Preparation of 5-HMF from cellulose catalyzed by SnCl4 under microwave in ZnCl2 solution
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摘要: 将纤维素溶解在ZnCl2溶液中，以SnCl4为催化剂，微波下使纤维素降解成5-羟甲基糠醛（5-HMF）。实验考察了微波功率、纤维素的质量、ZnCl2溶液浓度、反应时间及催化剂与纤维素物质的量比等对5-HMF产率的影响。结果表明，以SnCl4为催化剂，在优化条件：1.0 g纤维素溶解在100 mL 70% ZnCl2溶液中，微波功率为420 W，降解反应9 min，SnCl4与纤维素物质的量比2：1下，5-HMF的产率达到39.4%。Abstract: Conversion of cellulose into 5-hydroxymethylfurfural (5-HMF) catalyzed by SnCl4 in ZnCl2 solution with microwave was studied. The effects of microwave power, cellulose content, concentration of ZnCl2, reaction time and the molar ratio of SnCl4 to cellulose on the yields of 5-HMF were investigated. The results showed that under the optimum reaction condition of 1.0 g cellulose dissolved in 100 mL 70% ZnCl2 solution, the molar ratio of SnCl4 to cellulose of 2:1, the microwave power of 420 W, and the reaction time of 9 min, the yield of 5-HMF reaches 39.4%.
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Key words:
- microwave /
- cellulose /
- ZnCl2 solution /
- SnCl4 /
- 5-HMF
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图 1 标准样品和降解产物的HPLC谱图
Figure 1 HPLC chromatogram of standard samples and degradation products
(a): standard samples of 5-HMF and FUR; (b): degradation products
图 2 不同催化剂对5-HMF产率的影响
Figure 2 Effect of different catalysts on the yield of 5-HMF reaction condition: 100 mL 70% ZnCl2 solution, 1 g cellulose, the molar ratio of catalysts to cellulose=2 :1, 420 W, 9 min
图 3 微波功率对5-HMF产率的影响
Figure 3 Effect of microwave power on the yield of 5-HMF reaction condition: 100 mL 70% ZnCl2 solution, 1 g cellulose, the molar ratio of SnCl4 to cellulose=2 :1, 9 min
图 4 纤维素质量对5-HMF产率的影响
Figure 4 Effect of the quantity of cellulose on the yield of 5-HMF reaction condition: 100 mL 70% ZnCl2 solution, the molar ratio of SnCl4 to cellulose=2 :1, 420 W, 9 min
图 5 SnCl4为催化剂不同浓度ZnCl2对5-HMF产率的影响
Figure 5 Effect of ZnCl2 solution of different concentrations on the yield of 5-HMF with SnCl4 as the catalyst reaction condition: 100 mL ZnCl2 solution, 1 g cellulose, the molar ratio of SnCl4 to cellulose=2 :1, 420 W, 9 min
图 6 反应时间对5-HMF产率的影响
Figure 6 Effect of reaction time on the yield of 5-HMF reaction condition: 100 mL 70% ZnCl2 solution, 1 g cellulose, the molar ratio of SnCl4 to cellulose=2 :1, 420 W
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[1] POTOČNIK J. Renewable energy sources and the realities of setting an energy agenda[J]. Science, 2007, 315(5813):810-811. doi: 10.1126/science.1139086 [2] WILEY L F, GOSTIN L O. The international response to climate change:An agenda for global health[J]. JAMA, 2009, 302(11):1218-1220. doi: 10.1001/jama.2009.1381 [3] ROSE M, PALKOVITS R. Cellulose-based sustainable polymers:State of the art and future trends[J]. Macromol Rapid Comm, 2011, 32(17):1299-1311. doi: 10.1002/marc.201100230 [4] WANG S, LIN H, CHEN J, ZHAO Y, RU B, QIU K, ZHOU J. Conversion of carbohydrates into 5-hydroxymethyl furfural in an advanced single-phase reaction system consisting of water and 1, 2-dimethoxyethane[J]. RSC Adv, 2015, 5(102):84014-84021. doi: 10.1039/C5RA18824E [5] ROSATELLA A A, SIMEONOV S P, FRADE R F, AFONSO C A. 5-Hydroxymethyl furfural (HMF) as a building block platform:Biological properties, synthesis and synthetic applications[J]. Green Chem, 2011, 13(4):754-793. doi: 10.1039/c0gc00401d [6] VAN PUTTEN R J, VAN DER WAAL J C, DE JONG E D, RASRENDRA C B, HEERES H J, DE VRIES J G. Hydroxymethyl furfural, a versatile platform chemical made from renewable resources[J]. Chem Rev, 2013, 113(3):1499-1597. doi: 10.1021/cr300182k [7] TEONG S P, YI G, ZHANG Y. Hydroxymethyl furfural production from bioresources:Past, present and future[J]. Green Chem, 2014, 16(4):2015-2026. doi: 10.1039/c3gc42018c [8] ZHANG Y, PAN J, GAN M, OU H, YAN Y, SHI W, YU L. Acid-chromic chloride functionalized natural clay-particles for enhanced conversion of one-pot cellulose to 5-hydroxymethyl furfural in ionic liquids[J]. RSC Adv, 2014, 4(23):11664-11672. doi: 10.1039/c3ra46561f [9] ZHOU L, HE Y, MA Z, LIANG R, WU T, WU Y. One-step degradation of cellulose to 5-hydroxymethyl furfural in ionic liquid under mild conditions[J]. Carbohyd Polym, 2015, 117:694-700. doi: 10.1016/j.carbpol.2014.10.062 [10] CAO N J, XU Q, CHEN L F. Acid hydrolysis of cellulose in zinc chloride solution[J]. Appl Biochem Biotechnol, 1995, 51(1):21-28. doi: 10.1007/BF02933408 [11] SEN S, MARTIN J D, ARGYROPOULOS D S. Review of cellulose non-derivatizing solvent interactions with emphasis on activity in inorganic molten salt hydrates[J]. ACS Sustain Chem Eng, 2013, 1(8):858-870. doi: 10.1021/sc400085a [12] LAI B, ZHAO Y, YAN L. Preparation of 5-hydroxymethyl furfural from cellulose via fast depolymerization and consecutively catalytic conversion[J]. Chin J Chem Phys, 2013, 26(3):355-360. doi: 10.1063/1674-0068/26/03/355-360 [13] LIU B, ZHANG Z, ZHAO Z K. Microwave-assisted catalytic conversion of cellulose into 5-hydroxymethyl furfural in ionic liquids[J]. Chem Eng J, 2013, 215:517-521. doi: 10.1016/j.cej.2012.11.019 [14] DE S, DUTTA S, SAHA B. Microwave assisted conversion of carbohydrates and biopolymers to 5-hydroxymethyl furfural with aluminium chloride catalyst in water[J]. Green Chem, 2011, 13(10):2859-2868. doi: 10.1039/c1gc15550d [15] QI X, WATANABE M, AIDA T M, SMITH R L. Fast transformation of glucose and di/polysaccharides into 5-hydroxymethyl furfural by microwave heating in an Ionic liquid/catalyst system[J]. ChemSusChem, 2010, 3(9):1071-1077. doi: 10.1002/cssc.v3:9 [16] SHI N, LIU Q, WANG T, ZHANG Q, TU J, MA L. Conversion of cellulose to 5-hydroxymethylfurfural in water-tetrahydrofuran and byproducts Identification[J]. Chin J Chem Phys, 2014, 27(6):711-717. doi: 10.1063/1674-0068/27/06/711-717 [17] WANG Y, PEDERSEN C M, DENG T, QIAO Y, HOU X. Direct conversion of chitin biomass to 5-hydroxymethyl furfural in concentrated ZnCl 2 aqueous solution[J]. Bioresource Technol, 2013, 143:384-390. doi: 10.1016/j.biortech.2013.06.024 [18] 朱萍, 汤颖, 薛青松, 李剑锋, 路勇.微波辅助的金属氯化物Lewis酸催化纤维素水解[J].燃料化学学报, 2009, 37(2):244-247. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17436.shtmlZHU Ping, TANG Ying, XUE Qing-song, LI Jian-feng, LU Yong. Microwave-assisted hydrolysis of cellulose using metal chloride as Lewis acid catalysts[J]. J Fuel Chem Technol, 2009, 37(2):244-247. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17436.shtml [19] CHOUDHARY V, MUSHRIF S H, HO C, ANDERKO A, NIKOLAKIS V, MARINKOVIC N S, FRENKEL A Z, SANDLER S I, VLACHOS D G. Insights into the interplay of Lewis and Br nsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl) furfural and levulinic acid in aqueous media[J]. J Am Chem Soc, 2013, 135(10):3997-4006. doi: 10.1021/ja3122763 [20] 杨磊, 黎钢, 杨芳, 刘雅莉, 张松梅.微波辐射下氯化锌催化纤维素转化为呋喃类物质的研究[J].燃料化学学报, 2012, 40(3):326-330. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17904.shtmlYANG Lei, LI Gang, YANG Fang, LIU Ya-li, ZHANG Song-mei. Conversion of cellulose to furans catalyzed by zinc chloride under microwave irradiation[J]. J Fuel Chem Technol, 2012, 40(3):326-330. http://rlhxxb.sxicc.ac.cn/CN/abstract/abstract17904.shtml [21] VANOYE L, FANSELOW M, HOLBREY J D, ATKINS M P, SEDDON K R. Kinetic model for the hydrolysis of lignocellulosic biomass in the ionic liquid, 1-ethyl-3-methyl-imidazolium chloride[J]. Green Chem, 2009, 11(3):390-396. doi: 10.1039/b817882h [22] WRIGSTEDT P, KESKIVÄLI J, REPO T. Microwave-enhanced aqueous biphasic dehydration of carbohydrates to 5-hydroxymethyl furfural[J]. RSC Adv, 2016, 6(23):18973-18979. doi: 10.1039/C5RA25564C -
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