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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

By David Dreisinger

The cyanidation of copper containing gold ores results in the co-dissolution of copper along with gold. Copper dissolution results in elevated cyanide consumption that may make the treatment of the gold ore uneconomic. Copper-cyanide species in gold mill effluents may increase the environmental toxicity of the gold mill solutions. The objective of this study was to examine the use of solvent extraction to recover the copper cyanide species from gold mill effluents. Solvent extraction with Cognis (formerly Henkel) reagents LIX 79 and LIX 7950 was studied. Excellent extraction of copper and cyanide was achieved using pH control in extraction. Copper and cyanide may be stripped from the reagents using basic eluants. Various routes for copper and cyanide recovery from the strip solution were studied. Excellent results were obtained using electrowinning in both divided (Nation membrane) and undivided cells. Cyanide recovery was obtained by AVR treatment of a bleed stream from electrowinning. Full results of solvent extraction, copper and cyanide recovery are reported.

Jan 1, 1998

By F. T. Principe

In order for solvent extraction technology to be acceptable as an alternative to existing jarosite precipitation circuits, iron must be cleanly separated and concentrated into a feed stream suitable for downstream iron by-product recovery which meets market specifications and economics. Ten years ago, significant progress was made in a joint McCill University/CANMET project that involved iron extraction with mono(2-ethylhexyl) phosphoric acid and stripping with HCI. Our iron solvent extraction research was reactivated recently by looking into this and other members of the organophosphorus extractant family. Our research focuses on the mechanisms and control of anion (SO42/CI) transport across the various phases (Rafinate/Organic/Strip), iron build-up in the strip liquor, and extractant stability/selectivity. In this paper, these issues along with some other performance parameters are discussed using data derived from an extensive search of the two commercially available and best known members of the organophosphorus family, di-2-ethylhexyl (D2EHPA) and mono-2-ethylhexyl (M2EHPA) phosphoric acid. Further in this discussion, the challenges lying ahead in the development of sx systems that overcome the deficiencies of D2EHPA and M2EHPA are outlined. In particular, the necessity of considering secondary separation technologies that can further concentrate iron values in the chloride strip liquor to levels economically attractive for the production of saleable iron oxide by pyrohydrolysis is addressed.

Jan 1, 1998

By Lætitia H. Delmau

SXFIT is the latest in a series of programs developed in our group to model solvent extraction systems of increasing complexity. SXFIT permits the user complete freedom to define the constituents from which the composition of each phase is to be specified in the data and from which all species of a model for a system are assumed to be formed. Activity coefficients in the nonaqueous and aqueous phases, water activity, apparent molar volumes of aqueous species, and solution density needed for the conversion of concentration from the molarity to the molarity scale are all taken into account by the program. Several extraction systems relevant to nuclear-waste treatment were modeled successfully using this program. As an example, the cesium extraction efficiency of the CSSX process chosen by the USDOE for cesium removal from high-level waste stored at the Savannah River Site can be predicted correctly for varying feed composition.

Jan 1, 2003

By J. Murdoch Mackenzie

Two commercial nickel solvent extraction plants treating laterite leach solutions and using LIX®84-I have been operated in Australia. These circuits employ similar extraction chemistry but differ in their leaching and stripping operations. An alternative process involving elements of both can be conceived. The preparation of the feed solution to solvent extraction plays an important role in nickel extraction using LIX®84-I and the special features of manganese removal and cobalt oxidation in the preparation of the PLS are discussed. This paper compares these three circuit configurations with special reference to the extraction and reductive stripping of cobalt, the transfer of zinc and copper to the strip aqueous, ammonia transfer and sulfur transfer. The potential degradation of the organic and remediation using re-oximation is discussed. Keywords: Nickel, Solvent Extraction, Oxime

Jan 1, 2004

By M. T. Thomas

Sufficient development of the X-Ray Photoelectron Spectroscopy (XPS), the Auger Electron Spectroscopy (AES), and the Secondary Ion Mass pectroscopy (SIMS) has made these instruments ideal for solving problems related to mineral processing -particularly gold ore processing. XPS can determine both the surface composition and chemistry of ores and tailings, and the various phases within either of them. AES can also determine surface composition with the further advantage of having greater spatial resolution so the surface chemistry associated with specific minerals in the ore can be identified. This identification helps to clarify why some minerals pass through a chemical process unaffected, while others can be successfully treated. SIMS has an elemental sensitivity from one to four orders of magnitude greater than XPS or AES which makes it useful for detecting the presence of some elements in very low concentration (parts per million).

Jan 1, 1981

By Fernando Castro

Electric furnace steelmaking dust is a polluting residue that needs to be treated in order to recover metals contained and to produce an environmentally acceptable residue. Some hydrometallurgical approaches for its treatment have been evaluated, namely: caustic soda leaching followed by electrolytic recovery of zinc, ammonia leaching followed by zinc compounds precipitation and acetic acid leaching followed by lead, zinc hydroxide and gypsum precipitation.

Jan 1, 1992

By Neil E. Izatt, Ronald L. Bruening, Steven R. Izatt

"IBC has developed environmentally friendly Molecular Recognition Technology (MRT) processes to selectively extract, recover, and purify a wide range of metals from a variety of process streams. The incorporation of MRT into process flow sheets can improve the economics of the processes. MRT separations are effective even at low (mg/L to \i%JV) metal levels. MRT processes are sustainable, being economically viable, energy efficient, and environmentally friendly as well as having a low carbon footprint. Examples of MRT processes will be presented and discussed involving platinum group metals, gold, rhenium, and other metals of interest to the mining community.IntroductionA significant portion of the earth's precious metal resources has been moved during the past century from underground to above ground [1]. This movement has important economic, health, environmental, ecological, and sustainability implications for the earth and its population. There is concern that recycling of certain precious and specialty metals from end-of-life (EOL) electronic wastes (e-wastes), catalyst wastes, mining waste streams, and other waste products such as rechargeable batteries is not adequate to maintain supplies of these metals sufficient for future needs [2-4]. Improved metal recycling rates and more efficient metal recovery from the enumerated wastes would significantly reduce the amount of virgin metals that must be mined to support our lifestyle [5]. More efficient separation procedures in ore processing flow sheets and more effective recovery of metals from low-grade waste streams would reduce metal loss in the mining industry."

Jan 1, 2012

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts. The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10.1 atm. The concentration ofCu2+ in such slags becomes significant at oxygen potentials of greater than 10'1 atm at 1300 ?C. The activities of CuOo.s and AsOl.S in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of Si02 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2xlO?3 cm2/s at 1350 °C and activation energy of 16 kcal/mol Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300 °c. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material.

Jan 1, 2003

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003

By Ian M. Ritchie

Cementation or metal displacement reactions such as Cu2+ + Fe Cu + Fe2+ are among the oldest known hydrometallurgical reactions. They are still used in the recovery of some metals and in the purification of process liquors and waste water streams. However, they are often more complex than the stoichiometric reaction would suggest because they involve the simultaneous deposition of one metal onto a second which is dissolving. For example, sometimes a cementation will not take place, even though it is thermodynamically favoured. On other occasions, a cementation reaction will start but come to a halt as the depositing metal blankets the reacting surface. On yet other occasions, side reactions, catalyzed by the deposit, can be important. In this paper, the electrochemical basis of cementation reactions is described. The conditions for each of the complications encountered in these reactions are described and illustrated by examples drawn from a number of hydrometallurgical processes. The cementation reaction between activated carbon and gold thiosulfate is also briefly described, this reaction being unusual in that no dissolution of the carbon occurs.

Jan 1, 2003