Impact of sulphur contamination on the performance of mixed ionic-electronic conducting membranes for oxygen separation and hydrogen production

Abstract

Mixed ionic-electronic conducting (MIEC) membranes are a promising technology for oxygen separation but they are not commercialised yet due to sealing issue and sensitivity to impurities in feedstock. In this study, La0.6Sr0.4Co0.2Fe0.8O3- (LSCF6428) was successfully sealed for long-term operation of 963 h using a gold-glass-ceramic sealant. The membrane was then tested for air separation in presence of hydrogen sulphide for 100 h and results showed that the impurity caused a drop in oxygen flux to zero within few hours. The flux could not be fully restored after hydrogen sulphide removal and only 6 to 35% was recovered. It was proposed that hydrogen sulphide was adsorbed on the membrane in the form of sulphur and it occupied oxygen vacancies. With time, strontium segregates toward sulphur to form irreversible layer of strontium sulphate. To restore the damaged surface, the membrane was treated by 1% (mol) of hydrogen for 20 h and the recovery improved from 6 to 12%. It was discovered that the poisoning mechanism is a function of oxygen partial pressure and change of partial pressure from 0.21 to 0.01 bar resulted in 90% recovery and this can be used as a strategy to reduce the damage. The next step was to test the membrane for hydrogen production using 1% (mol) of methane and results showed that methane conversion was steady at 33% for 350 h. Methane oxidation was also carried in presence of hydrogen sulphide but it resulted in drop of conversion to 8%. However, the conversion was slowly regenerating with time and it reached a constant value of 15%. This recovery was interpreted by the reaction of methane with hydrogen sulphide or methane decomposition and the membrane acted as a catalyst for these reactions. After hydrogen sulphide removal from the feed, the conversion kept on decreasing and this was linked to the change of membrane properties and therefore the membrane could not provide the sites for methane-oxygen reaction. For better stability under hydrogen sulphide, the membrane was modified by adding a powder of LSCF6428 material over the dense membrane. This dual layer membrane was stable for air separation under hydrogen for 33 h and the flux was only reduced by 5%.