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By Donald R. Sadoway

"Molten salt electrolysis is a proven technology for the extraction of metals -- all· the world's primary aluminum is produced in this manner. The unique properties of molten salts also make them excellent media in which to treat a variety of forms of waste. Of special note in this regard is electrolysis in molten oxides, a concept put forward by the author, initially as a ""clean technology"" for producing primary metal. However, in the context of waste treatment, electrolysis in molten oxides is a process offering the prospect of changing the-valence of dissolved heavy metals while making pure oxygen gas as the main by-product. Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3, SiO2; CaO, and MgO have confirmed electrochemical production of oxygen on a carbon-free anode. IntroductionMolten salt electrolysis is the electrolytic decomposition of a compound dissolved in an ionic melt. The prime example of this process can be found in the production of aluminum. The compound, alumina (Al2O3)' derived from the mineral bauxite, is dissolved in an ionic melt comprising a multicomponent solution of cryolite (Na3AlF6)' aluminum fluoride (AlF3)' and calcium fluoride (CaF2,). The products of electrolysis are molten aluminum and carbon dioxide, the latter due to the attendant consumption of the carbon anode. Primary aluminum is produced in a reactor known as the Hall cell.' Alternatively, the compound undergoing electrolytic decomposition can be derived from waste. Processing in molten salts, with their capacity to dissolve materials to very high concentrations compared to those attainable in aqueous solutions, can be rather advantageous. High solubilities lead to high limiting current densities, and this, in tum, results in high productivities: For a primer on molten salt electrolysis and a review of the basic literature in the field of molten salts the reader is directed to an earlier publication of the author (1)."

Jan 1, 1996

By Rodney J. Ishak

The reduction of Mn3O4 to MnO has been investigated in a thermobalance apparatus. The charge was composed of manganese ore (decomposed by heating/calcination or pre-reduction to mainly Mn304) and coke. The material was charged to a crucible, which was suspended in the balance. CO-gas was distributed through a grid in the bottom of the crucible. Two sizes of ores were used; 2.4-4.8 mm and 6.7-9.5 mm. Coke particles were in the size range 4.8-6.7 mm. Experiments were conducted in the 900-1100°C temperature range. The composition of the product gas was monitored continuously. External mass transport between bulk gas and particle surface does not seem to limit the rate of reduction. Assuming that both diffusion through product layer and chemical reaction at the interface between MnO and Mn304 are rate controlling, the data was tried both in a shrinking core model and in a grain model using regression. The grain model gives the best physical description of the process, because the reactant is in fact a porous medium. With this model the effective diffusivity was calculated to be in the 1.5-6.10-5 m2/s range. The pore size was mainly between 0.1 and 10 um.

Jan 1, 2003

By Suguru Kohno, Yoshihiro Momose, Masakazu Honma, Tokirou Kamosawa

Copper metal surfaces have been examined by an extremely sensitive surface analysis technique called temperature programmed photoelectron emission (TPPE). The surfaces were ultrasonically cleaned and subsequently abraded by a screw in organic solvents and water. The TPPE apparatus is composed of a Geiger counter with Q gas (He+ iso-C4H10). The curve of photoelectron emission (PE) intensity vs. wavelength from 300 to 170 nm, termed PE spectrum, was repeatedly measured at different temperatures in the temperature- increase process from 25 to 350°C. The number of emitted electrons in a PE spectrum (PE total count) increased, reached a maximum at-250°C, and decreased with increasing temperature. With the surfaces cleaned alone in the liquids the maximum PE total count decreased in the order C3H70H > (CH3) 2CHOH > C2HpH > CHPH > H2O. With the mechanically abraded surfaces in the liquids the maximum PE total count changed as a function of the abrasion period and the maximum tended to appear at higher temperature with increasing abrasion period; the maximum value at 10-min abrasion decreased in the order H2O > CHpH > C2HPH > (CH3) 2CHOH > n-C3HpH. It was suggested that the TPPE behavior can be related to the acid-base interaction between the alcohols and the abraded metal surfaces and the presence of a contaminant over layer on the surface. From the XPS analysis of the 01 s spectra it was suggested that the chemical change of the adsorbed oxygen to oxide oxygen with temperature plays a substantial role in the appearance of the maximum PE total count.

Jan 1, 2000

By Alicia Esther Ares, Carlos Enrique Schvezov, Alejandra Silvina Roman, Claudia Marcela Méndez

In this paper the structure of aluminum based alloys and their corrosion behavior by using different electrochemical techniques as characterization methods are considered. Currently, it becomes imperative to know the role of the Al2Cu against the susceptibility to corrosion of these alloys. The present work aims to studying the electrochemical behavior of aluminum base alloys with the following compositions: Al-1wt.%Cu, Al-4.5wt.%Cu and Al-15wt.%Cu (with different grain structures), in 1M NaCl solutions, at room temperature. Cyclic potentiodynamic polarization tests were performed and were found that the alloys with more than 1wt.%Cu in the matrix have an unstable behavior and without tendency to reach passivity. The equivalent circuits derived from electrochemical impedance spectroscopy technique (EIS) generally showed two capacitive contributions. The susceptibility to corrosion becomes a complex function, not only of copper concentration and structure, but also with interdendritic spacings and distribution of phases in the alloys.

Jan 1, 2015

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 H. D. Freeman

The occurrence of gold in refractory gold ores varies widely and affects the recovery process. The determination of gold and the composition of the associated minerals are important in selecting an appropriate processing scheme. However, locating the gold in an ore sample is a difficult task which requires perseverance, luck, and experience. Our experience has led to the development of a relatively fast and reliable means of deter-mining the mineralogy of ore samples through analysis combining an energy-dispersive x-ray analyser coupled to a scanning electron microscope (SEM). In some cases, a wave length dispersive spectrometer or microprobe is used to further quantify the various mineral compositions. The SEM/microprobe analysis identifies the source of problems that may arise during the recovery of gold from refractory gold ores.

Jan 1, 1981

By Yuanyuan Zhang, Patrick J. Masset

"The reduction of FexO in slag is one of the fundamental reactions in iron and steelmaking technology, including the blast furnace process (BF). Experiments on the reduction reaction of iron oxide using CaO-SiO2-Al2O3-FexO-C mixtures were carried out using thermogravimetric analysis (TGA) under reducing conditions at temperatures up to 1100°C. The composition of the primary slag was chosen so that the FexO concentration varied between 0 and 75 wt % and the CaO/SiO2 ratio being kept constant to 0.90. From the TGA curves recorded isothermally at different temperatures the kinetic parameters of the iron oxide reduction were determined.IntroductionIn blast furnace the iron ores and coke are charged in layers from the top. The reduction of iron oxide by coke is one of the fundamental reactions in the blast furnace process. Although a great amount of work has been done on the topic of reduction of composites [1, 2, 3], gasification of carbon [4, 5] and reduction of iron oxides by CO [4, 5, 6], the mechanism of reduction in iron oxide - carbon powder mixtures is not fully understood. Fruehan [1] and Rao [2] studied the reaction rate of the reduction of iron oxide by different types of carbon and concluded that the reaction mechanism is controlled by the oxidation of carbon at temperatures up to 1200°C. Rao [2] studied the reaction of hematite with graphite as carbon source up to 1080°C. An activation energy close to 300 kJ/mol was calculated within the temperature range of 950°C to 1087°C. In his study, Fruehan [1] determined the rate of reduction of Fe2O3 and FeO by coal, coke and coconut charcoal as carbon sources within the 900°C to 1200°C temperature range. He found that the reduction of Fe2O3 by carbon occurs in two stages and that the reduction of Fe2O3 to FeO is faster than that of FeO to Fe. This is due to the fact that the CO2/CO equilibrium ratio is higher, and hence, the rate of oxidation of carbon is faster. Fortini and Fruehan [3] have studied the reduction reaction of wustite by graphite and wood charcoal. They found that the wustite reduction can have a significant effect on the overall rate of reduction in composites at high temperatures or in the presence of a large excess of carbon. The calculated activation energy of the reduction reaction by wood charcoal was close to 368 kJ/mol, while the activation energy of the reduction reaction by graphite was 444 kJ/mol."

Jan 1, 2011

By Yuanbo Zhang, Huanpeng Mi, Guanghui Li, Binjun Liang, Zhiwei Peng, Tao Jiang

Ludwigite ore has not yet been utilized on an industrial scale due to its complex mineralogy and fine mineral dissemination. In this study, sodium salts were employed to enhance the separation of iron and boron by reductive roasting-magnetic separation. It was found that the separation of iron and boron as well as the iron grade and recovery were significantly improved b y the addition of Na2SO4 or Na2CO3. Under the reduction temperature of 1050 °C, reduction time of 60 min and magnetic intensity of 0.1T. Compared with the inexistence of sodium salts, the iron grade and recovery of the magnetic concentrate increased from 83.3% and 88.6% to 93.2% and 95.1%, respectively, by adding 6% Na2CO3. The XRD and microstructure analyses indicated that the iron oxides were transformed into metallic iron and the average metallic iron grains were grown to over 40μm which was beneficial for separation of metallic iron from gangue.

Jan 1, 2016

By Yan Zeng

Lithium metal silicates (Li2MSiO4, M = Fe or Mn) composed of abundant and non-toxic elements are important cathode materials for Li-ion batteries (LIB). In contrast to solid-state or sol-gel methods, hydrothermal synthesis conducted in pressure reactors is a favorable processing route as it provides the potential for scalable production and is environmentally benign. However, the key is to control the precipitation reaction to obtain powders with desired properties to meet battery specifications. Through a systematic study, we have found that Li2MSiO4 with tunable size from 300 nm to 1.5 μm can be produced by adjusting precursor concentrations, temperature, and reaction time. Under optimum conditions, high purity Li2MSiO4 with minimum defects were successfully produced and examined as an LIB cathode. The use of complexing agents promoted the formation of unique hollow particles via the self-assembling of elongated crystals. A four-step formation mechanism is proposed based on extensive characterizations with XRD, HR-TEM, SEM, and Mössbauer spectroscopy.

By Shuai Wang, Gang-hua Fu, Lu Yang, Yu-feng Guo, Tao Jiang

The fluorine-bearing iron concentrate is one of the refractory raw materials for pelletization, which is mainly used in Baotou iron and steel company with lots of problems, such as narrow roasting temperature range and low compressive strength of products. According to its specific character, the effects of roasting temperature, time on the compressive strength and microstructure of pellets were researched. The results show that low melting substances formed during the roasting was the dominant reason of those problems. High melting substances were added in the roasting to investigate their effects on the roasting properties of fluorine-bearing iron concentrate pellets. Low melting substances were reduced when chromite was added. The compressive strength of products was 3100N/P when the 2% chromite was added at the roasting temperature of 1150 ºC, which was increased 700 N/P compared with the pellets without chromite, and the roasting temperature range was expanded by 170 ºC.

Jan 1, 2016

By C. S. Griffith

Lithium Australia NL (ASX:LIT) and ANSTO Minerals have been working together since 2015 on the development of halide accelerated leaching for the extraction of lithium from lithium-bearing micas, spodumene and clays. This technology has been termed SiLeach® process. The driving force behind development of the SiLeach® process, initially, was to develop a hydrometallurgical process to extract lithium from micas and spodumene without the need for the energy intensive, high temperature processing conventionally applied to lithium extraction. This driving force remains today and continues to hold promise in realising the value of previously under-utilised lithium resources. A comprehensive understanding of the technology and its applicability to the processing of micas and spodumene currently exists, and the flowsheet has been rigorously piloted. Production of battery grade lithium carbonate has been demonstrate

By C. Liliane Carvalho

In the current study, bio-oxidation tests were carried out in shaking flasks with a flotation concentrate containing the sulphides pyrite, arsenopyrite and gudmidite. The tests were performed with mesophilic microorganisms (At. ferrooxidans) at 30 °C and also with the moderate thermophile S. thermosulfidooxidans, at 50 °C. The effects of (i) previous adaptation of the microorganisms to the concentrate, (ii) ferrous iron concentration and (iii) pulp density (2%, 4% and 6% (w/v)) on the dissolution of the sulphide were studied through arsenic extractions. S. thermosulfidooxidans was more sensitive to the pulp density in comparison to At. ferrooxidans as a reduction in sulphide oxidation was observed with the increase in the solid content to 6%. Therefore, the mesophilic strain was selected for further work, which comprised a rolling bottle experiment at 10% solids. After 40 days of bio-oxidation, the solid material was subjected to cyanidation, which revealed 85% gold extraction as compared to 21% from the original concentrate. The antimony sulphide grains in the bio-oxidized product showed similarity to what was observed in the original sample, suggesting such particles were not susceptible to the bio-oxidation process.

By Brommerm Tracey, Britt Elin Gihleengen, Elsa Olivetti, Hans Ole Riddervold, Randolph Kirchain, Geir Øyen

"Compositional uncertainty in secondary materials and variable processing conditions inhibits secondary material utilization in the production of aluminum alloys. Efforts to implement optimization models that direct batch planning have limited industrial presence due to factors such as the insensitivity of these optimization models to dynamic plant circumstances. This paper describes a chance constrained model formulation that generates lower cost, robust batch plans with significant flexibility towards changes in processing conditions. The principal attribute of the chance constrained formulation is its inherent mitigation of risk by diversifying the batch plan. This paper compares aluminum remelter batch planning using the chance constrained formulation with a traditional deterministic model and a manual batch planner. With the expectation that volatile material prices, restricted scrap material availability, and pressure by consumers and legislation for increased recycled raw material input will continue in the future, batch planning tools that inherently diversify a production portfolio will become increasingly advantageous for industrial aluminum remelters.IntroductionAluminum remelters must develop strategies to incorporate lower cost secondary materials into finished alloys to remain competitive amidst increasingly demanding market and regulatory conditions. Determining the optimal combination of incoming raw materials to produce an alloy that meets compositional specifications presents remelters with a complex problem that has driven the development of computational tools commonly referred to as batch planning or blending algorithms. The ubiquity of the ingredient or raw material blending problem in production has motivated ongoing development of batch planning algorithms since the classic nut-mix problem in the 1950's [1]. The most common model formulation for industrial aluminum remelters are deterministic, linear optimization programs [2]. These blending problems determine the optimal combination of raw materials by minimizing cost subject to constraints around demand, availability, and compositional specification. Despite extensive research and moderate computational requirements, batch planning algorithms are inconsistently used in industry. Insufficient incorporation of the complexity of real world remelting conditions into these models provides an obstacle for their implementation [3]. For example, many batch planning algorithms do not explicitly incorporate the impact of compositional variation of the raw materials on overall batch cost. Additionally, they do not allow for endogenous specification of tolerance to error in batch planning, so provide little flexibility where a batch planner would like to incorporate materials of greater uncertainty. Incomplete accounting for quality variability undervalues secondary materials leading to overly conservative use [ 4, 5]."

Jan 1, 2011

By Axel Hoppe

Although Tantalum is not usually regarded as a precious metal, its pricing structure is very similar to that of Silver. Different from precious metals, Tantalum has only industrial applications and its use is about 1000 metric tons per year. The intrinsic value of Tantalum already in .the past was a driving force for its recycling. Based on these facts the Tantalum industry world-wide is approaching the closed-loop concept of its recycling. A detailed material flow of Tantalum processing as well as recovery of residues and used products will be discussed.

Jan 1, 1995

By Kiyoshi Takai

The Para-Eco Incinerator Ash Processing System for cleaning slag has been developed after a seven-year pilot plant study. The major part of the system is an electric furnace heated to 1773 K. The feed material consists of a municipal solid waste incinerator ash mixture containing a reducing agent of a coke and an inorganic flux of calcium and magnesium. With this furnace system, three kinds of products are produced. They are an inorganic molten salt that is slag, molten iron alloy absorbing non-ferrous metals, and fly ash. Due to the reducing atmosphere in the furnace, the slag does not contain any metal components as well as chlorine components just like natural rock and/or aggregate. A retreatment plant modifies this slag into a practically useful aggregate. The plant consists of a slow cooling step for crystallizing the slag as well as a water granulation step. The iron components in the ash are reduced to molten iron droplets, which concentrate at the furnace bottom. The non-ferrous metal components such as copper, chromium, and others are absorbed into the molten iron but not into the molten slag. Volatile metals such as lead, zinc, cadmium and others as well as sodium, potassium, and chlorine go back into the fly ash. A solvent extraction method and/or other appropriate procedures can be used to extract the metal components from this fly ash.

Jan 1, 2003

By Cheryl S. Lim

New technologies such as direct reduction and smelting reduction processes are increasingly being used in iron-making and steel-making in addition to conventional blast furnace technology. Critical parameters for control of these processes include the degree of metallization, degree of pre-reduction, and carbon and silica levels. On-line monitoring of these parameters is difficult because measurements often need to be made on hot ores (at or higher than -1000'C) in circumstances where representative sample streams are not readily accessible. A nuclear analyser has been developed which provides continuous, non¬intrusive, real-time measurements of iron, oxygen, carbon and silicon levels in hot ores undergoing reduction. The analyser has been tested in a plant using a direct smelting process on pre-reduced feed to the smelting vessel-, accuracies of 1% relative, 0.5 w'.96 (25% relative) and 1.0 wt.% (9% relative) were obtained for the degree of pre-reduction, carbon and silica respectively. The underlying method, capabilities and potential applications of the analyser will be discussed.

Jan 1, 2001

By Sun Ying, Zhang Jing, Li Qiuju

A new process of enrichment Cu in molten copper slag under electric field is presented in this article. The experiments were carried out in the laboratory on a kilogram scale. The mobility of copper slag was improved by the technique of carbon reduction. The effects of temperature, electric field strength and intermittent feeding speed were investigated on Cu migration. The results showed that the best experimental conditions were the temperature at 1523K, electric field strength was 1.5V•cm-1 and feeding rates was 15 g•(10min)-1. The copper content of the slag decreased below 0.6wt%. The process was compared to the traditional electric furnace process of slag cleaning, there was reduced the energy consumption and heat loss, and also harmful gas emissions such as SO2 and CO2, accompanied by improved the efficiency of slag cleaning.

Jan 1, 2016

By M. A. Neri

A lead-free solder alloy Sn-57.5Bi-0.5Ag has been developed by mechanical alloying and foundry processes, and has great potential as a lead-free solder system, to low temperature applications. The mechanical alloying powders show a microstructure different to the microstructure obtained by the foundry process for the same alloy. Its melting point of 142°C is slightly higher than that of eutectic tin- bismuth solder. Examination of the microstructure revealed that eutectic microstructure is refined by the mechanical alloying process Ag additions. The lamellar structure of tin-bismuth gradually disappeared with the process of mechanical alloying, while intermetallic compounds AgaSn phase was formed. The Cu-Sn intermetallic compound layer formed at solder-copper interface is the Cu6Sn5 phase. Keywords: Lead-free solder, Microstructure. Mechanical alloying

Jan 1, 2003

By Fangqing Yin, Qingyu Deng, Zhengfeng Qu, Mengjun Hu, Meilong Hu

Titanium bearing blast furnace slag, which contains 20%-30% TiO2, is a valuable secondary titanium resource. Based on the thermodynamics calculation effect of the temperature on the reduction of the slag in vacuum were studied at certain vacuum degrees. The results show that magnesium vapor and silicon monoxide vapor can be obtained at the condition of high temperature and low pressure. The purity of TiC increases with temperature increasing. When the temperature arrives at 1623K TiC can be obtained besides the reductant carbon. XRD result of the powder collected from the furnace cover show that magnesium and silicon in the titanium bearing BF slag leave the slag system during carbothermal reduction in vacuum. From the above it can be concluded that TiC can be obtained from the titanium bearing BF slag and silicon and titanium in the slag can be separated by carbothermal reduction in vacuum and acid leaching.

Jan 1, 2016

By Petre Stelian Nita

In small steelmaking shops, in foundries and forging plants, there are not too many option to recycle the basic slags, which are not suitable for many purposes of recycling, because of their low chemical and structural stability. A solution of an adequate recycling is a direct recycling in EAF. Several quality requirements, physico-chemical properties and proportions of slags must be analysed. The progress in this fields permites to establish an adequate proportion of recycled slag, based on enough exact computation of the related property. For oxydizing slag, obtained during melting and in the first part of decarburization operation, the problem of phosphoms contents can be analysed using the phosphate capacity (C PO34-). For reducing periods, during deoxidization operation, desulphurization also occurs and the problem of the sulphur contents can be analysed using the sulphur and sulphide capacities ( Cs / Cs) Between this two complex thermodynamic indicators of the slags. a direct relation is established, using thermodynamic aspects, resulting from the equilibrium constants for dephosphorization and desulphurization process and also, using the optical basicity of slags, computable from the chemical analysis of the slags. On this basis starting from the steel quality requirements. adequate strategies can be established in order to obtain high rates of recycling (between 50-80%) of steelmaking slags. Important cost savings are obtained through this procedure, based on the correct amounts of the fresh lime, iron ore and fluidizers. Keywords: Slag, Properties, Recycling

Jan 1, 2003