ABSTRACT
Since the discovery of size-selective metal-organic frameworks (MOFs), researchers have tried to incorporate these materials into gas separation membranes. Impressive gas selectivities were found, but these MOF membranes were mostly made on inorganic supports, which are generally too bulky and expensive for industrial gas separation. Forming MOF layers on porous polymer supports is industrially attractive but technically challenging. Two features to overcome these problems are described: 1)â a metal chelating support polymer to bind the MOF layer, and 2)â control of MOF crystal growth by contra-diffusion, aiming at a very thin nanocrystalline MOF layer. Using a metal chelating poly-thiosemicarbazide (PTSC) support and adjusting the metal and organic ligand concentrations carefully, a very compact ZIF-8 (ZIF=zeolitic imidazolate framework) layer was produced that displayed interference colors because of its smooth surface and extreme thinness-within the range of visible light. High performances were measured in terms of hydrogen/propane (8350) and propylene/propane (150) selectivity.
ABSTRACT
A novel generic method is reported for the synthesis of a spirobifluorene-based dianhydride (SBFDA). An intrinsically microporous polyimide was obtained by polycondensation reaction with 3,3'-dimethylnaphthidine (DMN). The corresponding polymer (SBFDA-DMN) exhibited good solubility, excellent thermal stability, as well as significant microporosity with high BET surface area of 686 m2/g. The O2 permeability of a methanol-treated and air-dried membrane was 1193 Barrer with a moderate O2/N2 selectivity of 3.2. The post-treatment history and aging conditions had great effects on the membrane performance. A significant drop in permeability coupled with an increase in selectivity was observed after long-term aging. After storage of 200 days, the gas separation properties of SBFDA-DMN were located slightly above the latest Robeson upper bounds for several gas pairs such as O2/N2 and H2/N2.
ABSTRACT
Increases in hydrogen selectivity of more than 100% compared with the most selective ladder polymer of intrinsic microporosity (PIM) reported to date are achieved with self-polymerized A-B-type ladder monomers comprising rigid and three-dimensional 9,10-dialkyl-substituted triptycene moieties. The selectivities match those of materials commercially employed in hydrogen separation, but the gas permeabilities are 150-fold higher. This new polymer molecular sieve is also the most selective PIM for air separation.
ABSTRACT
Understanding the removal of trace organic contaminants is critical for membrane applications in water recycling. This study investigates the relationship between trace contaminant sorption and their rejection by nanofiltration (NF) membranes. A mass balance is developed that quantitatively links the rejection decline over time seen with some sorbing compounds to the total mass found sorbed on the membrane. The sorbed mass of perfluorooctane sulfonamide (FOSA) and fluoxetine evaluated from the mass balance agreed to within approximately 30% of the quantity analytically determined via extraction. Static sorption experiments show that sorption takes place predominantly within the polyamide separating layer of the membrane. Finally, the relationship between the steady-state rejection and sorption tendency of ten trace organic compounds is elucidated. A greater tendency to sorb results in lower steady-state rejection, both when comparing compounds of similar size, as well as when comparing the same compound under different conditions. As a result, a major finding is that in the presence of competitive sorption, that is, the presence of other trace organic compounds in the membrane matrix, some compounds sorb less and are therefore rejected more than when these compounds are alone in the feed. At no point during experimentation was any effect on the water flux observed.
