Effect of ZrO2 on Catalyst Structure and Catalytic Sulfur-Resistant Methanation Performance of MoO3/ZrO2–Al2O3 Catalysts

Abstract

A series of MoO3/ZrO2–Al2O3 catalysts was prepared and investigated in the sulfur-resistant methanation aimed at production of synthetic natural gas. Different methods including impregnation, deposition precipitation, and co-precipitation were used for preparing ZrO2–Al2O3 composite supports. These composite supports and their corresponding Mo-based catalysts were investigated in the sulfur-resistant methanation, and characterized by N2 adsorption–desorption, XRD and H2-TPR. The results indicated that adding ZrO2 promoted MoO3dispersion and decreased the interaction between Mo species and support in the MoO3/ZrO2–Al2O3 catalysts. The co-precipitation method was favorable for obtaining smaller ZrO2 particle size and improving textural properties of support, such as better MoO3 dispersion and increased concentration of Mo6+ species in octahedral coordination to oxygen. It was found that the MoO3/ZrO2–Al2O3 catalyst with ZrO2Al2O3 composite support prepared by co-precipitation method exhibited the best catalytic activity. The ZrO2 content in the ZrO2Al2O3 composite support was further optimized. The MoO3/ZrO2–Al2O3 with 15 wt % ZrO2 loading exhibited the highest sulfur-resistant CO methanation activity, and excess ZrO2 reduced the specific surface area and enhanced the interaction between Mo species and support. The N2 adsorption-desorption results indicated that the presence of ZrO2 in excessive amounts decreased the specific surface area since some amounts of ZrO2 form aggregates on the surface of the support. The XRD and H2-TPR results showed that with the increasing ZrO2 content, ZrO2 particle size increased. These led to the formation of coordinated tetrahedrally Mo6+(T) species and crystalline MoO3, and this development was unfavorable for improving the sulfur-resistant methanation performance of MoO3/ZrO2–Al2O3 catalyst.