Asim Laeeq Khan

Modulated UiO-66-Based Mixed-Matrix Membranes for CO2 Separation

Mixed-matrix membranes (MMMs) composed of polyimide (PI) and metal-organic frameworks (MOFs) were synthesized using Matrimid as the polymer and zirconium terephthalate UiO-66 as the filler. The modulation approach, combined with the use of amine-functionalized linkers, was used for synthesis of the MOF fillers in order to enhance the intrinsic separation performance of the MOF and improve the particle-PI compatibility. The presence of amine groups on the MOF outer surface introduced either through the linker, through the modulator, or through both led to covalent linking between the fillers and Matrimid, which resulted in very stable membranes. In addition, the presence of amine groups inside the pores of the MOFs and the presence of linker vacancies inside the MOFs positively influenced CO2 transport. MMMs with 30 wt % loading showed excellent separation performance for CO2/CH4 mixtures. A significant increase in the mixed-gas selectivity (47.7) and permeability (19.4 barrer) compared to the unfilled Matrimid membrane (i.e., 50% more selective and 540% more permeable) was thus achieved for the MMM containing the MOF prepared from 2-aminoterephthalic acid and 4-aminobenzoic acid, respectively used as the linker and as the modulator.

SPEEK and functionalized mesoporous MCM-41 mixed matrix membranes for CO2 separations

Mixed matrix membranes (MMMs) composed of sulfonated aromatic poly(ether ether ketone) (SPEEK) and –SO3 functionalized mesoporous MCM-41 were prepared by the solution casting method. A SPEEK polymer with a fixed degree of sulfonation was used for membrane synthesis. CO2 permeation data and SEM images of the synthesized MMMs suggest that the functionalized fillers adhered well to the polymer matrix. Gas permeation tests indicated that the addition of functionalized MCM-41 to the polymer matrix increased both the gas permeability and selectivity. The highest selectivities obtained here for CO2/N2 and CO2/CH4 were 40.46 and 22.86 (at a CO2 permeability of 21.04 Barrer), respectively. In order to initiate the evaluation of the practical commercial viability of these membranes, they were tested under different operating pressures and temperatures.

Highly Selective Separation of Carbon Dioxide from Nitrogen and Methane by Nitrile/Glycol-Difunctionalized Ionic Liquids in Supported Ionic Liquid Membranes (SILMs)

Novel difunctionalized ionic liquids (ILs) containing a triethylene glycol monomethyl ether chain and a nitrile group on a pyrrolidinium or imidazolium cation have been synthesized and incorporated into supported ionic liquid membranes (SILMs). These ILs exhibit ca. 2.3 times higher CO2/N2 and CO2/CH4 gas separation selectivities than analogous ILs functionalized only with a glycol chain. Although the glycol moiety ensures room temperature liquidity of the pyrrolidinium and imidazolium ILs, the two classes of ILs benefit from the presence of a nitrile group in different ways. The difunctionalized pyrrolidinium ILs exhibit an increase in CO2 permeance, whereas the permeances of the contaminant gases rise negligibly, resulting in high gas separation selectivities. In the imidazolium ILs, the presence of a nitrile group does not always increase the CO2 permeance nor does it increase the CO2 solubility, as showed in situ by the ATR-FTIR spectroscopic method. High selectivity of these ILs is caused by the considerably reduced permeances of N2 and CH4, most likely due to the ability of the -CN group to reject the nonpolar contaminant gases. Apart from the CO2 solubility, IL-CO2 interactions and IL swelling were studied with the in situ ATR-FTIR spectroscopy. Different strengths of the IL-CO2 interactions were found to be the major difference between the two classes of ILs. The difunctionalized ILs interacted stronger with CO2 than the glycol-functionalized ILs, as manifested in the smaller bandwidths of the bending mode band of CO2 for the latter.

CO2 reverse selective mixed matrix membranes for H2 purification by incorporation of carbon–silica fillers

By filling a PDMS top layer with porous carbon–silica microspheres, a defect-free mixed matrix membrane was created with notable CO2 reverse selective separation properties. For the separation of CO2 over H2 at room temperature and 10 bar inlet pressure, these membranes demonstrate high CO2 gas fluxes up to 3 × 10−7 mol cm−2 s−1, in combination with ideal separation factors in the range of 6 to 9. The present separation data signify an important step forward in the removal of CO2 from H2 using a reverse selective separation strategy. Moreover, they elucidate the potential of such mixed matrix membranes in the emerging field of CO2 separation.

Synergistic effect of Chitosan-Zinc Oxide Hybrid Nanoparticles on antibiofouling and water disinfection of mixed matrix polyethersulfone nanocomposite membranes

Antifouling polyethersulfone (PES) membranes for water disinfection were fabricated by incorporating varying concentrations of carbohydrate polymer chitosan and Zinc oxide hybrid nanoparticles (CS-ZnO HNPS). The CS-ZnO HNPS were prepared using chemical precipitation method and were characterized using SEM, XRD and FTIR. The membranes were then fabricated by incorporating nanoparticles of CS-ZnO HNPS with three different concentrations of 5%, 10% and 15% w/w in the casting solution of PES through phase inversion method. The influence of nano-sized CS-ZnO HNPS on the properties of PES was characterized to study morphology, contact angle, water retention, surface roughness and permeability flux. The membranes with the maximum concentrations of 15% HNPS resulted in larger mean pore sizes and lowest contact angle value as compare to the pristine PES membrane. The prepared membranes exhibited significant water permeability, hydrophilicity and prevention against microbial fouling. The prepared membranes were observed to have significant antibacterial as well as antifungal properties due to the synergistic effect of chitosan and ZnO against both bacteria of the type of S. Aureus, B. Cereus, E. coli, and fungi such as S. typhi, A. fumigatus and F. solani.

Mixed matrix membranes prepared from non-dried MOFs for CO2/CH4 separations

Mixed matrix membranes (MMMs) aim at combining the processibility of polymers with the molecular sieving of fillers to improve gas separation performance. Metal–organic frameworks (MOFs) are a new family of materials with promising potential as fillers. The first part of this work reports on exploiting the versatility of MOF synthesis routes by forming ZIF-8 particles in polymer solutions to subsequently cast membranes directly from the solution. Although MOFs can be synthesised in a polymer medium, the decline in the synthesis yield does not allow for high loading in the MMMs. The second part describes a method for preparing MMMs with the commercial polyimide (PI) Matrimid® and ZIF-8, ZIF-7 and NH2-MIL-53(Al) as non-dried filler with 30 wt% and 50 wt% loading. A comparison of this method with the conventional approach of drying MOFs prior to incorporation exhibits the flexibility MOFs provide in membrane synthesis, in contrast to e.g. zeolites which intrinsically have to be calcined to become useful. The membranes with non-dried MOFs show some improvement in performance as compared to the unfilled polymer-only membranes, while those with dried MOFs even lose the inherent selectivity of the polymer.

Two-way switch: Maximizing productivity of tilted panel in membrane bioreactor

Membrane fouling is a major challenge in membrane bioreactors (MBRs) and its effective handling is the key to improve their competitiveness. Tilting panel system offers significant improvements for fouling control but is strictly limited to one-sided panel. In this study, we assess a two-way switch tilting panel system that enables two-sided membranes and project its implications on performance and energy footprint. Results show that tilting a panel improves permeance by up to 20% to reach a plateau flux thanks to better contacts between air bubbles and the membrane surface to scour-off the foulant. A plateau permeance could be achieved at aeration rate of as low as 0.90 l min-1, a condition untenable by vertical panel even at twice of the aeration rate. Switching at short periods (<5min) can maintain the hydraulic performance as in no-switch (static system), enables application of a two-sided switching panel. A comparison of vertical panel under 1.80 l min-1 aeration rate with a switching panel at a half of the rate, switched at 1 min period shows ≈10% higher permeance of the later. Since periodic switching consumes a very low energy (0.55% of the total of 0.276 kWh m-3), with reduction of aeration by 50%, the switching tilted panel offers 41% more energy efficient than a referenced full-scale MBR (0.390 kWh m-3). Overall results are very compelling and highly attractive for significant improvements of MBR technologies.

Anaerobic membrane bioreactors for biohydrogen production: Recent developments, challenges and perspectives

Biohydrogen as one of the most appealing energy vector for the future represents attractive avenue in alternative energy research. Recently, variety of biohydrogen production pathways has been suggested to improve the key features of the process. Nevertheless, researches are still needed to overcome remaining barriers to practical applications such as low yields and production rates. Considering practicality aspects, this review emphasized on anaerobic membrane bioreactors (AnMBRs) for biological hydrogen production. Recent advances and emerging issues associated with biohydrogen generation in AnMBR technology are critically discussed. Several techniques are highlighted that are aimed at overcoming these barriers. Moreover, environmental and economical potentials along with future research perspectives are addressed to drive biohydrogen technology towards practicality and economical-feasibility.