New morphological Ba0.5Sr0.5Co0.8Fe0.2O3−α hollow fibre membranes with high oxygen permeation fluxes

Perovskite Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?α (BSCF) hollow fibre membranes were fabricated by a combined phase inversion and sintering technique. The membranes were characterised by XRD, SEM and tested for air separation. The membrane possesses a novel morphology consisting of one dense layer and one porous layer. Oxygen permeation fluxes through the obtained hollow fibre membranes were measured in the temperature range 650–950 °C using helium sweep gas rates from 50 to 200 mL min^?1. Experimental results indicated the oxygen permeation flux through the BSCF hollow fibre membrane sintered at 1050 °C was approximately 11.46 mL min^?1 cm^?2 at 950 °C when the helium sweep rate was kept at 200 mL min^?1. The BSCF hollow fibre membrane showed a stable oxygen permeation flux of 8.60 mL min^?1 cm^?2 over the investigated period of 120 h at 900 °C.     

Study of pervaporation for dehydration of caprolactam through PVA/nano silica composite membranes

We investigated nano silica/PVA composite membranes to propose an improved caprolactam pervaporation (PV) dehydration process. The membranes were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X-ray diffraction, and contact angle measurement. Compared with the pure PVA membranes, the nano silica/PVA composite membranes showed different surface morphologies with enhanced hydrophilicity because of their unique formation. To evaluate PV performance and mechanism, we assessed the permeation flux, separation factor, diffusivity/sorptivity selectivity, and activation energy of the composite membranes. The evaluated results indicate that the nano silica/PVA composite membranes induced a breakthrough in the dehydration of a caprolactam-water mixture with a maximum flux of 3.8 kg m^? 2 h^? 1 and an acceptable separation factor of 150.     

Dynamic removal of n-hexane from water using nanocomposite membranes: Serial coating of para-aminobenzoate alumoxane,boehmite-epoxide and chitosan on Kevlar fabrics

Nanocomposite membranes were fabricated by dip-coating technique. Para-aminobenzoate alumoxane, boehmite–epoxide and chitosan were consecutively coated on the Kevlar fabric surface. The membranes were utilized for removing n-hexane from water using a gravity-driven dead-end filtration setup. UV–vis, FTIR and SEM analyses were performed for characterization. Water affinity analyses revealed highly hydrophilic nature of the modified membranes. Effect of pH was examined with the pH 2 providing the best condition for oil–water separation. Maximum flux and rejection were obtained as 1128 L m⁻² h⁻¹) and 94%, respectively. Deposited oil layer was effectively removed from the membrane surface using hot citric acid solution.     

Pressure-assisted self-assembly technique for fabricating composite membranes consisting of highly ordered selective laminate layers of amphiphilic graphene oxide

We prepare highly ordered flexible layers of graphene oxide (GO) on modified polyacrylonitrile substrates by the pressure-assisted self-assembly technique. This composite membrane shows excellent performance during the pervaporation separation of a 70 wt.% isopropyl alcohol (IPA)/water mixture: 99.5 wt% water in permeate and 2047 g m⁻² h⁻¹ permeation flux. Despite the specific GO deposition increase from 4.3 to 43.3 × 10⁻⁵ g cm⁻² (ninefold layer thickness growth), its effect on the permeation flux is not significant, as manifested by only a little decrease in the flux. At 70 °C feed temperature, the permeate water concentration remains 99.5 wt% and the permeation flux reaches 4137 g m⁻² h⁻¹. The high selectivity may be due to the dense GO film consisting of highly ordered and packed laminates, allowing water but inhibiting IPA molecules to pass through. GO is demonstrated to be amphiphilic: water molecules adsorb first at the hydrophilic edge (hydroxides) and then rapidly diffuse through the hydrophobic core (mainly carbon), forming a water passage channel that promotes high permeation flux. When water molecules permeate through the GO layers, they accumulate and form a monolayer structure that pushes the successive layers away from each other, leading to widening of the d-spacing.     

Development of asymmetric BTDA-TDI/MDI (P84) copolyimide flat sheet and hollow fiber membranes for ultrafiltration: Morphology transition and membrane performance

In this paper, the effects of γ-butyrolactone (GBL) weight ratio (w_GBL) and membrane thickness on the formation of asymmetric flat sheet membranes prepared with P84 (BTDA-TDI/MDI co-polyimide)/N-methyl-2-pyrrolidone (NMP)/GBL casting solutions are investigated. With the increase of membrane thickness, the transition of membrane morphology from sponge-like to finger-like structure occurs at critical structure-transition thickness L_c. L_c and the general sponge-like structure thickness (L_gs) increase with w_GBL. For 20 wt.% P84/NMP/GBL casting solution, the membrane morphology changes from finger-like to sponge-like structure at the critical weight ratio of GBL (w^? = 0.69). The membrane morphology and performance of hollow fibers spun with various w_GBL are observed. Compared with the hollow fiber membranes made of 18 wt.% P84/NMP/GBL dope solution with w_GBL = 0.75, the hollow fiber membranes spun with w_GBL = 0.25 present a higher permeation flux and a larger MWCO. As w_GBL increases from 0.25 to 0.75, the membrane morphology transfers from finger-like to sponge-like structure. An increase in shear rate shifts the rejection curves towards left, and lowers the MWCO of hollow fiber membranes. For hollow fiber membranes spun with w_GBL = 0.75, a relatively high permeation flux and a large MWCO are obtained by the wet spinning process.     

Pervaporative desalination of water using natural zeolite membranes

Several deposits of dense natural clinoptilolite, including one from British Columbia, Canada, have been identified which exhibit both high zeolite content and essentially no macroporosity or intercrystalline voids. Sections of zeolite mineral from the British Columbia deposit were machined into thin membranes and used in the pervaporative desalination of water samples with varying salinity levels, including synthetic seawater. Essentially complete rejection of Mg²⁺ and Ca²⁺ (99.99% and 98.52%) and high levels of rejection of Na⁺ and K⁺ (over 97.5%) were observed when using a synthetic seawater feed at 75 °C and 1 atm feed-side pressure. Water flux through the natural zeolite membranes was dependent on the ion concentration in the feed, the operating temperature and the feed salinity. At 93 °C, water fluxes of 2.5 kg/m²·h and 0.39 kg/m²·h were obtained for feed concentrations of 100 mg/L Na⁺ and 5500 mg/L Na⁺, respectively. The high ion rejection and water flux observed for these rugged and economical natural clinoptilolite membranes indicates their potential utility for desalination applications.     

Effect of cellulosic sugar degradation products (furfural and hydroxymethyl furfural) on acetone–butanol–ethanol (ABE) fermentation using Clostridium beijerinckii P260

Studies were performed to identify chemical compounds present in wheat straw hydrolysate (WSH) that enhance acetone butanol ethanol (ABE) productivity. These compounds were identified as furfural and hydroxymethyl furfural (HMF). Control experiment resulted in the production of 21.38 g L^?1 ABE with a productivity of 0.30 g L^?1 h^?1. WSH contained 0.04–0.34 g L^?1 furfural and 0.12–0.88 g L^?1 HMF. Addition of furfural to the fermentation medium at a concentration of 0.50 g L^?1 resulted in a productivity of 0.88 g L^?1 h^?1 which is 293% of the productivity obtained in control experiments. Supplementation with 1.00 g L^?1 HMF into the fermentation medium produced 25.27 g L^?1 ABE with a productivity of 0.68 g L^?1 h^?1. A combination of furfural (0.50 g L^?1) and HMF (0.50 g L^?1) also enhanced ABE production and productivity when added to the fermentation medium. Both furfural and HMF enhanced specific productivity (233–308%) of ABE. In brief, WSH contained an adequate concentration of furfural and HMF that enhanced ABE productivity, specific productivity, and product concentration.     

SrCo0.9Sc0.1O3−δ perovskite hollow fibre membranes for air separation at intermediate temperatures

SrCo_0.9Sc_0.1O₃ (SCSc) perovskite powders with sub-micron particle size were synthesized by a modified Pechini method combined with a post-treatment of sintering and ball-milling. From the prepared powders, the SCSc hollow fibre membranes with asymmetric structure and gas-tight property were fabricated by spinning a polymer solution containing 58.4 wt% SCSc followed by sintering at 1200 °C for 5 h. The oxygen permeation properties of the obtained SCSc fibres were measured under air/He gradients at 500–800 °C. This showed the oxygen flux of 1 mL cm^?2 min^?1 at 750 °C and 4.41 mL cm^?2 min^?1 at 900 °C. Modeling analysis reveals that the oxygen permeation process is predominated by oxygen surface exchange kinetics with an activation energy of 95.0 kJ mol^?1. The SCSc membranes showed excellent oxygen permeation performance while exhibiting high structural and permeating stability at intermediate temperatures (500–800 °C).     

Enhanced water desalination performance through hierarchically-structured ceramic membranes

Developments of membrane water desalination are impeded by low water vapor flux across the membrane. We present an innovative membrane design to significantly enhance the water vapor flux. A bilayer zirconia-based membrane with a thick hierarchically-structured support and a thin functional layer is prepared using a combined freeze drying tape casting and screen printing method. The hierarchically-structured YSZ support has a porosity of 42.6%, pores of 4.5 μm or larger, and a relatively low tortuosity of 1.58 along the thickness direction. The bilayer membrane is then converted from naturally hydrophilic to hydrophobic via grafting with a fluoroalkylsilane. A water flux of 28.7 Lm⁻² h⁻¹ and a salt rejection of 99.5% are achieved by exposing the functional layer to 80 °C salt water of 2 wt.% NaCl and the support layer to 20 °C distilled water. These results are the best performing ones for ceramic membranes in direct contact membrane distillation operation.     

Microfiltration of whole milk with silicon microsieves: Effect of process variables

The impact of high-frequency cross-flow back-pulsing on microsieves permeation performance during the microfiltration of whole milk is described in this work. Silicon nitride microsieves (0.8 μm rectangular) combined with a dynamic permeate cross-flow back-pulsing technique to control fouling were used. Results showed that the transmembrane pressure (TMP_pos) and the back-pulsing frequency were the process variables that most influenced microsieves performance. Permeation rates in the range of 5000 up to 27,000 L h^?1 m^?2 which are one order of magnitude higher than those reported for skim milk microfiltration were obtained depending on the process conditions selected. It was concluded that higher permeation rates are obtained when the back-pulse pressure, i.e., the negative TMP is set equal to the positive TMP, both at 150 mBar and the back-pulsing frequency at 15 Hz.     

Processing of alumina-coated clay–diatomite composite membranes for oily wastewater treatment

Crack-free alumina-coated clay–diatomite composite membranes were successfully prepared by a simple pressing and dip-coating route using inexpensive raw materials at a temperature as low as 1000 °C in air. The changes of porosity, flexural strength, pore size, flux, and oil rejection rate of the membranes were investigated while changing the diatomite content. A simple burn-out process subjected to the used membranes in air completely recovered the specific surface area, steady state flux, and oil rejection rate of the virgin membranes. The recycled membranes showed an exceptionally high oil rejection rate (99.9%) with a feed oil concentration of 600 mg/L at an applied pressure of 101 kPa. The typical porosity, pore size, flexural strength, oil rejection rate, and steady state flux of the recycled alumina-coated clay–diatomite composite membrane were 36.5%, 0.12 μm, 32 MPa, 99.9%, and 6.91×10⁻⁶ m³ m⁻² s⁻¹, respectively, at an applied pressure of 101 kPa.     

Preparation and characterization of BaCe0.95Tb0.05O3−α hollow fibre membranes for hydrogen permeation

BaCe_0.95Tb_0.05O_3?α (BCTb) perovskite hollow fibre membranes were fabricated by spinning the slurry mixture containing 66.67 wt% BCTb powder, 6.67 wt% polyethersulphone (PESf) and 26.67 wt% N-methyl-2-pyrrolidone (NMP) followed by sintering at elevated temperatures. The influence of sintering temperature on the membrane properties was investigated in terms of crystal phase, morphology, porosity and mechanical strength. In order to obtain gas-tight hollow fibres with sufficient mechanical strength, the sintering temperature should be controlled between 1350 and 1450 °C. Hydrogen permeation through the BCTb hollow fibre membranes was carried out between 700 and 1000 °C using 50% H₂–He mixture as feed on the shell side and N₂ as sweep gas in the fibre lumen. The measured hydrogen permeation flux through the BCTb hollow fibre membranes reached up to 0.422 μmol cm^?2 s^?1 at 1000 °C when the flow rates of the H₂–He feed and the nitrogen sweep were 40 mL min^?1 and 30 mL min^?1, respectively.     

Electrochemical degradation of textile dyeing industry effluent in batch and flow reactor systems

Electrochemical oxidation of organic pollutants present in the dye-bath and wash water effluents from the textile industry was carried out in batch, batch recirculation and recycle reactor configurations under different conditions of current density, treatment duration, effluent flow rate and electrode specific surface. COD reduction of 52.63% to 82.61% could be obtained when the Procion blue dye-bath effluent was treated in the batch reactor for 8 h. In batch recirculation reactor, the reduction was 94.3% for dye-bath effluent and 91.4 for wash water effluent after 6 h of operation at a current density of 5.0 A dm^?2 and flow rate of 100 L h^?1. The specific energy consumption was found to be 4.32 kWh (kg COD)^?1 for dye-bath effluent and 83.8 kWh (kg COD)^?1 for wash water effluent. The results for wash water effluent under continuous operation of recycle reactor conditions showed 52.86% of COD removal at recycle flow rate of 100 L h^?1 with discharge flow rate of 3 L h^?1. The specific energy consumption was found to be 11.9 kWh (kg COD)^?1.     

Experimental investigation and mathematical modeling of oxygen permeation through dense Ba0.5Sr0.5Co0.8Fe0.2O3−δ (BSCF) perovskite-type ceramic membranes

Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3?δ (BSCF) perovskite powder was synthesized via EDTA/citrate complexation method. BSCF membranes were formed by pressing powder at 400 MPa and sintering at 1100 °C for 10 h. XRD patterns showed that a high pure powder with cubic structure was obtained. SEM micrographs revealed that the membranes are dense with large grains. Effects of temperature, feed and permeate side oxygen partial pressures, flow rates and membrane thickness on oxygen permeation flux were studied experimentally. A Nernst–Planck based mathematical model, including surface exchange kinetics and bulk diffusion, was developed to predict oxygen permeation flux. Considering non-elementary surface reactions and introducing system hydrodynamics into the model resulted in an excellent agreement (RMSD = 0.0617, AAD = 0.0487 and R² = 0.985) between predicted and measured fluxes. The results showed that oxygen permeation flux increases with temperature, feed side oxygen partial pressure and flow rates, however decreases with permeate side oxygen partial pressure and membrane thickness. Contribution of feed side surface exchange reactions, bulk diffusion and permeate side surface exchange reactions resistances in the total resistance are in the range of 8–32%, 10–81% and 11–59%, respectively. Permeation rate-limiting step was determined using the membrane dimensionless characteristic thickness.     

Preparation of mullite ceramic microfilter membranes using Response surface methodology based on central composite design

In this paper effect of free silica removal from mullite microfilter membranes using different sodium hydroxide (NaOH) concentrations at different temperatures and for different removal times was studied. The prepared membranes were subjected to XRD, SEM, porosity analysis, and mechanical strength measurement. Response surface methodology (RSM) based on central composite design (CCD) was used to design the experiments and analyze three operating parameters including; NaOH solution concentration, NaOH solution temperature and removal time. The optimum porosity of 49.4 was obtained with NaOH solution concentration of 35 wt% at temperature 75 °C and removal time equal to 8 h.Water flux and mechanical strength as important characteristics were measured for all the membranes. For the membrane with the optimum porosity, water flux, mechanical strength, and free silica removal percentage were 61.7 kg/m² h, 21.6 MPa, and 28.2%, respectively. The maximum rejection percentage was 97.2% and emulsion flux for this state was 15.6 kg/m² h at temperature 25 °C and cross flow velocity of 1.5 m/s.     

Lactose hydrolysis from milk/whey in batch and continuous processes by concanavalin A-Celite 545 immobilized Aspergillus oryzae β galactosidase

The present study deals with the immobilization of Aspergillus oryzae β galactosidase on concanavalin A layered Celite 545 as bioaffinity support. The activity yield of crosslinked enzyme was 71%. Michaelis constant, K_m was 2.45 mM and 5.58 mM for soluble and crosslinked adsorbed β galactosidase, respectively. V_max for soluble and crosslinked adsorbed enzyme was 0.52 mM/min and 0.38 mM/min, respectively. Moreover, Ki_app value of crosslinked β galactosidase was 366 × 10^?6 M while its soluble counterpart exhibited lower Ki_app value, 181 × 10^?6 M at 2% galactose concentration. Soluble and immobilized β galactosidase exhibited same pH and temperature optima at pH 4.5 and 50 °C. The crosslinked adsorbed enzyme retained 90% activity after 1 month of storage at 4 °C and 71% activity after its seventh repeated use. Moreover, crosslinked β galactosidase showed greater resistance to product inhibition mediated by glucose and galactose. Crosslinked Con A-Celite adsorbed β galactosidase showed increased efficiency in hydrolyzing lactose from milk and whey in batch processes at 50 °C as compared to the adsorbed and soluble enzyme. The hydrolysis of lactose in the continuous reactors containing crosslinked β galactosidase was 92% and 81% at flow rate of 20 mL h^?1 and 30 mL h^?1 after 1 month of operation, respectively.     

Development of novel grafted hybrid PVA membranes using glycidyltrimethylammonium chloride for pervaporation separation of water–isopropanol mixtures

Tetraethylorthosilicate incorporated hybrid poly(vinyl alcohol) membranes were grafted with glycidyltrimethylammonium chloride (GTMAC) in different mass%. The resulting membranes were subjected to physico-chemical investigations using Fourier transform infrared (FTIR) spectroscopy, wide-angle X-ray diffraction (WAXD), differential scanning calorimetry (DSC), thermogravimetry analysis (TGA) and scanning electron microscopy (SEM). The effects of grafting and feed composition on pervaporation performance of the membranes were systematically investigated. The membrane containing 30 mass% of GTMAC exhibited the highest separation selectivity of 1570 with a flux of 1.92 × 10^?2 kg/m² h at 30 °C for 10 mass% of water in the feed. The total flux and flux of water are almost overlapping each other, manifesting that these membranes could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependent diffusion and permeation values, the Arrhenius activation parameters were estimated. The activation energy values obtained for water permeation (E_pw) are two to three times lower than those of isopropanol permeation (E_pIPA), suggesting that the developed membranes have higher separation ability for water–isopropanol system. The E_p and E_D values ranged between 63.73 and 33.07, and 62.78 and 32.75 kJ/mol, respectively. The positive heat of sorption (ΔH_s) values was obtained for all the membranes, suggesting that Henry's mode of sorption is predominant in the process.     

Improving the POM performance of YBa2Cu3O7−δ membrane reactor by Co doping

The performance of Co doped YBa₂Cu₃O_7−δ (YBCO) membrane reactor have been investigated in a process of the partial oxidation of methane (POM) to syngas. The results shows that doping YBCO membrane with a little Co can enhance its oxygen permeation flux and improve its stability in reducing atmosphere noticeably. At 900 °C, with feed flow at 50 ml/min, CH₄ 6.0 v%, SV = 12,000 h⁻¹, and Ni/ZrO₂ catalyst, CH₄ conversion rate, CO selectivity, and oxygen permeation flux can reach to 98%, 92% and 1.41 ml min⁻¹ cm⁻² respectively.     

Synthesis and adsorption studies of novel hybrid mesoporous copolymer functionalized with protoporphyrin for batch and on-line solid-phase extraction of Cd2+ ions

A hybrid copolymer [poly(ethylene glycol dimethacrylate-co-protoporphyrin)-silica], synthesized by free radical copolymerization and sol–gel process was evaluated as novel adsorbent for solid-phase extraction of Cd²⁺ ions. Characterization of hybrid polymer was performed by FTIR, SEM and surface area analyzes. Adsorption isotherms built at pH 8.9 were very well adjusted (R² = 0.9982) to hybrid non-linear Langmuir–Freundlich model for two sites, indicating the existence of different affinity constants for binding sites, which was confirmed by Scatchard plot. The estimated maximum adsorption capacity was found to be 8.28 mg g^?1. The adsorption kinetics data also corroborated to the isotherm, where the Cd²⁺ ions adsorption followed the pseudo-second-order kinetic (R² = 0.998). The on-line preconcentration procedure, optimized by means of factorial designs, was based on sample preconcentration (16 mL) at pH 8.9 through 50.0 mg of hybrid copolymer packed in mini-column at 8.0 mL min^?1 flow rate. The on-line desorption of Cd²⁺ ions towards the FAAS detector was carried out in countercurrent at 5.0 mL min^?1 flow rate using 0.8 mol L^?1 HNO₃. Using the on-line preconcentration procedure, the maximum adsorption capacity determined from breakthrough curve was found to be 2.25 mg g^?1. Analytical curve ranged from 0.0 up to 50.0 μg L^?1 (r = 0.997), limit of detection of 0.27 μg L^?1, preconcentration factor of 38.4, sample throughput of 30 h^?1 and consumptive index of 0.41 mL, were achieved. The preconcentration method, very tolerable to several foreign ions, was successfully applied to the Cd²⁺ ions determination in water samples and cigarette sample. The accuracy was checked from analysis of certified reference materials.     

Vapor permeation of ethyl acetate,propyl acetate,and butyl acetate with hydrophobic inorganic membrane

This study is focused on the permeation characteristics of ester compounds from aqueous solutions through hydrophobic membrane; ethyl acetate (EA), propyl acetate (PA) and butyl acetate (BA). A surface-modified tube-type alumina membrane (Al₂O₃) was used for ester compounds recovery by vapor permeation. Experiments were performed to evaluate the effects of the feed concentration (0.15–0.60 wt.%) and feed temperature (30–50 °C) on the separation of EA, PA, and BA from dilute aqueous solutions. It was found that the permeation flux increased with increasing feed ester concentration and operating temperature. The fluxes of EA, PA, and BA at 0.60 wt.% feed concentration and 40 °C were 282, 526, 661 g/m² h, which were much higher than those of polymer membranes. The separation factors for the 0.15–0.60 wt.% feed solution of EA, PA, and BA at 40 °C were in the range of 28.1–93.9, 83.6–129.4, and 190.7–209.9, respectively. The membrane tested showed high flux and high selectivity.