石油炼制与化工 ›› 2022, Vol. 53 ›› Issue (1): 14-20.

• 基础研究 • 上一篇    下一篇

Fe对渣油加氢过程中结焦行为及焦炭结构影响的研究

孙谦,韩伟,杨清河,贾燕子,聂红   

  1. 中国石化石油化工科学研究院
  • 收稿日期:2021-03-16 修回日期:2021-04-16 出版日期:2022-01-12 发布日期:2021-12-24
  • 通讯作者: 聂红 E-mail:niehong.ripp@sinopec.com
  • 基金资助:
    适应国六清洁柴油生产关键技术

STUDY ON THE EFFECT OF Fe ON COKE FORMATION AND MICROSTRUCTURE IN RESIDUE HYDROTREATING PROCESS

  • Received:2021-03-16 Revised:2021-04-16 Online:2022-01-12 Published:2021-12-24

摘要: 在固定床渣油加氢转化过程中,原料中的铁会沉积至催化剂颗粒表面和颗粒之间,对加氢转化过程产生直接影响。采用高压釜反应器,借助扫描电镜、热重-质谱、碳氢元素分析、拉曼光谱、红外光谱、X射线光电子能谱等多种分析技术,在工业装置运转末期的温度条件下,考察了两种形态的Fe(FeS和环烷酸铁)对渣油加氢过程中结焦行为的影响,重点考察了Fe对焦炭组成、类型和微观结构的影响。结果表明,FeS和环烷酸铁均会造成渣油加氢反应过程中结焦,前者会导致焦炭缩合程度提高,后者会促进焦炭缩合程度降低,这主要归因于环烷酸铁需先通过脱铁生成Fe1-xS,进而影响结焦,同时环烷酸铁会直接参与结焦反应。

关键词: 渣油加氢, 结焦, 硫化亚铁, 环烷酸铁

Abstract: Under the same temperature as the operation end of fixed-bed residue hydrogenation unit, the effect of different Fe species on the coking behavior of the residue hydrogenation process is observed using the unloaded catalyst from a refinery to carry out a series of batch tests in autoclave. The effects of Fe on the composition,type and microstructure of coke are investigated by many characterization methods including thermogravimetry, Raman spectroscopy, and scanning electron microscopy. The results show that the existence of large amounts of iron naphthenate and FeS leads to the increase of coke amount in residue hydrogenation reaction. The addition of iron naphthenate leads to the decrease of coke condensation degree, while the addition of FeS leads to the increase of coke condensation degree. This is mainly related to the fact that iron naphthenate needs to be transformed to Fe1-xS, which can affect coke formation reaction, and part of iron naphthenate directly participates in coke formation.

Key words: residue hydrotreating, coke, ferrous sulfide, iron naphthenate