Simultaneous Transport and Separation of Cu(II) and Zn(II) in Cu-Zn-Co Sulfate Solution by Double Strip Dispersion Hybrid Liquid Membrane (SDHLM)

A double strip dispersion hybrid liquid membrane (SDHLM) was successfully used in the simultaneous extraction and separation of Cu(II), Zn(II), and Co(II) from Cu-Zn-Co dilute feed phase. In the double SDHLM system, Acorga M5640-loaded membrane was placed between the 1st and the 2nd compartment, whereas the mono(2-ethylhexyl) 2-ethylhexyl phosphonate [HEH(EHP)]-loaded membrane was placed between the 1st and the 3rd compartment of the transport cell. The feed solution was filled in the central feed compartment(1st compartment) of the transport cell. The effect of the different experimental variables on separation was examined. The optimum separation conditions were summarized.

An analysis of mass transfer resistances in the double SDHLM system shows that the mass transfer resistance for the diffusion of Zn(II) ions in the microporous membrane phase is dominant and the mass transfer resistances for the diffusion of copper (II) ions in the aqueous boundary layer and in the microporous membrane phase are dominant in comparison with the overall mass transfer resistance. The experiments verify that the double strip dispersion hybrid liquid membrane (SDHLM) possesses the nonequlibrium mass transfer characteristic.     

Synergistic Solvent Extraction and Transport of Zn(II) and Cu(II) across Polymer Inclusion Membranes with a Mixture of TOPO and Aliquat 336

Separation of zinc(II) and copper(II) ions from aqueous solutions by synergistic extraction and transport through polymer inclusion membranes (PIMs) has been investigated. A mixture of trioctylphosphine oxide (TOPO) and trioctymethylammonium chloride (Aliquat 336) was used as a selective extractant as well as an ion carrier in polymer membranes. The effects of hydrochloric acid concentration in the aqueous phase and extractants concentration in the organic phase on the separation process of zinc(II) and copper(II) ions have been studied. Zn(II) ions were successfully separated from Cu(II) ions in solvent extraction process using 0.025 M TOPO and 0.06 M Aliquat 336 in kerosene. Polymer inclusion membranes (PIMs) containing a mixture of TOPO and Aliquat 336 as the ion carrier have been prepared and the facilitated transport of Zn(II) and Cu(II) ions has been studied. The influence of membrane composition on the transport kinetic of Zn(II) and Cu(II) has been evaluated. Zn(II) ions were preferably transported from the aqueous solutions containing Cu(II) and above 87% of Zn(II) ions were effectively recovered from the 0.5 M HCl solution as the source phase through PIM into 0.5 M H₂SO₄ as the stripping phase.     

Transport and separation of cobalt,nickel and copper ions with alamine liquid membranes

The transfer and separation of Co(II), Ni(II) and Cu(II) ions across a flat-sheet supported liquid membrane containing Alamine 336 as the mobile carrier dissolved in kerosene solvent has been investigated. Both the Alamine composition in the organic solution and the hydrochloric acid concentration in the feed solution have a marked effect on Co(II) and Cu(II) transport. A maximum flow of these ions at 50% of Alamine in the diluent was obtained. Ni(II) ion was not transported in the whole range of experimental conditions studied and good separation from Co(II) and Cu(II) could thus be performed. With decreasing hydrochloric acid concentration in the feed solution the separation factor of Cu(II) from Co(II) increases thus decreasing the Cu(II) recuperation factor.     

PC-88A为载体的大块液膜体系Cu(II)传输动力学

采用以2-乙基己基膦酸-2-乙基己基单酯(PC-88A)为载体、CHCl3为膜溶剂的大块液膜分离体系,研究了搅拌速度、载体浓度、体系温度对铜离子迁移的影响. 获得了不同反应温度下的表观反应速率常数,萃取与反萃取表观反应活化能分别为41.97和8.59 kJ/mol. 铜离子的迁移过程可用2个串联的准一级不可逆过程描述,萃取过程化学反应为控速步骤,反萃取过程扩散为控速步骤.     

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.     

Transport of chromium(VI) through a Cyanex 921‐supported liquid membrane from HCl solutions

The transport of chromium(VI) through a flat‐sheet supported liquid membrane containing Cyanex 921 as a carrier has been investigated. The permeation of the metal is investigated as a function of various experimental variables: hydrodynamic conditions, concentration of chromium(VI) and HCl in the feed phase, carrier concentration and diluent in the membrane and strippant concentration in the stripping phase. The mass transfer coefficient and the thickness of the aqueous boundary layer were calculated from the experimental data. Furthermore, the selectivity of Cyanex 921‐based flat‐sheet supported liquid membrane towards different metal ions and the behaviour of the system against other carriers are presented. Copyright © 2003 Society of Chemical Industry     

Concave carrier molecules: selective transport of copper(II) and lead(II) nitrates through supported liquid membranes

Concave 1,10-phenanthrolines 1 are selective and efficient carrier molecules for membrane transport of copper(II) and lead(II) ions. With competitive membrane transport experiments the selectivity patterns of three concave 1,10-phenanthroline membrane carriers have been determined. Measurements with copper(II) and lead(II) nitrates confirmed the predicted selectivities and revealed high transport rates for 1a and 1b . While 1b shows a high preference for copper(II) nitrate, 1a transports lead and copper nitrates equally well, but with much higher flux. In bulk liquid membranes, the carrier mediated ion flux remained constant over an extended period, whereas it decreased significantly in reused supported liquid membranes, which indicates rapid loss of carrier from the membrane under these conditions.     

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

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

Performance of hollow fiber supported liquid membrane on the extraction of mercury(II) ions

The extraction and recovery or stripping of mercury ions from chloride media using microporous hydrophobic hollow fiber supported liquid membranes (HFSLM) has been studied. Tri-n-octylamine (TOA) dissolved in kerosene was used as an extractant. Sodium hydroxide was used as a stripping solution. The transport system was studied as a function of several variables: the concentration of hydrochloric acid in the feed solution, the concentration of TOA in the liquid membrane, the concentration of sodium hydroxide in the stripping solution, the concentration of mercury ions in the feed solution and the flow rates of both feed and stripping solutions. The results indicated that the maximum percentages of the extraction and recovery of mercury ions of 100% and 97% were achieved at the concentration of hydrochloric acid in the feed solution of 0.1 mol/l, the concentration of TOA at 3% v/v, the concentration of sodium hydroxide at 0.5 mol/l and the flow rates of the feed and stripping solutions of 100 ml/min. However, the concentration of mercury ions from 1–100 ppm in the feed solution had no effect on the percentages of extraction and recovery of mercury ions. Thus, these results have identified that the hollow fiber supported liquid membrane process has high efficiency on both the extraction and recovery of mercury (II) ions. Moreover, the mass transfer coefficients of the aqueous phase (k _i ) and membrane or organic phase (k _m ) were calculated. The mass transfer coefficients of the aqueous phase and organic phase are 0.42 and 1.67 cm/s, respectively. The mass transfer coefficient of the organic phase is higher than that of the aqueous phase. Therefore, the mass transfer controlling step is the diffusion of the mercury ions through the film layer between the feed solution and the liquid membrane.     

中空纤维支撑液膜萃取Cu(II)的传递性能

The transport of Cu(II) from aqueous solutions containing buffer media through hollow fiber supported liquid membrane (HFSLM) using di(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in kerosene as membrane phase and hydrochloric acid as striping phase was investigated. A set of factors were studied, including tube side velocity, shell side velocity, pH of the feed phase, Cu(II) concentration in the feed phase, buffer media concentration and D2EHPA concentration in the membrane phase. Experimental results indicate that the mass transfer coefficient increases with increasing both carrier concentration in the organic phase and flow rates on the tube side and shell side, and decreases with increasing initial Cu(II) concentration in the feed phase. With increasing pH value and acetate concentration in the feed phase, the mass transfer coefficient reaches a maximum value then decreases. The optimal operating conditions are obtained at pH value of 4.44 and 0.1 mol&;#8226;L－1 acetic ion concentration in feed phase, and carrier volume fraction of around 10% in kerosene as organic phase. A mathematical model of the transport mechanism through HFSLM is devel-oped. The modeled results agree well with the experimental ones.     

Separation of cadmium(II) from spent nickel/cadmium battery by emulsion liquid membrane

Experiments were conducted to investigate the separation of cadmium(II) from spent nickel/cadmium battery by emulsion liquid membrane. Liquid membrane mainly consisted of a diluent (kerosene), a surfactant (Span 80), a carrier (di(2‐ethylhexyl) phosphoric acid, D2EHPA) and an internal phase (sulfuric acid). Main research effort was focused on the identification of optimal parameters affecting the separation process, such as D2EHPA (4.4 vol%), Span 80 (6.6 vol%), pH in the external phase (3.0), treat ratio (0.4), agitation time (10 min), and sulfuric acid concentration (1500 mol / m³). With the selected emulsion liquid membrane to separate cadmium(II) from the leaching solution of spent nickel/cadmium battery, the fraction extracted of cadmium(II) ions (0.963) was much more than that of nickel(II) ions (0.026). The organic membrane phase after demulsification was re‐mulsification and recycled up to eight times.     

Permeation study on the hollow-fiber supported liquid membrane for the extraction of Cobalt(II)

The transport of Co(II) through hollow-fiber-supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted in kerosene was examined. The mass transfer rate, expressed as permeability, P, focused on diffusion through the aqueous layer in the feed solution, the organic layer and the aqueous layer in the stripping solution. Experiments were performed as a function of aqueous feed solution velocity (100-500 ml/min), carrier concentration (0.1-20% v/v), aqueous stripping solution velocity (100-1,000 ml/min) and feed concentration (100-1,000 ppm) with 0.1 M HCl in the product phase. pH of the feed solution was 5.0. The measured permeabilities were compared to generally accepted mass transfer correlations. The validity of the prediction was evaluated with the experimental data, and the data were found to tie in well with the theoretical values. The model is the reported describing that the rate limiting step in the transport of the ion was the diffusion through both aqueous films, feed and stripping, whereas the organic resistance of the membrane was negligible. From this study, the model has good potential for the prediction of permeability of Co(II).     

Removal of Ag(l), Cu(II) and Zn(ll) ions with a supported liquid membrane containing cryptands as carriers

The interface behaviour in the facilitated co-transport of Ag(I), Cu(II) and Zn(II) ions through supported liquid membranes (SLMs) made of a flat-sheet polypropylene membrane support containing cryptands (2.2.2 or 2.2.1) as carriers was studied. The liquid-liquid extraction tests showed a maximum distribution coefficient when the carrier concentration was greaterthan 10⁻⁴M. In transport experiments the transmembrane flux increased with increasing carrier concentration reaching a limiting value at greater than 10⁻³M concentration. The calculation ofthe diffusion coefficients in membranes showed ahigherdiffusivityof2.2.2-metal complexes with respect to 2.2.1-metal complexes for silver ions. A sequence of diffusivity D(Ag+)>D(Cu²⁺)>D(Zn²⁺) was obtained, but carrier 2.2.1 showed a higher selectivity through copper ions. A sequence of diffusivity D(Cu²⁺)>D(Zn²⁺)>D(Ag⁺) was obtained. The diffusivity was significantly higher when using Celgard 2500 support compared to Celgard 2400 or 2402. Variable metal ion concentrations in the feed phase fluxes almost zero, at less than 10⁻² M concentration, were obtained. In the transient state of the transport through the SLM, different molar flow rates at the feed-membrane and membrane-strip interfaces were observed. The selectivity of the interfaces containing 2.2.2 in the separation binary mixtures of ions showed the following separation factors: SF_AgZn = 2.50, SF_AgCu = 1.64, SF_cuZn = 1.42.     

Mass Transfer Investigation of Liquid Membrane Transport of Gold (III) by Methyl Isobutyl Ketone Mobile Carrier

Extraction of Au^III ions by an emulsion liquid membrane (ELM) system with methyl isobutyl ketone (MIBK) as the mobile carrier and also liquid‐liquid extraction of Au^III from aqueous solutions have been studied. Experiments on the transport of the gold ions in a liquid‐liquid extraction system and stripping of the extracted ions from the organic phase as well as the extraction by a three‐phase W/O/W emulsion liquid membrane system have been performed. The results showed that even when the distribution coefficient of the diffusing species in the phases is small, the extraction by emulsion liquid membranes would be an effective process. A first‐order extraction rate was proposed and examined for the extraction system.     

Coupled transport of copper through different commercial supports containing LIX 984 as carrier

The coupled transport of copper(II) ions through a supported liquid membrane containing LIX 984 as the mobile carrier dissolved in kerosene has been studied. Many commercial membrane supports were investigated at different stirrer speeds in a permeation cell. An equation describing the permeation rate has been derived, taking into account stagnant layer aqueous diffusion and liquid membrane diffusion. By means of this treatment the copper overall transfer resistance and the experimental determination of the effective porosity factor (ε/τ), for each support have been performed. The Accurel^® 2E-PP membrane showed a relatively high value of ε/τ (0·91), which makes this membrane an adequate support when the transport properties of the supported liquid membrane are concerned. © 1998 SCI     

Silver Recovery from Dilute Aqueous Solutions Using Semi‐Batch RF‐Pertraction

Silver recovery from dilute nitrate solution was studied by using a rotating film‐pertraction technique in a semi‐continuous mode. Tri‐isobutylphosphine sulphide (TIBPS) dissolved in kerosene was used as a carrier and an aqueous ammonia solution as a stripping phase. A high transfer flux of silver ions during the pertraction process was observed. It was shown that the selectivity of silver transport through the TIBPS‐containing liquid membrane provides an excellent separation of silver from other metals such as copper, nickel, and iron presented in the treated solutions.     

Two-Component Emulsion Liquid Membranes with Macromolecular Carriers of Divalent lons

Abstract

Experimental investigations are presented on the application of poly-[poly(ethylene glycol) phosphate] (PEGP) as a macromolecular, multisite, carrier of ions in an emulsion liquid membrane system. This polymer acts as a mobile carrier and surfactant-stabilizing W/O/W emulsion. The transport properties of PEGP have been checked for systems composed of (a) a feed phase containing Ni(II), Co(II) or Cu(II) ions; (b) an organic phase, i.e., PEGP dissolved in 1,2- dichloroethane; and (c) 1 M sulfuric acici as a receiving solution. Fast and effective membrane extraction of Ni(II) has been found for membranes with PEGP of molecular weight 22,000. It has been proved that the affinity of PEGP toward the studied ions is reversed in comparison with that for poly(ethylene glycol). The affinity order of PEGP toward the tested ions is Ni(II) > Co(II) > Cu(II).     

New liquid membrane technology for simultaneous extraction and stripping of copper(II) from wastewater

In this paper, a new liquid membrane technique, hollow fiber renewal liquid membrane (HFRLM), is presented, which is based on the surface renewal theory, and integrates the advantages of fiber membrane extraction, liquid film permeation and other liquid membrane processes. The results from the system of CuSO₄+D2EHPA in kerosene+HCl show that the HFRLM process is very stable. The liquid membrane is renewed constantly during the process, the direct contact of organic droplets and aqueous phase provides large mass transfer area. These effects can significantly reduce the mass transfer resistance in the lumen side. Then the mixture of feed phase and organic phase flowing through the lumen side gives a higher mass transfer rate than that of stripping phase and organic phase, because the aqueous layer diffusion of feed phase is the rate-controlling step. The overall mass transfer coefficient increases with increasing flow rates and D2EHPA concentration in the organic phase, and with decreasing initial copper concentration in the feed phase. The overall mass transfer coefficient also increases with increasing pH in the feed phase, and reaches a maximum value at pH of 4.44, then decreases. Also, there is a favorable w/o volume ratio of 20:1 to 30:1 for this process. Compared with hollow fiber supported liquid membrane and hollow fiber membrane extraction processes, HFRLM process has a high mass transfer rate. Mathematical model for the HFRLM process based on the surface renewal theory is developed. The calculated results are in good agreement with experimental results under the conditions studied.     

A Reaction Flux Model for Extraction of Cu(II) with LIX84I in HFSLM

Hollow fiber supported liquid membrane (HFSLM) is a favorable method to extract both valuable compounds and heavy metal pollutants such as chromium, copper, and nickel at a very low concentration. In this work, the extraction of Cu(II) by LIX84I dissolved in kerosene was theoretically and experimentally investigated. A model to estimate the percentage of extraction of copper ions from synthetic water considering the effect of reaction flux in membrane phase of the HFSLM system was studied. H₂SO₄ solution was used as the stripping solution. The facilitated transport mechanism of the chemical reaction at the feed-membrane interface was taken into account in the model equations. The percentage of copper ion extraction was plotted against its initial concentration in feed and also feed flow rate. Subsequently, the separation time and separation cycle were determined in accordance with the simulated values of copper ion concentration and the feed flow rate from the model. The modeled results were in good agreement with the experimental data at the average percentage of deviation about 2%.     

Highly Efficient and Selective Transport of Cu(II) with a Cooperative Carrier Composed of Tetraaza-14-Crown-4 and Oleic Acid through a Bulk Liquid Membrane

Tetraaza-14-crown-4 and oleic acid was successfully applied for transport of Cu(II) in chloroform bulk liquid membrane. The uphill moving of Cu(II) during the liquid membrane transport process has occurred. The main effective variable such as the type of the metal ion acceptor in the receiving phase and its concentration, tetraaza-14-crown-4 and oleic acid concentration in the organic phase on the efficiency of the ion-transport system were examined. By using L-cysteine as a metal ion acceptor in the receiving phase, the maximum amount of copper (II) transported across the liquid membrane was achieved to 96 ± 1.5% after 140 minutes. The selectivity of copper ion transport from the aqueous solutions containing Pb²⁺, Tl⁺, Ag⁺, Co²⁺, Ni²⁺, Mg²⁺, Zn²⁺, Hg²⁺, Cd²⁺ and Ca²⁺ ions were investigated. In the presence of CH₃COONH₄ and Na₄P₂O₇ as suitable masking agents in the source phase, the interfering effects of Pb⁺² and Cd²⁺ were diminished drastically.