Effects of Acid Sites and Formaldehyde Decomposition on the Catalyst Lifetime for Methanol-to-Olefins over Ca-Modified HZSM-5

The pursuit for higher light olefin selectivity and extended catalyst lifetime has been a hot topic in the methanol-to-olefins (MTO) process. The incorporation of Ca in HZSM-5 (Ca-modified HZSM-5) could exhibit outstanding catalytic stability and high C3+ olefins yield. In this work, synchrotron radiation photoionization mass spectrometry was applied to study the lifetime enhancement mechanism of Ca-modified HZSM-5. It is interesting to note that the mechanism differs in the cases of different Ca-loading. Under low Ca-loading, the main reason for lifetime enhancement is the modification of acid sites, which limited hydrogen transfer reactions and subsequent coking process. While higher Ca-loading would introduce CaO species over HZSM-5, which showed prominent activity for HCHO elimination. The decomposition of HCHO would suppress the HCHO-mediated aromatic formation pathway during the MTO process, therefore alleviating the coking process. Moreover, the elimination mechanism of HCHO over CaO was investigated using in situ IR measurements. This study provides some additional insights into the role of acid sites and CaO during the Ca-modified HZSM-5 catalyzed MTO process.