Characterization of zeolite membranes by gas permeation


Thesis Type: Doctorate

Institution Of The Thesis: Orta Doğu Teknik Üniversitesi, Faculty of Engineering, Department of Chemical Engineering, Turkey

Approval Date: 2009

Student: BELMA SOYDAŞ

Supervisor: HALİL KALIPÇILAR

Abstract:

Zeolite membranes are attractive materials to separate gas and liquid mixtures. MFI is a widely studied zeolite type due to its ease of preparation and comparable pore size with the molecular size of many substances. In this study MFI type membranes were synthesized over porous α-Al2O3 supports and characterized with XRD, SEM and gas permeation measurements. In the first part of this study the effect of soda concentration of the synthesis solution on the membrane morphology and crystal orientation was investigated. The synthesis was carried out from solutions with a molar composition of (0- 6.5)Na2O:25SiO2:6.9TPABr:1136H2O at 150oC. At soda concentrations between 0.45 and 1.8 the membrane layers with (h0h)/c-directed orientation were obtained. At lower and higher soda concentrations membrane layer formed from randomly oriented crystals. The (h0h)/c-oriented membranes showed H2/n-C4H10 ideal selectivities of 478 and 36 at 25°C and 150°C, respectively.In the second part, MFI membranes were synthesized from mixtures with different concentrations of template molecules. Tetrapropylammonium hydroxide, tetrapropylammonium bromide or mixture of both types were used as template. The nucleation period, the size of MFI crystals, membrane thickness decreased as the tetrapropylammonium hydroxide concentration increased. Besides conversion of SiO2 in the synthesis solution to MFI passed through a maximum with increasing concentration of tetrapropylammonium hydroxide in the synthesis solution. When tetrapropylammonium bromide was used as template thicker membranes were obtained. In the third part MFI type membranes with a thickness of 1.5-2 μm were synthesized by mid-synthesis addition of silica to the synthesis medium. The membranes synthesized with and without mid-synthesis addition of silica have n-C4H10/i-C4H10 ideal selectivities of 47 and 8 at 100oC, respectively. The change of composition during the synthesis increases the crystal growth rate and the size of the crystals forming the membrane, thus better quality membranes can be obtained by mid-synthesis addition of silica to the synthesis medium. In the last part of this study, thin MFI type zeolite membranes were synthesized in a recirculating flow system at 95°C on the inner side of the tubular α- alumina supports. A membrane synthesized by two consecutive synthesis steps had a separation selectivity of 38 and 86 for equimolar mixtures of n- C4H10/CH4 and n-C4H10/N2 at 25oC, respectively. The membrane selectively permeated large n-C4H10 over small CH4 and N2, suggesting that the separation is essentially adsorption-based and the membrane has few nonselective intercrystalline pores.