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By Cristiän Vargas, Jaime Simpson, Gerardo Cifuentes

"This paper presents a new process for the precipitation of Sb and Bi present in copper refinery electrolytes in the presence of Pb02 (Chilean Patent No. 45,037). To establish the conditions under which the precipitating compounds form, it was necessary to evaluate the amount of PbCh consumed, antimony extraction efficiency, precipitate stability, reaction kinetics, diffraction analysis and X-ray fluorescence, separation of size, plus observation of the precipitates in the electron microscope. Preliminary tests were carried with synthetic copper refinery electrolyte, and then the final testing was done with electrolytes from Chilean refineries. This process provides a real alternative for the treatment of copper refinery electrolytes for the control of Sb and Bi in solution; it is very simple to operate and is low cost compared with competing processes.Introduction.A high quality copper cathode implies a cathode free of impurities. The electrorefining process seeks to eliminate these impurities from the copper anode (99.5% purity) by its dissolution in an acid electrolyte using chemical and electrochemical reactions. As a result of this process, a cathode (99.99% purity) is obtained. If the concentration of impurities in the electrolyte, from the dissolved anodes, begins to increase; particularly if the antimony concentration in the electrolyte increases up 500 ppm, the formation of floating slimes which are a major cause of contamination of the cathode is favoured. The most important impurities from the point of view of their effect on the quality of the cathode copper, are Ag, As, Sb, Bi, Pb, Se and Te. Silver is necessary for the control of Se and Te. To control all of these impurities, it is necessary to establish different methods or parameters of control in copper electrorefining. These parameters are anode composition, additives, purification of the electrolyte, current density, acidity, etc."

Jan 1, 2012

By Nickolas J. Themelis

Nearly thirty two million tons of municipal solid wastes (MSW) are combusted annually in over one hundred U.S. Waste-to-Energy (WTE) power plants, thus reducing the use of fuel oil by about 1.6 billion gallons of fuel oil. One of the advanced WTE processes is the 0.9-million ton/y SEMASS facility at Rochester. Mass. Most of the combustion in the three giant combustion chambers occurs while the injected shredded wastes are in suspension, i.e .? in flash combustion mode. The velocity. temperature, and concentration profiles in the SEMASS combustion chamber were simulated by representing the combustible fraction of MSW by the simplified formula C6HIO04 and using the CFD program Fluent to solve the turbulent energy and mass transport equations. After validation against plant data. this model will be used to examine options for increasing the productivity of WTE combustion chambers, such as optimum distribution of primary and secondary air and oxygen enrichment.

Jan 1, 2003

By Adam Powell, Soobhankar Pati

"Solid Oxide Membrane (SOM) Electrolysis is a new energy-efficient zero-emissions process for producing high-purity magnesium and high-purity oxygen directly from industrial-grade MgO. SOM Recycling combines SOM electrolysis with electrorefining, continuously and efficiently producing high-purity magnesium from low-purity partially oxidized scrap. In both processes, electrolysis and/or electrorefining take place in the crucible, where raw material is continuously fed into the molten salt electrolyte, producing magnesium vapor at the cathode and oxygen at the inert anode inside the SOM. This paper describes a three-dimensional multi-physics finite-element model of ionic current, fluid flow driven by argon bubbling and thermal buoyancy, and heat and mass transport in the crucible. The model predicts the effects of stirring on the anode boundary layer and its time scale of formation, and the effect of natural convection at the outer wall. MOxST has developed this model as a tool for scale-up design of these closely-related processes.IntroductionSolid Oxide Membrane (SOM) Electrolysis is a variation on the Hall-Héroult process for molten salt electrolysis of oxides which promises to solve many of the problems of its predecessors. Magnesium in particular is both soluble in molten salts and highly reactive, such that it migrates to the anode and reacts with the oxygen or C02 anode product, reducing current efficiency to as low as 10-20%. But a zirconia solid electrolyte between the molten salt and anode blocks this reaction, boosting current efficiency to at least 90%. Separating the anode from the molten salt also opens up anode material selection to liquid metals and SOFC cathode materials such as Lai.xSrxMn03 (LSM) and YCr03. And zirconia's selectivity makes the oxygen by-product very pure."

Jan 1, 2012

By V. Blet

Rare earth elements (REE) are regarded today as highly critical raw materials but currently lack suitable recycling processes. A combined hydro- and pyrometallurgical process aimed at REE recovery from used NdFeB permanent magnets was recently developed by the CEA. The process integrates the physico-chemical treatment of magnets, followed by a solvent extraction step for the recovery and intra-REE separation using a selective extractant. A subsequent pyrometallurgical treatment via molten chloride salt electrolysis allowed the isolation of pure Dy metal. Technical-economic assessment and life-cycle analysis were also conducted. Following this first successful demonstration, a new project aimed at the recovery of REE from end-of-life nickel-metal-hydride batteries is currently being developed in association with industrial and academic partners. The project aims at evaluating from an experimental and economic perspective different processes converging at the production of value-added products such as cermet materials for catalytic applications, purified REO concentrates, or metallic alloys.

By Pertti Koukkari

The novel Jarogain process combines treatment of the jarosite residue of zinc manufacturing and processing of arc furnace dust from steelmaking to a holistic recovery technology. The new hydrometallurgical approach is targeted to recover the major constituents (Fe, Zn, Pb) as well as valuable components such as Ag, Au, In and Ga from the jarosite-dust mixture as reusable concentrates. The fractionation process proposed by VTT and Aalto University takes advantage of jarosite being readily fine powder and directly available for wet chemical processing. Jarogain process provides an energy efficient opportunity for jarosite utilization as value added products. The experimental proof-of-concept of key stages of the process will be outlined with a comparison of available pyrometallurgical treatments of jarosite waste. The techno-economical assessment is based on estimated investment and variable production cost using the discounted cash flow (DCF) analysis.

By Zhihe Dou

SHS reaction system has advantages of heat flux density, energy concentration and reaction speed, with sufficient conditions in thermodynamic and kinetic reaction. This paper invented a new technology of SHS metallurgy of preparing melting point alloys and refractory compounds using its own chemical energy. SHS-leaching process for preparing nano boron powder or ultrafine boride powder and SHS-casting process for preparing titanium-based alloy and immiscible alloy were studied. The results indicate that highly active boron powder of greater than purity of 93%, particle size less than 100nm and purity greater than 98.5%, particle size less than 400nm REB6 can be prepared. With SHS-Casting process, the oxygen content of less than 0.59% ferrotitanium, oxygen content of less than 0.5% titanium alloy and ?40-80*100mm large size of CuCr, Cu-Fe alloy ingots were prepared. This technology has greatly enhanced the thermal reduction method added values of preparing metallurgical products and its competitiveness.

Jan 1, 2014

By Bien Ferrer

In most smelting operations, there is a strong incentive to improve safety, reduce downtime and extend the campaigns of furnaces and related equipment. An asset management strategy that is based on information, rather than simple throughput metrics and intuition, can be developed to improve uptime and unlock value currently unrealized at existing smelters. Advances in digital technology, including data analysis, modelling and monitoring for hot pyro-metallurgical vessels, make it possible to assess the current condition of an asset, as well as to make more informed projections about its future condition, using on-line and historical data. This would allow practices around asset management to be more proactive and less reactive, with the end-result of optimized uptime. ‘Digital Asset Management’ describes a concept in which digital technology is used to support an asset management strategy and accelerate decision-making by providing information on what, why and how an asset should be designed, operated or maintained. With the overall goals of effective resource utilization, optimized operations, capital efficiency and social acceptance, Smelter 4.0 is a program of holistic improvement and is underpinned by the effective use of data to drive decisions. This paper focuses on Asset Reliability, which is one of the improvement pillars of Smelter 4.0, and introduces a methodology that is aimed at closing the gap between recorded data and evidence-based decision-making through Digital Asset Management.

By D. G. Mason

During the design of copper refinery tankhouses, there is a need to develop mass balance calculations for many process components, so that optimum physical plant configuration is achieved. Each mass balance is complex, possibly with over 120 interactive variables as basic input data. Recent developments in tankhouse design (e.g. permanent cathodes) have greatly increased the design options available for any project, multiplying even further the requirement for calculations. In the past these calculations were tedious and susceptible to human error. A comprehensive computer program can now simplify the task of the process metallurgist, enabling more sophisticated and sensitive plant designs to be produced. The paper describes the successful development of a flexible mass balance program that originallly was used in a feasibility study which had to be completed within a short time schedule. The program has been further developed and used for design and energy calculations; it can be usefully applied to existing plants to assess the impact of variations in operating parameters. The software takes account of staged liberation, electrolyte purification bleed and generates a reliable process inventory listing: it can also cope with stripper starting sheet options and disparate commercial circuits.

Jan 1, 1987

By G. H. Khoe

Neutralisation of acid uranium mill tailings with lime or other alkaline materials is usually practised to reduce the dissolved concentration of heavy metals and radio nuclides. Computer modelling of this process was carried out using the geochemical equilibrium code MINTEQA2. Computed dissolved metal and sulfate concentrations were compared with laboratory-based experimental data. It was found necessary to include the modelling of adsorption of trace metals (such as uranium and lead) by the precipitated ferric hydroxide in order to obtain acceptable concentrations in the neutralised liquors. There were limitations of the modelling exercise due to important aspects which were not addressed or properly accounted for such as chemical reaction kinetics and the effect of high ionic strength. These are discussed in the paper.

Jan 1, 1991

By S. Tandon

Equilibria studies of selenium distribution for sodium-borate slags were initiated at 1473k under reducing condition as a function of slag composition and alloy composition. The Se distribution coefficient (% Se in slag/% Se in metal) increased from 0.4 to 2.9 with increase in basicity (0.53 to 0.86) for Cu-0.446% Se alloy. However, the results are not very useful from industrial application viewpoint. Therefore, in order to improve the distribution of Se, CaO (10% to 50%) was added to the sodium-borate slag of basicity 0.864. On addition of 502 CaO, the distribution coefficient increased roughly by 100% for slag composition - 44.5% Borax, 22.2% Na2C03, 33.3% CaO and Cu-0.44677 Se alloy. Further, the value of this distribution coefficient has been found to increase by an additional 80% on addition of 20% CaF2 to the above slag for all Cu-Se alloy compositions. Also with increase in initial concentration of Se, the distribution coefficient has been noted to increase.

Jan 1, 1992

By Theo Lehner

The Rönnskär smelter has wide experience in the field of recycling of non-ferrous metals. Today, smelting and refining from primary and secondary raw materials are integrated in a complex flow sheet. Boliden operates a lead flash smelter, a lead refinery, a copper smelter and refinery, a sulphuric acid and sulphur dioxide plant, a slag fuming plant and precious metal plant at its Rönnskär smelter in the North of Sweden. The Business Area Smelter Operations also incorporates Boliden Bergsöe, Sweden's lead-acid battery recycler, and Norzink, Norway, where recycled zinc accounts for more than 20% of it's production. Raw materials for the Rönnskär smelter include concentrates, ashes, slags, metallic scrap, electronic scrap and electric arc furnace (EAF) steel-making dust. This paper briefly describes current operations and illustrates current measures to improve productivity. Limits to recycling as experienced by a non-ferrous smelter are, illustrated. The deportment of critical elements contained in raw materials is also discussed.

Jan 1, 1998

By John O. Marsden

The past fifteen years have seen a number of important developments in copper hydrometallurgy, including the commercial application of biological heap leaching of secondary (chalcocite-dominant) copper ores, the commercial demonstration of chalcopyrite concentrate leaching technology using pressure leaching and biological processes, and the application of novel configurations of solution extraction circuits. Significant emphasis is now being placed on the development of effective stockpile leaching practices for primary ores (chalcopyrite and bornite-dominant mineralization). Some of these developments have been highly successful, and will pave the way for further development and commercialization. Others have been less successful. These developments are reviewed in the context of the metal price cycle and trends for the future are identified.

Jan 1, 2006

By Kezhuan Gu

Data on the kinetics and thermodynamics of dephosphorization are analyzed in terms of the dynamic partition ratio, determined by a combination of slag thermodynamic properties and the balance of oxygen supply and consumption. A recently developed phosphate capacity correlation is combined with data on kinetics to quantify the most significant parameters in controlling the interfacial oxygen potential. The role of slag composition, entrained gas fraction and temperature are discussed in addition to metal carbon and sulfur content. It is demonstrated that the mass transport of oxygen in the slag is enhanced by factors increasing conductivity and inhibited by entrained gas. The mass transfer of phosphorus in the metal is described considering surface renewal induced by CO bubbles.

By Bryn Harris

Much has been written over the past twenty years on the removal and chemical stabilization of arsenic from metallurgical process solutions. This paper reviews again the latest developments in this field, and concludes as before that the high-iron arsenical ferrihydrites, together with the high temperature arsenic minerals, scorodite and Type II, remain as the best and most viable vehicles for industrial control and disposal. However, a cautionary note is introduced, in that chemical environments cannot be considered in isolation, and that cogniscence has to be taken of microbiological activity in determining the disposal method. Data are also presented on a survey of industrial practice, which shows that arsenical ferrihydrite is by far the most widely-practiced and accepted method used worldwide. Finally, the disaster in Bangladesh is briefly discussed with reference to lessons that the metallurgical community might learn from this.

Jan 1, 2003

By C. E. Abbey

Cobalt, iron and manganese play various roles in copper electrowinning using lead–calcium–tin alloyed anodes. Cobalt catalyzes electrochemical water decomposition resulting in lower anode potential and reduced corrosion rates. Iron reduces cathodic current efficiency, but is used to reduce higher oxidation states of manganese that oxidize organics in solvent extraction. Manganese also produces anode scale and is generally considered a problematic impurity. The effect of the combined interaction of these three metal ions on the anode potential has not been quantified yet. The current work used a three factor, two level, three replicate central composite design of experiments to analyze the effects and potential interactions among cobalt, iron and manganese. The experiments consisted of chronopotentiometric analysis to assess anode potential after 24 h of operation. Higher [Co], lower [Mn] and either high or low [Fe] yielded lower anode potentials. Two regression models were developed to predict anode potential as a function of [Co], [Fe] and [Mn]. A method to estimate electrical energy consumption for copper electrowinning is also presented.

By R. W. Adams

A new process has been developed for leaching zinc sulphide concentrates at atmospheric pressure using air or oxygen plus nitrogen dioxide in dissolved or gaseous form as? an oxygen carrier. The process is flexible and can cope with variations in the degrees of retention and regeneration of dissolved nitrogen dioxide in the leaching phase. By controlled addition of concentrate a leach solution with low residual nitrate concentration can be produced. Following separation by filtration of unleached solids and elementa1 sulphur and conventional oxidation/precipitation of dissolved iron, the leach liquor can be treated with metallic zinc to remove the remaining nitrate and other meta111c impurities such as copper, cadmium and cobalt to provide a solution suitable for electrolytic recovery of zinc. Pilot scale testing of the process .has given zinc recoveries in the high nlnet1es, production of a hi.gh grade jarosite-free Pb/Ag residue (50% Pb.) and a saleable high grade of elemental sulphur. .A wide range of concentrates can be treated containing substantial levels of lead and copper as well as zinc. Indicative cost estimates suggest that the new process is competitive with alternative procedures such as pressure leaching.

Jan 1, 1990

By B. Manana

In heap leaching, the oxidative dissolution of value minerals encapsulated deep within large particles cannot be fully understood on the basis of the bulk solution conditions relative to variable solution conditions near the mineral surface. In the present study, the diffusion of the oxidising species through inner particle pores is simulated in a model apparatus that separates an inert platinum electrode under controlled reduction potential from the bulk solution through narrow pores of varying length. The Cu-NH3 system was selected as a model system and Cu(II)/Cu (I) as the redox couple of interest. Platinum probes inserted in the pores allowed the measurement of varying redox potentials along the pore length. Results showed that in a 10 mm pore, there exists a narrow (0.5 mm) zone near the reduction surface that is depleted of the oxidant and in which its supply is strongly diffusion limited, even if it is in abundance in the bulk solution. The consistent presence of this narrow diffusion region across all experimental results indicated that the transportation of the reduced species away from the reaction surface had the most significant influence on the potential variations within the pore. This was further supported by the minimal effect of varying concentrations of both Cu(II) and dissolved oxygen on the solution potential within this region.

By Florian Kongoli

Slags and fluxes are important interchangeable dimensions of pyrometallurgical processes. They can increase the efficiency of the smelting, converting and refining processes and improve the quality of the final products. A good slag should have appropriate physicochemical properties such as low liquidus temperature, optimal viscosity, maximum ability to attract undesirable elements, minimum potential of attracting valuable elements, etc .. A good flux, on the other hand, when properly used, can considerably improve the physicochemical properties of the slag since by modifYing its chemical composition it could decrease the liquidus temperature, improve viscosity etc.. Consequently, the choice of a good slag and the corresponding fluxing strategies has become indispensable in most of industrial processes. However, the properties of multi component slags as well as the effect of several fluxes are known only empirically and confusion exists in the literature and in the industrial practice. In today's reality of frequent changes in the composition of raw materials and that of the fluxes themselves, in the existing or new developing technologies, the quantification of the thermophysicochemical properties of multicomponent slags and the effect of fluxes becomes indispensable. This paper reviews some of the work carried out by the author's group during the last ten years on the quantification of the thermophysicochemical properties of multicomponent slags and on the effect of fluxes in several smelting and converting processes in close relation to their individual characteristics. Several examples have been given in order to demonstrate the fact that when taken outside the context some fluxes can become in fact anti-fluxes.

Jan 1, 2003

By R. S. Celmer

The distributions of cobalt, molybdenum, copper, and selenium between nickel matte and silica-saturated iron silicate slag have been determined in the region of the metallic saturation boundary, at 1523 K. Results are given as a function of the composition of the coexisting Fe-Ni alloy and the activity of iron in the system. Under strongly reducing conditions, these minor elements display a marked preferential accumulation in the sulphide phase. It is shown that the dissolution of cobalt and molybdenum in slag follows an oxidative mechanism, and distribution equilibria are correlated with the oxygen potential. From these data, the thermodynamic properties of cobalt in nickel matte are computed. Further, comparisons of minor element partitions are made between the nickel and copper matte smelting cases under metal saturation conditions.

Jan 1, 1988

By Chang Wei, Zhigan Deng, Minting Li, Cunxiong Li, Xingbin Li

A direct hydrometallurgical process of extraction molybdenum and nickel from molybdenum-nickel ore by pressure water leaching without reagent was studied. The extraction of Mo and Ni from molybdenum-nickel ore by oxygen pressure leaching, which exploit the characteristic of molybdenum-nickel minerals contain high concentration amorphous sulfide which has highly active, and make the most of easily oxide to sulfuric acid and sulfate at low temperature and excess oxygen presence of the amorphous sulfide. Under oxygen pressure conditions, considerable molybdenum and almost all the nickel were extracted into solution in the leaching process. The results show that with the leaching time for 3~4h, temperature at 150o C, liquid-to-solid ratio of 2mL/g, mineral granularity of 0.074mm, oxygen partial pressure of 0.4~0.5MPa without other reagent, molybdenum leaching percentage can be over 80% and nickel leaching percentage can be more than 97%. Furthermore, about 80% sulfur in the Mo-Ni ore has been transformed into sulfuric acid.

Jan 1, 2014