Permporometry analysis of zeolite membranes

In permporometry analysis of zeolite membranes, the permeance of a non-adsorbing gas, such as helium, is measured as a function of pressure of a strongly adsorbing compound, such as n-hexane in the case of silicalite-1 membranes. The adsorbing compound effectively blocks the transport of the non-adsorbing gas already at very low activity of the adsorbing compound. The plot of the permeance of the non-adsorbing gas as a function of relative pressure of the adsorbing compound is denoted a permporometry pattern. The present work is based on experimental data for a number of thin MFI membranes with a film thickness ranging from 300 to 1800 nm. An adsorption-branch permporometry experiment is simple and straightforward and after activation of the membrane by removing adsorbed species at 300 °C in a flow of dry gas, a full permporometry pattern is recorded within about 7 h for such membranes. It is shown how the distribution of flow-through defects can be estimated from the permporometry pattern using a simple model for permeation based on Knudsen diffusion. The estimated defect distribution is supported by SEM observations. In addition, the permeance of the non-adsorbing gas through defects measured in permporometry can be used to predict the permeance of molecules diffusing through defects in the membrane in mixture separation experiments and also indicate the separation factor. For instance, the helium permeance through defects in an MFI membrane measured by helium/n-hexane permporometry at room temperature can be used to estimate the permeance of 2,2-dimethylbutane (DMB) in a mixture separation experiment at a higher temperature with a feed containing both DMB and n-hexane by assuming Knudsen diffusion for both helium and DMB in the defects. Also, the separation factor αn-hexane/DMB in a mixture separation experiment at a certain temperature with an MFI membrane with a given defect distribution can be estimated from n-hexane/helium permporometry data recorded at the same temperature through an empirical correlation. In summary, adsorption-branch permporometry is a very effective tool for analysis of thin zeolite membranes, that in short time gives data that can be used to estimate the distribution of flow-through defects in the membrane and to estimate the transport of large molecules through defects in separation experiments and also estimate separation performance.