Solvent Extraction Of Cu Research Articles

Efficient ammoximation and regeneration of degraded hydroxyoxime CP150 over TS-1 molecular sieve/H2O2 system and reuse for solvent extraction of Cu(II)

The regeneration of failed hydroxyoxime extractants in the copper hydrometallurgy industry is crucial. However, the existing regeneration system has limitations in terms of operability, yield, and environmental friendliness, which restricts its industrial application. This paper presents a clean one-pot ammoximation regeneration system for the in-situ preparation of hydroxylamine for the oximation of aldehydes, catalyzed by TS-1 with NH3 and H2O2. It was tailored based on the characteristics of the degraded organic phase produced by long-term operation at the copper solvent extraction site. The developed system demonstrates an excellent regeneration conversion efficiency (>90%) for the degraded copper-extracted organic phase. Following regeneration, the copper extraction efficiency of the organic phase reaches the same level as the fresh organic phase and maintains good copper extraction stability even after multiple extraction cycles. Moreover, the phase separation performance was improved through optimization. This regeneration system meets the demand for environmentally friendly and resourceful utilization of degraded waste organic phases in copper extraction systems.

Selective solvent extraction of Cu(II) from aqueous solutions using an acyl-based thiourea: Extraction study and DFT analysis of reaction mechanism

Currently, copper-containing wastewater poses a great threat to the surrounding living areas due to its toxic and non-biodegradable properties. The solvent extraction technique for removing copper(II) from wastewater has been identified as a straightforward and effective method. In this study, novel acyl-containing thiourea extractants, namely N-benzoyl-N′,N′-diethyl thiourea (BDETU), N-benzoyl-N′,N′-dibutyl thiourea (BDBTU) and N-benzoyl-N′-butyl thiourea (BBTU), were prepared and employed as extractants for the efficient removal of Cu(II) ions from aqueous solution. Experimental results indicated that the highest extraction efficiency of Cu(II) by BDETU was 99.4% under the optimal extraction conditions, which surpassed the performance of both BDBTU and BBTU. The reusability and selectivity experiments further confirmed the enduring high extraction efficiency of BDETU over 8 consecutive extraction-stripping cycles. These findings suggest that BDETU exhibits promising prospects for wide-ranging applications owing to its excellent extraction stability and selectivity. The investigation into the extraction mechanism of Cu(II) with acyl thiourea molecule revealed that one mole of Cu(II) was extracted with two moles of extractants through the formation of Cu-O-C and Cu-S-C bonds.

A near-zero waste process for the full-component utilization of deep-sea polymetallic nodules based on reductive leaching with SO2 followed by separation and recovery

Recovery of critical metals from marine minerals is a promising option to ensure the sustainable supply of critical metals, but existing recovery processes suffer from technical bottlenecks in terms of low resource utilization and large waste discharge. This paper presents a complete hydrometallurgical route for the full-component utilization of deep-sea polymetallic nodules (DPN). Leaching experiments were first carried out in the presence of SO2 because cheap SO2 can destroy the original mineral structure based on a reductive mechanism. The leaching efficiencies of Ni, Co, Mn, Cu, La, Ce, and Fe were reached 99.2%, 99.3%, 98.7%, 95.9%, 95.3%, 95.4%, and 91.4%, respectively, under the optimal conditions of 30 °C, L/S ratio of 6:1 mL/g, H2SO4 dosage of 37.5 wt%. The downstream process aimed at the sequential recycling of metal ions from the pregnant leach solution (PLS) consists of Fe recovery by the hematite process, selective solvent extraction of Cu and rare earth elements (REEs), co-extraction of Ni/Co/Mn, and Mn electrowinning. As a result, high-grade hematite (60 wt% of Fe), industrial-grade CuSO4, mixed rare earth oxides, battery-grade (Ni, Co, Mn)SO4 solution, and electrolytic manganese were obtained. During the whole process, the recovery efficiency of Ni, Co, Mn, Cu, La, Ce, and Fe reached 97.1%, 97.1%, 96.9%, 91.5%, 91.1%, 91.1%, and 91.3%, respectively. Since the hydrometallurgical process achieves the resource utilization of all the DPN constituents, it has the advantages of near-zero waste and low energy consumption.

Spectrophotometric Determination of Fe(II) and Fe(III) Using 5-(4-Ethylphenyl azo ) 2-Hydroxybenzaldehyde Oxime Reagent

Spectrophotometric Determination of Fe(II) and Fe(III) Using 5-(4-Ethylphenyl azo ) 2-Hydroxybenzaldehyde Oxime Reagent

New diazo-containing phenolic oximes: structural characterization, computationalstudies, and solvent extraction of Cu(II), Ni(II), and Zn(II) ions

In the current study, four new phenolic oxime ligands (HL1ox-HL4ox) containing diazo groups (-N$=$N-) were synthesized and used for liquid-liquid extraction of heavy metal ions [Cu(II), Ni(II), and Zn(II)]. The new compounds were characterized by analytical and spectroscopic methods. Solid-state structures of HL1ox-HL3ox were determined by single-crystal X-ray diffraction studies. Hirshfeld surface analysis of the compounds was performed to determine the contribution of different intermolecular contacts to the stability of the structures. The HL1ox-HL4ox ligands showed higher extraction performance for Cu(II) ion than Ni(II) and Zn(II) ions. The effect of pH on extraction capacity was investigated and the oxime compounds showed high extraction capacity at low pH values. The effects of the substitute groups (at the meta position of the phenol ring) on the extraction were investigated. Within the oxime ligands, the HL3ox compound exhibited higher extraction capacity for Cu(II) ions. The better extraction value of HL3ox is attributed to the weak hydrogen bond type interactions, which result in more stable complexes.

Recovery of base metals, silicon and fluoride ions from mobile phone printed circuit boards after leaching with hydrogen fluoride and hydrogen peroxide mixtures

The recovery of copper, nickel, zinc, silicon, iron, aluminum, tin and fluoride ions from fluoride leach liquors of non-ground printed circuit boards (PCBs) from mobile phones is described in detail. These PCBs were leached with HF + H2O2 mixtures after previous treatment with 6 mol L−1 NaOH (removal of the solder mask). A combination of solvent extraction (SX) and precipitation techniques was used. 99.5 wt% zinc, copper and nickel, in this order, were extracted in one stage (Zn, Ni) or two stages (Cu) with di-2-ethylhexylphosphoric acid (D2EHPA) diluted in kerosene (25 °C, A/O = 1 v/v) after adjusting the pH of the leachate. They were easily stripped by aqueous H2SO4. Iron, aluminum and tin did not interfere because they were masked by fluoride ions. Iron and aluminum were precipitated together as Na3FeF6 + Na3AlF6 by careful addition of aqueous NaOH. Silicon, tin and fluoride ions were recovered together (Na2SiF6 + Na2SnF6 + NaF) by careful evaporation of the aqueous solution after SX of nickel. The tin salt was leached from this solid by absolute ethanol. High HF concentration (10 mol L−1) in the leachant affected SX of Cu(II) and precipitation of iron/aluminum flurocomplexes since some NaF partially precipitated at acidic pH.

A comparison of the use of commercial and diluent free LIX84I in poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP)-based polymer inclusion membranes for the extraction and transport of Cu(II)

The active component of the commercial extractant LIX84I, i.e. 2-hydroxy-5-nonylacetophenone (HNAPO), is usually below 50 wt%. The separation performance of polymer inclusion membranes (PIMs) generally increases with increasing the concentration of their liquid phase, consisting of the extractant (e.g., LIX84I) and a possible plasticizer or modifier. However, the use of high concentrations of the membrane liquid phase leads to worsening of the PIM mechanical stability. Therefore, the only way of increasing the concentration of HNAPO in PIMs without affecting their mechanical stability can be based on using diluent free LIX84I with concentration of HNAPO significantly higher than that in commercial LIX84I. This paper reports on a comparison between the performance of PIMs composed of poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) as the base-polymer, commercial or diluent free LIX84I as the extractant and 2-nitrophenyloctyl ether (NPOE) as the plasticizer when used for the extraction and transport of Cu(II) from ammonium sulfate solutions at pH 8.5. The diluent free LIX84I, obtained by a precipitation method, together with commercial LIX84I were characterized by gas chromatography-mass spectrometry and Fourier transform infrared spectroscopy. The percentage of HNAPO was determined by solvent extraction of Cu(II) and found to be 49 wt% and 72 wt% for the commercial and diluent free LIX84I, respectively. A comparative study between commercial and diluent free LIX84I-based PIMs was performed with regards to the extraction and transport of Cu(II) as well as their long term stability. Unexpectedly, the PIMs containing commercial LIX84I performed slightly better than the PIMs containing diluent free LIX84I in terms of extraction and transport rate of Cu(II). A selectivity study showed that both commercial and diluent free LIX84I-based PIMs had good selectivity for Cu(II) in the presence of Zn(II), Mg(II), Ni(II), and Co(II) in ammonium sulfate solutions, although the PIM containing commercial LIX84I was able to separate Cu(II) faster than the one composed of diluent free LIX84I.

Solvent extraction of Cu(II) from sulfate solutions containing Zn(II) and Fe(III) using an interdigital micromixer

Microfluidic solvent extraction of copper from sulfate solution containing Cu2+, Fe3+ and Zn2+ using DZ988N (a mixture of equal volumes of 5-nonylsalicylaldoxime and 2-hydroxy-5-nonyl-acetophenoneoxime) has been conducted for the first time using an interdigital micromixer with 30 channels of 40 μm width. Conventional batch extractions were carried out in parallel for comparison. Effects of the initial pH value of the aqueous phase, concentration of the extractant, and flow rate on the extraction efficiency of Cu2+ have been studied including determination of separation factors (βCu/Fe and βCu/Zn). According to single factor experiments, the optimal extraction parameters were an initial pH value of 1.96, extractant concentration of 15% and an aqueous or organic phase flow rate of 15 mL/min. Under these preferred conditions, copper extraction of 84.05% was achieved with βCu/Fe and βCu/Zn values of 644 and 7417, respectively. Compared with batch extraction, micromixer extraction exhibits faster extraction times, higher extraction efficiency of copper and an improved separation factor between copper and the impurity elements of iron and zinc.In addition, copper extraction isotherms (McCabe Thiele) from copper-only solutions for microfluidic extraction and batch extraction were constructed to determine the number of stages. The results show that the extraction efficiency with microfluidic extraction was better than that of traditional batch extraction. In the microfluidic extraction process, as much as 99% extraction efficiency was achieved in a single stage for the copper-only solution. However, in the corresponding batch extraction process, to get the same extraction efficiency, two stages of extraction were needed.

用Lix984萃取硫铜钴矿浸出液中的铜

用Lix984萃取硫铜钴矿浸出液中的铜

Solvent extraction of Cu, Mo, V, and U from leach solutions of copper ore and flotation tailings

Flotation tailings from copper production are deposits of copper and other valuable metals, such as Mo, V and U. New hydrometallurgical technologies are more economical and open up new possibilities for metal recovery. This work presents results of the study on the extraction of copper by mixed extractant consisting p-toluidine dissolved in toluene. The possibility of simultaneous liquid–liquid extraction of molybdenum and vanadium was examined. D2EHPA solutions was used as extractant, and recovery of individual elements compared for the representative samples of ore and copper flotation tailings. Radiometric methods were applied for process optimization.

Improvement of recovery performance in the solvent extraction of Cu(II) using [bmim][Tf2N] and a β-diketone as extractant and its stripping with supercritical carbon dioxide

This study deals with the improvement of the recovery performance in the solvent extraction of Cu(II) using the ionic liquid [bmim][Tf2N] and the β-diketone 1,1,1-trifluoro-2,4-pentanedione (TFA) as extractant and its stripping with supercritical carbon dioxide.This work describes a modified procedure, which shows better L-L extraction percentages with a decreasing of the concentration of TFA, the contacting time and the volumetric O/A ratio respect to the previously reported tests. Thus, the extraction was implemented with a concentration of TFA in [bmim][Tf2N] equal to 60molm−3, a contacting time of 5min and an O/A ratio equal to 1:7.The stripping of the metal complex from the organic phase was achieved in semi-continuous mode with scCO2. This configuration allowed obtaining a stripping percentage higher than the obtained with a previously tested procedure in batch mode with a consumption of CO2 4.3 times lower than the observed one in previous work.

Ditopic receptors containing urea groups for solvent extraction of Cu(ii) salts.

The ditopic receptor L3 [1-(2-((7-(4-(tert-butyl)benzyl)-1,4,7,10-tetraazacyclododecan-1-yl)methyl)phenyl)-3-(3-nitrophenyl)urea] containing a macrocyclic cyclen unit for Cu(ii)-coordination and a urea moiety for anion binding was designed for recognition of metal salts. The X-ray structure of [CuL3(SO4)] shows that the sulfate anion is involved in cooperative binding via coordination to the metal ion and hydrogen-bonding to the urea unit. This behaviour is similar to that observed for the related receptor L1 [1-(2-((bis(pyridin-2-ylmethyl)amino)methyl)phenyl)-3-(3-nitrophenyl)urea], which forms a dimeric [CuL1(μ-SO4)]2 structure in the solid state. In contrast, the single crystal X-ray structure of [ZnL3(NO3)2] contains a 1 : 2 complex (metal : anion) where one anion coordinates to the metal and the other is hydrogen-bonded to the urea group. Spectrophotometric titrations performed for the [CuL3(OSMe2)]2+ complex indicate that this system is able to bind a wide range of anions with an affinity sequence: MeCO2- > Cl- > H2PO4- > Br- > NO2- > HSO4- > NO3-. Lipophilic analogues of L1 and L3 extract CuSO4 and CuCl2 from water into chloroform with high selectivity over the corresponding Co(ii), Ni(ii) and Zn(ii) salts.

Recovery of high value copper and zinc oxide powder from waste brass pickle liquor by solvent extraction

Solvent extraction of Cu and Zn from spent brass pickle liquor has been carried out using LIX 984N as an extractant. Very high difference in ΔpH1/2 value for the two metals during the extraction indicates the ease of separating them under the appropriate conditions. Based on the bench scale results, metals were separated in a continuous mode using a laboratory scale mixer settler unit from the spent brass pickling solution containing 35kg/m3 Cu, 30kg/m3 Zn, 1.5kg/m3 Fe, 0.75kg/m3 Cr, 0.03kg/m3 Ni and 70kg/m3 H2SO4 with 30% LIX 984N in kerosene. High copper extraction (99.9%) at the phase ratio (O/A) of 2/1 was obtained at the equilibrium pH of 2.5 in a two-stage counter-current extraction process, leaving behind Zn, Cr and Ni in the raffinate. Zinc from the chromium free solution was then quantitatively extracted in three counter-current extraction stages at pH5.5 and O/A=2/1 with negligible co-extraction of nickel. From the respective loaded organic phases, copper and zinc were completely stripped off using 150kg/m3 H2SO4. The stripped solutions of Cu and Zn were utilized for the synthesis of high pure Cu metal powder and ZnO particles by the hydrothermal reduction/precipitation processes. Copper powder was synthesised in an autoclave at 20bar H2 pressure and 423K in 2h. On the other hand ZnO powder (4bar) was prepared from zinc striped solution at pH12 in an autoclave under autogenous pressure at 423K in 2h. The purity and morphology of the as-prepared powders were determined by chemical analysis, XRD and SEM-EDS studies.

Solvent extraction of Cu(II) from sulphuric acid by means of sodium diethyldithiocarbamate and characterization of the formed complex

The present work deals with the extraction of copper(II) from sulphuric acid solutions with sodium diethyldithiocarbamate (SDDT) as the extracting agent, testing six different organic solvents, namely dichloromethane, chloroform, carbon tetrachloride, toluene, xylene and cyclohexane, as diluents. The SDDT-chloroform pair showed to be the most selective in removing the copper cations, and hence was considered throughout the experimental study concerning the effects of operating parameters such as the initial concentration of the extracting agent, the agitation time, the agitation speed and the acid concentration. For an initial Cu(II) concentration of 63 mg/L in a 0.5 M sulphuric acid solution and an extracting agent mass of 20 mg, an extraction percentage around 97.8% and a distribution coefficient of 44.42 were obtained, confirming the good performance of the SDDT-chloroform pair. Different reliable analytical techniques such as thermogravimetric analysis, differential scanning calorimetry, ultraviolet-visible analysis, Fourier transform infrared spectroscopy and elementary analysis were used to demonstrate that the acidity did affect neither the complexing agent nor the formed complex. The obtained results compared reasonably well with reported values in the literature and hence supporting the adopted approach.

Copper(II) sulphate solutions treatment by solvent extraction with Na-Cyanex 272

Cyanex 272 (bis(2,4,4-trimethylpentyl)phosphinic acid) and its sodium salt were used as extractants to treat copper(II) sulphate solutions. Solvent extraction of Cu(II) is more efficient with Na-Cyanex 272 than with its acidic form, and a significant change in pH of the raffinate is observed after extraction. Two mol/dm 3 H 2SO 4 is an effective stripping solution of Cu(II) from the loaded Na-Cyanex 272, and gives 75% of the stripped metal ions in one step. Adsorption parameters show that molecules of Na-Cyanex 272 are populated more densely at the saturated water/toluene interface than Cyanex 272 molecules. Equilibrium and dynamic interfacial tension measurements confirm the interfacial mechanism of Cu(II) extraction and high surface activity of Na-Cyanex 272. Diffusion coefficients estimated for Na-Cyanex 272 are two orders greater than with its acidic form. The differences between both FT-IR and UV/VIS spectra of metal–ligand complexes point out the presence of two types of complex structures depending on the metal–ligand molar ratio (probably planar for 1:1 and tetrahedral for 1:2). Finally, photostability studies show that both extractants are chemically resistant even after contact with H 2SO 4. The results presented in this paper confirm that conditioning of Cyanex 272 greatly improves the efficiency of Cu(II) extraction in comparison to its acidic form.

Efficiency, stoichiometry and structural studies of Cu(II) removal from aqueous solutions using di-2-ethylhexylphosphoric acid and tributylphosphate diluted in soybean oil

Solvent extraction of Cu(II) from aqueous solutions by a soybean oil-based organic solvent (SOS) composing of soybean oil (diluent), di-2-ethylhexylphosphoric acid (extractant) and tributylphosphate (phase modifier) was investigated. Effects of initial Cu(II) concentration in the aqueous phase (25–500 mg/L (0.39–7.88 mM)) and temperature (298–323 K) on the percentage extraction (% E) of Cu(II) were studied. It was found that the initial Cu(II) concentration did not influence % E appreciably and high % E (>98%) was achieved throughout the experimental ranges studied. The % E at various temperatures, on the other hand, decreased consistently with temperature. The loading capacity of SOS (2400 mg/L (37.82 mM)), as well as the stoichiometry (4:1) and structure (inner sphere) of Cu(II)–organic complexes (extracted species) in SOS were also determined. Stripping of Cu(II) from the loaded SOS was investigated with various types (sulfuric acid (H 2SO 4), hydrochloric acid (HCl) and nitric acid (HNO 3)) and concentrations (0.05–2.00 M) of mineral acids. The decreasing order of percentage stripping (% S) of Cu(II) by various types of acids was found to be H 2SO 4 > HCl > HNO 3 throughout different concentrations studied, with H 2SO 4 attaining the highest % S (>99%) at 1.5 M.

Solvent extraction of Cu(I) from waste etch chloride solution using tri-butyl phosphate (TBP) diluted in 1-octanol

Cuprous ion has wide applications in various industries due to its properties to form stable coordination compound of high solubility with different ligands. Compared to extensive R&D work on solvent extraction of cupric ion, the limited work is reported on cuprous ion extraction using organic extractant. Therefore, in the present work, solvent extraction studies have been carried out for the extraction of cuprous ion Cu(I) from chloride solution using extractant tri-butyl phosphate (TBP) diluted in 1-octanol, for application to recover Cu(I) from the etch waste of printed circuit boards (PCBs). Initially, the studies were carried out for the selection of suitable diluent to be used for Cu(I) extraction from chloride solution. The organic 1-octanol was found effective diluent for TBP. The behavior and reaction mechanism of TBP diluted in 1-octanol was also studied for the extraction of Cu(I) from chloride solution. Various process parameters viz. contact time, concentration of chloride ion, hydrochloric acid and extractant, temperature, etc., were also studied. The extractant TBP diluted in 1-octanol was found suitable for the extraction of Cu(I) from the waste chloride solution (containing both Cu(I) and Cu(II)) generated from the plant of PCBs manufacturing. The extraction isotherm plot indicates the requirement of two stages for the complete extraction of Cu(I). The studies revealed the formation of complex [CuCl 2 −·H +·TBP] in the organic phase. The extraction and stripping studies showed the suitability of the TBP diluted in 1-octanol for the recovery of cuprous ion from the waste chloride etch solution of PCBs.

Extraction of Copper(II) by CYANEX 302 in Kerosene from Different Aqueous Media

The solvent extraction of Cu(II) with CYANEX 302 (bis(2,4,4‐trimethylpentyl) monothiophosphinic acid) in kerosene from different aqueous solutions including sulphate, chloride, and nitrate media has been systematically investigated. The effect of various parameters such as the time of equilibration, pH, the extractant and metal concentrations, the temperature, as well as the effect of anions on the extraction process has been studied. An equilibrium equation is proposed assuming that copper was first extracted as Cu2+ followed by reduction of to Cu+ while the CYANEX 302 extractant is correspondingly oxidized. The thermodynamic parameters, free energy (ΔG), enthalpy (ΔH), and entropy (ΔS), have been calculated. The stripping of Cu(II) from loaded organic solutions by using different stripping agents showed that effective stripping is obtained upon using high concentration of nitric acid which oxidizes the extracted Cu(I) to Cu(II).

Synthesis, characterization and structure effects on preconcentration and extraction of N, N′-bis-(salicylaldehydene)-1,4-bis-( p-aminophenoxy) butane towards some divalent cations

Separation with solvent extraction of Cu(II), Co(II) and Ni(II) from aqueous solution using N, N′-bis-(salicylaldehydene)-1,4-bis-( p-aminophenoxy)butane (H 2L) as the new extractant has been studied. The new Schiff base, was synthesized by reaction of 1,4-bis-( p-aminophenoxy)butane and salicylaldehyde. Microanalytical data, elemental analysis, UV–vis 1H NMR and 13C NMR spectra and IR-spectra were used to confirm the structures. The extractability and selectivity of divalent cations was evaluated as a function of relationship between distribution ratios of the metal and pH or ligand concentration. Cu +2 showed the highest extractability and selectivity at pH 7.8, whereas Ni +2 and Co +2 showed at pH 9.2. From the loaded organic phase, Cu(II), Co(II), Ni(II) stripping were carried out in one stage with aqueous acid solution including various concentrations of HCl. The stripping efficiency was found to be quantitative in case of 1.5 M HCl. From quantitative evaluation of the extraction equilibrium data, it has been deduced that the complexes extracted are the simple 1:1 chelates, CuL, CoL, NiL.

Recent advances in the solvent extraction of Cu, Ni, Co

Recent advances in the solvent extraction of Cu, Ni, Co