石油炼制与化工 ›› 2021, Vol. 52 ›› Issue (5): 50-60.

• 催化剂 • 上一篇    下一篇

工业装置渣油加氢失活催化剂孔结构研究

宋宇,辛靖,尉琳琳,范文轩,朱元宝,吕艳艳,张海洪,卢德庆   

  1. 中海油炼油化工科学研究院
  • 收稿日期:2020-10-28 修回日期:2020-12-16 出版日期:2021-05-12 发布日期:2021-04-23
  • 通讯作者: 宋宇 E-mail:songyu8@cnooc.com.cn

STUDY ON PORE STRUCTURE OF INDUSTRIAL SPENT CATALYSTS FOR RESIDUE HYDROTREATING

  • Received:2020-10-28 Revised:2020-12-16 Online:2021-05-12 Published:2021-04-23

摘要: 将渣油加氢失活催化剂进行甲苯抽提处理掉可溶油分后,采用碳硫分析、X射线荧光分析以及N2吸附脱附对催化剂进行表征。结果表明:沿物流方向,失活剂的孔容和比表面积均呈现先增加后减小的趋势,再生剂的孔容和比表面积则呈现了逐渐增加的趋势;金属沉积造成的不可逆失活影响越来越小;失活剂的N2吸附-脱附曲线回滞环范围增加,孔径尺寸变小。保护剂、保护-脱金属过渡剂、脱金属剂在失活后孔结构损坏程度较大,主要是由于金属沉积量大,再生后也不能恢复;而脱金属-脱硫过渡剂、脱硫剂、脱残炭剂在失活后孔结构损坏程度较小,积炭是其失活的主要原因,并且再生后孔结构可以恢复。最后归纳了催化剂的3种失活模式,对渣油加氢催化剂孔道结构的设计提出了建议。

关键词: 渣油加氢, 催化剂, 失活, 孔结构, 金属沉积, 积炭

Abstract: After the residue hydrotreating spent catalysts were washed with toluene for removing soluble hydrocarbon components, the catalysts were characterized by C-S elementanalysis, XRF and N2 adsorption-desorption. The results showed that along the flow direction the pore volume and specific surface area of the spent catalysts first increased and then decreased, while those of the regenerant increased gradually, the irreversible deactivation caused by metal deposition was becoming less and less. For spent catalysts, the range of hysteresis loop N2 adsorption-desorption widened and pore size deceased. The pore structure was damaged badly for the guard catalyst, guard-demetallization transition catalysts and demetallization catalysts, and could not be recovered after regeneration, mainly due to the large amount of metal deposit. After deactivation, the pore structure loss of metal-desulfurization transition agent, desulfurizer and reducing residual carbon agent was small, and coke deposition was the main cause of deactivation. Finally, three kinds of deactivation mechanisms were summarized, and some suggestions were put forward for the design of pore structure of residue hydrotreating catalyst.

Key words: residue hydotreating, catalyst, deactivation, pore structure, Metal impurity deposition, coke deposition