Catalytic transformation of biomass-derived polyols to diols

doi:10.16085/j.issn.1000-6613.2023-2286

Abstract

Abstract:

Diols (including ethylene glycol, propylene glycol, butanediol, et al.) are widely used in various fields, such as the chemical industry, medical treatment, biology, and agriculture, and the market demand is enormous. Currently, diols are mainly prepared from fossil resources, but there are limited reserves of fossil resources and environmental pollution in the process of use. Therefore, seeking a sustainable and green route for diols production has attracted significant attention. Biomass resources are the only renewable organic carbon resources in nature, and utilizing biomass-derived polyols for diols production is expected to overcome the shortage of fossil resources and achieve green and sustainable development. This review comprehensively summarizes the recent advances in the catalytic transformation of biomass-derived polyols (such as glycerol, erythritol, xylitol, and sorbitol) to diols. The catalytic types (exogenous hydrogenation and in-situ hydrogen source), catalytic efficiency, reaction solvents, reaction pathways, catalytic mechanisms, and catalyst stability for transforming polyols to diols are discussed in-depth. Based on the above discussion, future development for transforming biomass-derived polyols to diols is prospected, which could provide valuable references and theoretical guidance for researchers in this field.

Key words: biomass, diols, catalyst, polyols

摘要：

二元醇（包括乙二醇、丙二醇和丁二醇等）在化工、医疗、生物以及农业等许多领域都有广泛的应用，市场需求量大。目前，二元醇主要以化石资源为原料制备，但是化石资源有限的储量和使用过程中存在环境污染的问题，寻找一条可持续的、绿色的二元醇生产途径受到了越来越多的关注。生物质资源是自然界中唯一可再生的有机碳资源，以生物质基多元醇为原料制备二元醇有望克服化石资源的短缺并实现绿色可持续性发展。本文综述了国内外生物质基多元醇（甘油、赤藓糖醇、木糖醇和山梨醇）催化转化制备二醇催化剂的最新进展，总结了近年来多元醇催化氢解制备二醇的催化类型（外源氢体系和原位氢源体系）、催化效率、反应溶剂、反应途径、催化机制和催化稳定性，并对其未来的发展进行了展望，以期为生物质基多元醇高效催化转化为二元醇提供参考。

关键词: 生物质, 二醇, 催化剂, 多元醇

CLC Number:

O643.31

SONG Shunming, ZHANG Jingwen, ZHANG Liangqing, QIU Jiarong, CHEN Jianfeng, ZENG Xianhai. Catalytic transformation of biomass-derived polyols to diols[J]. Chemical Industry and Engineering Progress, 2025, 44(1): 228-252.

宋顺明, 张敬雯, 张良清, 邱佳容, 陈剑锋, 曾宪海. 生物质基多元醇催化转化制备二醇[J]. 化工进展, 2025, 44(1): 228-252.

Figures/Tables 13

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条目	催化剂	溶剂	条件	转化率/%	选择性/%	循环	参考文献
1	Ru/TiO₂	水	12h，5MPa H₂，443K	66.3	乙二醇，26.0；1,2-丙二醇，47.7	—	[31]
2	Ru/TiO₂	水	12h，5MPa H₂，453K	90.1	乙二醇，41.3；1,2-丙二醇，20.6	—	[31]
3	Ru/m-ZrO₂	水	3h，6MPa H₂，473K	22.9	乙二醇，21.0；1,2-丙二醇，45.7	—	[30]
4	Pt/m-ZrO₂	水	3h，6MPa H₂，473K	20.4	乙二醇，7.4；1,2-丙二醇，85.3	—	[30]
5	5%Ru/SiO₂（质量分数）	水	5h，8MPa H₂，513K	21.7	乙二醇，60.5；1,2-丙二醇，28.7	—	[36]
6	Ru-Cu/m-ZrO₂	水	12h，2.5MPa H₂，453K	14.0	乙二醇，6.0；1,2-丙二醇，89.0； 1,3-丙二醇，2.0	2次（稳定）	[37]
7	Ru₂Fe₁/CNT	水	12h，4MPa H₂，473K	86.0	乙二醇，23.5；1,2-丙二醇，52.3	—	[38]
8	Ru/MCM-41	水	4h，6MPa H₂，503K	62.0	乙二醇，9.0；1,2-丙二醇，38.0； 1,3-丙二醇，20.0	5次（稳定）	[47]
9	Pd/Co	异丙醇	24h，5MPa N₂，453K	100	乙二醇，8.2；1,2-丙二醇，64	—	[48]
10	Pd/Fe	异丙醇	24h，5MPa N₂，453K	100	乙二醇，1.8；1,2-丙二醇，55.9	—	[48]
11	Pt/m-WO₃	水	12h，5.5MPa H₂，453K	18.0	1,2-丙二醇，4.1；1,3-丙二醇，39.3	—	[49]
12	Pt/WO _x /Al₂O₃	水	6h，9MPa H₂，443K	21.2	1,2-丙二醇，21.0；1,3-丙二醇，58.9	—	[43]
13	Pt/WO₃/TiO₂	水	8h，4MPa H₂，393K	100	1,3-丙二醇，36.0；	4次（稳定）	[45]
14	Pt/Al-WO _x	水	12h，3MPa H₂，433K	79.0	1,2-丙二醇，1.4；1,3-丙二醇，40.6	4次（稳定）	[50]

条目	催化剂	溶剂	条件	转化率/%	选择性/%	循环	参考文献
1	Ru/TiO₂	水	12h，5MPa H₂，443K	66.3	乙二醇，26.0；1,2-丙二醇，47.7	—	[31]
2	Ru/TiO₂	水	12h，5MPa H₂，453K	90.1	乙二醇，41.3；1,2-丙二醇，20.6	—	[31]
3	Ru/m-ZrO₂	水	3h，6MPa H₂，473K	22.9	乙二醇，21.0；1,2-丙二醇，45.7	—	[30]
4	Pt/m-ZrO₂	水	3h，6MPa H₂，473K	20.4	乙二醇，7.4；1,2-丙二醇，85.3	—	[30]
5	5%Ru/SiO₂（质量分数）	水	5h，8MPa H₂，513K	21.7	乙二醇，60.5；1,2-丙二醇，28.7	—	[36]
6	Ru-Cu/m-ZrO₂	水	12h，2.5MPa H₂，453K	14.0	乙二醇，6.0；1,2-丙二醇，89.0； 1,3-丙二醇，2.0	2次（稳定）	[37]
7	Ru₂Fe₁/CNT	水	12h，4MPa H₂，473K	86.0	乙二醇，23.5；1,2-丙二醇，52.3	—	[38]
8	Ru/MCM-41	水	4h，6MPa H₂，503K	62.0	乙二醇，9.0；1,2-丙二醇，38.0； 1,3-丙二醇，20.0	5次（稳定）	[47]
9	Pd/Co	异丙醇	24h，5MPa N₂，453K	100	乙二醇，8.2；1,2-丙二醇，64	—	[48]
10	Pd/Fe	异丙醇	24h，5MPa N₂，453K	100	乙二醇，1.8；1,2-丙二醇，55.9	—	[48]
11	Pt/m-WO₃	水	12h，5.5MPa H₂，453K	18.0	1,2-丙二醇，4.1；1,3-丙二醇，39.3	—	[49]
12	Pt/WO _x /Al₂O₃	水	6h，9MPa H₂，443K	21.2	1,2-丙二醇，21.0；1,3-丙二醇，58.9	—	[43]
13	Pt/WO₃/TiO₂	水	8h，4MPa H₂，393K	100	1,3-丙二醇，36.0；	4次（稳定）	[45]
14	Pt/Al-WO _x	水	12h，3MPa H₂，433K	79.0	1,2-丙二醇，1.4；1,3-丙二醇，40.6	4次（稳定）	[50]

序号	催化剂	溶剂	条件	转化率/%	选择性/%	循环	参考文献
1	Cu/SBA-15	水	6h，4MPa H₂，503K	90.3	1,2-丙二醇，97.3	3次（稳定）	[51]
2	Cu/Zn/Al	水	20h，1.7MPa H₂，473K	72.6	乙二醇，7.6；1,2-丙二醇，76.4	—	[54]
3	Cu/Al₂O₃	水	6h，5MPa H₂，493K	61.0	乙二醇，1.1；1,2-丙二醇，56.9	—	[55]
4	Cu/B/Al₂O₃	水	12h，5MPa H₂，513K	93.8	1,2-丙二醇，97.70	300h	[56]
5	CuAl₂O₄	水	12h，5MPa H₂，513K	90.0	1,2-丙二醇，90.0	—	[57]
6	Cu/TiO₂	NaOH和水	24h，5MPa H₂，473K	52.0	1,2-丙二醇，92	—	[59]
7	Raney Ni	水	1h，0.1MPa N₂，453K	100	乙二醇，25.0；1,2-丙二醇，32.0	3次（稳定）	[60]
8	Ni/AC	水	6h，5MPa H₂，473K	44.3	乙二醇，7.9；1,2-丙二醇，76.1	—	[61]
9	Ni-Ce/AC	水	6h，5MPa H₂，473K	90.4	乙二醇，10.7；1,2-丙二醇，65.7	—	[62]
10	NiCuY	水	30h，4.6MPa N₂，533K	96.4	1,2-丙二醇，43.9	30h	[68]
11	Cu-Mg-Al	乙醇	10h，3MPa N₂，483K	95.1	1,2-丙二醇，92.2	—	[63]
12	Ni-Cu/Al₂O₃	甲酸	10h，4.5MPa N₂，473K	33.5	1,2-丙二醇，85.9	—	[64]
13	Cu/Zn/Al	甲醇	1h，2MPa H₂，523K	95.8	1,2-丙二醇，77.2	—	[65]
14	Cu-Ni/AC	水	3h，0.75MPa H₂523K	95.7	1,2-丙二醇，87.3	—	[69]

序号	催化剂	溶剂	条件	转化率/%	选择性/%	循环	参考文献
1	Cu/SBA-15	水	6h，4MPa H₂，503K	90.3	1,2-丙二醇，97.3	3次（稳定）	[51]
2	Cu/Zn/Al	水	20h，1.7MPa H₂，473K	72.6	乙二醇，7.6；1,2-丙二醇，76.4	—	[54]
3	Cu/Al₂O₃	水	6h，5MPa H₂，493K	61.0	乙二醇，1.1；1,2-丙二醇，56.9	—	[55]
4	Cu/B/Al₂O₃	水	12h，5MPa H₂，513K	93.8	1,2-丙二醇，97.70	300h	[56]
5	CuAl₂O₄	水	12h，5MPa H₂，513K	90.0	1,2-丙二醇，90.0	—	[57]
6	Cu/TiO₂	NaOH和水	24h，5MPa H₂，473K	52.0	1,2-丙二醇，92	—	[59]
7	Raney Ni	水	1h，0.1MPa N₂，453K	100	乙二醇，25.0；1,2-丙二醇，32.0	3次（稳定）	[60]
8	Ni/AC	水	6h，5MPa H₂，473K	44.3	乙二醇，7.9；1,2-丙二醇，76.1	—	[61]
9	Ni-Ce/AC	水	6h，5MPa H₂，473K	90.4	乙二醇，10.7；1,2-丙二醇，65.7	—	[62]
10	NiCuY	水	30h，4.6MPa N₂，533K	96.4	1,2-丙二醇，43.9	30h	[68]
11	Cu-Mg-Al	乙醇	10h，3MPa N₂，483K	95.1	1,2-丙二醇，92.2	—	[63]
12	Ni-Cu/Al₂O₃	甲酸	10h，4.5MPa N₂，473K	33.5	1,2-丙二醇，85.9	—	[64]
13	Cu/Zn/Al	甲醇	1h，2MPa H₂，523K	95.8	1,2-丙二醇，77.2	—	[65]
14	Cu-Ni/AC	水	3h，0.75MPa H₂523K	95.7	1,2-丙二醇，87.3	—	[69]

序号	催化剂	溶剂	条件	转化率/%	选择性/%	循环	参考文献
1	Ir-ReO _x /SiO₂	水	24h，8MPa H₂，373K	74.0	1,3-丁二醇，12.0；1,4-丁二醇，33.0	4次	[74]
2	Ir-ReO _x /TiO₂	水	30h，25bar H₂，473K	99.6	1,2-丁二醇，17.5；1,3-丁二醇，11.1； 1,4-丁二醇，2.1；2,3-丁二醇，22.3	—	[75]
3	Ir-ReO _x /TiO₂	水	4h，8MPa H₂，373K	36	1,4-丁二醇，36.0	—	[76]
4	Rh-ReO _x /TiO₂	水	14h，25bar H₂，473K	—	丁二醇，34.0	—	[77]
5	Ru-ReO _x /TiO₂	水	14h，25bar H₂，473K	—	丁二醇，55.0	—	[78]
6	ReO _x-Pd/CeO₂	1,4-二氧六环	24h，8MPa H₂，433K	98	1,2-丁二醇，79.0	—	[79]
7	Pt/W/SBA-15	水	12h，5MPa H₂，463K	82.2	1,4-丁二醇，37.6	—	[80]
8	Pt/W/Ti-SBA-15	水	12h，5MPa H₂，463K	94.0	1,3-丁二醇，20.3；1,4-丁二醇，34.7	—	[81]
9	Cu/CaO-Al₂O₃	水	10h，2.8MPa H₂，507K	85.4	1,2-丁二醇，38.6 1,2-丙二醇，15.7 乙二醇，10.9	—	[82]