B修饰的ZrO2及其制备pH值对PtSn/B-ZrO2丙烷脱氢反应性能的影响

doi:10.1016/S1872-2067(19)63395-4

摘要/Abstract

摘要： 丙烯作为一种重要的石油化工基础原料，传统上是从石脑油蒸汽裂解或催化裂化过程中作为副产物生产的.随着原油的枯竭和页岩气开发技术的成熟，通过乙烷蒸汽裂解制备乙烯更具吸引力并已得到广泛的工业应用，但该路线乙烯选择性高，而副产物丙烯数量有限.为满足不断增加的丙烯需求量，利用油田气和页岩气中低附加值的丙烷为原料，将其直接脱氢制丙烯（PDH）具有重要的现实意义.目前已开发成功的PDH技术采用的催化剂主要为负载PtSn型催化剂和Cr基催化剂.其中，Pt基催化剂较Cr基催化剂更加环境友好，因此得到了更广泛的应用.由于Pt元素的昂贵和稀有，制备低Pt含量和良好性能的催化剂极具吸引力.UOP Oleflex工艺开发的最新一代催化剂DEH-16仅含有0.3 wt% Pt，相对于前一代催化剂Pt含量降低30%.然而，许多文献报道，随着Pt含量的降低，催化剂的稳定性很容易恶化，降低Pt含量并保持催化剂性能仍具有一定的挑战.研究表明，含有更多Lewis酸性位点和更少Brönsted酸位点的催化剂显示出较好的丙烷脱氢活性和丙烯选择性.此外，源自缺陷位或配位不饱和位的Lewis酸性位也可为负载的金属颗粒提供锚定位点.BASF对ZrO₂作为载体的丙烷脱氢催化剂进行了广泛研究，但其催化剂尚未完全商业化.有文献报道，ZrO₂负载的PtSn催化剂在脱氢反应中的稳定性较差.将元素硼（B）加入到ZrO₂中可以极大地抑制Brönsted酸性而提高Lewis酸量和酸强度，因此我们推测含有适量配位不饱和Zr位点的ZrO₂作为PtSn丙烷脱氢催化剂载体可能具有优异的性能.载体的合成pH值对催化剂PDH性能也会有影响.然而，目前还没有硼改性的ZrO₂（B-ZrO₂）合成pH值对PDH催化性能影响的研究.
本文研究了B-ZrO₂的合成pH值（9，10和11）对PtSn/B-ZrO₂在丙烷脱氢反应中催化性能的影响.Py-IR结果表明各pH值下合成的B-ZrO₂均只有Lewis酸，NH₃-TPD结果则表明B-ZrO₂的Lewis酸量和强度随合成pH值的增加而增加.XPS结果显示，载体对Pt和Sn电子性质的影响不容忽视.由于OSC与CO氧化活性之间没有线性关系，因此Pt和Sn之间的相互作用程度在CO氧化反应中可能起主要作用，并有如下递增趋势：PtSn/B-ZrO₂-9 < PtSn/B-ZrO₂-11 < PtSn/B-ZrO₂-10.由于PtSn/B-ZrO₂-10中Sn⁰含量适中，适中的被负载金属与载体间的相互作用强度有利于Pt和Sn之间更紧密的相互作用，这可能是该催化剂丙烷脱氢催化活性和稳定性均较好的主要原因.

关键词: 丙烷脱氢, Pt-Sn, 丙烯, 载体, 稳定性

Abstract: Boron-modified ZrO₂ (B-ZrO₂) was synthesized under various pH values (9, 10, and 11) and used as the supports of PtSn catalysts (PtSn/B-ZrO₂-x) for non-oxidative dehydrogenation of propane. The NH₃-TPD and pyridine IR show that only Lewis acid is present and the acid strength increases with the synthesis pH. PtSn/B-ZrO₂-10 exhibits the best catalytic performance with an initial propane conversion of 36% and a deactivation rate constant (k_d) of 0.0127 h^-1. The XPS results indicate that the electronic properties of Pt and SnO_x are affected not only by their interaction but also by the interaction with support. After a careful analysis of the oxygen storage capacity and activity in CO oxidation, it is hypothesized that the interaction between Pt and Sn becomes stronger following the order:PtSn/B-ZrO₂-9 < PtSn/B-ZrO₂-11 < PtSn/B-ZrO₂-10. The characterization with TPO and Raman on spent catalysts exhibits that more hydrogen deficient coke forms on the support and less coke deposits on the metal surface of PtSn/B-ZrO₂-10. The results reveal that the interaction between Pt and Sn is influenced by their respective interaction with the support and a moderate interaction between the metal species and the support is desired.

Key words: Propane dehydrogenation, Platinum-tin, Propylene, Support, Stability

纪中海, 苗登云, 高丽君, 潘秀莲, 包信和. B修饰的ZrO₂及其制备pH值对PtSn/B-ZrO₂丙烷脱氢反应性能的影响[J]. 催化学报, 2020, 41(4): 719-729.

Zhonghai Ji, Dengyun Miao, Lijun Gao, Xiulian Pan, Xinhe Bao. Effect of pH on the catalytic performance of PtSn/B-ZrO₂ in propane dehydrogenation[J]. Chinese Journal of Catalysis, 2020, 41(4): 719-729.

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B修饰的ZrO₂及其制备pH值对PtSn/B-ZrO₂丙烷脱氢反应性能的影响

Effect of pH on the catalytic performance of PtSn/B-ZrO₂ in propane dehydrogenation

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