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By Michael S. Moats, Scott C. Campin, J. Brent Hiskey

"Electrochemical techniques are a valuable means of analyzing the passivation of commercial copper anodes. Electrochemical impedance spectroscopy (EIS) provides information concerning transport and reaction phenomena occurring at an electrode surface. Commercial. copper anodes of varying compositions have been examined using EIS. Experiments were conducted in a flat cell with an electrolyte of 40 gil Cu2 + and 160 gil H2S04 maintained at 65 DC. Impedance spectra were obtained at the potentials characteristic of the open circuit voltage and passive region for each anode. The spectra of the passivating films exhibited a flattened resistive/capacitive loop at middle to high frequencies and an inductive loop at low frequencies. An equivalent· circuit utilizing an inductor-resistor series in parallel with the double layer capacitance and charge transfer resistance was adequate in modeling the impedance data. The influence of anodes impurities on the components of the equivalent circuit is discussed and correlated with a hi-layer passivation model.IntroductionPassivation of copper anodes during industrial electrorefining has received considerable attention in the past few decades. Great strides have been made in understanding the roles of anode impurities [1-25], electrolysis parameters [20,26], and electrolyte chemistries [20,26]. Even so, passivation still occurs even in the most modem of refineries. The exact cause of passivation is not fully understood. It is known that the anode surface becomes covered by a passivating film. This film has been proposed to be CuS04'&5H20, Cu20, or mixed oxides. The localized concentrations of Ft, Cu+, and Cu2+ ions determines which phase is more favorable. The presence of these ions is controlled by the reaction kinetics and diffusion of species through the slimes layer.Reaction kinetics between Cu, Cu +, and Cu2+ are based on the dissolution mechanism of copper. There exists four different models to describe the dissolution of pure copper. The classical model of Mattsson and Bockris [27] involves two single electron transfers with the cuprous-cupric reaction being the rate detennining step. More recently, Wong, Collier, and MacFarlane [28] used ac impedance to elucidate a more complex mechanism involving the affect of pH and anions. Their findings indicate that the formation of cuprous ions in solution, Cu(I)so~ is favored over Cu(1I) ions adsorbed to the electrode surface in the presence of sulfate and as pH increases from pH 1 to pH 5."

Jan 1, 1997

By William Petruk

An investigation was conducted to determine whether mineral liberation data obtained by one image analysis technique are the same as data obtained by another image analysis technique. The liberated vs non-liberated, volume % and weight % techniques for measuring mineral liberations by image analysis were tested. The results show significant differences between the values obtained by the different techniques. The lowest liberation values were obtained by the liberated vs non-liberated technique and highest by the weight % technique. It is interpreted that the weight % technique produces the most realistic results. The weight % technique also produces data that can define mineral associations for the unliberated grains. These include (1) mineral quantities in particles that contain different amounts of unliberated mineral, (2) mineral quantities in particles that have different size ranges, and (3) mineral quantities and degrees of liberation for specific minerals in particles of different size ranges.

Jan 1, 1996

By John B. Cocanour

The U.S. Bureau of Mines (USBM) has developed a laboratory-scale on-line analysis and process control system for a decopperization electrolytic circuit. This system is software driven, running on a 486DX-33 personal computer (PC) utilizing a portable energy- dispersive x-ray fluorescence (XRF) spectrometer as the sample analyzer. The XRF copper reading obtained was used as the control variable through an RS-232 serial interface to the PC for software-based control of feed flowrates. When the copper concentration in the electrolytic cell (as measured by the XRF) deviated from the set point, the feed flowrate to the cell was automatically altered using software-based proportional-integral-differential (PID) computer control to yield the desired copper concentration at the electrolytic cell outlet.

Jan 1, 1994

By Gabriella Tranell

In the manganese ferroalloys industry, there is increasing focus on the performance of different carbonaceous materials within the smelting processes. With a developing scarcity of traditional raw materials, new carbon sources are being identified for potential use in the processes. For this purpose, it is important to be able to predict the suitability of different materials in the process. Hence, the effects of both the physical and chemical properties of the carbon material on the reduction kinetics of manganese and silicon from slag to metal, have been investigated using an advanced sessile drop technique. Using this technique, the reaction patterns of SiO2-MnO containing slag droplets in contact with various solid carbon materials (graphites with different properties as well as cokes and charcoals) at 1400 to 1600\\176;C were studied in-situ. In addition, slag and metal reaction products from kinetic experimental series were analysed. From these results, differences in reactivity between various carbon materials and slags were demonstrated and explained. Mechanisms for both manganese and silicon reduction were proposed.

Jan 1, 2006

By Giuseppe Granata

An innovative process using titanium tetrachloride (TiCl4) gas as reactant has shown successfully to obtain titanium through electro-winning of TiCl2 formed in-situ on titanium cathode. The process involves a continuous feed of TiCl4 gas reacting onto a titanium cathode immersed in a molten salt (NaCl-KCl), whereby in-situ formation of titanium dichloride (TiCl2) through a disproportion reaction. Simultaneously, the TiCl2, thus in-situ formed in the molten salt media, has been reacted into chlorine gas and titanium, the latest electrodeposited on the titanium cathode by electrowinning. The reaction kinetic of this innovative process was investigated in terms of TiCl2 in-situ formation rate and galvanostatic electrodeposition rate, where, in particular, the effect of operating variables such as TiCl4 partial pressure and flow rate, as well as temperature and galvanic potential applied was investigated.

Jan 1, 2014

By Chao Li, Shuai Wang, Hongxu Li, Lifeng Zhang, Xie Yang

The method of chloride-hypochlorite leaching has the advantages of short process, low pollution and higher in reaction rate compared with the traditional leaching method. In this research, NaCl - NaClO solution is used to leaching gold from a refractory gold concentrate, and the influence of NaCl and NaClO concentration, reaction time to the leaching rate were investigated in this experiment. The raw materials and the leaching residue were characterized by a series of analysis methods such as XRD, XRF, SEM and EDS. Results indicate that the leaching rate and the desulfurization rate can be achieved at 96.26% and 98% with most optimum conditions as follows: NaCl concentration 50g/L, NaClO concentration 200g/L, Liquid-solid ratio 10:1, the best reaction time was 150 mins. And these conditions should be guaranteed pH<8.0, ORP>900mV.

Jan 1, 2015

By Thomas P. Battle

Titanium is the ninth most common element in the Earth&apos;s crust, yet only in this century has titanium come into use as an engineering material, particularly in aircraft structures, as the metal, and in pigments, as the dioxide. In this presentation, the metallurgical aspects of processing titanium-containing raw materials will be reviewed. Particular emphasis will be given to the ores and beneficiation techniques which lead to the production of titanium dioxide pigment, which accounts for over 90% of world titanium production.

Jan 1, 1993

By Zhongning Shi, Ramana G. Reddy, Min Li, Zhaowen Wang

Electrodeposition of cobalt from cobalt tetrafluoroborate (Co(BF4)2) was investigated using 1- butyl-3-methylimidazolium tetrafluoroborate (BMIMBF4) ionic liquid. The experiments were conducted at 353 K. Chronoamperometry experiments confirm that the electrodeposition of cobalt on tungsten electrode proceeds via three-dimensional instantaneous nucleation with diffusion-controlled growth process. The average diffusion coefficient of Co(II) was found to be 7.5 × 10-8 cm2s-1 at 353 K, which is in good agreement with the estimated value from cyclic voltammetry. The electrochemical deposit was characterized using SEM-EDS and XRD methods. The SEM image shows formation of a dense and compact deposit at - 0.75 V. The EDS and XRD analysis confirm that the obtained deposit is pure cobalt metal.

Jan 1, 2015

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Hiroyuki Matsuura

The effects of P2OS or Na2O addition on the reaction rate of CO2 dissociation on the surface of FexO-base molten oxides was investigated at I 773K by isotope exchange method 1-6. The rate constant decreased with increasing P2Os content of molten oxides and the residual rate constant was observed at high P2OS content. On the other hand, the rate constant increased with increasing Na20 content for FexO-SiO2 melts, The rate constant was evaluated by the composition of oxides and the rate controlling step of CO2 dissociation was discussed.

Jan 1, 2003

By Peter Ryan

A patented process for agglomeration of Smelter ESP dusts is described. Addition of suitable binders followed by compaction, transforms fine, difficult to handle material into a dry, flowable agglomerate suitable for plant reentry. Details for the agglomeration process metallurgy and laboratory pilot plant testing are discussed. An example of full scale plant operations is described.

Jan 1, 1999

By Yuan She, Qihang Liu, Keng Wu, Hailiang Ren

By observing different coal char’s microstructures and microscopic morphologies during the coking process, the characteristics of COREX coal char’s microstructure and properties were analyzed. MCRI and MCSR were used to respectively describe the reactivity and the strength after reaction of coal char, with those of BF’s coke for reference, and then the physical meaning of MCRI and MCSR were given. MCRI and MCSR were determined by the composition of coal char. For the two kinds of COREX coal, the formula to forecast the hot performance of coal char was set up by making a multiple linear regression between the hot performance and microstructure of the coal char at 1100℃, and the predictive values of coal char’s hot performance at 600℃, 800℃ and 1000℃ coincided well with the measured values.

Jan 1, 2015

By Jonkion M. Font

An expression for the distribution ratio of arsenic between slag and copper matte or liquid copper was developed by both, an extension of the Reddy-Blander moderl for deriving a priori the arsenic capacity, and by a relationship between the arsenic capacity and the arsenic distribution ratio. In this study, the a priori arsenic capacities in the FeO-SiO2, CaO-SiO2,MgO-SiO2, FeO-CaO-SiO2, FeO1.5-CuO0.5-MgO-SiO2, FeO-FeO1.5-CuO0.5-CaO-Mgo and FeO-FeO1.5-CuO0.5-CaO-Mgo-SiO2, slags were calculated at 1573 K. The a priori arsenic distribution ratio between the FeO-FeO1.5-CuO0.5-CaO-MgO-SiO2 slag and copper matte mn (Lx, )&apos; and between the FeO-FeO1.5-SiO2 or FeO-FeO1.5-CuO0.5*-CaO-Mgo slag and liquid copper (Ls/cua) were calculated. The model calculated data are found to be in good agreement with the reported experimental data. The availability of reliable thermodynamic data for slag components and impurities in the slag-matte- metal system is essential for the accurate prediction of impurity capacities and distribution ratio data. The arsenic distribution ratio model developed here, can be extended for predication in multi-componet slags and mattes or liquid metal, and thereby may lead to the development of new slag systems for the efficient removal of arsenic in the copper smelting, converting and refining processes,

Jan 1, 2003

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn&apos;t significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By Yotamu Stephen Rainford Hara

"The aim of our work is to investigate a low energy and clean route for the recovery of copper and cobalt from complex sulphide mineral concentrates. The mineral concentrates were roasted in air, in the presence of CaO (MS + CaO + 202 =MO+ CaS04) at temperatures below 973K. The roasted products containing CuO, CoO and Fe203 were carbothermically reduced at 1073K within an hour to preferentially reduce copper and cobalt. The kinetics of reactions were studied using the thermogravimetric technique and by characterisation ofreaction products using the XRDSEM-EDX techniques. The effects of MS:CaO ratio, roasting temperatures and physical nature of the mineral concentrates were analysed. The method for capturing S02 by forming CaS04 was analysed for reuse in the process. The energy balance for the above process is compared with that of conventional continuous smelting/converting process.1.0 IntroductionCopper sulphide mineral concentrates from Zambia contains substantial amouot of cobalt. The cobalt metal content in the concentrates ranges between 0.7 and 2 % weight, which corresponds to 3 and 9 % weight copper, based on the spot price of copper ($7 386/tone) and cobalt ($31 000/tone). Although the traditional approach using a combination of roasting-leaching-electrowining steps can be applied to recover copper and cobalt from sulphide mineral concentrates [1-4], there are two major draw backs of the traditional process: (i) the S02 emitted during roasting is too lean for economical conversion for sulphuric acid manufacture, which causes serious environmental pollution. (ii) silver and gold which are normally present in the sulphide concentrates are lost out [5] because they are not leachable by H2S04 or HCl which are the common leachants. The above two problems have been overcome by adopting flash smelting in which a rich S02 gas above 20% is produced [1, 5] and successfully converted into sulphuric acid. The precious metals tend to partition to blister copper and recovered during refming. However, nearly all cobalt is lost into the slag phase uoder oxidising condition which prevails during flash smelting. It is important to note that the cobalt content in the slag can be up to 2.6 % weight [6]. The recovery of cobalt from the slag is a process which requires huge amouot of energy since the slag is smelted above 1873K [6]. With a view of minimising the amouot of energy and S02 emission during metal recovery, our investigation involves roasting the sulphide concentrates in the presence of lime and reducing the roasted samples with carbon."

Jan 1, 2013

By Kazuya Koyama

We are studying the hydrometallurgical recycling process of indium from an Indium-Tin-Oxide(ITO) target. For this process, it is necessary to remove Sn(IV) ions from the aqueous hydrochloric acid solutions containing In(III). In this study, the removal of Sn(IV) ions by a potentiostatic electrolysis method was examined. The polarization measurements and potentiostatic electrolyses were carried out under a nitrogen atmosphere. In the Sn(IV) solution, current begins to rise at the cathode potential of -0.26 V vs. SHE, and increases with a reduction in the cathode potential. In the In(III) solution, current begins to rise at a cathode potential of -0.43 V vs. SHE. Metallic tin was electrodeposited without indium electrodeposition at the cathode potentials of -0.30 and -0.40V vs. SHE. More than 98% of the Sn(IV) was removed at the cathode potential of -0.40 V after the electrolysis for 3hrs. Both tin and indium were electrodeposited at the cathode potential of -0.50V vs. SHE.

Jan 1, 2006

By Zhengjie Chen, Wenhui Ma, Jijun Wu, Kuixian Wei

The gasification reactivity of PC (petroleum coke), strengthened by addition of different potassium carbonate proportions using different grinding medium, was investigated by using thermogravimetric analysis (TGA). Results showed that the gasification reactivity of PC not only increased with the increase of catalyst-loaded, but also showed the effective improvement by anhydrous alcohol. The PC was mixed with potassium carbonate [K2CO3] catalyst at 0.5%, 0.8%, 1.0% and 1.5%, and then ground wet with distilled water. The CO2-gasification rate of PC was only 77.35%, 80.55%, 84.07% and 85.88% under the gasification temperature 1100 °C and holding time 120 min, at different K2CO3 respectively. However, when the PC was ground in anhydrous alcohol at the same condition of catalyst-loading, the gasification rate of PC reached 95.43%, 96.63%, 95.50% and 95.61% at the holding time of 108 min, 101 min, 74 min and 35 min, respectively. It was shown by FTIR, SEM and EDX determinations that the anhydrous alcohol used as the grinding medium can further improve the gasification reactivity of PC when compared with the distilled water.

Jan 1, 2016

By Ryszard Prajsnar

During copper production in shaft and flash smelting processes at KGHM Polska Miedz S.A., lead bearing material of sulfide, sulfate, and oxide character is generated in forms such as slime from shaft furnace gas handling systems, converter dusts, and dusts from an electric furnace for copper removal from flash smelting slag. These materials are polymetallic concentrates of Pb, Zn, and Cu, with As, Cl, and Cd as impurities. Shaft furnace slime, containing. about 50% PbS and 15% bituminous substances, is the main lead-bearing material. At the Glogów copper mill, a new plant was commissioned in June 2001 to process 80,000 tonnes per year of lead bearing materials to produce 26,000 tonnes per year of crude lead. The plant consists of a feed conditioning system, three (3) rotary rocking furnaces with a capacity of sixteen (16) tonnes of lead feed fired with natural gas and oxygen-enriched air containing up to 45 vol% O2, and a gas handling system. The gas handling system includes a post-combustion chamber, a gas cooling chamber with Cl neutralization, gas mixing chamber, bag filter, and dry limestone scrubbing system for SO2 removal. The lead-bearing feed is smelted with five (5) wt% Na2CO3 and thirteen (13) wt% iron scrap at a temperature of 950 to 1050°C for three (3) hours. The smelting process consists of four (4) stages; feed drying, firing of gaseous hydrocarbons and solid coal from the feed, lead reduction from slag, and separation of molten products. The flow rates of natural gas and oxygen to the burners are controlled to ensure combustion of the bituminous material in the furnace. The process produces crude lead bullion containing (wt%) 0.1 to 0.5% Cu, 0.02 to 0.5% As, 0.05 to 0.07% Bi, 0.1 to 0.5% Sb, and 0.1 to 0.6%Sn. The process also produces a mixture of sodium silicate slag, Fe-Zn-Pb-Cu-S matte, and Fe-As speiss containing (wt%) 5 to 10% Pb, 2 to 6% Cu, 10 to 15% Zn, 1 to 3% As, 10 to 15% S, 0.5 to 3.0% Cl, 2 to 4% K, 4 to 7% Na, 20 to 30% Fe, and 5 to 10% SiO2. The dust is made up of PbO, ZnO, PbSO4, and PbCI2, KCI, and NaCI with a chemical composition (wt%) of 35 to 50% Pb, 5 to 15% Zn, 3 to 6% As, 4 to 8% Cl, 2 to 5% K, and 2 to 5% Na. The construction of the new lead production plant at the Glogów copper mill will process both current lead-bearing materials as well as lead-bearing material that have been stockpiled over the last fifteen (15) years to give a significant improvement in protection of the natural environment.

Jan 1, 2002

By Fiseha Tesfaye, Pekka Taskinen

"Thermodynamics of the equilibrium phase assemblage Ago_9Cul.lS-Cu2-xS-CuS have been studied by an EMF -method. The ternary phase was synthesized from the pure Cu2S and Ag2S in vacuum furnace at high-temperature and mixed with appropriate compositions of Cu2S and CuS to form the cathode electrode. The EMF-measurements were made on the solid-state galvanic cell Pt(-) I Ag I RbAg,ils I Ago9Cu1.1S-Cu2-xS-CuS I Pt(+), in a temperature range from 316 K to 498K.Based on the measured EMF vs. T relations, thermodynamic functions (?fG° , ?fS and ?fH°) of stromeyerite (Ag0.9Cu1.1S) in equilibrium with Cu2-xS and CuS have been determined. The obtained experimental values have been compared with the available literature values. New experimentally determined thermodynamic properties of the solid solution (Ag,Cu)2Sss were determined.IntroductionDue to intense mining of high grade sulfide ore minerals in the past, recently, the available sulfide ores are poor in metals and becoming increasingly complex; such that, the production of high grade metals by the conventional pyrometallurgical processes is compromised. Consequently, smelters are in need to modify their operating flow sheets and strategies for processing more complex feed materials economically, while meeting the strict environmental regulations. To make the appropriate modifications, accurate thermochemical data of phases and phase assemblages which exist in these complex ore minerals are essential.Silver-bearing sulfosalts are encountered in ore minerals for the production of base metals and are common sources of silver. Among the silver-based sulfosalts, stromeyerite (Ag0_9Cu1.1S) is relatively common ore mineral in most hydrothermal vein and replacement deposits [1]. Recently, the ternary chalcogenide compound Ago0.93Cu1,07S has been studied, intensively, due to its high ionic conductivity and gradual disorder in the sequential phase transitions [2]. Therefore, accurate knowledge of the thermodynamic properties of stromeyerite has considerable fundamental and practical interest in many aspects of extractive, chemical and physical metallurgy."

Jan 1, 2014

By Vasil Kopaleishvili

The bainitic Fe-C-Si alloys with optimum content of retained austenite serve as ?containers? for storing of hydrogen. Both the vacancies of fcc lattice and the possibility of forming hydrides of silicon and other alloying elements will be used. The idea is based on our scientific hypothesis. There is the silicon threshold (Si=0,50%) in "Fe-Si" system and Fe-C bainitic alloys, above which it causes self-organized phenomena: sudden increase of hydrogen solubility and amount of retained austenite in the alloy after ??ß transformation, formation of two supersaturated solid solutions <a??r>, "rejuvenation? and its reverse process. Rapprochement of iron atoms when Si=0,50%, causes appearance of new covalent forces where uncompensated electrons of 3d-subshell are involved and it provokes synergetic phenomena. They ?free? silicon atoms from the previous bonds. After that silicon itself becomes a getter of hydrogen using vacancies (14) of 3P2(6)d0(10) subshell and it results in sudden increase of hydrogen solubility in metal. Simultaneously sudden decrease of iron activity takes place. That in its turn ?releases? the carbon. Thus, its redistribution, controlling the bainitic transformation, is hastened. It stipulates for creation of ?brittle bainite" B[a(C,H)+?r(C,H)] after ??ß transformation. While weathering of metal, "rejuvenating", hydrogen diffuses in ?islets? of retained austenite and ?relaxed bainite? (B[(C)+?r(C,H+H)]) is obtained. When heating austenite ?(C,H) is obtained, and after cooling ?brittle bainite? is obtained, etc. Presented scientific hypothesis explains the available experimental facts ("rejuvenation? and its reverse process, graphitization, weldability, forming of flakes, reaching high strength, etc.) in a new manner, as well as, gives real opportunity for creating of new trends in many fields, e.g. iron based HAA. Provisional data having been obtained are encouraging.

Jan 1, 2006