Biomass-based catalytic transformation for producing hexanol, hexanediol, and their derivatives

doi:10.16085/j.issn.1000-6613.2023-1730

Abstract

Abstract:

Given the current energy crisis and concerns regarding environmental pollution, biomass is considered as a sustainable energy source that can potentially replace fossil fuels, and extensive research of biomass conversion has been directed towards the catalytic transformation of biomass into valuable hexanol and hexanediol. Hexanol and hexanediol are regarded as highly industrially valuable C₆ alcohols, with hexanediol playing a crucial role in polyester industry, and hexanol being considered as a suitable alternative fuel. This review provided a comprehensive overview of biomass-derived production of hexanol and hexanediol, considering various feedstocks and catalytic approaches. It systematically outlined recent advancements in the catalytic conversion of biomass-derived compounds, such as cellulose-based substrates, 5-hydroxymethylfurfural and its derivatives, as well as hexanedioic acid and its esters, into hexanol and hexanediol. The review also summarized the applications of 1,6-hexanediol in the catalytic synthesis of C₆ compounds (ε-caprolactone, adipic acid, 6-hydroxycaproic acid, and hexanediamine). Furthermore, it provided an outlook on the future trends in catalytic hydrogenation for producing hexanol and hexanediol, aiming to offer theoretical guidance and valuable insights for the eco-friendly and sustainable production of C₆ compounds.

Key words: biomass-based, hexanol, hexanediol, catalyst, C₆ compound

摘要：

在如今能源危机以及环境污染的大背景下，生物质作为一种能够代替化石燃料的可再生能源之一，如何将生物质催化转化为有价值的己醇和己二醇在生物质转化领域受到了广泛的研究关注。己醇和己二醇被认为是一种具有高度工业价值的C₆醇，其中己二醇在聚酯工业发展的领域有重要的作用，己醇则被认为是一种合适的替代燃料。本文根据原料和不同催化剂对生物质基制备己醇和己二醇的研究工作进行了归纳总结，系统阐述了近年来通过纤维素基、5-羟甲基糠醛及其衍生物、己二酸及其酯类等生物质基催化转化制备己醇和己二醇的研究进展，分析了1,6-己二醇在催化制备C₆化合物（ε-己内酯、己二酸、6-羟基己酸和己二胺）方面的应用，并在此基础上对催化加氢制备己醇和己二醇的发展趋势进行了展望，为未来进一步绿色地生产可持续的C₆化合物提供理论指导和有益参考。

关键词: 生物质基, 己醇, 己二醇, 催化剂, C₆化合物

CLC Number:

O643.31

HONG Zelong, ZHOU Ben, QIU Jiarong, ZHANG Liangqing, CHEN Jianfeng, WANG Bingshu, ZENG Xianhai, LIN Lu. Biomass-based catalytic transformation for producing hexanol, hexanediol, and their derivatives[J]. Chemical Industry and Engineering Progress, 2024, 43(11): 6091-6110.

洪泽龙, 周本, 邱佳容, 张良清, 陈剑锋, 汪炳叔, 曾宪海, 林鹿. 生物质基催化转化制备己醇和己二醇及其衍生品[J]. 化工进展, 2024, 43(11): 6091-6110.

Figures/Tables 8

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序号	催化剂	底物	溶剂	反应条件	转化率/%	目标产物，产率/%	目标产物选择性/%	催化剂稳定性	参考文献
1	Ir-ReO _x /SiO₂	纤维素	正癸烷+H₂O	24h；10MPa H₂； 413K	—	HOL，60	—	—	[34]
2	Ru-MoO _x /Mo₂C	山梨醇	H₂O	6MPa H₂； 523K	—	1-HOL，28.7	—	72h	[36]
3	Pt-WO _x /SiO₂	山梨醇	H₂O	72h；7MPa H₂； 453K	100	HOL，65.8 HDO，9.4	—	3次	[38]
4	ReO _x -Pd/CeO₂	山梨醇	1,4-diox	72h；8MPa H₂； 433K	>99	HDO，85	—	—	[30]
5	Pt/C+Pt/W/SiO₂	LGO	H₂O	6h；5.5MPa H₂； 433K	—	1,6-HDO，62	—	—	[31]
6	5%Au/ZrO₂	HMF	1,4-diox	12h；5MPa H₂； 503K	100	2-HOL，65.8	—	5次	[12]
7	Pd/ZrP	HMF	FA	21h； 413K	96.9	1,6-HDO，43	—	5次	[39]
8	Pd/SiO₂+Ir-ReO _x /SiO₂	HMF	H₂O+THF	7MPa H₂； 373K	100	1,6-HDO，57.8 1-HOL，8.2	1,6-HDO，57.8 1-HOL，8.2	24h	[40]
9	Cu-Mg-Al	HMF	IA	5h；4MPa H₂； 423K	100	1,2-HDO，42	—	4次	[41]
10	Pt/POM	DHMF	H₂O	3h；1MPa H₂； 353K	100	2-HOL，72.5	—	—	[42]

序号	催化剂	底物	溶剂	反应条件	转化率/%	目标产物，产率/%	目标产物选择性/%	催化剂稳定性	参考文献
1	Ir-ReO _x /SiO₂	纤维素	正癸烷+H₂O	24h；10MPa H₂； 413K	—	HOL，60	—	—	[34]
2	Ru-MoO _x /Mo₂C	山梨醇	H₂O	6MPa H₂； 523K	—	1-HOL，28.7	—	72h	[36]
3	Pt-WO _x /SiO₂	山梨醇	H₂O	72h；7MPa H₂； 453K	100	HOL，65.8 HDO，9.4	—	3次	[38]
4	ReO _x -Pd/CeO₂	山梨醇	1,4-diox	72h；8MPa H₂； 433K	>99	HDO，85	—	—	[30]
5	Pt/C+Pt/W/SiO₂	LGO	H₂O	6h；5.5MPa H₂； 433K	—	1,6-HDO，62	—	—	[31]
6	5%Au/ZrO₂	HMF	1,4-diox	12h；5MPa H₂； 503K	100	2-HOL，65.8	—	5次	[12]
7	Pd/ZrP	HMF	FA	21h； 413K	96.9	1,6-HDO，43	—	5次	[39]
8	Pd/SiO₂+Ir-ReO _x /SiO₂	HMF	H₂O+THF	7MPa H₂； 373K	100	1,6-HDO，57.8 1-HOL，8.2	1,6-HDO，57.8 1-HOL，8.2	24h	[40]
9	Cu-Mg-Al	HMF	IA	5h；4MPa H₂； 423K	100	1,2-HDO，42	—	4次	[41]
10	Pt/POM	DHMF	H₂O	3h；1MPa H₂； 353K	100	2-HOL，72.5	—	—	[42]

序号	催化剂	底物	溶剂	反应条件	转化率/%	目标产物，产率/%	目标产物，选择性/%	催化剂稳定性	参考文献
1	Rh-ReO _x /SiO₂+ Nafion SAC-13	BHMTHF	H₂O	20h；8MPa H₂； 392K	100	1,6-HDO，86 1,5-HDO，14	—	—	[24]
2	Pt-WO _x /TiO₂	BHMTHF	H₂O	8h；5.5MPa H₂； 433K	100	1,6-HDO，70	—	46h	[59]
3	Pt/W/TiO₂	BHMTHF	H₂O	24h；5.5MPa H₂； 433K	—	1,6-HDO，83	—	—	[60]
4	Pt-WO _x /TiO₂	1,2,6-HTO	H₂O	4h；6.9MPa H₂； 453K	89	1,6-HDO，62	—	—	[61]
5	Pt/ZrO₂	1,2,6-HTO	H₂O	2.5h；4.6MPa H₂； 433K	91	1,6-HDO，61	1,6-HDO，68	—	[62]
6	Pt-Mo/SiO₂	1,2,6-HTO	H₂O	2.5h；4.6MPa H₂； 433K	78	1,6-HDO，55	1,6-HDO，69	—	[62]
7	Pt-W/β	1,2,6-HTO	H₂O	2.5h；4.6 MPa H₂； 433 K	100	1,6-HDO，65	1,6-HDO，65	—	[62]
8	Rh-ReO _x /C	1,2,6-HTO	H₂O	14h；3.4MPa H₂； 393K	59.3	—	1,6-HDO，61.9	120h	[63]
9	Rh-MoO _x /C	2-THPM	H₂O	4h；3.4MPa H₂； 393 K	25.8	—	1,6-HDO，88.6 1-HOL，3.5	—	[63]
10	Rh-ReO _x /C	2-THPM	H₂O	4h；3.4 MPa H₂； 393K	27.3	—	1,6-HDO，97 1-HOL，3	—	[64]
11	Rh-ReO _x /C	2-THPM	H₂O	84h；8MPa H₂； 373K	—	1,6-HDO，84	—	4次	[65]

序号	催化剂	底物	溶剂	反应条件	转化率/%	目标产物，产率/%	目标产物，选择性/%	催化剂稳定性	参考文献
1	Rh-ReO _x /SiO₂+ Nafion SAC-13	BHMTHF	H₂O	20h；8MPa H₂； 392K	100	1,6-HDO，86 1,5-HDO，14	—	—	[24]
2	Pt-WO _x /TiO₂	BHMTHF	H₂O	8h；5.5MPa H₂； 433K	100	1,6-HDO，70	—	46h	[59]
3	Pt/W/TiO₂	BHMTHF	H₂O	24h；5.5MPa H₂； 433K	—	1,6-HDO，83	—	—	[60]
4	Pt-WO _x /TiO₂	1,2,6-HTO	H₂O	4h；6.9MPa H₂； 453K	89	1,6-HDO，62	—	—	[61]
5	Pt/ZrO₂	1,2,6-HTO	H₂O	2.5h；4.6MPa H₂； 433K	91	1,6-HDO，61	1,6-HDO，68	—	[62]
6	Pt-Mo/SiO₂	1,2,6-HTO	H₂O	2.5h；4.6MPa H₂； 433K	78	1,6-HDO，55	1,6-HDO，69	—	[62]
7	Pt-W/β	1,2,6-HTO	H₂O	2.5h；4.6 MPa H₂； 433 K	100	1,6-HDO，65	1,6-HDO，65	—	[62]
8	Rh-ReO _x /C	1,2,6-HTO	H₂O	14h；3.4MPa H₂； 393K	59.3	—	1,6-HDO，61.9	120h	[63]
9	Rh-MoO _x /C	2-THPM	H₂O	4h；3.4MPa H₂； 393 K	25.8	—	1,6-HDO，88.6 1-HOL，3.5	—	[63]
10	Rh-ReO _x /C	2-THPM	H₂O	4h；3.4 MPa H₂； 393K	27.3	—	1,6-HDO，97 1-HOL，3	—	[64]
11	Rh-ReO _x /C	2-THPM	H₂O	84h；8MPa H₂； 373K	—	1,6-HDO，84	—	4次	[65]

序号	催化剂	底物	反应条件；溶剂	转化率/%	目标产物，产率/%	目标产物，选择性/%	催化剂稳定性	参考文献
1	Ru-Sn/Al₂O₃	AA	6.5MPa H₂，513K；1,4-diox	97.3	1,6-HDO，89.4	—	—	[71]
2	Pt-W/SiO₂	AA	2.5h，4.6MPa H₂，393K；H₂O	100	1,6-HDO，88	—	—	[70]
3	Ru-MoB/γ-Al₂O₃-300	AA	5.5MPa H₂，493K；H₂O	90	1,6-HDO，77	1,6-HDO，85.6	5次	[73]
4	Re-Pd/SiO₂	AA	96h，8MPa H₂，413K；1,4-diox	100	1,6-HDO，74	—	—	[75]
5	Ir-Re/AC	AA	16h，10MPa H₂，453K；H₂O	100	—	1,6-HDO，59	4次	[76]
6	20CuPS-red	AA	6h，9MPa H₂，513K；H₂O	100	1,6-HDO，96.6	1,6-HDO，97.4	3次	[77]
7	Ru-Sn/TiO₂	DMA	16h，5MPa H₂，528K；H₂O	57	—	1,6-HDO，70	—	[78]
8	Ru-Sn/Al₂O₃	DMA	5MPa H₂，528K；H₂O	98	—	1,6-HDO，49	—	[79]
9	Ru-Sn-Co/AlO(OH)	DMA	10h，5MPa H₂，493K；H₂O	98	—	1,6-HDO，95	—	[80]
10	Cu-Zn-Al-500	DMA	0.5h，5MPa H₂，488K；H₂O	99	—	1,6-HDO，99	—	[82]
11	CuO-ZnO-Al₂O₃	DMA	4h，553K	98.8	1,6-HDO，73	—	—	[83]
12	732树脂	DMA	5.5h，2.5MPa H₂，523K；H₂O	—	1,6-HDO，>96	—	7次	[84]
13	DNW树脂	DMA	6MPa H₂，473K；H₂O	99.71	—	1,6-HDO，97.35	—	[85]
14	CuAl₅/SBA-15	DMA	6h，6MPa H₂，513K；1,4-diox	—	1,6-HDO，87	—	36h	[86]