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By Tim Robinson, Michael S. Moats, Masatsugu Moritmitsu, Kathryn C. Sole, Lauri Palmu, Frank K. Crundwell

"Process technology and design trends for copper, zinc, and nickel electrowinning cellhouses include focusing on energy reduction, productivity, and acid mist abatement. Larger electrodes, longer cells, automation, and higher current densities are leading to more capital-effective designs. The latest cellhouse designs include installation of automated electrode-handling systems, thereby removing more operators from the cellhouse. These technology and design trends result in lower electrowinning operating costs and improved purity of electro won cathode.INTRODUCTIONTechnology transfer between similar industries is an important process in improving product quality and productivity, and reducing operating costs. The electrowinning (EW) recovery of base metals, such as zinc, copper and nickel, is no different. The zinc industry with its larger EW product-handling requirements as compared to nickel and copper, has been driven to automation technology and the use of larger equipment. This technology has been transferred to copper. Nickel has led development and application in large-scale anode and divided-cell technologies but, due to nickel being produced in multiple forms (not just cathode) and being a small part of the whole complex nickel process route, the quantities of electrowon nickel are small compared to copper and zinc. Copper process technology in acid mist abatement was recently transferred to nickel. The focus in copper EW has been on energy reduction and productivity."

Jan 1, 2012

By T. T. Chen

Secondary copper anodes are generally rich in Sn, Pb, Ni and Sb, but are notably deficient in Se, Te and Ag. In the secondary copper anodes, most of the Ni, virtually all of the Ag, slightly more than one-fifth of the Pb, about one-third of the As and Sb, and approximately one-tenth of the Sn are in solid solution in the copper. The remaining impurity contents occur as 1-5 µm grain-boundary inclusions in the anodes, and these are mainly Cu2O, SnO2, Cu-Pb-As-Sb-Bi oxide, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide, Cu-Sb-Ni oxide (Kupferglimmer) and trace Cu2(Se,Te). Barium sulphate, which originates from the mold wash used in casting, is also present in the anodes. During electrorefining, the BaSO4, SnO2, Pb-Sb oxide, Sn-Ni-Zn oxide, Cu-Sn-Ni oxide and Cu- Sb-Ni oxide inclusions are liberated and accumulate in the slimes layer. Solid solution Ni dissolves and the Ni accumulates in the electrolyte. Solid solution Sn and Pb dissolve, but partly reprecipitate as Sn arsenate and PbSO4, respectively. Solid solution Ag dissolves but rapidly reacts to form Ag2(Se,Te), Ag powder, Ag-bearing Cu2O, (Cu,Ag)SO4 or a complex oxidate phase. Partial dissolution of the Cu-Pb-As-Sb-Bi oxide particles takes place; the Pb component is converted to PbSO4, whereas Cu, As, Sb and Bi dissolve. The reacted particles retain the morphology of the original Cu-Pb-As- Sb-Bi oxide phase. Some of the solubilized As, Sb and Bi remains in solution, but much reprecipitates as SbAsO4, As-Sb-Bi oxide, and as a poorly defined oxidate phase which consists mostly of Cu-Ag-Pb arsenate-sulphate. The high Sn contents of secondary copper anodes do not seem to affect the behaviour of the anodes during electrorefining.

Jan 1, 1999

By Jian Li, S. Penttila, W. Zheng

"Materials selection for Gen IV supercritical water reactor in-core components faces major challenges due to severe operating condition. Beside high-temperature mechanical properties, SCC and general corrosion resistance of commercially available materials are also major focuses in recent research. Recent reports suggest that certain types of surface modifications are beneficial to SCW corrosion resistance. In this study, the effects of surface modifications are investigated, and possible mechanisms for improved corrosion performance are discussed.IntroductionThe current Canadian pressure-tube supercritical water reactor (SCW) design specifies a core outlet temperature of 625°C under 25 MPa of pressure, with peak cladding temperature as high as 850°C. Challenges in materials selection include high-temperature mechanical properties, corrosion resistance, SCC resistance and radiation damage. Most of the SCW corrosion test results available are below 730°C. Early work by Allen [1] summarized the corrosion resistance of alloy groups including Ni-based super alloys, stainless and ferritic/matensitic (F/M) steels that can potentially be used for SCW reactors. F/M steels can only be used at low temperature sites (e.g. down stream piping). At 500°C and 25 MPa, F/M steels develop a thick but mechanically stable oxide layer. However, the long term stability of the surface oxide layer is largely unknown. Ni-based alloys appear to form very thin surface oxide, however pitting was observed in the vicinity of some intermetallic precipitates [2-5], and dissolution of major alloying components could pose significant problems for down stream piping [6]. In addition, concerns of Helium formation due to Ni transmutation prevented this alloy group to be used as fuel cladding. The corrosion resistant austenitic stainless steels (e.g. 316L) are found to be susceptible to localized corrosion such as pitting, intergranular attack and stress corrosion cracking (SCC) [7]."

Jan 1, 2012

By H. Fukushima, T. Ohgai, N. Baba

The electrodeposition behavior of Zn and the morphology of the deposited Zn were studied in electrowinning solutions containing polymer additives such as gelatin and polyethylene glycol (PEG). The cathode potential was shifted in a less noble direction and the polarization resistance for Zn deposition increased with increasing concentrations and molecular weights of both gelatin and PEG added to the electrolytic solutions. However, when the molecular weights of these additives exceeded about lxlO4, the cathode was depolarized and the polarization resistance for Zn deposition decreased with increasing molecular weight. The crystal grain size and the (002) orientation of the deposited Zn became smaller when the concentration and molecular weight of the additives increased, and the cathode was polarized.

Jan 1, 2000

By Rudolf Keller

In the electrolysis of neodymium oxide from a molten fluoride electrolyte, anode effects may occur at the carbon anodes, interfering with smooth cell operation. In laboratory experiments, we attempted to circumvent this problem by selecting electrolytes with a high oxide concentration, possibly at relatively low rare earth content, but cathodic deposition was not satisfactory. A regime at higher cell voltage was discovered to yield good cell performance, but evolution of considerable amounts of fluorocarbon compounds suggested that a reactive treatment of the off-gases would be necessary for environmental acceptability. Subsequent experimentation at low cell voltage revealed conditions for satisfactory operation without occurrence of anode effects and without formation of any CF4 or C2F8.

Jan 1, 1997

By Li Cheng

The SKS copper smelting process was jointly developed by Shuikoushan Mining Corp. and ENFI (Beijing Central Engineering and Research Institute for Non-ferrous Metallurgical Industries) in China. It is a new bath copper concentrate smelting process with oxygen enriched air. The pilot plant testwork was completed successfully in 1993. SKS has demonstrated to be an advanced bottom blown smelting process. This technology got the First Class Prize of Scientific and Technological Progress awarded by CNNC (China National Non-ferrous Metal Industry Corp.) in 1994. The SKS process has significant capital and operating cost advantages. Its environmental and industrial safety and hygiene performance represents a substantial improvement when compared to conventional technologies. The technology has generated great interest in the Chinese metallurgical industry. Feasibility studies and basic designs have been carried out to incorporate in retrofit and green field smelter projects in China and abroad. This paper describes the history of the pilot plant operating data (50 tonnes dry feed/day), and discusses the features of the SKS technology, its application and possible future trends.

Jan 1, 1999

By M. C. Nielson

The paper describes the design and operation of pulsed columns as replacements for conventional mixer/settlers. The advantages, which the columns offer, include a reduction in real estate for the plant, elimination of diluent evaporation, containment of noxious vapors and reduced crud formation. In addition to the description of operation, the paper presents the findings of laboratory tests of pulsed columns extracting copper from pregnant leach solutions and also delineates potential advantages of the pulsed column in copper solvent extraction.

Jan 1, 1999

By J. Miernik, D. Krupka, B. Ochab

The electrolytic zinc plant, with a capacity 75,000 tonnes per year, is part of Zaklady Gorniczo-Hutnicze BOLESLAW. It is the biggest zinc producer in Poland. The electrolytic zinc plant started up in 1955 with a capacity 15,000 tonnes per year, and multiplied its production by 5 till nowadays. At the beginning, the plant processed only calcine from zinc oxides (60% Zn, 3-4% Pb, 0,03 % Cd) which were produced from Waeltz fumes by calcination in a rotary kiln. Participation of calcine from zinc sulfide concentrates in the feed grew during the BOLESLAW plant expansion. Currently, only roasted sulphide concentrates, calcine from fluid-bed roasters, is processed. This paper presents a general description of the ZGH BOLESLAW plant and discusses the processes of roasting, leaching, purification and electrolysis. Also shown are the chemical analyses of the various process materials.

Jan 1, 2000

By Tae-Hyun Kim, Kang-In Rhee, Jeong-Soo Sohn

The synthesis of Mn-Zn ferrite powder from spent zinc-carbon batteries was investigated using a series of physical treatment, sulfuric acid leaching and coprecipitation. Physical separation methods such as crushing, magnetic separation and sieving were applied to generate a non-magnetic material of 8- mesh undersize for subsequent leaching process. The 8-mesh undersize of the spent zinc-carbon batteries was assayed 23.9% Mn, 14.9% Zn, and 4% Fe. Metal extractions obtained in sulfuric acid leaching at the solid/liquid ratio of 1:10, 2 M H2SO4, and 60? with 6 vol.% H2O2 addition were 97.9% Mn, 98.0% Zn and 55.2% Fe. The leach liquor was finally adjusted to the Mn:Zn:Fe mole ratio of 1:1:4 suitable for producing MnZnFe4O8 ferrite powder by the addition of Mn, Zn and Fe sulfates followed by pH control. A co-precipitation test for Mn-Zn ferrite powder was performed at 80?, O2 gas flowing at 1.3 L/min. As a result of co-precipitation, Mn-Zn ferrite nanoparticles in 20 nm size with spinel structure were successfully synthesized. The saturation magnetizations of Mn-Zn ferrite powder (Mn1-xZnxFe2O4) were determined to be 39-91 emu/g with various zinc contents (X=0.2-0.8).

Jan 1, 2008

By C. Allen, A. Roy, J. W. Evans

A spouted bed electrode (SBE) has been used, in laboratory experiments, to electrowin zinc from zinc chloride electrolytes with the objective of determining the suitability of this electrode for commercial application. Zinc was successfully electrowon at current densities ranging up to 4,38 lA/m2, which are an order of magnitude larger than those used at present in the zinc industry. Current efficiencies, for the cell with the SBE, have been as high as 90% and DC energy consumption as low as 2.8 kWh/kg zinc deposited. The performance of the cell has been measured as a function of current density, anode type, cell diaphragm, addition of tributyl ammonium chloride and purging of the electrolyte (to remove dissolved chlorine).

Jan 1, 2000

By Mark F. Vancas

Virtually every new process plant project goes through the ?Feasibility Study? phase before actually being built. The Feasibility Study is used by the owners and the bankers to evaluate the economics of the project and determine whether or not the proposed investment meets their respective investment guidelines. With a positive result, the project is approved and goes to construction and operation. Then, the actual costs are incurred and these actual costs may or may not agree with what the Feasibility Study predicted. Just how good have Feasibility Studies been? This paper looks at various projects and compares predicted to actual results and also gives information on how to spot a poor feasibility study.

Jan 1, 2003

By D. F. Liub, Z. Y. Liu, W. Y. Xue, Y. F. Shenb, Y. D. Wang

"The microstructure characteristics and deformation behavior of ultrafme grained (UFO) 304SS fabricated by accumulative rolling and armealing have been investigated by means of tensile tests, electron-backscatter-diffraction (EBSD) and transmission electron microscopy (TEM) techniques. The volume fraction of martensite phase decreases with increasing armealing temperature. In the grain sizes ranging from 300 nm to 10 µm, the strength held Hall-Petch relationship. The sample with an average grain size of 300 nm exhibited extra high yield strength of 1700 MPa and a tensile strength of 1780 MPa, while the elongation retains 12%. The limited uniform elongation in the UFO materials could be explained in terms of plastic instability. Very interestingly, for the bulk material with an average grain size of 1.200 µm, the high yield strength and uniform elongation were simultaneously achieved to be as 1000 MPa and 18%, respectively.IntroductionUltra-high strengths have been achieved in elemental metals by employing heavy plastic deformation, or by creating ultra-fine-grained (UFO) structure. Here UFO materials are defined as polycrystalline solids with property-controlling microstructural features below the 1 µm level. Typical processing routes include severe plastic deformation (SPD) [1, 2], which decomposes the grains through dislocation accumulation and reorganization (polygonization). Several different kinds of SPD process for bulk materials are typically as equal-charmel angular pressing (ECAP) [3], high-pressure torsion (HPT) [4] and accumulative roll-bonding (ARB) [5]. One of the main motivations for such a push for the very small grain sizes stems from the expectation of unprecedented mechanical strength, as predicted by the well-known Hall-Petch relationship that projects a continuous rise of strength with decreasing grain size [6]. However, these ultra-high strength metals no longer have the high ductility typical of their conventional coarse-grained counterparts, because the undesirable inhomogeneous deformation on the microstructure level can lead to the early onset of failure, severely limiting the useful ductility [2]. Recently, the interesting strategies have been performed to increasing simultaneously the ductility and strength ofUFG pure copper and nanostructured alloys by Zhao et al [7, 8]. In a pure copper, a high ductility has been achieved without sacrificing strength by introducing a high density of pre-existing twins and a large fraction of high-angle grain boundaries. Their encouraging results trigger our motivation to obtain high strength and ductility from the commercially bulk material."

Jan 1, 2013

By Yuan Zeping

The Guixi smelter is the first Outokumpu flash smelter in China .It was commissioned on December 31, 1985. Originally, the smelter was designed to produce 90,000 tonnes of copper annually. After the implementation of oxygen enrichment and other modifications, the smelter will reach its anticipated annual capacity of 200,000 tonnes of copper in December 1999. This paper describes the performance of the smelter, the first phase modification project and the second phase expansion project which have made Guixi one of the best copper smelters in the word through the use of existing and innovative technologies.

Jan 1, 1999

By Julian Szekely

Transport phenomena, that is heat transfer, mass transfer and fluid flow, play a critical part in the operation of metallurgical reactors. In this paper, we shall present a review of our current state of ability to model these systems mathematically, with emphasis on the use of computational codes that are generally accessible to the public and on the comparison of the theoretical predictions with measurements.

Jan 1, 1993

By Akram Alfantzai, Farzad Mohammadi, Maysam Mohammadi

"Degradation of lead anodes has always been a major concern among the electrowinning industries. In this study, the effect of agitation of the zinc electrowinning solution on the integrity of lead anodes was investigated. Galvanostatic experiments were performed at 37±0.5°C using 0,600 and l000rpm magnetic stirring rates for 24 hours. The Pb02 layer formed on the anode surface was reduced to PbS04 (discharged). The discharge information was used to calculate the amount of Pb02 present on the surface. Weight loss measurements along with the discharge calculations revealed that the degradation rate of the lead anode increased as the solution was stirred more vigorously. Furthermore, the amount of remaining Pb02 on the surfaces was decreased as a function of solution velocity. Therefore, it may be concluded that, degradation rate oflead anodes is controlled by detachment of the corrosion products from the surface rather than by electrochemical reactions. IntroductionElectrowinning is one of the extraction stages of zinc, in which pure zinc is deposited from acidic solution after froth flotation, roasting and leaching processes. The anode electrode materials play important roles in the electrowinning process. Their electrocatalytical capacities determine the oxygen evolution overpotential, and consequently the cell potential and energy efficiency of the zinc electrodeposition [l]. Purity of the zinc deposited on the cathode is affected by the solubility and corrosion resistance of the anode materials. Using insoluble materials as anode in the electrowinning leads to the higher purity of the deposited metal on the cathode[2]. Lead (Pb) and its alloys have been used as the anode in the zinc electrowinning because of its special properties such as relatively low cost, low melting point, insolubility in solutions containing sulphuric acid and high conductivity in both states of metallic and oxidized [3, 4]. In zinc electrowinnig, zinc reduction occurs on the cathode (reaction 1) and the oxygen evolution reaction (OER) (reaction 2) is the main anodic reaction [5, 6]."

Jan 1, 2013

By B. Rourke, O&apos

Copper Refineries Ltd. (CRL), Townsville is Australia's largest producer and exporter of refined copper cathode. This status has been maintained by the implementation of a significant capital works program that increased the production capacity to 270,000 t/y by June 1999. In 1979, CRL was the first in the world to commission the ISA Process Technology which has now been marketed to 47 licensees worldwide. The new tankhouse design has focused particular attention on customer requirements, operational improvements, materials handling and equipment modernisation. Equipment which has been upgraded includes cranes, anode preparation, cathode stripping and scrap washing machines along with the total replacement of the electrolyte and electrical reticulation systems. Side stream electrolyte filtration has been introduced. Improvements to electrode alignment afforded by the conversion to polymer concrete cells, precise electrode location, and the upgrade of the electrode handling machines will ensure that CRL. continues to be one of the world's major quality copper cathode producers.

Jan 1, 1999

By Melissa L. Trapani

The removal of molten products from metallurgical furnaces is one of the most hazardous and labour intensive processes in a non-ferrous smelter. The proximity of operators to the molten metal and slag during tapping and the oxygen lancing that facilitates the flow have led to many reported injuries on tapping floors. In most cases, tapholes are opened and closed periodically leading to extreme thermal cycling in the tapping assembly. As a consequence, refractory wear rates are high and unpredictable in the taphole. This paper provides a review of the current state of taphole development, and gives a methodology that is now being applied to gain a better understanding of the taphole region to allow design improvements.

Jan 1, 2002

By Benjamin Vidales

Copper in concentrations above 0.5 weight percent in iron and steel causes hot shortness. This tendency is intensified in the presence of dissolved tin above 0.05 weight percent in the alloy. The understanding of the mechanism of removal of copper from molten iron and steel is of industrial importance. In this investigation, we present the experimental results of the removal of copper from molten iron using sulphide flux in the temperature range 1000°-1500°C. The solution thermodynamic properties of binary sulphide melts have been estimated by using the relevant phase diagrams and the behaviour of copper sulphide in these melts is discussed. The kinetics and thermodynamics of the removal reaction are also explained and, the experimental results are also reported showing the equilibrium distribution of copper and sulphur in molten iron.

Jan 1, 1995

By P. M. Pincheira Brown

The widely accepted inverse relationship between copper prices ail stocks, has been commonly used by analysts to explain the behavior of the copper market and to forecast film copper pries. However, empirical data have not shown such a clear relationship between copper prices and stacks. Existing evidence only indicates a weak tong-nut relationship that vanishes in some periods. In this paper a simple comprehensive model is provided which explains both parallel and opposite direction movements between prices and stocks. Former are explained mainly by stocks demand expansions-contractions while the latter are in essence due to increases in the supply curve. Furthermore, econometric estimations are provided, thus giving a powerful tool to forecast and explain price developments of the copper market.

Jan 1, 1999

By Hiroyuki Matsuura

Treatment of electric arc furnace (EAF) dusts has become an important issue from the viewpoint of the environmental protection and recycling of variable resources because these dusts contain considerable amount of zinc and lead. A new recovery process of these metals has been proposed, in which the metals in the dusts react with waste polyvinyl chloride to form metal chlorides. Therefore, it is important to clarify the physicochemical properties and behaviors of zinc, lead and those chlorides and oxychlorides. In the present study, the kinetics of chlorination of ZnO, PbO and ZnFe2O4 mainly contained in the EAF dusts were investigated at 1023 K to 1273 K with Ar-O2-Cl2 gas. Based on these results, the selective chlorination and evaporation process of zinc and lead from the mixture of Fe2O3-ZnFe2O4-ZnO-PbO was examined and the high efficiency of selectivity has been demonstrated.

Jan 1, 2006