Pervaporative Dehydration of Organic Solvents Using High-Silica CHA-Type Zeolite Membrane.

A high-silica chabazite (CHA) type zeolite membrane was prepared on the porous α-Al2O3 support tube by the secondary growth of seed particles. The dehydration performances of the membrane were determined using methanol, ethanol, 2-propanol, acetone, acetic acid, methyl ethyl ketone (MEK), tetrahydrofuran (THF), N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and N-methyl-2-pyrolidone (NMP) at 303-373 K. As a result, the dehydration performances of the membrane were categorized to following three types: (1) 2-propanol, acetone, THF, and MEK; (2) ethanol and acetic acid; and (3) methanol, DMF, and DMSO, and NMP. The adsorption isotherms of water, methanol, ethanol, and 2-propanol were determined to discuss the influences of the organic solvents on the permeation and separation performances of the membrane. For 2-propanol, acetone, MEK, and THF solutions, the high permeation fluxes and separation factors were obtained because of the preferential adsorption of water due to molecular sieving. In contrast, the permeation fluxes and separation factors were relatively low for methanol, DMF, and DMSO, and NMP solutions. The lower dehydration performance for the methanol solution was due to the adsorption of methanol. The permeation fluxes for ethanol and acetic acid solution were ca. 1 kg m-2 h-1. The significantly low flux was attributed to the similar molecular diameter to the micropore size of CHA-type zeolite.

Gas Permeation Properties of High-Silica CHA-Type Zeolite Membrane.

The polycrystalline CHA-type zeolite layer with Si/Al = 18 was formed on the porous α-Al2O3 tube in this study, and the gas permeation properties were determined using single-component H2, CO2, N2, CH4, n-C4H10, and SF6 at 303-473 K. The membrane showed permeation behavior, wherein the permeance reduced with the molecular size, attributed to the effect of molecular sieving. The separation performances were also determined using the equimolar mixtures of N2-SF6, CO2-N2, and CO2-CH4. As a result, the N2/SF6 and CO2/CH4 selectivities were as high as 710 and 240, respectively. However, the CO2/N2 selectivity was only 25. These results propose that the high-silica CHA-type zeolite membrane is suitable for the separation of CO2 from CH4 by the effect of molecular sieving.

Development of Pure Silica CHA Membranes for CO2 Separation.

Thin pure-silica chabazite (Si-CHA) membranes have been synthesized by using a secondary growth method on a porous silica substrate. A CO2 permeance of 2.62 × 10-6 mol m-2 s-1 Pa-1 with a CO2/CH4 permeance ratio of 62 was obtained through a Si-CHA membrane crystallized for 8 h using a parent gel of H2O/SiO2 ratio of 4.6. The CO2 permeance through the Si-CHA membrane on a porous silica substrate was twice as high as that through the membrane synthesized on a porous alumina substrate, which displayed a similar zeolite layer thickness.