concentrates are refined directly by the ammonia pressure leach process. Matte refining processes in commercial operation include the direct electrolysis of matte, the ammonia pressure leach, sulphuric acid leaching using air or oxygen at elevated pressure, or at ambient pressure, and chlorine or chloride leaching. Refined nickel is recovered either as electrolytic cathode, or as metal powder by hydrogen, reduction. Hydrometallurgy has also found application in the treatment of nickel laterite ores, both in the reduction roast ammonia-ammonium carbonate leach process, pioneered by Caron and in the Moa Bay acid leach process. Cobalt is recovered as a co-product of copper in central Africa, and as a byproduct of hydrometallurgical nickel refining elsewhere. In the African plants, the copper-cobalt concentrates are roasted and leached in sulphuric acid solution, and copper and cobalt are recovered separately from the leach solution by direct electrowinning. A variety of hydrometallurgical techniques are used for the separation of cobalt from nickel, including selective precipitation and crystallization, solvent extraction, and ion exchange. Like nickel, refined cobalt is recovered either as electrolytic cathode or as metal powder by hydrogen reduction.

Jan 1, 1988

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 H. H. Kellogg

The Process Fuel Equivalent (PFE) for nine different flowsheets for production of anode copper from sulfide concentrates has been evaluated and compared for a set of uniform conditions and a "standard" concentrate analysis. The processes considered are: reverberatory smelting, (wet-charge and hot-calcine charge), electric furnace smelting, Outokumpu flash smelting (2 versions), mom flash smelting, Noranda Continuous Process (2 versions), and the Mitsubishi Continuous Process. The energy required for the numerous processes auxiliary to the principal smelting processes-¬roasting, drying, air compression, gas handling, dust collection, slag cleaning, acid manufacture, etc.--are separately evaluated and incor¬porated into the process comparisons. The factors in process design that lead to important energy savings are: use of fuel rather than electric energy; use of oil or coal rather than natural gas; maximum use of oxygen enrichment of the process air; drying of charge before smelting, or, even better, drying and preheating of charge by partial roasting in a fluid-bed; recovery of waste heat from all major hot process gases.

Jan 1, 1976

By W. Kunda

A laboratory study was carried out on the treatment of sulphidic copper concentrates in aqueous chloride systems under elevated temperatures and oxygen overpressure. Exploratory tests showed that chalcopyriteoxidizes with various chloride salts to form, depending upon the pH of the system, soluble copper chloride or insoluble copper oxychloride salts; the copper can then readily be recovered from the solution or residues respectively. During the leaching, iron was oxidized to iron oxide and remained in the leach residue while the bulk of the sulphide sulphur was oxidized to the elemental form with a minor portion oxidized further to sulphate. The presence of metal chloride salts in the system increased the oxidation rates of chalcopyrite and depressed the solubilization of iron in the system. A systematic oxidation leach study carried out in (1) ammonium chloride and (2) sodium chloride systems showed that the former system required little or no HC1 addition while the latter required 2 mol of HC1 per mol of dissolved copper (plus zinc). The copper was recovered from the cuprous or cupric chloride leach solutions by cementation with iron. Extractions of 99% copper and zinc, 97% silver, and negligible iron were obtained. Sulphur was oxidized to the elemental or sulphate form; the relative proportions of the total sulphur were 60 and 30% for system (1) and 80 and 10% for system (2). A flowsheet for a conceptual process with minimal reagent requirements was proposed.

Jan 1, 1976

By T. Shibaraki

A new larger, more efficient and economical Mitsubishi furnace line at Naoshima was put into operation in May 1991. Naoshima Smelter had produced previously about 230,000 mtpy anode copper with two smelter lines, i.e., a conventional reverberatory furnace line and Mitsubishi furnace line, which had been shutdown at the same time of the start up of the new smelter. At the beginning of the operation, there were several initial problems at the area of off gas trains and feeding system. By overcoming them now the process has been continuing satisfactory operation at the design rate. The paper describes about the design concepts and the actual operation of the new smelter.

Jan 1, 1993

By L. E. Murr

Preliminary studies of bacterial attachment to MoSp (molybdenite) have indicated a low correlation between dislocation density in the (0001) basal plane and the density of attached microbes. In the present investigation, poly- crystalline thin sections of CuFeSp (chalcopyrite) have been ion-etched or carefully comminuted to electron transparency and observed in the transmission electron microscope. The thinned test sections were then immersed in a culture solution in which bacterial attachment occurred. The attached bacteria were biologically stained in a uranyl acetate solution and the entire thin CuFeSp sections or tiny particles containing thin, electron transparent edges with bacteria attached were observed in the transmission electron microscope, allowing the coincidence of bacteria and their density to be directly observed in relation to lattice dislocations and crystallographic orientations of the exposed surfaces. This technique has the advantage of exposing crystallographic orientations where dislocation lines intersect the free mineral surface, and the emergence sites of dislocations could in principle be directly investigated as a possible preferential attachment site for bacteria. Bacteria morphologies were also extensively observed in the scanning electron microscope. The implications of the results are that although a strong correlation between dislocation density and distribution and bacterial attachment, density, and distribution has not been established, systematic multiplication of dislocation densities in crystalline mineral particles to be leached could enhance leaching rates by increasing the reaction rates as well as the density of attached bacteria at crystalline, metal-rich phases. Techniques for dislocation production in mineral and ore bodies and the particular implications in chalcopyrite leaching are discussed in relation to in-situ leaching where comminution is attained by explosives and the generation of strong shock waves in an ore body. The present study demonstrates the use of microanalytical and microscopic techniques in the investigation of fundamental microstructural phenomena in hydrometallurgical processes.

Jan 1, 1976

By K. J. Cathro

A hydrometallurgical process is described for the recovery of copper from chalcopyrite concentrates. The process is based on a cupric chloride leach, the concentrate having first been "activated" by heating it with sulphur at a temperature near 400°C. This activation process converts most of the iron of the chalcopyrite to pyrite, which is insoluble in the cupric chloride leachant. The copper is converted to the mineral idaite, which dissolves readily in hot cupric chloride: at 106°C, 98% of the copper is extracted in a three-stage countercurrent leach, the leaching tirqe being 1 hour per stage. The sulphur of the chalcopyrite appears as elemental sulphur, which is recycled for the activation of further concentrate, the final leach residue consisting of pyrite, plus the gangue present in the original concentrate. The copper extracted can be recovered by electrowinning, using a diaphragm cell. Current efficiency (one-electron basis) is about 70% but the cell voltage is only about 1 V, so that power consumption is three times lower than for the conventional sulphate electrowinning process. The leachant is simultaneously regenerated in the anode compartment. The behaviour of minor elements in the concentrate has also been studied.

Jan 1, 1976

By C. E. M. Meskers, U. Boin

"The increasing use of coated magnesium in consumer products results in creation of coated Mg scrap during product manufacture and after End-of-Life product treatment. Currently this material is generally not recycled, leaving a material resource unused. Closure of the magnesium cycle in a sustainable manner is necessary. In order to do so, the effect of coatings on the recycling process has to be quantified, predicted and minimized. For this purpose metrics have been developed, based on first principles supported by detailed understanding of the recycling process. The developed 3D metric enables quantitative assessment of the recyclability and links coating design, product design and recycling to each other in a visual manner. The parameters that form the metric can be measured and predicted, hence an engineering basis for Design for Sustainability of coated magnesium is provided.IntroductionEvery product progresses through the four phases of the product life cycle depicted by figure 1. In each phase residues are created. Their amount and composition is largely determined by the complex material combinations created/invented during product design in the manufacture phase. Compared to the ideal cycle the magnesium cycle is far from closed (fig. 2). Most noticeable is absence of the link between the EoL phase and raw materials production. A closed cycle only exists for class 1 scrap, which goes from the product manufacture phase directly to production from industrial material and returns to the manufacture phase as magnesium alloys. The four problematic streams are marked by ???. Coated semi-products are present in two of the four residues, namely in rejects and collected scrap. When these semi-products are recycled the amount and composition of the dross and salt slag residue is affected as well.During product design selection of the coating takes place, fixing the coating character¬istics and properties from this moment on for the rest of its life cycle. The choices made in the manufacturing phase are therefore critically linked to the recyclability of coated semi-products as well as the sustainability of the magnesium cycle as a whole. Sustainable closed life cycles, in which the quality of materials is preserved and residue creation and resource depletion are minimized, can be attained by selecting the appropriate alternative during product design. To realize this the effect of design choices on the life cycle and more specific the recycling process has to be known and quantified."

Jan 1, 2008