Effect of carrier concentration on the facilitated oxygen transport in a polymer membrane

Facilitated transport of oxygen in a solid Polymer membrane containing cobaltporphyrin (CoP) which carries oxygen specifically and reversibly, leads to permselectivity of oxygen against nitrogen in the membrane. The increase in concentration of the CoP carrier is expected to enhance the oxygen transport. The membranes of poly(octylmethacrylate-co-vinylimidazole) containing 0.8 ～ 10 wt% CoP were prepared, and the effects of the CoP-concentration on the transport and the diffusion constants of oxygen are studied. Although the induction period before the steady state of oxygen permeation was prolonged with the CoP concentration in the polymer membrane, the glass transition temperature (T_g) of the membrane was increased and the diffusion constants of oxygen were decreased with the CoP concentration to yield unexpected reduction of the oxygen permeation in the highly CoP loaded membrane.     

Ion transport across a bilayer lipid membrane facilitated by valinomycin

The facilitated ion transport from one aqueous phase, W1, to another, W2, across a bilayer lipid membrane, BLM, containing valinomycin, Val, as an ionophore was investigated by voltammetry. Cyclic voltammograms for the ion transfer were symmetrical about the origin (0 V, 0 A) and the magnitude of the ion transfer current increased with an increase in the absolute value of the applied potential. The magnitude of the ion transfer current at a definite potential in the voltammograms depended on the cation species added to W1 and W2 and was proportional to the concentration of Val in the BLM. The magnitude of the ion transfer current at a definite potential also varied in proportion to the hydrophobicity of the counter anion in W1 and W2. Taking into account the conjugated ion transfers at the W1|BLM and BLM|W2 interfaces, the positive current that flowed from W1 to W2 across the BLM was attributable to both the transfer of the complex-forming cation from W1 to the BLM and the transfer of the anion, which was distributed in the BLM as the counter ion from W2 to W1. The transfer from the BLM to W1 occurred at the W1|BLM interface and both the transfer of the cation from the BLM to W2 and the transfer of the anion from W2 to the BLM at the BLM|W2 interface. The negative current was then attributed to the opposite reaction. The voltammograms were asymmetrical with the origin when the ion components in W1 and W2 were different.     

Nanocomposite membranes containing positively polarized gold nanoparticles for facilitated olefin transport

Positively polarized gold nanoparticles have been demonstrated for use as stable olefin carriers for facilitated olefin transport membranes. The formation and size of gold nanoparticles stabilized by 4-dimethylaminopyridine (DMAP) were monitored using X-ray diffraction (XRD), transmission electron microscopy (TEM) and UV–visible spectroscopy. Nanocomposite membranes that deliver high separation performance for olefin/paraffin mixtures were prepared by dispersing gold nanoparticles stabilized by DMAP in a polymer matrix, poly(vinyl pyrrolidone) (PVP). X-ray photoelectron spectroscopy (XPS) and zeta potential measurements revealed that gold nanoparticles stabilized by DMAP exhibited a high positive polarity, which is responsible for the reversible interaction between the gold nanoparticles and olefin molecules. Compared to neat PVP membranes, the composite membranes consisting of PVP and the polarized gold nanoparticles showed stable and enhanced separation of olefin/paraffin mixtures.     

Investigation of the carrier saturation in facilitated transport of unsaturated hydrocarbons

Single-component facilitated transports of ethylbenzene, styrene, cyclohexene and 1-hexene were carried out using the feed concentrations ranging from 0.5 M to pure. Equilibrium constants of the Ag⁺-solute complex formation, determined by distribution method, were 0.7, 2.2, 32.0, 129.1 M⁻¹, respectively. Carrier saturation was not found with the membrane incorporated with 2.67 M Ag⁺-ion. As the carrier concentration was reduced to 0.51 M, increase in the feed concentration beyond 4.5 M had very little effect on ethylbenzene flux, suggesting the onset of carrier saturation. Styrene and cyclohexene underwent the carrier saturation when the carrier loading was 0.25 M, while a complete saturation was not observed with 1-hexene. Extraction of solute from the membranes revealed that less than 50% of Ag⁺-ions were occupied when the carrier saturation occurred. It was also found that the ability of solute to use available Ag⁺-ions in the membrane was dependent on the equilibrium constant.     

Effect of the polarity of silver nanoparticles induced by ionic liquids on facilitated transport for the separation of propylene/propane mixtures

The effect of ionic liquids on the formation of a partial positive charge on the surface of silver nanoparticle and its subsequent effect on facilitated olefin transport were investigated. Three different ionic liquids of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIM⁺BF₄⁻), 1-butyl-3-methylimidazolium triflate (BMIM⁺Tf⁻), and 1-butyl-3-methylimidazolium nitrate (BMIM⁺NO₃⁻) were employed to control the positive charge density of the surface of silver nanoparticles. The positive charge density of the silver nanoparticles, as characterized by the binding energy of the silver atom, was in the following order: BMIM⁺BF₄⁻/Ag ? BMIM⁺Tf⁻/Ag > BMIM⁺NO₃⁻/Ag. This order was consistent with the tendency of ionic liquids to form free ions. The best separation performance for the propylene/propane mixtures was a mixed gas selectivity of 17 and a permeance of 7 GPU through a composite membrane consisting of BMIM⁺BF₄⁻/Ag. A better separation performance for olefin/paraffin mixtures was observed with a higher positive charge density of the silver nanoparticles. It was therefore concluded that facilitated olefin transport was a direct consequence of the surface positive charge of the silver nanoparticles induced by ionic liquids.     

Mass transfer determining parameter in facilitated transport through di-(2-ethylhexyl) dithiophosphoric acid activated composite membranes

Activated composite membranes (ACMs) containing di-(2-ethylhexyl) dithiophosphoric acid (D2EHDTPA) as a carrier have been found to facilitate the transport and separation of several cations. This paper describes an approach to the chemical characterisation of the transport phenomena of Zn²⁺, Cd²⁺, Cu²⁺, Ni²⁺, Sn²⁺ and In³⁺ by an ACM. The selectivity of D2EHDTPA based ACM towards different metal ions is presented and discussed focusing in Zn²⁺ and Cd²⁺ transport and recovery. Selectivity demonstrates that zinc ions are removable from mixtures due to the different extraction strength of D2EHDTPA. Such selectivity is based on the differences of the dynamic behaviour of the metal ions transport. In addition, a correlation of the chemical behaviour of those ACM systems with the corresponding solvent extraction systems has been found.     

An ab initio study of ionic liquid silver complexes as carriers in facilitated olefin transport membranes

Liquid phase isoprene/n-pentane mixtures can be separated through the use of facilitated transport membranes containing complexes of silver ions with an ionic liquid (IL). 1-Butyl-3-methyl imidazolium tetrafluoroborate and zwitterion-type imidazolium compounds containing covalently-bound sulfonate groups form complexes with AgX (X = BF₄, NO₃, and ClO₄). Facilitated isoprene transport has been observed with selectivities that depend on the counteranion of the silver salt. The facilitated transport phenomena of the olefin and IL/silver complexes were investigated theoretically by calculating their complexation energies (i.e., the energy of formation of the silver complexes with the olefin) with the density functional theory method. Among polymer/silver salt systems, the polymer/AgBF₄ system has been found to be generally more favorable for facilitated olefin transport than the polymer/AgNO₃ system because of the low lattice energy of AgBF₄. However, there is a different trend for IL/AgX systems. This difference may arise because the positively charged components of the IL can interact with the anions of the silver salt, which changes the olefin complexation activity. For IL/AgX systems, the selectivity varies inversely with the complexation energy, which implies that the diffusion of the carrier may be the significant factor affecting isoprene/n-pentane separation, once the appropriate complexation has occurred between olefin molecules and the ILsilver complexes.     

Facilitated transport of Am(III) through a flat-sheet supported liquid membrane (FSSLM) containing tetra(2-ethyl hexyl) diglycolamide (TEHDGA) as carrier

Facilitated transport of Am(III) in nitric acid medium using tetra(2-ethyl hexyl) diglycolamide (TEHDGA) in n-dodecane as carrier was studied. It was aimed at finding out the physico-chemical model for the transport of Am(III) using TEHDGA/n-dodecane as carrier under various experimental parameters like feed acidity, carrier concentration, varying strippant, varying membrane pore size, etc. The feed acidity and carrier concentrations were varied from 1 M to 6 M HNO₃ and 0.1 M to 0.3 M TEHDGA/n-dodecane, respectively. The transport of Am(III) increased with increase in feed acidity and carrier concentration reaching maximum at 3 M HNO₃ and 0.2 M TEHDGA/n-dodecane, respectively. Several stripping agents were tested and 0.1 M HNO₃ was found to be the most suitable stripping agent for this system. Almost quantitative transport of Am(III) was observed at about 180 min with feed acidity of 3 M HNO₃, 0.1 M HNO₃ as strippant and 0.2 M TEHDGA/n-dodecane as carrier. The pore size of the membrane support was varied from 0.20 μm to 5 μm and the permeation coefficient increased with increase in pore size up to 0.45 μm (2.43 × 10⁻³ cm/s), and then decreased with further increase in pore size. The plot between permeation coefficient vs. (membrane thickness)⁻¹ was linear which showed that the Am(III) transport was membrane diffusion limited. The membrane diffusion coefficient calculated from the graph was found to be 1.27 × 10⁻⁶ cm²/s and its theoretical value was 1.22 × 10⁻⁶ cm²/s. The stability of the carrier against leaching out of the membrane support as well as the integrity of membrane support was studied over a period of 30 days and was found to be satisfactory within the studied time period.     

Mathematical modeling of silver extraction by an emulsion liquid membrane process

A general physical model of a typical batch extraction system employing an emulsion liquid membrane process for the extraction of silver has been developed. The model takes into account the extraction reaction between the silver ion and the carrier molecules at the external interface, the diffusion of the complex in the membrane phase, the stripping reaction at the internal interface and the reaction of silver ion with the reagent, HCL, in the internal phase to yield silver chloride incapable of permeating through the membrane phase. In addition, the leakage of the internal aqueous phase to the external aqueous phase due to membrane breakage has been incorporated in this model. The batch extraction of silver using D2EHPA as a carrier has been carried out under various experimental conditions. The experimental data can be well explained by the present model.     

Facilitated transport of CO2 in novel PVAm/PVA blend membrane

A defect-free ultra thin PVAm/PVA blend facilitated transport membrane cast on a porous polysulfone (PSf) support was developed and evaluated in this study. The target membrane was prepared from commercial polyvinyl amine (PVAm) and polyvinyl alcohol (PVA). Effects of experimental conditions were investigated for a CO₂–N₂ mixed gas. A CO₂/N₂ separation factor of up to 174 and a CO₂ permeance up to 0.58 m³(STP)/(m² h bar) were documented. Experimental results suggest that CO₂ is being transported according to the facilitated transport mechanism through this membrane. The fixed amino groups in the PVAm matrix function as CO₂ carriers to facilitate the transport whereas the PVA adds mechanical strength to the blend by entanglement of the polymeric chains hence creating a supporting network. The good mechanical properties obtained from the blend of PVA with PVAm, enabled an ultra thin selective layer (down to 0.3 μm) to be formed on PSf support (with MWCO of 50,000), resulted in both high selectivity and permeance. The PVAm/PVA blend membrane also exhibited a good stability during a 400 h test.     

Quantitative analysis of transport process of cerium(III) ion through polymer inclusion membrane containing N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) as carrier

The facilitated transport mechanism of cerium(III) ions through polymer inclusion membrane (PIM) consisting of cellulose triacetate (CTA) as a polymer matrix, 2-nitrophenyl n-octyl ether (NPOE) as a solvent and N,N,N′,N′-tetraoctyl-3-oxapentanediamide (TODGA) as a carrier was studied. In order to evaluate the mass transport phenomena in the PIM, a mathematical model was derived from the Fick's first law and the equations for the extraction and the material balance. Methods to determine the values of the transport parameters such as the diffusion coefficient are described, and the dependency of the flux on the experimental condition was calculated. The model is very useful as a design tool to analyze and optimize the concentration process of low level radioactive wastewater using the PIM.     

Effect of operating conditions on separation performance of reactive dye solution with membrane process

Membrane process has increasingly developed as a reliable and effective means of improving product yield and reducing manufacturing costs in the reactive dye industry. In order to improve a product's quality, ultrafiltration (UF) membrane has been applied to perform Reactive Brilliant Blue KN-R desalting and concentration. The performance of this membrane's separation process was evaluated under different operating conditions, through which the influence of operating pressure, temperature, cross-flow velocity, pH, concentration of feed and operating time on permeate flux, rejection of Reactive Brilliant Blue KN-R and sodium sulfate were studied.     

Facilitated transport of CO2 across a liquid membrane: Comparing enzyme, amine, and alkaline

In this work we compare the efficiency of facilitated transport of CO₂ across a liquid membrane by different facilitators as tested in either a supported liquid membrane (SLM) or a hollow fiber contained liquid membrane (HFCLM) configuration. Permeance and selectivity were evaluated by both experimental test and numerical simulation. These comparisons were used to define the best liquid membrane composition to maximize separation performance. We also consider other factors that affect the choice of the facilitator, e.g. operation temperature and cost. Under ambient operating conditions, carbonic anhydrase (CA) combined with an alkaline carbonate gives better performance than does diethanolamine (DEA).     

High temperature separation of carbon dioxide/hydrogen mixtures using facilitated supported ionic liquid membranes

Efficiently separating CO₂ from H₂ is one of the key steps in the environmentally responsible uses of fossil fuel for energy production. A wide variety of resources, including petroleum coke, coal, and even biomass, can be gasified to produce syngas (a mixture of CO and H₂). This gas stream can be further reacted with water to produce CO₂ and more H₂. Once separated, the CO₂ can be stored in a variety of geological formations or sequestered by other means. The H₂ can be combusted to operate a turbine, producing electricity, or used to power hydrogen fuel cells. In both cases, only water is produced as waste. An amine-functionalized ionic liquid encapsulated in a supported ionic liquid membrane (SILM) can separate CO₂ from H₂ with a higher permeability and selectivity than any known membrane system. This separation is accomplished at elevated temperatures using facilitated transport supported ionic liquid membranes.     

CO2/H2 separation by facilitated transport membranes immobilized with aqueous single and mixed amine solutions: Experimental and modeling study

An experimental and theoretical analysis to separate CO₂ using facilitated transport membranes immobilized with different aqueous single and mixed amine solutions have been performed. The membranes containing monoethanolamine (MEA), diethanolamine (DEA), monoprotonated ethylenediamine (EDAH⁺) and piperazine (PZ), as well as aqueous blends of PZ with MEA, DEA or EDAH⁺ were considered. The aqueous solution of PZ showed the highest CO₂ permeation rate with respect to other single amine solutions. Therefore blends of PZ with MEA, DEA and EDAH⁺ increased the permeance of carbon dioxide through mixed amine membranes.     

Gas transport property of polyallylamine–poly(vinyl alcohol)/polysulfone composite membranes

Polyallylamine (PAAm) was synthesized by free radical polymerization and characterized by Fourier transform infrared resonance (FT-IR) spectroscopy, hydrogen nuclear magnetic resonance (¹H NMR) spectroscopy and differential scanning calorimetry (DSC). The composite membranes were prepared by using PAAm–poly(vinyl alcohol) (PVA) blend polymer as the separation layer and polysulfone (PSF) ultrafiltration membranes as the support layer. The surface and cross-section morphology of the membrane was inspected by environmental scanning electron microscopy (ESEM). The gas transport property of the membranes, including gas permeance, flux and selectivity, were investigated by using pure CO₂, N₂, CH₄ gases and CO₂/N₂ gas mixture (20 vol% CO₂ and 80 vol% N₂) and CO₂/CH₄ gas mixture (10 vol% CO₂ and 90 vol% CH₄). The plots of gas permeance or flux versus feed gas pressure imply that CO₂ permeation through the membranes follows facilitated transport mechanism whereas N₂ and CH₄ permeation follows solution–diffusion mechanism. Effect of PAAm content in the separation layer on gas transport property was investigated by measuring the membranes with 0–50 wt% PAAm content. With increasing PAAm content, gas permeance increases initially, reaches a maximum, and then decreases gradually. For CO₂/N₂ gas mixture, the membranes with 10 wt% PAAm content show the highest CO₂ permeance of about 1.80 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/N₂ selectivity of 80 at 0.1 MPa feed gas pressure. For CO₂/CH₄ gas mixture, the membranes with 20 wt% PAAm content display the highest CO₂ permeance of about 1.95 × 10⁻⁵ cm³ (STP) cm⁻² s⁻¹ KPa⁻¹ and CO₂/CH₄ selectivity of 58 at 0.1 MPa feed gas pressure. In order to explore the possible reason of gas permeance varying with PAAm content, the crystallinity of PVA and PAAm–PVA blend polymers was measured by X-ray diffraction (XRD) spectra. The experimental results show an inverse relationship between crystallinity and gas permeance, e.g., a minimum crystallinity and a maximum CO₂ permeance are obtained at 20 wt% PAAm content, indicating that the possibility of increasing CO₂ permeance with PAAm content due to the increase of carrier concentration could be weakened by the increase of crystallinity.     

Nitrate and chloride transport through a smart membrane

To develop membranes having ionic selective properties under control of external stimuli is a challenge of the membrane and material scientific community. Conducting polymers swell and shrink under electrochemical control, so they are good candidates to prepare such smart membranes. The ionic transport through a new free-standing polypyrrole film working as a membrane in a diffusion cell was studied. The driving forces were transversal electric fields or concentration gradients across the film. The obtained ionic conductivity was dependent on both the electrolyte nature and concentration, as well as on the oxidation degree of the film, which was controlled by the applied external electric potential. Reverse and continuous changes of up to one order of magnitude on the transversal ionic conductivity are obtained when the membrane is in stationary oxidation states attained by polarisations at a constant potential in the range between −0.6 V and +0.4 V, respectively. A prevalent conductivity of anions (t₋ = 0.94) was obtained from Donnan potential measurements. The experimental results indicate that the oxidised film behaves as a nanoporous membrane highly permeable to nitrate ions, while the rejection of these ions is very high in the reduced film. The free-standing polypyrrole film works then as a smart membrane selective to nitrate ions under concentration gradient.     

Improved analytical prediction of facilitation factors in facilitated transport

An improved analytical solution for the facilitation factor in facilitated transport that covers a wide range from diffusion-limited to reaction-limited mass transport has been developed. This solution is attained after assuming a small non-zero solute concentration at the membrane exit. Based on previous analysis a graph that provides a reasonable downstream solute concentration was extracted. The exit solute concentration was found to be dependent on both the mobility ratio, , and the inverse Damkohler number, ε. The quick and reasonable results in this work can be used for design and scale-up purposes.