乳状液膜法分离富集废旧镍镉电池中的镉

该文介绍了乳状液膜法分离富集废旧镍镉电池中的镉离子。乳状液膜主要由溶剂(煤油)、表面活性剂(Span80)、载体〔二(2-乙基己基)膦酸,P204〕和内水相氨水组成。对影响镉离子渗透和分离过程的重要变量进行了考察,分析了乳状液膜的载体体积分数、外水相pH、搅拌时间、乳水比(乳液与外水相体积比)及Span80体积分数对镍镉分离效果的影响,从而选择出最佳的分离条件为:φ(P204)=4.4%,φ(Span80)=8.8%,pH=5.5,乳水比0.5,搅拌时间10min。用此乳状液膜进行100L反应釜的工业放大实验,镉的迁移率可达93.3%,而镍的迁移率仅为14.6%。     

Zinc and Copper Separation through an Emulsion Liquid Membrane Containing Di‐(2‐Ethylhexyl) Phosphoric Acid as a Carrier

The separation of zinc and copper ions from sulfuric acid solutions by an emulsion liquid membrane (ELM), using di‐(2‐ethylhexyl) phosphoric acid (D2EHPA) as a carrier, has been investigated. The batch extraction of zinc and copper was carried out while varying a selection of experimental conditions, i.e., stirring speed, treatment ratio, concentrations of metal ions in the feed phase, carrier and Span 80 concentration in the membrane, and internal phase concentration. The results obtained demonstrate the effectiveness of D2EHPA as a carrier for the separation of zinc and copper from sulfuric acid media using an ELM. An increase of the D2EHPA concentration beyond 2 vol.‐% does not result in the improved extraction of zinc because the viscosities of the membrane and emulsion have a trend to increase for higher carrier concentrations. It was found that the extraction rate of copper was affected by the carrier concentration in the liquid membrane and by the pH and metal content in the external phase. A 3 vol.‐% concentration of surfactant in the organic phase was required to stabilize the emulsion. The number of stages required for the extraction of zinc and copper by an ELM was determined from McCabe‐Thiele plots.     

Separation of Ni(II) and Cd(II) Ions with Supported Liquid Membranes (SLM) using D2EHPA as a Carrier

Separation of nickel(II) and cadmium(II) ions from sulphate solution with use of supported liquid membranes (SLM) has been studied. Di(2-ethylhexyl)phosphoric acid (D2EHPA) dissolved in kerosene was used as the ion carrier. Obtained data were compared with data from polymer inclusion membranes (PIM) experiments. It was shown that use of SLM membranes enables separation of Ni(II) and Cd(II) ions. Experimental results data show that faster transport and higher recovery factor values were obtained for supported liquid membranes.     

Separation of di- and tripeptides with solvent extraction and an emulsion liquid membrane

The extraction equilibria of various di- and tripeptides with di-2-ethylhexylphosphoric acid (D2EHPA) were studied at low pH values. The complex extracted to organic phase consisted of one molecule of peptide and two molecules of D2EHPA dimer. The extraction constants of the peptides correlated well with the distribution coefficients of peptides between 1-octanol and water, which is a measure of hydrophobicity. The permeation rates of peptides through an emulsion liquid membrane were examined by using D2EHPA as a carrier, Span 80 as an emulsifier and kerosene as a diluent. The rates varied considerably with peptide type, depending upon the hydrophobicity.     

Recovery of cadmium from a zinc hydrometallurgical leachate using reactive emulsion liquid membrane technology

A new emulsion liquid membrane process using 3,5‐diisopropylsalicylic acid (DIPSA) and triisobutylphosphine sulfide (TIBPS) as carriers, and ammonium sulfide (NH₄)₂S as precipitant is described. The reactive nature of sulfide ions with extracted cadmium ions in the internal aqueous phase significantly increases cadmium recovery and minimizes zinc impurities. The new process is applied to the enrichment of a low concentration of cadmium ions from a solution containing a high concentration of zinc ions. Under optimum operating conditions, a single stage process produced a cadmium recovery of 98% at a cadmium sulfide content of 99.6%. The results are encouraging for potential applications in zinc hydrometallurgy for recovery of cadmium from sulfuric acid leaching solution of zinc ores. Copyright © 2004 Society of Chemical Industry     

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.     

Extraction of cadmium from solutions containing various heavy metal ions by Amberlite LA-2

In present study, selective extraction of cadmium from acidic leach solutions, containing various heavy metal ions, by emulsion liquid membrane (ELM) is studied. For this reason, the zinc plant copper cake was leached with sulfuric acid and main acidic leach solution containing Zn(II), Cu(II), Fe(II), Cd(II), Co(II) and Ni(II) ions was obtained. After Zn(II), Cu(II), Fe(II) and Cd(II) ions in the acidic leach solution were separated, the important parameters influencing the extent of cadmium extraction were investigated and optimum conditions were determined. Cadmium extraction was influenced by number of parameters like initial metal ion concentration, mixing speed, phase ratio, extractant concentration, surfactant concentration, the stripping solution type and concentration, and the feed solution acid concentration. The optimum values of parameter above mentioned were used and cadmium in the acidic leach solution containing 650 mg Cd/L, 365 mg Co/L, 535 mg Ni/L, and 1260 mg Zn/L was almost completely extracted within 10 min. The results showed that it is possible to extract 99% of cadmium after 10 min contact time by using ELM from aqueous solutions, containing Fe(II), Al(III), Cu(II), Zn(II), Pb(II), Co(II) and Ni(II) ions, at the optimum operating conditions.     

Cobalt removal from waste‐water by means of supported liquid membranes

BACKGROUND: Supported liquid membranes (SLM) are an alternative technique to remove and recover metals from diluted process solutions and waste‐water. In the present work, the removal of Co(II) from a synthetic CoSO₄ solution containing initial amounts of cobalt(II) in the range 100–200 ppm (0.1–0.2 g dm^?3) has been studied on a pilot scale. By performing batch equilibrium experiments, the optimal settings, i.e. the composition of the organic phase, the pH of the feed, the type and concentration of the stripping agent were determined. RESULTS: It is shown that the equilibrium characteristics of a synergistic extractant mixture containing di‐2‐ethyl‐hexylphosphoric acid (D2EHPA) and 5‐dodecylsalicylaldoxime (LIX 860‐I) are superior to D2EHPA. Both hydrochloric acid and sulfuric acid have been evaluated as stripping solutions in liquid–liquid extraction tests and as the receiving phase in a SLM configuration. Although equilibrium tests showed no difference in stripping characteristics between both chemicals, it was observed that in a SLM configuration the stability of the system when hydrochloric acid is used is poor. With a commercially available SLM module (Liqui‐Cel Extra‐Flow 4 × 28) having a surface area of 19 m², a steady Co(II) flux of 0.140 gm^?2h^?1 has been obtained at influent concentrations of cobalt between 100 and 200 ppm with 3 mol dm^?3 sulfuric acid as stripping phase. CONCLUSIONS: The results obtained show that a supported liquid membrane containing a synergistic mixture of LIX 860‐I and D2EHPA gives the possibility of recovering cobalt from dilute solutions. Copyright © 2008 Society of Chemical Industry     

乳状液膜分离提取荷叶中3种生物碱

建立了用W/O型乳状液膜分离提取荷叶中3种生物碱——N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的方法。通过对迁移时间、表面活性剂Span 80用量、载体D2EHPA浓度、油内比、乳水比和内水相盐酸浓度的优化,获得了高效的液膜体系,为:迁移时间2.5 min,表面活性剂Span 80的质量分数为3.0%,载体D2EHPA的浓度为0.01 mol/L,油内比为10∶6,乳水比为10∶60,内水相盐酸浓度为0.2 mol/L。在优化的实验条件下,对荷叶中3种生物碱N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的萃取率分别达到了95.6%、100%和97.9%,相应的富集因子依次为8.73、8.50和8.04。说明该乳状液膜体系能够很好地分离提取荷叶中的N-去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱。     

Liquid Emulsion Membrane (LEM) Process for Vanadium (IV) Enrichment: Process Intensification

Abstract

A liquid emulsion membrane (LEM) system for vanadium (IV) transport has been designed using di‐2‐ethylhexyl phosphoric acid (D2EHPA), dissolved in n‐dodecane as carrier. The selection of extractant, D2EHPA, was made on the basis of conventional liquid‐liquid extraction studies. The work has been undertaken by first carrying out liquid‐liquid extraction studies for vanadium (IV) to get stoichiometric constant (n), and equilibrium constant (K_ex), which are important for process design.

Transport experiments were carried out at low vanadium (IV) concentration (ppm level). The studies on liquid emulsion membrane included i) the influence of process parameters i.e. feed phase pH, speed of agitation, treat ratio, residence time and ii) emulsion preparation study i.e., organic solvent, extractant concentration, surfactant concentration, internal strip phase concentration. When the strip phase concentration was 2 mol/dm³ (H₂SO₄) and feed phase pH 3 better extraction of vanadium was obtained. Higher V_m/V₁ gave higher extraction of vanadium (IV). A simplified, design engineer friendly model was developed.     

Separation and Recovery of Cadmium from Acidic Leach Liquors of Spent Ni-Cd Batteries using Molten Paraffin Wax Solvent Extraction

Separation and recovery of cadmium from sulphate leach liquors of spent Ni-Cd batteries using TBP, HDEHP (D2EHPA), EHEHPA (PC 88A or Ionquest 801 or P507) have been investigated in a laboratory scale. Cadmium can be extracted into paraffin waxes from acidic solutions in the temperature range of 55–75°C using different extractants. The influence of various parameters on extraction and stripping were studied in detail. The feasibility of separation of cadmium from nickel using these extractants and their combination was studied. The mixture extractant of EHEHPA and TBP was found to be the best for the separation of Cd and Ni. A three-stage counter-current extraction simulation test for cadmium extraction was carried out at an A/O phase ratio of 4:1 and pH 2.5. More than 99.97% Cd²⁺ was extracted with the organic phase containing 0.7 mol L^?1 EHEHPA and 0.5 mol L^?1 TBP, while more than 99.97% nickel was left in the raffinate. The cadmium loaded organic phase was stripped with 2 mol L^?1 hydrochloric acid in the stripping stage. The present method can be applied to the separation and recovery of cadmium from acidic leach liquor of spent Ni-Cd batteries or related waste liquor.     

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.     

Recovery and Concentration of Metal Ions. II Multimembrane Hybrid System

Abstract

The multimembrane hybrid system (MHS) has been developed and used for the transportation and separation of divalent metal ions from multicomponent solutions. The system consists of three membranes in series

ion-exchange membrane | liquid membrane | ion-exchange membrane

The experiments were performed with liquid membranes composed of di(2-ethylhexyl)phosphoric acid in kerosene and Nafion-120 perfluorosulfonic acid polymer membranes. The fluxes and separation characteristics have been determined for MHS separating a solution of Zn(II), Mn(II), Cu(II), and Ni(II) sulfates as the feed phase, and the strip phase containing sulfuric acid. The results of competitive permeation experiments have shown the selectivity order Zn(II) > Mn(II) > Cu(II) ? Co(II), Ni(II). High separation coefficients were found for Zn(II), Cu(II), and Mn(II) compared to Ni(II) and Co(II).     

EFFECTS OF THE EMULSIFIER IN COPPER EXTRACTION BY LIX64N-SPAN 80 LIQUID SURFACTANT MEMBRANES

Span 80-LIX65N-LIX63 liquid surfactant membranes (LSMs) were used to extract copper from sulfate solutions at a pH of 2.0. The physico-chemical effects of Span 80 (sorbitan monooleate) were investigated with the aid of measurements of emulsion stability (as determined by leakage of K ions from the internal to the external phase), membrane phase viscosity, emulsion viscosity, and inter-facial tension. As the concentration of Span 80 was increased, copper extraction rate at first increased, rose through a maximum, and then decreased. The initial increase corresponded to a significant improvement in the stability of emulsion globules. Inter-facial tension measurements indicated that in order to achieve stable emulsion globules, a high adsorption density of the emulsi-fier at the emulsion interfaces in a LSM system was needed. It was further shown that a bulk phase emulsifier-extractant interaction at high extractant concentrations had an adverse effect on the stability of emulsion globules by removing emulsifier molecules from the interface. However, the high emulsifier adsorption density required for emulsion stability led to a decrease in the extractant concentration at the interface and therefore reduced the rate of copper complexation at the membrane phase/external phase interface. In addition, the viscosity measurements suggested that the decrease in metal extraction at emulsifier concentrations above the optimum might also be partly a result of the restricted movement of the internal phase droplets, an increase in the inter-facial viscosity, and/or a decrease in the membrane phase/external phase interfacial area.     

Emulsion liquid membrane for selective extraction of bismuth from nitrate medium

The novelty of this work is the selective extraction of bismuth ions from nitrate medium by emulsion liquid membrane. Di(2-ethylhexyl)phosphoric acid was used as extractant of bismuth ions from nitrate medium by emulsion liquid membrane, and Triton X-100 was used as the biodegradable surfactant in n-pantanol n-pentanol bulk membrane. The extraction of bismuth ions was evaluated by the yield of extraction. The experimental parameters were evaluated and were optimized. They included the ratio of di(2-ethylhexyl)phosphoric acid concentration to the concentration of /Triton X-100 concentration (1.0: 0.5% w/w), nature of diluents (n-pentanol), nature and concentration of the stripping solution (sulfuric acid, 0.5M), stirring speed (1,800 rpm) and equilibrium time of extraction (20min), initial feed solution of bismuth (350 ppm) and the volume ratio of the internal stripping phase to the membrane phase (14 times). The experimental parameters of kinetic extraction revealed that the bismuth ions were extracted at 100% 97%.     

Membrane stability and enrichment of nickel in the liquid emulsion membrane process

The parameters affecting the stability of a liquid emulsion membrane (LEM) for enrichment of nickel were studied. The liquid membrane is made up of a carrier (di‐2‐ethylhexylphosphoric acid), organic diluent and an emulsifying agent (sorbitan monooleate). Swelling of the internal phase during extraction results in breakage of the emulsion. The role of pH is very important in the LEM process for extraction of nickel. A significant decrease in swelling was observed by maintaining the pH of the feed phase constant during extraction. A lower osmotic pressure difference between the external and internal phase brings about lower changes in the swelling and membrane breakdown. © 2000 Society of Chemical Industry     

Process for the Recovery of Cobalt and Nickel from Sulphate Leach Liquors with Saponified Cyanex 272 and D2EHPA

Abstract

In this paper, a process is reported for the recovery of cobalt and nickel from copper raffinate solutions using partially saponified Cyanex 272 and D2EHPA as the extractants. The aqueous feed contains 1.65 g/L cobalt and 16.42 g/L nickel. More than 99.9% cobalt separation was achieved with 0.13 M Cyanex 272 (60% neutralized with alkali) in two counter‐current stages at an aqueous to organic phase ratio of 1.1:1. Co‐extraction of nickel was 0.18% only. Stripping of cobalt from a loaded organic phase was carried out with synthetic spent electrolyte solution at an organic to aqueous phase ratio of 2.5 in two counter‐current stages to generate a pregnant electrolyte solution to produce cobalt metal by electrowinning. Similarly, optimum conditions for nickel extraction with 60% neutralized 1 M D2EHPA at O/A ratio of 1.4 in 2 two stages and stripping of metal with synthetic spent electrolyte at O/A ratio of 1.6 in two stages were standardized. Extraction and stripping efficiencies were >99% and the flowsheet of the process is demonstrated.     

Separation of Nickel(II) and Cadmium(II) with Ion-Exchange Process

Separation of nickel(II) and cadmium(II) ions from sulphate solution has been studied. The solutions of Ni(II) and Cd(II) have been treated with different exchange resins: Lewatit OC-1026, Lewatit TP-207, and Lewatit MonoPlus SP 112. Data obtained from the ion-exchange process was compared with data from the supported liquid membrane experiment. It was shown that the use of the supported liquid membrane process enables separation of investigated ions. In this process the highest recovery factor was obtained. The best separation of metal ions was obtained for the ion-exchange process with Lewatit OC 1026.     

乳状液膜法提取红土矿浸出液中镍

采用Span-80-TBP-NH3×H2O体系乳状液膜法提取红土矿浸出液中的Ni(II),研究了膜相组成、内水相试剂浓度、膜相与内水相体积比(油内比)、乳水体积比对镍离子提取效果的影响. 采用微分法测定并比较了反应的浓度级数nC和时间级数nt. 结果表明,膜相组成为Span-80:TBP:石蜡:煤油(体积比)=5:4:2:89、内水相氨水浓度为2 mol/L、油内比为1:1、乳水体积比为1:3、外水相硫酸浓度为0.3 mol/L的条件下,经过二级提取后,红土矿浸出液中Ni(II)去除率可达80%;由浓度级数(nC=1)小于时间级数(nt=2.8)可知,该过程为化学反应控制过程.     

乳化液膜法脱除磷酸中镉的研究

镉是磷酸中的有害杂质之一,其对环境的污染和对人体的毒害日趋严重,所以必须控制磷酸中镉等有害杂质的含量。用乳化液膜法除去磷酸中的镉,采用单因素实验法,重点考察了表面活性剂Span-80,T151,T154及用量、萃取剂TBP,P204及用量、萃取时间对脱除磷酸中镉的影响。结果显示：表面活性剂T154用量为2.0 mL及萃取剂P204用量为2.0 mL时,乳化液膜具有较好的稳定性,且萃取时间为15 min时,从磷酸中除镉的效果最优。