Synthesis of Porous BPPO-Based Anion Exchange Membranes for Acid Recovery Via Diffusion Dialysis

Diffusion dialysis (DD) is an anion exchange membrane-based functional separation process used for acid recovery. TMA (trimethylamine) and BPPO (brominated poly (2,6-dimethyl-1,4-phenylene oxide) were utilized in this manuscript to formulate AEMs (anion exchange membranes) for DD (diffusion dialysis) using the phase-inversion technique. FTIR (Fourier transfer infrared) analysis, proton NMR spectroscopy, morphology, IEC (ion exchange capacity), LER (linear expansion ratio), CR (fixed group concentration), WR (water uptake/adsorption), water contact angle, chemical, and thermal stability, were all used to evaluate the prepared membranes. The effect of TMA content within the membrane matrix on acid recovery was also briefly discussed. It was reported that porous AEMs have a WR of 149.6% to 233.8%, IEC (ion exchange capacity) of 0.71 to 1.43 mmol/g, CR (fixed group concentration) that ranged from 0.0046 mol/L to 0.0056 mol/L, LER of 3.88% to 9.23%, and a water contact angle of 33.10° to 78.58°. The UH (acid dialysis coefficients) for designed porous membranes were found to be 0.0043 to 0.012 m/h, with separation factors (S) ranging from 13.14 to 32.87 at the temperature of 25 °C. These observations are comparable to those found in the DF-120B commercial membrane with UH of 0.004 m/h and S of 24.3 m/h at the same temperature (25 °C). This porous membranes proposed in this paper are excellent choices for acid recovery through the diffusion dialysis process.

Tailoring the Stabilization and Pyrolysis Processes of Carbon Molecular Sieve Membrane Derived from Polyacrylonitrile for Ethylene/Ethane Separation

For ethylene/ethane separation, a CMS (carbon molecular sieve) membrane was developed with a PAN (polyacrylonitrile) polymer precursor on an alumina support. To provide an excellent thermal property to PAN precursor prior to the pyrolysis, the stabilization as a pre-treatment process was carried out. Tuning the stabilization condition was very important to successfully preparing the CMS membrane derived from the PAN precursor. The stabilization and pyrolysis processes for the PAN precursor were finely tuned, and optimized in terms of stabilization temperature and time, as well as pyrolysis temperature, heating rate, and soaking time. The PAN stabilized at >250 °C showed improved thermal stability and carbon yield. The CMS membrane derived from stabilized PAN showed reasonable separation performance for ethylene permeance (0.71 GPU) and ethylene/ethane selectivity (7.62), respectively. Increasing the pyrolysis temperature and soaking time gave rise to an increase in the gas permeance, and a reduction in the membrane selectivity. This trend was opposite to that for the CMS membranes derived from other polymer precursors. The optimized separation performance (ethylene permeance of 2.97 GPU and ethylene/ethane selectivity of 7.25) could be achieved at the pyrolysis temperature of 650 °C with a soaking time of 1 h. The separation performance of the CMS membrane derived from the PAN precursor was comparable to that of other polymer precursors, and surpassed them regarding the upper bound trade off.

Optimal Water Backwashing Condition in Combined Water Treatment of Alumina Microfiltration and PP Beads

Membrane fouling is a dominant limit of the membrane separation process. In this research, the optimal water backwashing to solve the membrane fouling problem was investigated in the combined water treatment process of alumina MF and pure polypropylene (PP) beads. Additionally, the influence of membrane shape (tubular or seven channel) was examined, depending on the water backwashing period. The optimal backwashing time (BT) could be 20 s in the combined water treatment process, because of the highest total treated volume (VT) in our BT 6–30 s conditions. The optimal backwashing period (BP) could be 6 min, because of the minimum membrane fouling and the maximum VT in the combined process of tubular alumina MF and PP beads. The resistance of reversible membrane fouling (Rrf) showed a major resistance of total membrane fouling, and that of irreversible membrane fouling (Rif) was a minor one, in the combined process using tubular or seven channel MF. The Rif showed a decreasing trend obviously, as decreasing BT from NBW to 2 min for seven channel MF. It means that the more frequent water backwashing could be more effective to control the membrane fouling, especially irreversible fouling, for seven channel membranes than tubular membranes.

Real-Time Monitoring of HT-PEMFC

During the electrochemical reaction of a high temperature proton exchange membrane fuel cell (HT-PEMFC), (in this paper HT-PEMFC means operating in the range of 120 to 200 °C) the inhomogeneity of temperature, flow rate, and pressure in the interior is likely to cause the reduction of ion conductivity or thermal stability weight loss of proton exchange membrane materials, and it is additionally likely to cause uneven fuel distribution, thereby affecting the working performance and service life of the HT-PEMFC. This study used micro-electro-mechanical systems (MEMS) technology to develop a flexible three-in-one microsensor which is resistant to high temperature electrochemical environments; we selected appropriate materials and process parameters to protect the microsensor from failure or damage under long-term tests. The proposed method can monitor the local temperature, flow rate, and pressure distribution in HT-PEMFC in real time.

New Membrane-Forming Aromatic Co-Poly(amide-imide)s: Influence of the Chemical Structure on the Morphological, Thermal and Transport Properties

Polymer film membranes are used to solve specific separation problems that dictate structural requirements. Structural and morphological parameters of film membranes based on glassy polyheteroarylenes can be controlled in the process of preparation from solutions that opens up prospects for obtaining structured membranes required for targeted separation. In the case of aromatic poly(amide-imide)s, the possibility of controlling film formation and structure virtually has not been studied. In the present work, a series of homologous co-poly(amide-imide)s differing in the number of repeating units with carboxyl-substituted aromatic fragments was synthesized by polycondensation. Comparative analysis of the processes of formation of membranes with different morphologies based on these polymers under equal conditions was performed. New information was obtained about the influence of the amounts of carboxyl groups and the residual solvent on structural properties of asymmetric membranes. The influence of these factors on transport properties of dense membranes under pervaporation conditions was studied. It was demonstrated that in the case of carboxyl-containing poly(amide-imide)s, the domains formed during film preparation had a significant effect on membrane properties.

On the Potential of a Poly(vinylidenefluoride-co-hexafluoropropylene) Polymer Inclusion Membrane Containing Aliquat® 336 and Dibutyl Phthalate for V(V) Extraction from Sulfate Solutions

A polymer inclusion membrane (PIM) composed of 50 wt% base polymer poly(vinylidenefluoride-co-hexafluoropropylene), 40 wt% extractant Aliquat® 336, and 10 wt% dibutyl phthalate as plasticizer/modifier provided the efficient extraction of vanadium(V) (initial concentration 50 mg L−1) from 0.1 M sulfate solutions (pH 2.5). The average mass and thickness of the PIMs (diameter 3.5 cm) were 0.057 g and 46 μm, respectively. It was suggested that V(V) was extracted as VO2SO4− via an anion exchange mechanism. The maximum PIM capacity was estimated to be ~56 mg of V(V)/g for the PIM. Quantitative back-extraction was achieved with a 50 mL solution of 6 M H2SO4/1 v/v% of H2O2. It was assumed that the back-extraction process involved the oxidation of VO2+ to VO(O2)+ by H2O2. The newly developed PIM, with the optimized composition mentioned above, exhibited an excellent selectivity for V(V) in the presence of metallic species present in digests of spent alumina hydrodesulfurization catalysts. Co-extraction of Mo(VI) with V(V) was eliminated by its selective extraction at pH 1.1. Characterization of the optimized PIM was performed by contact angle measurements, atomic-force microscopy, energy dispersive X-ray spectroscopy, thermogravimetric analysis/derivatives thermogravimetric analysis and stress–strain measurements. Replacement of dibutyl phthalate with 2-nitrophenyloctyl ether improved the stability of the studied PIMs.

Pilot-Scale Test Results of Electrodialysis Bipolar Membrane for Reverse-Osmosis Concentrate Recovery

In this study, it is aimed to investigate the potential of electrodialysis bipolar membrane (EDBM) systems for the recovery of the concentrate originating from an organized industrial estate (OIE) wastewater treatment system with reverse osmosis (RO). Acids and bases were obtained from a pilot-scale treatment plant as a result of the research. Furthermore, the sustainability and affordability of acids and bases obtained by EDBM systems were investigated. Six cycles were carried out in continuous-flow mode with the EDBM system as batch cycles in the disposal of the concentrate and the production of acids and bases with the EDBM system. For each cycle, the EDBM system was operated for 66, 48, 66, and 80 min, respectively, and the last two cycles were operated for a total of 165 min (70 + 90) with 5 min of waiting. In the EDBM system, a working method was determined such that the cycle flow rate was 180 L/hour, energy to be given to the system was 25 V, and the working pressure was in the range of 0.8–2.5 bar. In the six cycles with the EDBM system, the concentrate, acid and base, conductivity, pH, and pressure increase values were investigated depending on time. Throughout all these studies, the cycles were continued over the products formed in the acid and base chamber. As a result of all the cycles, acid (HCl) production at a level of 1.44% and base (NaOH) production at a level of 2% were obtained.

Hydrophobic Mismatch Controls the Mode of Membrane-Mediated Interactions of Transmembrane Peptides

Various cellular processes require the concerted cooperative action of proteins. The possibility for such synchronization implies the occurrence of specific long-range interactions between the involved protein participants. Bilayer lipid membranes can mediate protein–protein interactions via relatively long-range elastic deformations induced by the incorporated proteins. We considered the interactions between transmembrane peptides mediated by elastic deformations using the framework of the theory of elasticity of lipid membranes. An effective peptide shape was assumed to be cylindrical, hourglass-like, or barrel-like. The interaction potentials were obtained for membranes of different thicknesses and elastic rigidities. Cylindrically shaped peptides manifest almost neutral average interactions—they attract each other at short distances and repel at large ones, independently of membrane thickness or rigidity. The hourglass-like peptides repel each other in thin bilayers and strongly attract each other in thicker bilayers. On the contrary, the barrel-like peptides repel each other in thick bilayers and attract each other in thinner membranes. These results potentially provide possible mechanisms of control for the mode of protein–protein interactions in membrane domains with different bilayer thicknesses.

The Optimization of Dispersion and Application Techniques for Nanocarbon-Doped Mixed Matrix Gas Separation Membranes

In this work, supported cellulose acetate (CA) mixed matrix membranes (MMMs) were prepared and studied concerning their gas separation behaviors. The dispersion of carbon nanotube fillers were studied as a factor of polymer and filler concentrations using the mixing methods of the rotor–stator system (RS) and the three-roll-mill system (TRM). Compared to the dispersion quality achieved by RS, samples prepared using the TRM seem to have slightly bigger, but fewer and more homogenously distributed, agglomerates. The green γ-butyrolactone (GBL) was chosen as a polyimide (PI) polymer-solvent, whereas diacetone alcohol (DAA) was used for preparing the CA solutions. The coating of the thin CA separation layer was applied using a spin coater. For coating on the PP carriers, a short parameter study was conducted regarding the plasma treatment to affect the wettability, the coating speed, and the volume of dispersion that was applied to the carrier. As predicted by the parameter study, the amount of dispersion that remained on the carriers decreased with an increasing rotational speed during the spin coating process. The dry separation layer thickness was varied between about 1.4 and 4.7 μm. Electrically conductive additives in a non-conductive matrix showed a steeply increasing electrical conductivity after passing the so-called percolation threshold. This was used to evaluate the agglomeration behavior in suspension and in the applied layer. Gas permeation tests were performed using a constant volume apparatus at feed pressures of 5, 10, and 15 bar. The highest calculated CO2/N2 selectivity (ideal), 21, was achieved for the CA membrane and corresponded to a CO2 permeability of 49.6 Barrer.

Targeted Delivery of Exosomes Armed with Anti-Cancer Therapeutics

Among extracellular vesicles, exosomes have gained great attention for their role as therapeutic vehicles for delivering various active pharmaceutical ingredients (APIs). Exosomes “armed” with anti-cancer therapeutics possess great potential for an efficient intracellular delivery of anti-cancer APIs and enhanced targetability to tumor cells. Various technologies are being developed to efficiently incorporate anti-cancer APIs such as genetic materials (miRNA, siRNA, mRNA), chemotherapeutics, and proteins into exosomes and to induce targeted delivery to tumor burden by exosomal surface modification. Exosomes can incorporate the desired therapeutic molecules via direct exogenous methods (e.g., electroporation and sonication) or indirect methods by modifying cells to produce “armed” exosomes. The targeted delivery of “armed” exosomes to tumor burden could be accomplished either by “passive” targeting using the natural tropism of exosomes or by “active” targeting via the surface engineering of exosomal membranes. Although anti-cancer exosome therapeutics demonstrated promising results in preclinical studies, success in clinical trials requires thorough validation in terms of chemistry, manufacturing, and control techniques. While exosomes possess multiple advantages over synthetic nanoparticles, challenges remain in increasing the loading efficiency of anti-cancer agents into exosomes, as well as establishing quantitative and qualitative analytical methods for monitoring the delivery of in vivo administered exosomes and exosome-incorporated anti-cancer agents to the tumor parenchyma.