Research progress of ionic liquid-based heteropolyacids in fuel oxidation desulfurization

doi:10.16085/j.issn.1000-6613.2023-0787

Abstract

Abstract:

Oxidative desulfurization, with features such as mild reaction conditions and low cost, is widely used in fuel oil desulfurization. In recent years, researchers have found that the structure of zwitterion in ionic liquid is adjustable, which allows highly efficient multi-acid catalysts to be prepared in ionic liquid through physicochemical method, so that conducive conditions for deeper oxidation desulfurization could be attained. This review summarizes the synthesis and classification of ionic liquid polyacids and describes in detail the characteristics of simple ionic liquid polyacid and loaded ionic liquid polyacid with metal-organic frame or inorganic non-metallic materials as the carrier, as well as its research progress in the field of fuel oxidation desulfurization, including desulphurization desulfurization rate and reuse times. All the primary desulfurization efficiency of simple ionic solution with multiple acids are higher than 80%, with the highest up to 99.2%, whereas the desulfurization rate of loaded ionic liquid polyacid is above 98%, and most of them are as high as 100%, and can be reused up to 13 times. Many researchers agree that the loaded ionic liquid polyacid can not only effectively enhance the catalytic activity of the polyacid, but also improve the thermal stability and reutilization of the catalyst. It has a good performance in fuel oxidation and desulfurization. Finally, the paper points out that development of ionic liquid polyacid with good catalytic performance, good reutilization and high efficiency is the future research direction.

Key words: ionic liquids-based heteropolyacids, support, metal-organic framework, oxidation, catalyst

摘要：

氧化脱硫，因其反应条件温和、成本较低等特点被广泛应用于燃油脱硫领域。近年来，有研究者发现离子液体中的阴阳离子结构具有可调性，可借此通过物理化学法制备出高效的催化剂，为更深度的氧化脱硫提供有利条件。本文总结了离子液体多酸的合成与分类，详细叙述了单纯离子液体多酸和以金属有机框架或无机非金属材料为载体的负载型离子液体多酸的特点以及目前其在燃油氧化脱硫领域的研究进展，包括脱硫率和重复使用次数等脱硫效果。单纯离子液体多酸的初次脱硫效率都在80%以上，最高可达99.2%，而负载后的离子液体多酸的脱硫率都在98%以上，大多数高达100%，重复利用次数最高可达13次。众多研究者一致认为负载型离子液体多酸不仅能有效增强多酸的催化活性，而且可提高催化剂的热稳定性与重复利用性，在燃油氧化脱硫中有着良好的使用效果。最后对离子液体多酸在氧化脱硫领域的发展方向提出了展望，指出了具有良好催化性能、可重复利用性好、绿色高效的离子液体多酸是未来的研究方向，为进一步研究离子液体多酸提供了参考。

关键词: 离子液体多酸, 载体, 金属有机框架, 氧化, 催化剂

CLC Number:

X511

LI Siwen, LEI Min, LIU Yushuang, DONG Zhaoqi, XUE Lili, ZHAO Jianshe. Research progress of ionic liquid-based heteropolyacids in fuel oxidation desulfurization[J]. Chemical Industry and Engineering Progress, 2024, 43(6): 3322-3335.

李斯文, 雷敏, 刘玉霜, 董兆琪, 薛丽丽, 赵建社. 离子液体多酸在燃油氧化脱硫中的研究进展[J]. 化工进展, 2024, 43(6): 3322-3335.

Figures/Tables 17

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循环次数	脱硫率/%	循环次数	脱硫率/%
1	99.2	6	98.2
2	99.0	7	98.1
3	98.7	8	97.5
4	98.5	9	97.3
5	98.4	10	97.1

循环次数	脱硫率/%	循环次数	脱硫率/%
1	99.2	6	98.2
2	99.0	7	98.1
3	98.7	8	97.5
4	98.5	9	97.3
5	98.4	10	97.1

离子液体多酸	萃取剂	氧化剂	n(催化剂)/n(S)	n(O)∶n(S)	反应时间/min	反应温度/℃	脱除物质	脱硫率/%
[HMIM]₅PMo₁₀V₂O₄₀	—	H₂O₂	0.062	4∶1	100	60	DBT	99.10
[HMIM]₃PMo₁₂O₄₀	[BMIM][PF₆]	H₂O₂	0.040	4∶1	90	60	DBT	87.80
[HMIM]₃PMoO₄₀	乙腈	H₂O₂	0.040	6∶1	90	70	BT	84.60
[C₈MIM]₂Mo₂O₁₁	C₈MIMBF₄	H₂O₂	0.005	6∶1	30	40	DBT	98.83

离子液体多酸	萃取剂	氧化剂	n(催化剂)/n(S)	n(O)∶n(S)	反应时间/min	反应温度/℃	脱除物质	脱硫率/%
[HMIM]₅PMo₁₀V₂O₄₀	—	H₂O₂	0.062	4∶1	100	60	DBT	99.10
[HMIM]₃PMo₁₂O₄₀	[BMIM][PF₆]	H₂O₂	0.040	4∶1	90	60	DBT	87.80
[HMIM]₃PMoO₄₀	乙腈	H₂O₂	0.040	6∶1	90	70	BT	84.60
[C₈MIM]₂Mo₂O₁₁	C₈MIMBF₄	H₂O₂	0.005	6∶1	30	40	DBT	98.83

制备方法	优点	缺点
一步法
固液混合法	反应直接；方便操作	均一复合结构不易形成
液液混合法	操作简单；所得产物结构均匀；能进一步加工	适用于可溶物质
多步法
原位聚合	可设计原材料和聚合方法	操作复杂
原位转化	可设计；可控制材料中物质的大小和空间分布	合成复杂；在前一步反应过程中要求聚离子液体化学稳定性好