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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

By Cashman R. S. Mason

Removal of halides (fluoride, chloride) from metallurgical solutions can reduce corrosion rates and improve hygiene from decreased anodic chlorine evolution. This is particularly true for zinc sulphate electrowinning solutions. This paper describes the chemistry of a new process for the removal of halides from such solutions by solvent extraction ? the Teck Cominco Halogon? process, for which patents are pending. In this process, the halides are loaded directly from commercial zinc sulphate solutions and are stripped into a form suitable for disposal. Sulphate extraction efficiency is variable while maintaining halide extraction efficiency. The method of optimizing the solvent composition is demonstrated.

Jan 1, 2003

By G. Haesebroek

In L969 Metallurgie Hoboken-Overpelt started an industrial plant for the separation of iron and zinc from a concentrated CoCL2 solution. Iron and zinc are extracted in column contactors by a solvent containing 12 vol % of tertiary amines in xylene. The extracted metals are stripped from the pregnant organic phase by precipitation with a NaOH solution at pH LL. In this paper an overview is given of the industrial process. In order to overcome some drawbacks of this process (low flash point of the diluent, reagent consumption, batchwise stripping) an alternative solvent extraction process has been examined. In this alternative process, iron and zinc are extracted with an or¬ganic phase containing 50 vol % of TBP in Escaid 110. The pregnant solvent is stripped with water in conventional mixer settlers. Despite the ability of this process to overcome most of the inconveniences due to the use of tertiary amines, it suffers from the poor stability of TBP in concentrated chloride solutions, resulting in unavoidable and inacceptable precipitation phenomena in the stripping section.

Jan 1, 1988

By Mikiya Tanaka

Keywords: Solvent extraction, nickel, electroless plating, accelerating effect With the increasing importance of electroless nickel plating technology in many fields such as the electronic and automobile industries, the treatment of spent baths is becoming a serious problem. Although the spent baths are currently treated by a conventional precipitation method, a method with no sludge generation is desired. Previously, we proposed the solvent extraction recovery of nickel from the spent baths by means of solvent extraction using LIX84I as the extractant. However, a problem of this method was that the extraction and stripping of nickel were not fast enough to achieve high efficiencies when the continuous extractor was used. We have overcome this difficulty by finding that the addition of an acidic organophosphorous reagent in small amount into the organic phase markedly promotes the extraction and stripping rates of the nickel. Shaking-out tests using a separatory funnel at 240 spm revealed that the time to reach the equilibria is more than 60 min with only 20 vol% LIX84I, but is reduced to 10 min and 2.5 min by adding 2 vol% DP8R, respectively, during the extraction and the stripping with sulfuric acid.

Jan 1, 2004

By Hirokazu Narita

Keywords: solvent extraction, precious metals, thiodiglycolamide, rapid separation, hydrochloric acid The solvent extraction of some precious metals (Pd(II), Pt(IV), Rh(III) and Au(III)) and base metals (Fe(III), Cu(II) and Zn(II)) in a hydrochloric acid solution was carried out using N,N'-dimethyl-N,N'-dioctyl-thiodiglycolamide (MOTDA) dissolved in the mixed solution of 80 vol-% dodecane and 20 vol-% 2-ethylhexanol. The extraction percentages of Pd(II) and Au(III) in the 0.01 M MOTDA-1.0 M HCl solution system are 99.6% and 71.8%, respectively. In contrast, the other metal ions are hardly extracted under the studied conditions. The Au(III) and Pd(II) extracted in the organic phase are easily back-extracted with a 1.0 M thiourea/1.0 M HCl solution. A comparison with the conventional extractant for the Pd(II) separation, di-n-hexyl sulfide (DHS), revealed that the extraction rate of Pd(II) with MOTDA is much greater than that with DHS. The extraction percentage reached over 99% in less than a 2 min contact time. However, in the DHS-Pd(II) system, it takes about 240 min to achieve the extraction equilibrium. Furthermore, MOTDA can quantitatively extract Pd(II) up to half the molar amount of MOTDA. Therefore, MOTDA is a promising extractant for Pd(II) from the HCl solution after the removal of Au(III).

Jan 1, 2005

By Jeong-Soo, Joon Soo Kim, Rajesh Kumar, Sohn, Jin-Young Lee

"Liquid-liquid extraction (LLE) studies of tetravalent platinum from acidic chloride solutions have been carried out with Alamine 336 as an extractant diluted in kerosene. The title metal shows the inverse behavior at higher acid concentrations. Plot of log D vs. log [Acid], mol.L-1 gave a straight line with a negative slope of 0.8±0.03 indicating the exchange of one mole of hydrogen ions for every mole of platinum(IV) extracted into the organic phase. Extraction of platinum(IV) increases with increase of extractant concentration. The plot of log D vs. log [Extractant], mol.L-1 is linear with slope 1±0.3, indicating the association of one mole of extractant with the extracted metal species. The plot between metal distributions to aqueous to organic phases is 1.3±0.01; it indicates monomeric species was formed in organic phase. Stripping of metal from the loaded organic (LO) with mineral acids such as hydrochloric, sulphuric, nitric acids and bases like ammonia, hydrogen peroxide and sodium hydroxide are studied. The results indicated that hydrochloric acid and sodium hydroxide are the better stripping agents when compared with other acids and bases. Increase of temperature decreases the percentage extraction of metal indicating the process is endothermic. Regeneration and recycling capacity of Alamine 336 and extraction behavior of associated elements such as aluminium(III), magnesium(II), cobalt(II), iron(III) and nickel(II) were studied.IntroductionThe demand for platinum group metals (PGM’s) has risen in the last five years expected to keep in rising. Right now, the demand is already beyond the supply. The primary use of PGM’s today is in the automotive industry. Catalytic converters used in the PGM’s process to reduce greenhouse gases. Because of the current demand to reduce the green house effect the expected need for platinum is here stay. Country’s now advancing in the use of car production also are phasing increasing the needs for this metal. Chemical processing also use it, too. These industries account for more than 50% of all platinum production. Jewelry is other primary use of this precious metal whose value is much greater than gold. Other uses include computer data storage, scientific developments, fuel cell technology and in the glass manufacturing processes."

Jan 1, 2008

By H. Y. Cheng

A pulse column solvent extraction system was evaluated as an alternative to mixer-settlers for the separation and purification of rare earths. The column tested had an inside diameter of 44.5 mm and had 36 sieve plates with a free area of 25%. Pulsing was provided pneumatically using a solenoid valve controlled by a timer so that both pulse amplitude and frequency could be varied. Feed to the column was a mixed rare earth chloride solution containing 10 g RE L-1. The extractant was 5% Ionquest® 801 in Shellsol 2037 diluent. Hydraulic performance of the pulse column was excellent with no propensity towards stable emulsions or crud formation under normal operating conditions. The column was operated in organic-continuous mode with flow rates chosen so that yttrium and the heavy rare earths were extracted with high efficiency while the light rare earths were rejected. Yttrium extraction varied from 83 to 99.2%. Concentration profiles were measured in both the aqueous and organic phases, and, from this data, the height of a transfer unit (HTU), the mass transfer coefficient (Kxa) and the continuous-phase axial dispersion coefficient (Ey) were computed. The HTU ranged from 17-92 an which is within the range of values reported for other (non rare earth) pulse column systems.

Jan 1, 1992

By T. M. Dreher

The difficulties associated with the operation of a classical rhodium refining process have prompted many attempts to develop a viable solvent extraction flowsheet for rhodium. Recent investigations at McGill University have involved the activation of rhodium prior to its solvent extraction. The role of activation is to convert the aquochloro complexes of rhodium to a form extractable by conventional solvent extraction reagents. In the novel separation scheme identified, chloro complexes of rhodium are converted to bromo complexes, which undergo aquation to a lesser extent, making them more easily extracted. Rhodium is then extracted using Kelex 100, and stripping is achieved by use of a concentrated chloride based solution. Separation of rhodium from iridium is achieved by either prior reduction of Ir(IV) to Ir(III), as the latter is not extracted, or via co-extraction and differential stripping. A conceptual flowsheet for the refining of rhodium using this method is proposed.

Jan 1, 1998

By ZHANG Ting

In view of the high consumption and contamination of traditional vanadium extraction technology, a new process of leaching the converter vanadium slag without roasting with titanium dioxide waste was proposed. Extraction mechanism of P204 in the leaching solution had been researched and single factor experiments show that after a prereduction of Fe, and under conditions: ambient temperature，leaching solution original pH=2.5, phase ratio (A/O)=1:3, shaking time 8min, the extraction rate of V is more than 98.62% meanwhile the separation rate between V and Fe is up to 135.3 in the 20%P204-10%TBP-Sulfonated kerosene extraction system.

Jan 1, 2015

By A. P. Paiva

Although the advantages of Solvent Extraction for separation/purification of relatively concentrated solutions are well known in Extractive Metallurgy, its use for the recovery of elements present in low levels only recently has been discussed, with particular attention devoted to precious metals. In this work, the extraction behaviour of Cyanex 471X towards silver, from an acidic chloride medium is reported, the extraction and stripping isotherms and related kinetic features analysed. Results on the selectivity of silver extraction against high contents of iron, copper and lead are discussed. Phosphine sulphide extractants are generally associated with solvation mechanisms: analysis of the extraction pathways along with the possibility of reaching a suitable loading in the organic phase are also presented.

Jan 1, 1993