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By C. Kathryn Sole

The close proximity of cobalt and nickel on the Periodic Table and their frequent occurrence together in nature means that their separation in primary hydrometallurgical flowsheets is not only often necessary, but requires the use of innovative chemistry to achieve high selectivity. Today, increasingly stringent demands for the high-purity cobalt and nickel salts required for battery applications in consumer electronics, electric vehicles, and solar applications are again challenging the state of the art. The evolution of cobalt–nickel separations is traced from the basic precipitation technologies employed in 1960s, through commissioning of the first cobalt solvent-extraction plant in South Africa in 1974, to the commercialisation of organophosphinic-acid extractants (which provided a step-change improvement in selectivity) and their eventual widespread use in the 1980s and ’90s. This was followed later by their sulphur analogue, which enabled different possibilities for laterite processing in the new millennium. Separations in chloride media, which take advantage of the different speciation chemistries, and nickel extraction by oximes in ammoniacal systems are also discussed. More recently, chelating and solvent-impregnated resins have added further dimensions to the possibilities for flowsheet design and enabled higher purity products to be attained from both primary and secondary sources. Selected case studies and flowsheets are described.

By Masahiro Hirasawa

"As a fundamental study on pyrometallurgical process that involves recycling steel-making dusts, of which major components are oxides of Zn and Fe, and waste polyvinyl chloride simultaneously ·at. a temperature below 1273 K, the reactions between the mixture of ZnO + Fe20 3 and PVC or the compound ZnFez04 and PVC are investigated in a series of thermogravimetric and small scale reactor experiments under inert atmosphere at below 1273 K. The reaction mechanisms are discussed· on the .basis of the thermogravimetric data. From the results of reactor experiments, it is shown that the chlorination of Zn in the oxides by Cl in PVC, the vaporization of ZnC12, the reduction of iron oxide to metal Fe by C and H in PVC, and, thereby, the separation of Zn and Fe in the oxides take place simultaneously at the temperature ~= 1200 K.IntroductionSteelmaking dusts are metallurgical wastes consisting mainly of oxides of Zn and Fe with smaller amounts of other heavy metal elements, such as Pb. In the recent investigation, [1] the present authors have investigated the fundamental aspects of a potential pyrometallurgical process· of recycling steel-making dust with polyvinyl chloride (PVC) at temperature T < 1273 K under Ar atmosphere. The performance of a similar process, in which HCl in the combustion gas of PVC is used to chlorinate Zn in the EAF dust under oxidizing atmosphere, has been investigated by Tailoka and Fray [2] with fundamental experiments. Figure 1 shows an example of the potential ·diagram of Zrt-Cl-0 and Fe-Cl-0 systems. In the figure, we can find two regions where ZnCl2(g) can be separated from Fe containing compounds. One is ZnCiz-Fe20 3 coexistence region at higher oxygen and chlorine potentials and the other is ZnCl2-Fe coexistence region at lower oxygen and chlorine potentials. The process adopted by Fray and coworkers is aimed mainly at the performance of Zn/Fe separation in the higher oxygen potential region. In the present study, the lower oxygen potential region is focused on."

Jan 1, 2000

By I. D. Reznik

Regularities of cobalt and nickel distribution between slag and matte, slag and metallic alloy on the base of concepts on exchange reaction equilibrium are considered. It is shown that the distribution of cobalt and nickel in industrial processes approaches to equilibrium one. Oxysulphiae influence on the bahaviour of cobalt, nickel and sulphur is shown. The recommendations on conduction of the processes of smelting, converting and slag cleaning based on the analysis of the methods or" non : ferrous metal separation from iron are given.

Jan 1, 1993

By B. Zilbergleyt

Current understanding of chemical equilibrium is based exclusively on the probabilistic considerations that are correct for isolated systems with only one chemical reaction to take place. For the systems with multiple chemical interactions, current paradigm of chemical thermodynamics promotes the idea of openness, artificially flavored with coefficients of thermodynamic activity. Recently introduced thermodynamics of chemical systems and the Method of Chemical Dynamics (MCD) offer explicit accounting for the multiple chemical interactions within the system. In the new theory, thermodynamic equilibrium of the j-subsystem obeys the logistic equation derived exclusively from the currently recognized concepts of thermodynamics. Having the only one new parameter -the subsystem&apos;s reduced chaotic temperature &apos;tj to describe external interactions, and reaction extent Ilj as independent variable, this equation covers the whole domain of the system&apos;s possible states from true thermodynamic equilibrium through the open equilibrium to bifurcations and chaos depending on the &apos;tj value. The MCD brings new opportunities to thermodynamic simulation of complex metallurgical and chemical systems, allowing for the analysis of their domains of states and the area limits, and for more accurate calculation of the equilibrium compositions. Its usage is exemplified in this paper by several applications. Keywords: chemical thermodynamics, open systems. complex systems, chemical dynamics.

Jan 1, 2003

By Bradley C. Bockrath

Some thirty coals were evaluated for liquefaction activity under a mixture of CO and H2 at 425° C. The viscosity of the liquid products was taken as an indicator of the degree of liquefaction. It was found that the direct liquefaction of a particular coal may be beneficially influenced by the presence of pyrite. Active pyrites are often found in the native mineral matter of the coal itself. For example, subbituminous and bituminous coals and lignites of relatively high pyrite content were found to liquefy more readily than similar coals or lignites which were poor in pyrite. The reactivity of inactive coals could be improved by using blends with active, pyrite-rich coals. In addition, pyrite was effective when added separately as pyrite concentrates obtained from coal beneficiation operations. Various other iron- and sulfur-bearing additives were also effective when used in combination as added slurry-phase catalysts, including iron oxides and mineral residues derived from liquefaction of active coals. Under liquefaction conditions, pyrrhotite ( Fe I- x5) is formed from pyrite or from the iron oxides and many sulfur containing species. Pyrrhotite was shown to be a hydrogenation/dehydrogenation catalyst for tetralin but is not active for initiating a variety of free radical reactions that do occur when pyrite is heated with tetralin. The role of pyrite in coal liquefaction is complex and still not well understood.

Jan 1, 1981

By R. Hurman Eric

The flow of molten slag and matte and the estimation of the mass of settled matte in electric furnaces is discussed and the action of the electric furnace as a settler is considered. Particle size of the concentrate and its grade are major contributors to settler dimensions. Discussion on the production capacity of the electric furnace with reference to operating current, power input, furnace dimensions such as width and length and electrode diameter are given. These discussions are based on considerations derived mainly from experimentally determined properties of the slag such as its resistivity, viscosity and liquidus temperature. Extension of the design and operating considerations to circular furnace symmetry is also discussed.

Jan 1, 1995

By Robert W. Bartlett

Chalcopyrite in copper flotation concentrates can be hydrothermally converted to digenite with oxygen in a continuous process, with rapid kinetics when operated above 200°C. This eliminates large amounts of sulfur and iron. These "super-concentrates" have potential for debottlenecking smelters and avoiding capital intensive future smelter expansions, otherwise required in the late 1990s. The technology of producing super- concentrates is described, with cost estimates, and the use of super-concentrates as smelter feed is discussed, with examples.

Jan 1, 1992

By Renato G. Bautista

The prospect for recovery of rare earths from red mud, the bauxite tailings from the production of alumina is examined. The Jamaican red mud by far has the higher trace concentrations of lanthanum, cerium, neodymium, and yttrium. Scandium is also present. The dissolution of the rare earths is a major extraction problem because of the large volume of other materials present. The recovery processes that have been proposed include the production of co-products such as iron, alumina, and titania concentrates, with the rare earths going with the titania A critical examination of the possible chemical processes for the complete utilization of the red mud are presented Recommendations for research projects considered to be important in the development of a chemical separation process where no pig iron product is contemplated are also discussed.

Jan 1, 1992

By R. G. Reddy

To better understand the behavior of bacterial-mineral interfacial reactions, a thermodynamic model based on the- studies of bacteria adhesion on mineral surfaces has been evaluated. The bacteria adhesion to the mineral surface would be increased by l &apos; d1;1creasing the change in Gibbs free energy of adhesion and it would be reduced if the change in Gibbs free energy of adhesion of the system is increased. From the combination -of Young&apos;s equation and equation of state, the change in Gibbs free energy of adhesion -for bacterium-mineral system- was calculated. Influence of liquid surface tension, mineral surface tension on the change in Gibbs free energy of adhesion and consequently bacteria behavior on mineral systems- has been discussed.

Jan 1, 1991

By Renato G. Bautista

The solvent extraction separation of nickel, cobalt and their associated metals have been considered for industrial application since the early 1960&apos;s. This review of the solvent extraction processes is limited to the industrial applications, pilot plant and the more extensive bench scale studies reported in the literature. The processes with their significant chemical and technological contributions are discussed in detail whenever the information are available. The application of solvent extraction to the nickel-cobalt processing has so far been limited to the secondary separation of nickel-cobalt containing feedstocks derived from other primary nickel-cobalt separation methods.

Jan 1, 1993

By Qingwei Wang

Heavy metal-containing wastewater from hydrometallurgical processes of lead-zinc was treated by biologics in a 200 m3/h industrial scale experiment. The result shows that Zn concentration declined from 50.28 mg/L~240.81 mg/L to 0.21 mg/L~1.98 mg/L, Pb from 1.00 mg/L~13.47 mg/L to 0.083 mg/L~0.71 mg/L, Cu from 0.24 mg/L~2.38 mg/L to 0.059 mg/L~0.40 mg/L, Cd from 2.12 mg/L~23.47 mg/L to 0.011 mg/L~0.071 mg/L and As from 0.50 mg/L~6.00 mg/L to 0.005 mg/L~0.10 mg/L. The concentrations of the above heavy metals in the treated water were lower than that in Integrated Wastewater Discharge Standard (GB8978~1996) in China. Furthermore, the treated wastewater was recycled and reused in smelter plant. Zinc content in hydrolytic sludge reached up to 34.04%, which indicates that this sludge can be used to recover valuable metals.

Jan 1, 2010

By Donald R. Sadoway

The viability of treating certain forms of hazardous waste by direct electrolysis in molten oxides is under investigation. Secondary residue or waste mud produced in the course of chromate chemical production is the focus of attention in this study. The goal is to reduce the water soluble hexavalent chromium either to insoluble trivalent chromium or to chromium metal. Electrolysis tests have been conducted in a high temperature cell containing chromate sludge dissolved in an electrolyte composed of Al2O3, SiO2, CaO, and MgO. Oxygen production on a carbon-free anode has been confirmed.

Jan 1, 1992

By Guo Xueyi

The method of Substance Flow Analysis (abbreviated as SFA) provides a helpful tool for the study of the industrial metabolism of a certain metal within a regional level. In this work the flow of lead in China, 2006, was traced within the STAF model, and the situation of production, consumption and recycling of lead resources in China were introduced. The SFA is performed on lead flows during its one year life cycle in detail. As one of the biggest producer and consumer of lead in the world, China is facing a problem depletion of lead resources. How to increase the resource efficiency is a significant issue for lead industry of China. Based on the result, several suggestions were proposed in the paper, aiming to contribute important reference information for the industrial metabolism and resource management and recycling of lead industry in China.

Jan 1, 2009

By R. M. G. S. Berezowsky

Treatment of Hudson Bay Mining and Smelting Co. Ltd. (HBM&S) zinc concentrate in the Sherritt zinc pressure leach process produces a residue containing elemental sulphur, residual sulphides, precipitated iron species, si1ver and gold. Flotation of the residue recovers most of the elemental sulphur and residual sulphides to the concentrate, leaving iron oxides and bask sulphates in the tailings. The tailings also contain most of the sflver and some gold. Direct cyantde leaching of the oxide tailings (220 g/t Ag, 1.4 g/t Au) was capable of leaching most of the gold, but only a minor portion of the silver. This paper reports testwork, conducted by Sherritt on behalf of HBM&S, to define a process for a high recovery of the precious metals from the oxide tailings. A si1ver enhancement treatment, consisting basically of digestion of the residue with lime at 90°C to render the silver amenable to enhanced recovery by subsequent cyanidation, was selected as the most promising approach. Batch silver enhancement and cyanidation tests showed that treatment of the oxide residue with 80 kg/t CaO at 90°C for 1 to 2 h increased the silver extractability in subsequent cyanidation from <20% to 96%. A 96 h continuous miniplant test (1 kg/h solids feed rate), of a circuit including a silver enhancement treatment step followed by conventional cyanidation and carbon in pulp silver and gold recovery, confirmed metal recoveries to the carbon of 90% Au and 96% Ag. Reagent consumption rates were 1ess than 100 ?kg/t CaO and 5 kg/t NaCN.

Jan 1, 1990

By W. K. Connor, O&apos

The U.S. Bureau of Mines, in cooperation with the Idaho National Engineering Laboratory (INEL), conducted over 30 hours of melting tests to vitrify simulated low-level radioactive wastes from the INEL Radioactive Waste Management Complex (RWMC). Five separate waste compositions were investigated, each consisting of noncontarninated soil from the RWMC and surrogate materials used to simulate the actual buried wastes. The RWMC soil and five waste compositions were melted in a 50-lb, single-phase electric arc furnace with a water-cooled shell. These tests were conducted to determine melting parameters in preparation for a large-scale melting campaign to be conducted in the Bureau&apos;s 1-metric ton (mt), water-cooled-wall, 3-phase electric arc fumace. Bulk chemical composition was determined for each of the feed materials and for the slag, metal, fume solids, and offgas furnace products, and distributions were calculated for the key elements. The material balance for the furnace operation indicates that from 63 to 84 pct of the feed reported to the slag. Cerium, used as the surrogate for the radionuclides in the wastes, demonstrated an extremely strong affinity for the slag product. Although slag temperatures as low as 1250° C were recorded when melting the RWMC soil, temperatures in excess of 1600° C were necessary to achieve the fluidity required for a successful slag tap.

Jan 1, 1994

By Nobuaki Sato

For the recovery of uranium from spent nuclear fuel, sulfide reprocessing process, which consists of voloxidation, selective sulfurization, and magnetic separation or selective dissolution steps, are proposed. In this paper selective sulfurization of rare-earth oxides in the presence of uranium oxides was studied by thermogravimetry and X-ray diffractometry. In case of the mixture with UO2, the rare earth oxides R2O3 (R=Nd, Eu, etc.) were preferentially sulfurized by CS2 formingoxysulfides and sulfides, while UO2 remained at temperatures lower than 500 °C. When R2O3was mixed with U3O8, first, the reduction of U3O8 to UO2 occurred at low temperatures followed by the sulfurization of R2O3. The separation of rare earth elements from UO2 in suspensionsolution by the use of permanent magnet was examined. The advantage of the proposed process was also discussed by compared with current process.

Jan 1, 2006

By I. Ohnaka

Although many works have been reported on the semisolid casting, the mold filling behavior of semi-solid alloys has not been so well understood. This paper compares the physical and numerical simulation results on the mold filling behavior. Physical simulation was performed by using solid-water mixture. The numerical simulation was made under the assumption of one phase flow with an effective viscosity. It was found that the solid particles stabilize the flow greatly if the kaction solid exceeds about 0.4, because viscosity increases greatly. The overall flow behavior can be estimated by the numerical simulation. Interesting flow behavior was also found which can not be observed in the case of one phase flow and which is difficult to simulate by the one phase flow assumption.

Jan 1, 1997

By Junji Shibata

The waste acid mixture whose main component is phosphoric acid, is discharged from the etching process in the liquid crystal production industry. In order to separate impurity acids from the phosphoric acid, trioctyl phosphate (TOP) is used as an extractant. TOP can extract acetic and nitric acids selectivity. The extraction and stripping operations are carried out for the acid mixture by beaker-scale experiments and countercurrent multistage operations with mixer-settler equipment. TOP selectively extracts the acetic and nitric acids in the acid mixture. From the results of the McCabe-Thiele analysis obtained by beaker-scale tests, the extraction for acetic and nitric acids are approximately 100%, respectively, by 6-stage extraction with a phase ratio (A/O) of 0.4. On the other hand, almost all of acetic and nitric acids are stripped with water from the organic phase by 4-stage stripping with a phase ratio (A/O) of 1.0. About 95% of acetic and 98% of nitric acids can be removed from the acid mixture without extracting phosphoric acid in case of the mixer-settler equipment operation. There are several steps such as slicing, lapping, chemical etching and mechanical polishing in the silicon wafer production process. The chemical etching step is necessary to remove any damaged layer caused in the slicing and lapping steps. The typical etching liquor is the acid mixture comprising nitric acid, acetic acid and hydrofluoric acid. The waste acid is treated by a neutralization method with a high alkali cost and balky solid residue. A solvent extraction method is applicable to separate and recover each acid. Acetic acid is first separated from the waste liquor using 2-ethlyhexyl alcohols as an extractant. Then, nitric acid is recovered using TBP (Tri-butyl phosphate). Finally hydrofluoric acid is separated with TBP solvent extraction. The expected recovered acids in this process are 2mol/L acetic acid, 6mol/L nitric acid and 6mol/L hydrofluoric acid. The yields of this process are almost 100% for acetic acid and nitric acid. On the other hand, it is important to recover and reuse the metal values contained in various industrial wastes from a viewpoint of environmental preservation. Most industrial products are made through processes to separate impurities in raw materials, solid and liquid wastes being necessarily discharged as industrial wastes. Chemical methods such as solvent extraction, ion exchange and membrane separation, and physical methods such as heavy media separation, magnetic separation and electrostatic separation are considered as the methods for separation and recovery of the metal values from the wastes. Some examples of the application of solvent extraction to the treatment of wastes such as Ni-Co alloy scrap, Sm-Co alloy scrap, fly ash and flue dust, and liquid wastes such as plating solution, the rinse solution, etching solution and pickling solution are introduced.

Jan 1, 2003

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By C. Lupi

In 1996 the Italian Agency for Environmental Protection (ANPA) has initiated a study of the environmental impact of the industrial sector of steel produced by Electric Arc Furnace (EAF). Within the framework of this study a hydrometallurgical process to treat EAF dusts was considered and developed. The paper describes the zinc and lead recovery from fumes coming from carbon steel production. The zinc extraction consists in acidic leaching followed by SX-EW steps. The leaching sludge containing lead sulfates was treated to obtain pure lead salt and inert solid residue. The whole process, that minimizes effluents by recycling the main liquid streams, has been developed to obtain marketable products. The solid waste, containing spinels, was subjected to elution tests in order to verify its compatibility with environmental regulation. The process, that has been set-up and tested in the laboratories of the University of Rome, will be transferred and studied on a pilot plant in order to assess its industrial and economical feasibility.

Jan 1, 1999