石油学报(石油加工) ›› 2020, Vol. 36 ›› Issue (4): 677-687.doi: 10.3969/j.issn.1001-8719.2020.04.004

• 研究报告 • 上一篇    下一篇

N-甲基咪唑氟硼酸盐基低共熔溶剂的制备及其氧化脱硫性能

刘昊然,陈思宇,李秀萍,赵荣祥,毛微   

  1. 辽宁石油化工大学 化学与材料学院,辽宁 抚顺 113001
  • 收稿日期:2019-07-15 修回日期:2020-01-13 出版日期:2020-07-25 发布日期:2020-09-23
  • 通讯作者: 赵荣祥,男,副教授,博士,从事清洁燃料生产方面的研究,E-mail: zylhzrx@126.com E-mail:zylhzrx@126.com;zylhzrx@163.com
  • 作者简介:第一作者:刘昊然,男,硕士研究生,从事清洁燃料生产方面的研究,E-mail:lhrlsh1002@126.com
  • 基金资助:
    辽宁省博士启动基金项目(201501105)资助

Preparation of N-Methylimidazoliun Fluoroborate-Based Deep Eutectic Solvent and Its Oxidative Desulfurization Performance

LIU Haoran, CHEN Siyu, LI Xiuping, ZHAO Rongxiang, MAO Wei   

  1.  College of Chemistry, Chemical Engineering and Environmental Engineering, Liaoning Shihua University, Fushun 113004, China
  • Received:2019-07-15 Revised:2020-01-13 Online:2020-07-25 Published:2020-09-23
  • Supported by:
     

摘要: 以N-甲基咪唑氟硼酸盐([HMIM]BF4)和苯丙酸(C9H10O2)为原料合成了[HMIM]BF4/xC9H10O2(x=0.5、1、2)型低共熔溶剂(DESs);对其进行FT-IR、1H NMR和TGA表征分析;将[HMIM]BF4/0.5 C9H10O2低共熔溶剂作为萃取剂和催化剂、H2O2作为氧化剂脱除模拟油中的二苯并噻吩(DBT),分别考察了n(C9H10O2)/n([HMIM]BF4)、反应温度、n(H2O2)/n(S)、低共熔溶剂的加入量和不同含硫化合物对脱硫率的影响。结果表明:在模拟油体积为5 mL、n(C9H10O2)/n([HMIM]BF4)=0.5、反应温度为60 ℃、n(H2O2)/n(S)=8、反应180 min、[HMIM]BF4/0.5 C9H10O2的加入量为1.0 mL的最佳反应条件下,[HMIM]BF4/0.5 C9H10O2对DBT、4,6-二甲基二苯并噻吩(4,6-DMDBT)和苯并噻吩(BT)的脱硫率分别达98.4%、93%和89.6%;红外分析表明DBT与DESs之间存在较强的相互作用,可使DBT的结构发生畸变;在5次循环反应后,[HMIM]BF4/0.5 C9H10O2的脱硫率仍高达90.2%,表明其具有较高的稳定性。

关键词: [HMIM]BF4/0.5C9H10O2; 低共熔溶剂(DESs), 氧化;动力学;活化能

Abstract: [HMIM]BF4/xC9H10O2 (x=0.5, 1, 2) type acidic deep eutectic solvents (DESs) were synthesized using N-methylimidazoliun fluoroborate ([HMIM]BF4) and phenylpropionic acid (C9H10O2) as raw materials, and then these DESs were characterized by FT-IR, 1H NMR and TGA. In addition, with using [HMIM]BF4/0.5 C9H10O2 deep eutectic solvent as extractant and catalyst, and H2O2 as oxidant, desulfurization was performed with dibenzothiophene(DBT) as model compound in a simulated oil system. Effects of n(C9H10O2)/n([HMIM]BF4), reaction temperature, n(H2O2)/n(S), the amount of deep eutectic solvent and different sulfur compounds on desulfurization performance were investigated. Experimental results indicate that, under the optimum conditions (i.e., 5 mL oil volume, n(C9H10O2)/n([HMIM]BF4)=0.5, reaction temperature 60 ℃, reaction time 180 min,n(H2O2)/n(S)=8, V(DESs)=1.0mL), desulfurization ratios of DBT, 4,6-dimethyl-dibenzothiophene (4,6-DMDBT) and benzothiophene (BT) are 98.4%, 93% and 89.6%, correspondingly. Infrared spectroscopy analysis show there are strong interactions between DBT and DESs, which can cause DBT structure to be distorted. After 5 cycles of reaction, desulfurization ratio is still as high as 90.2%, which indicates that [HMIM]BF4/0.5 C9H10O2 demonstrates high stability.

Key words: [HMIM]BF4/0.5C9H10O2; deep eutectic solvents(DESs);oxidation, dynamics, activation energy

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