炼油技术与工程 ›› 2022, Vol. 52 ›› Issue (12): 49-53.

• 催化剂和助剂 • 上一篇    下一篇

工业固定床渣油加氢废催化剂杂质沉积与分布研究

曹坤, 张成, 关月明, 曹禹, 隋宝宽, 王志武, 袁胜华   

  1. 中石化(大连)石油化工研究院有限公司
  • 收稿日期:2022-06-16 出版日期:2022-12-15 发布日期:2022-12-21
  • 通讯作者: 袁胜华，正高级工程师。联系电话：0411-39699487,E-mail:yuanshenghua.fshy@sinopec.com。;
  • 作者简介:曹坤，助理工程师，硕士，2020年毕业于中国石油大学(北京),主要从事重质油加氢处理催化剂研发工作。联系电话：0411-39699539,E-mail:caokun.fshy@sinopec.com。

Study of impurities’ deposition and distribution on fixed-bed residue hydrotreating spent catalyst in industrial plant

Cao Kun, Zhang Cheng, Guan Yueming, Cao Yu, Sui Baokuan, Wang Zhiwu, Yuan Shenghua   

  1. SINOPEC (Dalian) Research Institute of Petroleum and Petrochemicals Co., Ltd.
  • Received:2022-06-16 Online:2022-12-15 Published:2022-12-21

PDF

摘要：

利用元素分析、电子探针显微分析等手段对工业运转后的系列固定床渣油加氢处理催化剂上杂质沉积与分布规律进行研究。结果表明：除物流最前端的保护剂HG-1外，系列渣油加氢失活剂上的积炭量基本在7%～14%,沿物流方向总体呈逐渐增加的趋势，氮含量与积炭量成正相关，硫含量呈降低的趋势；金属沉积量在反应床层沿物流方向呈先增加后减少分布趋势，主要以Ni3S4和NiV2S4形式沉积在催化剂上；铁、钙主要沉积在催化剂颗粒的外表面，镍沿催化剂颗粒横截面径向分布较为均匀，钒易于在催化剂的近表面沉积，呈现边缘高、中间低的类“M”型分布趋势；积炭和金属沉积共同作用导致保护剂和脱金属剂的孔结构发生明显损失，热处理后孔结构恢复率相对较低；脱硫剂和脱残炭剂的孔结构损失主要受积炭影响，消除积炭后孔结构得到较大恢复。

关键词: 固定床, 渣油加氢, 废催化剂, 杂质沉积, 非金属, 金属, 物化性质

Abstract:

The deposition and distribution of impurities on a series of fixed bed residue hydrotreating spent catalysts were studied by elemental analyzer, electron microprobe, etc. Results indicated that along the flow direction, the amount of coke on spent catalysts increased which was basically within the range of 7%～14% except HG-1 and the nitrogen amount was positively related to the amount of coke, while sulfur amount declined in spent catalysts; The amount of metal deposition along the flow direction of the reaction bed increased first and then decreased, and was mainly deposited on the catalyst in the form of Ni3S4 and NiV2S4; Iron and calcium were mainly deposited on the outer surface of the catalyst particles, the radial distribution of nickel was relatively uniform along the cross section of the catalyst particles, meanwhile, vanadium easily deposited on the near surface of the catalyst, showing “M”-shaped like pattern with more at the edge of the catalyst and lower in center; The pore structure of protective agents and demetallization agents was damaged badly due to the combined action of coke deposition and metal deposition and the recovery ratio of pore structure was relatively low after heat treatment; Coke deposition seriously affected the pore structures of both desulfurization agents and carbon residue removal agents and the pore structure was greatly recovered due to the elimination of coke deposition.

Key words: fixed bed, residue hydrotreating, spent catalysts, impurities deposition, non-metal, metal, physicochemical properties;