The regeneration of supercritical carbon dioxide from a mixture containing caffeine by the prepared mesoporous silica and microporous silicalite membrane filters was studied. The mesoporous silica layer, with an average pore opening of 2.5 nm, was deposited on a tubular a-alumina filter. The experimental data showed that a caffeine rejection as high as 0.98 in the first 6 h and a supercritical carbon dioxide permeation flux of 0.074 mol/m(2)/s could be obtained at 35 degreesC and 13.79 MPa. The mass transfer resistance in the coated mesoporous silica layer was found to be negligible and the adsorption in the silica layer to be the major mechanism in the separation. Because of the occurrence of adsorption, a steady state operation was hard to achieve and caffeine rejection would drop when the adsorption equilibrium was approached. For the prepared microporous silicalite membrane with pore openings of 0.5-0.6 nm, a caffeine rejection of 1.0 was observed at a temperature of 35 degreesC and a pressure equal to or lower than 12 MPa. The separation under these pressures was based on the molecular sieving mechanism. Due to the presence of some defects, mainly resulting from inter-grain porosity in the coated layer, a high caffeine rejection but not 1.0 could be achieved when the pressure was larger than 12 MPa. At these pressures, adsorption also occurred in the microporous silicalite layer. The mass transfer resistance in a thin silicalite layer was not significant, resulting in a CO2 permeation flux sufficiently close to that of the parent filter. (C) 2002 Elsevier Science B.V. All rights reserved.