Synthesis of Citric Acid Type Deep Eutectic Solvent and Its Application in Oxidative Desulfurization

doi:10.12422/j.issn.1672-6952.2023.05.003

Journal of Liaoning Petrochemical University ›› 2023, Vol. 43 ›› Issue (5): 14-19.DOI: 10.12422/j.issn.1672-6952.2023.05.003

• Chemistry and Chemical Engineering • Previous Articles Next Articles

Synthesis of Citric Acid Type Deep Eutectic Solvent and Its Application in Oxidative Desulfurization

Qinggong MENG¹(), Xinyi ZHU¹, Chensheng CHANG², Yanhui LI³, Yuhang ZHU³, Yan ZHAO³, Xiuping LI³, Rongxiang ZHAO³()

^1.School of Environmental and Safety Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China
^2.School of Innovation and Entrepreneurship，Liaoning Petrochemical University，Fushun Liaoning 113001，China
^3.School of Petrochemical Engineering，Liaoning Petrochemical University，Fushun Liaoning 113001，China

Received:2022-03-03 Revised:2022-04-08 Online:2023-10-25 Published:2023-11-06
Contact: Rongxiang ZHAO

柠檬酸型低共熔溶剂的合成及其在氧化脱硫中的应用

孟庆功¹(), 朱昕怡¹, 常晨生², 李晏辉³, 朱宇航³, 赵岩³, 李秀萍³, 赵荣祥³()

^1.辽宁石油化工大学环境与安全工程学院，辽宁抚顺 113001
^2.辽宁石油化工大学创新创业学院，辽宁抚顺 113001
^3.辽宁石油化工大学石油化工学院，辽宁抚顺 113001

通讯作者: 赵荣祥
作者简介:孟庆功（2000⁃），男，本科生，环境科学专业，从事油品脱硫方面的研究；E⁃mall：1634762504@qq.com。
基金资助:
辽宁省自然科学基金指导计划项目(2019?ZD?0064);辽宁省大学生创新创业训练计划项目(2020101480039)

Abstract

Abstract:

Citric acid type deep eutectic solvent was synthesized using citric acid（CA） and choline chloride (ChCl) as raw materials. The existence of hydrogen bonding in deep eutectic solvents (DESs) was determined by infrared spectrum and hydrogen spectra. Sulfide in simulated oil was removed using DESs as extractant and potassium bisulfate as oxidant. The effects of the amount of water, the amount of oxidant, the ratio of hydrogen bond donor and acceptor, reaction temperature and different sulfides on desulfurization rate were investigated, and the optimum reaction conditions were determined. The results showed that the removal rate of DBT in simulated oil was 98.50% at V（model oil）=5 mL, n（ChCl）/n（CA）=1.0∶0.5, V（DES）=2.0 mL, T=30 ℃, m(catalyst)=0.6 g, m(water)=0.4 g. After five times of recycling, the desulfurization rate remains above 95.00%.

Key words: Deep eutectic solvents, Citric acid, Potassium bisulfate, Oxidation desulfurization

摘要：

以柠檬酸和氯化胆碱为原料合成柠檬酸型低共熔溶剂，通过红外光谱和氢谱确定了低共熔溶剂中存在氢键作用。以低共熔溶剂为萃取剂、过硫酸氢钾为氧化剂，脱除模拟油中的硫化物。对低共熔溶剂中水的质量、氧化剂的质量、n（ChCl）/n（CA）、反应温度和不同硫化物的影响进行考察，并确定了最佳反应条件。结果表明，在模拟油体积为5 mL、n（ChCl）/n（CA）=1.0∶0.5、低共熔溶剂体积为2.0 mL、反应温度为30 ?C、过硫酸氢钾溶液质量为0.6 g、水的质量为0.4 g的条件下，模拟油中的二苯并噻吩（DBT）脱除率为98.50%。低共熔溶剂经过5次重复回收利用后，DBT脱除率仍在95.00%以上。

关键词: 低共熔溶剂, 柠檬酸, 过硫酸氢钾, 氧化脱硫

CLC Number:

TE624

Qinggong MENG, Xinyi ZHU, Chensheng CHANG, Yanhui LI, Yuhang ZHU, Yan ZHAO, Xiuping LI, Rongxiang ZHAO. Synthesis of Citric Acid Type Deep Eutectic Solvent and Its Application in Oxidative Desulfurization[J]. Journal of Liaoning Petrochemical University, 2023, 43(5): 14-19.

孟庆功, 朱昕怡, 常晨生, 李晏辉, 朱宇航, 赵岩, 李秀萍, 赵荣祥. 柠檬酸型低共熔溶剂的合成及其在氧化脱硫中的应用[J]. 辽宁石油化工大学学报, 2023, 43(5): 14-19.

Figures/Tables 11

References 29

1	柳月，田景芝，郝欣，等. 燃油光催化氧化脱硫催化剂的研究进展［J］.石油化工， 2021，50（4）：381⁃388.
2	孙强，兰政达，郭绪强，等. 离子液体萃取脱除残渣燃料油中硫化物［J］.石油化工， 2021，50（8）：766⁃771.
3	王子淇，王仲戎，郝媛媛，等. 金属有机骨架材料用于燃料油脱硫的研究进展［J］.石油炼制与化工， 2023， 54（9）：24⁃32.
4	赵岩，李秀萍，郭永成，等. 乳酸基低共熔溶剂⁃钼酸铵体系催化氧化脱硫性能研究［J］. 石油炼制与化工， 2021， 52（4）：99⁃105.
5	ABID M F， AHMED S M， ABOHAMEED W H， et al. Study on hydrodesulfurization of a mixture of middle distillates［J］. Arabian Journal for Science and Engineering， 2018， 43（11）： 5837⁃5850.
6	TANG M X， ZHOU L G， DU M X， et al. A novel reactive adsorption desulfurization Ni/MnO adsorbent and its hydrodesulfurization ability compared with Ni/ZnO［J］. Catalysis Communications， 2015， 61： 37⁃40.
7	LI Z， FU Y H， ZHOU A N， et al. Desulfurization of model FCC gasoline by extraction with Ionic liquid and conventional extraction solvents［J］. Petroleum Science and Technology， 2017， 35（16）： 1699⁃1705.
8	ELWAN H A， ZAKY M T， FARAG A S， et al. A coupled extractive⁃oxidative process for desulfurization of gasoline and diesel fuels using a bifunctional ionic liquid［J］. Journal of Molecular Liquids， 2017， 248： 549⁃555.
9	ZHANG Q， ZHANG J H， YANG H W， et al. Efficient aerobic oxidative desulfurization over Co-Mo-O bimetallic oxide catalysts［J］. Catalysis Science & Technology， 2019， 9（11）： 2915⁃2922.
10	YANG Y X， LV G Q， DENG L L， et al. Ultra⁃deep desulfurization of diesel fuel via selective adsorption over modified activated carbon assisted by pre⁃oxidation［J］. Journal of Cleaner Production， 2017， 161： 422⁃430.
11	WANG J L， ZHAO D S， ZHOU E P， et al. Desulfurization of gasoline by extraction with N⁃alkyl⁃pyridinium⁃based ionic liquids［J］. Journal of Fuel Chemistry and Technology， 2007， 35（3）： 293⁃296.
12	DEDUAL G， MACDONALD M J， ALSHAREEF A， et al. Requirements for effective photocatalytic oxidative desulfurization of a thiophene⁃containing solution using TiO₂［J］. Journal of Environmental Chemical Engineering， 2014， 2（4）： 1947⁃1955.
13	LI J J， ZHOU F， TANG X D， et al. Deep desulfurization of gasoline by electrochemical oxidation⁃distillation［J］. Petroleum Science and Technology， 2016， 34（5）： 442⁃448.
14	ABBOTT A P， CAPPER G， DAVIES D L， et al. Novel solvent properties of choline chloride/urea mixtures［J］. Chemical Communications， 2003， 9（1）： 70⁃71.
15	GANO Z S， MJALLI F S， AL⁃WAHAIBI T， et al. Solubility of thiophene and dibenzothiophene in anhydrous FeCl₃⁃ and ZnCl₂⁃based deep eutectic solvents［J］. Industrial & Engineering Chemistry Research， 2014， 53（16）： 6815⁃6823.
16	SMITH E L， ABBOTT A P， RYDER K S. Deep eutectic solvents （DESs） and their applications［J］. Chemical Reviews， 2014， 114（21）： 11060⁃11082.
17	SUDHIR N， YADAV P， NAUTIYAL B R， et al. Extractive desulfurization of fuel with methyltriphenyl phosphonium bromide⁃tetraethylene glycol⁃based eutectic solvents［J］. Separation Science and Technology， 2020， 55（3）： 554⁃563.
18	SUN L L， ZHU Z G， SU T， et al. Novel acidic eutectic mixture as peroxidase mimetics for oxidative desulfurization of model diesel［J］. Applied Catalysis B： Environmental， 2019， 255： 117747.
19	YIN J M， WANG J P， LI Z， et al. Deep desulfurization of fuels based on an oxidation/extraction process with acidic deep eutectic solvents［J］. Green Chemistry， 2015， 17（9）： 4552⁃4559.
20	安洪欣. 单过硫酸氢钾的复合钠盐的杀菌消毒效果的应用研究［J］. 科技创新导报， 2010（13）： 4⁃5.
21	郁佳，王伟，郑琳娟，等. 过硫酸氢钾复合盐在印度发漂白工艺中的应用［J］. 印染助剂， 2020， 37（3）： 54⁃56.
22	JIN B D， NIU J T， DAI J W， et al. New insights into the enhancement of biochemical degradation potential from waste activated sludge with low organic content by Potassium Monopersulfate treatment［J］. Bioresource Technology， 2018， 265： 8⁃16.
23	张星，姚吉伦，徐文思，等. 过硫酸氢钾在水处理中的应用研究进展［J］. 化学与生物工程， 2018， 35（2）： 8⁃14.
24	DELGADO⁃MELLADO N， LARRIBA M， NAVARRO P， et al. Thermal stability of choline chloride deep eutectic solvents by TGA/FTIR⁃ATR analysis［J］. Journal of Molecular Liquids， 2018， 260： 37⁃43.
25	ALI M C， LIU R R， CHEN J， et al. New deep eutectic solvents composed of crown ether， hydroxide and polyethylene glycol for extraction of non⁃basic N⁃compounds［J］. Chinese Chemical Letters， 2019， 30（4）： 871⁃874.
26	XU H， ZHANG D D， WU F M， et al. Deep desulfurization of fuels with cobalt chloride⁃choline chloride/polyethylene glycol metal deep eutectic solvents［J］. Fuel， 2018， 225： 104⁃110.
27	ZHAO R X， LI X P， SU J X， et al. Preparation of WO₃/g⁃C₃N₄ composites and their application in oxidative desulfurization［J］. Applied Surface Science， 2017， 392： 810⁃816.
28	JIANG W， ZHU K， LI H P， et al. Synergistic effect of dual Brønsted acidic deep eutectic solvents for oxidative desulfurization of diesel fuel［J］. Chemical Engineering Journal， 2020， 394： 124831.
29	ZUO M G， HUANG X Q， LI J X， et al. Oxidative desulfurization in diesel via a titanium dioxide triggered thermocatalytic mechanism［J］. Catalysis Science & Technology， 2019， 9（11）： 2923⁃2930.

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Synthesis of Citric Acid Type Deep Eutectic Solvent and Its Application in Oxidative Desulfurization

柠檬酸型低共熔溶剂的合成及其在氧化脱硫中的应用

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Figures/Tables 11

References 29

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