Synthesis of Zirconium Oxychloride⁃Based Deep Eutectic Solvents and Their Oxidative Desulphurization Properties

doi:10.12422/j.issn.1672-6952.2026.03.003

Abstract

Abstract:

A zirconium oxychloride (ZOC)?based deep eutectic solvent (DES) was successfully prepared through thermal mixing of ethylene glycol (EG) with ZOC. The structure of the DES was systematically characterized using FT?IR and 1H NMR, confirming its successful synthesis, while its viscosity was determined using a rotational viscometer. An extraction?oxidation coupled desulfurization system was constructed using hydrogen peroxide as the oxidant and the DES as both an extractant and a catalyst. The effects of DES composition, reaction temperature, oxygen?to?sulfur molar ratio, solvent?to?oil mass ratio, and different types of sulfides on the desulfurization rate were systematically investigated. The results demonstrated that under optimal conditions (zirconyl chloride to ethylene glycol molar ratio of 1∶24, reaction temperature of 50 ℃, solvent?to?oil mass ratio of 1∶5, and oxygen?to?sulfur molar ratio of 8), the system achieves a desulfurization rate of 99.8%, 94.0%, and 69.8% for dibenzothiophene (DBT), 4,6?dimethyldibenzothiophene (4,6?DMDBT), and benzothiophene (BT) in model oil, respectively. Notably, the DES maintains a desulfurization rate of 94.9% after five reuse cycles, demonstrating excellent recyclability. Through experimental data analysis, the reaction mechanism was further elucidated, revealing the synergistic mechanism of DES in both sulfide oxidation and extraction processes.

Key words: ZrOCl₂, Oxidative desulfurization, Deep eutectic solvent, Ethylene glycol, Synergistic effect

摘要：

通过乙二醇（EG）与八水合氧氯化锆（ZOC）的简单加热混合，成功制备了ZOC基低共熔溶剂(DES)；采用FT?IR和1H NMR对DES的结构进行了系统表征，证实其成功合成；利用旋转式黏度计测定了该溶剂的黏度；构建以双氧水为氧化剂、DES为萃取剂和催化剂的萃取?氧化耦合脱硫体系，系统考察了DES组成、反应温度、氧硫物质的量比、剂油质量比及硫化物类型对脱硫率的影响。结果表明，在最优条件下(ZOC与EG物质的量比为1∶24，反应温度为50 ℃，剂油质量比为1∶5，氧硫物质的量比为8)，该体系对二苯并噻吩（DBT）、4,6?二甲基二苯并噻吩（4,6?DMDBT）和苯并噻吩（BT）模拟油的脱硫率分别达到99.8%、94.0%和69.8%。值得注意的是，该DES经5次循环使用后，脱硫率仍保持94.9%，展现出优异的重复使用性能。通过实验数据分析，进一步探讨了该体系的反应机理，揭示了DES在硫化物氧化及萃取过程中的协同作用机制。

关键词: ZrOCl₂, 氧化脱硫, DES, 乙二醇, 协同作用

CLC Number:

TE624

Jiayin ZHANG, Xingyu WANG, Lianjing REN, Linlin CAI, Jiawei SI, Haoran ZHANG, Xingjia YU, Rongxiang ZHAO. Synthesis of Zirconium Oxychloride⁃Based Deep Eutectic Solvents and Their Oxidative Desulphurization Properties[J]. Journal of Liaoning Petrochemical University, 2026, 46(3): 17-24.

张佳音, 王兴宇, 任连婧, 蔡琳琳, 司佳伟, 张浩然, 宇兴佳, 赵荣祥. 氧氯化锆基低共熔溶剂的合成及其氧化脱硫性能[J]. 辽宁石油化工大学学报, 2026, 46(3): 17-24.

Figures/Tables 15

Fig.1 Synthesis process of ZOC?based DES

Fig.2 FT?IR spectra of EG, ZOC, and the DES

Fig.3 1H NMR spectra of EG and the DES

Table 1 Viscosity of DES at various temperatures

温度/℃	黏度/（mm²·s^-1）
30	598.68
40	191.36
50	111.74
60	73.56

Fig.4 Effects of metal ligands on desulfurization rate

Fig.5 Effect of ZOC to EG molar ratio on desulfurization rate

Fig.6 Effect of reaction temperature on desulfurization rate

Fig.7 First?order kinetics equation at different temperature

Fig.8 Effect of oxygen?to?sulfur molar ratio on desulfurization rate

Fig.9 Effect of solvent?to?oil mass ratio on desulfurization rate

Fig.10 Desulfurization rate for different sulfides

Fig.11 Effect of DES recycling on desulfurization rate

Fig.12 FT?IR spectra of dibenzothiophene (DBT) and its reaction products.

Fig.13 Radical trapping experimental results

Fig.14 Mechanism of extraction and catalytic oxidative desulfurization

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