石油炼制与化工 ›› 2025, Vol. 56 ›› Issue (8): 59-66.

• 基础研究 • 上一篇    下一篇

固定床渣油加氢过程的脱硫规律研究

任金成1,于传瑞1,巫进文1,谢新亚1,聂鑫鹏2   

  1. 1. 中科(广东)炼化有限公司
    3. 中石化石油化工科学研究院有限公司
  • 收稿日期:2025-03-04 修回日期:2025-04-08 出版日期:2025-08-12 发布日期:2025-07-28
  • 通讯作者: 聂鑫鹏 E-mail:niexp.ripp@sinopec.com

RESEARCH ON DESULFURIZATION RULES OF FIXED BED RESIDUE HYDROTREATING PROCESS

  • Received:2025-03-04 Revised:2025-04-08 Online:2025-08-12 Published:2025-07-28

摘要: 通过分析固定床渣油加氢装置运行后期的原料性质、主要操作条件和产品性质,探究固定床渣油加氢过程的脱硫规律。结果表明:原料轻馏分(≤350 ℃)中硫醇、硫醚类硫化物中的硫较易脱除,加氢产物中剩余的较难反应硫化物是苯并噻吩和二苯并噻吩;原料重馏分(>350 ℃)中含有大量的噻吩类和环硫醚类硫化物,其加氢产物中主要以等效双键数(DBE)大于等于9的二苯并噻吩类硫化物为主。含有长烷基链的硫醇、噻吩类硫化物由于空间位阻大,其硫脱除率低;增加环烷烃取代基可以降低空间阻碍,提高相应硫化物的脱除率;硫化物的环数(环烷烃和芳烃)增加到五环及五环以上时,由于内扩散受阻影响,硫化物的脱除率开始明显下降。

关键词: 渣油加氢, 脱硫, 硫分布, 硫转化

Abstract: By analyzing the properties of the feedstock, main operating conditions and product properties in the later stage of residue oil hydroprocessing, the desulfurization rules and sulfur distribution during the hydrogenation process were explored. The results show that the sulfur in the mercaptans and sulfides of the light fractions (≤ 350 ℃) of the feedstock is relatively easy to remove, and the remaining refractory benzothiophene and dibenzothiophene are in the hydroprocessed heavy oil. The heavy fractions (>350℃) of the feedstock contain a large amount of thiophene and cyclic sulfide sulfur compounds, and the hydroprocessed heavy oil heavy fractions are mainly dibenzothiophene sulfides with an equivalent double bond number greater than or equal to 9. The mercaptans and thiophenes containing long-chain alkane structures have low conversion rates due to large steric hindrance. Increasing the cycloalkane substituents can reduce the steric hindrance and increase the conversion of the corresponding sulfur compounds. When the number of rings (cycloalkanes and aromatics) of the sulfur compounds increases to five or more, the conversion rate of the sulfur compounds begins to decrease significantly due to the internal diffusion effect.

Key words: residue hydrotreating, desulfurization, sulfur distribution, sulfur conversion