Research process of preparation of aromatic aldehyde by oxidative depolymerization of lignin

doi:10.16085/j.issn.1000-6613.2023-0113

Abstract

Abstract:

Lignin as the most abundant resource of aromatic compounds in nature, can be degraded by oxidative depolymerization to produce aromatic aldehydes containing functional groups, which is an effective way to realize value-added utilization of lignin. Aromatic aldehydes are used as the important flavor compounds in food industry, synthetic dyes, perfumes, pharmaceutical intermediates and bulk chemicals, which are now mainly produced from petrochemical industry. In this review, the latest research progress of production of aromatic aldehydes from lignin is elaborated, including chemical oxidative depolymerization, electrochemical depolymerization, photocatalytic depolymerization, and biological depolymerization, especially, focusing on the conversion yield and selectivity of aldehydes to compare the cons and pros of various catalytic depolymerization process.Based on the characteristics of different catalytic depolymerization process, this paper analyzes the future research directions for the production of aromatic aldehydes from lignin. It is pointed out that existing catalytic methods still have various limitations for the large-scale industry production, and multi-method coupling is a promising strategy to further improve the aldehyde yield.

Key words: lignin, oxidative depolymerization, aromatic aldehyde, value-added utilization

摘要：

木质素作为自然界最丰富的芳香族化合物资源，通过可控的氧化解聚方式得到小分子芳香醛类化合物是实现木质素高附加值利用的重要途径。芳香醛作为重要的食用及日化香料、医药中间体、大宗化学品，目前主要通过石油化工产业链生产，以木质素生产芳香醛是具有重要研究意义和应用潜力的可再生资源利用途径。本文综述了国内外有关木质素制备芳香醛的最新研究进展，包括化学氧化解聚、电化学解聚、光催化解聚和生物催化解聚；对不同方法制备芳香醛的转化率和产率进行了对比，基于不同的解聚工艺与催化体系的特点进行评述与分析，展望未来木质素生产芳香醛的研究方向，以实现木质素的高值化利用。得出多方法耦合催化是可能进一步提高木质素生产芳香醛转化率与选择性的有效策略。

关键词: 木质素, 氧化解聚, 芳香醛, 高值化转化

CLC Number:

CHEN Yuting, BAI Yuchen. Research process of preparation of aromatic aldehyde by oxidative depolymerization of lignin[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6576-6588.

陈禹婷, 白宇辰. 木质素氧化解聚制备芳香醛研究进展[J]. 化工进展, 2023, 42(12): 6576-6588.

Figures/Tables 13

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底物	氧化剂	溶剂	反应条件	芳香醛主要产物	参考文献
异子丁香酚	H₂O₂	乙腈	现制0.5Fe/Al-SBA-15, 90℃	香草醛	[34]
有机溶剂木质素	O₂	甲醇	Pd/CeO₂	香草醛，对羟基苯甲醛	[28]
碱木质素	空气	水	150~200℃	香草醛，对羟基苯甲醛	[29]
有机溶剂木质素	硝基苯	水	NaOH,170℃	香草醛，丁香醛	[26]
有机溶剂木质素	—	丙酮	300℃，40min	对羟基苯甲醛	[30]
有机溶剂木质素	—	乙醇	300℃，41min	丁香醛	[30]

底物	氧化剂	溶剂	反应条件	芳香醛主要产物	参考文献
异子丁香酚	H₂O₂	乙腈	现制0.5Fe/Al-SBA-15, 90℃	香草醛	[34]
有机溶剂木质素	O₂	甲醇	Pd/CeO₂	香草醛，对羟基苯甲醛	[28]
碱木质素	空气	水	150~200℃	香草醛，对羟基苯甲醛	[29]
有机溶剂木质素	硝基苯	水	NaOH,170℃	香草醛，丁香醛	[26]
有机溶剂木质素	—	丙酮	300℃，40min	对羟基苯甲醛	[30]
有机溶剂木质素	—	乙醇	300℃，41min	丁香醛	[30]

原料	催化剂	溶剂	氧化剂	反应条件	芳香醛主要产物	转化率/%	产率/%	参考文献
酶水解蒸汽爆破玉米秆	LaCoO₃	氢氧化钠水溶液	O₂	120℃，2MPa，0~3h	香草醛	8~60	3.9~4.55	[40]
					对羟基苯甲醛		0.85~2.23
					丁香醛		2.1~9.99
酶水解蒸汽爆破玉米秆	LaFe_1-_x Cu _x O₃ (x=0、0.1、0.2)	氢氧化钠水溶液	O₂	120℃，2MPa，0~3h	香草醛	0~70	2.4~4.6	[41]
					对羟基苯甲醛		0.4~2.5
					丁香醛		0~11.5
有机溶剂木质素	Pd/CeO₂	甲醇	O₂	185℃，0.1MPa	香草醛	—	5.2	[28]
有机溶剂木质素	Pd/CeO₂	甲醇	O₂	185℃，0.1MPa	对羟基苯甲醛	—	2.4	[28]
有机溶剂木质素	La/SBA-15	氢氧化钠水溶液	H₂O₂	60℃，5~1440min	香草醛	—	0.38~9.94	[45]
有机溶剂木质素	La/SBA-15	氢氧化钠水溶液	H₂O₂	60℃，5~1440min	丁香醛	—	0.52~15.66	[45]
香草醇	Co₃O₄	H₂O	O₂	140℃，0.689~4MPa	香草醛	86	—	[46]
香草醇	MnCo-MO	乙腈	空气	140℃，2.1MPa，2h	香草醛	62	51	[42]
藜芦醇	Co-ZIF-9	甲苯/氢氧化钠	O₂	150℃，0.5MPa，0~4h	藜芦醛	0~45	46	[21,43]
香草醇	Co-ZIF-9	甲苯/氢氧化钠	O₂	150℃，0.5MPa，0~4h	香草醛		90	[43]
异子丁香酚	CH₃ReO₃	叔丁醇	H₂O₂	70℃，4h	香草醛		90.3	[47]

原料	催化剂	溶剂	氧化剂	反应条件	芳香醛主要产物	转化率/%	产率/%	参考文献
酶水解蒸汽爆破玉米秆	LaCoO₃	氢氧化钠水溶液	O₂	120℃，2MPa，0~3h	香草醛	8~60	3.9~4.55	[40]
					对羟基苯甲醛		0.85~2.23
					丁香醛		2.1~9.99
酶水解蒸汽爆破玉米秆	LaFe_1-_x Cu _x O₃ (x=0、0.1、0.2)	氢氧化钠水溶液	O₂	120℃，2MPa，0~3h	香草醛	0~70	2.4~4.6	[41]
					对羟基苯甲醛		0.4~2.5
					丁香醛		0~11.5
有机溶剂木质素	Pd/CeO₂	甲醇	O₂	185℃，0.1MPa	香草醛	—	5.2	[28]
有机溶剂木质素	Pd/CeO₂	甲醇	O₂	185℃，0.1MPa	对羟基苯甲醛	—	2.4	[28]
有机溶剂木质素	La/SBA-15	氢氧化钠水溶液	H₂O₂	60℃，5~1440min	香草醛	—	0.38~9.94	[45]
有机溶剂木质素	La/SBA-15	氢氧化钠水溶液	H₂O₂	60℃，5~1440min	丁香醛	—	0.52~15.66	[45]
香草醇	Co₃O₄	H₂O	O₂	140℃，0.689~4MPa	香草醛	86	—	[46]
香草醇	MnCo-MO	乙腈	空气	140℃，2.1MPa，2h	香草醛	62	51	[42]
藜芦醇	Co-ZIF-9	甲苯/氢氧化钠	O₂	150℃，0.5MPa，0~4h	藜芦醛	0~45	46	[21,43]
香草醇	Co-ZIF-9	甲苯/氢氧化钠	O₂	150℃，0.5MPa，0~4h	香草醛		90	[43]
异子丁香酚	CH₃ReO₃	叔丁醇	H₂O₂	70℃，4h	香草醛		90.3	[47]

催化剂类型	催化剂	溶剂	氧化剂	反应时间	底物（木质素/木质素模型化合物）	芳香醛主要产物	转化率 /%	产率 /%	参考文献
金属卟啉催化剂	CoTBrPP	氢氧化钠水溶液	H₂O₂	150℃，30min	1-(3,4-二甲氧基苯基)-2- (2-甲氧基苯氧基)乙烷-1-醇	藜芦醛	86	20.4	[60]
	TPPFeCl	—	叔丁酸	过夜	β-1木质素模型化合物	藜芦醛	—	50	[50]
	TSPCMnCI	磷酸盐水溶液	叔丁酸	室温	藜芦醇	藜芦醛	—	16	[63]
金属-席夫碱配合物	Co(salen)	甲醇	O₂	室温，40min	丁香醇	丁香醛	98	36	[53]
	Co(salen)	氢氧化钠水溶液	O₂	80℃，28h	藜芦醇	藜芦醛	—	43	[54]
多金属氧酸盐	H₅PV₂Mo₁₀O₄₀	[HC₄im][HSO₄]	O₂	100℃，5h	硬木木质素	丁香醛	—	5	[59]
	H₃PMo₁₂O₄₀	水/甲醇	O₂	170℃，0.33h	硫酸盐木质素	香草醛	—	5.18	[58]
	K₆[SiV₂W₁₀O₄₀]	水/甲醇	O₂	150℃，2MPa	酶解木质素	香草醛	—	5.46	[48]
简单金属盐催化剂	Cu(OH)₂	—	O₂	160℃	香草醛丙酮	丁香醛	—	60	[61]
	FeCl₃	—	O₂	160℃	Clason&酸解木质素	香草醛	—	8.8	[62]
	FeCl₃	—	O₂	160℃	Clason&酸解木质素	丁香醛	—	0.7	[62]