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     

Separation of cobalt and nickel from acidic sulfate solutions using mixtures of di(2‐ethylhexyl)phosphoric acid (DP‐8R) and hydroxyoxime (ACORGA M5640)

DP‐8R and ACORGA M5640 extractants diluted in Exxsol D100 were used to co‐extract cobalt and nickel from aqueous acidic sulfate media. The influences of equilibration time, temperature, equilibrium pH and reagent concentrations on the extraction of both metals have been studied. It was observed that both cobalt and nickel extraction are slightly sensitive to temperature but are pH dependent. Metal extraction equilibria are reached within about 5 min contact time. In addition, cobalt extraction depends on the extractant concentration in the organic phase. For a solution containing 0.5 g dm^?3 each of cobalt and nickel and an initial pH of 4.1, conditions were established for the co‐extraction of both metals and selective stripping (with H₂SO₄) of cobalt and nickel. Using the appropriate reagent concentrations the yield (extraction stage) for both metals exceeded 90%, and stripping of cobalt and nickel was almost quantitative. Copyright © 2004 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     

Synergistic extraction and separation of Fe(III) and Zn(II) using TBP and D2EHPA

Waste chloride pickle liquors from hot-dip galvanizing plants, steel plants and flue dust contain reasonable amounts of heavy metals such as Zn, Cr, Ni, etc. Iron is invariably associated with most of these materials and comes into solution during leaching. Thus, the synergistic extraction of zinc(II) and iron(III) from leach solutions in tri-n-butyl phosphate (TBP)–di(2-ethylhexyl) phosphoric acid (D2EHPA) system diluted in kerosene was investigated. The Zn and Fe concentrations in the leach liquor used in the present study were 2 g/L. Experiments were carried out in the pH range of 0.5–4.0, temperature of 25°C, using sole D2EHPA, sole TBP and D2EHPA–TBP mixtures at different ratios. Results showed that the co-extraction of zinc(II) and iron(III) increased with increasing equilibrium pH using D2EHPA. It is demonstrated that the mixtures of TBP and D2EHPA are more efficient and selective than D2EHPA alone. At low pH values, the separation factor is low when pure D2EHPA is used as an extractant; however, using TBP as a synergist, the separation factor increases and results in a better separation of zinc from iron. Increasing TBP to D2EHPA ratios in the organic phase caused a slight shift to the right in the extraction isotherm of iron and a marked shift to the right in the extraction isotherm of zinc, and the maximum separation factor of 13.3 × 10³ was achieved at a TBP to D2EHPA volume ratio of 4:1 (0.58 M TBP: 0.12 M D2EHPA). Furthermore, the effect of equilibrium pH, organic to aqueous phase ratio and Cl^? concentration on the selective extraction was investigated. Using two extraction stages at the O/A ratio of 2:1 and pH_e (equilibrium pH) of 3 and 1 for zinc and iron, respectively, 99% of zinc(II) and 96.25% of iron(III) were extracted.     

Separation and recovery of heavy metals from concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime and bis(2,4,4-trimethylpentyl) -phosphinic acid

Extraction and separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater by synergistic solvent extraction using a mixture of 2-hydroxy-5-nonylacetophenone oxime (Mextral 84H) and bis(2,4,4 -trimethylpentyl)-phosphinic acid (Cyanex 272) in an aliphatic diluent (DT-100) was studied. The effects of extractant concentrations, equilibrium pH, organic-to-aqueous phase ratios, system temperature, and extraction and stripping efficiencies on the extraction performance of the heavy metals were investigated. Extraction of pH isotherms showed that addition of Cyanex 272 to Mextral 84H causes obvious synergistic shifts for zinc and cadmium and a slightly antagonistic shift for nickel. The separation factor of cadmium over magnesium was 155.7 and the ΔpH₅₀ values between the metals were over 1.00 pH units. Semi-continuous tests for the metals extraction, scrubbing, and stripping were conducted in a continuous extraction apparatus with conditions further optimized for separation of the metals. Nearly 100% of the copper and nickel and over 98% of the zinc and cadmium were recovered with less than 0.1 mg/L copper and nickel, 26 mg/L of zinc, and 10 mg/L of cadmium remaining in the raffinate. A process in which all valuable metals are extracted simultaneously and stripped selectively at optimal conditions is proposed that is entirely feasible for the separation of copper, zinc, nickel, and cadmium from calcium and magnesium in concentrated smelting wastewater. The study determines the fundamental parameters for the treatment of smelting wastewater by solvent extraction.     

Nickel and copper removal from aqueous solution by an immature coal (leonardite): effect of pH,contact time and water hardness

The removal of Ni(II) and Cu(II) from aqueous solutions by a low cost sorbent (leonardite) was studied. The metal uptake was pH‐dependent and the maximum sorption for two metals was obtained at around pH 5–6. Batch kinetic studies showed that equilibrium time was reached after 2 h of contact time. Equilibrium isotherms were obtained for the adsorption data of the two metals in single and binary systems. Equilibrium data were fitted to Langmuir and Freundlich models and the maximum adsorption capacities were found to be 0.33 mmol of copper and 0.26 mmol of nickel per gram of leonardite. In binary solutions containing the two metals an important reduction of nickel uptake was observed while the sorption of copper was less affected. The presence of Ca²⁺ affected the removal of both copper and nickel ions, although the adsorption of nickel was reduced more than that of copper. Copyright © 2005 Society of Chemical Industry     

从电镀污泥浸出液中选择性萃取铜的研究

采用M5640-磺化煤油作为萃取剂,H2SO4为反萃剂,对电镀污泥浸出液中的铜进行选择性萃取实验,确定了萃取铜及反萃的最佳工艺参数。结果表明,实验采用二级萃取,萃取剂浓度为5％,VO/VA=1：1,混合时间为2min时,铜的萃取率可达到9996以上,另外采用已优化的反萃工艺参数,铜的反萃率可达99％以上。同时,萃取剂对Ni、Zn的共萃率较低,表明M5640-磺化煤油体系对电镀污泥液中铜的萃取选择能力较高,可以达到与溶液中Ni、Zn有较好的分离效果。     

Separation of Copper and Nickel from Ammoniacal/Ammonium Carbonate Solutions Using ACORGA PT5050

ABSTRACT

ACORGA PT5050 diluted with iberfluid (kerosene-type diluent, mostly aliphatic) was used to coextract copper and nickel from ammoniacal carbonate solutions. The influence of kinetics, temperature, equilibrium pH, and extractant concentration on the extraction of both metals has been studied. It was observed that nickel extraction is very sensitive to aqueous pH and that the extraction falls beyond an equilibrium pH of 9. For a typical solution containing near 3 g/L each of copper and nickel and 60 g/L ammonium carbonate, conditions were established for the coextraction and selective stripping of nickel and copper.     

Adsorption of Cd(II) from aqueous solution onto pyrite

The physicochemical factors such as equilibrium time, solution pH, initial concentration of Cd(II), particle size and temperature that control the adsorption of Cd(II) from aqueous solutions onto pyrite has been investigated through batch experiments. Prior to this study, pyrite was characterized through chemical and XRD-analysis. The point of zero charge, pH_pzc was determined using the batch equilibrium technique and was found to be 6.4. The equilibrium time was 30 min at the solution pH of 6.0. The pH influence of Cd(II) adsorption was remarkable and maximum metal uptake was observed at 6.0 which is closer to pH_pzc. Under this weakly acidic condition Cd(II) ions are responsible for adsorption. Concentration dependence of metal uptake indicates that saturation of pyrite surface by adsorbate occurs at an initial Cd(II) concentration of 350 mg/L and the corresponding metal uptake was 576.5 mg/L of −150 mesh size pyrite at pH 6.0 and 30 °C. Particle size affects the adsorption capacity to a great extent and a decrease in particle diameter enhances metal uptake. The effect of temperature on adsorption performance reveals that the effective temperature for Cd(II) adsorption is 30 °C. The empirical Freundlich isotherm was applied to represent the adsorption process, which fits the experimental data quite well. The work reveals that natural pyrite is a very good choice as an adsorbent for the removal of toxic metals from industrial wastewater and bears significant industrial implications.     

Solvent Extraction Studies for Separation of Zn(II) and Mn(II) from Spent Batteries Leach Solutions

This study aims at assessing the possibility of using solvent extraction processes for separating Zn(II) and Mn(II) dissolved in aqueous solutions obtained by acid bioleaching of spent alkaline and Zn-C batteries. In this context, Cyanex 272 and DEHPA were tested as extractant agents, and the former was shown to have better performance. Hence, the effect of four factors (equilibrium pH, extractant concentration, A/O ratio, and temperature) into three response variables (extraction efficiency of Zn, Y_Zn; extraction efficiency of Mn, Y_Mn; separation factor, β) were tested according to a full factorial design (2⁴) with two replicated center points. Our study revealed that Y_Zn depends mainly on the extractant concentration, Y_Mn on the equilibrium pH and β on the equilibrium pH, extractant concentration, and A/O ratio as well as on second and third order interactions. One extraction step is sufficient to reach high extraction of zinc in synthetic solutions, but two stages were required for real leaching liquor. The extraction kinetics is fast (less than 15 min) for both metals, even when real liquor was tested. The organic solvent can be efficiently recovered using a stripping solution of H₂SO₄ 1 M and thus the process can be considered environmentally sustainable.     

pH Dependent formations of dinuclear molybdenum(V) and incomplete cubane molybdenum(IV) complexes with nitrilotriacetate

Nitrilotriacetato oxomolybdenum(V) dinuclear complex (NH₄)₄[cis-Mo₂O₄(nta)₂] · 7H₂O (1) (H₃nta = nitrilotriacetic acid) and its incomplete cubane-type trinuclear molybdenum(IV) complex [Mo₃O(OH)₃(Hnta)₃] · Cl · 3H₂O (2) are isolated in a weak acidic and an acidic solutions, respectively (pH 4.5 and 1.0). The nitrilotriacetate ligand in the anion 1 or the cation 2 displays tridentate mode through the nitrogen atom and the oxygen atoms of β-carboxy groups. Unusual protonations of bridged oxygen atoms in 2 have not effect on the skeleton of molybdenum(IV) cap Mo₃O unit. There are obvious dissociations of molybdenum(V) complexes based on ¹³C NMR observations in solution.     

Conformational Transitions of the Amyloid-β Peptide Upon Copper(II) Binding and pH Changes

Amyloid-β (Aβ) is a natively unfolded peptide found in all Alzheimer's disease patients as the major component of fibrillar plaques, which are recognized as an important pathological hallmark in Alzheimer's disease. The binding of copper to Aβ increases its neurotoxicity, as Cu²⁺ causes Aβ to become redox active and decreases the lag time associated with Aβ aggregation. In addition, the pH is a major factor that influences both the Aβ aggregation rates and Cu²⁺ binding. Hamiltonian replica exchange molecular dynamics (H-REMD) simulations enable atomistic insights into the effects of pH and Cu²⁺ complexation on the structure and dynamics of Aβ. To study the Aβ_1–42/Cu²⁺ complex, we have developed new force-field parameters for the divalent copper ion ligated by the two histidine residues, His6 and His13, as well as the amine and carbonyl groups of Asp1, in a distorted square-planar geometry. Our comparative simulations reveal that both Cu²⁺ binding and a low pH-mimicking acidosis, linked to inflammatory processes in vivo, accelerate the formation of β-strands in Aβ_1–42 and lead to the stabilization of salt bridges, previously shown to promote Aβ aggregation. The results suggest that Cu²⁺ binding and mild acidic conditions can shift the conformational equilibrium towards aggregation-prone conformers for the monomeric Aβ.     

Efficient co-extraction of strontium and cesium from nitric acid medium by mixtures of di-tert-butylcyclohexano-18-crown-6 and 1,3-di(2-propoxy)calix[4]arene-crown-6 in n-octanol

The co-extraction of strontium and cesium from nitric acid medium by di-tert-butylcyclohexano-18-crown-6 (DtBuCH18C6) and 1,3-di(2-propoxy)calix[4]arene-crown-6 (iPr-C[4]C-6) in n-octanol was studied. The effects of contact time, nitric acid concentration, extractant concentration and temperature on the co-extraction behavior were systematically investigated. Effective extraction of the two metals was achieved under a variety of conditions. The co-extraction from a simulated high-level liquid waste (HLLW) was also conducted, and strontium and cesium could be selectively extracted in the presence of a large number of other metals. Results in this work illustrate the feasibility of partitioning radioactive strontium and cesium simultaneously from HLLW by a mixture of DtBuCH18C6 and iPr-C[4]C-6 in n-octanol.     

Removal of lead,cadmium and zinc from aqueous solutions by precipitation with sodium Di‐(n‐octyl) phosphinate

Sodium di‐(n‐octyl) phosphinate (NaL) was used as a precipitating agent to remove heavy metals from aqueous nitrate solutions. Cadmium, zinc and mixtures of lead, cadmium and zinc were precipitated in the form of PbL_2(s), CdL_2(s), and ZnL_2(s). Lowering the pH of the feed solution reduced the removal of the metals as some of the phosphinate precipitated in the acid form as HL_(S). The removal of lead, cadmium, and zinc, from a solution containing the three metals gave a selectivity in the order Zn > Pb > Cd. Predictions of an equilibrium‐constant model, using measured solubility products of the precipitates and literature values of stability constants, gave metal removals, loss of precipitating agent, and equilibrium pH in good agreement with measured values.     

Pilot plant investigation on petrochemical wastewater treatmentfor the removal of copper and chromium with the objective of reuse

There has been great demand for development of technologies that remove toxic heavy metal ions from wastewater. Chemical precipitation operation is known to remove heavy metal ions from water. In this study applicability of alkaline reagents such as Ca(OH)₂ (lime) and NaOH (caustic soda) in removing copper and chromium ions were evaluated. Separation of heavy metals such as chromium compounds from petrochemical industries' cooling water wastes was achieved by conversion of hexavalent chromium, Cr(VI), to trivalent chromium, Cr(III). Maximum conversion occurred in the pH range of 2.0 and 2.3, adjusted by ferrous sulfate and sulfuric acid. Maximum precipitation of Cr(III) occurred at pH 8.7 with addition of Ca(OH)₂, followed by mixing and 2-h sedimentation. At the end, the concentration of chromate was reduced from 30 ppm to 0.01 ppm. In the case of copper, which is found in the form of cupro-ammonia in ammonia plant wastes, it was observed that the presence of ammonia in wastewater prevents effective chemical precipitation. Therefore, the quantity of ammonia was reduced by aeration. The optimum aeration rate was determined to be 70 L/min, and it was found that ammonia concentration reached equilibrium after 5.0 h o f aeration. Furthermore, hydroxide and carbonate methods were evaluated with respect to precipitation of heavy metals at bench scale, and the former was selected as the method of choice. The results obtained in the Jar test were then applied to pilot scale, and it was determined that the optimum pH for maximum copper precipitation was about 12.0 for both lime and caustic soda used in the hydroxide precipitation method. Lime was preferred due to economics and its high speed of precipitation. Finally, using established methods described here, the concentration of copper followed by coagulation with lime, mixing, 2-h sedimentation and filtration through Whatman 0.45 Am filters was reduced from 48.51 mg/L to 0.694 mg/L, which is below the environmental standards for water resources.     

Solution equilibrium characteristics of electroless copper deposition on thermally-activated palladium-catalysed polyimide substrates

Solution equilibrium characteristics of two electroless copper baths containing EDTA and tartrate as the complexing agents were studied as functions of pH. Equilibrium diagrams were constructed for both Cu-tartrate and Cu-EDTA systems. It was determined that copper is chiefly complexed as Cu2L2 in acidic conditions and as Cu(OH)2L2–4 in alkaline conditions in the tartrate bath, and as CuA–2 in the EDTA bath, where L and A are the complexing tartrate and EDTA ligands, respectively. Electroless copper deposition rates were studied from a tartrate bath on thermally activated palladium-catalysed polyimide substrates as functions of copper and formaldehyde concentrations, and pH.     

Electrochemical study of the Eu(III)/Eu(II) system in molten fluoride media

The electrochemical behaviour of the Eu(III)/Eu(II) system was examined in the molten eutectic LiF–CaF₂ on a molybdenum electrode, using cyclic voltammetry, square wave voltammetry and chronopotentiometry. It was observed that EuF₃ is partly reduced into EuF₂ at the operating temperatures (1073–1143 K). The electrochemical study allowed to calculate both the equilibrium constant and the formal standard potential of the Eu(III)/Eu(II) system. The reaction is limited by the diffusion of the species in the solution; their diffusion coefficients were calculated at different temperatures and the values obey Arrhenius’ law. The second system Eu(II)/Eu takes place out of the electrochemical window on an inert molybdenum electrode, which inhibits the extraction of Eu species from the salt on such a substrate.     

Voltammetric characterization of the self-assembled monolayer (SAM) of octabutylthiophthalocyaninatoiron(II): a potential electrochemical sensor

The fabrication of a self-assembled monolayer (SAM) of 2,3,9,10,16,17,23,24-octa (butylthio)-phthalocyaninatoiron(II) [FePc(SBu)₈] on gold electrode is described. The integrity of the SAM, with respect to its ability to block certain Faradaic processes, is interrogated using cyclic voltammetric experiments in aqueous solutions. The experiments show that this SAM provide an excellent blocking capability to the Faradaic processes emanating from gold surface oxidation, underpotential deposition (UPD) of copper and redox chemistry of Fe(NH₄)(SO₄)₂ in HClO₄. It is revealed by cyclic voltammetry that an ill-defined reversible couple of the SAM of FePc(SBu)₈ can be greatly improved by a simple repetitive cycling of the modified electrode in a DMF solution containing TBAP within a short space of time (ca. 2 min). This ‘activation’ process provides good information concerning the surface coverage and orientation of the monolayer. The reversible redox wave shows a potential shift of about −57 mV per pH in the pH range of 2-9. A preliminary investigation indicates that FePc(SBu)₈-SAM modified gold electrode shows electrocatalytic activity toward the oxidation of l-cysteine in acidic medium. The monolayer is stable and easily reproducible. However, due to its susceptibility to destruction via oxidative and reductive desorptions, its potential application as an electrochemical sensor would be much better in acidic and neutral than alkaline environments.     

Some aspects of the electrochemistry of the flotation of pyrrhotite

The iron sulfide mineral, pyrrhotite (Fe_(1–x)S), has long been known to be more difficult to recover by flotation from alkaline slurries than many other base metal sulfide minerals. This paper summarizes the results of an electrochemical study of the surface reactions that occur during the flotation of nickeliferous pyrrhotite in the recovery of nickel and the platinum group metals. Mixed potential measurements conducted with natural pyrrhotite electrodes in various stages of an operating flotation plant showed that the mineral potential is positive to the equilibrium potential of the xanthate/dixanthogen couple. Similar results were obtained during batch flotation experiments and in synthetic solutions in the laboratory. Cyclic voltammetric and potentiostatic current/time transient experiments were used to investigate the oxidation of pyrrhotite under various conditions. In addition, the reduction of oxygen, the reaction of copper ions and the oxidation of xanthate ions at the mineral surface were investigated. The formation of dixanthogen on pyrrhotite surfaces is thermodynamically favourable in plant flotation slurries. However the interaction with xanthate at pH values above 7 is inhibited by a surface species formed during the conditioning prior to xanthate addition. In acidic solutions copper ions react readily with pyrrhotite to form a species, possibly CuS that can be oxidized at potentials above 0.4 V. At pH 9 this species does not form and there is no electrochemical reaction between pyrrhotite and copper ions. The beneficial effects of copper ions to flotation performance appear to be related to an enhancement of the oxidation of xanthate.     

Adsorption of copper(II) and EDTA‐chelated copper(II) onto granular activated carbons

Waste streams generated by electroless copper plating in the printed circuit boards manufacturing industry often contain copper complexed by strong chelating agents such as EDTA. The consequence of metal complexation by chelating agents is that alternative treatment to chemical precipitation is often necessary to achieve the low metal concentrations required by increasingly stringent environmental regulations. This paper examines the feasibility of using activated carbon to remove EDTA‐chelated copper(II) species as well as free copper(II) ions from aqueous solution. The adsorption characteristics of copper(II) and EDTA‐chelated copper(II) on two granular activated carbons prepared from coal and coconut shell were evaluated. Adsorption equilibrium data of copper(II) on the two carbons corresponded well to the Langmuir model. The coconut shell‐based carbon exhibited a greater adsorption capacity for copper(II) than the coal‐based carbon under similar experimental conditions. Solution pH had a considerable influence on copper(II) adsorption by the two carbons. Low adsorption levels of copper(II) at pH 3 and high adsorption levels in the pH range of 4–6 were observed. However, a reverse adsorption trend was observed when the chelating agent EDTA was added to the copper(II) solution. Adsorption of EDTA‐chelated copper(II) by the two carbons was higher at pH 3 than at pH 6. The contrasting adsorption behaviour of copper(II) ions and EDTA‐chelated copper(II) species can be readily explained in terms of electrostatic interaction in that solution pH influences the surface charge of the carbons as well as the charge property of copper(II) ions and EDTA‐chelated copper(II) species. © 2000 Society of Chemical Industry