Optimal mixing method of ZnZrOx and MOR-type zeolite to prepare a bifunctional catalyst for CO2 hydrogenation to lower olefins

Abstract

In recent years, the issue of global warming caused by CO2 emissions has become a critical problem and poses a worldwide challenge. To address this issue, we have developed a bifunctional catalyst that can convert CO2 to lower olefins in a single stage. Our bifunctional catalysts are a combination of two catalysts, a CO2-to-methanol hydrogenation catalyst (Zn-doped ZrO2, named ZnZrOx) and a methanol-to-olefin catalyst (MOR-type zeolite, named MOR104). In this research, we examined the impact of various mixing modes of the two catalysts on product distribution. We tested four different mixing modes using a down-flow fixed bed reactor: (a) ZnZrOx in the upper layer and MOR104 in the lower layer, (b) catalysts were mixed randomly after being pelletized separately, (c) MOR104 in the upper layer and ZnZrOx in the lower layer, and (d) granulated catalyst produced by physically mixing both catalyst powders. Our findings indicated that the best performance was achieved with catalyst (d), where the two catalysts were mixed in close proximity. This proximity resulted in efficient supply of methanol produced on ZnZrOx to MOR104. In other words, the MTO reaction in MOR104 efficiently consumed methanol molecules produced via equilibrium-limited CO2-to-methanol hydrogenation. When ZnZrOx and MOR104 were thoroughly mixed, the conversion of CO2 to methanol shifted towards the product side, resulting in a greater overall utilization of CO2. Furthermore, the bifunctional catalyst we developed was stable for six hours. Since there have been few studies of bifunctional catalysts containing zeolites other than ZSM-5 and SAPO-34, this study opens up new opportunities for bifunctional catalysts specialized for one-pass hydrocarbon synthesis through CO2 hydrogenation.