Polyphenylsulfone (PPSU)-Based Copolymeric Membranes: Effects of Chemical Structure and Content on Gas Permeation and Separation.

Although various polymer membrane materials have been applied to gas separation, there is a trade-off relationship between permeability and selectivity, limiting their wider applications. In this paper, the relationship between the gas permeation behavior of polyphenylsulfone(PPSU)-based materials and their chemical structure for gas separation has been systematically investigated. A PPSU homopolymer and three kinds of 3,3',5,5'-tetramethyl-4,4'-biphenol (TMBP)-based polyphenylsulfone (TMPPSf) copolymers were synthesized by controlling the TMBP content. As the TMPPSf content increases, the inter-molecular chain distance (or d-spacing value) increases. Data from positron annihilation life-time spectroscopy (PALS) indicate the copolymer with a higher TMPPSf content has a larger fractional free volume (FFV). The logarithm of their O2, N2, CO2, and CH4 permeability was found to increase linearly with an increase in TMPPSf content but decrease linearly with increasing 1/FFV. The enhanced permeability results from the increases in both sorption coefficient and gas diffusivity of copolymers. Interestingly, the gas permeability increases while the selectivity stays stable due to the presence of methyl groups in TMPPSf, which not only increases the free volume but also rigidifies the polymer chains. This study may provide a new strategy to break the trade-off law and increase the permeability of polymer materials largely.

Green Layer-by-Layer Method for the Preparation of Polyacrylonitrile-Supported Zinc Benzene-1,4-dicarboxylic Acid Membranes.

Ultrafiltration-level polyacrylonitrile (PAN) flat sheet membranes were chemically modified through cross-linking and hydrolysis to provide a suitable surface for the growth of a selective layer composed of a Zn benzene-1,4-dicarboxylic acid (Zn(BDC)) metal-organic framework (MOF). Unlike typical membrane modification methods or conventional MOF synthesis procedures, deionized (DI) water was the only solvent used for each of the modification steps. To better understand the layer-by-layer MOF growth process, several MOF growth conditions were also studied, including the effects of solution concentration, growth temperature, membrane immersion time and the number of layers. Subsequently, organic solvent nanofiltration (OSN) was used to test the effectiveness of the modifications and compare the performances of the fabricated membranes. With the appropriate combination of the MOF growth conditions, the layer-by-layer method was used to produce an OSN membrane with an isopropanol permeance of 2.39 L m-2 h-1 bar-1 and an 86 % rejection of the dye Brilliant Blue R (Mw 825.97 g mol-1 ).

Blends of a Polymer of Intrinsic Microporosity and Partially Sulfonated Polyphenylenesulfone for Gas Separation.

Polyphenylenesulfone (PPSU) and sulfonated polyphenylenesulfone (sPPSU) are widely used for liquid separations in the medical and food industries. However, their potential applications for gas separation have not been studied extensively owing to their low intrinsic gas permeability. We report here for the first time that blending with sPPSU can significantly improve the gas separation performance of highly permeable polymers of intrinsic microporosity (PIMs), specifically PIM-1, because of the strong molecular interactions of the sulfonic acid groups of sPPSU with CO2 and O2 . In addition, a novel co-solvent system has been discovered to overcome the immiscibility of these polymers. The presence of a higher degree of sulfonation in sPPSU results in better gas separation performance of the blend membranes close to or above the Robeson upper bound lines for O2 /N2 , CO2 /N2 and CO2 /CH4 separations. Interestingly, the blend membranes have comparable gas selectivity to sPPSU even though their sPPSU content is only 5-20 wt %. Moreover, they also display improved anti-plasticization properties up to 30 atm (3 MPa) using a binary CO2 /CH4 feed gas. The newly developed PIM-1/sPPSU membranes are potential candidates for air separation, natural gas separation, and CO2 capture.

Experiments and Modeling of Boric Acid Permeation through Double-Skinned Forward Osmosis Membranes.

Boron removal is one of the great challenges in modern wastewater treatment, owing to the unique small size and fast diffusion rate of neutral boric acid molecules. As forward osmosis (FO) membranes with a single selective layer are insufficient to reject boron, double-skinned FO membranes with boron rejection up to 83.9% were specially designed for boron permeation studies. The superior boron rejection properties of double-skinned FO membranes were demonstrated by theoretical calculations, and verified by experiments. The double-skinned FO membrane was fabricated using a sulfonated polyphenylenesulfone (sPPSU) polymer as the hydrophilic substrate and polyamide as the selective layer material via interfacial polymerization on top and bottom surfaces. A strong agreement between experimental data and modeling results validates the membrane design and confirms the success of model prediction. The effects of key parameters on boron rejection, such as boron permeability of both selective layers and structure parameter, were also investigated in-depth with the mathematical modeling. This study may provide insights not only for boron removal from wastewater, but also open up the design of next generation FO membranes to eliminate low-rejection molecules in wider applications.

Removal of organic micro-pollutants (phenol, aniline and nitrobenzene) via forward osmosis (FO) process: Evaluation of FO as an alternative method to reverse osmosis (RO).

In this study, we have explored and compared the effectiveness of using (1) lab-fabricated forward osmosis (FO) membranes under both FO and reverse osmosis (RO) modes and (2) commercially available RO membranes under the RO mode for the removal of organic micro-pollutants. The lab-fabricated FO membranes are thin film composite (TFC) membranes consisting of a polyamide layer and a porous substrate cast from three different materials; namely, Matrimid, polyethersulfone (PESU) and sulfonated polyphenylene sulfone (sPPSU). The results show that the FO mode is superior to the RO mode in the removal of phenol, aniline and nitrobenzene from wastewater. The rejections of all three TFC membranes to all the three organic micro-pollutants under the FO processes are higher than 72% and can be even higher than 90% for aniline when a 1000 ppm aromatic aqueous solution and 1 M NaCl are employed as feeds. These performances outperform the results obtained from themselves and commercially available RO membranes under the RO mode. In addition, the rejection can be maintained even when treating a more concentrated feed solution (2000 ppm). The removal performance can be further enhanced by using a more concentrated draw solution (2 M). The water flux is almost doubled, and the rejection increment can reach up to 17%. Moreover, it was observed that annealing as a post-treatment would help compact the membrane selective layer and further enhance the separating efficiency. The obtained organic micro-pollutant rejections and water fluxes under various feasible operating conditions indicate that the FO process has potential to be a viable treatment for wastewater containing organic micro-pollutants.

Anti-fouling behavior of hyperbranched polyglycerol-grafted poly(ether sulfone) hollow fiber membranes for osmotic power generation.

To sustain high performance of osmotic power generation by pressure-retarded osmosis (PRO) processes, fouling on PRO membranes must be mitigated. This is especially true for the porous support of PRO membranes because its porous structure is very prone to fouling by feeding river water. For the first time, we have successfully designed antifouling PRO thin-film composite (TFC) membranes by synthesizing a dendritic hydrophilic polymer with well-controlled grafting sites, hyperbranched polyglycerol (HPG), and then grafting it on poly(ether sulfone) (PES) hollow fiber membrane supports. Compared to the pristine PES membranes, polydopamine modified membranes, and conventional poly(ethylene glycol) (PEG)-grafted membranes, the HPG grafted membranes show much superior fouling resistance against bovine serum albumin (BSA) adsorption, E. coli adhesion, and S. aureus attachment. In high-pressure PRO tests, the PES TFC membranes are badly fouled by model protein foulants, causing a water flux decline of 31%. In comparison, the PES TFC membrane grafted by HPG not only has an inherently higher water flux and a higher power density but also exhibits better flux recovery up to 94% after cleaning and hydraulic pressure impulsion. Clearly, by grafting the properly designed dendritic polymers to the membrane support, one may substantially sustain PRO hollow fiber membranes for power generation.

Highly permeable double-skinned forward osmosis membranes for anti-fouling in the emulsified oil-water separation process.

Forward osmosis (FO) has attracted wide attention in recent years. However, the FO performance may be restricted due to internal concentration polarization (ICP) and fast fouling propensity that occurs in the membrane sublayer. Particularly, these problems significantly affect the membrane performance when treating highly contaminated oily wastewater. Recently, double-skinned flat sheet cellulose acetate (CA) membranes consisting of two selective skins via the phase inversion method have demonstrated less ICP and fouling propensity over typical single-skinned membranes. However, these membranes exhibit low water fluxes of <12 LMH under 2 M NaCl draw solution. Therefore, a novel double-skinned FO membrane with a high water flux has been aimed for in this study for emulsified oil-water treatment. The double-skinned FO membrane comprises a fully porous sublayer sandwiched between (i) a truly dense skin for salt rejection and (ii) a fairly loose dense skin for emulsified oil particle rejection. The former dense skin is a polyamide synthesized via interfacial polymerization, while the latter one is a self-assembled sulfonated pentablock copolymer (Nexar copolymer) layer. The resultant double-skinned membrane exhibits a high water flux of 17.2 LMH and a low reverse salt transport of 4.85 gMH using 0.5 M NaCl as the draw solution and DI water as the feed. The double-skinned membrane outperforms the single-skinned membrane with much lower fouling propensity for emulsified oil-water separation.

Development of thin-film composite forward osmosis hollow fiber membranes using direct sulfonated polyphenylenesulfone (sPPSU) as membrane substrates.

This study investigates a new approach to fabricate thin-film composite (TFC) hollow fiber membranes via interfacial polymerization for forward osmosis (FO) applications. Different degrees of sulfonation of polyphenylenesulfone (PPSU) were adopted as membrane substrates to investigate their impact on water flux. It has been established that the degree of sulfonation plays a role in both creating a macrovoid-free structure and inducing hydrophilicity to bring about higher water fluxes. The fabricated membranes exhibit extremely high water fluxes of 30.6 and 82.0 LMH against a pure water feed using 2.0 M NaCl as the draw solution tested under FO and pressure retarded osmosis (PRO) modes, respectively, while maintaining low salt reverse fluxes below 12.7 gMH. The structural parameter (S) displays remarkable decreases of up to 4.5 times as the membrane substrate is switched from a nonsulfonated to sulfonated one. In addition, the newly developed TFC-FO membranes containing 1.5 mol % sPPSU in the substrate achieves a water flux of 22 LMH in seawater desalination using a 3.5 wt % NaCl model solution and 2.0 M NaCl as the draw solution under the PRO mode. To the best of our knowledge, this value is the highest ever reported for seawater desalination using flat and hollow fiber FO membranes. The use of sulfonated materials in the FO process opens up a frontier for sustainable and efficient production of potable water.

A conceptual demonstration of freeze desalination-membrane distillation (FD-MD) hybrid desalination process utilizing liquefied natural gas (LNG) cold energy.

The severe global water scarcity and record-high fossil oil price have greatly stimulated the research interests on new desalination technologies which can be driven by renewable energy or waste energy. In this study, a hybrid desalination process comprising freeze desalination and membrane distillation (FD-MD) processes was developed and explored in an attempt to utilize the waste cold energy released from re-gasification of liquefied natural gas (LNG). The concept of this technology was demonstrated using indirect-contact freeze desalination (ICFD) and direct-contact membrane distillation (DCMD) configurations. By optimizing the ICFD operation parameters, namely, the usage of nucleate seeds, operation duration and feed concentration, high quality drinkable water with a low salinity ∼0.144 g/L was produced in the ICFD process. At the same time, using the optimized hollow fiber module length and packing density in the DCMD process, ultra pure water with a low salinity of 0.062 g/L was attained at a condition of high energy efficiency (EE). Overall, by combining FD and MD processes and adopting the optimized operation parameters, the hybrid FD-MD system has been successfully demonstrated. A high total water recovery of 71.5% was achieved, and the water quality obtained met the standard for drinkable water. In addition, with results from specific energy calculation, it was proven that the hybrid process is an energy-saving process and utilization of LNG cold energy could greatly reduce the total energy consumption.