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By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By Alan M. Russell

In recent years, several rare earth intermetallic compounds with the B2-type structure have been reported to exhibit high tensile ductility and high KIC fracture toughness at room temperature. These materials retain considerable ductility even at 77K. These are noteworthy findings because most intermetallics possess poor room temperature ductility and low fracture toughness unless one or more special contrivances are applied (e.g., doping with small additions of interstitial elements, offstoichiometric compositions, testing in ultra-dry atmospheres, etc.). This paper summarizes recent findings on rare earth B2 intermetallics. These include the determination of the active slip systems; the strain rate sensitivities; yield strength maxima at elevated temperatures; the search for possible twinning and stress-induced phase transformations; ab initio calculations of their defect energies and the anisotropy of dislocation line tension. Potential applications of these materials and the possibilities that this study may suggest strategies for increasing ductility in other intermetallic compounds are discussed.

Jan 1, 2008

By Zhongning Shi, Ramana G. Reddy

"By cyclic voltammetry and potentiostat electrodeposition using Potentiostat/Galvanstat, electrochemical behavior on Ag electrode in electrolyte 0.2M NaOH+0.01MPb(NO3)2-0.01M TeO2 -0.01M TlNO3 solution were also carried out at 298K. The processes of electrodeposition of Tl2Te3 and PbTl4Te3, a thermoelectric material, are reported along with analysis of the composition of the obtained deposits. The results showed that two different underlying processes are occurring depending on deposition potential. One process involves the reduction of TeO3 2- and Tl+ to Tl2Te3 in a potential interval of -0.70V < E < - 0.89V (vs. Hg/HgO). A second process at more negative reduction potentials involves reduction of TeO3 2-, Pb2+ and Tl+ to PbTl4Te3 in a potential interval of -1.02V < E < - 1.19V. The crystalline Tl2Te3 and PbTl2Te3 were deposited electrochemically on Ag substrates at -0.84V and -1.10V respectively. Thermoelectric (TE) material can form a temperature gradient across the material to make electric voltage, which is popular in waste heat utilization and recovery industry. Lead telluride, PbTe, is a small band gap semiconductor of 0.32eV at 300K. PbTe can change its n-type semiconductors with Pb-rich to p-type semiconductors with Te-rich[1]. And it is one of the best TE materials used in thermoelectric generators working between 500K and 600K, or even at a higher temperature of 800K.Three facto,rs play a role in the performance of a thermoelectric material: electrical conductivity (s), thermal conductivity(?), and the Seebeck coefficient (S). These can be combined with absolute temperature (T) to give a figure of merit (ZT) for the material, ZT = s2sT/?. By increasing the electrical conductivity and decreasing the thermal conductivity, which can enhance the ZT value, many efforts, such as alloying with other elements and making the materials nano-sized, have been done to improve its properties recently. Hsu et al. reported that the ZT value of Cubic AgPbmSbTe2+m is increased to 2.2 by doping Ag-Sb to PbTe.[2]."

Jan 1, 2011

By Tailoka F.

Various metallurgical residues from iron and steel making processes have been treated by chlorination in excess air with hydrogen chloride gas generated from the combustion of scrap polyvinyl chloride (PVC). The residues include dust from both the electric arc and blast &maces, hydrocyclone overflow, zinc - lead blast furnace slags and dust rich in zinc and copper from copper refining. Chlorination is achieved either directly by mixing the residues with scrap PVC or indirectly in a two furnace system. In the latter, scrap PVC is combusted between 523 and 573 K in a horizontal furnace and the resulting gases are then reacted with metallurgical residues in a vertical furnace at 1166 to 1329 K. Gas chromatography, thermogravimetric measurements, XRD and AAS have been utilised to study the reactions. The recovery of non ferrous metals is as high as 80 to 90 % and only a negligible amount of iron is carried over. The optimum temperature for combustion is between 518 and 573 K. Above 600 K, the evolution of HCI is so fast that sufficient chlorination is not achieved. Analysis showed that no dioxins were present in the gases, the residues or the chlorides.

Jan 1, 1997

By Hsin H. Huang

Equilibrium calculational software programs can be effectively utilized to model the importance of activity or concentration, solubility, temperature, solution pH, solution potential, and ligand complexation on extraction and recovery processes. Illustrative examples using the calculational program ST ABCAL for the creation of diagrams such as EwpH, activity or concentration-pH, and activity or concentration-EH are presented to demonstrate the fundamental characteristics of real hydrometallurgical mercury dissolution and recovery processes. An industrial application will include leaching of mercury from K 106 mercury sulfide waste and solution purification by iron cementation.

Jan 1, 2003

By Musa Karakus

In an attempt to explain the phenomena of lead entrainment during Cu drossing of lead bullion, two different synthetic lead bullions were heated to 1050°C, cooled slowly to various temperatures, and then quenched. The morphology and composition of dross particles that form when Mn is used to desulphurize bullion also were examined. Polished sections of these pyrometallurgical products were examined by process mineralogical techniques to identify the impurity phases, determine their chemical compositions, examine the morphology of the impurity phases and evaluate the potential for lead entrainment in such crystals, and characterize pre-quench and quench-generated phases. The phases crystallized were metallic lead, metallic copper, galena, chalcocite, albandite, Cu14.4Pb2S9. and 5.5Pb2S3.5. Metallic copper formed isometric skeletal crystals, chalcocite formed platy and skeletal crystals, and 1formed crystals and eutectic intergrowth with chalcocite and Cu14.4Pb2S9 or Cu5.5Ph2S3.5. The pre-quench crystals are larger and usually exhibit skeletal forms; the quench-generated phases are only a few micrometers across and disseminated throughout the lead matrix. Skeletal crystals of metallic copper and chalcocite form three dimensional networks that entrain large amounts of metallic lead.

Jan 1, 1989

By Chen Song

In the experiments of purifying the solution of chlorine leaching from nickel concentrate with N235, the effects of organic phase composition on purifying efficiency have been studied. From the results obtained, the optimal organic phase composition is found to be 25%N235+12%isomerous alcohol +63%sulfonic kerosene (VIV) and the saturated content of cobalt in organic phase is7.95 g*dm3. And then the serial experiment is carried out. The results show that at the given organic phase composition, the purified solution contains p(Ni) >200 gm dm3, p(Ni)l p(Co) >50000 and the contents of Cu, Fe, Mn, Zn meet the technical criterion of standard nickel electrolyte. The cobalt chloride solution contains p(Co) >I10 g L-1, p(Co) lp(Ni)>50000 and the enrichment of cobalt has been achieved.

Jan 1, 2006

By Pingchao Ke

A crystalline polyferric sulfate (PFS) adsorbent was synthesized by oxidizing and precipitating ferrous ions under atmospheric conditions. The morphology, structure, composition and specific surface area (SSA) and adsorptive efficacy to As (III) of the adsorbent were characterized by SEM/EDS and TEM images, XRD patterns, FT-IR spectra, BET SSA analyses and adsorption experiments. The adsorbent presents as morphology of near-spherical aggregate and good crystallinity. A small amount of goethite co-precipitated with PFS in the case of the initial ferrous concentration of 1 mol/L and increased the SSA of the aggregates. The absorbent with co-precipitation of goethite showed good adsorption to As(III) and good filtering performance in the high As(III)-content solution of 10–100 mg/L under acidic, neutral and alkaline conditions (pH 2.09–9.01), and its maximal adsorption capacity and adsorption efficiency were 7911 μg/g and 96% separately. After Adsorption, the stability of the absorbents adsorbing As(III) were evaluated by TCLP tests, and the results indicated that the absorbents adsorbing As(III) were extremely stable, and the concentration of arsenic in all leaching solutions were less than 0.01 mg/L.

By Antoine Allanore, Luis A. Ortiz, Donald R. Sadoway

"The steelmaking industry has drastically reduced its energy consumption in the last fifty years, and today’s technologies are considered to operate at their optimal efficiency with respect to energy needs. To cope with new constraints related to greenhouse gas (GHG) emissions, a change of paradigm is necessary. One of the promising technologies that could be deployed to help reach CO2 mitigation targets relies on the intensive use of electricity: molten oxide electrolysis (MOE). This paper presents the key process parameters that need to be tuned to address the practical needs for both high productivity in a steelmaking reactor and for an energy efficient process. Herein we show that contrary to common perception, the electrolysis process for ironmaking requires less energy than today’s chemical reduction route. Furthermore, we prove that most of the energy that must be provided to operate the electrolytic iron production cell is thermal energy which is readily generated by joule heating during electrolysis due to large currents being passed through the electrolyte. The energy consumption of the electrolysis cell is therefore shown to be highly dependent on the cell configuration and the chemistry of the electrolyte. As a consequence, the CO2-impact of the technology strongly depends on both the power production mode and the technological choices for design of the process, including cell configuration. Surprisingly enough, even when the electricity generation is not carbon-free, MOE still appears to be viable from the perspective of reducing GHG emissions providing sound reactor design considerations are made.IntroductionIn the context of greenhouse gas (GHG) emissions mitigation, the steelmaking industry is considering several techniques that could sustain the efforts and progress achieved by this sector in the last decades [1]. A recent report [2] on potential routes for low-CO2 steelmaking highlighted for all techniques both the strong dependency of CO2 emissions on electric power production mode and the need for a decrease in energy consumption per tonne of steel. Incited to innovate with respect to this last criterion, the steel industry considers electrolysis to be a promising technological solution, and in particular the molten oxide electrolysis (MOE) process. This process conducts electrolysis in a mixture of oxides that dissolve the iron oxide feed, which by the action of electric current is decomposed into liquid iron and oxygen gas. The opportunity for reduction in energy consumption during steelmaking by MOE is commonly attributed to the “direct” pathway from iron oxide to liquid metal offered by the use of a molten oxide melt and operation at a temperature above the melting point of iron, ideally 1600°C, to provide enough superheat for tapping the molten iron product:"

Jan 1, 2011

By C. Takano

The integrated iron and steelmaking industry generates large amounts and many types of solid dusts and sludge, at different phases of the production. Within these are: sludge of the Blast Furnace; coke fines; fine and coarse fractions from oxygen converters; sludge from water treatment at rolling mill unit; and others. In this paper the above dusts and sludge were physically and chemically characterized. The obtained results allowed defining self-reducing pellets using these materials. The high temperature behavior of the pellets were evaluated. Good results, with no decrepitation and swelling, and high yield of reduction, show that it is feasible to recycle them, as self-reducing pellets, in oxygen steelmaking converter.

Jan 1, 2001

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 Michael Sheedy

Recoflo® ion exchange technology utilizes fine mesh resin beads, a fully packed resin bed, and counter-current regeneration. These unique features help to improve exchange kinetics, reduce regenerant consumption, and increase the concentration of strip solutions. Commercially, Recoflo technology has been extensively used in the following areas: the separation of strong mineral acids from dissolved metal salts, the purification, removal and recycle of dissolved metals in the surface finishing industries, and the production of high purity water. In the mining and metallurgical industries Recoflo ion exchange systems have been installed to treat a copper refinery bleed stream at Falconbridge&apos;s Kidd Creek plant and to treat a nickel and cobalt bearing ammonium sulfate effluent stream at another primary metal producer&apos;s facility. In the first application an APU® Recoflo system is used to separate the sulfuric acid at 200g/L from the dissolved copper and nickel sulfate salts at 80 g/L. The absorbed sulfuric acid is recovered from the resin by elution with water and is then returned to the refinery electrolyte circuit. In the second application a chelating ion exchange resin is used to remove nickel and cobalt at 0.01 - 3.0 g/L from process streams containing 120 - 240 g/L ammonium sulfate. This Recoflo system has been designed to reduce the nickel and cobalt levels to 0.001 - 0.002 g/L while recovering cobalt and nickel at concentrations up to 30 g/L and 15 g/L respectively. Case studies for both these metallurgical applications and other Recoflo processes are presented in this paper.

Jan 1, 1998

By A. S. Usmani

The flow associated with the pouring of molten metal into moulds has been modelled on the basis of certain simplifying assumptions. A finite element based Navier-Stokes equation solver has been used to analyse the flow. The velocities obtained from the Navier-Stokes equation solver are used to advect a pseudo-concentration function for modelling the fluid front. A simple problem with a known analytical solution is solved first to test the model. Subsequently, several more examples with varied geometrical configurations are modelled, including one with curved flow boundaries.

Jan 1, 1992

By Bogdan Petkovic, Boban Todorovic

In the early 90's a completely unknown problem was encountered at the converter Department: it was a chronic shortage of the cold copper charge needed for the second operating period. A high temperature operating regime was caused which further provoked a chain of consequences such as a drastic drop of the number of operations in campaigns. The consumption of repair bricks reached the quantity of 8.3955 kg / tonne of anode Cu. In 1994, we won the process of cold material smelting during the "copper" blowing [2]. The number of operations per campaign reached 180-200 again. Also in 1994 we won the process of smelting cold materials to obtain "tin" blowing with the purpose of completing their processing cycle [2]. During the period 1994 – 2007 a total of 107,845 tonnes of cold material were remelted to make copper and 56,794 tonnes were re-smelted to obtain "tin". Upon synthesizing these two processes, a completely new model was achieved in 2005, by Bogdan Petkovic, which entirely utilized all available energy of the Peirce-Smith (PS) converters of the Bor Copper Smelter and now represents the basis of the time cycle. The cold material now enters the converter plant, copper recovery is increased and the method itself is environmentally friendly. 167

Jan 1, 2009

By S. Castro, P. Alfaro, C. Moctezuma

IMMSA operates a conventional roasting-leaching-purification-electrolysis plant for the production of zinc from concentrates in San Luis Potosi, Mexico. The leaching circuit was designed to take into consideration a feed mixture to the roaster with a maximum iron content of 7%. Since the start-up of the plant in 1982, the zinc recovery increased to 94.5%. However, an increase in the iron content in 1997 caused an important decrease in the global zinc recovery. Two new steps were added to the leaching circuit and modifications were made to the other steps in order to increase zinc extraction. Two new automated press filters were installed to replace the original vacuum drum filters and to minimize soluble zinc losses. Additionally, the residue treatment steps in purification were modified and a calcium removal circuit is just starting operation. These actions, besides improving the operations, have as the main objective to increase the global zinc recovery to levels above 94.5%.

Jan 1, 2000

The paper concerns an unconventional, yet promising, use of waste magnesite dust and fines. In India a significant amount of this dust is generated from some of the integrated iron and steel industries, refractory and cement plants, during calcination of raw magnesite. However. it is possible to utilize this dust, which is normally a waste, conveniently and economically for the production of magnesium. chemicals. A bench scale study was carried out to determine the rate of formation of sulfated com¬pounds of Mg.Ca,and Fe, inter alla, present in the dust system containing MeO constituents (in which Me=Mg.Ca,Fe,Si,Al etc.) Effects of various process parameters, which affect the reaction rate as also the purity of the product ,were also studied. Some work carried out to develop the process flow charts involving the salient steps to produce magnesium chemicals commercially is reported in the paper .

Jan 1, 1992

By Yutaka Shiraishi

Two methods were developed to measure the viscosity of the slag from the glassy to the liquid states in an ascending temperature process. The first method employs rotating parallel plates within which is placed a solid cylindrical sample in line with a sphere. The second method uses a tube which is pushed into a sample held in a rotating crucible. Both methods were tested using standard glasses, including boron trioxide and NBS standard glass #711. The main difference between these two methods is in sample preparation. Comparative measurements between two methods were performed using a sodium boro-disilicate glass containing 5%mol of alumina. The results showed good agreement in the mid-range of glassy viscosities, 105 to 107 Pa.s. In the liquid state, there were no significant differences between the two methods.

Jan 1, 2003

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Carlos Ortiz

The Huelva Flash Smelting Furnace was commissioned in September 1975. The Smelter and the Acid Plant were expanded in 1995 to their present capacity of 300,000 tpa new copper equivalent and one million tonnes of concentrate per year. During these years of operational experience, most of the initial practices have been reviewed, process control has drastically improved and main process equipment has been modernised. The fourth Flash Furnace campaign lasted 9 years (1995-2004) during which 8 million tonnes of concentrate were smelted. Increasing sulphur content in concentrates and new environmental requirements imply new challenges for smelters to keep production and operation costs down. This paper is an overview of the modifications and improvements carried out in the 2007 general shutdown in Smelter and Acid Plants. Al

Jan 1, 2008

By Yutaka Shiraishi

Two methods were developed to measure the viscosity of the slag from the glassy to the liquid states in an ascending temperature process. The first method employs rotating parallel plates within which is placed a solid cylindrical sample in line with a sphere. The second method uses a tube which is pushed into a sample held in a rotating crucible. Both methods were tested using standard glasses, including boron trioxide and NBS standard glass #711. The main difference between these two methods is in sample preparation. Comparative measurements between two methods were performed using a sodium boro-disilicate glass containing 5%mol of alumina. The results showed good agreement in the mid-range of glassy viscosities, 105 to to7 Pa.s. In the liquid state, there were no significant differences between the two methods.

Jan 1, 2003