Facilitated oxygen transport through a Nafion membrane containing cobaltporphyrin as a fixed oxygen carrier

A Nafion membrane containing a cobaltporphyrin (CoP) complex as a fixed oxygen carrier was prepared with a view to facilitate oxygen transport through the membrane. The design concept of the CoP-loaded Nafion membrane was based on the CoP's modification to place the CoP complex in a hydrophobic domain of the microphase-separated structure, in order to facilitate the oxygen transport and to maintain proton conductivity. The oxygen permeability through the CoP-loaded Nafion membrane was higher than the nitrogen permeability, and significantly enhanced at relatively-low oxygen pressures of the upstream, indicating that the fixed CoP complex acted as an oxygen hopping site to facilitate the oxygen transport. The oxygen/nitrogen permselectivity increased with the content of CoP in the Nafion membrane. Electrochemical reduction of oxygen at a glassy carbon electrode, modified with a Pt/C catalyst and the CoP-loaded Nafion membrane, provided additional support for the facilitated oxygen transport by the membrane. Increased current for the reduction of oxygen on the modified electrode by loading CoP indicated that the CoP offered the oxygen hopping site in the Nafion membrane.     

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     

Mathematical modelling of CO2 facilitated transport through liquid membranes containing amines as carrier

An approximate analytical solution for the facilitated transport of carbon dioxide across a liquid membrane containing aqueous primary and secondary amine solutions has been developed in which the reversible reaction A(CO₂) + 2B(amine) AB(carbamate) + BH(protonated amine) occurs inside the liquid membranes. The current approximate analytical solution predicts the facilitated factor of CO₂ through the membrane and is based on the dimensionless, nonlinear diffusion‐reaction transport problem. The approximate analytical solution predicts the facilitation factors for the range from the moderate reaction rate to the equilibrium chemical reaction regime, allowing unequal diffusivities of complexes and carrier and cases of zero and nonzero permeate side solute concentrations. In the present mathematical model, a constant free carrier concentration is assumed throughout the membrane phase. In comparison with the numerically calculated results, the results obtained were found to be in well agreement.     

Selective transport of radio-cesium by supported liquid membranes containing calix[4]crown-6 ligands as the mobile carrier

Facilitated transport of Cs-137 across supported liquid membranes (SLM) containing a calix-crown ligand viz. caliz[4]arene-bis(crown-6) (CC), calix[4]arene-bis(o-benzocrown-6) (CBC) or calix[4]arene-bis(napthocrown-6) (CNC) was investigated. The feed consisted of dilute nitric acid solutions while the carrier solutions contained mainly CNC in several organic diluents inside the pores of polypropylene (PP) as well as PTFE flat sheet membranes. PTFE membranes containing CNC in a diluent mixture of 2-nitrophenyloctyl ether (NPOE) and n-dodecane were found to have high stability. Selectivity studies were carried out using simulated high level waste (SHLW) as well as fission products obtained from an irradiated natural uranium target.     

Facilitated transport of benzylpenicillin through immobilized liquid membrane

The rate of benzylpenicillin transport, as an ionic pair with a tetrabutyl ammonium cation, from aqueous media through a liquid membrane consisting of n-decanol supported in a porous Teflon membrane has been investigated as a function of the chemical composition of the system and the hydrodynamic conditions at 25°C. The measured transfer rates have been explained in terms of the diffusion of the ionic pair species through the liquid membrane. The results are in agreement with theoretical predictions and it is demonstrated that the transport of benzylpenicillin takes place against a concentration gradient.     

Transport of lanthanides and fission products through supported liquid membranes containing N,N,N′,N′-tetraoctyl diglycolamide (TODGA) as the carrier

Facilitated transport of trivalent lanthanides, viz. La(III), Eu(III), Lu(III) and several fission product elements such as Tc, Mo, Zr, Pd, I, Cs and Ru across a flat sheet supported liquid membrane made of PTFE impregnated with N,N,N′,N′-tetraoctyl diglycolamide (TODGA) in n-dodecane was investigated from dilute nitric acid solutions. The transport rates of lanthanides increased with nitric acid concentration in a manner similar to their distribution ratios. The trend in metal ion transport after 75 min followed the order: La > Eu > Lu > Zr > Sr > I > Pd ~ Tc > Ru > Mo ~ Cs, which was consistent even after 5 h of operation. However, the transport of I reached the maximum value of ~26% in 100 min and remained constant thereafter. In the case of Am(III) transport studies, excellent decontamination from Zr was achieved when 0.4 M oxalic acid was added to the feed solution.     

Highly selective and efficient transport of toluene in bulk ionic liquid membranes containing Ag as carrier

Ionic liquids have very low vapour pressure and a very high boiling temperature and are therefore a potentially environmentally friendly solvent. In this paper, room-temperature ionic liquids are used as a bulk liquid membrane for separation of toluene from n-heptane. Aromatic hydrocarbon, toluene, is successfully transported through the ionic liquid membrane based on 1-methyl-3-octyl imidazolium chloride. Using silver ion as a carrier in 1-methyl-3-octyl imidazolium chloride membranes, batch wise extraction experiments are carried out. The separation performances, represented by the permeation rate and separation factor, are analyzed systematically by varying the operating parameters: the contact time, concentration of Ag⁺, stirring effect, initial feed phase concentration and temperature.     

Specific membrane transport of silver and copper as Ag(CN)3 and Cu(CN)4 ions through a supported liquid membrane using K-crown ether as a carrier

Facilitated transport of silver and copper from cyanide solutions through a supported liquid membrane (SLM) containing K⁺-crown ether as a carrier is described. The SLM used is a thin porous polypropylene (Celgard 2500, 2400) membrane impregnated with dibenzo-18-crown-6 (DB18C6), diaza-18-crown-6 (DA18C6), hexathia-18- crown-6 (HT18C6) and hexaaza-18-crown-6 (HA18C6) dissolved in a mixture of ethanol/chloroform (v/v). K₋⁺-crown ether showed a high efficiency to carry silver and copper as Ag(CN)₃²⁻ and Cu(CN)₄³⁻ species through the SLM. However, the mass flux of both silver and copper ions decreases when concentration of cyanide ions in the feed phase increases due to the difference in stability of the complexes M(CN)_nⁿ⁻(M=Ag, Cu) when n increases from 2 to 4. This was related to the partition of the species in the aqueous phase using a theoretical model.     

Rate and mechanism of divalent metal transport through supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier

The rate and mechanism of copper, cobalt, nickel and zinc transport through a supported liquid membrane containing di(2-ethylhexyl) phosphoric acid as a mobile carrier were studied, respectively. The permeation rate equations have been derived taking into account aqueous film diffusion, interfacial chemical reaction and membrane diffusion as simultaneous controlling steps. The possible rate-controlling steps were estimated by comparing the relative values of the three successive resistances. The measured permeation rates of zinc agreed well with the proposed mechanism in this study.     

Effect of carrier type on coupled transport kinetics of thiocyanate ions through liquid membranes

Coupled transport of thiocyanate ions through a liquid membrane containing quaternary ammonium chloride salts in chloroform was examined. The influences of the carrier type in the membrane phase on the coupled transport of thiocyanate ions were investigated. The kinetics of the coupled transport were analyzed in the formalism of two consecutive irreversible first-order reactions and the kinetic parameters (k_1d, k_2m, k_2a, R_m^max, t_max, J_d^max, J_amax) were also calculated. For the coupled transport of thiocyanate ions, quaternary ammonium chloride salts having different carbon atom numbers (C_n) used as carriers were found to increase thiocyanate ions transport efficiency with increasing carbon atom numbers. Tetradecyl trimethylammonium chloride (TDTMACl), hexadecyl trimethylammonium chloride (HDTMACl), and tetraoctyl ammonium chloride (TOACl) were found to be the most effective carrier types for transport of thiocyanate ions when C_n is greater than 16. The activation energies for maximum membrane entrance and exit fluxes were calculated as 32.45 kJ/mol and 34.75 kJ/mol, respectively. The values of the activation energy indicate that the process is controlled by species diffusion.     

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.     

Transport of mercury(II) ion through a supported liquid membrane containing a triisobutylphosphine sulfide (Cyanex 471X) as a mobile carrier

Carrier‐facilitated transport of mercury(II) against its concentration gradient from aqueous 0.1 mol dm^?3 hydrochloric acid solution across a flat‐sheet supported liquid membrane (SLM) containing triisobutylphosphine sulfide (Cyanex 471X) as the mobile carrier in kerosene as diluent has been investigated. Dilute sodium thiocyanate solution (0.11 mol dm^?3) was the most efficient stripping agent among several aqueous reagents tested. Various parameters such as stirring rate, concentration of HCl in the feed solution, concentration of NaSCN in the strippant, concentration of Cyanex 471X in the membrane, and contact time were investigated. Under optimum conditions the transport of Hg(II) across the liquid membrane is about 100% after 6 h. The carrier, Cyanex 471X, selectively and efficiently transported Hg(II) ions in the presence of other associated metal ions. The method has been demonstrated to recover selectively mercury from waste samples and mercurochrome solution. © 2002 Society of Chemical Industry     

On the permeation rate of copper extraction through liquid membranes

The understanding of the permeation rate of metal ions through liquid membranes is important for the design of such systems. In this paper, the permeation rates of copper ions through liquid surfactant membranes, including interfacial reaction rates and the diffusion rate of the copper ion, were analyzed using a model based on a mobilized hollow spherical globule configuration. The analysis shows that the extracting reaction is dominant at the external interface of the membrane and the stripping reaction is dominant at the internal interface; this means the reactions at both interfaces are not in equilibrium during the course of extraction. It also shows that the extraction rate, the diffusion rate and the stripping rate are not of equal value, especially at the early stage of the run.     

Non-steady-state kinetic analysis of coupled transport of thiocyanate ions through binary liquid membranes

The coupled transport of thiocyanate (SCN⁻) ions through binary liquid membranes of various compositions was investigated using trichloromethane and dichloromethane as membrane components in non-steady-state kinetics. The influence of the membrane composition on the kinetic parameters (k_1d, k_2m, k_2a, R^max_m, t_max) were calculated. The present work shows the importance of the nature of binary liquid membranes in establishing transport efficiency, which is increased by varying membrane composition. Striking variations of the kinetic parameters with the membrane composition were observed. It is shown that transport kinetics obeys the competitive preferential solvation theory in the whole concentration range.     

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.     

聚酰胺胺-1,2-环氧辛烷树状大分子的合成及其作为乳化液膜载体的性能

引言 树状大分子是一类三维、高度有序的新型高分子,合成时,可以在分子水平上进行设计来控制其分子大小、形状、结构和官能团,来满足不同的目的和要求,而且产物对称性好,相对分子质量的单分散性好,因而具有广阔的潜在应用领域[1-6].     

Highly efficient and selective membrane transport of silver(I) using hexathia-18-crown-6 as a specific ion carrier

Hexathia-18-crown-6 (HT18C6) was used as a specific ion carrier for the transport of silver ion through a chloroform bulk liquid membrane. In the presence of thiosulfate ion as a suitable stripping agent in the receiving phase, the amount of silver transported across the liquid membrane after 60 min is 99.5±1.0%. The selectivity of Ag⁺ transport from the aqueous solutions containing other Mⁿ⁺ cations such as Tl⁺, Mg²⁺, Ca²⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Pb²⁺, Hg²⁺, and Cr³⁺ ions was investigated. Except with Hg²⁺ ion, non of the cations used interfere the silver transport, even at a Mⁿ⁺/Ag⁺ molar ratio of 500. The interfering effect of Hg²⁺ ion was successfully eliminated in the presence of EDTA at pH 5.     

A selective uphill transport of copper through bulk liquid membrane using Janus Green as an anion carrier

A bulk liquid membrane consisted of 1.8×10⁻⁴ M Janus Green in chloroform that placed between an aqueous source phase containing 0.5 M sodium thiocyanate at pH 7 and an aqueous receiving phase with 0.1 5 M histidine at pH 7 results in an uphill transport of copper from the source phase to the receiving phase. The amount of copper transport through the liquid membrane after 180 min was 97.0±1.7%. The presence of other metals such as Cd²⁺, Zn²⁺, Hg²⁺, Mg²⁺, Ag¹⁺, Ni²⁺, Pb²⁺, Fe³⁺, K¹⁺, Co²⁺ doesn't change the efficiency of copper transport.