Novel Crosslinked Anion Exchange Membranes Based on Thermally Cured Epoxy Resin: Synthesis, Structure and Mechanical and Ion Transport Properties.

Limitations in existing anion exchange membranes deter their use in the efficient treatment of industrial wastewater effluent. This work presents an approach to fabricating novel anion-conducting membranes using epoxy resin monomers like hydrophobic or hydrophilic diglycidyl ether and quaternized polyethyleneimine (PEI). Manipulating the diglycidyl ether nature, the quantitative composition of the copolymer and the conditions of quaternization allows control of the physicochemical properties of the membranes, including water uptake (20.0-330%), ion exchange capacity (1.5-3.7 mmol/g), ionic conductivity (0.2-17 mS/cm in the Cl form at 20 °C), potentiostatic transport numbers (75-97%), as well as mechanical properties. A relationship was established between copolymer structure and conductivity/selectivity trade-off. The higher the quaternized polyethyleneimine, diluent fraction, and hydrophilicity of diglycidyl ether, the higher the conductivity and the lower the permselectivity. Hydrophobic diglycidyl ether gives a much better conductivity/selectivity ratio since it provides a lower degree of hydration than hydrophilic diglycidyl ether. Different mesh and non-woven reinforcing materials were also examined. The developed membranes demonstrate good stability in both neutral and acidic environments, and their benchmark characteristics in laboratory electrodialysis cells and batch-mode dialysis experiments are similar to or superior to, commercial membranes such as Neosepta© AMX, FujiFilm© Type1, and Fumasep FAD-PET.

Membranes Based on Polyvinylidene Fluoride and Radiation-Grafted Sulfonated Polystyrene and Their Performance in Proton-Exchange Membrane Fuel Cells.

Proton-exchange membranes based on gamma-irradiated films of PVDF and radiation-grafted sulfonated polystyrene with an ion-exchange capacity of 1.8 meq/g and crosslinking degrees of 0 and 3% were synthesized. A solvent-free, environmentally friendly method of styrene grafting from its aqueous emulsion, with a styrene content of only 5 vol.% was used. Energy dispersive X-ray mapping analysis showed that the grafted sulfonated polystyrene is uniformly distributed throughout the membrane thickness. The obtained materials had a proton conductivity up to 132 mS/cm at 80 °C and a hydrogen permeability of up to 5.2 cm2/s at 30 °C, which significantly exceeded similar values for Nafion®-212 membranes. The resulting membranes exhibited a H2/O2 fuel cell peak power density of up to 0.4 W/cm2 at 65 °C. Accelerated stability tests showed that adding a crosslinking agent could significantly increase the stability of the membranes in the fuel cells. The thermal properties and crystallinity of the membranes were investigated through differential scanning calorimetry and X-ray powder diffraction methods. The conductivity, water uptake, and mechanical properties of the membranes (stress-strain curves) were also characterized.

Recovery of Hydrochloric Acid from Industrial Wastewater by Diffusion Dialysis Using a Spiral-Wound Module.

In the present study, the possibility of using a spiral-wound diffusion dialysis module was studied for the separation of hydrochloric acid and Zn2+, Ni2+, Cr3+, and Fe2+ salts. Diffusion dialysis recovered 68% of free HCl from the spent pickling solution contaminated with heavy-metal-ion salts. A higher volumetric flowrate of the stripping medium recovered a more significant portion of free acid, namely, 77%. Transition metals (Fe, Ni, Cr) apart from Zn were rejected by >85%. Low retention of Zn (35%) relates to the diffusion of negatively charged chloro complexes through the anion-exchange membrane. The mechanical and transport properties of dialysis FAD-PET membrane under accelerated degradation conditions was investigated. Long-term tests coupled with the economic study have verified that diffusion dialysis is a suitable method for the treatment of spent acids, the salts of which are well soluble in water. Calculations predict significant annual OPEX savings, approximately up to 58%, favouring diffusion dialysis for implementation into wastewater management.

Recovery of Spent Sulphuric Acid by Diffusion Dialysis Using a Spiral Wound Module.

In this study, we assess the effects of volumetric flow and feed temperature on the performance of a spiral-wound module for the recovery of free acid using diffusion dialysis. Performance was evaluated using a set of equations based on mass balance under steady-state conditions that describe the free acid yield, rejection factors of metal ions and stream purity, along with chemical analysis of the outlet streams. The results indicated that an increase in the volumetric flow rate of water increased free acid yield from 88% to 93%, but decreased Cu2+ and Fe2+ ion rejection from 95% to 90% and 91% to 86%, respectively. Increasing feed temperature up to 40 °C resulted in an increase in acid flux of 9%, and a reduction in Cu2+ and Fe2+ ion rejection by 2-3%. Following diffusion dialysis, the only evidence of membrane degradation was a slight drop in permselectivity and an increase in diffusion acid and salt permeability. Results obtained from the laboratory tests used in a basic economic study showed that the payback time of the membrane-based regeneration unit is approximately one year.

Hydration and Diffusion of H+, Li+, Na+, Cs+ Ions in Cation-Exchange Membranes Based on Polyethylene- and Sulfonated-Grafted Polystyrene Studied by NMR Technique and Ionic Conductivity Measurements.

The main particularities of sulfonate groups hydration, water molecule, and alkaline metal cation translation mobility were revealed by nuclear magnetic resonance (NMR) and ionic conductivity measurements techniques in cation-exchange membranes MSC based on cross-linked sulfonated polystyrene (PS) grafted on polyethylene with ion-exchange capacity of 2.5 mg-eq/g. Alkaline metal cation hydration numbers (h) calculated from temperature dependences of 1H chemical shift of water molecule for membranes equilibrated with water vapor at RH = 95% are 5, 6, and 4 for Li+, Na+, and Cs+ ions, respectively. These values are close to h for equimolar aqueous salt solutions. Water molecules and counter ions Li+, Na+, and Cs+ diffusion coefficients were measured by pulsed field gradient NMR on the 1H, 7Li, 23Na, and 133Cs nuclei. For membranes as well as for aqueous chloride solutions, cation diffusion coefficients increased in the following sequence: Li+ < Na+ < Cs+. Cation and water molecule diffusion activation energies in temperature range from 20 °C to 80 °C were close to each other (about 20 kJ/mol). The cation conductivity of MSC membranes is in the same sequence, Li+ < Na+ < Cs+ << H+. The conductivity values calculated from the NMR diffusion coefficients with the use of the Nernst-Einstein equation are essentially higher than experimentally determined coefficients. The reason for this discrepancy is the heterogeneity of membrane pore and channel system. Ionic conductivity is limited by cation transfer in narrow channels, whereas the diffusion coefficient characterizes ion mobility in wide pores first of all.