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In the last decade, zeolitic imidazolate frameworks (ZIFs) have been studied extensively for their potential as selective separation membranes. In this review, we highlight unique structural properties of ZIFs that allow them to achieve certain important separations, like that of propylene from propane, and summarize the state of the art in ZIF thin-film deposition on porous substrates and their modification by postsynthesis treatments. We also review the reported membrane performance for representative membrane synthesis approaches and attempt to rank the synthesis methods with respect to potential for scalability. To compare the dependence of membrane performance on membrane synthesis methods and operating conditions, we map out fluxes and separation factors of selected ZIF-8 membranes for propylene/propane separation. Finally, we provide future directions considering the importance of further improvements in scalability, cost effectiveness, and stable performance under industrially relevant conditions. 

Zeolite nanosheets with improved thickness and orientation uniformity yield effective separation membranes for xylene isomers. 

Nanosheet-based MFI membranes, known to be highly selective for hydrocarbon isomer separations, exhibit an NH 3 /N 2 mixture separation factor of 2236 with NH 3 permeance of 1.1 × 10 −6 mol m −2 s −1 Pa −1 , and NH 3 /H 2 separation factor of 307 with NH 3 permeance of 2.3 × 10 −6 mol m −2 s −1 Pa −1 at room temperature. Consistent with a competitive sorption-based separation, lower operating temperatures and higher pressures result in increased separation factor. At 323 K, with an equimolar mixed feed of NH 3 /N 2 , the fluxes and separation factors at 3 and 7 bar are 0.13 mol m −2 s −1 and 191, and 0.26 mol m −2 s −1 and 220, respectively. This performance compares favorably with that of other membranes and suggests that MFI membranes can be used in separation and purification processes involving mixtures of NH 3 /N 2 /H 2 encountered in ammonia synthesis and utilization. The membranes also exhibit high performance for the separation of ethane, n -propane and n -butane from H 2 . 

1,3-Pentadiene (piperylene) is an important monomer in the manufacturing of adhesives, plastics, and resins. It can be derived from biomass by the tandem ring-opening and dehydration (dehydra-decyclization) of 2-methyltetrahydrofuran (2-MTHF), but competing reaction pathways and the formation of another isomer (1,4-pentadiene) have limited piperylene yields to <60%. In this report, using detailed kinetic measurements of 2-MTHF dehydra-decyclization on zeolites with disparate acidities (boro-, and alumino-silicates) and micropore environments (MFI, MWW, and BEA), weakly acidic borosilicates were shown to exhibit ca. 10–30% higher selectivity to dienes at about five-to-sixty times lower proton-normalized rates than aluminosilicates (453–573 K). Dehydra-decyclization site time yields (STYs) were invariant for aluminosilicates within the investigated frameworks, indicating the absence of pore-confinement influence. However, individual site-normalized reaction rates varied by almost an order of magnitude on borosilicates in the order MWW > MFI > BEA at a given temperature (523 K), indicating the non-identical nature of active sites in these weak solid acids. The diene distribution remained far from equilibrium and was tuned towards the desirable conjugated diene (1,3-pentadiene) by facile isomerization of 1,4-pentadiene. This tuning capability was facilitated by high bed residence times, as well as the smaller micropore sizes among the zeolite frameworks considered. The suppression of competing pathways, and promotion of 1,4-pentadiene isomerization events lead to a hitherto unreported ∼86% 1,3-pentadiene yield and an overall ∼89% combined linear C5 dienes’ yield at near quantitative (∼98%) 2-MTHF conversion on the borosilicate B-MWW, without a significant reduction in diene selectivities for at least 80 hours time-on-stream under low space velocity (0.85 g reactant per g cat. per h) and high temperature (658 K) conditions. Finally, starting with iso-conversion levels ( ca. 21–26%) and using total turnover numbers (TONs) accrued over the entire catalyst lifetime as the stability criterion, borosilicates were demonstrated to be significantly more stable than aluminosilicates under reaction conditions (∼3–6× higher TONs).