Oxidative cleavage of C—O and benzene ring in lignin catalyzed by polyoxometalate ionic liquids

LIN Zeying; ZHENG Xinlai; LONG Jinxing; LIU Sijie; LI Xuehui

doi:10.11949/0438-1157.20200419

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Oxidative cleavage of C—O and benzene ring in lignin catalyzed by polyoxometalate ionic liquids

Catalysis\, kinetics and reactors | 更新时间：2026-07-24

- Oxidative cleavage of C—O and benzene ring in lignin catalyzed by polyoxometalate ionic liquids
- CIESC Journal Vol. 71, Issue 12, Pages: 5541-5550(2020)
- 作者机构：
  
  华南理工大学化学与化工学院，制浆造纸工程国家重点实验室，广东广州 510640
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200419
  CLC： O 643.3
- Received：22 April 2020，
  
  Revised：2020-06-13，
  
  Online First：17 December 2020，
  
  Published：05 December 2020
- 稿件说明：
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林泽英, 郑歆来, 龙金星, 刘思洁, 李雪辉. 杂多酸离子液体催化木质素C—O键和苯环氧化裂解[J]. 化工学报, 2020, 71(12): 5541-5550

LIN Zeying, ZHENG Xinlai, LONG Jinxing, LIU Sijie, LI Xuehui. Oxidative cleavage of C—O and benzene ring in lignin catalyzed by polyoxometalate ionic liquids[J]. CIESC Journal, 2020, 71(12): 5541-5550
林泽英, 郑歆来, 龙金星, 刘思洁, 李雪辉. 杂多酸离子液体催化木质素C—O键和苯环氧化裂解[J]. 化工学报, 2020, 71(12): 5541-5550 DOI： 10.11949/0438-1157.20200419.

LIN Zeying, ZHENG Xinlai, LONG Jinxing, LIU Sijie, LI Xuehui. Oxidative cleavage of C—O and benzene ring in lignin catalyzed by polyoxometalate ionic liquids[J]. CIESC Journal, 2020, 71(12): 5541-5550 DOI： 10.11949/0438-1157.20200419.

摘要

木质素是自然界中含量最丰富的可再生芳香聚合物，具备取代或部分替代石油用于生产大宗化学品的潜力。然而，由于木质素复杂的分子结构和化学键连接方式，当前木质素综合利用技术普遍存在目标产物选择性低等问题。因此，新型催化体系的研究对于设计与开发木质素高效转化过程具有重要意义。利用一种新型高效的杂多酸离子液体催化体系，通过选择性氧化裂解木质素的C—O键和苯环，将木质素转化为重要化工产品马来酸二乙酯，并提出了可能的反应机理。研究结果表明，当以含有β-O-4连接的典型木质素模型化合物4-甲氧基-α-[(2-甲氧基苯氧基)甲基

]

-苯甲醇为反应底物时，在杂多酸离子液体催化剂[BSmim

]

CuH

PMo

的作用下，180℃下反应5 h后，上述木质素模型化合物转化率可达到98.5%，得到84.3%(质量)和62.2%的马来酸二乙酯收率和选择性。同时，杂多酸离子液体可以通过温度的调节实现与产物的分离，简化了催化剂的回收过程，而且该催化剂具有良好的循环使用性能，重复使用6次后仍表现出较好的催化活性。

Abstract

Lignin is the most abundant renewable aromatic polymer in nature and has the potential to replace or partially replace petroleum for the production of bulk chemicals. However

due to the complex molecular

structure and chemical bond connection of lignin

the current comprehensive utilization of lignin generally has problems such as low target product selectivity. Therefore

the development of novel catalysts plays a significance role in the utilization of lignin. Herein

a novel and efficient polyoxometalate ionic liquid (POM-IL) catalytic system was provided for the conversion of lignin to diethyl maleate (DEM)

a universally used biochemical

through the selective cleavage of the C—O bond and benzene ring of lignin in the ethanol solvent. 4-Methoxy-α-[(2-methoxyphenoxy)methyl

]

-benzenemethanol

a representative lignin model compound containing b-O-4 linkage

is used as the feedstock. Over [BSmim

]

CuH

PMo

98.5% of the lignin model compound can be converted at 180℃ for 5 h

affording 84.3%(mass) yield and 62.2% selectivity of DEM. Furthermore

this POM-IL could be handily recovered through self-separation with temperature control. Moreover

the catalyst of [BSmim

]

CuH

PMo

shows good recyclability

where a satisfactory DEM yield is demonstrated even after six consecutive runs. Moreover

a plausible pathway for this process was proposed. Therefore

this work provides a new route for the selective conversion of renewable lignin to bulk petrochemicals.

关键词

Keywords

references

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