刘迎新¹,曾茂¹,楼炯涛²,刘晓爽¹,舒慧敏¹,魏作君²

• 1:浙江工业大学 药学院，催化加氢研发基地，浙江杭州 310014
• 2:浙江大学生物质化工教育部重点实验室
• 3:浙江大学 化学工程与生物工程学院 制药工程研究所，浙江 杭州 310027

摘要(Abstract)：

2，5-二甲基呋喃是21世纪最有发展前景的生物质能源之一。由生物质方法制备2，5-二甲基呋喃是目前研究的热点。文章综述了近年来由碳水化合物和5-羟甲基糠醛制备2，5-二甲基呋喃的研究成果，重点讨论了反应机理、催化反应体系和常用溶剂等方面的进展。目前该反应体系中使用的催化剂以负载的单金属Ru、Pd、Ni，双金属催化剂以及金属-氧化态金属催化剂为主；常用溶剂包括四氢呋喃和醇类。从生物质一步制备2，5-二甲基呋喃有利于降低反应成本，提高碳水化合物的利用率，是未来值得研究的方向。

关键词(KeyWords)： 2,5-二甲基呋喃;5-羟甲基糠醛;选择性加氢;反应机理;金属催化剂;生物质

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金（21476211）；浙江省自然科学基金（LY14B060003，LY18B060016）。

作者(Author): 刘迎新¹,曾茂¹,楼炯涛²,刘晓爽¹,舒慧敏¹,魏作君²

DOI: 10.3969/j.issn.1003-9015.2018.02.002

参考文献(References)：

• [1] Wei Z J, Lou J T, Li Z B, et al. One-pot production of 2,5-dimethylfuran from fructose over Ru/C and a Lewis-Brønsted acid mixture in N,N-dimethylformamide[J]. Catalysis Science & Technology, 2016, 6(16):6217-6225.
  [2] Li J, Liu J L, Liu H Y, et al. Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran over heterogeneous iron catalysts[J]. ChemSusChem, 2017, 10(7):1-10.
  [3] Roman-Leshkov Y, Barrett C J, Liu Z Y, et al. Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates[J]. Nature, 2007, 447(7147):982-985.
  [4] Xu N, Gong J, Huang Z. Review on the production methods and fundamental combustion characteristics of furan derivatives[J]. Renewable and Sustainable Energy Reviews, 2016, 54:1189-1211.
  [5] YANG Yue (杨越), LIU Qi-ying (刘琪英), CAI Chi-liu (蔡炽柳), et al. Advances in DMF and C5/C6 alkanes production from lignocellulose (木质纤维素催化转化制备DMF和C5/C6烷烃)[J]. Progress in Chemistry (化学进展), 2016, 28(z2):363-374.
  [6] LI Yan (李艳), WEI Zuo-jun (魏作君), CHEN Chuan-jie (陈传杰), et al. Preparation of 5-hydroxymethylfurfural by dehydration of carbohydrates (碳水化合物降解为5-羟甲基糠醛的研究)[J]. Progress in Chemistry (化学进展), 2010, 22(8):1603-1609.
  [7] Teong S P, Yi G, Zhang Y. Hydroxymethylfurfural production from bioresources:past, present and future[J]. Green Chemistry, 2014, 16(4):2015-2026.
  [8] LI Li-feng (李黎峰), SHEN Zhong-quan (沈忠权), LI Cen-yi (厉岑怡), et al. Catalytic conversion of fructose to 5-hydroxymethylfurfural by a novel sulfonated carbonaceous material (新型磺化碳基材料催化果糖制备5-羟甲基糠醛)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2016, 30(6):1341-1347.
  [9] Hu L, Lin L, Wu Z, et al. Recent advances in catalytic transformation of biomass-derived 5-hydroxymethylfurfural into the innovative fuels and chemicals[J]. Renewable and Sustainable Energy Reviews, 2017, 74:230-257.
  [10] Gawade A B, Tiwari M S, Yadav G D. Biobased green process:selective hydrogenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran under mild conditions using Pd-Cs_2.5H_0.5PW₁₂O₄₀/K-10 clay[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(8):4113-4123
  [11] Luo J, Arroyo-Ramírez L, Wei J, et al. Comparison of HMF hydrodeoxygenation over different metal catalysts in a continuous flow reactor[J]. Applied Catalysis A:General, 2015, 508:86-93.
  [12] Saha B, Bohn C M, Abu-Omar M M. Zinc-assisted hydrodeoxygenation of biomass-derived 5-hydroxymethylfurfural to 2,5-dimethylfuran[J]. ChemSusChem, 2014, 7(11):3095-101.
  [13] Zu Y, Yang P, Wang J, et al. Efficient production of the liquid fuel 2,5-dimethylfuran from 5-hydroxymethylfurfural over Ru/Co₃O₄ catalyst[J]. Applied Catalysis B:Environmental, 2014, 146(3):244-248.
  [14] Srivastava S, Jadeja G C, Parikh J. Synergism studies on alumina-supported copper-nickel catalysts towards furfural and 5-hydroxymethylfurfural hydrogenation[J]. Journal of Molecular Catalysis A:Chemical, 2017, 426(1):244-256.
  [15] Goyal R, Sarkar B, Bag A, et al. Studies of synergy between metal-support interfaces and selective hydrogenation of HMF to DMF in water[J]. Journal of Catalysis, 2016, 340:248-260.
  [16] Verevkin S P, Emel'Yanenko V N, Stepurko E N, et al. Biomass-derived platform chemicals:thermodynamic studies on the conversion of 5-hydroxymethylfurfural into bulk intermediates[J]. Industrial & Engineering Chemistry Research, 2009, 48(22):10087-10093.
  [17] Chidambaram M, Bell A T. A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids[J]. Green Chemistry, 2010, 12(7):1253.
  [18] Kong X, Zhu Y F, Zheng H Y, et al. Switchable synthesis of 2,5-dimethylfuran and 2,5-dihydroxymethyltetrahydrofuran from 5-hydroxymethylfurfural over Raney Ni catalyst[J]. RSC Advances, 2014, 4(105):60467-60472.
  [19] Shi J, Wang Y, Yu X, et al. Production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over reduced graphene oxides supported Pt catalyst under mild conditions[J]. Fuel, 2016, 163:74-79.
  [20] De S, Dutta S, Saha B. One-pot conversions of lignocellulosic and algal biomass into liquid fuels[J]. ChemSusChem, 2012, 5(9):1826-1833.
  [21] Nakagawa Y, Tamura M, Tomishige K. Catalytic reduction of biomass-derived furanic compounds with hydrogen[J]. ACS Catalysis, 2013, 3(12):2655-2668.
  [22] Birdsall A W, Miner C R, Mael L E, et al. Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide[J]. Atmospheric Chemistry & Physics Discussions, 2014, 14(14):19917-19954.
  [23] Chen M Y, Chen C B, Zada B, et al. Perovskite type oxide-supported Ni catalysts for the production of 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural[J]. Green Chemistry, 2016, 18(13):3858-3866.
  [24] Nishimura S, Ikeda N, Ebitani K. Selective hydrogenation of biomass-derived 5-hydroxymethylfurfural (HMF) to 2,5-dimethylfuran (DMF) under atmospheric hydrogen pressure over carbon supported PdAu bimetallic catalyst[J]. Catalysis Today, 2014, 232(17):89-98.
  [25] Lucas N, Kanna N R, Nagpure A S, et al. Novel catalysts for valorization of biomass to value-added chemicals and fuels[J]. Journal of Chemical Sciences, 2014, 126(2):403-413.
  [26] Nagpure A S, Venugopal A K, Lucas N, et al. Renewable fuels from biomass-derived compounds:Ru-containing hydrotalcites as catalysts for conversion of HMF to 2,5-dimethylfuran[J]. Catalysis Science & Technology, 2015, 5(3):1463-1472.
  [27] Nagpure A S, Lucas N, Chilukuri S V. Efficient preparation of liquid fuel 2,5-dimethylfuran from biomass-derived 5-hydroxymethylfurfural over Ru-NaY catalyst[J]. ACS Sustainable Chemistry & Engineering, 2015, 3(11):2909-2916.
  [28] Jae J, Zheng W, Lobo R F, et al. Production of dimethylfuran from hydroxymethylfurfural through catalytic transfer hydrogenation with ruthenium supported on carbon[J]. ChemSusChem, 2013, 6(7):1158-1162.
  [29] Hu L, Tang X, Xu J X, et al. Selective transformation of 5-hydroxymethylfurfural into the liquid fuel 2,5-dimethylfuran over carbon-supported ruthenium[J]. Industrial & Engineering Chemistry Research, 2014, 53(8):3056-3064.
  [30] Chatterjee M, Ishizaka T, Kawanami H. Hydrogenation of 5-hydroxymethylfurfural in supercritical carbon dioxide-water:a tunable approach to dimethylfuran selectivity[J]. Green Chemistry, 2014, 16(3):1543-1551.
  [31] Mitra J, Zhou X Y, Rauchfuss T. Pd/C-catalyzed reactions of HMF:decarbonylation, hydrogenation, and hydrogenolysis[J]. Green Chemistry, 2015, 17(1):307-313.
  [32] Scholz D, Aellig C, Hermans I. Catalytic transfer hydrogenation/hydrogenolysis for reductive upgrading of furfural and 5-hydroxymethylfurfural[J]. ChemSusChem, 2014, 7(1):268-75.
  [33] Shi J J, Wang Y Y, Yu X N, et al. Production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over reduced graphene oxides supported Pt catalyst under mild conditions[J]. Fuel, 2016, 163:74-79.
  [34] Kong X, Zhu Y, Zheng H, et al. Ni nanoparticles inlaid nickel phyllosilicate as a metal-acid bifunctional catalyst for low-temperature hydrogenolysis reactions[J]. ACS Catalysis, 2015, 5(10):5914-5920.
  [35] Kong X, Zheng R, Zhu Y, 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.
  [36] Iriondo A, Mendiguren A, Güemez M B, et al. 2,5-DMF production through hydrogenation of real and synthetic 5-HMF over transition metal catalysts supported on carriers with different nature[J]. Catalysis Today, 2017, 279:286-295.
  [37] Zhu Y, Kong X, Zheng H, et al. Efficient synthesis of 2,5-dihydroxymethylfuran and 2,5-dimethylfuran from 5-hydroxy-methyl-furfural using mineral-derived Cu catalysts as versatile catalysts[J]. Catalysis Science & Technology, 2015, 5(8):4208-4217.
  [38] Hansen T S, Barta K, Anastas P T, et al. One-pot reduction of 5-hydroxymethylfurfural via hydrogen transfer from supercritical methanol[J]. Green Chemistry, 2012, 14(9):2457-2461.
  [39] Zhang F, Liu Y, Yuan F, et al. Efficient production of the liquid fuel 2,5-dimethylfuran from 5-hydroxymethylfurfural in the absence of acid additive over bimetallic PdAu supported on graphitized carbon[J]. Energy & Fuels, 2017, 31(6):6364-6373.
  [40] Luo J, Yun H, Mironenko A V, et al. Mechanisms for high selectivity in the hydrodeoxygenation of 5-hydroxymethylfurfural over PtCo nanocrystals[J]. ACS Catalysis, 2016, 6(7):4095-4104.
  [41] Wang G H, Hilgert J, Richter F H, et al. Platinum-cobalt bimetallic nanoparticles in hollow carbon nanospheres for hydrogenolysis of 5-hydroxymethylfurfural[J]. Nature Materials, 2014, 13(3):294-301.
  [42] Yu L, He L, Chen J, et al. Robust and recyclable nonprecious bimetallic nanoparticles on carbonnanotubes for the hydrogenation and hydrogenolysis of 5-hydroxymethylfurfural[J]. ChemCatChem, 2015, 7(11):1701-1707.
  [43] Luo J, Monai M, Wang C, et al. Unraveling the surface state and composition of highly selective nanocrystalline Ni-Cu alloy catalysts for hydrodeoxygenation of HMF[J]. Catalysis Science & Technology, 2017, 7(8):1735-1743.
  [44] Yang P, Xia Q, Liu X, et al. Catalytic transfer hydrogenation/hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over Ni-Co/C catalyst[J]. Fuel, 2017, 187:159-166.
  [45] Yang P, Xia Q, Liu X, et al. High-yield production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over carbon supported Ni-Co bimetallic catalyst[J]. Journal of Energy Chemistry, 2016, 25(6):1015-1020.
  [46] Chen B, Li F, Huang Z, et al. Carbon-coated Cu-Co bimetallic nanoparticles as selective and recyclable catalysts for production of biofuel 2,5-dimethylfuran[J]. Applied Catalysis B:Environmental, 2017, 200:192-199.
  [47] Srivastava S, Jadeja G C, Parikh J. Influence of supports for selective production of 2,5-dimethylfuran via bimetallic copper-cobalt catalyzed 5-hydroxymethylfurfural hydrogenolysis[J]. Chinese Journal of Catalysis, 2017, 38(4):699-709.
  [48] Guo W, Liu H, Zhang S, et al. Efficient hydrogenolysis of 5-hydroxymethylfurfural to 2,5-dimethylfuran over cobalt and copper bimetallic catalyst on N-graphene-modified Al₂O₃[J]. Green Chemistry, 2016, 18(23):6222-6228.
  [49] Huang Y B, Chen M Y, Yan L, et al. Nickel-tungsten carbide catalysts for the production of 2,5-dimethylfuran from biomass-derived molecules[J]. ChemSusChem, 2014, 7(4):1068-1072.
  [50] Yang P, Cui Q, Zu Y, et al. Catalytic production of 2,5-dimethylfuran from 5-hydroxymethylfurfural over Ni/Co₃O₄ catalyst[J]. Catalysis Communications, 2015, 66(6):55-59.
  [51] Yang Y, Liu Q, Li D, et al. Selective hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran on Ru-MoO _x/C catalysts[J]. RSC Advances, 2017, 7(27):16311-16318..
  [52] CHEN Lun-gang (陈伦刚), LIU Yong (刘勇), ZHANG Xing-hua (张兴华), et al. Progress on reaction and catalyst for production of C5/C6 alkane fuels from cellulose by catalytic conversion (纤维素催化转化制备C5/C6烷烃燃料的反应与催化体系的研究进展)[J]. Chemistry and Industry of Forest Products (林产化学与工业), 2017, 37(2):22-34.
  [53] Thananatthanachon T, Rauchfuss T B. Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent[J]. Angewandte Chemie-International Edition, 2010, 49(37):6616-6618.
  [54] Insyani R, Verma D, Kim S M, et al. Direct one-pot conversion of monosaccharides into high-yield 2,5-dimethylfuran over a multifunctional Pd/Zr-based metal-organic framework@sulfonated graphene oxide catalyst[J]. Green Chemistry, 2017, 19(11):2482-2490.
  [55] Gmeiner J, Seibicke M, Behrens S, et al. Investigation of the hydrogenation of 5-methylfurfural by noble metal nanoparticles in a microcapillary reactor[J]. ChemSusChem, 2016, 9(6):583-587.
  [56] WEI Zuo-jun (魏作君), HOU Ya-xin (侯雅欣), LIU Ying-xin (刘迎新), et al. Acid-resistant performance of Ni-based hydrogenation catalysts supported by hydrophobic activated carbon (疏水活性炭负载的镍基加氢催化剂的抗酸性能)[J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2016, 30(2):391-397.
  [57] Jagadeesh R V, Surkus A E, Junge H, et al. Nanoscale Fe₂O₃-based catalysts for selective hydrogenation of nitroarenes to anilines[J]. Science, 2013, 342(6162):1073-1076.
  [58] Luo J, Yun H, Mironenko A V, et al. Mechanisms for high selectivity in the hydrodeoxygenation of 5-hydroxymethylfurfural over PtCo nanocrystals[J]. ACS Catalysis, 2016, 6(7):4095-4104.
  [59] Rozmysłowicz B, Kirilin A, Aho A, et al. Selective hydrogenation of fatty acids to alcohols over highly dispersed ReO _x/TiO₂ catalyst[J]. Journal of Catalysis, 2015, 328:197-2079.
  [60] Takeda Y, Tamura M, Nakagawa Y, et al. Characterization of Re-Pd/SiO₂ catalysts for hydrogenation of stearic acid[J]. ACS Catalysis, 2015, 5(11):7034-7047.
  [61] Usman M, Li D, Li C, et al. Highly selective and stable hydrogenation of heavy aromatic-naphthalene over transition metal phosphides[J]. Science China Chemistry, 2014, 58(4):738-746.
  [62] Hollak S A W, Gosselink R W, van Es D S, et al. Comparison of tungsten and molybdenum carbide catalysts for the hydrodeoxygenation of oleic acid[J]. ACS Catalysis, 2013, 3(12):2837-2844.
  [63] Monnier J, Sulimma H, Dalai A, et al. Hydrodeoxygenation of oleic acid and canola oil over alumina-supported metal nitrides[J]. Applied Catalysis A General, 2010, 382(2):176-180.
  [64] ZHAO Guan-hong (赵冠鸿), ZHENG Ming-yuan (郑明远), WANG Ai-qin (王爱琴), et al. Catalytic conversion of cellulose to ethylene glycol over tungsten phosphide catalysts (磷化钨催化转化纤维素制乙二醇)[J]. Chinese Journal of Catalysi s (催化学报), 2010, 31(8):928-932.
  [65] WANG An-jie (王安杰), WANG Yao (王瑶), YU Zhi-quan (遇治权), et al. Advances in hydrodeoxygenation catalysts for upgrading bio-oils (生物质油提质加氢脱氧催化剂研究进展)[J]. Journal of Dalian University of Technology (大连理工大学学报), 2016, 56(3):321-330.
  [66] WANG Dong-jun (王东军), LIU Hong-yan (刘红岩), LIU Yu-xiang (刘玉香), et al. Research progress in catalysts for biofuel hydrodeoxygenation (生物燃料加氢脱氧催化剂的研究进展)[J]. Petrochemical Technology (石油化工), 2012, 41(10):1214-1219.
  [67] SHEN Qiang (沈强), LU Chun-shan (卢春山), MA Lei (马磊), et al. Preparation of transition metal nitrides and their applications in catalysis (过渡金属氮化物的制备及其在催化中的应用)[J]. Chemical Production and Technology (化工生产与技术), 2004, 11(1):33-36.
  [68] Wang A, Zhang T. One-pot conversion of cellulose to ethylene glycol with multifunctional tungsten-based catalysts[J]. Accounts of Chemical Research, 2013, 46(7):1377.
  [69] Hu L, Lin L, Liu S J. Chemoselective hydrogenation of biomass-derived 5-hydroxymethylfurfural into the liquid biofuel 2,5-dimethylfuran[J]. Industrial & Engineering Chemistry Research, 2014, 53(24):9969-9978.
  [70] Zhang J H, Lin L, Liu S J. Efficient production of furan derivatives from a sugar mixture by catalytic process[J]. Energy & Fuels, 2012, 26(7):4560-4567.
  [71] Li H, Zhao W, Riisager A, et al. A Pd-catalyzed in situ domino process for mild and quantitative production of 2,5-dimethylfuran directly from carbohydrates[J]. Green Chemistry, 2017, 19(9):2101-2106
  [72] Upare P P, Hwang D, Hwang Y K, et al. An integrated process for the production of 2,5-dimethylfuran from fructose[J]. Green Chemistry, 2015, 17(6):3310-3313.
  [73] Xiang X, Cui J, Ding G, et al. One-step continuous conversion of fructose to 2,5-dihydroxymethylfuran and 2,5-dimethylfuran[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(9):4506-4510.
  [74] 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.
  [75] Wei Z J, Liu Y X, Dilantha T, et al. Entrainer-intensified vacuum reactive distillation process for the separation of 5-hydroxylmethylfurfural from the dehydration of carbohydrates catalyzed by a metal salt-ionic liquid[J]. Green Chemistry, 2012, 14(4):1220-1226.
  [76] Jae J, Zheng W, Karim A M, et al. The role of Ru and RuO₂ in the catalytic transfer hydrogenation of 5-hydroxymethylfurfural for the production of 2,5-dimethylfuran[J]. ChemCatChem, 2014, 6(3):848-856.
  [77] Nilges P, Schroder U. Electrochemistry for biofuel generation:production of furans by electrocatalytic hydrogenation of furfurals[J]. Energy & Environmental Science, 2013, 6(10):2925-2931.
  [78] Wei Z J, Li Y X, 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.