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By M. Cavallini, G. Cannavale, P. P. Milella, A. Pescetelli, C. Lupi

Ni-Cd sealed and vented cells have been widely used in the last few years. The environmental hazard related to the heavy metals contained in Ni-Cd batteries is well known. Therefore, a number of scientific studies and commercial processes have been implemented in order to recycle them. Since spent batteries are a heterogeneous and complex material, any kind of recovery process needs some preliminary treatments. The proposed process described in this paper has been tested in laboratory and further developed in a pilot plant. It consists of a combination of mechanical and hydrometallurgical treatment steps, and is able to treat all type of Ni-Cd batteries. In particular, the mechanical treatments have to be done separately on vented and sealed cells, while the hydrometallurgical step is performed on a mixture of the two products obtained from mechanical steps. A fully automated dismantling line would allow the separate recovery of the plastic or metallic casing, terminals, KOH electrolyte, and electrodes to be further processed· for Ni and Cd recovery. The electrodes coming from dismantling line and sealed batteries are submitted separately to an original crushing and elutriation treatment to separate metallic and active paste in the first case and metallic, plastic and active paste in the second case. The hydrometallurgical treatment is carried out on active paste bearing product to produce Ni, Cd, and Fe comn1ercial salts through acidic leaching followed by a multi-step solvent extraction operation to obtain pure solutions.

Jan 1, 2000

By Guolin Zheng, Jian Pan, Deqing Zhu, Xianlin Zhou

"In ferronickel production, nickel oxide and part of the iron oxide are reduced to metal by agglomeration and smelting in blast furnace. Due to the physical and chemical properties of the laterite ores, a large fraction of fines is generated during the pre-treatment stages and the strength of agglomeration is weakened, which results in low productivity and bad quality. In this paper, the process of pelletization of nickel laterite was developed, and some parameters to strengthen the pelletization of nickel laterite have been optimized. The results show that the compressive strength of fired nickel laterite pellet can reach over 2000 Newton per pellet while firing at the temperature of 1220 °C~1250 °C in 12 min. The product pellet can be used as high-quality burden for blast furnace to manufacture ferronickel.IntroductionIn recent years, the global stainless steel market was developed exuberantly, which greatly promoted the needs of the basic raw material of stainless steel smelting - metal nickel. Currently nickel sulfide ores are only 40% of global nickel reserves, but offer 60% of all the nickel production. However, with the deficit of resources, the nickel sulfide ore (high grade ore) is depleting, so there is an increasing focus on the utilization of low-grade nickel laterite. Recent research has focused on the wet treatment process to utilize nickel laterite, and less on the use of other technologies [1-8]. The economical and efficient technology relies on the reduction of nickel oxide and part of the iron oxide metal by agglomeration and smelting in blast furnace in China. Some domestic steel companies have adopted this process [9, 10]. Unfortunately a large fraction of fines is generated during the pre-treatment stages and the strength of agglomeration is weakened, which results in low productivity and bad quality of fired pellets. In this study, the process of pelletization of nickel laterite was developed firstly, and some parameters to strengthen the pelletization of nickel laterite have been optimized, and the product pellet can be used to produce stainless steel and ferronickel alloy by blast furnace."

Jan 1, 2011

By Grigore Matei

The thermodynamic properties of CU2S-FeS system are important not only in the case of copper smelting but also in the case of general pyro-mctallurgy, However there are not many reported activity data In this study, activities of FeS and CU2S in the CU2S-FeS system were calculated using the Darken's method from the activity data of the CU2S-FeS-Sb2SJ systems measured by the transportation method at 10S0°C. The activities of CU2S and FeS in the CU2S-FeS system showed negative deviation from the ideal behaviour and satisfied the relation of the Gibbs-Duhem equation,

Jan 1, 2003

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Army Research Laboratory (ARL) has an interest in the recovery and processing of rare earth elements. At Montana Tech, elevated temperature chlorination of rare earth oxides is presently being investigated as a potential methods leading to the selective separation and recovery of rare earth elements from mineral ores and concentrates. After preliminary evaluation, ytterbium oxide was selected as a representative surrogate material for more extensive chlorination studies. Methods used to determine the conversion and recovery include X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis. These data have been used to establish and confirm process conditions that consistently yield high conversion efficiencies. Based on the promising results, further experimentation is underway to ascertain the metallurgical response of other rare earth oxides and carbonates to the roasting process. The end goal is to create a robust process for industrial application that has greater efficiency and reduced costs as compared to current practice.

Jan 1, 2015

By Xiaoyan Xiang, Wenqiang Yang, Wentang Xia

Magnesium aluminate spinel is widely used in the metallurgical industry as refractory material, however, natural magnesium aluminate spinel is rare and most of the magnesium aluminate spinel is synthetic. The traditional synthesis of magnesium aluminate spinel often needs high temperature, which leads to more energyconsumption. In this article, solid phase sintering process was employed to synthesize magnesium aluminate spinel, in which, magnesium and aluminum oxide were used as raw materials and magnesium and aluminum powder were used as composite additives. The mass ratio of magnesium and aluminum on the effect of synthesis of magnesium aluminate spinel and the characteristic of the synthesis at different temperature and time was discussed. Experiment found that the synthesis temperature was observably lowered when the addition of magnesium and aluminum was 2.0% and 1.0% respectively.

Jan 1, 2016

By Guangshi Li, Xionggang Lu, Xueliang Xie, Xingli Zou, Yuyang Bian, Hongwei Cheng, Kai Zheng, Changyuan Lu

The corrosion resistance and corroded microstructure of MgO-C refractory in molten slag are investigated by immersion test in muffle furnace at 1600 °C . The microstructure and chemical compositions of the specimens after erosion experiment are characterized by scanning electron microscope (SEM) and energy dispersive X-ray (EDX). The results confirm that the oxidation of graphite is the most important degradation mode of MgO-C refractory. The structure of the refractory material is damaged due to the decrease of graphite, as a result, the periclase substrate reacts with the molten slag directly. The corrosion process is controlled by the dissolution of the refractory materials into slag, low melting point oxides are therefore generated which lead to the damage of MgO-C refractory finally.

Jan 1, 2015

By K. Yarnaguchi

In the Mitsubishi Continuous Copper Converting Furnace, calcium femte slag is used. Due to its extremely high basicity, the improvement of corrosion resistance of the refractory lining is in need. In order to clarify the corrosion mechanism and to search for a new corrosion resistant material, first, the surface snuctures of bricks corroded in molten slags were observed by EPMA. Second, the dissolution behaviors of sintered MgO-based pellets containing various oxide additives were examined. It was found that the formation and the dissolution of magnesiofemte at the surface of the bricks play an important role in their corrosion and an addition of NiO, Mn02, or Ti02 to MgO is effective in stabilizing the magnesio-femte and improving the corrosion resistance of MgO.

Jan 1, 1994

By Fumitaka Tsukihashi

Phase diagrams of the CaO-SiO2-FeOx-MgO, Al2O3 systems are necessary for the analysis of copper smelting reactions and sintering process of iron ore. The effect of MgO and Al2O3 addition on the liquidus of the phase diagram of the CaO-SiO2-FeOx system at low oxygen partial pressure was observed. The liquid phase area changed by the addition of MgO and Al2O3 with a changing oxygen partial pressure from 10-8 to 10-3 atm (10-1 to 102 Pa) at 1573K. The effect of Fe3+/Fe2+ ratio on the melting mechanism is discussed.

Jan 1, 2003

By Fumitaka Tsukihashi

Phase diagrams of the CaO-SiO2-FeOx-MgO, Al2O3 systems arc necessary for the analysis of copper smelting reactions and sintering process of iron ore. The effect of MgO and Al2O3 addition on the liquidus of the phase diagram of the CaO-SiO2-FeOx system at low oxygen partial pressure was observed. The liquid phase area changed bi the addition of MgO and Al2O3 with a changing oxygen partial pressure from 10-8 to 10-3 atm (10-3 to 10 2 Pal at 1573K. The effect of Fe3+ / Fe2+ ratio on the melting mechanism is discussed.

Jan 1, 2003

By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. In 1996, however, it successfully shifted to a single furnace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Ozgul Dere Ozdemir, Muge Sari Yilmaz, Sabriye Piskin, Deren Sibel Kasap

"Galvanic sludge is generated at the end of the waste water treatment process of metal plating system. The waste sludge is one of the main hazardous solid wastes produced by metallurgical industries. It is caused the harm of human health and damage of the environment due to containing reasonable amounts of toxic metals (e.g., nickel, zinc, copper, chromium, iron, lead, cadmium, etc). The concentration of those toxic metals in the wastewater might reach 30% (w/w, dry weight) making their removal and recovery an interesting issue.In this study, synthesized titanium dioxide is used as adsorbent to remove nickel in leachate of galvanic sludge. The adsorption experiments were carried out isothermally at four different temperatures. The effects of pH, temperature, and contact time on nickel adsorption efficiency were investigated, and the optimum parameters were determined from the experimental studies. The experimental results indicated that pH, temperature, and contact time played a significant role on the adsorption capacity of nickel.IntroductionRapid industrialization has caused increasing the heavy metal concentration in biosphere with the industrial wastes. These wastes are generated in various industrial processes such as electroplating. Galvanic sludge is a hazardous waste that generates from metal plating industry by chemical precipitation of heavy metals from acidic or alkaline solutions during the waste water treatment process. Heavy metals are tend to bioaccumulate thus they are treated the living organism [1-2].Galvanic sludge is mainly disposed on landfills for these reason it is a big problem for environment. Galvanic sludge containing nickel (II) is common because nickel (II) is used in electroplating process [3]. In drinking water, nickel may cause health problems if found in amounts greater than the health standard set (MCLG: 0.1 mg/L) by the United States Environmental Protection Agency (EPA). The higher concentration of nickel (II) in ingested water may cause severe damage to lungs, kidneys, gastrointestinal distress, e.g., nausea, vomiting, diarrhea, pulmonary fibrosis, renal edema, and skin dermatitis [ 4]. For these reasons, it must be treated before disposed to landfill."

Jan 1, 2011

By H. J. Thevik, A. K. Dahle

"A mathematical model that calculates the stress development in a coherent and stationary dendritic network due to interdendritic flow is proposed. The fluid flow is assumed to be related to the solidification shrinkage, and under the assumption of no porosity formation and unidirectional solidification, the shrinkage-induced flow within the mushy zone is calculated analytically. The interdendritic melt flow exerts a force on the solid network and an analytical expression for the stress build-up in the network is developed. Parameter studies illustrating the influence of cooling conditions, mushy zone length, dendrite coherency, fraction solid, volume fraction of eutectic, and solidification shrinkage upon the stress development within the solid network are presented. Comparing the magnitude of the calculated stresses to measurements of the strength in equiaxed mushy zones shows that it is possible for the stresses to exceed the strength, thereby resulting in reorientation or collapse of the dendritic network.IntroductionInterdendritic fluid flow is at present regarded as a very important mechanism for feeding of shrinkage during solidification of metal alloys. Solidification of many alloys is often characterised by heterogeneous nucleation of the primary phase on substrates in the melt with subsequent evolution of equiaxed dendrites. These equiaxed dendrites can initially grow freely, but impinge on each other and form a continuous dendritic network, ie. dendrite coherency, quite early in the solidification process. Measurements of the dendrite coherency point have shown that the dendritic network is established at solid fractions ranging between 0.1 and 0.5, and most often around about 0.2 [l]. Depending on the alloy composition this means that as much as 70 to 80% of the volumetric shrinkage has to be compensated by flow of liquid through the interdendritic network. Interdendritic flow occurs with a much larger resistance compared to free flow of the liquid and flow of a liquid with dispersed crystals. The pressure drop associated with the interdendritic flow increases rapidly with decreasing fraction ofliquid."

Jan 1, 1999

By Baptiste Laubie

Agromining is a phytotechnology aiming at producing commercial metal compounds from low-grade ores thanks to hyperaccumulating plants. The fern Dichranopteris dichotoma is a rare earth element (REE) hyperaccumulator, which naturally grows on former mine tailings in China. It accumulates up to 0.35% of REEs in its aerial parts. Different hydrometallurgical processes are currently developed to recover these elements directly from the biomass or from ashes after combustion. The process presented here consists of a direct extraction by EDTA solution, followed by precipitation with acid oxalic. Optimal precipitation pH and influence of organic matter are determined by modelling and by experimental studies. The final solid contains 4.3% of REEs, with calcium as the main cationic impurity (0.45% of the precipitate). The recovery yield is similar for major REEs and is around 70%. After optimization, upscaling of the process will allow the agromining development to recover REEs from secondary resources with more environmentally friendly techniques.

By Aliye Arabaci

In the present investigation, an attempt has been made to study the reduction behavior of composite pellets consisting two different types of iron oxide fines (high and low grade) and coke or lignite fines as reducing agents. The reduction experiments were carried out under isothermal conditions and constant flow of nitrogen gas in the temperature range of 900 ? 1100 oC. The variables investigated are the reduction temperature, Cfix/Fe3O4 ratio, reduction time and reductant type. In the experiments carried out with Sivas Divrigi A head magnetite ores (high grade) at a temperature of 1100 oC, for 40 minutes and on the condition that Cfix/Fe3O4 ratio is 0.2, in which lignite and coke fines were used as reductant, degree of reduction was obtained as 91 % and 86 %, respectively. Whereas, in the experiments realized with Malatya-Hekimhan-Hasançelebi magnetite ores (low grade) on the same conditions by using lignite as the reductant, around 60 % degree of reduction was found.

Jan 1, 2008

By Sungdon Kim, Chuljoo Kim, Joonsoo Kim, Hosung Yoon

"This study was performed to establish the optimum leaching condition through the experiments for the oxidized roasting followed by leaching of fluorocarbonate rare earth mineral (bastnasite) using sulfuric acid, and to establish the optimum condition for the recovery of cerium by ion- sieve method from the leached solution of bastnasite. The optimum conditions for the sulfuric acid leaching by the oxidizing roasting of bastnasite concentrates are that the roasting temperature is 550 -600 °C, the roasting time is 2 hrs, the concentration of sulfuric acid is 6N, the leaching temperature is S0°C and the leaching time is 3 hrs. At this time, the leaching yield of total rare earth oxides in the leaching of bastnasite concentrates is about 91%. When cerium is recovered by ion-sieve method from the solution obtained by the sulfuric acid leaching of the roasted bastnasite, the optimum conditions are that the TREO(total rare earth oxide) of leached solution is below 70 g/l, the flow rate of leached solution is 9.6 ml/min and the ratio of height to diameter of resin packed in column is above 9. In these conditions, the recovery of cerium of yield 85% and purity 96% is possible.IntroductionThe rare earths are generally called to Lanthanides, which are totally 17 elements including Scandium of atomic number 21 and Yttrium of atomic number 39 in addition to 1 S elements from Lanthanum of atomic number 57 to Lutetium of atomic number 71. Since the separation to each element is very difficult because of their similar chemical properties, the rare earths were used as the mixed rare earths and the mischmetal without separating to each element. However, the high purity rare earths are recently produced commercially to each element so that they are used as the materials for high tech. industry such as electric and electronic materials, catalysts, optical materials, special alloy and 8Uperconductive materials, and their consumption is rapidly increasing. Therefore, the purpose of this study is firstly to prepare leached solution by using the series of process of the oxidation-roasting and leaching by sulfuric acid. Next, second purpose is the separation and recovery of cerium by ion-sieve method."

Jan 1, 1998

By Mingchun Lu, Zhe Wang, Mingming Cao, Xiangdong Xing, Shan Ren, Jianliang Zhang, Zhengjian Liu

"The effect of reduction temperature on the vanadium titano-magnetite carbon composite pellets was investigated by X-ray diffraction (XRD) and scanning electron microscopy (SEM), and the discussion has put emphasis upon the enhanced reduction mechanism of additives containing CaF2 and NaF in this paper. The results showed that the reduction temperature of 1350°C was needed for the generation, mergence and growing up of metallic iron as well as monomer dissociation between metallic iron particles and slag phase in the vanadium titano-magnetite metallization pellets. The iron compound was completely reduced into metal iron, and Fe2Ti04 was mainly transformed into metal iron, (Fe,Mg)Ti205 and FeTi03 at 1350°C. The maximum metallization ratio was only 88.5% at 13500 for 30 min without any additive. However, with the addition of 3.0% CaF2 or NaF, the metallization degree of pellets could reach up to 94.8% and 92.5%, respectively.IntroductionVanadium titano-magnetite which is mainly distributed in the area of Panxi, Chengde and Maanshan in China is a kind of complex iron ore which contains various valuable metal elements such as iron, vanadium, titanium, etc. Among the above areas, Panzhihua (Sichuan Province in China) area possesses the largest deposits of vanadium titano-magnetite and the future reserves are more than 100x108t, and the reserves of Ti existing as Ti02 reach to 8.7x108t which occupy over 91% of the whole nation and ranked No.1 in the world[1]. Lots of researches on the comprehensive utilization of vanadium titano-magnetite have been conducted in the world. And many technological processes have been applied successfully in industrial production. Among these processes, the process of rotary kiln-electric furnace is employed to recover iron and vanadium in South-Africa, while the process of blast furnace-rotary furnace is widely used in Russia and China. Besides, many researchers have made efforts on employing new direct reduction process to realize the effective comprehensive utilization of vanadium titano-magnetite[2-4]. However, the direct reduction process is only researched in laboratory and it has not been used in industry."

Jan 1, 2013

By Metehan Erdogan, Ishak Karakaya, Fuat Erden, Emre Ergül

"The FFC Cambridge process was suggested as a promising Si production technique for the expanding solar energy industry. Direct electrochemical reduction of bulk SiO2 plates and porous SiO2 pellets in molten CaCl2-NaCl salt mixture were investigated at 750°C by applying 2.8 V potential difference. The produced Si powder was brown and found to be contaminated by the Ni and stainless steel plates used as the cathode contacting materials. The reduction rates of the bulk SiO2 plates and porous SiO2 pellets were compared from variations of current and accumulative electrical charge that passed through the cell during the electrochemical reduction. The amorphous bulk SiO2 plates were reduced slightly faster than porous pellets of crystalline SiO2. The overall reduction potential of SiO2 pellets against the graphite anode at 750°C in molten CaCl2-NaCl salt mixture was determined as 2.3 V by cyclic voltammetry. This potential was supported by calculations.IntroductionMetallurgical grade Si cannot be directly used in electronic industry and some intermediate steps are required to produce industrial solar grade silicon (SOG-Si). A promising alternative solar grade silicon production technique is the FFC Cambridge Process [1]. Production of Si by electrochemical reduction of SiO2 at 850oC in molten CaCl2 electrolyte was first studied by Nohira et.al. [2]. In their study; Si formation was observed on bulk SiO2 cathodes after 1 hour of electrolysis. Complete electrochemical reduction of porous SiO2 pellets was first reported by Jin and his coworkers [3]. The mechanism of electrochemical reduction of SiO2 to Si in molten CaCl2 was explained in another study [4]. Reduction rates of bulk SiO2 and porous SiO2 pellets were also compared previously and it was found that reduction rates for bulk plates were higher [5]. Furthermore, it was reported that mixing Si into porous SiO2 pellet increased the reduction rate [5]. Mo [2, 4-7], Ni [3, 8, 9] or Si [6] were used as cathode contacting materials in various studies. Yasuda et. al. [6] produced Si with 99.80 % purity using Si plates as cathode contacting material to reduce metal contamination."

Jan 1, 2012

By Kinya Atsumi, Kanjana Khunathai, Hisaya Kato, Hidetka Kawakita, Keisuke Ohto, Katsutoshi Inoue

"Crosslinked microalgae were prepared from the residue generated in the production of biofuel, by crosslinking-condensation in concentrated sulfuric acid. These microalgae were tested for adsorption of various metal ions in hydrochloric acid medium. The crosslinked microalgae exhibited high selectivity for Au(III) over other precious and base metal ions. From an isotherm experiment, the maximum adsorption capacity was evaluated to be 3.25 mol/kg of dry gel for Au(III) which was many times higher than that of the original microalgae residue. SEM and X-ray diffraction confirmed the formation of metallic gold particles, suggesting the occurrence of a redox reaction between surface functional groups on the gel surface and trivalent gold ion.IntroductionSubstantial quantities of precious metals are being used by the electronic industry because of their excellent electrical conductivity and resistance to corrosion. In recent years, recovery of precious metals from secondary sources such as electronic scrap [1,2 ], and leach liquors is being favored because of environmental concerns. Of course, recovery is only practical, if its cost is lower than the value of the metals (gold, platinum and palladium) recovered.Traditional methods of separation and refining do not fulfill this requirement. In order to overcome this problem, attempts have been made in recent years to develop new processes including total leaching in hydrochloric acid containing chlorine gas or hypochlorite, followed by solvent extraction and ion exchange [3]. In the new processes, new solvent extraction reagents or ion exchange resins with high selectivity and high loading capacity are used to simplify the process and to reduce the operating costs."

Jan 1, 2011

By R. Y. Wan

Low grade sulfidic-carbonaceous refractory ore from Newmont Gold Company's Carlin deposit was microbially pretreated. The biological pretreatment process gave partial oxidation of the sulfidic components of the refractory ore but the preg-robbing carbon continued to be active resulting in approximately zero cyanide gold extraction. A 495 ton pilot plant test heap was conducted using acidic thiourea leach following biooxidation. Activated carbon and cation exchange resin adsorption were tested for gold recovery from the thiourea pregnant solution. The results obtained from the test heap were not satisfactory. Gold extraction was low due to slow reaction kinetics which was caused by relatively large particles and very low winter temperatures. Problems existed in the thiourea-test heap and are discussed in this paper. An alternative heap leach process using thiosulfate has been successfUl at the pilot scale for gold extraction following biooxidation pretreatment of refractory sulfidic-carbonaceous ores.

Jan 1, 1995

By J. Méndez-Nonell

The thermodynamic and chemical properties of SrSO4 and SrS in a gaseous flow of CO and CO2 at high temperature are discussed. The thermodynamic analysis of the system was made using data from the literature. The results obtained from the thermodynamic analysis were experimentally verified using the thermogravimetric technique. The experimental results suggest the formation of a complex compound between SrO and SrSO4. It was also found a change in the chemical mechanism of the process between SrSO4 and CO-CO2 and in the chemical mechanism of the process between SrS and pure CO2.

Jan 1, 1995