载体效应对Ru基催化剂费托合成制烯烃的性能影响

Support effects on Ru-based catalysts for Fischer-Tropsch synthesis to olefins

  • 摘要: 本研究考察了不同载体(CeO2、ZrO2、MnO2、SiO2和活性炭)对负载型Ru基费托合成制烯烃(FTO)催化剂结构和催化性能的影响。结果表明,载体的本征属性和金属-载体相互作用(MSI)对催化性能有很大影响。在同一反应条件下的催化活性关系为:Ru/SiO2 > Ru/ZrO2 > Ru/MnO2 > Ru/AC > Ru/CeO2。对于烯烃选择性,Ru/SiO2和Ru/MnO2得到的总烯烃选择性最高,超过70%,而Ru/ZrO2催化剂的烯烃选择性低至29.9%。由于金属Ru与SiO2的金属载体相互作用较弱,反应后的Ru/SiO2催化剂得到适中的Ru纳米颗粒尺寸( ~ 5 nm)且反应活性也最高。对于Ru/AC和Ru/MnO2,其Ru纳米颗粒尺寸仅为1−3 nm,表现出较低的CO转化率。较高的烯烃二次加氢能力导致Ru/AC和Ru/ZrO2催化剂的烯烃选择性偏低。此外,由于存在强的MSI效应,部分Ru纳米颗粒被可还原性CeO2活性层包覆,导致Ru/CeO2催化活性最低。

     

    Abstract: The effects of supports (CeO2, ZrO2, MnO2, SiO2 and active carbon) on the structure and catalytic performance of Ru-based catalysts for Fischer-Tropsch synthesis to olefins (FTO) were investigated. It was found that the intrinsic characteristics of supports and the metal-support interaction (MSI) would greatly influence the catalytic performance. The catalytic activity followed the order: Ru/SiO2 > Ru/ZrO2 > Ru/MnO2 > Ru/AC > Ru/CeO2. As far as olefins selectivity was concerned, both Ru/SiO2 and Ru/MnO2 possessed high selectivity to olefins (>70%), while olefins selectivity for Ru/ZrO2 was the lowest (29.9%). Ru/SiO2 exhibited the appropriate Ru nanoparticles size ( ~ 5 nm) with highest activity due to the relatively low MSI between Ru and SiO2. Both Ru/AC and Ru/MnO2 presented low CO conversion with Ru nanoparticles size of 1−3 nm. Stronger olefins secondary hydrogenation capacity led to the significantly decreased olefins selectivity for Ru/AC and Ru/ZrO2. In addition, partial Ru species might be encapsulated by reducible CeO2 layer for Ru/CeO2 due to strong MSI effects, leading to the lowest activity.

     

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