Abstract: SAPO-34 zeolite membranes show high efficiency for CO₂/CH₄ separation but suffer from the reduction of separation performance when exposed to humid atmosphere. In this work, n-dodecyltrimethoxysilane (DTMS) was used to modify the hollow fibers supported SAPO-34 membranes to increase the external surface hydrophobicity and thus sustain their performance under moisture environment. The modified membranes were fully characterized. Their separation performance was extensively investigated in both dry and wet gaseous systems and compared with the un-modified ones. The un-modified SAPO-34 membrane exhibited a high separation selectivity of 160 and CO₂ permeance of 1.18×10^-6 mol·m^-2·s^-1·Pa^-1 for separation of dry CO₂/CH₄ at 298 K. However, its separation selectivity declined to 0.9 and the CO₂ permeance was only about 1.7×10^-8 mol·m^-2·s^-1·Pa^-1 for wet CO₂/CH₄ at same temperature. High temperature (e.g. 353 K) could reduce the effect of moisture to improve SAPO-34 separation selectivity, but further increasing temperature (e.g. 373 K) led to decrease in CO₂/CH₄ separation selectivity. A significant decrease of selectivity was observed at higher pressure drop. The modified SAPO-34 membrane showed decreased CO₂ permeance but increased separation selectivity for dry CO₂/CH₄ gas mixture, and super performance for wet CO₂/CH₄ gas mixture due to the improved hydrophobicity of membrane surface. A separation selectivity of 65 and CO₂ permeance of 4.73×10^-8 mol·m^-2·s^-1·Pa^-1 for wet CO₂/CH₄ mixture can be observed at 353 K with a pressure drop of 0.4 MPa. Furthermore, the modified membrane exhibited stable separation performance during the 120-hour test for wet CO₂/CH₄ mixture at 353 K. The hydrophobic modification paves a way for SAPO-34 membranes in real applications.

Key words: SAPO-34 membrane, CO₂/CH₄ separation, Hydrophobic modification, Stability, Moisture environment