Copper(II) Extraction from Phosphoric Acid Media by 5‐Dodecylsalicylaldoxime (LIX 622)

Abstract

The extraction of Cu(II) from phosphoric acid media (0.4–7.3 M) by the commercial reagent LIX 622 in toluene has been studied. Experimental results have been treated numerically and the formation in the organic phase of the complex CuR₂, HR being 5‐dodecylsalicylaldoxime, has been proposed. Values of the conditional extraction constants, which increase with the phosphoric acid concentration, are given. Organic extracts have been analyzed by EPR spectroscopy. The presence of a square planar complex of Cu(II) has been deduced confirming the stoichiometry CuR₂.     

Solvent extraction of gold by LIX 79: experimental equilibrium study

The extraction of gold(I) from aurocyanide aqueous solutions using LIX 79 has been studied. Different variables that could affect the extraction system were evaluated: equilibration time, aqueous pH, metal and extractant concentrations, organic phase diluent and aqueous ionic strength. The extraction of the aurocyanide complex with respect to other metal‐cyano complexes has also been studied on both synthetic and real leach solutions. Gold experimental data have been analysed numerically to determine the stoichiometry of extracted species and its equilibrium constant. It was found that gold(I) was extracted into the organic phase by the formation of the species RHAu(CN)₂ (LIX 79=R). Stripping of gold from loaded organic phases was carried out using NaOH or NaCN solutions. © 1999 Society of Chemical Industry     

Recovery of Copper from a Waste Heat Boiler Dust Leach Liquor using LIX 84I and LIX 622N

The dust collected from the waste heat boiler of a copper plant was leached with sulfuric acid and the leach liquor contained 31.63 kg/m³ Cu, 14.78 kg/m³ Fe, 2.21 kg/m³ Zn, 0.26 kg/m³ Co, 0.09 kg/m³ Ni, and 0.23 kg/m³ Cd. The iron content in the leach liquor was precipitated out using Ca(OH)₂ and from the filtrate copper was extracted with the extractants LIX 84I and LIX 622N in kerosene. Extraction of copper with either extractant increased with increasing equilibrium pH and extractant concentration. The McCabe-Thiele plots for quantitative extraction of copper indicated 3-stages at O:A ratio of 3:2 with 30% extractants. The counter-current extraction study showed 0.21 kg/m³ and 6.77 g/m³ copper in the third stage raffinates of LIX 84I and LIX 622N indicating 98.64% and 99.95% extraction, respectively. For extraction of a mole of copper ion, two moles of the extractant was required to release two moles of hydrogen ion to the aqueous phase. The quantitative stripping of copper from the loaded organic phases of LIX 84I and LIX 622N with 180 kg/m³ H₂SO₄ was possible in 3-stages at O:A ratio of 3:1 and 3:2, respectively. The thermodynamic parameters such as ΔH, ΔG, and ΔS were calculated for both the systems. The enthalpy change (ΔH) values were positive for extraction of Cu with either extractant indicating the processes to be endothermic. The IR spectra indicated the association of phenolic-OH group of oxime molecules in the formation of copper complexes.     

Mechanistic study of active transport of copper (II) using LIX 54 across a liquid membrane

The present work describes the mechanism of active transport of copper(II) through an immobilized liquid membrane (ILM) containing LIX 54 (β‐diketone) dissolved in Iberfluid as mobile carrier. An uphill transport model has been described and equations have been derived taking into account aqueous boundary layer diffusion and liquid membrane diffusion as simultaneous controlling factors. In the present model, various cases were discussed using the carrier LIX 54 and different chemical species; the diffusional membrane resistance for lower and higher concentrations of extractant was evaluated. The diffusion coefficients were observed to decrease with increase in ­the extractant concentration, ranging from 4.1 × 10⁻³ to 1.65 × 10⁻² mol dm⁻³ Plotting [Cu]₀−[Cu]_t vs time resulted in a slope of [HR]₀A/2Δ_orgV taking into account the complex species, CuR₂, in the membrane. The mass transfer coefficient (Δ_org ⁻¹), the diffusion coefficient of the metal carrier species (D_org) and the thickness of the aqueous boundary layer were calculated from the proposed model for LIX 54. More than 90% of the Cu(II) could be separated using LIX 54 in the presence of various metals such as Ni, Co(II) and Zn. © 2000 Society of Chemical Industry     

Extraction of molybdenum(VI) from sulfate solutions by LIX 622

The application of LIX 622 (oxime derivative) as an extraction reagent of molybdenum (VI) from sulfate media was studied. The extraction system was studied as a function of contact time, temperature, aqueous pH, diluent of the organic phase and metal and extractant concentrations. The extraction is exothermic and it is dependent on the organic diluent, aqueous pH and reagent concentration. The data have been analysed numerically to determine the stoichiometry of extracted species and their equilibrium constants. It was found that molybdenum was extracted into the organic phase by a complex mechanism which involves the formation of three species (MoO₂L₂, MoO₄H₃HL⁺HSO₄⁻ and MoO₄H₂HL, where L represents the extractant). Molybdenum stripping by acidic and ammonium hydroxide solutions was also studied. © 2000 Society of Chemical Industry     

Recovery of copper from ammoniacal/ammonium sulfate medium by LIX 54

The extraction‐stripping reaction of Cu(II) by LIX 54 in Iberfluid from aqueous ammonium sulfate medium at pH 8.5 has been investigated. The effects of pH, metal ion, extractant concentration as well as the loading capacity of the reagent were studied. The extraction equilibrium constant for copper was determined numerically to be 7 × 10⁻⁷. Experimental data can be explained assuming the formation of CuR₂ species in the organic phase (R represents the extractant). Copper stripping was studied using typical spent copper electrowinning solutions as stripping medium. The number of stages required for the extraction and stripping of copper was also evaluated. The results were used to asses the conditions for purification of industrial waste solutions (eg spent etchants) containing copper through counter‐current extraction‐stripping. © 1999 Society of Chemical Industry     

Synergistic Extraction of Cobalt(II) by Mixtures of Bis(2-Ethylhexyl)Phosphoric Acid and LIX 860

The extraction of Co(II) from 1.0 M KNO₃ medium by mixtures of HDEHP (bis-2-ethylhexylphosphoric acid) and LIX 860 (5-dodecylsalicylaldoxime) dissolved in toluene has been studied. The effects of pH, metal, and extractant mixture concentrations on the extraction behavior have been examined. Synergistic extraction of the metal ion with the binary mixture of extractants has been found. Experimental results have been treated graphically and numerically by means of the Letagrop-Distr program and can be explained by assuming the extraction of two mixed complexes of general stoichiometry CoR₂(HR)(HL) and CoR₂(HR)(HL)₃, HR being bis-2-ethylhexylphosphoric acid and HL standing for 5-dodecylsalicylaldoxime. The corresponding extraction constant values have also been determined.     

Copper Solvent Extraction from Waste Cyanide Solution with LIX 7820

The use of a solvent mixture of a quaternary amine and nonylphenol (LIX 7820) to extract copper cyanide from waste cyanide solution has been studied. Copper extraction is favorable at low pH, whereas a high cyanide‐to‐copper ratio tends to suppress copper loading. The preferential extraction of Cu(CN)₃ ^2? over Cu(CN)₄ ^3? and CN^? has been confirmed by the examination of both the extraction of copper and cyanide by the solvent mixture under different experimental conditions. The solvent mixture also strongly extracted zinc and nickel from the cyanide solution, but it exhibits weak affinity for iron cyanide complex and free cyanide. The important findings suggested the potential application of the solvent mixture for the recovery of copper and cyanide from waste cyanide solutions, by which copper can be extracted and concentrated into a small volume of solution and the barren cyanide solution recycled to the cyanidation process.     

Fundamental aspects of the extraction and stripping of palladium by LIX 65N

The fundamental aspects of the extraction and stripping of palladium from its chloride solution by LIX 65N diluted with Kermac 470B have been studied. Equilibria of extraction and stripping, temperature effect, the variation of sodium thiosulphate concentration on stripping and rate of extraction and stripping on the system Pd²⁺-LIX 65N-Kermac 470B are reported. The fundamental aspects of the extraction and stripping of palladium from its chloride solution by LIX 65N diluted with Kermac 470B have been studied. Equilibria of extraction and stripping, temperature effect, the variation of sodium thiosulphate concentration on stripping and rate of extraction and stripping on the system Pd²⁺-LIX 65N-Kermac 470B are reported.     

Solvent Extraction of Copper from Nitrate Media with Chelating LIX‐Reagents: Comparative Equilibrium Study

Abstract

Comparative experimental studies were carried out on extraction of copper(II) cations from aqueous acid nitrate media using four LIX‐reagents, representatives of different extractant classes: LIX 984N‐I, LIX 860N, LIX 84‐I and LIX 65N. As a diluent, liquid hydrocarbon undecane was used. The extraction behavior of the LIX‐reagents was compared based on an analysis of the influence of the main factors on the two‐phase mass transfer process: aqueous pH‐value, initial copper and extractant concentrations, and temperature. The experimental data received were used in the calculation of important parameters characterizing the efficiency of copper extraction from nitrate media with different LIX reagents: distribution ratios D, concentration extraction constants K _ex, pH_0.5‐values, and thermodynamic parameters such as enthalpy, entropy, and free energy changes (ΔH ⁰, ΔS ⁰, ΔG ⁰‐values).     

Extraction of zinc from ammoniacal/ammonium sulphate solutions by LIX 54

The extraction of zinc from ammoniacal/ammonium sulphate aqueous media using LIX 54 has been studied. The metal extraction rate has been examined and also the effect of temperature on the extraction of zinc (ΔH° = −8·8 kJ mol⁻¹). The effect of the aqueous pH, and therefore zinc ammine complex formation, on the extraction of zinc was studied. Stripping of the metal from loaded organic phases was carried out at various rates, temperatures (ΔH° = 3·2 kJ mol⁻¹) and sulphuric acid concentrations. The results obtained were compared with others obtained from the literature wherein different extractants were used. © 1998 SCI.     

SPECTROSCOPIC STUDY OF THE EXTRACTION OF NICKEL BY 2-HYDROXY-5-NONYLBENZOPHENONE OXIME (LIX 65N) AND 5,8-DIETHYL-7-HYDROXYDODECANE-6-ONE OXIME (LIX 63).

ABSTRACT

A novel method for determination of solvent extraction equilibria and kinetics using Infrared attenuated total reflectance spectroscopy (ATR) is described. The method allows complete, quantitative kinetic studies using a total of one gram of extractant. Solvent extraction of aqueous Ni²⁺ into 0.5 - 1.0 μm films of Apiezon M (ApM, aliphatic hydrocarbon) containing the title reagents was examined. In contrast with LIX 65N extraction which proceeds solely through the LIX 65N anion, extraction of Ni²⁺ by LIX 63 proceeds through both neutral and anionic forms of LIX 63. This results in a kinetic rate law having two terms, each exhibiting first order dependence on both [Ni²⁺] and [LIX 63]₀. For mixtures of LIX 65N and LIX 63 (LIX 63:LIX 65N ≤ 0.12) In the ApH films, the rate law has only one term, of orders [LIX 65N]₀ ¹, [LIX 63] ₀ ¹, [Ni²⁺]¹, and [H⁺]^?1. While the equilibrium constants favor Ni(LIX 65N)₂, the relatively large rate of reaction of the neutral LIX 63 leads to a catalysis of the overall LIX 65N extraction.     

Structure of the Extracted Complex in the Ni(II)‐LIX84I System and the Effect of D2EHPA Addition

Abstract

The structure of the Ni(II) complex extracted with the commercial hydroxyoxime, LIX84I, and the effect of adding bis(2‐ethylhexyl) phosphoric acid (D2EHPA) to LIX84I on the extraction rate and the coordination of Ni(II) were investigated by solvent extraction and XAFS methods. The XANES spectrum and the curve fits of the EXAFS spectrum of the Ni‐LIX84I complex showed that the complex is four‐coordinate square‐planar with a 1:2 stoichiometry. In the Ni(II)–D2EHPA–LIX84I system, the coordination geometry changes from square‐planar to six‐coordinate octahedral with an increase in the D2EHPA concentration. Although the rate of Ni(II) extraction from the model spent electroless nickel plating bath with LIX84I is significantly accelerated by adding a small amount of D2EHPA ([LIX84I]: 0.5 M, [D2EHPA]: 0.05 M), most of the Ni(II) complexes extracted with this organic solution remain square‐planar. This indicates that the increase in the extraction rate does not depend on the change in the coordination structure of the extracted complex.     

Selective and Synergistic Extraction of Nickel from Simulated Cr-Ni Electroplating Bath Solutions using LIX 63 and D2EHPA as Carriers

The main goal of the present study is to explain synergistic extraction of nickel from simulated Cr-Ni electroplating bath solutions (SEBS) using 5,8-diethyl-7-hydroxydodecane-6-one oxime (LIX 63) and di-(2-ethylhexyl) phosphoric acid (D2EHPA) as extractants by emulsion liquid membrane (ELM) technique. The importance of membrane composition and aqueous phase properties on nickel extraction percentage has been highlighted for the selective extraction of nickel. Some important parameters like acid concentration, stripping solution type and concentration, mixing speed, extractant concentrations, phase ratio, and surfactant concentration was studied to improve the extraction and stripping efficiencies. Higher than > 99% of nickel was recovered at optimum conditions within 6 min. The higher separation factors (β_Ni/Cr) were obtained as 580. As a result, the nickel extraction kinetic with D2EHPA has been defined as faster than LIX63. So, the kinetic transport of nickel mainly depends on LIX63 than D2EHPA. According to these results, D2EHPA behaves as a synergistic extractant in the present extraction mechanism.     

The catalytic effect of quaternary ammonium salt On the Extraction of Palladium(II) With 2-Hydroxy-5-Nonyi-Benzophenone Oxime(LIX 65N) In Heptane-Chloroform Solvents

Extraction of Pd(II) from acidic chloride media using 2-hydroxy-5-nonyi-benzophenone oxime (LIX 65N,KL) in heptane is 60% more rapid than that using chloroform under comparable conditions, as well as more complete, reflecting an eight-fold increase in the extraction constant. A further substantial increase in the ex traction rate was achieved using the quaternary ammonium sait, Aliquat 336S, without any change in the extraction constant. The extraction probaly occurs through rapid phase transfer of PdCl via ion pair extraction followed by formation of the chelate, PdL₂-, in the organic phase.     

Solvent extraction with LIX 973N for the selective separation of copper and nickel

LIX 973N diluted with Iberfluid was used to co‐extract copper and nickel from ammoniacal/ammonium carbonate aqueous media. The influence of equilibration time, temperature, equilibrium pH and extractant concentration on the extraction of both metals has been studied. It was observed that neither copper nor nickel extraction is sensitive to temperature and equilibrium pH, however nickel extraction equilibrium is reached at a longer contact time (20 min) than that of copper (5 min), in addition nickel extraction depends greatly on the extractant concentration in the organic phase. For a solution containing 3 g dm⁻³ each of copper and nickel and 60 g dm⁻³ ammonium carbonate, conditions were established for the co‐extraction of both metals, ammonia scrubbing and selective stripping (with H₂SO₄) of nickel and copper. Using the appropriate extractant concentration the yield (extraction stage) for both metals is near 100%, whereas the percentage of nickel and copper stripping is also almost quantitative. © 1999 Society of Chemical Industry     

THE SELECTIVITY OF NICKEL OVER IRON IN THE LIX63-HDNNS SOLVENT EXTRACTION SYSTEM

ABSTRACT

The effects of the aqueous phase pH and the organic phase HDNNS concentration on the distribution coefficients of Ni and Fe in pure HDNNS or mixed LIX63-HDNNS systems have been investigated. With the mixed extractants, there is antagonistic extraction of iron below pH 1.4 whereas synergistic extraction occurs above this pH. At pH 2.5 and a fixed LIX63 concentration, iron distribution increases markedly in comparison with the oxime-free system and goes through a maximum with increase in HDNNS concentration. A similar behavior is shown by nickel at both pH 1.0 and 2.5. The log D_Feversus pH plot gives a curve with a slope of two for the LIX63-HDNNS mixed system, which suggests that iron is extracted in the form of a species with an ionic charge of 2, probably Fe(OH)²⁺. The extracted complexes are proposed as Ni(H₂L)₃D₂where all three oxime molecules function as bidentate ligands, and Fe(OH) (H₂L) ₃D₂where one of the oxime molecules functions as a monodentate ligand. The Ni/Fe selectivity is high at low pH and changes mainly as a result of variations in the nickel distribution coefficient, but it is low at high pH because of the synergistic extraction of iron.     

NONDISPERSIVE LIQUID-LIQUID EXTRACTION OF COPPER AND ZINC FROM AN AQUEOUS SOLUTION BY DEHPA AND LIX 984 IN A HOLLOW FIBER MEMBRANE MODULE

ABSTRACT

A liquid-liquid extraction procedure was used to study the amounts of Zn²⁺ and Cu²⁺ that could be simultaneously extracted from aqueous solution with di(2-ethylhexyl) phosphoric acid (DEHPA) and LIX 984 diluted with n-heptane at equilibrium. LIX 984 is a 1:1 volume blend of LIX 860 (5-dodoecylsalicylaldoxime) and LIX 84 (2-hydroxy-5-nonylacetophenone oxime). At equilibrium, a 0.3 mol/L DEHPA-20% (v/v) LIX 984 solution extracted 99% of both the zinc and copper from a solution that had 100 ppm of each metal.

A polysulfone hollow-fiber membrane module with 1 mm ID and 5,000-molecular weight cutoff was used to study the amounts of Zn²⁺ and Cu²⁺ that could be simultaneously extracted with a mixture of DEHPA and LIX 984. The aqueous and organic streams were operated at 100% recycle. With a 0.6 mol/L DEHPA-10% (v/v) LIX 984 solution, a 90.5 ± 1.7% (s.d.) extraction of zinc and a 93.70 ± 0.79% (s.d.) extraction of copper was obtained after 180 min.     

Selective removal of copper ions from aqueous solutions using modified silica beads impregnated with LIX 84

Silica beads immobilized with 2‐hydroxy‐5‐nonylacetophenoneoxime (LIX 84) were prepared after silica surface modification by γ‐aminopropyltriethoxysilane (SB‐L). Batch and packed‐column tests were conducted to evaluate the metal ion removal capabilities of the prepared adsorbent. Equilibrium isotherms of the SB‐L with aqueous solutions containing copper ions were obtained. In addition, the kinetic performances for copper ion removal from aqueous solutions were investigated. The results showed that the amount of extraction increases with solution pH in the range between 1.5 and 5. The selectivity was also experimentally investigated, these results showed that the SB‐L adsorbed copper ions selectively in the presence of other metal ions such as Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Ca²⁺ and Mg²⁺. From the regeneration experiments, it was found that the copper ions adsorbed at the SB‐L surface were recovered by acidic solutions. The recovery ratios were between 78% and 90%, depending on the types of acidic solutions. The results showed that the SB‐L prepared may be used for the selective extraction of copper ions from aqueous solutions. © 1999 Society of Chemical Industry     

Separation of Cobalt and Zinc from Manganese,Magnesium, and Calcium using a Synergistic Solvent Extraction System Consisting of Versatic 10 and LIX 63

Abstract

The Boleo leach solution contains large amounts of manganese (45 g/L), magnesium (25 g/L) and small amounts of cobalt (0.2 g/L) and zinc (1 g/L) in sea water. Due to the high manganese concentration, it is very difficult to separate cobalt and zinc from manganese, magnesium, and calcium using conventional solvent-extraction processes, which has led to the development of a synergistic solvent extraction (SSX) system consisting of Versatic 10 and LIX®63. By adding 0.4 M LIX 63 to 0.5 M Versatic 10, large synergistic shifts were obtained for cobalt (max. ΔpH₅₀ 4.24) and zinc (max. ΔpH₅₀ 1.62). After a single contact at pH 4.5, the extraction of cobalt was almost complete and that of zinc 80%. The extraction of manganese was 1.55%, and almost no magnesium and calcium were extracted, indicating excellent separation of cobalt and good separation of zinc from manganese, magnesium, and calcium. The SSX system was further optimized to reduce the co-extraction of manganese with the synthetic Boleo demonstration plant solution. It was found that with 0.33 M Versatic 10 and 0.30 M LIX 63, the SSX system composition approached optimum. After a single contact at pH 5.5, the extractions of cobalt and zinc were 93% and 70%, respectively, while the manganese concentration in the loaded organic solution was only 0.28 g/L. The extraction and stripping kinetics of cobalt and zinc were rapid. The SSX system was tested in two integrated pilot-plant trials with excellent results. Baja Mining has planned to implement the SSX circuit in their future Boleo plant.