石油炼制与化工 ›› 2021, Vol. 52 ›› Issue (4): 33-44.

• 催化剂 • 上一篇    下一篇

工业渣油加氢失活催化剂上沉积金属及积炭研究

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:2020-10-22 修回日期:2020-12-16 出版日期:2021-04-12 发布日期:2021-03-30
  • 通讯作者: 宋宇 E-mail:songyu8@cnooc.com.cn

STUDY OF COKE AND METALLIC IMPURITIES DEPOSITION ON SPENT RESIDUE HYDROTREATING CATALYSTS IN INDUSTRIAL PLANT

  • Received:2020-10-22 Revised:2020-12-16 Online:2021-04-12 Published:2021-03-30

摘要: 采用碳-硫元素分析、X射线荧光光谱、X射线衍射光谱、扫描电镜以及热重分析等手段对处理后的工业固定床渣油加氢失活催化剂进行表征。结果表明:保护剂、保护-脱金属过渡剂、脱金属剂、脱金属-脱硫过渡剂主要拦截杂质金属,并以NiV2S4的形态存在于催化剂中,脱硫剂、降残炭剂积炭更多。沿物流方向,积炭从软炭向硬炭转变,积炭量增加;金属沉积量和分解温度均先增加后降低,在脱金属剂中沉积量最大,沉积物分子结构最复杂;脱金属-脱硫过渡剂和脱金属剂床层出现严重板结;V元素含量先增加后下降,Fe元素含量逐渐下降,Ni和Ca元素含量的分布则相对平均。沿催化剂颗粒横截面,Fe元素主要沉积在外表面;Ni元素分布较为均匀;V在催化剂边缘处存在较多,中心处沉积量较低,在脱金属剂和脱金属-脱硫过渡剂横截面处呈V形分布,在脱硫剂和降残炭剂横截面处呈U形分布,多数分布在催化剂颗粒表面。在分析基础上提出了催化剂改进建议。

关键词: 渣油加氢, 催化剂, 失活, 积炭, 沉积金属

Abstract: Residue hydrotreating spent catalysts after pretreatment with toluene were characterized by C and S content analysis, XRF, XRD, SEM and TG techniques. The results showed that the metallic impurity was mainly captured by layered catalysts system consisted of the guard catalyst, guard-demetallization catalysts, demetallization catalysts and demetallization-desulfurization catalysts in sequence. The captured metal ultimately deposited on the spent catalyst as NiV2S4, while coke was mostly observed on desulfurization catalysts and carbon removal catalyst. Along the flow direction, the coke deposited gradually transferred from soft coke to hard coke and the amount increased. The amount of metal deposition and decomposition temperature increased first and then decreased, and the amount of metal deposition was the maximum in demetallization catalysts, and the molecular structure of sediment was the most complex. The guard-demetallization catalyst and demetallization catalyst system was hardened badly and along the flow direction, V content firstly increased and then decreased, Fe content decreased, while Ni and Ca content was evenly distributed where Fe was mainly deposited on the outer surface, the distribution of Ni element was relatively uniform, V existed more at the edge of the catalyst with lower in center. The distributions of V along the cross section of demetallization catalyst and demetallization-desulfurization catalyst were V-shaped, while on the desulfurization catalyst and carbon residue removal catalyst were U-shaped and distributed on the surface of catalyst particles. Suggestions for catalyst design were proposed.

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