Power Generation Performance of Reverse Electrodialysis (RED) Using Various Ion Exchange Membranes and Power Output Prediction for a Large RED Stack.

Reverse electrodialysis (RED) power generation using seawater (SW) and river water is expected to be a promising environmentally friendly power generation system. Experiments with large RED stacks are needed for the practical application of RED power generation, but only a few experimental results exist because of the need for large facilities and a large area of ion-exchange membranes (IEMs). In this study, to predict the power output of a large RED stack, the power generation performances of a lab-scale RED stack (40 membrane pairs and 7040 cm2 total effective membrane area) with several IEMs were evaluated. The results were converted to the power output of a pilot-scale RED stack (299 membrane pairs and 179.4 m2 total effective membrane area) via the reference IEMs. The use of low-area-resistance IEMs resulted in lower internal resistance and higher power density. The power density was 2.3 times higher than that of the reference IEMs when natural SW was used. The net power output was expected to be approximately 230 W with a pilot-scale RED stack using low-area-resistance IEMs and natural SW. This value is one of the indicators of the output of a large RED stack and is a target to be exceeded with further improvements in the RED system.

Effect of Ion Selectivity on Current Production in Sewage Microbial Fuel Cell Separators.

This study compared the performance of two microbial fuel cells (MFCs) equipped with separators of anion or cation exchange membranes (AEMs or CEMs) for sewage wastewater treatment. Under chemostat feeding of sewage wastewater (hydraulic retention time of approximately 7 h and polarization via an external resistance of 1 Ω), the MFCs with AEM (MFCAEM) generated a maximum current that was 4-5 times greater than that generated by the MFC with CEM (MFCCEM). The high current in the MFCAEM was attributed to the approximately neutral pH of its cathode, in contrast to the extremely high pH of the MFCCEM cathode. Due to the elimination of the pH imbalance, the cathode resistance for the MFCAEM (13-19 Ω·m2) was lower than that for the MFCCEM (41-44 Ω·m2). The membrane resistance measured as the Cl- mobility of AEMs for the MFCAEM operated for 35, 583, and 768 days showed an increase with operation time and depth, and this increase contributed minimally to the cathode resistance of the MFCAEM. These results indicate the advantage of the AEM over the CEM for air-cathode MFCs. The membrane resistance may increase when the AEM is applied in large-scale MFCs on a meter scale for extended periods.

Long-term evaluation of an air-cathode microbial fuel cell with an anion exchange membrane in a 226L wastewater treatment reactor.

Although the treatment of municipal wastewater using microbial fuel cells (MFCs) has been extensively studied, scaling the systems up for practical use remains challenging. In this study, a 226 L sewage treatment reactor was equipped with 27 MFC units, and its chemical oxygen demand (COD) removal and electricity production were evaluated. The MFC units were tubular air cores with a diameter of 5 cm and length of 100 cm, which were wrapped with a carbon-based cathode, anion exchange membrane (AEM), and nonwoven graphite fabric. The air-cathode-AEM MFC generated 0.12-0.30 A/m2, 0.072-0.51 W/m3, and 1.7-4.6 Wh/m3 in a chemostat reactor with a COD of 140-36 mg/L and hydraulic retention time (HRT) of 9-42 h throughout a year. The decrease in the COD was represented as the first-order rate constant of 0.038. The rate constant was comparable to that of other air-cathode MFCs with cation exchange membranes, indicating the necessity of a posttreatment to meet the discharge standard. It has been estimated that the MFC operation for 24 h before post-aeration can reduce the energy required to meet the discharge standard by 70%, suggesting the potential applicability of MFC in long HRT-treatments such as oxidation ditch. The resistances of the anode, cathode, and AEM were 15, 7.0, and 0.51 mΩ m2, respectively, and surface dirt rather than deterioration primarily increased the AEM resistance. A current exceeding 0.2 A/m2 significantly increases the anode potential, indicating that the current was limited by low COD. Increasing the anode-specific surface area can improve air-AEM MFCs used for practical applications.

Ionic Transport Properties of Cation-Exchange Membranes Prepared from Poly(vinyl alcohol-b-sodium Styrene Sulfonate).

Membrane resistance and permselectivity for counter-ions have important roles in determining the performance of cation-exchange membranes (CEMs). In this study, PVA-based polyanions-poly(vinyl alcohol-b-sodium styrene sulfonate)-were synthesized, changing the molar percentages CCEG of the cation-exchange groups with respect to the vinyl alcohol groups. From the block copolymer, poly(vinyl alcohol) (PVA)-based CEMs, hereafter called "B-CEMs", were prepared by crosslinking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations CGA. The ionic transport properties of the B-CEMs were compared with those previously reported for the CEMs prepared using a random copolymer-poly(vinyl alcohol-co-2-acrylamido-2-methylpropane sulfonic acid)-hereafter called "R-CEMs". The B-CEMs had lower water content than the R-CEMs at equal molar percentages of the cation-exchange groups. The charge density of the B-CEMs increased as CCEG increased, and reached a maximum value, which increased with increasing CGA. A maximum charge density of 1.47 mol/dm3 was obtained for a B-CEM with CCEG = 2.9 mol% and CGA = 0.10 vol.%, indicating that the B-CEM had almost two-thirds of the permselectivity of a commercial CEM (CMX: ASTOM Corp. Japan). The dynamic transport number and membrane resistance of a B-CEM with CCEG = 8.3 mol% and CGA = 0.10 vol.% were 0.99 and 1.6 Ωcm2, respectively. The B-CEM showed higher dynamic transport numbers than those of the R-CEMs with similar membrane resistances.

Comparison of Pressure-Retarded Osmosis Performance between Pilot-Scale Cellulose Triacetate Hollow-fiber and Polyamide Spiral-Wound Membrane Modules.

Pressure-retarded osmosis (PRO) has recently received attention because of its ability to generate power via an osmotic pressure gradient between two solutions with different salinities: high- and low-salinity water sources. In this study, PRO performance, using the two pilot-scale PRO membrane modules with different configurations-five-inch cellulose triacetate hollow-fiber membrane module (CTA-HF) and eight-inch polyamide spiral-wound membrane modules (PA-SW)-was evaluated by changing the draw solution (DS) concentration, applied hydrostatic pressure difference, and the flow rates of DS and feed solution (FS), to obtain the optimum operating conditions in PRO configuration. The maximum power density per unit membrane area of PA-SW at 0.6 M NaCl was 1.40 W/m2 and 2.03-fold higher than that of CTA-HF, due to the higher water permeability coefficient of PA-SW. In contrast, the maximum power density per unit volume of CTA-SW at 0.6 M NaCl was 4.67 kW/m3 and 6.87-fold higher than that of PA-SW. The value of CTA-HF increased to 13.61 kW/m3 at 1.2 M NaCl and was 12.0-fold higher than that of PA-SW because of the higher packing density of CTA-HF.

Power Generation Performance of a Pilot-Scale Reverse Electrodialysis Using Monovalent Selective Ion-Exchange Membranes.

Reverse electrodialysis (RED) is a promising process for harvesting energy from the salinity gradient between two solutions without environmental impacts. Seawater (SW) and river water (RW) are considered the main RED feed solutions because of their good availability. In Okinawa Island (Japan), SW desalination via the reverse osmosis (RO) can be integrated with the RED process due to the production of a large amount of RO brine (concentrated SW, containing ~1 mol/dm3 of NaCl), which is usually discharged directly into the sea. In this study, a pilot-scale RED stack, with 299 cell pairs and 179.4 m2 of effective membrane area, was installed in the SW desalination plant. For the first time, asymmetric monovalent selective membranes with monovalent selective layer just at the side of the membranes were used as the ion exchange membranes (IEMs) inside the RED stack. Natural and model RO brines, as well as SW, were used as the high-concentrate feed solutions. RW, which was in fact surface water in this study and close to the desalination plant, was utilized as the low-concentrate feed solution. The power generation performance investigated by the current-voltage (I-V) test showed the maximum gross power density of 0.96 and 1.46 W/m2 respectively, when the natural and model RO brine/RW were used. These are a 50-60% improvement of the maximum gross power of 0.62 and 0.97 W/m2 generated from the natural and model SW, respectively. The approximate 50% more power generated from the model feed solutions can be assigned to the suppression of concentration polarization of the RED stack due to the absence of multivalent ions.

Effect of Alkali Treatment on the Mechanical Properties of Anion-Exchange Membranes with a Poly(vinyl Chloride) Backing and Binder.

An alkali treatment under various operating conditions is conducted on a commercial anion-exchange membrane containing poly(vinyl chloride) (PVC) as a backing and binder to study the effect of the treatment on the mechanical properties by both Müllen burst and tensile tests. Contrary to our expectations, the Müllen burst pressure and tensile strain at break improved significantly after the alkali treatment in comparison to the pristine membrane and then decreased as the treatment period progressed. A good correlation is observed between the area below the stress-strain curve and burst pressure. To understand the obtained results, the PVC degradates are recovered by Soxhlet extraction and characterized via nuclear magnetic resonance and gel permeation chromatography. It is discovered that the PVC main chains degraded in the alkali solution. We propose a composite model to explain the burst pressure improvement mechanism by the change in the chemical structure of the PVC binder.

Alkali Attack on Cation-Exchange Membranes with Polyvinyl Chloride Backing and Binder: Comparison with Anion-Exchange Membranes.

Systematic alkali immersion tests of cation-exchange membranes (CEM) with polyvinyl chloride (PVC) as their backing and binder were conducted to compare that of an Anion-exchange membrane (AEM) with the same PVC materials to investigate the mechanism of dehydrochlorination. In the immersion tests, originally colorless and transparent AEM turned violet, and chemical structure analysis showed that polyene was produced by the dehydrochlorination reaction. However, the CEM did not change in color, chemical structure or membrane properties during the test with less than 1M alkali solutions. According to the Donnan equilibrium theory and the experiments using CEM and AEM, the hydroxide ion concentration in the CEM was much lower than that in the AEM under the same conditions. However, when the alkali immersion test was performed using the CEM under more severe conditions (6 M for 168 h at 40 °C), there was a slight change in the color and chemical structure of the CEM, clearly indicating that not only AEMs, but also CEMs with PVC matrixes were deteriorated by alkali, depending on the conditions.

Preparation of PVA-Based Hollow Fiber Ion-Exchange Membranes and Their Performance for Donnan Dialysis.

Hollow fiber type cation-exchange (C-HF) membranes and hollow fiber type anion-exchange (A-HF) membranes were prepared from poly (vinyl alcohol) (PVA)-based copolymer with cation-exchange groups and by blending PVA and polycation, respectively, by a gel fiber spinning method. In order to control the water content of the hollow fiber membranes, the membranes were cross-linked physically by annealing, and then cross-linked chemically by using glutaraldehyde (GA) solutions at various GA concentrations. The outer diameter of C-HF and A-HF membranes were ca. 1000 µm and ca. 1500 µm, respectively, and the thickness of the membranes were ca. 170 µm and 290 µm, respectively. Permeation experiments were carried out in two Donnan dialysis systems, which included mixed 0.1 M NaCl and 0.1 M CaCl2/C-HF /3 × 10-4 M CaCl2 and mixed 0.1 M NaCl and 0.1 M NaNO3/A-HF/3 × 10-4 M NaNO3 to examine ionic perm selectivity of the membranes. In the Donnan dialysis experiments using C-HF membranes, uphill transport of the divalent cations occurred, and, in the case of A-HF membranes, uphill transport of NO3- ions occurred. C-HF and A-HF membranes had about half of the flux in the uphill transported ions and also about half of the selectivity between the uphill transport ions and driven ions in comparison with those of the commercial flat sheet cation-exchange membrane (Neosepta® CMX) and anion-exchange membrane (Neosepta® AMX). Yet, IEC of C-HF and A-HF membranes were about one fifth of CMX and less than half of AMX, respectively. Since hollow fiber membrane module will have higher packing density than a flat membrane stack, the hollow fiber type ion-exchange membranes (IEMs) prepared in this study will have a potential application to a Donnan dialysis process.

Polyelectrolyte Composite Membranes Containing Electrospun Ion-Exchange Nanofibers: Effect of Nanofiber Surface Charges on Ionic Transport.

Poly(vinyl alcohol) (PVA)-based ion-exchange nanofibers (IEX-NFs) and their composite polyelectrolyte membranes were prepared and characterized. The PVA-based NFs are well dispersed and form a three-dimensional network structure in the polymer matrix, Nafion. All of the prepared membranes show a similar ion-exchange capacity of ∼1.0 mmol g-1. The ionic conductivities through the PVA- b-PSS-NF/Nafion composite membranes are superior to that of the Nafion membranes, but the conductivity through the PVA-NF/Nafion composite membrane is half that of the Nafion membrane. Our electrokinetic measurements clearly indicate that a high density of ion-exchange groups on the NF surface results in a continuous ionic transport path in the polymer matrix. In addition, the mechanical strength of all of the NF-composite membranes is improved compared with that of the membranes without NF.

Preparation of robust braid-reinforced poly(vinyl chloride) ultrafiltration hollow fiber membrane with antifouling surface and application to filtration of activated sludge solution.

Braid-reinforced hollow fiber membranes with high mechanical properties and considerable antifouling surface were prepared by blending poly(vinyl chloride) (PVC) with poly(vinyl chloride-co-poly(ethylene glycol) methyl ether methacrylate) (poly(VC-co-PEGMA)) copolymer via non-solvent induced phase separation (NIPS). The tensile strength of the braid-reinforced PVC hollow fiber membranes were significantly larger than those of previously reported various types of PVC hollow fiber membranes. The high interfacial bonding strength indicated the good compatibility between the coating materials and the surface of polyethylene terephthalate (PET)-braid. Owing to the surface segregation phenomena, the membrane surface PEGMA coverage increased upon increasing the poly(VC-co-PEGMA)/PVC blending ratio, resulting in higher hydrophilicities and bovine serum albumin (BSA) repulsion. To compare the fouling properties, membranes with similar PWPs were prepared by adjusting the dope solution composition to eliminate the effect of hydrodynamic conditions on the membrane fouling performance. The blend membranes surface exhibited considerable fouling resistance to the molecular adsorption from both BSA solution and activated sludge solution. In both cases, the flux recovered to almost 80% of the initial flux using only water backflush. Considering their great mechanical properties and antifouling resistance to activated sludge solution, these novel membranes show good potential for application in wastewater treatment.

Electrodialytic Transport Properties of Anion-Exchange Membranes Prepared from Poly(vinyl alcohol) and Poly(vinyl alcohol-co-methacryloyl aminopropyl trimethyl ammonium chloride).

Random-type anion-exchange membranes (AEMs) have been prepared by blending poly(vinyl alcohol) (PVA) and the random copolymer-type polycation, poly(vinyl alcohol-co-methacryloyl aminopropyl trimethyl ammonium chloride) at various molar percentages of anion-exchange groups to vinyl alcohol groups, Cpc, and by cross-linking the PVA chains with glutaraldehyde (GA) solution at various GA concentrations, CGA. The characteristics of the random-type AEMs were compared with blend-type AEMs prepared in our previous study. At equal molar percentages of the anion exchange groups, the water content of the random-type AEMs was lower than that of the blend-type AEMs. The effective charge density of the random-type AEMs increased with increasing Cpc and reached a maximum value. Further, the maximum value of the effective charge density increased with increasing CGA. The maximum value of the effective charge density, 0.42 mol/dm3, was obtained for the random-type AEM with Cpc = 4.2 mol % and CGA = 0.15 vol %. A comparison of the random-type and blend-type AEMs with almost the same Cpc showed that the random-type AEMs had lower membrane resistance than the blend-type ones. The membrane resistance and dynamic transport number of the random-type AEM with Cpc = 6.0 mol % and CGA = 0.15 vol % were 4.8 Ω cm2 and 0.83, respectively.

Pseudo helix-sense-selective polymerisation of achiral substituted acetylenes.

Pseudo helix-sense-selective polymerisation of a wide range of achiral substituted acetylenes having dynamic covalent bonds has been realised to yield static one-handed helical polymers without any other chiral moieties.

Synthesis of stable and soluble one-handed helical homopoly(substituted acetylene)s without the coexistence of any other chiral moieties via two-step polymer reactions in membrane state: molecular design of the starting monomer.

A soluble and stable one-handed helical poly(substituted phenylacetylene) without the coexistence of any other chiral moieties was successfully synthesized by asymmetric-induced polymerization of a chiral monomer followed by two-step polymer reactions in membrane state: (1) removing the chiral groups (desubstitution); and (2) introduction of achiral long alkyl groups at the same position as the desubstitution to enhance the solubility of the resulting one-handed helical polymer (resubstitution). The starting chiral monomer should have four characteristic substituents: (i) a chiral group bonded to an easily hydrolyzed spacer group; (ii) two hydroxyl groups; (iii) a long rigid hydrophobic spacer between the chiral group and the polymerizing group; (iv) a long achiral group near the chiral group. As spacer group a carbonate ester was selected. The two hydroxyl groups formed intramolecular hydrogen bonds stabilizing a one-handed helical structure in solution before and after the two-step polymer reactions in membrane state. The rigid long hydrophobic spacer, a phenylethynylphenyl group, enhanced the solubility of the starting polymer, and realized effective chiral induction from the chiral side groups to the main chain in the asymmetric-induced polymerization. The long alkyl group near the chiral group avoided shrinkage of the membrane and kept the reactivity of resubstitution in membrane state after removing the chiral groups. The g value (g = ([θ]/3,300)/ε) for the CD signal assigned to the main chain in the obtained final polymer was almost the same as that of the starting polymer in spite of the absence of any other chiral moieties. Moreover, since the one-handed helical structure was maintained by the intramolecular hydrogen bonds in a solution, direct observation of the one-handed helicity of the final homopolymer has been realized in CD for the solution for the first time.