Ni–MgO–CeO₂ Catalysts for Reforming of Mixed Alkanes: Structure‐Performance Relationship and Reaction Networks

Abstract Purge gas that is by‐produced during syngas conversion contains significant amounts of low carbon alkanes (CH 4 and C 2 H 6 in particular), and their flare and release represent one of the major sources of CO 2 emission for C1 chemistry. In this context, reforming of the mixed alkanes (RMA) in the purge gas and recycling of the produced syngas can effectively enhance the carbon and hydrogen efficiency of C1 chemistry. However, in‐depth structure‐performance relationships and catalytic mechanisms were rarely investigated for RMA, which forms a major research gap for further development. Herein, a series of Ni–MgO–CeO 2 catalysts with different Mg and Ce contents were prepared, and the catalytic performance in reforming of mixed alkanes was investigated. It was found that smaller Ni particles on the Mg‐rich samples (NM 6 C 0 and NM 5 C 1 ) are more effective for the activation of C 2 H 6 . However, the generated C x H y intermediates cannot be converted with matching kinetics, which resulted in the formation of unwanted CH 4 and more importantly, larger amounts of carbon deposition. On the other hand, despite a moderate C 2 H 6 conversion is observed on Ce‐rich samples, appropriate balance between the generation of C x H y intermediates from alkanes and their conversion aided by the activated CO 2 and H 2 O can be established, resulting in excellent anticarbon properties. Overall, the optimum catalyst (NM 3 C 3 ) showed stable CH 4 and C 2 H 6 conversion (28% and 43%, respectively) and negligible carbon formation in 100‐h operation. Upon the comparison with individual reforming of CH 4 and C 2 H 6 , this study also presented in‐depth understanding on the different mechanism and reaction network for reforming of mixed alkanes, which solidifies the foundation of catalyst design in related areas including CO 2 utilization or C1 reforming.