SYNERGIC EXTRACTION OF AMMONIACAL Ni

The synergic extraction of Ni from ammoniacal sulfate solution by mixtures of LIX 64N and Kelex 100 was studied using slope analysis, continuous variation, and mathematical modeling. This extractant pair was discovered as part of a study to find extractants that perform ?at the higher pH level needed for leaching Cu, Ni, and Co, and thus eliminate ammonia stripping/recharging steps in current processes. Ni was more efficiently extracted at higher pH with the LIX 64N/Kelex mixture than with either extractant alone. A model is proposed based on four different stoichiometrics, each contributing to the overall reaction. Those four Ni/LIX 64N/ Kelex species are 1/2/0, 1/0/3, 1/1/1, and 1/2/1. Ammonia is coextracted, but can be selectively scrubbed with 2 g/L H₂S0₄ Ni can be selectively stripped from the Ni- and Cu-loaded extractants with 10 g/L H₂S0₄ then Cu is stripped with 150 g/L H₂S0₄ A continuous process was simulated with a batchwise circuit, which showed no loss of extraction efficiency in 10 cycles.     

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     

Co-extraction and selective stripping of copper (II) and molybdenum (VI) using LIX 622

LIX 622 diluted with kerosene was used to co-extract copper (II) and molybdenum (VI) from acidic sulphate solutions. The influence of equilibrium pH and extractant concentration on metal co-extraction has been studied. The extraction of both metals is sensitive to equilibrium pH; however, molybdenum is extracted preferably to copper at acidic pH values. For aqueous phases containing both metals, conditions were established for the co-extraction, selective stripping of copper and molybdenum and NH₃ removal from the stripped organic solution.     

Continuous Laboratory Gold Solvent Extraction from Cyanide Solutions using LIX 79 Reagent

Continuous laboratory solvent extraction of gold from cyanide solutions has been investigated by using LIX 79 guanidine‐based extractant. Different variables that affected the extraction included aqueous pH, extractant concentration and modifier concentration. Extraction isotherms of the aurocyanide complex with respect to the other cyanoanions were compared, and the following order of selectivity was observed: Au > Ag > Cu > Zn > Fe. According to the pH isotherms, aurocyanide can be extracted in alkaline media, and a better separation with respect to other cyano anions was obtained in the pH range 10.5–11.2. From the McCabe‐Thiele diagrams, better recovery was observed when using LIX 79 and tridecanol at 10 vol.‐%. Stripping gold from the loaded organic was carried out at pH > 12 by using NaOH and NaCN solutions. The pilot plant tests indicate that a two‐stage extraction followed by one strip step are more than adequate to obtain an overall process efficiency of 92 %. However, for those cases where copper is present significantly, a copper wash stage is recommended before gold stripping. In this case, stripping of copper is accomplished at a pH 10.8, whereas the gold stripping was done at a pH of 12.0.     

Extraction of copper from dilute solutions by LIX 64N. Effect of dekalin and tetralin as diluents on the equilibrium and rate of mass transfer

Liquid-liquid equilibrium data and mass transfer rates for the extraction of copper from dilute aqueous sulphate solutions by LIX 64N with dekalin (decahydronaphthalene) and tetralin (1,2,3,4-tetrahydronaphthalene) as diluents are reported. The stripping of copper from the organic phase was also studied. For an initial copper concentration of 1.5 g dm^?3 extraction efficiency decreases as the concentration of tetralin increases in the diluent mixtures of dekalin-tetralin. This behaviour is explained as a result of the formation of oxime aggregates and the interaction between the oxime and the diluent. Initial rates of extraction and stripping were determined by the single drop technique. The linear relation between initial rates of extraction and the difference of interfacial tension between the extractant in the diluent and the diluent itself holds for the system under investigation.     

Purification of nickel sulphate solutions containing iron,copper, cobalt,zinc and manganese

Acidic nickel-bearing solution containing iron, cobalt, manganese, zinc and copper was processed through a solvent extraction and precipitation technique to obtain a pure nickel sulphate solution. Iron was extracted using 0.2M Cyanex-272 (partially neutralised) as the extractant. Stripping of iron from the loaded organic has also been studied. After iron recovery through solvent extraction the raffinate still contained 0·25 g dm^?3 of iron which was quantitatively separated by a lime precipitation technique. During this iron precipitation there was no loss of cobalt and nickel but copper, manganese and zinc were coprecipitated to some extent. From the iron-free nickel sulphate solution the other impurities were extracted using the same extractant (Cyanex-272) in a single stage. The metal ions from the loaded organic were stripped using a 0·5% (v/v) H₂SO₄ solution in a single stage. The entire operation needs only seven stages: two stages for iron extraction, three stages for iron stripping from the loaded organic, and one stage each for extraction and stripping of other impurities. In the entire operation the loss of nickel was less than 0·5%.     

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.     

Co-Extraction — Selective stripping for the recovery of nickel and copper from the leach liquor of ocean nodules

Ferromanganese deep sea nodules of the Indian Ocean have recently been recognised as a potential source of metals like copper, nickel, cobalt and manganese. For the treatment of the sea nodules following the reduction roast-ammonia leach process, the leach liquor containing copper, nickel and cobalt was processed to separate and recover these metals by solvent extraction (SX) using 25% LIX 64N in kerosene. Almost quantitative extraction of copper and nickel was realized in a continuous run. During nickel stripping, the small amount of copper in the nickel solution was removed by incorporating a copper extraction step using 10% LIX 64N in kerosene. The purified pregnant nickel electrolyte was electrowon in a non-diaphragm cell. Copper was similarly recovered by electrowinning (EW). A closed circuit of SX-EW was run to produce cathodes of nickel and copper with energy consumptions of 3.85 and 2.01 kWh/kg for the respective metals.     

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.     

Separation of Copper and Zinc by Solvent Extraction During Reprocessing of Flotation Tailings

Results from the solvent extraction of copper and zinc from pregnant solutions after bioleaching of re-floated tailings from the Kipushi concentrator in DR of Congo are presented. LIX984N has been used as extractant for copper, while D2EHPA as such for zinc, following prior removal of the ferric iron via precipitation. The McCabe-Thiele diagrams constructed for Cu and Zn extraction have theoretically suggested the need for two stages for copper and one for zinc. Stripping these metals to the aqueous phase by sulphuric acid has yielded rich electrolytes with 48.5 g/L copper and 85.5 g/L zinc. Thus, copper and zinc could be further recovered from the stripped solutions by electrolysis.     

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     

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.     

Selective transport of cobalt (II) from ammoniacal solutions containing cobalt (II) and nickel (II) by emulsion liquid membranes using 8-hydroxyquinoline

The selective transport of cobalt (II) from ammoniacal solutions containing nickel (II) and cobalt (II) by emulsion liquid membranes (ELMs) using 8-hydroxyquinoline (8-HQ) as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (ECA 4360J), and an extractant (8-HQ). Very dilute sulphuric solution buffered at pH 5.0 has been used as a stripping solution. The ammoniacal feed solution pH was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt (II) have been studied. These variables are membrane composition, pH of the feed solution, cobalt (II) and nickel (II) concentrations of the feed solution, stirring speed, surfactant concentration, extractant concentration, complexing agent concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively transport 95.0% of cobalt (II) from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt (II) with respect to nickel (II), based on initial feed concentration, have experimentally found to be of as high as 31 for equimolar Co(II)–Ni(II) feed solution.     

COPPER EXTRACTION FROM CHLORIDE SOLUTIONS WITH MIXTURES OF SOLVATING AND CHELATING REAGENTS

ABSTRACT

Equimolar mixtures of N,N,N',N'-tetrahexylpyridine-3,5-dicarboxamide (L) with 2-hydroxy-5-t-octylbenzophenone oxime or l-phenyldecane-l,3-dione (HB), were used to extract copper from chloride solutions of various concentration of chloride ions. Chloride ions were then scrubbed out with water or ammoniacal solutions and copper was transferred from the solvate CUCl₂L₂ to chelate CuB₂- Both studied systems permit effective extraction of copper and removal of chloride ions from the organic phase. Some protonation of solvating reagent L occurs, however, when copper is stripped from the chelate with hydroxyoxime. This negative effect can be suppressed when 1-phenyl decane-1,3-dione is used as a chelating agent. The scrubbing of chloride ions must be then carried out with ammoniacal solutions to avoid simultaneous stripping of copper.     

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).     

Simultaneous solvent extraction of cobalt and magnesium in the presence of nickel from sulfate solutions by Ionquest 801

The simultaneous extraction of Co(II) and Mg(II) from nickel sulfate solutions has been carried out using the organophosphonic extractant Ionquest 801 diluted in Exxsol D‐80. Statistical design and analysis of experiments were used in order to determine the main effects and interactions of the solvent extraction parameters, which were the extraction pH at equilibrium, the temperature, the extractant concentration and the organic/aqueous phase ratio. A statistically designed experiment was also carried out to study the stripping of the Ionquest 801 organic phase loaded with cobalt and magnesium by sulfuric acid solution. The number of stages required for both extraction and stripping processes of cobalt and magnesium was evaluated. The results of continuous counter‐current mini‐plant tests demonstrated the simultaneous recovery of cobalt and magnesium from nickel sulfate solution. Copyright © 2005 Society of Chemical Industry     

SOLVENT EXTRACTION EQUILIBRIUM OF NICKEL FROM AMMONIACAL SOLUTIONS BY LIX 64N

Equilibrium data for the solvent extraction of nickel from amraoniacal solutions by LIX 64N (10 vol%) dissolved in kerosene (15% aromatic content) are reported. The effect of NH3/aq) concentration, LIX 64N concentration, pH and temperature are shown. The stoichiometry of the Ni-active oxime in LIX 64N complex was ascertained by spectrophotometry studies. A mathematical mechanistic model was developed for the prediction of extraction distribution coefficients as a function of pH. The model predicts more accurate results at high pH values, as could be expected taking into consideration the assumptions made in developing the model.     

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.     

Recovery of Zinc by LIX 984N‐C from Electroplating Rinse Bath Solution

The development of a complete solvent extraction process at the laboratory scale for recovering zinc from the zinc electroplating first rinse bath solution (alkali solution) containing ～1.9 g/L zinc (ZEFRBS) by a solvent extraction route using LIX 984N‐C, which is a new SX reagent developed by Cognis, and dissolved in commercial kerosene was investigated. By using LIX 984N‐C, an electrolyte from ZEFRBS with ～12 g/L zinc content, which was addable to the alkali zinc electroplating bath, was generated by 10 vol.% LIX 984N‐C in commercial kerosene at the O/A ratio of 1/4 and equilibrium pH value of 8.00 ± 0.05 with a two‐stage countercurrent extraction, and stripping of the loaded organic by a strip solution with 150 g/L sulfuric acid and with the O/A ratio of 1.5 at a two‐stage countercurrent stripping process. A new complete flow sheet of 10 vol.% LIX 984N‐C process for the recovery of zinc from ZEFRBS has been demonstrated.     

Extraction of zinc(II) from ammoniacal solution into hydrophobic ionic liquids

BACKGROUND: Separation and recovery of zinc from ammoniacal solutions with solvent extraction is very important in the hydrometallurgical industry. Ionic liquids (ILs) have considerable potential for the separation of metal ions. The extraction behaviour of zinc from ammoniacal solution into three hydrophobic ILs was investigated using β‐diketone as the extractant. RESULTS: The extraction efficiency of zinc for three ILs reached a maximum at pH 7.5 and subsequently decreased with increase of pH and it also decreases with increase of the total ammonia concentration. The overall extraction process is exothermic. The extractability decreases in the IL order: [BMIM]NTf₂ > [OMIM]PF₆ > [OMIM]NTf₂. The results of X‐ray absorption spectra indicate that the coordination number of the extracted zinc complexes decreases with increase in the hydrophobicity of the ILs. The results of five recycling experiments indicate that the three hydrophobic ILs are more stable than [BMIM]PF₆ for the extraction of zinc in ammoniacal solutions. CONCLUSION: Hydrophobic ILs combined with β‐diketone can be used to extract zinc from ammoniacal solutions. The extraction of zinc is dependent on the zinc species in ammoniacal solutions and the hydrophobicity of ILs. Moreover, the latter affects both the extractability of extraction systems and the structure of the extracted complexes. © 2012 Society of Chemical Industry