MFI-molecular sieve membranes : synthesis, characterization and modelling

Sammanfattning: This work concerns evaluation by permeation measurements and modeling of thin (<2µm) MFI molecular sieve membranes and, to a smaller extent, synthesis of such materials. The membranes have been synthesized on graded a-alumina microfiltration filters using The seed film method. Scanning electron microscopy and x-ray diffraction were used for characterization in addition to permeation measurements. Mathematical models describing membrane flux for real membranes and defect distributions were developed. Defect distributions were calculated from porosimetry data and were further used for prediction of single gas permeation characteristics for real membranes. The models confirm the experimental findings, with respect to ideal selectivities as a measurement of membrane quality. Membrane permeation simulations indicate increasing ideal selectivities, with increasing film thickness, for quotients containing SF6. Thereby a high quality membrane could possess low ideal selectivities. This finding was confirmed by comparing experimental data of several membranes with varying thickness. The correlation between multi component separation data and commonly used quality criteria was investigated. It was found that commonly used single gas permeation quotients (ideal selectivity) between light inorganic gases, especially those containing sulphurhexaflouride (SF6), is less appropriate for membrane quality measurement. The porosimetry experiment showed on the other hand a good agreement between experimental data and separation performance of the membranes, as expected. ZSM-5 membranes with low aluminum content and silicalite-1 membranes with similar material properties, such as defect distribution and thickness were evaluated with multi component hydrocarbon isomers permeation. The ZSM-5 membrane had lower permeances and a slightly better butane isomer separation performance than the silicalite-1 membrane. The latter membrane showed a minimum in separation selectivity between two C6 isomers whereas the ZSM-5 membrane showed an almost constant selectivity, independent of temperature, but with lower permeances. ZSM-5 membranes with a high aluminum content catalyzed the formation of diethylether and ethylen at temperatures exceeding 150°C from a water/ethanol mixture. The membrane separated a mixture of C4 isomers with good performance at elevated temperatures. However these membranes suffered from temperature instability problems.