Search Documents

By Thomas J. Keefe, O&apos

Results of metal electrodeposition experiments conducted at the University of Brussels and University of Missouri-Rolla over the past few years are reviewed in terms of the relationship and impact on industrial processes. Examples are cited from common electrowinning, electrorefining, or electroplating operations for copper, zinc, nickel, cobalt and silver. The following topics are considered : metallographic structure, crystallographic texture, surface morphology, nucleation and growth, additive monitoring and effects, high current density, substrate related properties including adhesion. The studies were conducted on a variety of scales from laboratory beaker tests to full sized pilot and industrial operating plants.

Jan 1, 1993

By Stephen Chryssoulis, Stamen Dimov

Detection and quantification of precious metals (Au, Pd, Pt, and Rh) in spinels and silicate minerals is important for establishing the maximum attainable recovery by sulphide flotation. To achieve this goal subpart per billion (ppb) detection limits are required plus the ability to quantify results. Existing quantitative microbeam techniques (EPMA, PIXE, SIMS, TOFLIMS) have limits of detection in the O. l-200ppm range. Time-of-flight resonance ionization mass spectrometry (TOF-RIMS) is a microbeam analytical technique that allows for the identification and quantification of atomic species in very small quantities. It utilizes a tunable laser source for resonant excitation and ionization of a particular element of interest and has some unique features: elemental selectivity, linear response over a large dynamic range and very high sensitivity. The analysis consist of three steps: (i) the solid sample is vaporized by laser ablation to form a plume containing neutral atoms, (ii) the neutral atoms of a specific atomic element in the plume are resonantly excited and ionized by another tunable laser, and finally (iii) the ions created are mass analyzed in a time-of-flight mass spectrometer. A TOF-RIMS mass spectrometer was developed at AMTEL for trace element analysis of Au, Pd, and Rh in minerals. The spectrometer was calibrated using homogeneous CANMET and NIST reference samples covering three orders of magnitude in concentration. Attained minimum detection limits (MDL=2cr of the background) are in the low ppb range.

Jan 1, 1999

By Jingwei Lou, Bing Li, Suzhen Li, Miao Shen, Jianguo Yu

"As a main impurity in primary lithium metal, magnesium is difficult to remove because of the very close relative volatility of the two metals. Electrochemical refining provides a possibility to completely remove Mg in the LiCl-KCl melt prior to Li reduction. MgCl2 reduction processes in LiCl-KCl- MgCl2 melt were investigated by cyclic voltammetry (CV), square wave voltammetry (SWV), chronoamperometry and chronopotentiometry. Then potentiostatic electrolysis was carried out and Mg (II) ion was reduced onto a liquid lead cathode from the LiCl-KCl-MgCl2 melt at the Mg deposition potential. The results show that Mg ( II ) is reduced in one step with two-electron transfer. The reduction potential of Mg ( II ) was well defined. The reduction of Mg( II) results in Li ( I ) underpotential deposition at 0.2V more negative potential than that of Mg( II) reduction. Therefore, in order to prevent Li ( I ) from codeposition with Mg, accurately controlling Mg ( II) reduction potential during the potentiostatic electrolysis was necessary. Ninety three to 99 % removal rate of MgCl2 was achieved after 8-12 h electrolysis when liquid lead was used as cathode.IntroductionMetallic Li has been widely used in batteries, light weight alloys and in fusion reactors because of its excellent properties. Currently, the only way in industry to produce metallic Li is by electrowinning from molten LiCl-KCl at about 450 °C [l-5]. LiCl-KCl is the only electrolyte used, because they presents a lower eutectic temperature and KCl shows a slightly higher theoretical decomposition voltage than LiCl, as shown in Table l .The produced metallic Li generally contains 1-2 wt% impurities including Na, K, Al, Ca, Mg, Si, etc. [6l, which are derived from the corresponding metal chloride compounds or metal oxide compounds existing in the LiCl and/or KCl raw materials. These impurities have to be removed by subsequent vacuum distillation at high temperatures to meet the requirements for metal Li purity in the final products. Separation of Mg from Li by vacuum distillation is difficult because their relative volatilities are very close, as shown in Table 2."

Jan 1, 2011

By Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998

By J. R. Sarazin

Density driven convection during solidification has been recognized for some time to result in macrosegregation particularly when lower density alloying elements are rejected into the interdendritic liquid. The resulting segregates are commonly referred to as channels, freckles or A-segregates. Buoyancy driven convection leading to channel formation has been examined in three model systems possessing somewhat different materials parameters. They are the Pb-Sn eutectic system, the transparent aqueous-salt NH C1-H 0 4 2 eutectic system and the transparent organic succinonitrile-ethanol monotectic system. Convection in these systems is controlled by a balance of buoyant and viscous forces, which are strong functions of composition and temperature. Composition, temperature and flow velocity were measured and elimination of channels through heavier ternary additions is discussed.

Jan 1, 1991

By G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By P. Henry

A novel electrochemical cell has been developed for the recovery of MnO2 from residue of pyrolusite ore leading loaded with Fe, Al Ni, Co and Si impurities, This new process can be considered as an alternative to the traditional methods : S02, H2O2 or bioleaching. It has been observed to proceed fairly rapidly and could prove to be a more economically viable process, as well as being more environmentally acceptable. Electrochemical characterization and kinetic studies have shown that MnO2 is effectively leached by electrogenerated ferrous ions at high current density from a pulp containing less than 5 g8 Fe. The chemical reactions are : Cathode (inox) : 2F23+ + 2e ? 2 Fe2+ Bulk: MnO2 + 2 fe2+ 4H+ ? Mn2+ + 2 Fe3+ + 2 H2O Anode (Pb-Ag) : H2O ? ½ O2 + 2H+ + 2e Global: MnO2 +2H+ Fe2+ = Mn2+ + H2O + 1/2 O2 The catholyte (MnO2 pulp) circulates upward in the expanded mesh cathode separated from the sulfuric acid solution anolyte by a separator which shows high mechanical resistance, low porosity, low potential drop, and reasonable cost. Laboratory and mini-pilot tests have led to the construction of an OT crating pilot plant (100 kg/hr) able to leach more than 95% of Mn, Ni, Co at 1000-1200 A/m2, 50°C with high faradic yield (> 95 %) and low power consumption (3.2 kWh/kg kWh/kg &4D). New applications like the treatment of spent Zn-Mn batteries, polluted soils, spent catalysts and oxide ore (cobalt, nickel) with electrogenerated redox species are now investigated at a laboratory and mini-pilot scale.

Jan 1, 2000

By José Carlos Abreu

This work presents a kinetics study covering the effects of temperature over the reduction rates of a carbon composite briquette, aiming its use as burden in some of the new alternate ironmaking technologies, such as the Tecnored process. It is reported that increases in the temperature increases the reaction rate. Additionally, the morphology of the iron phase generated during the reduction of these briquettes is presented. It was possible to verify that three types of iron morphology occurred during the process: an external, dense and continuous iron layer, the presence of iron globules at the center of the briquettes and whiskers at the briquette's core. The measurement of the carbon content on the globules and the external iron layer is also presented

Jan 1, 2003

By Chuanfu Zhang, Liwei Liang, Yanxin Wu, Jinliang Wang

"According to the reaction shaft operation characteristics during the flash smelting process, 15 groups of slag samples containing high Fe3O4 were prepared by some chemical reagents, and then the slag viscosities were measured using a RTW-10 type synthetic test instrument for melt physical property by the rotating cylinder method. The effects of Fe/SiO2 ratio (mFe/mSiO2), Fe3O4 content (wFe3O4), Cu2o), MgO content (WMgO) and Cao content (wCaO) on the slag viscosity were also studied. Results show that slag viscosity is decreased with the increase of temperature, mFe/mSiO2, wCu2o, wMgO and wCao, and with the decrease of wFe3O4, under the range of slag contents: mFe/mSiO2 1.36~1.78, wFe3O4 17.83%~21.18%, wCu2o 3.51%~8.34%m wNgI 2.21%~6.57%m w/caI 6.22%~9.387% and temperature range if 1250 o/c~1450 oC. Only wFe3O4m and w/caO have great influence on the slag viscosity when temperatures as high as 1400 oC. Only wFe3O4 and wCaO have great influence on the slag viscosity when temperatures as high as 1400 oC or so. To form a freeze slag with higher viscosity inside the reaction shaft, wFe3O4 should be more than 20% and wCaO should be less then 6%.IntroductionSince its appearance in 1949, Outokumpu flash smelting technology has making continuous innovation and has become the most competitive intensified smelting technology [1], widely considered to be the standard clean smelting process [2]. At present, flash smelting technology is adopted to newly build or reconstruct most of the world's copper or nickel smelting enterprise [3]. Reaction shaft is the most important part of the flash smelting furnace. During the flash smelting process, reaction shaft must be able to withstand the following harsh conditions at the same time: 1) high temperature varying from 1400 °C to 1500 °C. 2) strong oxidative atmosphere containing 50% - 80% oxygen. 3) solid particles and melt with speed up to l00 m/s. 4) high acidic or basic slag with strong chemical corrosiveness. 5) smelting gas containing 50% - 80% SO2. 6) matte with strong dissolution."

Jan 1, 2012

By Tatsuo Itou

Both sales volume of Aluminum Can and its recycling rate are remarkably increasing here in Japan. In 1993, recycled can volume was 11.78 billion cans ( 116,258 metric tons ) and its recycling rate 57.8 percent. We, MITSUBISHI MATERIALS CORPORATION. the leading manufacturer of aluminum can in Japan and our affiliated companies are very deeply involved in recycling used beverage cans ( U.B.C ) and recycling them back to can stock. In this paper. I would like to present the following; 1. Recent trend of beverage can consumption in Japan. 2. Trend of aluminum can and its recycling rate in Japan. 3. Future of aluminum can business in Japan.

Jan 1, 1995

By H. Matsuda, T. Iwashita, H. Awata, H. Liwei, D. Hirabayashi, Y. Saito, S. Ozawa, Y. Goto

"The present study is concerned with investigating the effect of chemical treatment on enhancing the HCl absorption capacities of coal burnt ash and slag. It was found that the HCl absorption capacity of coal burnt ash discharged from fluidized bed combustor was improved by hydration with water and 5% polyethylene glycol solution. This phenomenon was based on an increase of the specific surface area of treated coal burnt ash. The HCl absorption capacity of hydrated ash with polyethylene glycol solution was almost equivalent to that of standard CaO and Ca(OH)2. In particular, the specific surface area of hydrated ash with polyethylene glycol solution was found to be 19 m2/g, which was more than over eight times larger than that of raw sample. Hydrated slag treated with lON sodium hydroxide solution also showed high HCl absorption capacity, with highly improved surface area. It was found that the absorption capacity of slag for HCl depended on the treatment time, showing the maximum absorption capacity for 12 hours of hydration treatment.IntroductionA large amount of coal burnt ash, slag and dust are discharged from such industrial processes as coal combustion and metal refinery etc., and it becomes an serious problem to recover and diminish these solid wastes because of the shortage of dump sites and subsequent metal elution to the environment. Figure 1 shows the present situation of reutilization of coal burnt ash and slag in Japan [1,2]. It is shown in this figure that these solid wastes are recycled as materials in the fields of earthwork, agriculture and forestry etc. A part of these solid wastes, however, is still dumped to landfill. To decrease this dumped amount, the development of environmentally friendly reutilization technique for these solid wastes is of great importance."

Jan 1, 2000

By Yanhui Liu, Xuewei Lv, Chenguang Bai

A thermodynamic model for determining the surface tension of molten slag by considering the surface tension and molar volume of the pure oxide component, and their ionic radii was extended to the slag bearing high TiO2 (varying from 80 to 67%) at 1973 K. The iso-surface tension curves for the FeO-TiO2-Ti2O3 ternary system at 1973 K are almost parallel to the FeOTi2O3 line. TiO2 plays a role of surface-active solute, and its surface-active effect is attenuating with increasing the TiO2 content. The iso-surface tension curve shifts away from the TiO2 corner, indicating that the surface tension of the ternary slag decreases along with the addition of SiO2. The reasons include the addition of SiO2 with lower surface tension and the decrease of the total ion moment at the surface. Both CaO and MgO can bring about that the iso-surface tension curve shifts towards the TiO2 corner, indicating that the surface tension of the ternary slag increases along with the addition of CaO or MgO. CaO has a more pronounced effect on increasing the surface tension of the ternary slag than MgO at an equimolar amount addition. The increase of the surface tension results from both the compositional change and the variation of the slag structure.

Jan 1, 2015

By G. H. Khoe

Neutralisation of acid uranium mill tailings with lime or other alkaline materials is usually practised to reduce the dissolved concentration of heavy metals and radio nuclides. Computer modelling of this process was carried out using the geochemical equilibrium code MINTEQA2. Computed dissolved metal and sulfate concentrations were compared with laboratory-based experimental data. It was found necessary to include the modelling of adsorption of trace metals (such as uranium and lead) by the precipitated ferric hydroxide in order to obtain acceptable concentrations in the neutralised liquors. There were limitations of the modelling exercise due to important aspects which were not addressed or properly accounted for such as chemical reaction kinetics and the effect of high ionic strength. These are discussed in the paper.

Jan 1, 1991

By T. Innmi

The potential of the nickel matte anode was measured during the matte electrolysis in the commercial cell. The slime layer consists of elemental sulfur and was found to greatly influence the potential of anode. The measurements of porosity and permeability of the slime suggest that the voltage drop of the slime layer dominates the potential. Furthermore, the diffusion of the electrolyte through the slime layer is also one of the factors to determine the potential. In addition, the copper content of the nickel matte anode was found to affect the change in the anode potential during the electrolysis. The role of copper on the anodic dissolution of nickel matte is discussed in this work.

Jan 1, 1988

By Edgar Peek

"The two dominant metallurgical problems in treating most base metal sulphide concentrates in both the chloride and sulphate system are iron removal and sulphur elimination, respectively [1-3]. In this paper the opportunities, limitations and fundamentals of the chloride metallurgy system are described against this background. Only the treatment of oxide and sulphide ores is considered. Both hydrometallurgical and pyrometallurgical unit process operations are highlighted, since most successful base metal processes are based on a combination of the two. Hence, an overview of the technical and also some economical aspects of chloride metallurgy are presented.This overview summarizes the successful applications of chloride metallurgy, but it will not give exhaustive process and plant descriptions. It predominantly focuses on the essential technical features of the metallurgical unit process operations, while providing numerous references separately."

Jan 1, 2011

By Boyd Davis, Vladimiros Papangelakis, Joshua LaMarre, Jan de Bakker

"HCl leaching using molten salt hydrates has the potential to improve the extraction of nickel from laterite ores. However, as in other HCl leaching applications, recovery of HCl is key to process economics. Spray pyrohydrolysis, which is used in current chloride-based flowsheets, is associated with a high energy cost. The authors have developed a proposed laterite leach circuit using an alternative HCl recovery route. The leach circuit envisions a leach by concentrated (33%) HCl in an MgCl2 molten salt hydrate (MSH) or brine medium, followed by Ni/Co recovery and iron precipitation. Magnesium and chloride are precipitated from solution as magnesium hydroxychloride; this hydroxychloride is thermally decomposed to produce HCl gas. The proposed flowsheet employs a chloride leach circuit with simpler equipment and lower energy cost than in the conventional practice of pyrohydrolysis. Laboratory work investigated key aspects of the flowsheet, including precipitation of magnesium hydroxychlorides and their composition; magnesium hydroxychloride thermal decomposition; and iron control.Introduction As sulphide nickel ores become harder to mine and more complex to process, laterite ores will increase in importance. Laterite ore deposits can be divided into two main mineralogies. Limonite ores consist mostly of hydrated iron oxide, FeOOH, with 1-3% nickel substituting for the iron. Saprolite ores consist of iron-magnesium silicates, (Fe, Mg)2Si04, again with some nickel substituting for the metal ions. Limonite ores can be treated using the HP AL (High Pressure Acid Leach) process, in which the ore is reacted with sulphuric acid at high temperature in an autoclave. HP AL, however, cannot in general be used to treat saprolite ores because the magnesium enters solution and consumes sulphuric acid, which results in excessive spending on lixiviant. It is therefore desirable to find a hydrometallurgical process specifically for saprolite ores that can provide better results than the treatment options currently available."

Jan 1, 2011

By Guohui Zheng

The ever increasing quantities of solid wastes generated by various industries are at the source of the growing need for proper waste disposal methods. Thermal treatment of combustible wastes is a proven technology which permits the reduction of hazardous material having to be landfilled. However, this method is not universally applicable to waste disposal. For example, the transferal of heavy toxic metals into the thermal remediation products is a major issue of public concern. This paper focuses on the analysis of morphology changes from solid sludge to ash which is a product of the sludge combustion. The morphological parameters analyzed were particle size and external surface. They were determined using Jeol 840 Super Probe. The experiments were conducted in a computer-controlled high-temperature combustion system consisting of the thermogravimetric furnace coupled with Fourier transform infrared spectrometer (TGA-FTIR). Sludge particles were made of complex fibers trapped in the aluminosilicate matrix. At low temperatures, up to 680 K, the solid residue looked similar to the initial sludge. Between 680 K and 1180 K the sludge underwent intensive burning and steadily changed into powdered ash. At the temperature of 1050 K the ash was composed of separate, flat flakes with sizes ranging from 5 to 20 um. At 1470 K the flakes aggregated into large particles. The surface observed at 1670 K was a mixture of mullite crystals. Such structure could result from the solidification of the ash material after its melting. Morphological changes influenced the distribution of metals in the solid residue. For example, Cr was concentrated in small aggregates. Such distribution should allow for recovery of valuable metals from the solid waste residue.

Jan 1, 1996

By K. Yamada, T. Takaoka, A. Ozeki, M. Yamaga, Y. Kawai, S. Nishioka, Y. Kikuchi

"Recently, smelting reduction of chromium ore in BOF has been actively investigated as a key unit process for an innovative future stainless steelmaking. The prominent feature of this new process route is energy and process saving, and production cost saving. The development is already in the midst of application to the commercial production, however there still remain the following key technologies to be established for the full use of the process. One is a speed up of the reduction of chromium ore to match with sequential continuous casting, and the other is efficient combustion of carbonaceous materials in BOF to reduce their consumption, and hence to assure the steel quality. High degree of post combustion technology and new charging technology, i.e., ore-coal-flux-oxygen mixed injection, could be effective for those two subjects. In 2000 or beyond, the new process would have become quite popular owing to the establishment of those key technologies.Introduction Since stainless steel was invented, its production has continued to expand because of its attractive combinations of functions of excellent corrosion resistance, good formability, a pleasing appearance, and a wide range of strength levels. New types of stainless steels as well as new applications are continually being developed.Compared to the production of ordinary steels (1), stainless steel production (2,3) shows steady growth worldwide, while the former production remains on the same level, as Figure 1 shows. It can be estimated that future production would show further growth since materials consumer demands are more fashionable, or more functional, which could be satisfied by stainless steels.Thus market needs would be met, if it could be produced with reasonable production cost. The emergence of an innovative production technology is then potentially requested as VOD and AOD processes have emerged, which has saved substantial production cost. This paper describes a possibility of a future stainless steelmaking process, which uses the in-bath smelting reduction of chromium ore in BOF, and which would save production as well as energy cost."

Jan 1, 1988

By N. Kanari

Kinetics of the carbochlorination of Cr2O3 has been studied with C12+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 "C to 800 OC, the reaction order is about 1.34 and is independent of temperature. Changing the C12+CO content from 15 pct to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of C12/(Cl2+CO) from 0.125 to 0.857 do not modify the carbochlorination mechanism of Cr203. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl2/(C12+CO) ratio of about 0.5.

Jan 1, 1998

By Wenxian Zhu, Patrick R. Taylor

"The small dimensions of nano-sized materials leads to novel and enhanced mechanical and physical properties. A thermal plasma reactor has been developed to study the formation of nanometer sized metal powders. A supersonic nozzle and a powder filter were designed and built. By vaporizing coarse metal powders in the plasma flame, and quenching the metal vapors through the nozzle at the rate of 107 K/sec, nanometric sized powders have been produced. The powders were collected in an airtight secondary quench-filter system. The particle size of the product power is 5 -20 nanometers, obtained through TEM analysis. The XRD analysis showed that the powder did not oxidize after the filter was handled in an inert atmosphere glove box.IntroductionNanostructured materials have been shown to exhibit improved physical and mechanical properties compared to conventional materials with larger grain sizes (1,2). There have been several methods proposed for preparing nanometer size materials. Thermally induced vapor-phase reactions have been used to produce a variety of powders. A common feature of these processes is the rapid production and cooling of condensable reaction intermediates and products, by gas-phase reactions, leading to the formation of a large number of very small particles. Thermal plasma synthesis of ultra-fine size particles has been attracting increasing interest (3,4,9-11), because it offers many advantages, especially in refractory materials processing, compared to conventional processes: (a) thermal plasma temperatures are very high(> 5000 K); (b) the rates of chemical reaction are much faster than those encountered in conventional processes; (c) high-purity materials may be obtained using fewer processing steps by collecting the product at temperatures where the by-products are in the vapor phase; ( d) the mean particle diameter can be controlled; (e) unifom sized particles may be produced with clean surfaces (these particles are particularly suitable for pressureless sintering); and, (f) high throughput per reactor volume can be achieved. In addition, the process used for generating particles determines the degree of sintering ability of the powders, since the process dictates the morphologies, the purity and its size distribution. In the future, thermal plasma synthesis nanometer size particles may play an important role in vapor phase reaction techniques and might be expected to be one of the first full scale commercial installations in the future."

Jan 1, 1998