芬顿试剂催化糖类制备5-羟甲基糠醛

摘要

研究了在水-正丁醇双相体系中，芬顿试剂催化转化淀粉、葡萄糖和果糖为5-羟甲基糠醛（5-HMF）的反应。考察了多种影响因素，包括反应温度、反应时间、水和正丁醇比例、芬顿试剂（Fe²⁺和H₂O₂）比例，淀粉、葡萄糖和果糖为底物的5-HMF最高收率分别达到46.5%、47.4%和61.7%。探讨了芬顿试剂催化糖类制备5-HMF的作用机理，即芬顿试剂可以降解淀粉为葡萄糖，催化葡萄糖异构化为果糖，催化果糖生成5-HMF。

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	武艳
	杨真真
	齐崴
	苏荣欣
	何志敏

关键词：淀粉葡萄糖果糖 5-羟甲基糠醛芬顿催化

Abstract：

An efficient process for preparation of 5-hydroxymethylfurfural (5-HMF) from starch, glucose and fructose was developed via the Fenton reaction in water-butanol two-phase system. The influence factors of the reaction was investigated via the Fenton, including temperature, reaction time, the ratio of water to butanol, and the ratio of Fenton (Fe²⁺ and H₂O₂). The optimal conditions were obtained and the highest 5-HMF yields from starch, glucose and fructose were 46.5%,47.4% and 61.7%, respectively. Finally the mechanism of the Fenton reaction was discussed and found that Fenton could degrade starch to glucose, catalyze glucose to fructose and convert fructose to 5-HMF.

Keywords： starch； glucose； fructose； 5-hydroxymethylfurfural； Fenton； catalyze

Received 2016-05-09;

Fund:

天津市自然科学基金项目（2016）；北洋青年学者计划项目（2012）。

Corresponding Authors: 齐崴,E-mail:qiwei@tju.edu.cn。 Email: qiwei@tju.edu.cn

About author: 武艳(1989-),男,硕士研究生,研究方向为生物质利用。

引用本文:

武艳, 杨真真, 齐崴, 苏荣欣, 何志敏.芬顿试剂催化糖类制备5-羟甲基糠醛[J]. 化学工业与工程, 2018,35(1): 15-21

Wu Yan, Yang Zhenzhen, Qi Wei, Su Rongxin, He Zhimin.Conversion from Carbohydrate to 5-Hydroxymethylfurfural via the Fenton Reaction[J]. Chemcial Industry and Engineering, 2018,35(1): 15-21

[1] Gallezot P. Conversion of biomass to selected chemical products[J]. Chemical Society Reviews, 2012, 41(4):1538-1558
[2] 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
[3] 王军,张春鹏,欧阳平凯. 5-羟甲基糠醛制备及应用的研究进展[J]. 化工进展,2008, 27(5):702-707 Wang Jun, Zhang Chunpeng, Ouyang Pingkai. Advances in production and application of 5-hydroxymethyl furfural[J]. Chemical Industry and Engineering Progress,2008, 27(5):702-707(in Chinese)
[4] 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
[5] 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
[6] Gliozzi G, Innorta A, Mancini A, et al. Zr/P/O catalyst for the direct acid chemo-hydrolysis of non-pretreated microcrystalline cellulose and softwood sawdust[J]. Applied Catalysis B:Environmental, 2014(145):24-33
[7] Qi X, Watanabe M, Aida T M, et al. Catalytic dehydration of fructose into 5-hydroxymethylfurfural by ion-exchange resin in mixed-aqueous system by microwave heating[J]. Green Chemistry, 2008, 10(7):799-805
[8] Qi X, Watanabe M, Aida T M, et al. Sulfated zirconia as a solid acid catalyst for the dehydration of fructose to 5-hydroxymethylfurfural[J]. Catalysis Communications, 2009, 10(13):1771-1775
[9] Yan H, Yang Y, Tong D, et al. Catalytic conversion of glucose to 5-hydroxymethylfurfural over SO₄^2-/ZrO₂ and SO₄^2-/ZrO^2-Al₂O₃ solid acid catalysts[J]. Catalysis Communications, 2009, 10(11):1558-1563
[10] Chheda J N, An-Leshkov Y R, 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
[11] Wink D A, Nims R W, Saavedra J E, et al. The Fenton oxidation mechanism:Reactivities of biologically relevant substrates with two oxidizing intermediates differ from those predicted for the hydroxyl radical[J]. Proceedings of the National Academy of Sciences, 1994, 91(14):6604-6608
[12] Chemizmu K, Fentona R. Fenton reaction-controversy concerning the chemistry[J]. Ecological Chemistry and Engineering, 2009, (16):347-358
[13] Kato D M, Elía N, Flythe M, et al. Pretreatment of lignocellulosic biomass using Fenton chemistry[J]. Bioresource Technology, 2014, 162:273-278
[14] Guo N, Caratzoulas S, Doren D J, et al. A perspective on the modeling of biomass processing[J]. Energy & Environmental Science, 2012, 5(5):6703
[15] Román-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
[16] Kang S, Liao C, Po S. Decolorization of textile wastewater by photo-Fenton oxidation technology[J]. Chemosphere, 2000, 41(8):1287-1294
[17] Qi X, Guo H, Li L. Efficient conversion of fructose to 5-hydroxymethylfurfural catalyzed by sulfated zirconia in ionic liquids[J]. Engineering Chemistry Research, 2011, 50(13):7985-7989
[18] 王超. 金属氯化物催化葡萄糖和蔗糖高效转化为5-羟甲基糠醛的研究[D]. 天津:天津大学, 2012 Wang Chao. Efficient cnoversion of glucose and sucrose to 5-hydroxymethy1furfural catalyzed by metal chlorides[D]. Tianjin:Tianjin University, 2012(in Chinese)
[19] 邓小晖,张海涛,曹国民,等. 芬顿试剂处理废水的研究与应用进展[J]. 上海化工, 2007, 32(8):1-5 Deng Xiaohui, Zhang Haitao, Cao Guomin, et al. Progress of the research and application of Fenton reagent for wastewater treatment[J]. Shanghai Chemical Industry, 2007, 32(8):1-5(in Chinese)
[20] Qi X, Watanabe M, Aida T M, et al. Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids[J]. Green Chemistry, 2009, 11(9):1327-1331
[21] 苏琼,王彦斌. 淀粉精细化学品合成及其应用[M]. 北京:民族出版社, 2004
[22] 王伟,初本莉,王嘉承. 过硫酸盐法和芬顿法降解有机物的对比研究[J]. 广州化工, 2013, 41(22):4-7 Wang Wei, Chu Benli, Wang Jiachen. The comparative study of degradation of organic pollutants between persulfate method and Fenton method[J]. Guangzhou Chemical Industry, 2013, 41(22):4-7(in Chinese)
[23] 邵晓梅. 室温芬顿试剂高级氧化技术条件选择及效果评价研究[D]. 江苏苏州:苏州大学, 2009 Shao Xiaomei. Study on the effect appraisal and factor choice of Fenton advanced oxidation processes at room temperature[D]. Jiangsu Suzhou:Suzhou University, 2009(in Chinese)
[24] 范金石,赵剑雄,陈国华. 芬顿试剂降解壳聚糖[J]. 化学工程师, 2007(5):3-6 Fan Jinshi, Zhao Jianxiong, Chen Guohua. Degradation of chitosan by Fenton reagent[J]. Chemical Engineer, 2007(5):3-6(in Chinese)
[25] Qian X. Mechanisms and energetics for Brønsted acid-catalyzed glucose condensation, dehydration and isomerization reactions[J]. Topics in Catalysis, 2012, 55(3/4):218-226