半纤维素六碳糖转化为5-羟甲基糠醛的动力学

doi:10.16085/j.issn.1000-6613.2016.12.020

化工进展 ›› 2016, Vol. 35 ›› Issue (12): 3872-3878.DOI: 10.16085/j.issn.1000-6613.2016.12.020

半纤维素六碳糖转化为5-羟甲基糠醛的动力学

陈景平, 孙武星, 林海周, 茹斌, 赵源, 王树荣

浙江大学能源清洁利用国家重点实验室, 浙江杭州 310027

收稿日期:2016-05-18 修回日期:2016-06-03 出版日期:2016-12-05 发布日期:2016-12-05
通讯作者: 王树荣,教授,博士生导师。E-mail:srwang@zju.edu.cn。
作者简介:陈景平(1990-),男,硕士研究生,从事生物质液相分解制取高品位液体燃料的研究。E-mail:chenjp1001@zju.edu.cn。
基金资助:
国家自然科学基金项目（51476142）。

Kinetic of conversion of hemicellulose hexose to 5-hydroxymethylfurfural

CHEN Jingping, SUN Wuxing, LIN Haizhou, RU Bin, ZHAO Yuan, WANG Shurong

State Key Laboratory of Clean Energy Utilization, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2016-05-18 Revised:2016-06-03 Online:2016-12-05 Published:2016-12-05

摘要/Abstract

摘要： 选取甘露糖和半乳糖两种典型半纤维素六碳糖作为模化物，考察其在水相中较宽温度（100～200℃）和时间（10～240min）范围内的降解行为。实验结果表明，较高的反应温度能提高六碳糖的转化率和5-羟甲基糠醛（HMF）的产率；在200℃时甘露糖和半乳糖生成的HMF最高产率分别为26.82%和22.86%，乙酰丙酸（LA）的产率低于3%；半乳糖因容易异构化生成塔格糖而非果糖，导致其HMF产率较低。采用六碳糖平行生成HMF和Humin，随后HMF平行生成的LA和Humin的反应模型对六碳糖降解动力学进行分析，揭示了六碳糖的类型对HMF和Humin生成机制的影响。此外，针对六碳糖生成的Humin的Van Krevelen图和FTIR谱图进行分析进一步发现，Humin是通过脱水聚合生成的呋喃环基聚合物，同时其结构特征与单糖类型紧密相关。

关键词: 六碳糖, 液相分解, 5-羟甲基糠醛, 胡敏素, 动力学

Abstract: The conversion of mannose and galactose to 5-hydroxymethylfurfural(HMF)was investigated under aqueous conditions at a wide range of temperature(100~200℃)and time(10~240min)without catalyst. The results showed that higher temperature favored the decomposition of hexoses and increased the yield of HMF. At 200℃,the maximum yields of HMF for mannose and galactose were 26.82% and 22.86%,respectively,and their levulinic acid(LA)yields were at a low level below 3%. The lower yield of HMF from galactose because isomerization to tagatose is easier than that to fructose. A reaction model that hexose firstly decomposed to HMF and Humin,followed by the degradation of HMF to LA and Humin,was used to analyze the reaction kinetics. The model predicted the experiment results well. The obtained kinetic parameters revealed the varied mechanisms of HMF and Humin formation from different types of hexose. Finally,structural characterization of the Humins based on the Van Krevelen diagram and FTIR spectra showed that the Humins were furanic polymers formed by dehydration and condensation,and their structure were closely related to monosaccharide types.

Key words: hexose, liquid-phase decomposition, HMF, Humin, kinetic

中图分类号:

陈景平, 孙武星, 林海周, 茹斌, 赵源, 王树荣. 半纤维素六碳糖转化为5-羟甲基糠醛的动力学[J]. 化工进展, 2016, 35(12): 3872-3878.

CHEN Jingping, SUN Wuxing, LIN Haizhou, RU Bin, ZHAO Yuan, WANG Shurong. Kinetic of conversion of hemicellulose hexose to 5-hydroxymethylfurfural[J]. Chemical Industry and Engineering Progree, 2016, 35(12): 3872-3878.

参考文献

[1] SHI Y,XIA YF,LU B,et al.Emission inventory and trends of NO_x or China,2000-2020[J].Journal of Zhejiang University-Science A (Applied Physics&Engineering),2014,15(6):454-464.
[2] WANG S R,RU B,LIN H Z,et al.Degradation mechanism of monosaccharides and xylan under pyrolytic conditions with theoretic modeling on the energy profiles[J].Bioresource Technology,2013,143:378-383.
[3] GALLEZOT P.Conversion of biomass to selected chemical products[J].Chemical Society Reviews,2012,41(4):1538-1558.
[4] 欧阳四余,徐琼,伏再辉,等.生物质转化制5-羟甲基糠醛的酸催化研究新进展[J].化工进展,2014,33(5):1077-1085.
[5] 沈翔,魏小荣,王焰新,等.SO₄^2--TiO₂/MOR新型固体酸催化果糖制备5-羟甲基糠醛[J].化工学报,2011,62(12):3411-3418.
[6] WANG S R,LIN H Z,CHEN J P,et al.Conversion of carbohydrates into 5-hydroxymethylfurfural in an advanced single-phase reaction system consisting of water and 1,2-dimethoxyethane[J].RSC Advances,2015(5):84014-84021.
[7] CLIMENT M J CORMA A,IBORRA S.Conversion of biomass platform molecules into fuel additives and liquid hydrocarbon fuels[J].Green Chemistry,2014,16(2):516-547.
[8] 梁韬.基于Py-GC/MS的半纤维素热裂解机理研究[D].杭州:浙江大学,2013.
[9] WANG S R,RU B,LIN H Z,et al.Pyrolysis behaviors of four O-acetyl-preserved hemicelluloses isolated from hardwoods and softwoods[J].Fuel,2015,150:243-251.
[10] 田龙,马晓建.丙酸预处理小麦秸秆的纤维素水解动力学[J].农业机械学报,2012(09):111-115.
[11] BINDER J B,RAINES R T.Simple chemical transformation of lignocellulose biomass into furans for fuels and chemicals[J].Journal of the America Chemical Society,2009,131(5):1979-1985.
[12] MICHAEL J A Jr,WILLIAM S L Mok.Mechanism of formation of 5-hydroxymethyl-2-furaldehyde from D-fructose and sucrose[J].Carbohydrate Research,1990,199(1):91-109.
[13] 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.
[14] MATSUMURA Y,YANACHIS,YOSHIDAT.Glucose decomposition kinetics in water at 25MPa in the temperature range of 448-673K[J].Industrial&Engineering Chemistry Research,2006,45(6):1875-1879.
[15] KUPIAINEN L,AHOLA J,TANSKANEN J.Kinetics of glucose decomposition in formic acid[J].Chemical Engineering Research&Design,2011,89(12A):2706-2713.
[16] KABYEMELA B M,ADSCHIRI T,MALALUAN R,et al.Degradation kinetics of dihydroxyacetone and glyceraldehyde in supercritical and subcritical water[J].Industrial&Engineering Chemistry Research,1997,36(6):2025-2030.
[17] KABYEMELA B M,ADSCHIRI T,MALALUAN R M,et al.Glucose and fructose decomposition in subcritical and supercritical water:detailed reaction pathway,mechanisms and kinetics[J].Industrial&Engineering Chemistry Research,1999,38(8):2888-2895.
[18] KABYEMELA B M,ADSCHIRI T,MALALUAN R,et al.Kinetics of glucose epimerization and decomposition in subcritical and supercritical water[J].Industrial&Engineering Chemistry Research,1997,36(5):1552-1558.
[19] JING Q,LV X Y.Kinetics of non-catalyzed decomposition of glucose in high-temperature liquid water[J].Chinese Journal of Chemical Engineering,2008,16(6):890-894.
[20] PATIL S K R,LUND C R F.Formation and growth of Humins via aldol addition and condensation during acid-catalyzed conversion of 5-hydroxymethylfurfural[J].Energy&Fuels,2011,25(10):4745-4755.
[21] PATIL S K R,HELTZEL J,LUND C R F.Comparision of structural features of Humins formed catalytically from glucose,fructose and 5-hydroxymethylfurfural[J].Energy&Fuels,2012,26(8):5281-5293.
[22] BINDER Joseph B,CEFALI Anthony V,BLANK Jacqueline J,et al.Mechanistic insights on the conversion of sugars into 5-hydroxymethylfurfural[J].Energy&Environmental Science,2010,3(6):765-771.
[23] 林海周,孙武星,茹斌,等.不同溶剂下葡萄糖降解制取5-羟甲基糠醛的动力学研究[J].农业机械学报,2015(11):201-207.
[24] MAYES H B,NOLTE M W,BECKHAM G T,et al.The Alpha-Bet (a) of glucose pyrolysis:computational and experimental investigations of 5-hydroxymethylfurfural and levoglucosan formation reveal implications for cellulose pyrolysis[J].ACS Sustainable Chemistry&Engineering,2014(2):1461-1473.
[25] WANG S R,LIN H Z,RU B,et al.Comparison of the pyrolysis behavior of pyrolytic lignin and milled wood lignin by using TG-FTIR analysis[J].Journal of Analytical and Applied Pyrolysis,2014,10:78-85.
[26] HOANG T M C,VAN ECK E R H,BULA W P,et al.Humin based by-products from biomass processing as a potential carbonaceous source for synthesis gas production[J].Green Chemistry,2015,17:959-972.
[27] VAN ZANDVOORT I,Wang Y,RASRENDRA C B,et al.Formation,molecular structure,and morphology of Humins in biomass conversion:influence of feedstock and processing conditions[J].ChemSusChem,2013,6(9):1745-1758.

半纤维素六碳糖转化为5-羟甲基糠醛的动力学

Kinetic of conversion of hemicellulose hexose to 5-hydroxymethylfurfural

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