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By C. Anderson

Most applications of copper metallurgy are geared towards primary production. However, as recycling of materials is a growing industry, one future facility will rely on copper metallurgy as a means of processing precious metals. This paper will discuss the derivation of the proposed copper pyrometallurgical and electrometallurgical unit operations to be utilized in industrial recycling of secondary precious metals.

Jan 1, 1999

By Tuula Mäkinen

In 1959 Outokumpu started up an integrated nickel smelter and refinery at Harjavalta. The flash smelting ? Peirce-Smith converting route was applied, and the high-grade converter matte was further refined to nickel cathodes by leaching and electrowinning. In 1995 the production capacity was increased from 17 000 mtpa to 52 000 mtpa, based on the Direct Outokumpu Nickel Smelting Process. The additional refinery capacity is based on hydrogen pressure reduction, producing nickel powder and briquettes. The smelting operation is currently part of Boliden Group and the nickel refinery part of OM Group. In the DON technology, high-grade nickel matte with low iron content is produced in the flash smelting furnace directly without subsequent converting. The metal values in the smelting slag are recovered in an electric furnace as an iron containing Ni-matte. The mattes produced differ from the conventional nickel mattes in many respects, and therefore focused R&D efforts have been made in order to cope with their melting points, fluidities and settling properties. When developing and operating metallurgical processes it is crucial to manage and control the characteristics of the products as well as by-products generated in different steps of the process chain. The low melting points of the high-grade nickel mattes produced in the DON furnace, particularly those low in copper, have pointed out challenges in the furnace design, in particular in the hearth and its thermal engineering. Also key issues of the DON technology are smelting of high-magnesia concentrates, the recoveries of nickel and copper, as well as those of PGM`s and cobalt. These factors can be affected by a proper selection of the process concept, and the operational conditions in the processing vessels. This paper deals with the experience of the DON technology gained over the first ten years of operation, including the significant environmental impacts. Selected results of the thermo-dynamic modelling of DON and EF mattes and high-magnesia slags are reviewed, with the reference to the mattes produced. Also the design principles of the FSF and EF will be discussed.

Jan 1, 2006

By Jose Castro

The growing demand of scrap to supply the electric arc furnace has driven to search for new alternatives of raw material. The DRI produced using self-reducing pellets has become competitive due to the potential use of a wide range of carbonaceous materials such as coal, charcoal, biomass etc. In this context, the rotary kiln process using improved technologies such as post-combustion and self-reducing burden is a promising source of high quality raw materials. This paper presents a mathematical model of the rotary kiln process designed for self-reducing pellets and post-combustion. The model is based on the transport equation of two-phase flow, energy and mass transfer. The solid material is composed of a typical self-reducing pellet. The model considers the solid phase (C, volatiles, Fe2O3, Fe3O4, FeO, Fe, H2O, SiO2, Al2O3, MgO, P2O5, K2O, Na2O, FeS, CaO and gangue) and the gas phase (N2, O2, CO, CO2, H2, H2O, SO, SO2 and SiO). For each of the above components a conservation equation is solved and the mass and energy transport is accounted. The set of differential equations are coupled by the rate equations describing the kinetics of the several reactions, which take place within the rotary kiln. All the conservation equations are solved based on the finite volume method applied for a three-dimensional cylindrical coordinate system. Simulation results are presented for global parameters such as metallization degree, productivity, gas utilization ratio and calorific value. Inner conditions such as three-dimensional gas and solid temperature patter and compositions are discussed.

Jan 1, 2006

By Shengli Wu, Mingyin Kou, Laixin Wang, Xinliang Liu, Zhennan Qi, Yujue Wang

Softening and melting experiments were conducted on four kinds of imported lump ores named A-D, under different temperature intervals within the self-developed visualization high temperature furnace. By calculating the reduction and shrinking degree under different intervals, softening and melting indexes were determined. These ores all expanded firstly followed by shrinkage with the temperature increasing. The difference of lump ore’s own characteristic led to different softening and melting behavior. The results showed that the looser the structure was, the better the reducibility will be. The compact structure and good reducibility led to high expansion rate. The beginning softening temperature declined and the ending softening temperature increased because of high porosity, which resulted in wide softening temperature interval. The charging ratio of lump ore A should be improved. Lump ore B should be distributed in the center of the blast furnace. Lump ores C and D should be used less.

Jan 1, 2016

By Andreas Nolte

In 1999 HÜTTENWERKE KAYSER AG (HK) in Germany will produce more than 180,000 t/y of electrolytic refined copper. To achieve this production from materials with copper grades from two to seventy percent and diverse copper alloys, HK operates three blast furnaces, one holding furnace two Peirce Smith converters and two anode furnaces. Technical, metallurgical and economic factors for the ongoing process optimization are outlined. The fluctuating quality and quantity of raw materials renders complex this optimization. The principal variables are the quality and quantity of process consumables: coke, copper-iron, limestone, oxygen, as well as the blending of feedstock and a new organization of the operating crews. The search for new metallurgical process parameters is ongoing. HK started with an intensive research programm in November 1997. As a result it will be possible to cut processing costs by about ten per cent, to increase the blast furnace capacity by ten per cent and to lower the metallurgical losses of copper and tin in the slag by more than ten percent. The presentation concludes with information on future steps to continue the optimization process.

Jan 1, 1999

By David G. Dixon, Ahmad Ghahremaninezhad, Edouard Asselin

"In this study pertaining to the electrochemistry of chalcopyrite, the active/passive behavior of a chalcopyrite electrode in 0.5M sulfuric acid solution was investigated. Potentiostatic and potentiodynamic polarization and multi-cyclic voltanunetry were conducted to analyze the electrodissolution parameters of the electrode.The potentiodynamic and potentiostatic polarizations of chalcopyrite revealed the formation of a passive film on the surface of chalcopyrite. From the potentiostatic study in the passive potential region, a decrease in the dissolution current density by increasing the potential was observed. From this, it was concluded that the passive film is an n-type semiconductor and cation interstitial defects or anion vacancies are the charge carriers. From multi-cyclic voltammetry studies, four cathodic peaks at - 0.37, 0.30, -0.10 and-0.20 YsHE were detected on the surface of a passivated chalcopyrite electrode. The cathodic peaks at 0.37 and 0.30 V were connected to ferric to ferrous reduction and copper sulfide formation, respectively. The peaks at -0.10 and - 0.20 were related to chalcopyrite reduction. The products of the chalcopyrite reduction reactions were suggested to be Cu2S, Cu9fesS16 and Cu5feS4 and evolution of hydrogen sulfide gas (H2S).IntroductionChalcopyrite is the most abundant copper bearing mineral in the world and its dissolution behavior represents the most important technological consideration in the hydrometallurgical extraction of copper [I]. Since the current pyrometallurgical methods for copper extraction from chalcopyrite have environmental issues, many studies have considered the leaching and dissolution of CuFeS2 in different aqueous media [2-5]. The main problem associated with leaching processes is the slow dissolution rate of the mineral [6]. During the dissolution process, increasing the potential of the chalcopyrite in the anodic direction will cause the formation of surface layers which hinder the dissolution rate of the mineral [7]. The precise composition of the layers is in dispute. Previous studies have concluded that these layers could be sulfur [8-9], precipitated iron compounds [8], a solid electrolyte interphase (SEI) - which slows the rate of electron transfer- [10], a metal deficient sulfide [ll], or polysulfidic in nature [12-13]. In order to increase the leaching kinetics of chalcopyrite, the characterization of the layers formed during dissolution is essential and electrochemical methods are important to this end. Studies by Biegler [14] show nucleation and growth of a thin two-dimensional sulfide phase on the surface of chalcopyrite during the exposure of a polished sample in HzS04 solution or air. More studies by Biegler and Swift [15] have shown evidence for nucleation and growth of a 3-dimensional phase at low anodic potentials (around 200 mV vs. OCP). The current-time behavior of the dissolution process in this potential area has the characteristics of expansion and overlap of localized dissolution centers."

Jan 1, 2012

By Fei Ruan, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"Viscosity is an important physical parameter of slag in metallurgical processes. Most studies of aluminosilicate and aluminate systems assume that aluminum occurs in tetrahedral coordination. In this case, the O/Al value was utilized to describe the slag structure in terms of the network character of aluminosilicate and aluminate systems. Composition and viscosity data from the literature and the trends were analyzed according to the O/Al value and temperature. It is shown that the O/Al value explains the trends in more than ten systems, containing more than 200 data points. In aluminosilicate system, the trend that viscosity value changed with the O/Al value which implies that alumina works as network modifier such as basic oxides or works as network former. In aluminate system, irrespective of the system and temperature, viscosity decreased steadily when O/Al value increased.IntroductionMetallurgical slags, which are made of oxides and many also contain fluorides, play an important role in metallurgical processes such as iron making, steel making and secondary refining processes. Aluminosilicate slags are applied in a wide range in metallurgical processes. A polymerizing effect of the addition of aluminum and an association of aluminum with low-field strength cations is further supported by the physical variations in aluminosilicate and aluminate systems. The behavior of alumina in silicate melts has been studied by various authors [1-6]. It is generally accepted that Al2O3 is amphoteric [7] because Al3+ ions can behave in profoundly different ways in a silicate melt. When added to a pure silica melt, Al2O3 acted as a network modifier, breaking the bridging oxygen of the pure silica network, thereby decreasing the viscosity in a similar manner to other network modifiers, such as CaO, MgO etc. to form [1/2Ca (AlO4)]4- complexes. However, when added with alkali or alkali-earth metal oxides, some of the Al3+ ions assumed tetrahedral coordination and replaced Si in the liquid network, the missing charge was compensated by Me+ or Me2+ ions. Therefore Al2O3 acted as network former [8, 9]."

Jan 1, 2011

By F. F. Aplan

Though over 100 minerals are known to contain the rare earth (RE) or lanthanide elements, only a few provide the bulk of the world's source of these elements. The principal RE-containing mineral, monazite [(Ce,La,Th,Y)PO4], is recovered by gravity, magnetic, electrostatic and flotation concentration methods, while the other important source mineral, bastnasite [CeFC03], is concentrated by flotation. The processing of the lesser important source minerals is discussed, as is the recovery of the lanthanides from apatite [Ca5(P04)3(F,OH)] where the rare earth elements are present from trace amounts to over 10% as the mixed oxides.

Jan 1, 1989

By A. I. Okunev

The investigation results are submitted on separation into layers in the systems Cu (Ni) - Fe - Ca - 0 - S - (Si), as well as on physico-chemical properties of oxide - ferrite, oxide-sulfide melts (density, surface tention, viscosity, electric conductivity), on kinetics and oxidation macromechanism of iron and sulfur in the oxide-silicate, oxide-ferrite and oxide-sulfide melts, kinetics of reduction of oxide-silicate and oxide-ferrite systems. Conditions are discussed for copper, nickel and zinc recovery from oxide-silicate and oxide-ferrite slag in liquid and solid states. Some promising technique is the technique of future, as is considered.

Jan 1, 1988

By Torben L. Edens

Norddeutsche Affinerie is the largest copper producer in Europe. Two sites are in operation for the production of refined copper: primary copper production is located in Hamburg and secondary copper production in Lünen. A total of just under 560,000 tonnes of copper cathodes is produced annually at the two sites. Primary copper production using the flash smelter furnace has been in operation in Hamburg since 1972. Over the years, the capacity of the flash smelter has been increased in three expansion projects from 120,000 t to almost 500,000 t of anode copper p.a. The anode sector consisting of two anode furnaces and a 24 mould casting wheel still features just about the same equipment as in 1972. The paper describes the most important steps taken to optimise operation which have put NA in a position to cast meanwhile more than 500,000 t of anode copper annually with the two anode furnaces and 24 mould anode casting wheel.

Jan 1, 2006

By Zhang Yongzhu

Developments on bioleaching of low grade ores and refractory gold ores by T. Ferrooxidans in China are summarized. Effect of the ions on bacterial growth, bioelectrochemical reaction mechanism of sulfide minerals and bacterial reaction mechanism are also discussed.

Jan 1, 1992

By Michael S. Moats, Alexander Derrick

"The Winand Diagram was developed and has been used for decades to illustrate the interaction between polarization, mass transport and inhibition on the resulting structure of a metal electrodeposit. Recently, Adcock et al. criticized the Winand Diagram and developed their own structural diagram based on nucleation and plating overpotentials. Their work was based on zinc electrodeposition using a galvanostatic staircase method. This work explores the nucleation and plating overpotentials for copper electrodeposition using conditions typical for primary electrowinning and the galvanostatic staircase experimental technique. Additionally, the effects of organic additives and plating substrate on these overpotentials are reported.IntroductionThe control of electrodeposited structures is critically important to modem electrometallurgy operations to insure proper quality and efficient energy use. Electrodeposition of base metals for primary recovery (e.g. electrowinning or electrorefining), while similar to plating for decorative or device manufacturing, differs in the need to produce deposits that cover large areas and grow to significant thickness. Thus, controlling nucleation and particularly growth of electrodeposits is critically important for base metal electrometallurgical operations.The control of nucleation and growth on an industrial scale is most influenced by five parameters - current density, temperature, metal concentration, electrolyte agitation and additives. The effects of these parameters on electrodeposition are interrelated. To describe their effects on the type ofelectrodeposits generated and provide practitioners with a useful tool, Winand developed what is known as the Winand Diagram [1-2]. An adapted version of the Winand Diagram is shown in Figure 1.Winand characterized electrodeposits using Fischer's classification [3] and plotted the various deposit types versus inhibition on a vertical axis and the ratio of current density to bulk metal concentration on the horizontal axis. Inhibition intensity is a complex parameter and is still not well understood even though Fischer introduced the term in 1960 [4]. Often, inhibition intensity is simplified to equal the concentration of organic additive at the deposit surface and is related to the inverse of the exchange current density of the metal being deposited. The ratio of current density to bulk metal concentration is used to represent the ratio of crystallization overvoltage to mass transport of the depositing ion. As such i/iL could also be along the horizontal axis, where iL is the limiting current density of the electrodeposition reaction."

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 Ahmet Geveci

[Generally accepted formula related to sulfur slag-metal distribution ratio is given by the following equation: [ ] According to the above equation it can be deduced that sulfur distribution between slag and metal is governed mainly by metal composition (?s term), slag composition (slag basicity and in turn sulfide capacity), oxygen potential of the system (ao¬¬ term) and temperature(related to equilibrium constant, K). In this study, the results of ladle furnace operations conducted in Erdemir-Iron and Steel Works Co. (Turkey) in relation to sulfur removal, have been given. Typical ladle furnace slag analyses of 4937K quality steel have been presented. Activity coefficient of FetO,?FetO, have been calculated with the relation obtained fromthe literature. Activity calculations have been performed with the program written in Mathcad. The changes in activity of aFetO in the slag phase,, have also been studied in relation to the sulfur removal: The relation between % Decrease aFetO and %DeS (measured)have been investigated for 4937K runs and someother types of steel produced in the Erdemir Plant. Related to ladle operations %desulfurization defined as [(%Sinitial-%Sfinal)/S%initial]*100 values have been presented for different steel qualities.]

Jan 1, 2006

By E. Ilgar

"Deposition studies were conducted in acid copper electrolyte to determine the influence of chloride ions on cathode morphology. A statistically designed screening test was carried out in the absence and presence of 20 ppm CI- using a three factor, two level factorial design, in an electrolyte containing 36 gl'! Cu2+ and 150 gl-! H2S04, The independent variables evaluated were agitation; current density and temperature and their influence on surface roughness was determined. The copper deposited at current densities where activation was the primary control mechanism appeared similar in morphology whether stirring was used or not. The addition of 20 ppm CI- to the electrolyte gave rougher deposits under the same conditions. In the mixed control regions, considerably rougher, dendritic deposits were obtained when CI- was present. Agitation was effective in reducing the copper surface roughness both in the apparent activation and mixed control regions in the presence ofCI-. The results of this study showed that 20 ppm Cl- polarized the copper deposition at low overpotentials but caused depolarization at higher overpotentials.IntroductionChloride ion is inherently present in copper electrolyte, either as an additive or from other sources such as make up water. The behavior of the chloride ion is well documented in electrorefining operations, but its role in copper winning is less obvious. However in both cases there is evidence that cathode growth and solution chemistry are strongly influenced by its presence. The mechanism and electrochemical action of the Cl"" have been shown to be very complex, therefore a better understanding of its influence on electrocrystallization is essential for improved cathode deposit growth control. It was proposed that Cl"" polarizes the copper deposition reaction at low concentrations due to CuCI formation but depolarization occurs at higher concentrations due to the formation of a soluble CuCI2"" complex [1,2]. Franklin [3] reviewed the mechanism of additives in the electrodeposition process and proposed that the Cl"" complexed with copper, adsorbed on the cathode as an induced anion leading to an increase in the reduction rate. At cathodic overpotentials less than 100 mY, lppm NaCl had a polarizing effect, i.e. an increase in impedance of the charge transfer step. At higher Cl"" concentrations up to 100 ppm, depolarization occurred as evidenced by a decrease in impedance, which was attributed to soluble cuprous complexes [4]."

Jan 1, 1997

By Ken Baxter

The Sepon Copper Project is located in Laos and has a mineable reserve of approximately 16Mt of ore grading 5% copper with minor gold and silver values. The deposit is a clay-hosted secondary copper mineral suite, predominantly chalcocitic in nature with associated pyrite. The current project design is based on the production of 60,000t/a of LME Grade A cathode by an acid leaching process followed by solvent extraction and electrowinning. Significant metallurgical testwork was conducted as part of the Definitive Feasibility Study (DFS) with process challenges identified and overcome at each phase of testing. Flowsheet configuration is geared to autogenously generating sufficient acid and ferric iron to meet gangue acid consumption and to leach the copper. The ability to maintain acid and ferric levels in the process liquors is strongly influenced by the proportion of pyrite in the ore presented to the autoclave. This paper will outline flowsheet development from preliminary variability testing to pilot plant and DFS design. The Sepon process solution seeks a balance between operability and capital/operating costs, and provides insights into the basic mechanisms influencing flowsheet selection for these ore types.

Jan 1, 2003

By Michael S. Moats, Daniel Kim, Shijie Wang

"The behavior and deportment of lead, arsenic, antimony and bismuth are critical in producing high quality cathode by copper electrorefining. A critical review of research related to these elements is presented along with a comparison to industrial data, where appropriate. These elements exist predominantly in the anode as complex oxides along die grain boundaries. Upon dissolution, Group 15 elements report both to the electrolyte and slimes while lead essentially enters the slimes. The deportment of the Group 15 elements appears to be influenced by several chemical interactions which are discussed. The effect of these elements on floating slimes and anode passivation is reviewed. Under normal electrorefining conditions, lead, antimony and bismuth are thought to enter the cathode through the encapsulation of slime particles. The literature indicates that arsenic enters the cathode predominately by electrolyte entrainment. Finally, areas for future research regarding these elements are presented.IntroductionControlling lead, arsenic, antimony and bismuth is critically important for the production of high quality cathode in copper electrorefining. The reasons for this are twofold. First, ASTM Grade 1 Cathode specifications [1] for these elements are low, as listed in Table 1. Second, they can affect the efficiency of the electrorefining process (e.g., through passivation, current efficiency, slime processing)."

Jan 1, 2012

By Luciano B. Oliveira, Luis G. C. Marques, Sergio N. Monteiro, Marcos V. M. Fagundes

"Biodiesel production is normally associated with large plantations of oily vegetables such as soybean and colza, in large rural areas. However, in the municipal limits of the city of Rio de Janeiro, southeast of Brazil, biodiesel is being produced from wastes commonly generated by typical urban activities such as sewage sludge, discarded fat from meat markets and post-used cooking oils. In the present work, the experience of producing biodiesel from urban wastes in Rio de Janeiro is assessed. The type of precursor materials, equipments and logistics are presented. The environmental and economical advantages as well as the drawbacks are discussed.IntroductionThe interest for a liquid fuel that could substitute those obtained from petroleum started more than one hundred years ago when Rudolph Diesel tested his no-spark internal combustion engine, impelled by compression, with peanut oil. By that time, petroleum was beginning to be extracted in large scale and no one was concerned with the future environmental problems and its eventual depletion. In the last century, the successful association of petroleum based fuels with the automotive industry was an almost insurmountable obstacle to any attempt to use nonmineral oils [1]. In addition to the greater efficiency and, by then, lower price of the diesel from petroleum, the use of plain vegetable oils introduced undesirable carbon deposits and reduced the engine lifetime. Today, the situation is reverse. The continuous increase in the price of petroleum and, above all, its contribution to climate changes are strongly motivating the use of biofuels to replace those obtained from fossil fuels such as petroleum, natural gas and coal [2].In the case of the common petroleum derived diesel, many countries are now engaged in large scale substitution programs. The USA should produce more than 700 million litters of biodiesel, while the European Community is expected too produce around 6.5 billion litters in 2008. In Brazil, the federal biodiesel program imposed a minimum of 2% addition to the common diesel. This would demand a production of 800 million litters in 2008 [3]. The Brazilian biodiesel is made from a diversified source of vegetables mainly castor bean, African palm and soybean. The main producers are agrobusiness firms located in large rural areas of the Brazilian hinterland [4]."

Jan 1, 2008

By M. Dattilo

Research has been conducted over the past three years using the composite anodes versus the lead alloy anodes. The Merrlin composite anodes have shown the improved performance in copper electrowinning versus the lead-calcium-tin anodes. Using the composite anodes a 100-150 mV reduction in anode overpotential has been observed versus the lead alloy anodes in sulfuric acid electrolyte. The composite coating has excellent corrosion inhibiting properties, and reduces or eliminates the formation of manganese oxide scale. Laboratory evidences indicate that, the use of these composite anodes enhances the process of electrowinning by improving the lead alloy corrosion resistance, lowers the electrode potential, reduces the need for cobalt addition, eliminates the anode cleaning, and reduces the generation of acid mist. Field tests are underway.

Jan 1, 1999

By Natasa Mitevska

In order to ensure the minimal copper concentration in the reverb furnace slag, the graphical optimization method is used and the optimal slag composition of the reverberatory furnaces No.1 and No.2 in the RTB BOR, Copper Smelter and Refinery (Serbia) is obtained: (Si02) .. 38.0%; (FeO) .. 40.0%; (Fe3O4) = 5.0%; (CaO) = 5.0%; (Al2O3) .. 6.0%. Keywords: Optimization, Reverb Furnace Slag, Graphical Method

Jan 1, 2003