Natural gas sweetening, one of the most promising venues for the growth of the membrane gas separation industry, is dominated by polymeric materials with relatively low permeabilities and moderate selectivities. One strategy towards improving the gas transport properties of a polymer is enhancement of microporosity either by design of polymers of intrinsic microporosity (PIMs) or by thermal treatment of polymeric precursors. For the first time, the mixed-gas CO2/CH4 transport properties are investigated for a complete series of thermally-rearranged (TR) (440°C) and carbon molecular sieve (CMS) membranes (600, 630 and 800°C) derived from a polyimide of intrinsic microporosity (PIM-6FDA-OH). The pressure dependence of permeability and selectivity is reported up to 30bar for 1:1, CO2:CH4 mixed-gas feeds at 35°C. The TR membrane exhibited ~15% higher CO2/CH4 selectivity relative to pure-gas feeds due to reductions in mixed-gas CH4 permeability reaching 27% at 30bar. This is attributed to increased hindrance of CH4 transport by co-permeation of CO2. Interestingly, unusual increases in mixed-gas CH4 permeabilities relative to pure-gas values were observed for the CMS membranes, resulting in up to 50% losses in mixed-gas selectivity over the applied pressure range. © 2013 Elsevier B.V.

Sodium lignin sulfonate (NaLS), an abundant waste product of paper manufacturing, can be used in desert restoration. Combined with water and applied on arid land, NaLS has been shown to stabilize sand and provide a medium for plant growth. Here, we demonstrate that NaLS is an efficient draw solute in forward osmosis (FO) to extract water from impaired sources. The osmotic pressure of a 600. g. NaLS/kg water solution is 78. bar (7.8 MPa) as measured by freezing point depression. The FO performance using NaLS draw solute was evaluated with commercial FO membranes under various test conditions. The effects of draw solute concentration, feed salinity and membrane orientation were systematically investigated. Potential ways to optimize the process, e.g. combining fertilizer draw solutes and NaLS, are proposed. © 2013 Elsevier B.V.

The prototypical solution-processable polymer of intrinsic microporosity, PIM-1, and derivatives thereof offer combinations of permeability and selectivity that make them potential candidate materials for membrane-based gas separations. Paramount to the design and evaluation of PIMs for economical natural gas sweetening is a high and stable CO2/CH4 selectivity under realistic, mixed-gas conditions. Here, amidoxime-functionalized PIM-1 (AO-PIM-1) was prepared and examined for fundamental structure/property relationships. Qualitative NLDFT pore-size distribution analyses of physisorption isotherms (N2 at -196 oC; CO2 at 0 oC) reveal a tightened microstructure indicating size-sieving ultra-microporosity (<7Å). AO-PIM-1 demonstrated a three-fold increase in αD(CO2/CH4) over PIM-1, surpassing the 2008 upper bound with P(CO2)=1153Barrer and ideal α(CO2/CH4)=34. Under a 50:50 CO2:CH4 mixed-gas feed, AO-PIM-1 showed less selectivity loss than PIM-1, maintaining a mixed-gas α(CO2/CH4) ~21 across a 20bar pressure range. Conversely, PIM-1 endured up to 60% increases in mixed-gas CH4 permeability over pure-gas values concurrent with a selectivity of only ~8 at 20bar. A pervasive intermolecular hydrogen bonding network in AO-PIM-1 predominantly yields a rigidified microstructure that mitigates CO2-induced matrix dilations, reducing detrimental mixed-gas CH4 copermeation. © 2014 Elsevier B.V.

A simple and efficient approach towards the fabrication of a skinned membrane with highly ordered pores in the nanometer range is presented here. We successfully combined the self-assembly of PS-b-PEO block copolymer and water induced phase separation for the preparation of isoporous PS-b-PEO block copolymer membranes. We produced for the first time asymmetric isoporous PS-b-PEO membranes with a 100nm thin isoporous separating layer using water at room temperature as coagulant. This was possible by careful selection of the block lengths and the solvent system. FESEM, AFM and TEM measurements were employed to characterize the nanopores of membranes. The pure water fluxes were measured and the flux of membrane was exceptionally high (around 800Lm-2h-1bar-1). Protein rejection measurements were carried out for this membrane and the membrane had a retention of about 67% of BSA and 99% of γ-globulin. © 2013 Elsevier B.V.

In this study, a novel forward osmosis (FO) process for the removal of heavy metal ions from wastewater was demonstrated for the first time. The proposed FO process consists of a thin-film composite (TFC) FO membrane made from interfacial polymerization on a macrovoid-free polyimide support and a novel bulky hydroacid complex Na4[Co(C6H4O7)2]·r2H2O (Na-Co-CA) as the draw solute to minimize the reverse solute flux. The removal of six heavy metal solutions, i.e., Na2Cr2O7, Na2HAsO4, Pb(NO3)2, CdCl2, CuSO4, Hg(NO3)2, were successfully demonstrated. Water fluxes around 11L/m2/h (LMH) were harvested with heavy metals rejections of more than 99.5% when employing 1M Na-Co-CA as the draw solution to process 2000ppm(1 ppm=1 mg/L) heavy metal solutions at room temperature. This FO performance outperforms most nanofiltration (NF) processes. In addition, the high rejections were maintained at 99.5% when a more concentrated draw solution (1.5M) or feed solution (5000ppm) was utilized. Furthermore, rejections greater than 99.7% were still achieved with an enhanced water flux of 16.5LMH by operating the FO process at 60°C. The impressive heavy metal rejections and satisfactory water flux under various conditions suggest great potential of the newly developed FO system for the treatment of heavy metal wastewater. © 2014 Elsevier B.V.

The incorporation of membrane distillation (MD) into forward osmosis (FO) provides process sustainability to regenerate the draw solution and to produce clean water simultaneously. However, the reverse salt flux is the major hurdle in the FO-MD system because it not only reduces the effective osmotic driving force across the membrane but also increases the replenishment cost and scaling issue. For the first time, a hydroacid complex with abundant hydrophilic groups and ionic species is evaluated as the draw solutes in the hybrid FO-MD system consisting of multi-bore PVDF MD membranes for seawater/brackish desalination. In order to evaluate the practicality of the hydroacid complex in the FO-MD system, FO and MD experiments were conducted at elevated temperatures and concentrations. The hydroacid complex has displayed desired properties such as high solubility, low viscosity, excellent thermal stability and minimal reverse salt flux suitable for FO and MD operations. FO-MD desalination process was demonstrated with a highest seawater desalination flux of 6/32 LMH (FO/MD). This study may open up the prospective of employing the hydroacid complex as the draw solute in FO-MD hybrid systems for seawater /brackish desalination. © 2015 Elsevier B.V.

Purification and recovery of hydrogen from hydrocarbons in refinery streams in the petrochemical industry is an emerging research field in the study of membrane gas separation. Hollow fiber membrane modules can be easily implemented into separation processes at the industrial scale. In this report, hollow yttria-stabilized zirconia (YSZ) fiber-supported zeolitic imidazole framework-8 (ZIF-8) membranes were successfully prepared using a mild and environmentally friendly seeded growth method. Our single-component permeation studies demonstrated that the membrane had a very high hydrogen permeance (~15×10 -7mol/m 2sPa) and an ideal selectivity of H 2/C 3H 8 of more than 1000 at room temperature. This high membrane permeability and selectivity caused serious concentration polarization in the separation of H 2/C 3H 8 mixtures, which led to almost 50% drop in both the H 2 permeance and the separation factor. Enhanced mixing on the feed side could reduce the effect of the concentration polarization. Our experimental data also indicated that the membranes had excellent reproducibility and long-term stability, indicating that the hollow fiber-supported ZIF-8 membranes developed in this study have great potential in industry-scale separation of hydrogen. © 2012 Elsevier B.V.

In this work carbon dioxide selective membrane materials from a commercially available poly(amide-b-ethylene oxide) (Pebax (R), Arkema) blended with polyethylene glycol ethers are presented. The preferred PEG-ether was PEG-dimethylether (PEG-DME). PEG-DME is well known as a physical solvent for acid gas absorption. It is used under the trade name Genosorb (R) in the Selexol (R) process (UOP) for acid gas removal from natural gas and synthesis gas. The combination of the liquid absorbent with the multiblock copolymer resulted in mechanically stable films with superior CO(2) separation properties. The addition of 50 wt.% PEG-DME to the copolymer resulted in a 8-fold increase of the carbon dioxide permeability; the CO(2)/H(2)-selectivity increased simultaneously from 9.1 to 14.9. It is shown that diffusivity as well as solubility of carbon dioxide is strongly increased by the blending of the copolymer with PEG-ethers. (c) 2009 Elsevier B.V. All rights reserved.

A novel hydrophilic cellulose ester with a high intrinsic water permeability and a water partition coefficient was discovered to construct membrane supports for flat-sheet thin film composite (TFC) forward osmosis (FO) membranes for water reuse and seawater desalination with high performance. The performance of TFC-FO membranes prepared from the hydrophilic cellulose ester containing a high degree of OH and a moderate degree of Pr substitutions clearly surpasses those prepared from cellulose esters and other polymers with moderate hydrophilicity. Post-treatments of TFC-FO membranes using sodium dodecyl sulfate (SDS) and glycerol followed by heat treatment further enhance the water flux without compromising the selectivity. Positron annihilation lifetime analyses have confirmed that the SDS/glycerol post-treatment increases the free volume size and fractional free volume of the polyamide selective layer. The newly developed post-treated TFC-FO membranes exhibit a remarkably high water flux up to 90 LMH when the selective layer is oriented towards the draw solution (i.e., PRO mode) using 1. M NaCl as the draw solution and DI water as the feed. For seawater desalination, the membranes display a high water flux up to 35 LMH using a 2. M NaCl draw solution. These water fluxes exceeded the water fluxes achieved by other types of FO membranes reported in literatures. © 2014 Elsevier B.V.

Large amounts of oily wastewater have been produced from various industries. The main challenge of oily wastewater treatments is to separate the stable emulsified oil particles from water. Therefore, the aim of this study is to investigate the effectiveness of forward osmosis (FO) processes to treat the stable oil-water emulsions. The FO technique has been demonstrated successfully for the treatment of a wide range of oil-water emulsions from a low to a very high concentration up to 200,000. ppm. The dependence of separation performance on oily feed concentration and flow rate has been investigated. Water can be separated from oily feeds containing 500. ppm or 200,000. ppm emulsified oil at a relatively high flux of 16.5±1.2. LMH or 11.8±1.6. LMH respectively by using a thin film composite membrane PAN-TFC and 1. M NaCl as the draw solution. Moreover, this membrane can achieve an oil rejection of 99.88% to produce water with a negligible oil level. Due to the presence of emulsified oil particles in the oily feed solutions, the membrane fouling has been addressed in this study. Better anti-fouling TFC FO membranes are needed. © 2013 Elsevier B.V.