木质素基芳香醛类化合物的制备及其转化研究进展

doi:10.3969/j.issn.0253-2417.2023.04.016

摘要/Abstract

摘要：

芳香醛化合物是合成染料、香料、农药、药品等精细化学品的重要原料。木质素是木质纤维素生物质中第二大组分，也是目前唯一可以生产芳香性化合物的可再生资源。催化氧化可在温和条件下转化木质素为具有高度官能化的芳香醛(对羟基苯甲醛、香草醛、紫丁香醛等)，是实现木质素资源化利用的有效途径之一。首先介绍了木质素的结构特性和解聚机理，总结探讨了木质素结构对芳香醛制备的影响；进而从催化氧化解聚方式(湿式氧化与碱性硝基苯氧化，带均相和非均相催化剂的催化氧化解聚，光催化氧化以及电催化氧化)和催化剂类型(金属盐与金属卟啉、杂多酸等均相催化剂，金属氧化物及钙钛矿型氧化物等非均相催化剂)详细介绍当前木质素氧化解聚制备芳香醛的最新进展。此外，还对芳香醛升级转化制备2-甲氧基-4-甲基苯酚、芳腈、芳香酰胺及新型有机高分子材料等高附加值产品的具体研究情况进行总结。最后总结当前木质素氧化解聚研究存在的问题，并提出未来可能的发展方向。

关键词: 木质素, 催化氧化, 芳香醛, 制备, 转化

Abstract:

Aromatic aldehydes were important raw materials for the synthesis of fine chemicals such as dyes, spices, pesticides and drugs. Lignin was the second largest component in lignocellulosic biomass, and was the only renewable resource for producing aromatic compounds. Catalytic oxidation could transform lignin into highly functionalized aromatic aldehydes(e.g., p-hydroxybenzaldehyde, vanillin, syringaldehyde, etc.) under mild conditions, which was regarded as one of the effective ways to realize the resource utilization of lignin. Firstly, the structural characteristics and depolymerization mechanism of lignin were introduced, and the effects of lignin structure on the production of aromatic aldehydes were summarized and discussed. Then, recent progress in the preparation of aromatic aldehydes by oxidative depolymerization of lignin was introduced in detail from the methods of catalytic oxidative depolymerization methods(e.g., wet oxidation and alkaline nitrobenzene oxidation, catalytic oxidative depolymerization with homogeneous and heterogeneous catalysts, photocatalytic oxidation and electrocatalytic oxidation) and types of catalysts(e.g., metal salts and metal porphyrins, heteropoly acids and other homogeneous catalysts, metal oxides and perovskite oxides and other heterogeneous catalysts). Moreover, the upgrading and conversion of aromatic aldehydes into high value-added products such as 2-methoxy-4-methylphenol, aromatic nitrile, aromatic amides and new organic polymer materials were further summarized. Finally, the existing problems in the current research on lignin oxidative depolymerization were summarized, and the possible development direction in the future was proposed, which laid a foundation for lignin oxidative depolymerization and high value-added utilization.

Key words: lignin, catalytic oxidation, aromatic aldehydes, synthesis, conversion

中图分类号:

TQ35

谢葛亮, 周贤君, 董澄宇, 陈伟, 徐禄江, 方真. 木质素基芳香醛类化合物的制备及其转化研究进展[J]. 林产化学与工业, 2023, 43(4): 115-126.

Geliang XIE, Xianjun ZHOU, Chengyu DONG, Wei CHEN, Lujiang XU, Zhen FANG. Progress in the Preparation and Transformation of Lignin-based Aromatic Aldehydes[J]. Chemistry and Industry of Forest Products, 2023, 43(4): 115-126.

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催化剂 catalyzer	原料 raw material	溶剂 solvent	转化率/% conversion	芳香醛产率¹⁾/% aromatic aldehyde yield			文献 ref.
催化剂 catalyzer	原料 raw material	溶剂 solvent	转化率/% conversion	PHA	VA	SA	文献 ref.
CuSO₄	桉木木质素磺酸盐eucalyptus lignosulfonate	NaOH	—	—	4.5	16.1	[12]
CuSO₄	松木木质素pine lignin	NaOH	100	5.0	12.5	6.9	[15]
CuSO₄	有机溶剂木质素organic solvent lignin	Na₂HPO₄+Na₃PO₄	100	4.7	13.6	7.5	[16]
CuSO₄	碱木质素alkali lignin	Na₂HPO₄+Na₃PO₄	100	5.0	14.2	7.4	[16]
CuSO₄+FeCl₃	杨木水解木质素poplar hydrolyzed lignin	NaOH	71.5	—	4.6	9.8	[17]
Co(TPPS₄)	玉米秸秆酶解木质素enzymatic hydrolysis of lignin from corn straw	NaOH-H₂O₂	75.1	5.5	4.7	2.7	[18]
CPTPPS₃Co		NaOH-H₂O₂	—	5.7	4.4	2.6	[19]

催化剂 catalyzer	原料 raw material	溶剂 solvent	反应条件 reaction conditions	产物(产率)¹⁾ product yield	文献 ref.
H₃PMo₁₂O₄₀	硫酸盐木质素Kraft lignin	CH₃OH/C₂H₅OH-H₂O	170 ℃, 20 min	VA(5.18%)+MV	[22]
H₃PMo₁₂O₄₀	棉秆木质素cotton stalk lignin	γ-戊内酯γ-pentalactone	150 ℃, 4 h	转化率92.6% conversion 92.6%	[23]
H₅PV₂Mo₁₀O₄₀	麦草碱木质素wheat straw alkali lignin	[BMIM]Cl	140 ℃, 4 h	VA(6.97%)	[23]
H₅PV₂Mo₁₀O₄₀	酶解木质素enzymatic lignin	[BMIM]Cl	120 ℃, 3 h	VA(10.32%)	[24]

催化剂 catalyst	原料 substrate	芳香醛产率¹⁾/% aromatic aldehyde yield			文献 ref.
催化剂 catalyst	原料 substrate	PHA	VA	SA	文献 ref.
CuO	造纸黑液木质素lignin obtained from black liquor	—	1.16	2.55	[26]
Cu₂O		—	2.44	3.12	[26]
CuO-Cu₂O		—	10.24 ^a
Cu/γ-Al₂O₃	麦秸、甘蔗渣木质素wheat straw, bagasse lignin	—	~11.3	~4.8	[27]
Co₅₀-Fe₅₀	小麦有机溶剂木质素wheat organic solvent lignin	0.2	3.33	9.74	[28]
LaFeO₃	玉米秸秆酶解木质素enzymatic corn straw lignin	1.89	4.10	8.77	[29]
LaMnO₃		2.03	4.32	9.33	[30]
LaCoO₃		2.23	4.55	9.99	[31]
LaCo_0.8Cu_0.2O₃		2.88	5.30	12.8	[34]
LaMn_0.8Cu_0.2O₃		2.90	5.07	14.6	[35]
LaFe_0.8Cu_0.2O₃		2.49	4.56	11.51	[36]

催化剂 catalyst	溶剂 solvent	反应条件 reaction conditions	转化率 conversion rate	MMP选择性/% selectivity of MMP	文献 ref.
Pd/CM170	水/十氢萘H₂O/decalin	100 ℃, 14 500 kPa H₂, 1 h	>99	52.0	[48]
Pd/C	蒸馏水distilled H₂O	3 000 kPa H₂, 30 min	100	95	[50]
Pd_SA+C/SAPO-31	C₂H₅OH+HCOOH	80 ℃, 30 min	99	99	[51]
Mo₂C/AC	去离子水deionized H₂O	150 ℃, 1 MPa H₂, 6 h	33.8	12.9	[52]
Co@NC@C	去离子水deionized H₂O	140 ℃, 0.5 h, 101.3 kPa H₂	100.0	47.4	[53]
Ni₃Co@NC@C	去离子水deionized H₂O	140 ℃, 0.5 h, 101.3 kPa H₂	97.0	41.6	[53]
Cu/Zn₁₅Al₄Sn-LDH	2-丙醇2-propanol	180 ℃, 4 h, N₂	100.0	98.5	[54]
Co/N-C-600	2-丙醇2-propanol	180 ℃, 1 MPa H₂, 4 h	95	96	[55]
Co/N-C-700	2-丙醇2-propanol	180 ℃, 1 MPa N₂, 4 h	98	85	[56]
Pd/Ru@GO	CH₃OH	30 ℃, 1 000 kPa H₂, 12 h	100.0	96	[58]
ClMPA@Pd/Al₂O₃	C₂H₅OH	40 ℃, 1 378 kPa H₂	>99	87	[59]
Pd₁/WO_2.72	C₂H₅OH	40 ℃, 101.3 kPa H₂	>99	>99	[60]

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