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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 Vladimir I. Skorohodov

The technology for copper utilization from circuit boards etching is proposed. The technology is based on combination of electrochemical and sorption methods. The conditions of copper electroextraction from ammonia-chloride solutions with obtaining of cathode copper are defined. The stage of electrolysis is destined for copper recuperation from etching process. Due to the electrochemical processes are unacceptable for cathode precipitation of the copper from diluted solutions such as rinse waters, the concentration on the strong-based cationites are used. After filtration throw the sorption columns solution is directed to the stage of circuit boards washing. It allows organizing close loop water recirculation. After saturation. resin is 'regenerated by chloride ammonium solutions. Obtained eluate directed to the etching stage, Generally. the technology provides copper recuperation and minimize wastes amount.

Jan 1, 2001

By Steven R. Izatt

IBC Advanced Technologies, Inc. (IBC) has developed a mercury selective product, which can be used by sulfuric acid producers as either a polisher, or as the primary technology for mercury removal from sulfuric acid. The Molecular Recognition Technology (MRT) separations material selectively binds Hg2+, and to a lesser extent Hg+, out of concentrated sulfuric acid. Mercury output levels of less than 0.1 ppm can be attained by the MRT system. Pilot plant tests have been successfully conducted at base metal smelting operations. A large-scale commercial plant is due for commissioning in 2003. Results from these projects will be discussed.

Jan 1, 2003

By Jan Smit

Sulphidic copper concentrates are generally processed by pyrometallurgical means; while oxidative pressure leach processing of such materials has been shown to be technically feasible, there has traditionally been little incentive to choose this route in favour of a smelting option. However, for concentrates with elevated arsenic levels, oxidative pressure leaching offers distinct advantages, as smelter air emission standards and restrictions on concentrate importation have tightened. The current state of pressure leach technology allows for high copper extractions from arsenical copper concentrates, while producing an environmentally stable process residue, without atmospheric emissions of sulphur dioxide or arsenic. In its studies on pressure leaching of copper concentrates, Sherritt has shown that arsenical feed materials can be converted into environmentally stable residues, with excellent copper extractions. The results of recent batch and pilot plant test work are discussed, including the deportments of copper, arsenic and precious metals.

By Shengqin Zhang, Yousef Mohassab, Feng Chen, Hong Yong Sohn, Mohamed Elzohiery, Amr Abdelghany

The kinetics of hematite concentrate reduction by mixtures of hydrogen and CO of various compositions has been investigated as part of the development of a flash ironmaking process at the University of Utah. This process produces iron directly from iron oxides concentrates by the gas-solid flash reaction based on the partial oxidation of natural gas, resulting in a significant reduction in energy consumption and greenhouse gas emission. The reduction kinetics of hematite concentrate of an average particle size 21.3 μm by the above mentioned gases in the temperature range 1423 to 1623 K (1150 to 1350 ºC) was investigated. Hematite concentrate particles can be reduced to > 90% by any of these reductants in several seconds of residence time typically available in a flash reactor. The activation energy ranged from 214 kJ/mol for hydrogen to 231 kJ/mol for CO.

Jan 1, 2016

By M. S. Moats

Galvanic stripping, in conjunction with solvent extraction, has been proposed as a technical option to the challenging problem of iron removal in certain hydrometallurgical processes. The galvanic stripping process is based on the ability of a solid metal to directly reduce ferric ion to the ferrous state in an organic media. Stripping the iron into the aqueous phase is then easily accomplished. Previous work has shown the reaction kinetics and efficiency are affected by such operating parameters as water and oxygen contents, temperature, time and metal reductant. In this study, the optimum operating range for some of these variables was determined. Both zinc and iron metal were used in the separate stripping of iron from D2EHP A. Reasons for the differences in the extent of the reaction obtained using the various conditions are discussed.

Jan 1, 1996

By Chu Yong Cheng

Manganese is one of the main impurities in the recovery of base metals from their ores. This is especially true when laterite ores are processed using the pressure acid leach (PAL) process. The use of intermediate precipitation, solids/liquid separation and re-leach in the three Western Australian nickel laterite plants to separate nickel and cobalt from manganese and other impurities makes these processes complicated and costly in capital and operation. The research work carried out by the solvent extraction (SX) group at the A J Parker Cooperative Research Centre for Hydrometallurgy (CSIRO Minerals) has led to the development of direct solvent extraction processes to separate nickel and cobalt from manganese and other impurities. The simplicity of the process flowsheets and the expected savings in capital and operating costs are the major advantages of the new direct solvent extraction processes over the existing processes. By using a new synergistic organic system, Versatic 10 / dccyl-4-pyridinccarboxylatc ester, with a pilot plant leach solution from BHP¬Billiton (after iron precipitation), the metal values (Ni and Co) together with zinc and copper were separated from manganese and other major impurities (Mg, Ca and Cl) in the first SX circuit. The co-extracted manganese, magnesium and calcium were easily scrubbed out. The extraction and stripping kinetics of the metals with the new synergistic organic system were very fast and the synergistic system was found to be chemically stable. pH-extraction isotherms of metals with D2EHPA showed that the extraction order as a function of pH50 was Zn2+ > Ca2+ > Mn2+ > Cu2+ > Co2+> Ni2+> Mg2+. Semi-continuous test work with a cobalt pilot plant leach solution from Peko Rehabilitation Project Pty Ltd and a synthetic solution to simulate a concentrated laterite leach solution from BHP-Billiton showed that manganese, together with calcium, copper and zinc can be separated from nickel, cobalt and magnesium. This led to the development of another direct solvent extraction process to separate manganese and other impurities from nickel and cobalt and to recover nickel and cobalt from leach solutions. A project was initiated by HiTec Energy Ltd to recover manganese from waste laterite leach solutions using SX technology and to further purify it to produce high purity electrolytic manganese dioxide (EMD) for the high quality alkaline battery industry. Batch tests were conducted to select a suitable organic system for the extraction of manganese in terms of selectivity and extraction and stripping kinetics. A total of eight organic systems were tested using waste laterite processing solutions. A Versatie 10 / synergist system showed very promising results. By using the synergistic system, high manganese recovery would be obtained, fewer SX stages would be required and a higher A:O ratio could be used in extraction, resulting in a smaller organic inventory and lower capital costs. The risk of gypsum formation is also minimised with the synergistic system. Keywords: Solvent Extraction, Manganese, Laterite, Synergist

Jan 1, 2004

By Jianguo Yin, Wenqiang Yang, Xiaoli Yuan, Juan An, Wentang Xia

Low grade iron ore with phosphorus (LGIOWP), a raw and wasted industrial solid material was used as an adsorbent to remove Pb(II) from wastewater. The effects of initial pH value, adsorptive time, initial Pb(II) concentration, adsorptive temperature and LGIOWP dosage on the Pb(II) removal efficiency were studied. The results show that the Pb(II) removal efficiencies exceed 99.4% and Pb(II) concentrations are less than 0.30 mg/L under the conditions of pH value 7.0, adsorptive temperature 50 oC, adsorptive time 30 min, initial Pb(II) concentration 100 mg/L, particle size <0.25 mm, adsorbent dosage 5 g/L and stirring speed 260 r/min. After Pb(II) removal reaction, the Pb(II) concentrations of wastewater completely accord with the requirement of national discharge standards of pollutants from lead and zinc industries (GB 25466-2010) (TPb= 0.5 mg/L) in China. Therefore, it can be concluded that LGIOWP is a new low-cost adsorbent which is suitable for the adsorption of Pb(II) from wastewater.

Jan 1, 2015

By Hsing Kuang Lin

Extraction of zinc from chloride solution with dibutyl butylphosphonate (DBBP) in Escaid 110 has been investigated. The distribution coefficient of zinc was found to be independent of equilibrium pH. This independence indicates that the mechanism of the extraction may be solvation. Slope analysis for the system of dilute zinc chloride solution reveals that two moles of DBBP react with one mole of zinc. A series of tests were conducted to bring DBBP to its full loading capacity and the analysis of the results confirms this stoichiometric factor of 2. Extraction isotherms were established by varying either the AIO ratio or the concentration of zinc in the aqueous feed. Both curves were found to be identical.

Jan 1, 1990

By Kenneth L. Driggs

The 1988 shift in primary smelting facilities from low grade matte (35%) reverberatory furnaces to high grade matte (63%) flash smelting heavily impacted a very stable and successful converter operation. Low matte grade converter campaigns averaged 36,000 short tons of copper and revert production/consumption was in balance. The conversion to high matte grades necessitated oxygen enrichment of converter blast and revisions in operating practices. After two years of operational development, campaign life has risen to over 40,000 short tons and revert production/consumption is again in balance.

Jan 1, 1991

By Chuanfu Zhang

Based on Thermogravimetric and Differential thermal analysis (TGA-DTA), porous copper powder is prepared by thermal decomposition of complicated copper oxalate. The effects of various conditions on the morphology, crystalline grain size and specific surface area of copper powder were investigated, including temperature, duration, mixing ratio of nitrogen and hydrogen. Furthermore, composition and morphologies of the products were characterized by X-ray diffraction (XRD), Scanning electron microscope (SEM) and BET adsorption isotherm. It is found that porous copper powder was produced under optimum conditions. The specific surface area is over 6.74 m2?g-1, and average pore size in particles is about 30.3 nm. After comparison of SEM images, the final product Cu well inherits the morphology of the precursor, thus a mechanism of in-situ decomposition is proposed.

Jan 1, 2009

By Carlos A. Nogueira

Spent Ni-Cd batteries contain in the electrode materials heavy metals like Ni, Cd and Co, which must be recycled due to environmental problems. Pyrometallurgy is normally used for recycling these end-of-life products, but alternative processes by hydrometallurgy, integrating also physical operations, can be used. Hydrometallurgy seems to be useful, because metals can be efficiently recuperated in chemical forms with commercial value. The economical viability of this recycling process can be improved increasing the treatment capacity, through the application to different types of residues with similar characteristics like Ni-MH and domestic batteries, or other residues containing Ni/Co, like sludges, dusts or spent catalysts. Spent Ni-Cd batteries were first physically processed using shredding and wet sieving operations. Best results were achieved using an output of 6 mm in the shredder and 1.4-2 mm in the physical separation by wet sieving, resulting a fine fraction containing 70% of the initial electrode material and only 6% of the initial scrap. The acid leaching of the obtained material in the previous operation was studied, being the parameters like: temperature, H2SO4 concentration and the liquid/solid ratio (L/S) optimized. The values attributed to the factors which concerned the best results obtained on the leaching process were mainly influenced by Ni recovery. In opposition, Co and Cd were easily leached in a wide range of conditions. To attain an overall recovery, with minimum costs, of the three metals, the values of T~100ºC, [H2SO4]=2.3-2.7 M and L/S=8-10 L/kg were considered the most appropriate.

Jan 1, 2006

By Alex Luyima, Jaan Kers, Lifeng Zhang

"The pyrolysis of PWBs was investigated by a TG-DTA-MS furnace at 300–1173 K. The kinetics and the control of emitted gas during the pyrolysis of PWBs with and without chemical additives were studied. Moreover, the possibility of controlling the amount of toxic exhaust gases like HBr, C6H6, Br2, Cl2, HCl gas and recovering beneficial gaseous fuels like CH4 and H2 from pyrolysis process is discussed. The MS data for each PWB sample were examined as a function of temperature and particular m/z values could be associated with the mass loss steps in the TG data. The degradation of the organic material was characterized by m/z = 2, 16, 18, 28, 36, 44, 71, 78, 81, and 160. Fe2O3 was the best inhibitor of toxic HBr and C6H6 when compared to Al2O3, CaO Y-zeolite and ZSM-5. Moreover, it had no significant effect on the valuable H2 and CH4 gas evolution. This selective inhibition of toxic gases while maintaining the valuable ones make Fe2O3 the best candidate among the investigated additives in controlling gas emissions from PWB pyrolysis process.IntroductionThe electronic and electric industry is one of the world’s largest and fastest growing manufacturing sectors. As a consequence of this growth, electrical and electronic waste (e-waste), such as computers, washing machines, printers, mobile phones, television sets, stereos, radios, etc., is generated in large quantities around the world. Printed wiring boards (PWBs) are a common component of many electronic and electric systems.[1]. The rapid development and expansion of the electronics industry over the past several decades have led to a dramatic increase in the production of PWBs and a corresponding increase in the amount of waste generated from both production and disposal. The environmental impacts of the treatment and recycling of PWBs waste have become a major concern [1-2]. PWBs are particularly problematic to recycle because of the heterogeneous mix of organic material, metals, and glass fiber [1]."

Jan 1, 2012

By Tobias Dubberstein, Hans-Peter Heller

The viscosity of Fe-Cr-Mn-Ni TRIP/TWIP (Transformation Induced Plasticity, Twinning Induced Plasticity) steel with varied nickel content is investigated using a vibrating finger viscometer. The viscosity of the melt is calculated from the change in power input in the field coil by an immersed finger into the liquid steel to maintain a constant peak-to-peak amplitude of the sine wave of oscillator compared to the idle state. Nickel content in steel is varied from 3 wt% to 9 wt%. The dynamic viscosity (η) at 1600 °C for 3 wt% Ni is 3.73±0.14 mPas, for 6 wt% Ni 3.50±0.03 mPas, and for 9 wt% Ni 3.93±0.09 mPas. There is a kink from low to high nickel content in viscosity values of Fe-Cr-Mn-Ni alloys. This phenomenon can be explained by a change in coordination number in the melt, as reported for Fe-Ni binary system in literature. The availability of viscosity data delivers relevant input to model free fall atomization processes of FeCrMnNi alloys.

Jan 1, 2015

By Ximeng Zhu

The electrochemical behavior of mineral and coal pyrites in stirred and quiescent alkaline boratelsulfate solutions @H 7.9-10.5) have been investigated using cyclic voltammetry. Significant differences in the electrochemical response of these pyrites were observed. At the mineral pyrite surface, three anodic peaks at about -0.8 V, -0.1 V and +0.5 V (SCE) have been detected along with their corresponding reduction peaks. The first two peaks correspond to FeIFeOI) and FeOI)lFe(III) oxidation. The third peak is present for quiescent conditions but disappears as a distinct peak when the electrolyte is stirred. In the upper voltage region +0.30V (SCE), the current increases markedly during stirring and the reactions correspond to the oxidation of pyrite with the formation FeOII) oxides plus elemental sulfur. Also there is evidence that Fe oxy-ions form. Coal pyrites, under rapid sweep conditions display only the first two anodic peaks, the associated reduction peaks and an additional reduction peak corresponding to one or more of the high voltage oxidation products. After prolonged exposure to high potentials, coal pyrite displays reactions similar to those of mineral pyrite but at much higher current densities demonstrating the much higher reactivity of the coal pyrite. The reactivity sequence was Upper Freeport coal pyrite > Pittsburgh coal pyrite > mineral pyrite.

Jan 1, 1991

By C. Lupi

The electrorefining of primary copper is a well known technology: in this work copper scrap was directly processed in the same way. he copper and copper alloy scrap was previously pressed by means of a 20 tons apparatus in order to avoid pyrometallurgical operations. The samples obtained in this manner showed a good compactness so that they were used as anodes in the electrorefining tests. The tests were carried out on anodes made by copper scrap, copper alloy scrap and a mixture of the two. The electrorefining tests were performed at both 303 and 333 K, in a perspex cell having a volume of 500 ml using a current density of 250 A/m2. The cathode used was always a sheet of pure copper and the electrolyte composition was 40-50 g/l Cu as CuS04 and 150-200 g/l H2SO4. Current efficiency in the range of 92-97% and specific energy consumption ranging from 0.14- 0.20 kWg of copper were reached in all the tests. The refined copper deposits were analyzed by AAS to verify their purity and observed by SEM to highlight their morphology.

Jan 1, 1998

By Sheng-li Wu, Guo-liang Zhang, Bo Su

One of the major challenges for the Canadian Gen IV Super-Critical Water-cooled Reactor (SCWR) concept is the selection of fuel cladding materials. The Canadian SCWR concept will operate at a core outlet temperature of 625 oC and 25 MPa of pressure with peak cladding temperature reaching as high as 800 oC. Corrosion resistance is an important factor for material selection. Austenitic stainless steels that contain Cr contents greater than 18 wt.% are generally considered to provide adequate corrosion resistance. In this work, the pressure dependence of the corrosion of austenitic stainless steel 310 containing 24 wt% Cr is assessed at 625 C for exposures of 1000 hours to evaluate the suitability of superheated steam as a surrogate for supercritical water at 25 MPa. Transmission Electron Microscopy (TEM) revealed that 310 exposed to different pressure conditions at 625 oC. (i.e., 0.1, 8 and 29 MPa) had generally the same type of the oxide structure, i.e., a Cr-rich oxide with the spinel structure on outer surface adjacent to the water phase. The material exposed at 8 and 29 MPa had a double layer oxide structure, with the outer oxide layer having a much larger grain size, while the samples exposed at 0.1 MPa showed only a single spinel-phase oxide layer. Cr-depleted recrystallized austenite grains were found underneath the spinel phase oxide. The adjacent large-grained austenite substrate had M23C6 carbides in the grain interior. The implications of these results are discussed.

Jan 1, 2015

By Jonkion M. Font, Ramana G. Reddy

A thermodynamic model for a priori predictions of arsenic and antimony impurity capacity in Ni-Cu mattes and slags was developed based on the Reddy-Blander (RB) capacity model. The As and Sb capacities were calculated a-priori considering the RB capacity model in Ni-Cu mattes and FeO-FeO1.5-MgO-CuO0.5-NiO-SiO2 slag at 1573 K and 0.1 to 1 atm partial pressure of SO2. The results showed an excellent agreement between the model calculated and experimental data of arsenic and antimony capacities between the mattes and slag. The impurity capacity model developed here, can be extended for prediction of impurity capacities in multi-component base metal slags and base metal mattes. Such a priori predictions of impurity capacities can lead to develop or improve the efficiency of impurity removal from the base metal smelting, converting and refining processes.

Jan 1, 2014

By ZhiLong ZHAO, Lin Lin, Zhancheng Guo, Jingtao GAO, Huiqing Tang

Grain sticking often occurs in the fluidized bed reduction of f ine iron ore, which is closely related to the precipitation morphology of metallic iron on the surface of ore particles. In this work, simulating the gas-solid reduction process of iron ore, in situ observations were carried out to investigate effects of doping mineral oxides on the precipitation morphology evolution of metallic iron during reduction of iron oxides with CO. Results indicate that the precipitation morphology of metallic iron is related to the quantity of doped mineral oxides. The minimum mole fraction of doped oxide ( xyOA N ) that can inhibit the growth of iron whiskers is related to its cation radius ( Ax r ), extranuclear electronic layers ( Ax n ) and valence electrons ( Ax q ). Their relation can be expressed as:

Jan 1, 2016

By J. Pérez

A lead smelter slag with high copper, lead, arsenic and silver contents was treated at laboratory scale for arsenic removal. The slag was first leached at atmospberic pressure with sulfuric acid and oxygen. According to arsenic contents leaching of most of the arsenic was achieved in either one or two stages, producing a lead-silver rich residue and a solution high in copper and arsenic concentrations. Alternative routes were considered to treat the resulting solution. Firstly, solvent extraction of arsenic with a mixture of TBP and 2-etbyl-bexanol was tested and extractions of over 95 percent of arsenic were achieved. Secondly, a copper arsenate precipitation treatment was done to eliminate arsenic and copper from solution.

Jan 1, 1996