5-羟甲基糠醛制备及其应用研究进展

doi:10.3969/j.issn.0253-2417.2019.01.002

摘要/Abstract

摘要：

5-羟甲基糠醛(HMF)被认为是最重要的生物质基平台分子之一，广泛应用于制备精细化学品、关键医药中间体、功能聚酯、溶剂和液体燃料等多功能化合物。目前，HMF的制备是生物质领域研究的热点，大量的研究使得制备HMF的原料和方法得到不断扩展。简单介绍了HMF的主要制备方法及其反应机理，系统综述了制备HMF的催化体系，包括催化过程中所使用的催化剂(无机酸、离子液体、金属氯化物、固体酸及其他催化剂)种类及制备HMF的溶剂体系。归纳了HMF重要衍生物的制备路径及应用，总结了目前研究中所存在的问题，并展望了未来的研究方向。

关键词: 5-羟甲基糠醛, 生物质, 催化剂, 衍生化学品

Abstract:

5-Hydroxymethylfurfural (HMF) is one of the most important biomass-based platform molecules and widely used in the preparation of multifunctional compounds such as fine chemicals, key pharmaceutical intermediates, functional polyesters, solvents and liquid fuels. At present, the preparation of HMF is a hot spot in the field of biomass research, and the raw materials and methods for preparing HMF have been continuously expanded. This paper reviews the main preparation methods and research progress of HMF. Catalysis systems for HMF preparation is systematically described, including the types of the catalysts (mineral acids, ionic liquids, metal chlorides, solid acids and others) used in the catalytic process and the solvent systems. Then, the preparation paths and applications of important derivatives from HMF are summarized. Finally, suggestions for future research on HMF are provided based on the understanding of problems existing in the current research.

Key words: 5-hydroxymethylfurfural, biomass, catalyst, derivative chemicals

中图分类号:

TQ35

卢思,王琼,李浔,亓伟,王忠铭,袁振宏. 5-羟甲基糠醛制备及其应用研究进展[J]. 林产化学与工业, 2019, 39(1): 13-22.

Si LU,Qiong WANG,Xun LI,Wei QI,Zhongming WANG,Zhenhong YUAN. Progress on Preparation and Application of 5-Hydroxymethylfurfural[J]. Chemistry and Industry of Forest Products, 2019, 39(1): 13-22.

图/表 5

图1

表1

表2

表3

图2

参考文献 81

1	ISIKGOR F , BECER C R . Lignocellulosic biomass:A sustainable platform for the production of bio-based chemicals and polymers[J]. Polymer Chemistry, 2015, 6, 4497- 4559. doi: 10.1039/C5PY00263J
2	WETTSTEIN S G , ALONSO D M , GVRBVZ E I , et al. A roadmap for conversion of lignocellulosic biomass to chemicals and fuels[J]. Current Opinion in Chemical Engineering, 2012, 1, 218- 224. doi: 10.1016/j.coche.2012.04.002
3	VLACHOS D G , CARATZOULAS S . The roles of catalysis and reaction engineering in overcoming the energy and the environment crisis[J]. Chemical Engineering Science, 2010, 65 (1): 18- 29.
4	TONG X L , MA Y , LI Y D . Biomass into chemicals:Conversion of sugars to furan derivatives by catalytic processes[J]. Applied Catalysis A:General, 2010, 385 (1/2): 1- 13.
5	MUKHERJEE A , DUMONT M J , RAGHAVAN V . Review:Sustainable production of hydroxymethylfurfural and levulinic acid:challenges and opportunities[J]. Biomass & Bioenergy, 2015, 72, 143- 183.
6	MOREAU C , DURAND R , RAZIGADE S , et al. Dehydration of fructose to 5-hydroxymethylfurfural over H-mordenites[J]. Applied Catalysis A General, 1996, 145 (1/2): 211- 224.
7	AKIEN G R , QI L , HORVÁTH I T . Molecular mapping of the acid catalysed dehydration of fructose[J]. Chemical Communications, 2012, 48 (47): 5850- 5852. doi: 10.1039/c2cc31689g
8	AMARASEKARA A , WILLIAMS L , EBEDE C . Mechanism of the dehydration of D-fructose to 5-hydroxymethylfurfural in dimethyl sulfoxide at 150℃:An NMR study[J]. Carbohydrate Research, 2008, 343 (18): 3021- 3024. doi: 10.1016/j.carres.2008.09.008
9	ROMÁN-LESHKOV Y , CHHEDA J N , DUMESIC J A . Phase modifiers promote efficient production of hydroxymethylfurfural from fructose[J]. Science, 2006, 312 (5782): 1933- 1937. doi: 10.1126/science.1126337
10	CHHEDA J N , ROMÁN-LESHKOV Y , DUMESIC J A . Production of 5-hydroxymethylfurfural and furfural by dehydration of biomass-derived mono-and poly-saccharides[J]. Green Chemistry, 2007, 9 (4): 342- 350. doi: 10.1039/B611568C
11	HANSEN T S , WOODLEY J M , RⅡSAGER A . Efficient microwave-assisted synthesis of 5-hydroxymethylfurfural from concentrated aqueous fructose[J]. Carbohydrate Research, 2009, 344 (18): 2568- 2572. doi: 10.1016/j.carres.2009.09.036
12	LI C Z , ZHAO Z K , WANG A Q , et al. Production of 5-hydroxymethylfurfural in ionic liquids under high fructose concentration conditions[J]. Carbohydrate Research, 2010, 345 (13): 1846- 1850. doi: 10.1016/j.carres.2010.07.003
13	ANTAL J M J , MOK W S L , RICHARDS G N . Mechanism of formation of 5-(hydroxymethyl)-2-furaldehyde from D-fructose and sucrose[J]. Carbohydrate Research, 1990, 199 (1): 91- 109. doi: 10.1016/0008-6215(90)84096-D
14	SUN Y H , LIU P T , LIU Z . Catalytic conversion of carbohydrates to 5-hydroxymethylfurfural from the waste liquid of acid hydrolysis NCC[J]. Carbohydrate Polymers, 2016, 142, 177- 182. doi: 10.1016/j.carbpol.2016.01.053
15	DUTTA S , PAL S . Promises in direct conversion of cellulose and lignocellulosic biomass to chemicals and fuels:Combined solvent-nanocatalysis approach for biorefinary[J]. Biomass & Bioenergy, 2014, 62 (1): 182- 197.
16	MOREAU C , FINIELS A , VANOYE L . Dehydration of fructose and sucrose into 5-hydroxymethylfurfural in the presence of 1-H-3-methyl imidazolium chloride acting both as solvent and catalyst[J]. Journal of Molecular Catalysis A:Chemical, 2006, 253 (1): 165- 169.
17	BAO Q X , QIAO K , TOMIDA D , et al. Preparation of 5-hydroymethylfurfural by dehydration of fructose in the presence of acidic ionic liquid[J]. Catalysis Communications, 2008, 9 (6): 1383- 1388. doi: 10.1016/j.catcom.2007.12.002
18	LI C Z , ZHAO Z B K , CAI H L , et al. Microwave-promoted conversion of concentrated fructose into 5-hydroxymethylfurfural in ionic liquids in the absence of catalysts[J]. Biomass & Bioenergy, 2011, 35 (5): 2013- 2017.
19	RAMLI N A S , AMIN N A S . Thermo-kinetic assessment of glucose decomposition to 5-hydroxymethyl furfural and levulinic acid over acidic functionalized ionic liquid[J]. Chemical Engineering Journal, 2018, 335, 221- 230. doi: 10.1016/j.cej.2017.10.112
20	SERI K I , INOUE Y , ISHIDA H . Highly efficient catalytic activity of Lanthanide(Ⅲ) ions for conversion of saccharides to 5-hydroxymethyl-2-furfural in organic solvents[J]. Chemistry Letters, 2000, 29 (1): 22- 23.
21	ZHAO H B , HOLLADAY J E , BROWN H , et al. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural[J]. Science, 2007, 316, 1597- 1600. doi: 10.1126/science.1141199
22	BINDER J B , RAINES R T . Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals[J]. Journal of the American Chemical Society, 2009, 131 (5): 1979- 1985. doi: 10.1021/ja808537j
23	LIMA S , NEVES P , ANTUNES M M , et al. Conversion of mono/di/polysaccharides into furan compounds using 1-alkyl-3-methylimidazolium ionic liquids[J]. Applied Catalysis A:General, 2009, 363 (1/2): 93- 99.
24	ILGEN F , OTT D , KRALISCH D , et al. Conversion of carbohydrates into 5-hydroxymethylfurfural in highly concentrated low melting mixtures[J]. Green Chemistry, 2009, 11, 1948- 1954. doi: 10.1039/b917548m
25	RASRENDRA C B , MAKERTIHARTHA I G B N , ADISASMITO S , et al. Green chemicals from D-glucose:Systematic studies on catalytic effects of inorganic salts on the chemo-selectivity and yield in aqueous solutions[J]. Topics in Catalysis, 2010, 53 (15/16/17/18): 1241- 1247.
26	CAO Q , GUO X C , YAO S X , et al. Conversion of hexose into 5-hydroxymethylfurfural in imidazolium ionic liquids with and without a catalyst[J]. Carbohydrate Research, 2011, 346 (7): 956- 959. doi: 10.1016/j.carres.2011.03.015
27	田玉奎, 邓晋, 潘涛, 等. 离子液体中Lewis酸催化葡萄糖和果糖脱水制5-羟甲基呋喃甲醛[J]. 催化学报, 2011, 32 (6): 997- 1002.
	TIAN Y K , DENG J , PAN T , et al. Dehydration of glucose and fructose into 5-hydroxymethylfural catalyzed by lewis acid in ionic liquids[J]. Chinese Journal of Catalysis, 2011, 32 (6): 997- 1002.
28	WEI Z J , LI Y , THUSHARA D , et al. Novel dehydration of carbohydrates to 5-hydroxymethylfurfural catalyzed by Ir and Au chlorides in ionic liquids[J]. Journal of the Taiwan Institute of Chemical Engineers, 2011, 42 (2): 363- 370. doi: 10.1016/j.jtice.2010.10.004
29	YANG Y , HU C W , ABU-OMAR M M . Conversion of carbohydrates and lignocellulosic biomass into 5-hydroxymethylfurfural using AlCl₃·6H₂O catalyst in a biphasic solvent system[J]. Green Chemistry, 2012, 14 (2): 509- 513. doi: 10.1039/C1GC15972K
30	MITTAL N , NISOLA G M , CHUNG W J . Facile catalytic dehydration of fructose to 5-hydroxymethylfurfural by Niobium pentachloride[J]. Tetrahedron Letters, 2012, 53 (25): 3149- 3155. doi: 10.1016/j.tetlet.2012.04.045
31	ZHANG Z H , LIU B , ZHAO Z T . Conversion of fructose into 5-HMF catalyzed by GeCl₄, in DMSO and [Bmim]Cl system at room temperature[J]. Carbohydrate Polymers, 2012, 88 (3): 891- 895. doi: 10.1016/j.carbpol.2012.01.032
32	ZHOU X M , ZHANG Z H , LIU B , et al. Microwave-assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural by ScCl₃ in ionic liquids[J]. Carbohydrate Research, 2013, 375 (12): 68- 72.
33	YAN L , LASKAR D D , LEE S J , et al. Aqueous phase catalytic conversion of agarose to 5-hydroxymethylfurfural by metal chlorides[J]. RSC Advances, 2013, 3, 24090- 24098. doi: 10.1039/c3ra43293a
34	THOMBAL R S , JADHAV V H . Efficient conversion of carbohydrates to 5-hydroxymethylfurfural (HMF) using ZrCl₄ catalyst in nitromethane[J]. Biofuel Research Journal, 2014, 3, 81- 84.
35	WRIGSTEDT P , KESKIVÄ M , LESKELÄ M , et al. The role of salts and Brønsted acids in Lewis acid-catalyzed aqueous-phase glucose dehydration to 5-hydroxymethylfurfural[J]. ChemCatChem, 2015, 7 (3): 501- 507. doi: 10.1002/cctc.v7.3
36	WANG C , ZHANG L M , ZHOU T , et al. Synergy of Lewis and Brønsted acids on catalytic hydrothermal decomposition of carbohydrates and corncob acid hydrolysis residues to 5-hydroxymethylfurfural[J]. Scientific Reports, 2017, 7, 40908- 40917. doi: 10.1038/srep40908
37	JIA S Y , HE X J , XU Z W . Valorization of an underused sugar derived from hemicellulose:Efficient synthesis of 5-hydroxymethylfurfural from mannose with aluminum salt catalyst in dimethyl sulfoxide/water mixed solvent[J]. RSC Advances, 2017, 7, 39221- 39227. doi: 10.1039/C7RA07803J
38	CRISCI A J , TUCKER M H , DUMESIC J A , et al. Bifunctional solid catalysts for the selective conversion of fructose to 5-hydroxymethylfurfural[J]. Topics in Catalysis, 2010, 53 (15/16/17/18): 1185- 1192.
39	QI X H , WATANABE M , AIDA T M , et al. Efficient one-pot production of 5-hydroxymethylfurfural from inulin in ionic liquids[J]. Green Chemistry, 2010, 12 (10): 1855- 1860. doi: 10.1039/c0gc00141d
40	NIKOLLA E , ROMÁN-LESHKOV Y , MOLINER M , et al. "One-pot" synthesis of 5-(hydroxymethyl) furfural from carbohydrates using tin-beta zeolite[J]. ACS Catalysis, 2011, 1 (4): 408- 410. doi: 10.1021/cs2000544
41	WANG J J , XU W J , REN J W , et al. Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid[J]. Green Chemistry, 2011, 13 (10): 2678- 2681. doi: 10.1039/c1gc15306d
42	DE S , DUTTA S , PATRA A K , et al. Self-assembly of mesoporous TiO₂ nanospheres viaaspartic acid templating pathway and its catalytic application for 5-hydroxymethyl-furfural synthesis[J]. Journal of Materials Chemistry, 2011, 21 (43): 17505- 17510. doi: 10.1039/c1jm13229f
43	YANG Y , XIANG X , TONG D M , et al. One-pot synthesis of 5-hydroxymethylfurfural directly from starch over SO₄^2-/ZrO₂-Al₂O₃ solid catalyst[J]. Bioresource Technology, 2012, 116, 302- 306. doi: 10.1016/j.biortech.2012.03.081
44	GUO F , FANG Z , ZHOU T J . Conversion of fructose and glucose into 5-hydroxymethylfurfural with lignin-derived carbonaceous catalyst under microwave irradiation in dimethyl sulfoxide-ionic liquid mixtures[J]. Bioresource Technology, 2012, 112, 313- 318. doi: 10.1016/j.biortech.2012.02.108
45	LIU R L , CHEN J Z , HUANG X , et al. Conversion of fructose into 5-hydroxymethylfurfural and alkyl levulinates catalyzed by sulfonic acid-functionalized carbon materials[J]. Green Chemistry, 2013, 15 (10): 2895- 2903. doi: 10.1039/c3gc41139g
46	LI Y , LIU H , SONG C H , et al. The dehydration of fructose to 5-hydroxymethylfurfural efficiently catalyzed by acidic ion-exchange resin in ionic liquid[J]. Bioresource Technology, 2013, 133, 347- 353. doi: 10.1016/j.biortech.2013.01.038
47	JADHAV A H , KIM H , HWANG I T . An efficient and heterogeneous recyclable silicotungstic acid with modified acid sites as a catalyst for conversion of fructose and sucrose into 5-hydroxymethylfurfural in superheated water[J]. Bioresource Technology, 2013, 132, 342- 350. doi: 10.1016/j.biortech.2013.01.030
48	ZHANG J H , LI J K , LIN L . Dehydration of sugar mixture to HMF and furfural over SO₄^2-/ZrO₂-TiO₂ catalyst[J]. Bioresources, 2014, 9 (3): 4194- 4204.
49	NANDIWALE K Y , GALANDE N D , THAKUR P , et al. One-pot synthesis of 5-hydroxymethylfurfural by cellulose hydrolysis over highly active bimodal micro/mesoporous H-ZSM-5 catalyst[J]. ACS Sustainable Chemistry & Engineering, 2014, 2, 1928- 1932.
50	LIU J , LI H , LIU Y C , et al. Catalytic conversion of glucose to 5-hydroxymethylfurfural over nano-sized mesoporous Al₂O₃-B₂O₃, solid acids[J]. Catalysis Communications, 2015, 62, 19- 23. doi: 10.1016/j.catcom.2015.01.008
51	ZHAO J , ZHOU C M , HE C , et al. Efficient dehydration of fructose to 5-hydroxymethylfurfural over sulfonated carbon sphere solid acid catalysts[J]. Catalysis Today, 2016, 264, 123- 130. doi: 10.1016/j.cattod.2015.07.005
52	HAN B , ZHAO P , HE R , et al. Catalytic conversion of glucose to 5-hydroxymethyfurfural over B₂O₃ supported solid acids catalysts[J]. Waste Biomass Valorization, 2018, 9, 2181- 2190. doi: 10.1007/s12649-017-9971-4
53	DAI J H , ZHU L F , TANG D Y , et al. Sulfonated polyaniline as a solid organocatalyst for dehydration of fructose into 5-hydroxymethylfurfural[J]. Green Chemistry, 2017, 19 (8): 1932- 1939. doi: 10.1039/C6GC03604J
54	WANG Q f , HAO J Q , ZHAO Z B . Microwave-assisted conversion of fructose to 5-hydroxymethylfurfural using sulfonated porous carbon derived from biomass[J]. Australian Journal of Chemistry, 2018, 71 (1): 24- 31. doi: 10.1071/CH17154
55	DOU Y W , ZHOU S , OLDANI C , et al. 5-Hydroxymethylfurfural production from dehydration of fructose catalyzed by Aquivion@silica solid acid[J]. Fuel, 2018, 214, 45- 54. doi: 10.1016/j.fuel.2017.10.124
56	HUANG F M , SU Y W , TAO Y , et al. Preparation of 5-hydroxymethylfurfural from glucose catalyzed by silica-supported phosphotungstic acid heterogeneous catalyst[J]. Fuel, 2018, 226, 417- 422. doi: 10.1016/j.fuel.2018.03.193
57	WANG L , ZHANG L , LI H , et al. High selective production of 5-hydroxymethylfurfural from fructose by sulfonic acid functionalized SBA-15 catalyst[J]. Composites Part B:Engineering, 2019, 156, 88- 94. doi: 10.1016/j.compositesb.2018.08.044
58	AGARWAL B , KAILASAM K , SANGWAN R S , et al. Traversing the history of solid catalysts for heterogeneous synthesis of 5-hydroxymethylfurfural from carbohydrate sugars:A review[J]. Renewable and Sustainable Energy Reviews, 2018, 82, 2408- 2425. doi: 10.1016/j.rser.2017.08.088
59	LI Y , YAN X P , XU S Q , et al. One-pot synthesis of 5-hydroxymethylfurfural from carbohydrates using an inexpensive FePO₄ catalyst[J]. RSC Advances, 2015, 5 (26): 19900- 19906. doi: 10.1039/C4RA16145A
60	RUBY M P , SCHVTH F . Synthesis of N-alkyl-4-vinylpyridinium-based cross-linked polymers and their catalytic performance for the conversion of fructose into 5-hydroxymethylfurfural[J]. Green Chemistry, 2016, 18 (11): 3422- 3429. doi: 10.1039/C5GC02949J
61	ZHOU J X , TANG Z , JIANG X P , et al. Catalytic conversion of glucose into 5-hydroxymethyl-furfural over chromium-exchanged bentonite in ionic liquid-dimethyl sulfoxide mixtures[J]. Waste Biomass Valorization, 2016, 7 (6): 1- 12.
62	SAHA B , ABU-OMAR M M . Advances in 5-hydroxymethylfurfural production from biomass in biphasic solvents[J]. Green Chemistry, 2014, 16 (1): 24- 38.
63	BURKET C, SABESAN S. Process for furfural production from biomass: US 524924[P]. 2013-09-03.
64	ROSATELLA A A , SIMEONOV S P , FRADE R F M , et al. 5-Hydroxymethylfurfural (HMF) as a building block platform:Biological properties, synthesis and synthetic applications[J]. Green Chemistry, 2011, 13 (4): 754- 793. doi: 10.1039/c0gc00401d
65	VASUDEVAN V , MUSHRIF S H . Insights into the solvation of glucose in water, dimethyl sulfoxide (DMSO), tetrahydrofuran (THF) and N, N-dimethylformamide (DMF) and its possible implications on the conversion of glucose to platform chemicals[J]. RSC Advances, 2015, 5, 20756- 20763. doi: 10.1039/C4RA15123B
66	ZHANG T , KUMAR R , WYMAN C E . Enhanced yields of furfural and other products by simultaneous solvent extraction during thermochemical treatment of cellulosic biomass[J]. RSC Advances, 2013, 3, 9809- 9819. doi: 10.1039/c3ra41857j
67	CAI C M , ZHANG T , KUMAR R , et al. THF co-solvent enhances hydrocarbon fuel precursor yields from lignocellulosic biomass[J]. Green Chemistry, 2013, 15 (11): 3140- 3145. doi: 10.1039/c3gc41214h
68	CAI C M , NAGANE N , KUMAR R , et al. Coupling metal halides with a co-solvent to produce furfural and 5-HMF at high yields directly from lignocellulosic biomass as an integrated biofuels strategy[J]. Green Chemistry, 2014, 16 (8): 3819- 3829. doi: 10.1039/C4GC00747F
69	SHUAI L , LUTERBACHER J . Organic solvent effects in biomass conversion reactions[J]. ChemSusChem, 2016, 9 (2): 133- 155. doi: 10.1002/cssc.v9.2
70	QI L , MUI Y F , LO S W , et al. Catalytic conversion of fructose, glucose, and sucrose to 5-(hydroxymethyl) furfural and levulinic and formic acids in γ-valerolactone as a green solvent[J]. ACS Catalysis, 2014, 4 (5): 1470- 1477. doi: 10.1021/cs401160y
71	ZHANG L X , YU H B , WANG P , et al. Production of furfural from xylose, xylan and corncob in gamma-valerolactone using FeCl₃·6H₂O as catalyst[J]. Bioresource Technology, 2014, 151, 355- 360. doi: 10.1016/j.biortech.2013.10.099
72	GVRBVZ E I , ALONSO D M , BOND J Q , et al. Reactive extraction of levulinate esters and conversion to γ-valerolactone for production of liquid fuels[J]. ChemSusChem, 2011, 4 (3): 357- 361. doi: 10.1002/cssc.v4.3
73	MOTAGAMWALA A H, WON W, SENER C, et al. Toward biomass-derived renewable plastics: Production of 2, 5-furandicarboxylic acid from fructose[J/OL]. Science Advances, 2018, 4(1): 1-8[2018-04-22]. http://advances.sciencemag.org/content/4/1/eaap9722.full.DOI:10.1126/sciadv.aap9722.
74	ANTONYRAJ C A , JEONG J , KIM B , et al. Selective oxidation of HMF to DFF using Ru/γ-alumina catalyst in moderate boiling solvents toward industrial production[J]. Journal of Industrial & Engineering Chemistry, 2013, 19 (3): 1056- 1059.
75	LIU B , REN Y , ZHANG Z . Aerobic oxidation of 5-hydroxymethylfurfural into 2, 5-furandicarboxylic acid in water under mild conditions[J]. Green Chemistry, 2015, 17 (3): 1610- 1617. doi: 10.1039/C4GC02019G
76	HAN X W , LI C Q , GUO Y , et al. N-doped carbon supported Pt catalyst for base-free oxidation of 5-hydroxymethylfurfural to 2, 5-furandicarboxylic acid[J]. Applied Catalysis A:General, 2016, 526, 1- 8. doi: 10.1016/j.apcata.2016.07.011
77	VENTURA M , LOBEFARO F , GIGLIO E D , et al. Selective aerobic oxidation of 5-hydroxymethylfurfural to 2, 5-diformylfuran or 2-formyl-5-furancarboxylic acid in water by using MgO·CeO₂ mixed oxides as catalysts[J]. ChemSusChem, 2018, 11 (8): 1305- 1315. doi: 10.1002/cssc.v11.8
78	SCHOLZ D , AELLIG C , HERMANS I . Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-(hydroxymethyl)furfural[J]. ChemSusChem, 2014, 7 (1): 268- 275. doi: 10.1002/cssc.v7.1
79	KONG X , ZHENG R X , ZHU Y F , et al. Rational design of Ni-based catalysts derived from hydrotalcite for selective hydrogenation of 5-hydroxymethylfurfural[J]. Green Chemistry, 2015, 17 (4): 2504- 2514. doi: 10.1039/C5GC00062A
80	YANG P P , XIA Q N , LIU X H , et al. Catalytic transfer hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural to 2, 5-dimethylfuran over Ni-Co/C catalyst[J]. Fuel, 2017, 187, 159- 166. doi: 10.1016/j.fuel.2016.09.026
81	LI S S , CHEN F , LI N , et al. Synthesis of renewable triketones, diketones, and jet-fuel range cycloalkanes with 5-hydroxymethylfurfural and ketones[J]. ChemSusChem, 2017, 10 (4): 711- 719. doi: 10.1002/cssc.201601727

原料 raw material	反应介质 reaction medium	催化剂catalyst/%¹⁾		收率/% yield	文献 reference
原料 raw material	反应介质 reaction medium	名称species	加入量adding amount	收率/% yield	文献 reference
葡萄糖glucose	DMA/LiBr	CrCl₃	6%	79	[22]
纤维素cellulose	DMA-LiCl/[EMIM]Cl	CrCl₂/HCl	6%/6%	54	[22]
玉米秸秆corn stalks	DMA-LiCl/[EMIM]Cl	CrCl₃/HCl	10%/10%	48	[22]
葡萄糖glucose	[BMIM][Cl]	CrCl₃	6%	91	[23]
葡萄糖glucose	ChCl	CrCl₂	10%	45	[24]
葡萄糖glucose	H₂O	ZnSO₄	5%	15	[25]
果糖fructose	[BMIM]Cl	CrCl₃·6H₂O	10%	75	[26]
果糖fructose	[C₂MIM]Br	ErCl₃·6H₂O	6%	92	[27]
果糖fructose	[BMIM]Cl	IrCl₃	7%	89	[28]
纤维素cellulose	H₂O-THF	AlCl₃	40%	37	[29]
果糖fructose	[BMIM]Cl	NbCl₅	20%	79	[30]
果糖fructose	[BMIM]Cl/DMSO	GeCl₄	10%	70	[31]
果糖fructose	[BMIM]Cl	ScCl₃	10%	95	[32]
琼脂糖agarose	H₂O	MgCl₂	1%^a	41	[33]
果糖fructose	CH₃NO₂	ZrCl₄	10%	73	[34]
菊粉inulin	CH₃NO₂	ZrCl₄	10%	74	[34]
葡萄糖glucose	KBr/MeCN	CrCl₃·6H₂O	10%	50	[35]
葡萄糖glucose	CPME/H₂O	AlCl₃/HCl^b	2.5%	55	[36]
甘露糖mannose	DMSO/H₂O	AlCl₃·6H₂O	10%	60	[37]

催化剂类型 catalyst type	催化剂catalyst¹⁾		原料 raw material	反应介质 reaction medium	收率/% yield	文献 reference
催化剂类型 catalyst type	名称species	加入量adding amount	原料 raw material	反应介质 reaction medium	收率/% yield	文献 reference
离子交换树脂 ion exchange resin	Amberlyst-15	1%	菊粉inulin	[BMIM]HSO₄/ [BMIM]Cl	82	[39]
	D001-cc	100%	果糖fructose	[BMIM]Cl	93	[46]
	Aquivion@SiO₂	53%	果糖fructose	DMSO	85	[55]
分子筛 molecular sieve	Taa-SBA-15	3.30%	果糖fructose	H₂O	49	[38]
	Sn-Beta^a/HCl^b	200%	葡萄糖glucose	H₂O/THF/NaCl	72	[40]
	Sn-Beta/HCl^b	3.50%	淀粉starch	H₂O/THF/NaCl	69	[40]
	H-ZSM-5	200%	微晶纤维素MCC	H₂O	46	[49]
	SBA-15-SO₃H	200%	果糖fructose	DMSO	96	[57]
碳基固体酸 carbon-based solid acid	Glu-TsOH	125%	果糖fructose	DMSO	91	[41]
	CNT-PSSA	10%	果糖fructose	DMSO	89	[45]
	LCC	10%	果糖fructose	DMSO/[BMIM]Cl	84	[44]
	碳基固体酸CS	20%	果糖fructose	DMSO	90	[51]
	SPAN	33%	果糖fructose	H₂O/DX	71	[53]
	C₂-SO₃H	50%	果糖fructose	DMSO	87	[54]
金属氧化物及其络合物 metal oxides and complexes	介孔TiO₂	50%	果糖fructose	DMA-LiCl/ [BMIM]Cl	82	[42]
	Al₂O₃-B₂O₃	40%	葡萄糖glucose	DMSO	41	[50]
	B₂O₃/ZrO₂-Al₂O₃	40%	葡萄糖glucose	DMSO	41	[52]
超强酸 superacid	SO₄^2-/ZrO₂-Al₂O₃	6%	淀粉starch	DMSO/H₂O	55	[43]
	SO₄^2-/ZrO₂-TiO₂	50%	葡萄糖glucose	H₂O/NBA	26	[48]
	AgSTA	10%	果糖fructose	过热水 superheated water	86	[47]
	AgSTA	10%	蔗糖sucrose	过热水 superheated water	63	[47]
	SiO₂-ATS-PTA	100%	葡萄糖glucose	CP/H₂O	78	[56]

底物 substrate	水固比 water-solid ratio	催化剂 catalyst	有机相 organic phase	收率/% yield	文献 reference
枫木maple	20:1	H₂SO₄	MIBK/两相biphase	36	[66]
枫木maple	5:1	H₂SO₄	THF/均相homogeneous	21	[67]
枫木maple	4:1	金属盐metal salt/H₂SO₄	THF/均相homogeneous	51	[68]
玉米秸秆corn stalks	4:1	金属盐metal salt/H₂SO₄	THF/均相homogeneous	45	[68]

[1]	马帅, 胡笑颖, 董长青, 赵莹, 王孝强, 赵锦. 生物质焦油模型化合物脱除研究进展[J]. 林产化学与工业, 2019, 39(4): 1-8.
[2]	蔡炽柳, 朱长辉, 王海永, 王晨光, 刘琪英, 马隆龙. 生物质催化制备甲烷的反应路径和催化剂研究进展[J]. 林产化学与工业, 2019, 39(3): 1-9.
[3]	许嘉琍, 张海波, 姚姝凤, 高宏, 商士斌. 林业生物质基果蔬涂膜保鲜剂的研究进展[J]. 林产化学与工业, 2019, 39(3): 10-16.
[4]	刘世奇, 张素平, 于泰莅, 蔡勤杰. 生物质与塑料共热解协同作用研究[J]. 林产化学与工业, 2019, 39(3): 34-42.
[5]	陈超, 王傲, 孙康, 卢辛成, 许伟, 蒋剑春. 生物质原料的Ni催化石墨化研究[J]. 林产化学与工业, 2019, 39(3): 94-100.
[6]	宋豫龙,李伟,徐州,刘守新. 喷雾热解制备落叶松基炭球及其电化学性能[J]. 林产化学与工业, 2019, 39(2): 9-15.
[7]	熊兴泉,王彦龙,廖旭,赖石林,张辉. 核桃壳粉负载纳米Cu催化剂的制备及[J]. 林产化学与工业, 2019, 39(2): 103-108.
[8]	许升, 吕宗泽, 易雪亭, 张文, 李志国. 纸基炭电极材料的制备及其电化学性能研究[J]. 林产化学与工业, 2018, 38(6): 42-50.
[9]	董阜豪, 陈莉晶, 郭佳雯, 徐徐, 王石发, 刘鹤. 生物质改性水性聚氨酯的合成及应用研究进展[J]. 林产化学与工业, 2018, 38(5): 1-8.
[10]	吴凯, 朱锦娇, 朱跃钊, 杨烨. 废轮胎与生物质共热解特性研究[J]. 林产化学与工业, 2018, 38(5): 53-60.
[11]	杨艳, 任浩, 翟华敏. LiCl/DMSO溶剂体系中麦草溶解性能的评价方法[J]. 林产化学与工业, 2018, 38(4): 9-12.
[12]	孙佳明, 鄂雷, 马春慧, 李伟, 刘守新. N掺杂炭气凝胶的水热制备及其金属离子吸附性能[J]. 林产化学与工业, 2018, 38(4): 20-28.
[13]	徐贵生, 何志霞, 徐志祥, 纪长浩, 王谦. 醇水共溶剂中KOH高效催化液化互花米草制备生物油[J]. 林产化学与工业, 2018, 38(4): 79-86.
[14]	叶结旺, 蒋剑春, 马中青, 章卫钢, 卢凤珠. Cu掺杂多孔金属氧化物催化竹材的定向液化[J]. 林产化学与工业, 2018, 38(3): 48-54.
[15]	张伟, 吴永明. 基于Aspen Plus的固定床生物质气化过程的建模、仿真及工艺优化[J]. 林产化学与工业, 2018, 38(3): 75-82.