石油学报(石油加工) ›› 2016, Vol. 32 ›› Issue (6): 1221-1227.doi: 10.3969/j.issn.1001-8719.2016.06.019

• 研究报道 • 上一篇    下一篇

渣油加氢失活催化剂的积炭规律

陈程,曹晓娜,徐广通,刁玉霞,孙淑玲   

  1. 中国石化 石油化工科学研究院 石油化工催化材料与反应工程国家重点实验室,北京 100083
  • 收稿日期:2015-11-05 修回日期:2015-12-01 出版日期:2016-12-25 发布日期:2017-01-18
  • 通讯作者: 徐广通,男,教授级高级工程师,博士,从事催化剂和催化材料的表征技术及石油产品分析技术的研究;Tel:010-82368613;E-mail:xugt.ripp@sinopec.com E-mail:xugt.ripp@sinopec.com
  • 作者简介:第一作者:陈程,男,硕士研究生,从事催化材料表征的研究
  • 基金资助:
    中国石化股份有限公司科技开发支持项目(ST15030)资助

Pattern of Coke Deposition on the Spent Residue Hydrotreating Catalysts

 CHEN Cheng, CAO Xiaona, XU Guangtong, DIAO Yuxia, SUN Shuling   

  1.  State Key Laboratory of Catalytic Materials and Reaction Engineering, Research Institute of Petroleum Processing, Beijing 100083, China
  • Received:2015-11-05 Revised:2015-12-01 Online:2016-12-25 Published:2017-01-18
  • Supported by:
     

摘要: 以正庚烷为溶剂,采用索氏抽提法对渣油加氢工业失活催化剂进行预处理,以脱除表面吸附的烃类组分;采用碳硫元素分析仪、扫描电子显微镜能谱分析仪(SEMEDS)分别测定了失活催化剂的碳、硫含量及碳含量沿颗粒的径向分布,并采用热重质谱联用分析仪(TGMS)和BET低温物理吸附仪研究了失活催化剂的热解行为及其孔结构的变化。结果表明,沿着反应器物流方向,失活剂的积炭量呈上升趋势,硫含量呈下降趋势;脱金属失活剂的积炭沿颗粒径向分布比较均匀,而脱硫、脱残炭失活剂颗粒的碳含量呈现边缘部位较内部含量偏高;沿物流方向,积炭氧化温度逐渐升高;积炭影响催化剂的孔结构特性,对脱金属剂的孔结构影响相对较小,而对脱硫剂、脱残炭剂的孔结构影响比较大;脱硫、脱残炭失活剂高温脱炭后,比表面积和孔容可恢复率高,尤其是脱残炭剂。

关键词: 渣油加氢催化剂, 失活, 积炭, 表征

Abstract: Industrial residue hydrotreating spent catalysts were washed with hot nheptane in a Soxhlet extractor for removing hydrocarbon components adsorbed on the surface, and then were characterized by elemental analysis, SEMEDX, TGMS and low temperature physical adsorption methods to obtain their coke and sulfur contents, radial distribution of coke content, pyrolysis behavior and pore structure. The results showed that coke amount increased and sulfur amount declined in spent catalysts along the flow direction of reactor. For spent demetalization catalyst, the radial distribution of coke content was uniform relatively, while for spent desulfurization and decarbonization catalysts, it was high at the edge and low slightly in the middle of the radial direction. In addition, the temperature of coke oxidative pyrolysis increased gradually along the flow direction of reactor. Specific surface and pore volume of the catalyst lost seriously due to coke deposition. Coke deposition little affected the pore structure of demetalization catalyst, while seriously affected the pore structures of both desulfurization and decarbonization catalysts. By calcining the coked desulfurization and decarbonization catalysts, especially the coked decarbonization catalyst, the high recovery ratios of specific surface area and pore volume could be obtained.

Key words: residue hydrotreating catalyst, deactivation, coke deposition, characterization

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