Synthèse de membranes minérales de nanofiltration par formation de films minces de zéolithes sur un support tubulaire en alumine : étude de l'évolution des propriétés de surface et des caractéristiques de filtration en milieu aqueux

摘要

Zeolites are very well-known materials especially for their controlled porosity, their crystalline structures, but also for the different applications where they can be used (catalysis, air treatment,...) . During the past ten years, a lot of developments have been done on the preparation of zeolite membranes for pervaporation applications. The present work explores new developments in the preparation zeolite membranes dedicated to the filtration of salty water. More particularly, we prepared MFI films on specific macroporous alumina tubular supports used for nanofiltration applications. There are different key steps which influence the formation of the MFI films: the cleaning procedure of the substrats, the hydrothermal synthesis conditions, the use of a secondary growth method for when preparing a bi-layered membrane. A complete characterization of the mono and the bi-layered membranes was carried out using various techniques, such as X-ray diffraction, scanning electron microscopy, X-ray fluorescence, energy dispersive X-ray spectroscopy, mercury porosimetry and nitrogen sorption measurements. Results show that a dense, continuous and highly crystallized thin film of MFI bas been obtained on the u-alumina support after the secondary growth experiment. The weight of zeolite deposited on the support was also estimated by nitrogen sorption measurement using the method of mass assessment. The MFI membrane was stabilized by pure water filtration tests until the hydraulic permeability reached a plateau. This conditioning step was necessary to reach an equilibrium state of the hydraulic membrane performances. Particularly, hydration of the MFI layer was a crucial step of the conditioning process, which leads to the modification of the MFI surface properties. The hydraulic permeability of the mono and bi-layer MFI membrane decreased rapidly at the beginning of the conditioning process, and stabilized alter 15 hours to reach 1.08 x 10.141113.m.2 and 1.02 x 10-15 m3.m-2 respectively. Filtration tests were then carried out with a neutral molecule (VB 12) in order to evaluate the mean pore radius of the mono and the bi-layered membranes. A rejection rate of 5% was obtained with the monolayer MFI membrane, while it reaches a value of 50% with the bi-layered one. These results lead to mean pore radius corresponding to 6.4 and 1.7 mn respectively. It menus that even alter the synthesis of the second MFI layer, the membrane porosity remains higher than the porous diameter of the zeolite. Filtration may occur at the interface of the MFI crystals.