Page 170 - 精细化工2019年第10期

第 36 卷第 10 期 精 细 化 工 Vol.36, No.10
2019 年 10 月 FINE CHEMICALS Oct. 2019

油田化学品与油品添加剂
取代水杨醛 Schiff 碱金属配合物催化氧化脱硫性能

姜翠玉，刘 蕾，邵 雪，梁书源，李明轩，张龙力

〔中国石油大学（华东）理学院，山东 青岛 266580〕

摘要：以水杨醛类 Schiff 碱为配体，与 Co(NO 3 ) 2 、Cu(NO 3 ) 2 反应合成 6 种 Salen(M)型配合物Ⅰ~Ⅵ。以 1-己硫
醇、二丁基硫醚和 2-甲基噻吩为模型化合物配制模拟油体系，考察了配合物Ⅰ~Ⅵ的催化氧化脱硫性能，并分析
了配合物结构与氧化脱硫性能的关系。结果表明，6 种配合物在 75 min 时的总脱硫效果为Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ，
Ⅵ的总脱硫率为 31.9%。对 1-己硫醇及二丁基硫醚脱除效果最佳的是Ⅴ，脱除率分别为 74.2%和 65.1%；对 2-
甲基噻吩脱除效果最好的是Ⅰ，脱除率为 26.8%。构效关系研究表明，中心金属离子与 O 2 的配位能力越强，配
体的共轭体系越大、电子云密度越高，配合物的脱硫性能越好；通过 IR 和离子色谱对单一硫化物模拟油体系氧
化前后的产物进行分析发现，硫化物氧化后皆生成相应的砜类或亚砜类，且 1-己硫醇和二丁基硫醚被进一步氧
2–
2–
化生成 SO 3 或 SO 4 。
关键词：席夫碱金属配合物；取代水杨醛；有机硫化物；催化氧化脱硫；构效关系；油田化学品
中图分类号：TE624.9 文献标识码：A 文章编号：1003-5214 (2019) 10-2136-06

Catalytic Oxidative Desulfurization Performance of Substituted
Salicylaldehyde Schiff Base Metal Complexes

JIANG Cui-yu, LIU Lei, SHAO Xue, LIANG Shu-yuan, LI Ming-xuan, ZHANG Long-li
（College of Science, China University of Petroleum, Qingdao 266580, Shandong, China）

Abstract: Six Salen(M) complexes, Ⅰ~Ⅵ, were synthesized from salicylaldehyde Schiff base ligands and
Co(NO 3) 2 and Cu(NO 3) 2. The simulated oil system was prepared by using 1-hexanethiol, dibutyl sulfide and
2-methylthiophene as model compounds to investigate the catalytic oxidative desulfurization performance
of complexes Ⅰ~Ⅵ. The effects of central metal ions and ligands on the oxidative desulfurization
performance of complexes Ⅰ~Ⅵ were analyzed. The results showed that the order of the total
desulfurization effect for the six desulfurizers on the simulated oil in 75 min was Ⅵ>Ⅴ>Ⅳ>Ⅰ>Ⅲ>Ⅱ,
and the total desulfurization rate of complex Ⅵ was 31.9%. Among them, complex Ⅴ exhibited the best
removal effect for 1-hexanethiol and dibutyl sulfide with 74.2% and 65.1% removal rate, respectively.
While complex Ⅰ had the best removal effect for 2-methylthiophene with a removal rate of 26.8%.
According to the structure-property relationship analysis, the stronger the coordination ability between the
central metal ion and O 2, the larger the conjugated system of the ligand, and the higher density of electron
cloud, the better the desulfurization performance of the complex. The products before and after oxidation of
the single sulfide simulated oil system were analyzed by infrared spectroscopy(IR) and ion chromatography
(IC). It was found that three sulfides were oxidized to form corresponding sulfones or sulfoxides, and
2–
2–
1-hexanethiol and dibutyl sulfide were further oxidized to form SO 3 or SO 4 .
Key words: Schiff base metal complexes; substituted salicylaldehyde; organic sulfide; catalytic oxidation
desulfurization; structure-property relationship; oil field chemicals

石油作为应用最广、用量最大的燃料，在多种 领域有着广泛应用。然而，石油以及各种燃油中都

收稿日期：2019-04-01; 定用日期：2019-05-30; DOI: 10.13550/j.jxhg.20190260
基金项目：国家自然科学基金项目（21576292）；国家大学生创新创业训练项目（20171447）
作者简介：姜翠玉（1965—），女，教授，E-mail：cyjiang@upc.edu.cn。