石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (4): 75-81.

• 基础研究 • 上一篇    下一篇

Pt-Sn/γ-Al2O3工业失活重整催化剂的微观结构研究

向彦娟,郑爱国,忻睦迪,袁蕙,王春明,徐广通,马爱增   

  1. 中国石化石油化工科学研究院
  • 收稿日期:2021-08-20 修回日期:2021-09-02 出版日期:2022-04-12 发布日期:2022-03-29
  • 通讯作者: 郑爱国 E-mail:zhengag.ripp@sinopec.com
  • 基金资助:
    中国石化股份公司项目《催化剂微尺度及原子水平表征与构效关系研究》

STUDY ON MICROSTRUCTURE OF INDUSTRIAL SPENT Pt-Sn/γ-Al2O3 REFORMING CATALYST

  1. 1. Research Institute of Petroleum Processing
    2.
  • Received:2021-08-20 Revised:2021-09-02 Online:2022-04-12 Published:2022-03-29
  • Contact: Aiguo ZHENG E-mail:zhengag.ripp@sinopec.com

摘要: 采用多种表征手段对工业失活Pt-Sn/γ-Al2O3 型 PS-V 重整催化剂的载体形貌与微观结构,活性金属位置、尺寸与聚集状态等信息进行了深入表征。X射线衍射光谱表征结果显示失活剂载体结构完好,与新鲜剂无明显差异,但高分辨透射电子显微镜图像表明失活剂中载体部分转化为蜂窝状或片状结构的α-Al2O3;透射电子显微镜观测结果表明活性金属形成了大量的Pt-Sn合金聚集体,尺寸在20~150 nm之间,统计平均尺寸为50 nm左右;球差校正扫描透射电子显微镜(Cs-STEM)观测结果表明未聚集的Pt原子在载体表面依然呈现原子级分散特性;CO探针原位红外光谱表征结果表明失活剂中Pt金属形成聚集。同时从载体和金属两方面深入分析了工业失活剂微观结构,给出了其结构变化与催化剂性能下降之间的构效关系。

关键词: 球差校正扫描透射电子显微镜, CO探针原位红外光谱, Pt-Sn/γ-Al2O3, 重整催化剂, 失活剂, 微观结构

Abstract: The morphology and microstructure of support as well as the location, size and aggregation state of active metals in industrial spent catalysts Pt-Sn/γ-Al2O3 (PS-V) were comprehensively characterized by various characterization methods. The results of X-ray diffraction showed that the crystal structure and parameters of both spent and fresh catalysts had no obvious difference. The high-resolution transmission electron microscope (HRTEM) images showed that carrier part of the spent catalyst was transformed into α-Al2O3 from γ-Al2O3 with honeycomb or laminar microstructure. Meanwhile, massive Pt atoms reacted with Sn atoms to form Pt-Sn alloy aggregates with the dimension ranging from 20 nm to 150 nm, and the statistical average size of Pt-Sn alloy aggregates was about 50 nm. The results of aberration-corrected high-resolution scanning transmission electron microscopy (Cs-STEM) showed that the unaggregated Pt atoms were still dispersed at the atomic level on the surface of the carrier. The in-situ Fourier transform infrared spectrocopy of CO probe (CO-FTIR) showed that the Pt metals were aggregated in the spent catalyst, and the interaction with the carrier was basically disappeared. At the same time, the microstructure of industrial spent catalyst was analyzed from both support and metal, and the structure-activity relationship between the structure change and the performance decline of catalyst was given.

Key words: Cs-corrected STEM, CO-FTIR, Pt-Sn/γ-Al2O3, Reforming catalyst CR401, spent catalyst, microstructure