针对甲烷干重整反应中催化剂易积炭的问题，通过甲醇溶剂热的方法制备了以CoxSnyNi7.5-x-yMg92.5(OH)(OCH3)为单一前驱体的CoxSnyNi7.5-x-yMg92.5O系列催化剂，对其进行了抗积炭性能及反应动力学的研究，探讨了Co-Sn双助剂的作用及其抗积炭性能。在800 ℃的反应条件下进行了催化性能考评，研究发现，Co0.075SnxNi7.425-xMg92.5O系列催化剂可保持高活性、高稳定性长达100 h。动力学研究表明，以Co0.075SnxNi7.425-xMg92.5O为催化剂，CH4和CO2重整反应是CH4的1级反应，CO2的0级反应，Co能够降低反应活化能，Sn能够提高反应活化能。Sn可降低甲烷裂解速率和积炭生成速率，Co能够提高催化剂表面炭物种的气化速率。Co和Sn双助剂的引入能够同时大幅度降低可气化积炭和顽固性积炭的含量。因此，Co和Sn双助剂催化剂对于CH4-CO2重整反应催化剂的设计和应用具有很大的潜在价值。"/>
Study on Coke-Resistance and Kinetics of CH<sub>4</sub>-CO<sub>2</sub> Dry Reforming on Co<sub><em>x</em></sub>Sn<em><sub>y</sub></em>Ni<sub>7.5-<em>x</em>-y</sub>Mg<sub>92.5</sub>O Catalysts
Abstract In order to solve the problem of catalyst which was easy to deposit carbon during dry reforming of methane, a series of CoxSnyNi7.5-x-yMg92.5O catalyst were prepared using CoxSnyNi7.5-x-yMg92.5(OH)(OCH3) as single precursor by methanol solvothermal method. The anti-deposit performance and reaction kinetics of the catalysts were studied. The double auxiliary effect of Co and Sn and their anti-deposit performance were also discussed. The results showed that Co0.075SnxNi7.425-xMg92.5O catalysts could keep high activity and stability length out to 100 hours. The kinetic study showed that the reforming reaction of CH4 and CO2 is the first-order reaction of CH4 and the zero-order reaction of CO2. For the different composition of Co0.075SnxNi7.425-xMg92.5O catalysts, Co could reduce the activation energy of the reaction and Sn could increase the activation energy of the reaction. For the double auxiliary effect of Co and Sn, it was found that: 1. Sn could reduce the rate of methane cracking and carbon deposition, and Co could increase the gasification rate of carbon species on the catalyst surface. 2. The introduction of Co and Sn could significantly reduce the content of gasified carbon and refractory carbon at the same time. Therefore, Co and Sn catalysts have great potential value for the design and application of CH4-CO2 reforming catalyst.
ZHANG Tingting,LIU Zhongxian,ZHU Kake et al. Study on Coke-Resistance and Kinetics of CH4-CO2 Dry Reforming on CoxSnyNi7.5-x-yMg92.5O Catalysts[J]. 化学反应工程与工艺, 2019, 35(4): 289-295.
ZHANG Tingting,LIU Zhongxian,ZHU Kake et al. Study on Coke-Resistance and Kinetics of CH4-CO2 Dry Reforming on CoxSnyNi7.5-x-yMg92.5O Catalysts[J]. 化学反应工程与工艺, 2019, 35(4): 289-295.
