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By Thomas Schuman, Jaan Kers, Lucas N. W. Damoah, Xiangjun Zuo, Lifeng Zhang

"Rapid technological innovation has propelled the use of electronic equipment leading to the generation of more and more waste electrical and electronic equipments (WEEE). Printed wiring board (PWB) is a component made of one or more layers of insulating material with electrical conductors. To investigate an environmentally friendly process to recycle PWBs, PWB samples with and without additives were pyrolyzed. Liquid, gas and solid products were achieved with different conversion fraction. Analysis of the exhaust gases from the experiments using GC-MS and MS showed that without CaCO3 additives poisonous gases such as C6H6 and HBr were produced which were adequately controlled if CaCO3 was added.IntroductionPyrolysis is one of the best methods for treating complex mixtures of waste polymers and to recover the material and energy content. The process consists of thermal decomposition at moderate temperatures in total absence or small amount of oxygen in which the structures of polymers break down into smaller intermediate products "". The decomposition temperature of a substance is the temperature at which the substance breaks up into smaller substances or into its constituent atoms 2). Thermal treatment of PWBs were reported using DC Arc Plasma furnace 3), and fixed bed reactor 4). One drawback in dealing with thermal treatment of PWB scraps is the likely production of super-toxic halogenated dibenzodioxins and dibenzofurans from the bromine containing structures. Pyrolysis of organic materials contained in waste PWBs leads to the formation of gases, oils, and chars which can be used as chemical feedstock or fuels ""'. Dehalogenation of the pyrolysis product of electronic scraps is essential to make it commercially acceptable. It would be obviously the most advantageous solution as pyrolysis and dehalogenation are carried out simultaneously. Reported pyrolysis investigations are at experimental stage and have been carried out in vacuum, molten salt, fluidized bed, rotary kiln, entrained, stationary, and moving bed reactors 7). Comparing to the incineration and combustion of PWBs, the pyrolysis process has several characteristics: 8'"">) 1). Converting the organic solid substance into fuel gas, fuel oil and carbon-black as storage energy; 2) Emitting toxic substances such as sulfur, bromine and heavy metals in wastes; and 3) Keeping metals from being oxidized. Although many researches into the pyrolysis of PWB wastes have been reported, most of the works have been carried out using analytical pyrolysis techniques or very small batch reactors ""~'5). Also, most of the works for the pyrolysis of PWBs haves concentrated on the composition of the organic products, particularly the brominated organics. The current study is to investigate the pyrolysis of PWB powders in a small TG-DTA scale and a 50-gram tube furnace scale."

Jan 1, 2011

By Takashi Nakamura, Kenji Oosumi, Kazuhisa Fujisawa, Takayuki Kogishi

"Recycling of used aluminum beverage cans(UBCs) is one of the important issues for aluminum manufacturer presently. The direct re-melting of UBCs shows two problems. One is a reduction in molten aluminum recovery and the other is a contamination of other metals such as Ti and Fe from paints. Both problems are caused by paints coated on the surfaces of aluminum cans. Removal technique of the paints, therefore, has been required. Although roasting and shot blast techniques have been developed, both were not successful in removing the paints effectively. A swell-peeling method has been applied to remove them using a methylene chloride solution with acids and it works very well. Small laboratory scale tests have been carried out to develop the commercial process and clarify the mechanism of the swell-peeling method in the present study.When the surface area of UBC is more than 10 cm2, peeling time is independent of the surface area, about 60 seconds, because swelling phenomenon is controlled by the penetration of the liquid through the fine pits on the surface of the paint. This is good for a commercial process. Peeling takes place when the swelling force generated by methylene chloride exceeds the adhesion force between the film and the surface of aluminum, that is weakened by the coexisting acid, especially halogenated acetic acid."

Jan 1, 2000

By Nico Steenekamp

At Lonrho Platinum in South Africa, ores from both the Merensky and UG2 reefs of the Bushveld Igneous complex are treated by flotation and smelting to produce a nickel-copper matte which serves as a collector for the platinum group metals (PGM' s). The nickel-copper matte was originally shipped to Norway for treatment and recovery of the contained base metals, with the return of the PGM rich concentrate to South Africa. The Lonrho Platinum Base Metal Refinery was commissioned in 1985. The original process employed a Shenitt Gordon design. The converter matte is treated in a refinery which utilises both atmospheric and pressure leaches for the dissolution of base metals to produce nickel sulphate crystals, copper cathode and a PGM concentrate. This paper refers to flowsheet and operating changes as well as improvements within the Base Metal Refinery.

Jan 1, 1999

By Fumito Tanaka

The Converting Furnace (C-furnace) of the Mitsubishi process has solely provided opportunities for producing blister copper continuously from molten matte. Continuous converting originates from the proven technology for controlling the behavior of magnetite in lime-ferrite slag of the CaO-FeOX-Cu2O system. Recent improvements in the C-furnace operation have included the slag controls reflecting the impact of minor oxides on magnetite behavior. Although previous investigations focused on magnetite behavior, sulfur has also affected the C-furnace operation because it is of practical importance to avoid the precipitation of gypsum from lime-ferrite slag and the separation of matte from blister copper. This paper will quantify the behavior of sulfur in C-furnace with respect to the gypsum formation and matte separation, and discuss better controls for C-furnace operation.

Jan 1, 2006

By W. G. Davenport

The paper "Copper Smelting to the Year 2000" was presented at the CIM Conference of Metallurgists in Sudbury, August 1979. That paper predicted, in part, that high matte grade, high oxygen smelting - particularly in flash furnaces - would dominate copper smelting until the beginning of the next millennium. The present paper re-evaluates that prediction and examines the changes that have occurred and will occur in copper extraction in the 1990's. Of particular interest is the question as to whether major competitors are on the horizon for flash smelting and Peirce-Smith converting. Recent results with direct-to-blister smelting, lance smelting and submerged-tuyere smelting are reviewed and their roles in future copper smelting are predicted. Requirements for H2SO4 plants which handle the off-gases from modern smelting/converting processes are also examined.

Jan 1, 1993

By S. Ikenobu

This paper describes a method for processing high-silicate zinc concentrates by hydrometallurgical zinc refining. Silica in concentrates reacts to form zinc silicate during roasting. The zinc silicate readily dissolves and slowly precipitates in sulfuric acid solutions during leaching. However, if proper operating parameters are not maintained, the colloidal silica may form an unfilterable gel. That is, according to the investigation results obtained, the silica concentration in the reactor has to be maintained at 5 g/1 or less (preferably 2 g/1 or less) by promoting the precipitation reaction. The proposed method has made it possible to precipitate silica in a form having excellent solid-liquid separation characteristics, without the need for facilities having a high filtration capacity, and to maintain a low silica concentration in the reactor by feeding a composition containing pre-adjusted silica contents.

Jan 1, 2000

By María Cristina Ruiz

Hematite precipitation is a convenient alternative for the removal of iron from leaching circuits because of its chemical stability, high density and high iron content. The precipitation of hematite from ferrous sulfate solutions was studied in a batch reactor. The precipitation occurs by two sequential steps: oxidation of the ferrous to ferric ions followed by hydrolysis of the ferric to hematite. The main objective of this study was to determine the effect of the main operating variables on the rate of two steps of hematite precipitation. The variables studied included: stirring speed (100 to 600 rpm), temperature (160 to 200 ºC), concentration of sulfuric acid (1 to 10 g/L), initial iron concentration (1 to 15 g/L), and partial pressure of oxygen (1 to 6 atm). The sulfur content and the particle size of the solids that precipitated under various conditions were also determined. The results showed that at low temperature and high acid concentration the rate of Fe3+ hydrolysis is the step that controls the overall process. The variable that affects most the rate of Fe2+ to Fe3+ oxidation and the rate of hematite precipitation is the temperature.

Jan 1, 2008

By Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

By Roberto Parra

The operational control in a Flash Smelting Furnace is based on the mass and energy balance of the chemical and mineralogical composition of the concentrates. It is well known that many troubles in the dust formation and slag quality occur without a clear correlation to a specific process parameter such as the matte grade or heat balance. This paper outlines two new considerations that could both help improve the entire quality of the process: blend characterization and versatile slag composition control. Related to the blend control, laboratory scale study has shown that the magnetite and dust formation don't have a linear behavior with the weight proportion of the blend and some optimal blends of2 or 3 types of concentrates can be identified. Related to the control of stag composition, the quantification of the slag liquidus temperatures and viscosity could be an effective operational tool for both for ferrite and fayalite slag that can also directly help deciding the blending parameters. From these viewpoints the benefits of the combination of these two approaches for high temperature operation is discussed. Keywords: Optimization, Copper concentrates, Flash combustion, Blends, Slag composition

Jan 1, 2003

By Rodney T. Jones

Mintek has developed and piloted a novel process for the treatment of nickel-copper and PGM (platinum group metal) sulphide concentrates. The ConRoast process is based on the removal of sulphur by roasting, followed by smelting of the dead-roasted concentrate in a DC arc furnace using an iron-based alloy as a collector for nickel, copper, cobalt, and PGMs. The environmental benefits with respect to sulphur emissions are considerable, in that essentially all of the sulphur is removed from the enclosed roasting equipment in a continuous stream of SO2 of an appropriate strength for feeding to a sulphuric acid plant. This process allows great flexibility with respect to the selection of ore types, and does not impose limits on the minimum quantities of contained base metals or sulphur, and can tolerate very high contents of chromite in the concentrate. The furnace alloy is water-atomized prior to leaching. Iron may be rejected from the alloy hydrometallurgically, by precipitation as hematite for example. The ConRoast process achieves very high metal recoveries, and produces high-purity metals, and a clean high- grade PGM concentrate.

Jan 1, 2002

By M. Cross

Heap leaching presents a complex physico-chemical process to model and a significant challenge to develop a comprehensive model enabling reliable predictions of heap behavior over the long term. A computational modeling framework is described for the analysis of multi-phase flows in reactive porous media suitable for tracking metals recovery, for example, in heap leaching and environmental recovery processes. This modeling framework employs appropriately formulated, parameterized, and solution procedures to capture: 1) liquid and gas flow through heterogeneous porous media subject to variably saturated flow conditions, 2) the complex and dynamically changing nature of the porous media structure, 3) the transport of reactants and products of reaction, 4) the simultaneous mass and heat transfer, and 5) the role of bacteria as a catalyst for reactions. A second class of challenges to accurately model heap processes is to identify and then capture all the process data to characterize the reactivity of particular ores, the mine planning for the construction of the heap, leach schedules, meteorological data, etc. The objective of this paper is to outline these challenges and to describe a modeling framework that can cope with arbitrarily complex geometries and provide tools for rapid and accurate process assessment.

Jan 1, 2006

By John E. Dutrizac, Tzong T. Chen

"Laboratory experiments were undertaken to ascertain the behaviour of various ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C and in the presence of 40 or 50 g/L of hematite seed. Copper, nickel and zinc are not significantly incorporated in hematite precipitates. Although the nickel contents increase to 0.22% as the Ni concentration increases to 60 g/L, the solid solution Ni contents are low relative to the bulk Ni contents. Thus, part of the Ni may be present as tiny particles of poorly soluble NiS04.H20. Increasing germanium concentrations to 2,000 mg/L result in products containing up to 0.59% Ge. The Ge occurs either in solid solution in the hematite or is adsorbed on the nanometer-size hematite crystallites. Increasing As(V) concentrations to 10 g/L increase the AsO4 contents of the products up to 16%. However, the products consist of hematite together with As04-containing Fe(SO4)(OH) and an unknown Fe-AsO4 species. All the hematite products contain - 1% SO4 which appears to be adsorbed on the nanometer-size hematite crystallites.IntroductionDissolved iron is a common impurity in most hydrometallurgical processing circuits and, generally, the iron must be eliminated prior to the subsequent recovery of the sought after metals. Simple neutralization of iron-rich solutions yields slurries which are difficult to thicken and filter. To address these concerns, the jarosite, goethite and hematite processes have been developed, and these technologies are able to reject the dissolved iron in a readily filterable form [1]. Despite its higher cost, the hematite process offers several potential advantages. Because hematite is an iron-rich, high-density compound, its formation would reduce the mass of residue and the size of a residue storage pond. Hematite is the thermodynamically stable form of iron under ambient conditions, and this stability would facilitate the impoundment of hematite precipitates. Furthermore, hematite has some market potential for cement manufacture and even for iron making [2]. In all the commercial hematite processes, the dissolved ferric ions are first reduced to the ferrous state. Subsequently, the pH of the solution is adjusted and the solution is then oxidized. The ferric ions gradually generated during solution oxidation hydrolyze and precipitate mostly as hematite, although commercial hematite products also contain trace or minor amounts of jarosite-type compounds. However, there are potential advantages in precipitating hematite directly from ferric ion solutions, as the reduction and subsequent oxidation of the iron are not required. Although the precipitation of hematite directly from relatively concentrated ferric sulphate solutions (up to 0.5 M Fe(SO4)is) was recently demonstrated [3], the behaviour of impurity species during hematite precipitation is largely unknown. To address this issue, systematic laboratory experiments were undertaken to ascertain the behaviour of a number of ""impurity"" species during the precipitation of hematite directly from ferric sulphate solutions at 225°C, and the results are presented in this paper."

Jan 1, 2012

By Norbert Hort, Karl Ulrich Kainer, Carsten Blawert, Daniel Fechner

"With the development of new heat resistant magnesium alloys, the automotive industry has introduced several parts to the drive train. The rising number of large magnesium components will result in a higher quantity of automotive post consumer scrap and the changing legislation will force car manufacturers to take magnesium recycling into consideration. So far post consumer scrap has not been used for magnesium alloy production. Quite a reasonable amount of automotive scrap is likely to end up in a mixed light metal shredder fraction. The separation of mixed magnesium scrap according to several alloys is complex. Therefore secondary magnesium alloys made from blended post consumer scrap would be useful. For this work a matrix of potential recycling alloys was prepared by chill casting and high pressure die casting. The materials were investigated for their microstructure, mechanical properties, heat resistance and corrosion properties. The results will be presented in this paper.IntroductionWithin the last ten to fifteen years several heavy magnesium parts have been assembled in passenger cars, such as gear box housings and crank cases [1, 2]. Reasons are the lately developed new heat resistant alloys and the increasing responsibility of automotive manufacturers to reduce the vehicles weight and thereby CO2 emissions. The latter is pushed by international legislation [3, 4]. The rising quantity of magnesium in automobiles will result in an increasing amount of so called post consumer scrap at the end of the vehicles life.So far magnesium recycling was done only for clean scrap that is free from impurities, contaminations and sorted according to a chemical composition or a single alloy respectively [5- 15]. The latter is also called class 1 scrap and mainly consists of sprues and runners from magnesium die casters [15, 16]. For the upcoming automotive post consumer scrap the materials quality strongly depends on the way end of life vehicles are treated. By proper dismantling of old cars, the bigger magnesium components could be collected and possibly treated similar to class 1 scrap [15]. Up to date automotive manufacturers have no uniform recycling system for end of live vehicles. Most probably a considerable quantity of old cars will be shredded. The resulting light metal shredder fraction will contain aluminium and magnesium scrap, both from several alloys. A separation of mixed magnesium and aluminium scrap is feasible according to [17]. Other authors claimed that the grade of separation of magnesium from aluminium is still not sufficient for a proper industrial recycling process of magnesium post consumer scrap [15, 16]. If an automatic sorting is possible it will probably be very expensive [18]. Therefore, so far the main use of post consumer scrap has been the steel desulphurisation and aluminium production [15]. The use of post consumer scrap for magnesium alloy production has been considered already by [15] and [16] but some problems have to be approached."

Jan 1, 2008

By Shubin Wang

Copper(II) and nickel(II) are often recovered from ammoniacal alkaline solutions by solvent extraction using hydroxyoxime extractants: both copper(II) and nickel(II) are extracted from ammoniacal alkaline solutions and, from the loaded organic phase, nickel(II) is selectively stripped with a dilute acid followed by copper(II) stripping with an acid of higher concentration. Since a small portion of ammonia is co-extracted with copper and nickel, the extracted ammonia should be scrubbed using a dilute acid before metal stripping. In the present study, a mechanistic model has been developed in order to support design and control of this process. The equilibrium distribution ratios of copper(II), nickel(II), and ammonia at 298 K using LIX® 84-I (active component, 2-hydroxy-5-nonylacetophenone oxime) as the extractant are successfully correlated by considering the relevant equilibria. Based on these results, quantitative prediction of equilibrium distribution ratios in the process has been made possible, and suitable conditions for the efficient separation of copper(II) and nickel(II) are discussed.

By R. Togashi, S. Kuramochi, T. Yamada

In 1972, the Akita Zinc Co., Ltd. commenced operations with an annual capacity of 86,000 tonnes of electrolytic zinc, and it has operated with an annual capacity of 156,000 t-Zn since 1974. The business surroundings for non-ferrous metals production have become more severe with the high Yen rate for the dollar and low domestic demand in the last few years. Consequently, the company tried to survive with some improvements and succeeded to reduce operating costs and to improve profitability as follows: 1) expansion of its production capacity to. 196,000 t-Zn annually, 2) saving man-power by the introduction of fully-automated machines for cathode handling in the cellhouse, 3) improvement of the hematite process by means of the recovery of rare-metals. These improvements made Akita Zinc a competitive refinery in the modern world. We have been trying to improve the operations more and more. One of the challenges is to purify the iron oxide made in the hematite process by applying an As removal process, which is coming into operation in the near future.

Jan 1, 2000

By Daojin Cao

Aiming at many controversial reports on Raman spectral pattern of octamolybdate ion in aqueous solution appearing in the literature, a new method for the establishment of corresponding relation between Raman spectral pattern and chemical components of aqueous molybdate solution was put forward using spectroscopy measure and component analyses of saturated solution of ammonium octamolybdate hydrate known structure. It was found that the main characteristic of Raman spectral pattern of the saturated solution was described as the same ?double-peaks, hereinto a weak peak at the boundary? as some literature, but chemical components of the saturated solution were affirmed to be octamolybdate ion (Mo8O264-) and double protonated heptamolybdate ion (H2Mo7O244-), which were in equilibrium in aqueous solution each other. The authors propose that the pattern of the saturated solution can be regarded as the standard pattern of primiparous octamolybdate ion during acidified molybdate solution. It is satisfying that the standard pattern is applied to the identification of primiparous octamolybdate ion during acidified molybdate solution.

Jan 1, 2006

By Hiroshi Nakazawa

An acid mine drainage in abandoned Horobetsu mine in Hokkaido, Japan, contains arsenic and iron ions; total arsenic ca.10ppm, As(III) ca. 8.5ppm, total iron 379ppm, ferrous iron 266ppm, pH1.8. Arsenic occurs mostly as arsenite (As (III)) or arsenate (As (V)) in natural water. As(III) is more difficult to be remove than As(V), and it is necessary to oxidize As(III) to As(V) for effective removal. 5mL of the mine drainage or its filtrate through the membrane filter (pore size 0.45m) were added to arsenite solutions (pH1.8) with the concentration of 5ppm. After the incubation of 30 days, As(III) was oxidized completely with the addition of the mine drainage while the oxidation did not occur with the addition of filtrate, indicating the microbial oxidation of As(III). In this paper, we have investigated the microbial oxidation of As(III) in acid water below pH2.0.

Jan 1, 2006

The physico-chemical principles of chloride hydrometallurgy are reviewed to rationalise the complex chemistry in chloride-based processes for metal sulphides in terms of the predicted Eh-log[Cl-] relationships, measured changes in activity of H+, Mz+, Cl- and solubility of Ag(I), Cu(I), Cu(II), Pb(II), Ni(II), Au(III), Sb(III) and Bi(III). These changes reflect the nature of chemical speciation, competing effect of hydration/hydrolysis and chloro-complexation,composite effect of increasing acid and/or salt concentration and decreasing water activity. Rate data for the dissolution of PbS and ZnS in HCl containing Fe(III) or Cu(II) are compared and contrasted to highlight the effect of acid and chloride concentration, water activity, and the nature of oxidant. It is shown that LiCl, NaCl and HCl influence the kinetics of oxidative PbS leaching based on their effect on solubility of PbCl2 co-precipitated with elemental sulphur on the mineral surface. Evidence for the beneficial effect of Cu(II) in sulphide leaching is discussed.

Jan 1, 2003

By J. E. Dutrizac

Mineralogical studies were carried out on nodulated copper cathodes from three primary refineries to characterize the nodular growths and to elucidate the causes of the nodulation. Nodulation is often initiated at the surface of the starter sheet or the stainless steel plating blank, although a layer of smooth copper sometimes is deposited before nodulation commences. In some instances, the "roots" of the nodules exhibit a pronounced dendritic texture that is associated with an abundance of cavities. Slimes particles are not usually associated with these growth features which lead to a globular surface deposit. The globules sometimes develop into larger nodules, and this type of nodulation is likely caused by improper addition agent concentrations. The nodules on most cathodes, however, exhibit "roots" at the contact with the substrate that are associated with microcavities and large clusters (>40 µm) of slimes particles. The slimes constituents are commonly Ag powder, PbSO4 and Cu2(Se,Te) but not AgCu(Se,Te) or Ag,(Se,Te). The size of the slimes clusters, rather than their composition, appears to be the important factor causing the copper to grow into nodules. Tiny individual slimes particles themselves do not appear to cause cathode nodulation.

Jan 1, 1999

By Tracy Morris, Weldon Read, Luis Navarro

"Bismuth is a recognized contaminant in the electrolytic refining of copper that can render many cathodes to be outside ASTM standards and unsuitable for copper rod and other downstream products if not carefully controlled. This paper portrays the performance of Molecular Recognition Technology (MRT) for bismuth removal at the Amarillo Copper Refinery (ACR) and describes how the highly selectivity gel has been successfully used to achieve good bismuth removal and how many pit falls and draw backs have been overcome.IntroductionASARCO operates one of the largest copper refineries in the world at Amarillo, Texas. The main feed for this refinery is produced at the Hayden smelter in Arizona. During the operation of this smelter a variety of metals are carried as impurities in the copper anodes because of the diversity of concentrates and residue products used as raw materials in the smelter feed mix. Even though the impurities are concentrated enough to be detected at the smelter, it is difficult to remove them completely. A simple way to control impurities at the smelter is to minimize the addition of material with a high concentration of impurities to the charge in order to reduce the output of this metal species. All this leads us to have a ""refinery problem"" [1,2,3]."

Jan 1, 2012