Synthesis, characterization and reactive separation activity of acid-functionalized silicalite-1 catalytic membrane in m-xylene isomerization

Propylsulfonic acid-functionalized silicalite-1 membrane and arenesulfonic acid-functionalized silicalite-1 membrane were synthesized over alpha-alumina support via one-step in situ hydrothermal crystallization and subsequent post-synthesis modification. Propylsulfonic acid-functionalized silicalite-1 membrane was synthesized using 3-mercaptopropyltrimethoxysilane (3MP) as an organosilane source whereas for arenesulfonic acid silicalite-1 membrane, phenethyltrimethoxysilane (PE) was used as an organosilane source. The acid capacity of the membrane was varied by adjusting the concentration of organosilane from 5 mol% to 20 mol%. The membranes were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and nitrogen gas permeation. Ammonia temperature-programmed desorption (NH3-TPD) and Fourier transform infrared spectroscopy (FT-IR) showed the presence of strong Bronsted acid sites in both membranes. The total acid capacity increased with increase in organosilane concentration in the synthesis mixture. Both membranes were tested for their catalytic activity in m-xylene isomerization reaction in the temperature range of 355-450 degrees C. Due to higher acid density, arenesulfonic acid-functionalized silicalite-1 membrane gave higher catalytic activity compared to propylsulfonic acid-functionalized silicalite-1 membrane. At 450 degrees C, m-xylene conversion of 57% with 33% p-xylene yield was achieved using arenesulfonic acid-functionalized silicalite-1 membrane with 15 mol% of phenethyltrimethoxysilane, while m-xylene conversion of 46% with 28% p-xylene yield was achieved using propylsulfonic acid-functionalized silicalite-1 membrane with 15 mol% of 3-mercaptopropyltrimethoxysilane. The enhancement in p-xylene yield was due to the simultaneous isomerization reaction and separation of the reaction products through the catalytic membrane. Both catalytic membranes exhibited good structural stability after subjected to isomerization reaction study for 120h. (C) 2010 Elsevier B.V. All rights reserved.