Enhancing CO_(2) transport with plasma-functionalized ionic liquid membranes

The ionic liquid(IL) 1-butyl-3-methylimidazolium tetrafluoroborate treated with radiofrequency plasma is proposed for functionalization and immobilization on polyethersulfone supports to form supported ionic liquid membranes for CO_(2) separation.The effects of treatment time and transmembrane pressure difference on CO_(2) permeance were evaluated.The best gas permeation performance was obtained with a treatment time of 10 min and the transmembrane pressure difference was 0.25 MPa.Characterization of the materials by Fourier transform infrared spectroscopy,x-ray photoelectron spectroscopy and nuclear magnetic resonance spectroscopy demonstrates that the IL is grafted with carboxyl groups and deprotonated through plasma treatment.A preliminary mechanism for the plasma treatment and facilitated transport of CO_(2)has been proposed on this basis.

Recent development of ionic liquid membranes

The interest in ionic liquids(IL) is motivated by its unique properties, such as negligible vapor pressure, thermal stability, wide electrochemical stability window, and tunability of properties. ILs have been highlighted as solvents for liquid-liquid extraction and liquid membrane separation. To further expand its application in separation field, the ionic liquid membranes(ILMs) and its separation technology have been proposed and developed rapidly. This paper is to give a comprehensive overview on the recent applications of ILMs for the separation of various compounds, including organic compounds, mixed gases, and metal ions. Firstly, ILMs was classified into supported ionic liquid membranes(SILMs) and quasi-solidified ionic liquid membranes(QSILMs) according to the immobilization method of ILs. Then, preparation methods of ILMs, membrane stability as well as applications of ILMs in the separation of various mixtures were reviewed. Followed this, transport mechanisms of gaseous mixtures and organic compounds were elucidated in order to better understand the separation process of ILMs. This tutorial review intends to not only offer an overview on the development of ILMs but also provide a guide for ILMs preparations and applications.

Permeability and Selectivity of Sulfur Dioxide and Carbon Dioxide in Supported Ionic Liquid Membranes

Permeabilities and selectivities of gases such as carbon dioxide （CO2）, sulfur dioxide （SO2）, nitrogen （N2） and methane （CH4） in six imidazolium-based ionic liquids （[emim][BF4], [bmim][BF4], [bmim][PF6], [banim][BF4], [bmim][Tf2N] and [emim][CF3SO3]） supported on polyethersulfone microfiltration membranes are investigated in a single gas feed system using nitrogen as the environment and reference component at temperature from 25 to 45℃ and pressure of N2 from 100 to 400 kPa. It is found that SO2 has the highest permeability in the tested supported ionic liquid membranes, being an order of magnitude higher than that of CO2, and about 2 to 3 orders of magnitude larger than those of N2 and CH4. The observed selectivity of SO2 over the two ordinary gas components is also striking. It is shown experimentally that the dissolution and transport of gas components in the supported ionic liquid membranes, as well as the nature of ionic liquids play important roles in the gas permeation. A nonlinear increase of permeation rate with temperature and operation pressure is also observed for all sample gases. By considering the factors that influence the permeabilities and selectivities of CO2 and SO2, it is expected to develop an optimal supported ionic liquid membrane technology for the isolation of acidic gases in the near future.

Di(2-ethylhexyl) phosphoric acid-coconut oil supported liquid membrane for the separation of copper ions from copper plating wastewater

Permeation of Cu（Ⅱ） from its aqueous solution through a supported liquid membrane （SLM） containing di（2-ethylhexyl）phosphoric acid （D2EHPA） carrier dissolved in coconut oil has been studied. The effects of Cu（Ⅱ）, pH （in feed）, H2SO4 （stripping） and D2EHPA （in membrane） concentrations have been investigated. The stability of the D2EHPA-coconut oil has also been evaluated. High Cu（Ⅱ） concentration in the feed leads to an increase in flux from 4.1 × 10^-9 to 8.9 × 10^-9 mol/（m^2·s） within the Cu（Ⅱ） concentration range 7.8×10^-4-78.6×10^-4 mol/L at pH of 4.0 in the feed and 12.4 × 10^-4 mol/L D2EHPA in the membrane phase. Increase in H2SO4 concentration in strip solution leads to an increase in copper ions flux up to 0.25 mol/L H2SO4, providing a maximum flux of 7.4 × 10^-9 mol/（m^2·s）. The optimum conditions for Cu（Ⅱ） transport are, pH of feed 4.0, 0.25 mol/L H2SO4 in strip phase and 12.4 × 10^-4 mol/L D2EHPA （membrane） in 0.5 μm pore size polytetrafluoroethylene （PTFE） membrane. It has been observed that Cu（Ⅱ） flux across the membrane tends to increase with the concentration of copper ions. Application of the method developed to copper plating bath rinse solutions has been found to be successful in the recovery of Cu（Ⅱ）.

Instability Mechanisms of Supported Liquid Membrane for Phenol Transport

The instability mechanisms of the supported liquid membrane using Celgard 2500 membranes as support and tributyl phosphate dissolved in kerosene as carrier for phenol transport was studied by ele.etroehemical impedance spectroscopy. Emulsion formation is demonstrated to be one of the main causes for the instability of supported liquid membrane in the present system. The emulsion-facilitated conditions, such as higher membrane liquid concentration, faster stirring speed, lower salt concentration and higher HLB value, would accelerate the degradation of supported liquid membrane. Other mechanisms including solubility and osmotic pressure work together to increase the membrane liauid loss.

Separation of Eu^3＋ Using a Novel Dispersion Combined Liquid Membrane with P507 in Kerosene as the Carrier

The separation of Eu^3 ＋is studied with a dispersion combined liquid membrane（DCLM）,in which polyvinylidene fluoride membrane（PVDF）is used as the liquid membrane support,dispersion solution containing HCl solution as the stripping solution,and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester（P507）dissolved in kerosene as the membrane solution.The effects of pH value,initial concentration of Eu3 ＋and different ionic strength in the feed phase,volume ratio of membrane solution to stripping solution,concentration of HCl solution, concentration of carrier,different stripping agents in the dispersion phase on the separation are investigated.The optimum condition for separation of Eu3 ＋is that concentration of HCl solution is 4.0 mol·L 1,concentration of carrier is 0.16 mol·L 1,and volume ratio of membrane solution to stripping solution is 30︰30 in the dispersion phase, and pH value is 4.2 in the feed phase.The ionic strength has no significant effect on separation of Eu3 ＋.Under the optimum condition,when the initial concentration of Eu3 ＋is 0.8×10 4mol·L 1,the separation percentage of Eu 3＋is 95.3%during the separation time of 130 min.The kinetic equation is developed in terms of the law of mass diffusion and the theory of interface chemistry.The diffusion coefficient of Eu3 ＋in the membrane and the thickness of diffusion layer between feed phase and membrane phase are obtained and their values are 1.48×10 7m 2·s 1and 36.6μm,respectively.The results obtained are in good agreement with literature data.

Synthesis of New Aza-crown Ethers Containing Pyridine Ring and their Liquid Membrane Transport of Alkali Cations

Five new aza-crown ethers have been prepared by the condensation of 2,6-bis[(2-formylphenyl)oxymethyl] pyridine with different diamino compounds in hot methanol, the bis-Schiff bases without isolation were reduced with NaBH4 to afford the corresponding aza-crown ethers. The liquid membrane transport or alkali cations using the five new macrocycles as the ion-carriers was also studied.

Recovery of Copper Ions from Wastewater by Hollow Fiber Supported Emulsion Liquid Membrane

Recovery of copper ions from wastewater using a hollow fiber supported emulsion liquid membrane (HFSELM) was studied with LIX984N as carrier, kerosene as diluents, and sulfuric acid solution as stripping phase. Effects of compositions of feed and emulsion liquid phase, flow rates on both sides of membrane, and hollow fiber module parameters were investigated. The stability of the emulsion liquid phase without surfactant and the effect of buffer in the feed phase on the extraction rate were also evaluated. It is found that the stability of the emulsion phase without surfactant is poor. Higher flow velocity gives shorter residence time for the emulsion liquid phase on the tube side, reducing the effect of particle coalescence on the separation process. The extraction rate increases with the increase of feed phase pH, carrier concentration, hydrogen ion concentration in the stripping phase, and ef- fective hollow fiber area. The phase ratio in the emulsion liquid phase has a negative effect on extraction rate. The flow rates on both sides have little influence on the extraction performance of the HFSELM, while buffer addition in the feed solution improves the extraction efficiency.

Study of Transport and Separation of Rare Earth Ions through the Emulsion Liquid Membrane of Bis(2,4,4-trimethylpentyl)phosphinic Acid-Span 80-Toluene

It is indicated from a study of transport of rare earth ions through the emulsion liquid mem- brane of bis(2,4,4-trimethylpentyl)phosphinic acid-Span 80-toluene that transporting rare earth ions com- pletely and rapidly was realized under the optimum experimental conditions:1.0×10^(-3)～3.0×10^(-3)mol/L bis(2,4,4-trimethylpentyl)phosphinic acid and 2%～4%(W/V)Span 80 in toluene solution as membrane phase,0.50～2.0 mol/L HCl as inner phase,rare earth ion solutions with pH 3.5～5.0 as outer phase.Ac- cording to the differences of transport behavior for rare earth ions,it is possible to separate rare earth ions from mixed solutions of rare earth ions by this liquid membrane system.

Preparation of 6-APA by Enzymatic Bioconversion in an Emulsion Liquid Membrane Reactor

Production of 6-aminopenicillanic acid (6-APA) by hydrolysis using penicillin acylase (PA) was studied as a model of an enzymatic emulsion liquid membrane (ELM) process. The loss of PA activity was examined for various membrane compositions (organic solvent, surfactant, carrier). The effects of some experimental variables on the stability of emulsion were investigated. It was found that the choice of organic solvent greatly affected the stability of the emulsion. Increasing the concentration of the carrier in the membrane phase increases the transfer rate of substrate and products but also has a destabilizing effect on the emulsion. The recovery of 6-APA obtained by a di-carrier system (N263-N1923) was much higher than those when either of the di-carriers was used separately. The whole process was controlled both by the enzymatic reaction rate and by the transfer rate of the substrate and the products, however, the ratio of them could be changed by varying the composition of the system. For an optimum condition, it was obtained that the recovery ratio of 6-APA was over 80% and the conversion of benzyl penicillin (PG) was up to 90% in the external phase after 30 minutes. Meanwhile, the breakage percentage of the emulsion was less than 2%.

Study on the liquid membrane oscillation of water/oil/water system containing TTAB and picric acid

The liquid membrane oscillation of a novel water （aqueous tetradecyl trimethyl ammoniumbromide, TTAB and alcohol solution）/oil （picric acid in chloroform solution）/water （aqueous glucose solution） system was investigated. By using homemade device, the curves of various liquid membranes oscillation with different concentration of TTAB and picric acid, types of alcohol and other organic solvents at different temperature were measured. The results show that the water （aqueous 7 mmol/L of TTAB and 0.5 mol/L of n-propanol solution）/oil （0.5 mmol/L of picric acid in chloroform solution）/water （aqueous glucose solution） system performed sustained and stable oscillation at 30 ℃. And the novel system can recognise added amino acid.

Separation of Samarium(Ⅲ)and Gadolinium(Ⅲ)by A Push-pull Liquid Membrane System

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Tb(III) Transport in Dispersion Supported Liquid Membrane System with D2EHPA as Carrier in Kerosene

The transport of Tb（III） in dispersion supported liquid membrane（DSLM） with polyvinylidene fluoride membrane（PVDF） as the support and dispersion solution including HCl solution as the stripping solution and di（2-ethylhexyl） phosphoric acid（D2EHPA） dissolved in kerosene as the membrane solution, has been studied. The effects of pH value, initial concentration of Tb（III） and different ionic strength in the feed phase, volume ratio of membrane solution to stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on the transport of Tb（III） have also been investigated, respectively. As a result, the optimum transport conditions of Tb（III） were obtained, i.e., the concentration of HCl solution was 4.0 mol/L, the concentration of D2EHPA was 0.16 mol/L, the volume ratio of membrane solution to stripping solution was 30：30 in the dispersion phase and pH value was 4.5 in the feed phase. Ionic strength had no obvious effect on the transport of Tb（III）. Under the optimum conditions, the transport percentage of Tb（III） was up to 96.1% in a transport time of 35 min when the initial concentration of Tb（IIl） was 1.0× 10 -4 mol/L. The diffusion coefficient of Tb（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.82×10 -8 m2/s and 5.61 um, respectively. The calculated results were in good agreement with the literature data.

Transport Study of Cu （Ⅱ） Through Hollow Fiber Supported Liquid Membrane

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·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 developed.The modeled results agree well with the experimental ones.

Study on transport of Dy(Ⅲ) by dispersion supported liquid membrane

The transport of Dy（III） through a dispersion supported liquid membrane （DSLM） consisting of polyvinylidene fluoride membrane （PVDF） as the liquid membrane support and dispersion solution including HCI solution as the stripping solution and 2-ethyl hexyl phosphonic acid-mono-2-ethyl hexyl ester （PC-88A） dissolved in kerosene as the membrane solution, was studied. The effects of pH value, initial concentration of Dy（III） and different ionic strength in the feed phase, volume ratio of membrane solution and stripping solution, concentration of HCl solution, concentration of carrier, different stripping agents in the dispersion phase on transport of Dy（III） were also investigated, respectively. As a result, when the concentration of HCI solution was 4.0 mol/L, concentration of PC-88A was 0.10 mol/L, and volume ratio of membrane solution and stripping solution was 40：20 in the dispersion phase, and pH value was 5.0 in the feed phase, the transport effect of Dy（III） was the best. Ionic strength had no obvious effect on transport of Dy（III）. Under the optimum condition studied, when initial concentration of Dy（III） was 0.8×10^-4 mol/L, the transport rate of Dy（III） was up to 96.2% during the transport time of 95 rain. The kinetic equation was developed in terms of the law of mass diffusion and the theory of interface chemistry. The diffusion coefficient of Dy（III） in the membrane and the thickness of diffusion layer between feed phase and membrane phase were obtained and the values were 1.99×10^-7 m^2/s and 15.97 μm, respectively. The results were in good agreement with experimental results.

Germanium transport across supported liquid membrane with Cyanex 923: Mathematical modeling

A mathematical model was developed to monitor the facilitated transport of germanium(IV) from oxalic acid solutions through a flat sheet supported liquid membrane(FSSLM) containing four trialkylphosphine oxides(Cyanex 923). The FSSLM modeling was based on the extraction constant(Kext) calculated from the liquid-liquid extraction(LLX) modeling. The LLX model presented a reliable calculation of the extraction constant(Kex= 2.057×103 L/mol4). The FSSLM model was solved using Matlab■ software according to extraction constant, Fick’s law, and diffusional principles. The model predicts the overall mass transfer coefficient(Korg) to be 3.84 cm/s. Using this value, diffusion coefficients(Dm) for various Cyanex 923 concentrations of 0.126, 0.252, 0.378, 0.505, 0.631 and 0.757 mol/L are found to be 8.50×10^-4, 4.30×10^-4, 1.87×10^-4, 5.87×10^-5, 2.57×10^-5, 2.09×10^-5 cm2/s, respectively. The results show that the diffusion rate of the current study is approximately more than that of similar FSSLM systems containing Cyanex 923 used to transport various metals. The modeling values are in good agreement with the experimental data, showing the good reliability of the mathematical model.

Study on the oscillating phenomena of electrical potential across a liquid membrane

The electrical oscillations across a liquid membrane in water/oil/water system was studied with octanol as oil phase by introducing two opposite charged surfactants in oil and aqueous phase, respectively. The sustained and rhythmic oscillation was observed. To a certain extent, the features of the oscillation （e.g. induction time, frequency, life time and orientation of the pulse pikes） strongly depend on the property of surfactant, dissolved in octanol. The mechanism may be explained by the formation and destruction of dual-ion surfactant membrane accompanying with emulsification at the interface and considering the coupling effect of diffusion and associated reaction in the vicinity of the interface.

Easy removing of phenol from wastewater using vegetable oil-based organic solvent in emulsion liquid membrane process

Phenol is considered as pollutant due to its toxicity and carcinogenic effect.Thus,variety of innovative methods for separation and recovery of phenolic compounds is developed in order to remove the unwanted phenol from wastewater and obtain valuable phenolic compound.One of potential method is extraction using green based liquid organic solvent.Therefore,the feasibility of using palm oil was investigated.In this research,palm oil based organic phase was used as diluents to treat a simulated wastewater containing 300×10^(-6) of phenol solution using emulsion liquid membrane process(ELM).The stability of water-in-oil(W/O) emulsion on diluent composition and the parameters affecting the phenol removal efficiency and stability of the emulsion;such as emulsification speed,emulsification time,agitation speed,surfactant concentration,pH of external phase,contact time,stripping agent concentration and treat ratio were carried out.The results of ELM study showed that at ratio7 to 3 of palm oil to kerosene,5 min and 1300 r·min^(-1) of emulsification process the stabile primary emulsion were formed.Also,no carrier is needed to facilitate the phenol extraction.In experimental conditions of500 r·min^(-1) of agitation speed,3%Span 80,pH 8 of external phase,5 min of contact time,0.1 mol·L^(-1) NaOH as stripping agent and 1:10 of treat ratio,the ELM process was very promising for removing the phenol from the wastewater.The extraction performance at about 83%of phenol was removed for simulated wastewater and an enrichment of phenol in recovery phase as phenolate compound was around 11 times.

Assembling Synthesis of ZnSe Orthohexagonal Slices through Emulsion Liquid Membrane System of Gas-liquid Transport

Orthohexagonal slices assembled by ZnSe quantum dots were synthesized through emulsion liquid membrane system. These orthohexagonal slices were 1.5-3.5 μm in side length and were self-assembled by ZnSe quantum dots of 2-3 nm. It was proposed the surfactant molecules on ZnSe quantum dots played a key role in the self-assembly process.

The removal of Cr(Ⅵ) through polymeric supported liquid membrane by using calix[4]arene as a carrier

In this work, the transport and removal of Cr(Ⅵ) were achieved through supported liquid membrane(SLM) by using a 5,17, di-tert-butyl-11,23-bis[(1,4-dioxa-8-azaspiro [4,5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene carrier, dissolved in 2-nitrophenyl octyl ether dichloromethane.The studied parameters are the solvent effect in the membrane phase, the effect of carrier concentration, and the acid type in the donor phase.The Celgard 2500 was used as a membrane support.We used the Danesi mass transfer model to calculate the permeability coefficients for each studied parameter.In addition, AFM and SEM techniques were used to characterize the surface morphology of the prepared Celgard 2500 membrane that included the calix[4]arene carrier.