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.

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 of alkali cations using the five new macrocycles as the ion-carriers was also studied.

Synthesis of Bis-substituted Calix[4]arenes and Mechanism of Substituents Effect on K^+ and Hg^(2+) Ions Transports through Liquid Membrane

New calix[4]arene derivatives containing nitro,amino and benzoyl in the upper and lower rims of molecule were successfully synthesized.Their effectiveness towards K+ and Hg2+ across bubbling liquid membrane(BLM) was examined.For K+ ion transfer,preserving phenolic hydroxyl in the lower rim of calix[4]arene could enhance its transport ability.When benzoyl replaced phenolic hydroxyl,the transport would fall off,because benzoyl caused steric hindrance on the K+ transfer.The study also revealed that the group having the electron-withdrawing conjugative effect on phenolic hydroxyl,-NO2 in the upper rim of calix[4]arene,made transport ability of calix[4]arene fall off.On the contrary,-NH2 that had electron-repulsive conjugative effect enhanced the transport ability of the compound.For Hg2+ ion,only -NH2 in the upper rim of calix[4]arenes had high affinity for it and contributed to Hg2+ transfer.Transport amount of Hg2+ ion increased with increasing calix[4]arene5 concentration and ΔpH in BLM.

Supported liquid membrane extraction to treat coal gasification wastewater containing high concentrations phenol

The hollow fiber supported liquid membrane extraction was introduced to treat coal gasification wastewater to recover phenolic compounds,with tributyl phosphate (TBP) as carrier,kerosene as the membrane solvent,sodium hydroxide solution as the stripping agent and PVDF as the membrane material. Factors having strong impact on the extraction efficiency were studied in detail,including the mass transfer mode,twophase flow rate,stripping phase concentration. As extraction system with 20% TBP-kerosene,parallel flow mass transfer,stripping phase concentration 0.1 mol/L,the optimal operating conditions could be obtained. Under the optimum operating conditions,the time required to reach equilibrium for the extraction is 50 min, and extraction efficiency of phenol is 86. 2% and the phenol concentration of effluent is 98.64 mg/L.

Short review on liquid membrane technology and their applications in biochemical engineering

As a branch of membrane separation technology,liquid membrane has attracted great attention and expanded investigations in biological chemical engineering,with life and health concern in ecosystems.Composed of membrane solvent and mobile carrier,liquid membrane was acquired of function,performing the facilitated mass transfer across the diffusive solvent,so as for the separation and delivery achievement with efficacy.In this review,two types of liquid membrane are mainly focused,respectively on supported liquid membrane(SLM)of membrane solvent supporter in necessity,and on emulsion liquid membrane(ELM)of the required interfacial stabilizers and homogenization.Accordingly,the transfer mechanism,compositions,structure and features of SLM and ELM are introduced respectively.Moreover,the current investigations of liquid membrane have been discussed,focusing on the improvements of efficacy and stability in separation&detection,encapsulation and delivery,so as to scale up the favorable and efficient application with bio-life concern.Prospectively,this review could provide comprehensive insight into the bio-applications of liquid membrane,and guidelines for the further investigations on the efficacy and long-term applicable stability,in order to realize the industrialization.

Methyl Cholate and Resorcinarene New Carriers for the Recovery of Cr(Ⅲ) Ions by Supported Liquid Membranes (SLM)s

The technique of supported liquid membranes was used to achieve the facilitated transport of Cr(III) ions, using tow amphiphilic carriers, the methyl cholate and resorcinarene. For prepared SLMs, toluene as organic phase and film of polyvinylidene difluoride, as hydrophobic polymer support with 100 μm in thickness and 0.45 μm as the diameter of the pores. The macroscopic parameters (P and J0) on the transport of these ions were determined for different medium temperatures. For these different environments, the prepared SLMs were highly permeable and a clear evolution of these parameters was observed. The parameter J0 depended on the temperature according to the Arrhenius equation. The activation parameters, Ea, ΔH≠ and ΔS≠, for the transition state on the reaction of complex formation (ST) , were determined. To explain these results for this phenomenon, and achieve a better extraction of the substrate, a model based on the substrate complexation by the carrier and the diffusion of the formed complex (ST) was developed. The experimental results verify this model and determine the microscopic parameters (Kass and D*). These studies show that these parameters Kass and D* are specific to facilitated transport of Cr(III) ions by each of the carriers and they are changing significantly with temperature.

Artificial neural network based modeling of liquid membranes for separation of dysprosium

In recent years,the liquid membrane process has been widely investigated to remove rare earth metals.However,transport modeling of this process requires the accurate values of several parameters,which are difficult to measure.Thus,the accurate simulation of this process is a challenging task.In this study,the artificial neural network(ANN)based approach is used to model the liquid membrane process for removing dysprosium.Experimental results from a previous study were used to train the ANN.Initially,the number of neurons in the hidden layer was optimized.The minimum mean squared error between experimental results and model predictions is found with ten neurons.Model predictions were successfully validated with experimental results with correlation factor(R)of 0.9987,which confirms the authenticity of the trained network.Trained ANN was then used to study the effects of different operating parameters on transport rate.The higher volume ratio of membrane solution to feed solution(3-4)with 50-60 min of operation,higher feed pH(5),HCl concentration in stripping solution of 2 mol/L,and moderate concentration of carrier species(0.5 mol/L)with 0.5×10^(-4) mol/L dysprosium initial concentration are found to be optimum values of operating conditions for maximizing the transport rate.

Temperature-regulation liquid gating membrane with controllable gas/liquid separation

Membrane separation technology with the ability to regulate gas/liquid transport and separation is critical for environmental fields, such as sewerage treatment, multiphase separation, and desalination. Although numerous membranes can dynamically control liquid-phase fluids transport via external stimuli, the transport and separation of gas-phase fluids remains a challenge. Here, we show a temperature-regulation liquid gating membrane that allows in-situ dynamically controllable gas/liquid transfer and multiphase separation by integrating a thermo-wettability responsive porous membrane with functional gating liquid. Experiments and theoretical analysis have demonstrated the temperature-regulation mechanism of this liquid gating system, which is based on thermo-responsive changes of porous membrane surface polarity, leading to changes in affinity between the porous membrane and the gating liquid. In addition, the sandwich configuration with dense Au-coated surfaces and heterogeneous internal components by a bistable interface design enables the liquid gating system to enhance response sensitivity and maintain working stability. This temperature-regulation gas/liquid transfer strategy expands the application range of liquid gating membranes,which are promising in environmental governance, water treatment and multiphase separation.

THE STUDY ON THE MASS TRANSFER MECHANISM OF EUROPIUM ION THROUGH LIQUID SURFACTANT MEMBRANES

The transfer of trivalent europium ion in a liquid surfactant membrane system is investigated in order toclarify the characteristics of liquid membrane separation process and the availability of this technique forrecovering trivalent lanthanides and actinides.A layered structure model for the emulsion globule is sug-gested.The equations describing the relationship among the effective membrane thickness,the time andother factors are derived and verified experimentally.Results show that under certain conditions the decreas-ing concentration of europium ion in the external phase is proportional to the square root of the time,the acidity of the internal phase and the carrier concentration in the membrane phase.The membrane phase consists of kerosene（solvent）,Span-80（surfactant）and di-（2-ethylhexyl） phosphoricacid（HDEHP,carrier）.The internal phase is dilute nitric acid and the external phase is aqueous solu-tion containing Eu（NO3）3.The mass transfer rate of europium in this system is high and the recovery ofeuropium may be more than 99%.

Individual and Combined Effects of the Extractant,Surfactant and Modifier Concentrations on the Droplet Coalescence Time of the Primary Emulsion in the Liquid Surfactant Membrane Extraction Process

In this work, the individual and combined effects of the extractant, surfactant and modifier concentrations on the droplet coalescence time of the primary emulsion in the liquid surfactant membrane extraction process were evaluated, through emulsification experiments. Adogen 464 was used as extractant (carrier), and Escaid 110, as diluent. Two systems were studied. The first one composed by the extractant, the surfactant and the diluent, and the second one composed by the same reagents, but with the addition of 1-decanol as modifier. It was observed that, when the modifier is not present in the membrane phase, the surfactant not only stabilizes the primary emulsion, but, apparently, it also plays a role similar to that of the alcohol, promoting the solvation of the amine in a low polarity diluent. Furthermore, the extractant, a quaternary amine, helps to stabilize the primary emulsion in systems without a modifier. For membrane phases consisting of 1 or 5% w/w of Adogen 464 and 2% or 5% w/w of ECA 4360, a concentration of 3% w/w of 1-decanol was sufficient to promote the solvation of Adogen 464 in Escaid 110 and to obtain a low droplet coalescence time.

The kinetic analysis of optimization and selective transportation of Cu(Ⅱ)ions with TNOA as carrier by MDLM system

This study covers the transportation of Cu(Ⅱ) ions by multi-dropped liquid membrane(MDLM) system and tri-noctylamine(TNOA) as carrier in kerosene. Batch experiments are held to obtain optimum conditions for the transportation of Cu(Ⅱ) ions such as volume of donor, organic, and acceptor phase 100 ml, p H of donor phase9.00, temperature 298.15 K, concentration of H_2SO_4 in acceptor phase 1.00 mol·L^(-1), concentration of TNOA in organic phase 5.00 × 10^(-3)mol·L^(-1)and rate of peristaltic pump 50 ml·min^(-1). Optimum circumstances of this extraction are as follows: p H of donor phase is 9.00, concentration of TNOA is 5.00 × 10^(-3)mol·L^(-1),1.00 mol·L^(-1)H_2SO_4 as acceptor phase, and flux rate is 50 ml·min^(-1). Cu(Ⅱ) ion transportation is consecutive first order irreversible reaction. Activation energy is found as 5.22 kcal·mol-1(21.82 k J·mol^(-1), this process is called as diffusion controlled system. Selective transportation of Cu(Ⅱ) ions with alkaline, alkaline earth, and different heavy metal ions at optimum conditions of single Cu(Ⅱ) extraction was conducted. According to the selective transportation Cu(Ⅱ) ions with alkaline and alkaline earth metal ions, Na^+, K^+, and Ba^(2+)ions are not detected in the acceptor phase, but 12.00% of Ca^(2+)ions is transported from donor phase to acceptor phase. At the end of the simultaneous extraction of Zn(Ⅱ), Fe(ⅡI), and Mo(VI) with Cu(Ⅱ) ions, 2.20% of Mo(VI), 0.80% of Fe(Ⅲ) and 3.60% of Zn(Ⅱ) are detected in the acceptor phase.

Performance prediction of magnetorheological fluid‐based liquid gating membrane by kriging machine learning method

Smart liquid gating membrane is a responsive structural material as a pressure-driven system that consists of solid membrane and dynamic liquid,responding to the external field.An accurate prediction of rheological and mechanical properties is important for the designs of liquid gating membranes for various applications.However,high predicted accuracy by the traditional sequential method requires a large amount of experimental data,which is not practical in some situations.To conquer these problems,artificial intelligence has promoted the rapid development of material science in recent years,bringing hope to solve these challenges.Here we propose a Kriging machine learning model with an active candidate region,which can be smartly updated by an expected improvement probability method to increase the local accuracy near the most sensitive search region,to predict the mechanical and rheolo-gical performance of liquid gating system with an active minimal size of ex-perimental data.Besides this,this new machine learning model can instruct our experiments with optimal size.The methods are then verified by liquid gating membrane with magnetorheological fluids,which would be of wide interest for the design of potential liquid gating applications in drug release,microfluidic logic,dynamic fluid control,and beyond.