Acid-catalyzed dehydration of hexoses to 5-hydroxymethylfurfural: Reaction, separation and process coupling

doi:10.16085/j.issn.1000-6613.2023-2099

Chemical Industry and Engineering Progress ›› 2024, Vol. 43 ›› Issue (5): 2526-2543.DOI: 10.16085/j.issn.1000-6613.2023-2099

• New and renewable energy • Previous Articles

Acid-catalyzed dehydration of hexoses to 5-hydroxymethylfurfural: Reaction, separation and process coupling

LIU Miao¹(), JIAO Yingying¹, DING Ling¹, LI Chengcheng², HE Ying³, SUN Liangliang³, HAO Qingqing¹^,², CHEN Huiyong¹^,², LUO Qunxing¹^,²()

^1.International Science and Technology Cooperation Base of MOST for Clean Utilization of Hydrocarbon Resources, Chemical Engineering Research Center of the Ministry of Education for Advanced Use Technology of Shanbei Energy, Shaanxi Research Center of Engineering Technology for Clean Coal Conversion, Collaborative Innovation Center for Shanbei Energy and Chemical Industry Development, School of Chemical Engineering, Northwest University, Xi’an 710069, Shaanxi, China
^2.Shaanxi Key Laboratory for Carbon Neutral Technology, School of Carbon Neutrality (Yulin), Northwest University, Xi’an 710069, Shaanxi, China
^3.Key Laboratory of Syngas Conversion of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an 710119, Shaanxi, China

Received:2013-11-29 Revised:2024-02-02 Online:2024-06-15 Published:2024-05-15
Contact: LUO Qunxing

酸催化己糖脱水合成5-羟甲基糠醛：反应、分离和过程耦合

刘苗¹(), 焦莹莹¹, 丁玲¹, 李城城², 何颖³, 孙亮亮³, 郝青青¹^,², 陈汇勇¹^,², 罗群兴¹^,²()

^1.西北大学化工学院，国家碳氢资源清洁利用国际科技合作基地，陕北能源先进化工利用技术教育部工程研究中心，陕西省洁净煤转化工程技术研究中心，陕北能源化工产业发展协同创新中心，陕西西安 710069
^2.西北大学榆林碳中和学院，陕西省碳中和技术重点实验室，陕西西安 710069
^3.陕西师范大学化学化工学院，陕西省合成气转化重点实验室，陕西西安 710119

通讯作者: 罗群兴
作者简介:刘苗（1998—），女，硕士研究生，研究方向为生物质催化转化。E-mail：liumiao7@stumail.nwu.edu.cn。
基金资助:
国家自然科学基金(22178288);陕西省自然科学基础研究计划(2020JQ-572);西北大学青年学术英才支持计划(S202010697312);大学生创新创业训练计划(202210697150)

Abstract

Abstract:

5-hydroxymethylfurfural (HMF) is one of paramount platform chemicals for converting biomass into chemicals, fuels and polyester materials. The rational design of efficient catalysts, optimization of catalytic reaction processes, and development of the novel separation and reaction-separation coupling technologies can enhance the comprehensive efficiency in production of HMF, simplify the unit processes, and reduce carbon emissions and energy consumption. In this paper, the state-of-the-art towards catalytic reactions, separation technology and process coupling related during acid-catalyzed dehydration of hexoses to HMF were reviewed from the fundamentals in designing the bifunctional active sites for relay catalysis, integration of tandem reactions, regulation of surface hydrophilicity and hydrophobicity, selection of reaction medium, adsorbent materials, adsorption mechanism and structure-performance relationship, as well as process intensification. The knowledge and learning points gained from this review would be instructive for research communities working on catalysis and separation in biomass utilization.

Key words: biomass, 5-hydroxymethylfurfural, catalysis, separation, process intensification

摘要：

5-羟甲基糠醛（HMF）是生物质转化为化学品、燃料和聚酯材料的重要平台化合物之一。理性设计高效催化剂、优化催化反应过程、开发新型分离以及反应-分离单元耦合技术能够强化HMF生产综合效能，还可以简化工艺流程、降低碳排放和能耗。本文立足于酸催化己糖脱水合成HMF过程中反应和分离的关键科学问题，从催化剂活性位“接力式”设计、催化反应串联耦合、表面亲疏水性调控、反应溶剂匹配、固-液吸附材料、吸附机制和构-效关系、反应-分离过程强化等方面出发，系统综述酸催化己糖脱水合成HMF过程中的反应、分离和过程耦合相关研究进展，为生物质资源高效转化利用过程中催化和分离系统的综合设计提供参考与指导。

关键词: 生物质, 5-羟甲基糠醛, 催化, 分离, 过程强化

CLC Number:

TQ03-3

LIU Miao, JIAO Yingying, DING Ling, LI Chengcheng, HE Ying, SUN Liangliang, HAO Qingqing, CHEN Huiyong, LUO Qunxing. Acid-catalyzed dehydration of hexoses to 5-hydroxymethylfurfural: Reaction, separation and process coupling[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2526-2543.

刘苗, 焦莹莹, 丁玲, 李城城, 何颖, 孙亮亮, 郝青青, 陈汇勇, 罗群兴. 酸催化己糖脱水合成5-羟甲基糠醛：反应、分离和过程耦合[J]. 化工进展, 2024, 43(5): 2526-2543.

Figures/Tables 9

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反应体系	催化剂	反应溶剂	反应条件		催化性能			参考文献
反应体系	催化剂	反应溶剂	温度/℃	时间/h	X_Glu/%	S_HMF/%	Y_HMF/%	参考文献
均相	HCl+AlCl₃	H₂O/仲丁基苯酚	170	0.7	91	68	62	[13]
	HCl+CrCl₃	H₂O/THF	140	3	95	62	59	[14]
	[EMIM]Cl+CrCl₂	1-乙基-3-甲基咪唑氯盐	100	3	99	69.7	70	[15]
	HCl+NaCl	H₂O-GVL	140	1	96	64.5	62	[16]
	CrCl₃·6H₂O	DES of TEAB	130	0.25	n. m.	n. m.	76	[17]
均相-多相	Sn-Beta+HCl	H₂O-NaCl/丁醇-THF	180	1	79	72	57	[18]
	Cr-CP+HCl	H₂O-DMSO	170	4	97.7	65.4	63.9	[19]
	Cr-CP+H₂SO₄	H₂O-DMSO	170	4	98.8	56.4	55.7	[19]
	Cr-MIL-101+H₄SiW₁₂O₄₀	H₂O-GVL	140	8	92	n. m.	40	[20]
多相	Nb-Beta	H₂O-NaCl/MIBK	180	12	97.4	84.3	82.1	[21]
	Cr-MIL-101-SO₃H	H₂O-GVL	180	2	98	45.8	44.9	[22]
	SO₃H-NH-MCM-41	H₂O	120	2	n. m.	n. m.	89	[23]
	SnPCP@MnO₂-PDA	DMSO	150	5	92.2	60.5	55.8	[24]
	SO₃H-OAC	H₂O-NaCl/THF	160	3	93	99.9	93	[25]
	SnO _x /C	H₂O-NaCl/THF	180	2	92.1	91.3	84.1	[26]

反应体系	催化剂	反应溶剂	反应条件		催化性能			参考文献
反应体系	催化剂	反应溶剂	温度/℃	时间/h	X_Glu/%	S_HMF/%	Y_HMF/%	参考文献
均相	HCl+AlCl₃	H₂O/仲丁基苯酚	170	0.7	91	68	62	[13]
	HCl+CrCl₃	H₂O/THF	140	3	95	62	59	[14]
	[EMIM]Cl+CrCl₂	1-乙基-3-甲基咪唑氯盐	100	3	99	69.7	70	[15]
	HCl+NaCl	H₂O-GVL	140	1	96	64.5	62	[16]
	CrCl₃·6H₂O	DES of TEAB	130	0.25	n. m.	n. m.	76	[17]
均相-多相	Sn-Beta+HCl	H₂O-NaCl/丁醇-THF	180	1	79	72	57	[18]
	Cr-CP+HCl	H₂O-DMSO	170	4	97.7	65.4	63.9	[19]
	Cr-CP+H₂SO₄	H₂O-DMSO	170	4	98.8	56.4	55.7	[19]
	Cr-MIL-101+H₄SiW₁₂O₄₀	H₂O-GVL	140	8	92	n. m.	40	[20]
多相	Nb-Beta	H₂O-NaCl/MIBK	180	12	97.4	84.3	82.1	[21]
	Cr-MIL-101-SO₃H	H₂O-GVL	180	2	98	45.8	44.9	[22]
	SO₃H-NH-MCM-41	H₂O	120	2	n. m.	n. m.	89	[23]
	SnPCP@MnO₂-PDA	DMSO	150	5	92.2	60.5	55.8	[24]
	SO₃H-OAC	H₂O-NaCl/THF	160	3	93	99.9	93	[25]
	SnO _x /C	H₂O-NaCl/THF	180	2	92.1	91.3	84.1	[26]

吸附剂材料	吸附质				参考文献
吸附剂材料	果糖	HMF	乙酰丙酸	甲酸	参考文献
球形活性炭	n. m.	Langmuir	n. m.	n. m.	[83]
颗粒活性炭	n. m.	Freundlich	n. m.	n. m.	[101]
H-Beta	Henry	Redlich-Peterson	Redlich-Peterson	Freundlich	[86]
NU-1000	无吸附	Langmuir	n. m.	n. m.	[92]
ZIF-8	n. m.	Langmuir	n. m.	n. m.	[90]
HCP	Langmuir	Freundlich	Freundlich	Langmuir	[99]
	Freundlich	Redlich-Peterson	Freundlich	Freundlich
	Redlich-Peterson	Redlich-Peterson	Freundlich	Redlich-Peterson
H-PAP	n. m.	Langmuir	n. m.	n. m.	[100]
SY-01树脂	n. m.	Langmuir	Langmuir	Langmuir	[97]

吸附剂材料	吸附质				参考文献
吸附剂材料	果糖	HMF	乙酰丙酸	甲酸	参考文献
球形活性炭	n. m.	Langmuir	n. m.	n. m.	[83]
颗粒活性炭	n. m.	Freundlich	n. m.	n. m.	[101]
H-Beta	Henry	Redlich-Peterson	Redlich-Peterson	Freundlich	[86]
NU-1000	无吸附	Langmuir	n. m.	n. m.	[92]
ZIF-8	n. m.	Langmuir	n. m.	n. m.	[90]
HCP	Langmuir	Freundlich	Freundlich	Langmuir	[99]
	Freundlich	Redlich-Peterson	Freundlich	Freundlich
	Redlich-Peterson	Redlich-Peterson	Freundlich	Redlich-Peterson
H-PAP	n. m.	Langmuir	n. m.	n. m.	[100]
SY-01树脂	n. m.	Langmuir	Langmuir	Langmuir	[97]

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Acid-catalyzed dehydration of hexoses to 5-hydroxymethylfurfural: Reaction, separation and process coupling

酸催化己糖脱水合成5-羟甲基糠醛：反应、分离和过程耦合

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