5-羟甲基糠醛催化氢化制备2,5-呋喃二甲醇的研究进展

doi:10.16085/j.issn.1000-6613.2018-1968

摘要/Abstract

摘要：

2,5-呋喃二甲醇（BHMF）在合成树脂、药物等方面具有重要应用。随着化石资源的日益缩减，由可再生的生物质基平台分子5-羟甲基糠醛（HMF）催化制备BHMF引起人们的广泛关注。本文在总结了HMF及BHMF物化性质的基础上，介绍了HMF在分子氢、醇类、甲酸3种不同的氢供体中催化加氢制备BHMF的研究近况，总结了贵金属、非贵金属、双金属或多金属协同催化体系在该加氢反应中的应用进展，同时分析了反应过程中温度、时间、催化剂载体、反应溶剂种类及酸值等因素对HMF转化率及BHMF得率的影响。最后对HMF催化转化制备BHMF的研究前景进行了总结和展望，提出了使用醇类代替氢气作为氢供体，开发非贵金属及金属协同催化体系将是该选择性氢化反应的重要研究方向之一。

关键词: 生物质, 5-羟甲基糠醛, 2,5-呋喃二甲醇, 催化剂, 加氢

Abstract:

2,5-bishydroxymethylfuran (BHMF) has important applications in synthetic resins and drugs. The conversion from biomass based platform molecule，5-hydroxylmethylfurfural (HMF)，to BHMF has attracted extensive attention. On the basis of summarizing the physical and chemical properties of HMF and BHMF，the advances in the preparation of BHMF by catalytic hydrogenation of HMF in terms of the diversity of hydrogen sources were comprehensively generalized，mainly including molecular H₂，alcohols，formic acid. The application of noble metal，non-precious metal，bi-metal or multi-metal co-catalysts systems was summarized. What’s more，the effects of different reaction temperature，time，catalyst carrier，solvent type and acid value and other factors on HMF conversion and BHMF selectivity were evaluated. Finally，the prospect of the preparation of BHMF by catalytic conversion of HMF was summarized and forecasted，and the use of alcohols instead of hydrogen as hydrogen donors was proposed. The development of non-noble metal and metal co-catalysis system is one of the important research directions of this selective hydrogenation reaction.

Key words: biomass, 5-hydroxymethylfurfural, 2,5-bishydroxymethylfuran, catalyst, hydrogenation

中图分类号:

TQ35

张凯莉, 刘颖, 武书彬. 5-羟甲基糠醛催化氢化制备2,5-呋喃二甲醇的研究进展[J]. 化工进展, 2019, 38(06): 2707-2713.

Kaili ZHANG, Ying LIU, Shubin WU. Advances in catalytic hydrogenation of 5-hydroxymethylfurfural to 2,5-bishydroxymethylfuran[J]. Chemical Industry and Engineering Progress, 2019, 38(06): 2707-2713.

图/表 4

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化学品	5-羟甲基糠醛（HMF）	2,5-呋喃二甲醇（BHMF）
分子式	C₆H₆O₃	C₆H₈O₃
摩尔质量/g·mol^-1	126.11	128.13
熔点/℃	28～34	74～77
沸点/℃	114～116	275
密度/g·cm^-3	1.243	1.283
紫外吸收波长/nm	284	219

化学品	5-羟甲基糠醛（HMF）	2,5-呋喃二甲醇（BHMF）
分子式	C₆H₆O₃	C₆H₈O₃
摩尔质量/g·mol^-1	126.11	128.13
熔点/℃	28～34	74～77
沸点/℃	114～116	275
密度/g·cm^-3	1.243	1.283
紫外吸收波长/nm	284	219

序号	氢供体	溶剂	催化剂	温度/℃	时间/h	BHMF产率/%	文献
1	氢气	甲苯	Shvo’s	90	1	99	[24 ]
2	氢气	水	Ni/MCM-41	35	2	89	[ 25]
3	2-异丙醇	2-异丙醇	Ru/C	150	6	38	[ 26]
4	乙醇	乙醇	Al(OH)₃	150	2	58.8	[ 27]
5	乙醇	乙醇	Ti(OH)₄	150	2	18.7	[ 27]
6	乙醇	乙醇	ZrO(OH)₂	150	2	87.7	[ 27]
7	甲醇	甲醇	MgO	160	3	100	[ 28]
8	甲酸	THF	Cp*Ir(TsDPEN)	40	2	99	[29]
9	甲酸	THF	Pd/C	120	4	94	[ 30]
10	氢气	水	Au/Al₂O₃	120	2	96	[31]
11	氢气	水	Pd/Al₂O₃	140	4	20	[ 31]
12	氢气	水，正丁醇	Ru/CeO _x	130	2	81	[ 32]
13	氢气	水，正丁醇	Ru/CeO _x	130	6	32	[32 ]
14	1，4-丁二醇	1，4-丁二醇	Cu/AlO _x	220	6	93	[ 33]
15	氢气	丁醇	Ni-Fe/CNTs	110	18	96.1	[34 ]
16	氢气	丁醇	Ni/CNTs	110	18	76.4	[34 ]
17	氢气	丁醇	Fe/CNTs	110	18	—	[ 34]
18	氢气	乙醇	Cu/Zn	120	3	95	[35 ]
19	氢气	水	Ir-ReO _x /SiO₂	30	6	99	[ 36]
20	氢气	1，4-二氧己环	Cu-ZnO	100	2	99.1	[ 37]
21	氢气	水	Ir/C	50	3	95.4	[ 38]
22	氢气	水	Ir/TiO₂	50	3	69.7	[38 ]

序号	氢供体	溶剂	催化剂	温度/℃	时间/h	BHMF产率/%	文献
1	氢气	甲苯	Shvo’s	90	1	99	[24 ]
2	氢气	水	Ni/MCM-41	35	2	89	[ 25]
3	2-异丙醇	2-异丙醇	Ru/C	150	6	38	[ 26]
4	乙醇	乙醇	Al(OH)₃	150	2	58.8	[ 27]
5	乙醇	乙醇	Ti(OH)₄	150	2	18.7	[ 27]
6	乙醇	乙醇	ZrO(OH)₂	150	2	87.7	[ 27]
7	甲醇	甲醇	MgO	160	3	100	[ 28]
8	甲酸	THF	Cp*Ir(TsDPEN)	40	2	99	[29]
9	甲酸	THF	Pd/C	120	4	94	[ 30]
10	氢气	水	Au/Al₂O₃	120	2	96	[31]
11	氢气	水	Pd/Al₂O₃	140	4	20	[ 31]
12	氢气	水，正丁醇	Ru/CeO _x	130	2	81	[ 32]
13	氢气	水，正丁醇	Ru/CeO _x	130	6	32	[32 ]
14	1，4-丁二醇	1，4-丁二醇	Cu/AlO _x	220	6	93	[ 33]
15	氢气	丁醇	Ni-Fe/CNTs	110	18	96.1	[34 ]
16	氢气	丁醇	Ni/CNTs	110	18	76.4	[34 ]
17	氢气	丁醇	Fe/CNTs	110	18	—	[ 34]
18	氢气	乙醇	Cu/Zn	120	3	95	[35 ]
19	氢气	水	Ir-ReO _x /SiO₂	30	6	99	[ 36]
20	氢气	1，4-二氧己环	Cu-ZnO	100	2	99.1	[ 37]
21	氢气	水	Ir/C	50	3	95.4	[ 38]
22	氢气	水	Ir/TiO₂	50	3	69.7	[38 ]

序号	醇	还原电势/kJ·mol^-1
1	2-丁醇	69.3
2	异丙醇	70.0
3	1-丁醇	79.7
4	乙醇	85.4
5	甲醇	130.1