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By Jie Li, Shu Yang, Zhongliang Tian, Xun Hu, Yanqing Lai, Shaolong Ye

The electrolyte with high solubility for Sc2O3 is very important to realize the preparation of Al-Sc master alloy by the molten salt electrolysis. The solubility of Sc2O3 in K3AlF6- Na3AlF6-AlF3 melts is determined with an isothermal saturation method. The effects of KR (ratio of K3AlF6 to K3AlF6+Na3AlF6), the concentration of Al2O3 and the temperature on the solubility of Sc2O3 are also investigated. The results indicate that the solubility of Sc2O3 in K3AlF6-Na3AlF6-AlF3 melts increases and then decreases with KR increasing. The solubility of Sc2O3 is 8.698 wt.% in (K3AlF6-Na3AlF6)(KR25%)-18 wt.%AlF3 melts at 940℃. The effect of temperature on the solubility is little, and the values are 8.575 wt.% and 8.762 wt.% respectively when the temperatures are 930℃ and 960℃. The solubility decreases from 8.809 wt.% to 7.058 wt.% as the concentration of Al2O3 increases from 1.5 wt.% to 5.0 wt.% at 950℃.

Jan 1, 2015

By Ray Y. Lin

This study explores the formation of sodium pyrosulfate in molten sodium sulfate resulting from dissolution of SO3 at temperatures between 1160 and 1250 K. Solubility of SO3 in Na2SO4 melts at temperatures between 1160 and 1250 K under gas mixtures of SO2, O2 and argon was investigated applying a thermogravemetric analysis (TGA) technique. The activity of Na2O in the melt was determined with a high temperature electrochemical cell (ECC). Results showed that the SO3 solubility in molten Na2SO4 increases with decreasing temperatures and increasing SO3 partial pressures. Enthalpy of SO3 dissolution in molten Na2SO4 was calculated to be -119 kJ/mol for infinite dilute solutions. Thermochemistry of Na2SO4-Na2S2O7 melts was analyzed based on information obtained from both TGA and ECC techniques. Detailed examinations of the earlier low temperature measurements in the Na2SO4-Na2S2O7 system along with data from this study reveal that the solution behavior between Na2SO4 and Na2S2O7 can be satisfactorily treated as regular with the interaction parameter, , being 2.7 kJ/mol. The phase diagram and the field of SO3 partial pressure has been generated with the thermodynamic calculation using a regular solution approach.

Jan 1, 2006

The concepts of capacity and basicity have proved extremely useful in dealing with a wide range of solute species in metallurgical slags, and as a result have been widely applied. These two concepts are reviewed, and it is suggested that the Lewis approach to basicity has much to commend it. In some cases, it appears that the term capacity has been used without due consideration being given to the nature of the solution being formed, or even to whether a true solution was being formed at all. This paper proposes a rigorous definition of capacity, based on the true nature of the solution process in slags and glasses, and briefly reviews the repercussions of this approach on data available in the literature and the limitations which it may impose on future investigations in this area.

Jan 1, 1994

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carried out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XO > 10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Laurentiu Nastac

"The importance of investigating solute redistribution during the unidirectional solidification of multi-component alloys is broadly discussed in the literature. A previously developed analytical model that was experimentally validated for Al-Cu, Sn- Bi and Fe-Si dilute binary alloy systems is used in this article to study in detail the solute redistribution, the liquid/solid interface stability based on an extended transient constitutional undercooling criterion and the size of the initial transient region during the unidirectional solidification of Ti-6-4 and Ti-17 alloys. A comparison between Ti-6-4 and Ti-17 alloy systems with respect to interface stability and the size of the initial transient region is also provided. The effective partition coefficients of the alloying elements in these alloys were determined based on specially designed experimental measurements.IntroductionThe importance of investigating solute redistribution during alloy solidification is broadly discussed in the literature [1-5]. One of the relevant applications of this study would be the mathematical modeling of equiaxed and columnar solidification of multicomponent alloys. This includes the instability of the solid/liquid interface. There are several mass and heat transfer processes that involve the calculation of solute redistribution during directional solidification such as industrial directional solidification processes, continuous casting, remelting processes, Czochralski crystal growth technique, floating zone techniques, etc."

Jan 1, 2012

By Vladimiros G. Papangelakis

During the past five years, chemical modelling work at the University of Toronto has elucidated the role of soluble magnesium on the autoclave acidity and has demonstrated why feeds rich in magnesium, and other divalent metals, require more than the stoichiometric requirements in acid to produce a leaching performance comparable to that of low magnesium feeds. This understanding has allowed the calculation of acid additions to the pressure acid leach (PAL) on a less empirical basis. Optimizing acid additions to the PAL confers savings in neutralization costs, ensures high productivity and minimises corrosion problems. Hence, our picture of the solution chemistry inside the autoclave during the PAL process has been substantially improved and is reviewed here. Experimental techniques based on solubility and direct acidity measurements that support the theoretical predictions are presented. Concepts of chemical modelling of electrolyte systems at high temperature and software issues are also discussed. Finally, a better understanding of the solution chemistry at temperature has led to better kinetics models because all metal dissolution and precipitation reactions are acid driven and controlled. . Therefore, reactor modelling efforts by our group are also presented and a reactor model with very good performance, as compared to pilot-plant data, is also made here. Finally, in spite of the above success in PAL solution chemistry and reactor modelling, significant challenges lie ahead in theoretical data gaps and instrumentation; these are also discussed in this paper. Keywords: Laterites, process modelling, pressure acid leach, solution chemistry, chemical modelling, reactor simulation

Jan 1, 2004

By Annette Revet

Aluminum fluxes have been used for the remelting of secondary aluminum since the beginning of the recycling industry. During the last sixty years, a number of fluxes have been designed, researched and tested at the laboratory and plant scale. Fluxes are primarily a mixture of potassium chloride and sodium chloride with the addition of some other chloride and fluoride containing salts. The conventional Mining methods of potassium chloride and sodium chloride yield products that are not high in purity without costly reprocessing or additional refining. In 1993, Kalium Chemicals, Ltd. began supplying flux mixtures to the aluminum industry. Kalium produces potassium chloride and sodium chloride which are mined and refined by a patented solution-mining process. The salts produced by this process are high in purity with lower concentrations of iron oxide, sulfates, and other impurities. This paper will present the different mining methods used in the production of sodium chloride and potassium chloride. The paper Will address how these mining methods affect the purity of the final product as well as the effect of purity on the performance of the fluxing salt.

Jan 1, 1995

By V. V. Geikhman

The paper updates the Plant experience in the development and implementation of an advanced environmentally friendly zinc production technology complying with the technological and economic level of producers in the world and the standards of maximum permissible gas emissions stipulated by the Russian legislation. General water recycling engineering allowed to ensure 95.6% water rotation level. All solid wastes formed during treating zinc concentrate are processed into marketable products or semiproducts and sold. As a result of implementing innovation techniques production at the Chelyabinsk Zinc Plant is non-waste.

Jan 1, 2006

By Gang Qi

The solubility of nitrogen in pure molybdenum was measured over the temperature range 2173 to 2473 K and up to one atmosphere (101 kPa) of nitrogen gas pressure. Both thermochemical and kinetic aspects of this phenomenon were considered in this study. The solution of nitrogen in molybdenum may be expressed by the reaction 1/2N2(g) = {N} (Mo,s), for which the standard Gibbs energy is given by the expression {A}G° = 78,500 + 27.36T Joules/g atom N. The formation of molybdenum nitrides, specifically Mo2N, was considered. Attention was also focused on the mechanism of nitrogen solution in molybdenum. Estimates of the diffusivity of nitrogen atoms in solid molybdenum were derived from the kinetic data.

Jan 1, 1991

By Matti Hämäläinen

Outokumpu has developed a new chloride leaching process, HydroCopper?, for copper concentrates. The process utilizes the cupric ion as oxidant, which is able to dissolve chalcopyrite. After solution purification monovalent copper is precipitated as cuprous oxide, Cu2O, using sodium hydroxide. Copper product is produced from Cu2O by reduction, melting and casting. An essential part of the new process is chlor-alkali electrolysis, which regenerates the reagents used. All impurity metals are removed before Cu2O precipitation, because otherwise they would report to the copper product, impairing its quality. A multistage solution purification scheme has been developed consisting of firstly, chemical precipitation of impurity metals by pH increase, secondly, cementation of silver and thirdly, removal of trace multivalent ions using ion exchange. This paper describes the characteristics of solution purification in the HydroCopper? process based on the laboratory tests and pilot runs made by Outokumpu Research Oy.

Jan 1, 2003

By Milton Blander

A review of concepts and theories for predicting thermodynamic solution properties of multi- component high temperature liquid solutions is reviewed. During the last 50 years the ability to predict :such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.

Jan 1, 1996

By Milton Blander

"A review of concepts and theories for predicting thermodynamic solution properties of multicomponent high temperature liquid solutions is reviewed. During the last 50 years the ability to predict such properties for molten salts, silicates and metals based on the generally known properties of the lower order (often binary) systems has been developed and shown to provide predictions which are quite useful in science and technology. There are many gaps in our understanding of these high temperature solutions, especially for metals, and considerably more work is needed.INTRODUCTIONA number of solution theories and concepts have been developed which reliably predict the properties of multicomponent solutions from those of the lower order systems (often only the binaries). Because there is available data for a large fraction of the important binaries, the capability for making predictions for many multicomponent systems used in metallurgical separation processes is broad and potentially very useful. At the very least, the theories greatly minimize the data necessary for predicting properties of complex multicomponent solutions of molten salts, silicates and metals. It is the purpose of this paper to discuss the concepts which are demonstrably useful. We will discuss simple forms of the theories to make the concepts clear but we will refer to the publications which contain the more complex equations needed to treat the large majority of systems.A simple framework for understanding what we need to know in order to make technologically useful predictions is based on well known thermodynamic principles. In technologies and sciences where molten salts, slags magmas or molten metals are used or studied, one must often calculate the extent of a chemical reaction (or separation) or of phase changes. To do this, one must first write an equilibrium constant, K, for the reaction in terms of the standard free energy change of the reaction, ?G°."

Jan 1, 1996

By Pertti Pekkala

Outokumpu has 25 years of experience in the SX area. The development of the solvent extraction plants responds to an ever increasing demand for lower operational costs wd for adaptability to process disturbances with minimized risks. In this paper the features of the VSF ("Vertical Smooth Flow") SX technology are described, such as the separated pumping and mixing, the homogenous gentle mixing, the droplet coalescence and the ultra pure settling. A major advantage of the mixing technology is the high stage efficiency of above 99 per cent. The connection between this and some features of the settler front section is clarified. The present design of VSF plants is based on experience of existing operations at, for example, Zaldivar, Radomiro, Morenci, Kokkola and Harjavalta. These production plants cover a unit capacity range of 60 to 3,600 m3/h expressed as a total flow. It is evident that there are no restrictive factors to increase the total flow up to 5,000-6,000 m3/h by introducing the VSF technology. The copper SX technology has a long history reflecting many individual features of the separate copper SX plants. Still it is necessary to verify all actual running parameters by pilot tests taking into account impurities, chemicals used etc. The design of SX plants is not only about the delivery of equipment but also a process concept, and it is best tailor-made and adapted to specific local requirements.

Jan 1, 1999

By Henry Freiser

For the last several years, a systematic investigation of the equilibrium extraction behavior of selective tervalent lanthanides with representative chelating extractions of a variety of chelating agent families has been undertaken for the purpose of learning how to obtain chelating extractants of improved selectivity for separating individual lanthanide ions. The equilibrium extraction data (expressed as log Kex) for each reagent system are linearly related to the reciprocal ionic radius of the tervalent lanthanide ions. The role of adduct formation, steric hindrance, as well as the nature of the bonding atom in the chelate ring, represent some of the factors affecting selectivity arising out of our database of over 200 individual extraction systems, which will be discussed.

Jan 1, 1989

By Fathi Habashi

The recovery of uranium from wet process phosphoric acid was applied on industrial scale in the 1940's by using octylpyrophosphoric acid as an extractant. Later, more efficient reagents were used, e.g., di(2-ethylhexyl) phosphoric acid and actylphenyl phosphoric acid. In the 1970's the rare earths in Kola phosphate were recovered in Finland and recently (1997) in Norway using HNO, as a leaching agent and di(2-ethylhexyl) phosphoric acid as solvent. It was demonstrated later on laboratory scale that both uranium and rare earths could be extracted from the rock by tributyl phosphate but at different pH values provided that the rock is leached with nitric or hydrochloric acids instead of the commonly used sulfuric. This new concept opens the way to the possibility of treating phosphate rock by in-situ, dump, or vat leaching for the recovery of phosphate values as well as uranium and the rare earths. Another solvent extraction process is used industrially for the purification of phosphoric acid using butyl and amyl alcohols.

Jan 1, 1998

By P. D. Navarro

The behavior and operability of LIX 1104SM extraction was studied at laboratory scale on the Solvent Extraction at Sb3+, from high concentration sulfuric acid. In order to evaluate the reactant batch tests were made at laboratory scale as well for extraction as for re-extraction of Sb3+. Experiences achieved were: extraction kinetics, temperature effects, selectivity tests and re-extraction selectivity. A extraction kinetics was found, reaching equilibrium in 2 min, high selectivity of Sb3+ extraction in front of Cue , existing As5+ co-extraction and Fe3+ At the re-extraction stage, equilibrium was reached in 3 min, getting high Sb3+ re-extraction efficiency with HCl concentrations within 6 and 8 M. A high selectivity was achieved on Sb3+ re-extraction in front of As+5, existing Fe+5 re-extraction.

Jan 1, 1999

By George Owusu

A study has been carried out on the use of solvent extraction, instead of the traditional zinc dust cementation process, to remove copper from concentrated zinc sulphate leach solutions. In a series of experiments using plant solution containing 1.9 g/L Cu, 2 g/L Fe, 173 g/L Zn, 7.9 g/L H,SO,, 0.25 g/L Cd, 15 mg/L Co etc. and LIX 622 in SX-1, up to about 97-98 % of copper present in the zinc sulphate leach solution was extracted with negligible co-extractions of zinc, iron, cadmium, cobalt, etc. pH modification was not required for this reagent. The copper loaded organic was almost completely stripped using 150 g/L sulphuric acid. Investigations into the effect of any possible organiclextractant contamination on zinc electrowinning showed (if any) little effect on current efficiency if the organic contamination is less than 45 ppm; current efficiencies of 95-97 % were obtained. At organic contaminations higher than 45 ppm, the current efficiency dropped to about 92- 94 %. Visually, the organic-contaminated cathode sheets had rough surface morphology, becoming more intense with increasing organic concentration, compared to the non-contaminated cathode sheets.

Jan 1, 1998

By Jiang Feng, Li Chuanhua, Zhang Libo, Peng Jinhui, Ju Shaohua

Solvent extraction of Cu2+ from the leaching liquor contain Cu and Fe use a microfluidic technology. Currently, the conventional copper extraction process has many problems such as long distance and small driving force of mass transfer. In order to solve the problems, studies are carried out on the extraction process of low grade copper leaching liquid using Lix984N as an extractant with a new microfluidic solvent extraction technology. The effects of flow rate on the separation and extraction efficiency between Cu and Fe are studied, and the results show that a steady liquid-liquid interface of laminar flow is form in the micro-extractor, and extraction efficiency is 78 % and 2.5 % for Cu and Fe at the contact times of 0.84s respectively. Besides, the separation coefficient between Cu and Fe is as high as 140.04. The studied microfluidic technology has the advantages like improving extraction efficiency and reducing reaction time and providing the potential application in the hydrometallurgy extraction of Cu.

Jan 1, 2015

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998