A series of Si-modified membranes were prepared by chemical vapor depo
sition using 40 Angstrom gamma-alumina tubular membranes as supports.
Their hydrogen permeance ranged from 0.028 to 17.6 m(3)/m(2) h atm and
H-2/N-2 selectivity (permeance ratio) ranged from 12.6 to 72 at 600 d
egrees C. The selectivity to isobutane ranged from 40 to 240 at 300 de
grees C and could be higher at a higher temperature. Compared with sim
ilar membranes documented in the literature, these membranes exhibited
''order-of-magnitude'' improvement in the permeance while maintaining
a moderate selectivity. These membranes could be ideal for industrial
gas separations and catalytic reactions handling a large volume of st
reams. Hindrance diffusion through micropores (i.e., similar to 5 Angs
trom) and Knudsen diffusion through larger pores were suggested separa
tion mechanisms for these modified membranes. These mechanisms coupled
with hypothetical pore size distributions were tested satisfactorily
with a wide range of permeation behaviors delivered by a series of mem
branes with different microporous structures. Specifically, they expla
ined the subtle permeation difference between hydrogen and helium, and
the relative contribution between hindrance and Knudsen diffusion for
nitrogen. Separations of gas mixtures containing hydrogen were confir
med similar to the ideal separations determined by single components.
The modified membranes were thermally stable at 600 degrees C. The hyd
rothermal stability test indicated that the membrane structure approac
hed a new steady state immediately after exposing to moisture.