Influence of zeolite crystal expansion/contraction on NaA zeolite membrane separations

▶ Adsorption causes the NaA zeolite unit cell to contract or expand. ▶ Water and methanol adsorption contracted the NaA unit cell at low activities. ▶ At higher activities, water and methanol adsorption expanded the NaA unit cell. ▶ Changes in crystal size correlated with permeation changes through NaA membranes. In situ powder XRD measurements showed that adsorption causes the NaA zeolite unit cell to contract or expand, and these changes depend on adsorbate loading. Changes in zeolite crystal size correlated with permeation changes through NaA zeolite membranes. These membranes had high water/alcohol pervaporation selectivities, even though gas permeation was mainly through defects, as indicated by Knudsen selectivities for single gas permeation. At 300 K and a thermodynamic activity of 0.03, water contracted the NaA crystals by 0.22 vol%, and this contraction increased the helium flux through two NaA membranes by approximately 80%. Crystal contraction also increased the fluxes of i-butane during vapor permeation and i-propanol (IPA) during pervaporation (∼0.03 wt% water). At activities above 0.07, water expanded NaA crystals and correspondingly decreased the fluxes of helium, i-butane, and IPA through NaA zeolite membranes. Methanol also contracted NaA crystals, but by only 0.05 vol% at an activity of 0.02, and this contraction slightly increased the helium and i-butane fluxes through a NaA membrane. Above an activity of 0.06, methanol expanded the NaA crystals, and the fluxes of helium and i-butane through a NaA membrane decreased. These adsorbate-induced changes explain some pervaporation behavior reported by others, and they indicate that crystal expansion and contraction may increase or decrease zeolite NaA membrane selectivity by changing the defect sizes.