催化转移氢化制生物质基2,5-呋喃二甲醇研究进展

李微; 贡红辉; 史显磊

doi:10.1016/S1872-5813(23)60403-7

催化转移氢化制生物质基2,5-呋喃二甲醇研究进展

doi: 10.1016/S1872-5813(23)60403-7

李微^1,,
贡红辉^1,,
史显磊^{1, 2, ,}

1.
河南理工大学化学化工学院河南省煤炭绿色转化重点实验室, 河南焦作 454003
2.
天津化学化工协同创新中心, 天津 300072

基金项目: 国家自然科学基金(22378099, 21802034) ，中国博士后科学基金(2023M730983)，河南省高校基础研究专项（22ZX004），河南省科技研发计划联合基金(222301420047, 225200810106)和河南理工大学杰出青年基金（J2023-2）资助

详细信息

通讯作者:
Tel/Fax: 0391-3986810, E-mail: shixl@tju.edu.cn

中图分类号: TQ032.4
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- 被引次数: 0
出版历程
- 收稿日期: 2023-10-19
- 修回日期: 2023-11-30
- 录用日期: 2023-12-01
- 网络出版日期: 2023-12-11
- 刊出日期: 2024-05-01

Recent advances in preparing biomass-based 2,5-bis(hydroxymethyl)furan by catalytic transfer hydrogenation

LI Wei^1
,,
GONG Honghui^1
,,
SHI Xianlei^{1, 2
, ,}

1.
Henan Key Laboratory of Coal Green Conversion, College of Chemistry and Chemical Engineering, Henan Polytechnic University, Jiaozuo 454003, China
2.
Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Tianjin 300072, China

Funds: The project was supported by National Natural Science Foundation of China (22378099, 21802034), China Postdoctoral Science Foundation (2023M730983), Foundation of Henan Educational Committee (22ZX004), Henan Provincial Science and Technology Research and Development Joint Fund (222301420047, 225200810106) and Henan Polytechnic University (J2023-2).

摘要

摘要: 生物质基2,5-呋喃二甲醇（BHMF）可从廉价易得的糖类出发，经催化转化-选择性氢化制取，并作为一种用途广泛的化工中间体及燃料前体，尤其在改善传统聚酯性能以及合成绿色可降解的生物基聚酯新材料方面具有独特优势。BHMF制取过程中，传统的氢化方式消耗了大量高品位能源氢气，且高压氢气存在安全隐患并导致基础设施投入多。本工作立足于催化转移氢化的优势，综述了甲酸、醇类及其他类型氢供体通过催化转移氢化的方式选择性加氢制取BHMF的研究进展；并针对催化转移氢化过程中不同类型氢供体、催化剂和反应工艺的特点及存在的问题，分析了反应条件、强化手段等对BHMF选择性和收率的影响以及反应体系的优劣。在此基础上，提出了转移氢化制取BHMF新型催化体系的研究方向，并对清洁高效、本质安全BHMF制取工艺的发展进行了展望，为生物质转化中特定催化体系的研发提供科学参考。
- 2,5-呋喃二甲醇 /
- 催化转移氢化 /
- 5-羟甲基糠醛 /
- 氢供体 /
- 催化剂
Abstract: Biomass-based 2,5-bis(hydroxymethyl)furan (BHMF) is one of the important high value-added chemicals, which can be prepared from inexpensive and renewable carbohydrates through the way of catalytic conversion and selective hydrogenation, and as a widely used chemical intermediate and fuel precursor, it has unique advantages in improving the performance of traditional polyesters and synthesizing new biodegradable bio-based polyesters. In recent years, the research on the production of high value-added chemicals such as BHMF from carbohydrate has been attracting much attention from both academia and industry. However, cleanliness, high efficiency, high selectivity and low-cost remain key challenges in this area, especially for practical applications. In the process of BHMF production, the traditional hydrogenation method consumed a large amount of high-grade energy of hydrogen, and an excessive investment in infrastructure would be generated due to the security risks of higher pressure of hydrogen. On account of the advantages of catalytic transfer hydrogenation, the advances in selective hydrogenation to prepare BHMF using formic acid, alcohols and other types of hydrogen donors by the approach of catalytic transfer hydrogenation is systematically discussed in this review. In view of the features and problems of different types of hydrogen donors, catalysts and reaction processes during the catalytic transfer hydrogenation process, the effects of reaction conditions and process intensifications on the selectivity and yield of BHMF, and the merits and demerits of the reaction system were all investigated. On this basis, the future directions of new catalytic systems for preparation of BHMF by transfer hydrogenation is proposed, and the cleaner, more efficient and essential safety technologies for the production of BHMF is predicted, which will provide some scientific reference for the research and development of related catalytic systems in biomass conversion.
- 2,5-bis(hydroxymethyl)furan /
- catalytic transfer hydrogenation /
- 5-hydroxymethylfurfural /
- hydrogen donor /
- catalyst

HTML全文

FIG. 3136. FIG. 3136.

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图 1 高附加值化学品BHMF的用途

Figure 1 Usage of high value-added chemical BHMF

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图 2 生物质糖类催化转化制取BHMF的反应路径及副反应示意图

Figure 2 Reaction pathway and side reactions of catalytic conversion of carbohydrates to BHMF

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图 3 甲酸供氢Cp*Ir(TsDPEN)催化HMF转移氢化制BHMF的机制^[29]

Figure 3 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using Cp*Ir(TsDPEN) as the catalyst and formic acid as the hydrogen donor^[29]

(with permission from John Wiley and Sons)

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图 4 甲酸供氢Co-NC催化HMF转移氢化制BHMF的机理^[30]

Figure 4 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using Co-NC as the catalyst and formic acid as the hydrogen donor^[30]

(with permission from RSC Publications)

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图 5 NiCl₂/FA/Co-NC耦合策略催化葡萄糖等制BHMF示意图^[32]

Figure 5 Coupling strategy of NiCl₂/FA/Co-NC for catalytic synthesis of BHMF from glucose and others^[32]

(with permission from RSC Publications)

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图 6 甲醇供氢催化转移氢化HMF的反应历程^[37]

Figure 6 Reaction process of catalytic transfer hydrogenation of HMF to BHMF using methanol as the hydrogen donor^[37]

(with permission from Elsevier)

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图 7 乙醇供氢ZrO(OH)₂催化转移氢化HMF制BHMF可能的反应机理^[38]

Figure 7 Possible mechanism of catalytic transfer hydrogenation of HMF to BHMF using ZrO(OH)₂ as the catalyst and ethanol as the hydrogen donor^[38]

(with permission from RSC Publications)

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图 8 乙醇供氢CuO-Fe₃O₄/AC催化转移氢化HMF制BHMF的作用机制^[39]

Figure 8 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using CuO-Fe₃O₄/AC as the catalyst and ethanol as the hydrogen donor^[39]

(with permission from ACS Publications)

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图 9 CuO/Bhm催化剂界面位点上HMF加氢反应机理^[41]

Figure 9 Mechanism of HMF hydrogenation at the interface site of CuO/Bhm^[41]

(with permission from Springer Nature)

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图 10 以异丙醇为氢供体的HMF催化转移氢化制BHMF的反应机理^[44]

Figure 10 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using isopropanol as the hydrogen donor^[44]

(with permission from Frontiers of ACS Publications)

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图 11 异丙醇供氢RuCu@NFC催化HMF转移氢化制BHMF^[47]

Figure 11 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using RuCu@NFC as the catalyst and isopropanol as the hydrogen donor^[47]

(with permission from John Wiley and Sons)

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图 12 异丙醇供氢Zr-HTC催化HMF转移氢化制BHMF^[44]

Figure 12 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using Zr-HTC as the catalyst and isopropanol as the hydrogen donor^[44]

(with permission from ACS Publications)

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图 13 异丙醇供氢Zr-LS催化转移氢化应用示意图^[57]

Figure 13 Diagram of catalytic transfer hydrogenation of HMF to BHMF using Zr-LS as the catalyst and isopropanol as the hydrogen donor^[57]

(with permission from Elsevier)

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图 14 1,4-丁二醇供氢Cu/AlO_x催化HMF转移氢化示意图^[67]

Figure 14 Diagram of catalytic transfer hydrogenation of HMF using Cu/AlO_x as the catalyst and 1,4-butanediol as the hydrogen donor^[67]

(with permission from RSC Publications)

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图 15 2-丁二醇供氢Hf-DTMP催化HMF转移氢化可能的机制^[71]

Figure 15 Mechanism of catalytic transfer hydrogenation of HMF to BHMF using Hf-DTMP as the catalyst and 2-butanediol as the hydrogen donor^[71]

(with permission from RSC Publications)

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图 16 PHMS活化机制^[81]

Figure 16 Activation mechanism of PHMS^[81]

(with permission from ACS Publications)

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图 17 Ph₂SiH₂供氢HMF选择应氢化制BHMF可能的反应机理^[83]

Figure 17 Possible mechanism of selective hydrogenation of HMF to BHMF using Ph₂SiH₂ as hydrogen donor^[83]

(with permission from MDPI Publications)

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图 18 电化学-光化学结合用于HMF选择应氢化制BHMF^[89]

Figure 18 Selective hydrogenation of HMF to BHMF by combination of electrochemistry and photochemistry^[89]

(with permission from ACS Publications)

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图 19 两极还原-氧化耦合电催化HMF制BHMF和FDCA^[91]

Figure 19 Coupled bipolar reduction-oxidation of electro-catalyzing HMF to BHMF and FDCA^[91]

(with permission from RSC Publications)

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图 20 HMF阴极转化与阳极析氧耦合电催化示意图^[92]

Figure 20 Coupled electrocatalysis diagram of HMF conversion in cathode and oxygen evolution in anode^[92]

(with permission from KeAi)

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表 1 不同醇类化合物的还原电势

Table 1 Reduction potential of different alcohol compounds

No.	Alcohol	Reduction potential/(kJ·mol⁻¹)
1	Methanol	130.1
2	Propanol	87.3
3	Ethanol	85.4
4	1-Butanol	79.7
5	Isopropanol	70.0
6	2-Butanol	69.3

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表 2 以乙醇为溶剂和氢供体催化HMF选择性氢化效果

Table 2 Results of selective catalytic hydrogenation of HMF to BHMF using ethanol as the solvent and hydrogen donor

No.	Catalyst	Temperature/℃	Time/h	HMF conversion rate/%	BHMF yield/%	Ref.
1	ZrO(OH)₂	150	2.5	94.1	83.7	[38]
2	CuO-Fe₃O₄/AC	150	5	97.5	92.4	[39]
3	Ni-NiO/CNTs	160	1	100	96.7	[40]
4	CuO/Bhm	160	3	75.9	73.5	[41]
5	Zr/NC	150	5	>99	>95	[42]

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表 3 以异丙醇为溶剂和氢供体催化HMF选择性氢化效果

Table 3 Results of selective catalytic hydrogenation of HMF to BHMF using isopropanol as the solvent and hydrogen donor

No.	Catalyst	Temperature/℃	Time/h	HMF conversion rate/%	BHMF yield/%	Ref.
1	Pd/Fe₂O₃	150	−	50	35	[45]
2	Ru/Co₃O₄	190	6	100	82.8	[46]
3	RuCu@NFC	210	12	97	91.5	[47]
4	ZrBa-SBA	150	2.5	98.3	90.6	[48]
5	ZrCa@CNS	190	10	91.2	84.2	[49]
6	Zr/NC	130	2.5	99.9	99.9	[42]
7	Zr-DTPA	140	4	98.7	95.2	[50]
8	Zr-HTC	120	4	100	99.2	[44]
9	Zr-PN	140	2	99	98	[51]
10	m-PhP-Zr	120	2	99	93	[52]
11	Zr-FDCA	140	8	100	87	[53]
12	Zr-MOF-808	82	2	98.2	96.2	[54]
13	DUT-69(Zr)	130	6	97.2	86.2	[55]
14	Zr-tannin	100	5	95	89.3	[56]
15	Zr-LS	100	2	98	89	[57]
16	Hf-LigS	100	2	97.3	89.8	[58]
17	Hf-H₃IDC-T	100	4	94	92	[59]
18	FDCA-Hf	100	5	98	95	[60]
19	Hf-MOF-808	100	1.5	−	98	[61]
20	Co/UiO-66-NH₂	100	4	92.6	88.8	[62]
21	UiO-66	180	4	87	82	[63]
22	Co₃O₄/MC	140	12	100	97	[64]
23	MnO@C-N	170	21	98	93	[65]

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表 4 以丁醇为氢供体和溶剂HMF选择性加氢反应效果

Table 4 Results of selective catalytic hydrogenation of HMF to BHMF using different butanols as the solvent and hydrogen donor

Entry	Catalyst	Hydrogen donor	t/℃	Time/h	HMF conversion rate/%	BHMF yield/%	Ref.
1	Cu/AlO_x	1,4-butanediol	220	0.01	94	93	[67]
2	Zr/NC	1-butanol	160	6	>99	>95	[42]
3	MZCCP	2-butanol	140	5	98.7	93.4	[68]
4	MZH(Zr/Fe=2)	2-butanol	150	5	98.4	89.6	[69]
5	Zr-DTMP	2-butanol	140	3	100	96.5	[70]
6	Hf-DTMP	2-butanol	130	4	99.1	96.8	[71]

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表 5 催化转移氢化制BHMF不同氢供体的优劣

Table 5 Advantages and disadvantages of different hydrogen donors in catalytic transfer hydrogenation for the synthesis of BHMF

Hydrogen donor	Advantage	Disadvantage
Formic acid or formate salts	High atomic utilization rate, high safety and environmental friendliness, ideal liquid hydrogen storage material	Stronger acidity and corrosiveness, special requirements of catalyst structure
Methanol	Renewable, lower price, high hydrogen density	Higher reduction potential, harsher reaction conditions
Ethanol	Renewable, economical efficiency	Higher reduction potential
Isopropanol	Lower reduction potential, small steric-hinerance, and strong hydrogen supply ability	Higher cost and equipment corrosion
Butanol	More sources of hydrogen, high value-added by-product γ- butyrolactone	Toxic and cost-effective compared to methanol, ethanol, etc
Benzyl alcohol	Low price and low volatility	Flammable, toxic, irritating
Cyclohexanol	Higher boiling point, continuous hydrogen-supply, by-product cyclohexanone	Higher cost, less research
NaBH₄	High hydrogen storage capacity, high energy density, safety and reliability	Expensive and not easy to be separated
NaH₂PO₂	No obvious toxicity, stable to air and water, easy to handle, and large-scale application	Releasing heat, leading to flammability and corrosiveness
PMHS	It is a byproduct of the silicon industry, which is stable, inexpensive, and low toxic to water and air	The overall price is relatively expensive, which in turn leads to higher production costs
Ph₂SiH₂	Non toxic, biodegradable, and stable for air and water	Hydrogen production requires activation by metal containing catalysts
HMF	No additional hydrogen donors need to be added	Strong alkaline condition, complicated separation pathways
Water or protons	Electrocatalysis can be carried out at lower temperatures and pressures, HMF can simultaneously undergo hydrogenation and oxidation to obtain different types of high value-added chemicals	Lower efficiency

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