果糖低温快速热解制备5-羟甲基糠醛的机理研究

陆强; 廖航涛; 张阳; 张俊姣; 董长青

果糖低温快速热解制备5-羟甲基糠醛的机理研究

华北电力大学生物质发电成套设备国家工程实验室, 北京 102206

基金项目: 国家自然科学基金(51106052, 51276062);国家科技支撑计划(2012BAD30B01)。

详细信息

通讯作者:
陆强(1982-), 男, 江苏江阴人, 博士, 副教授, 主要从事生物质高效热解转化方面的研究, E-mail: qianglu@mail.ustc.edu.cn。

中图分类号: TK6
计量
- 文章访问数: 1937
- HTML全文浏览量: 32
- PDF下载量: 885
- 被引次数: 0
出版历程
- 收稿日期: 2013-02-26
- 修回日期: 2013-05-01
- 刊出日期: 2013-09-30

Reaction mechanism of low-temperature fast pyrolysis of fructose to produce 5-hydroxymethyl furfural

National Engineering Laboratory for Biomass Power Generation Equipment, North China Electric Power University, Beijing 102206, China

摘要

摘要: 提出了一种利用果糖低温快速热解制备5-羟甲基糠醛(HMF)并联产糠醛(FF)副产物的方法。通过Py-GC/MS(快速热解-气相色谱/质谱联用)实验,研究果糖快速热解的产物分布特性以及温度对HMF生成的影响。结果表明,HMF是果糖低温快速热解的最主要产物,在350 ℃下可获得最大产率,在250 ℃下可获得最高纯度,相对峰面积含量高达81.2%。此外,通过密度泛函理论计算,研究果糖热解形成HMF的五条可能反应途径。计算结果表明,果糖热解形成HMF的能量最优途径为路径1,即果糖首先发生C2位羟基与C1位氢的脱水,再发生C3位羟基与C1位羟基氢的脱水,最后发生C4位羟基与C5位氢的脱水而形成HMF。
- 果糖 /
- 快速热解 /
- 5-羟甲基糠醛 /
- Py-GC/MS /
- 密度泛函理论
Abstract: Low-temperature fast pyrolysis of fructose offered a promising way to produce 5-hydroxymethyl furfural (HMF) together with furfural (FF) as an important by-product. In this work, pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) measurements were performed to investigate the product distribution from fast pyrolysis of fructose; the effects of pyrolysis temperature on the HMF formation behaviors were considered. The results indicated that HMF is the predominant product from the fast pyrolysis of fructose; the product mixture with highest content of HMF (81.2%, determined by the gas chromatography peak areas) is obtained at 250 ℃, while the maximal yield of HMF is achieved at 350 ℃. Five possible pathways of HMF formation from fructose were considered by density functional theory (DFT). The DFT calculation results suggested that pathway 1 is most energetically favored, i.e. fructose molecule first undergoes a dehydration process by losing -OH at C2 and -H at C1 and then it is subjected to subsequent dehydrations involving -OH at C3 and -H of hydroxyl group at C1 as well as -OH at C4 and -H at C5, to form HMF.
- fructose /
- fast pyrolysis /
- 5-hydroxymethyl furfural /
- Py-GC/MS /
- density functional theory

HTML全文

参考文献(22)

BRIDGWATER A V. Review of fast pyrolysis of biomass and product upgrading[J]. Biomass Bioenergy, 2012, 38: 68-94.

ISAHAK W N R W, HISHAM M W M, YARMO M A, YUN H. A review on bio-oil production from biomass by using pyrolysis method[J]. Renew Sust Energ Rev, 2012, 16(8): 5910-5923.

朱锡锋, 陆强. 生物质快速热解制取生物油[J]. 科技导报, 2007, 25(21): 69-75. (ZHU Xi-feng, LU Qiang. Fast pyrolysis of biomass for producing bio-oil[J]. Science & Technology Review, 2007, 25(21): 69-75.)

吴逸民, 赵增立, 吴文强, 李海滨. 基于裂解气质联用分析的生物质逐级热解研究[J]. 燃料化学学报, 2010, 38(2): 168-173. (WU Yi-min, ZHAO Zeng-li, WU Wen-qiang, LI Hai-bin. Step-pyrolysis of biomass using pyrolysis-gas chromatography/mass spectrometry[J]. Journal of Fuel Chemistry and Technology, 2010, 38(2): 168-173.)

CZERNIK S, BRIDGWATER A V. Overview of applications of biomass fast pyrolysis oil[J]. Energy Fuels, 2004, 18(2): 590-598.

陆强, 朱锡锋. 利用固体超强酸催化热解纤维素制备左旋葡萄糖酮[J]. 燃料化学学报, 2011, 39(6): 425-431. (LU Qiang, ZHU Xi-feng. Production of levoglucosenone from fast pyrolysis of cellulose catalyzed by solid superacids[J]. Journal of Fuel Chemistry and Technology, 2011, 39(6): 425-431.)

WANG Z, LU Q, ZHU X F, ZHANG Y. Catalytic fast pyrolysis of cellulose to prepare levoglucosenone using sulfated zirconia[J]. Chem Sus Chem, 2011, 4(1): 79-84.

TORRI C, LESCI I G, FABBRI D. Analytical study on the production of a hydroxylactone from catalytic pyrolysis of carbohydrates with nanopowder aluminium titanate[J]. J Anal Appl Pyrol, 2009, 84(1): 25-30.

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 Chun-peng, OUYANG Ping-kai. Advances in production and application of 5-hydroxymethyl furfural[J]. Chemical Industry and Engineering Progress, 2008, 27(5): 702-707.)

姜楠, 齐崴, 黄仁亮, 苏荣欣, 何志敏. 生物质制备5-羟甲基糠醛的研究进展[J]. 化工进展, 2011, 30(9): 1937-1945. (JIANG Nan, QI Wei, HUANG Ren-liang, SU Rong-xin, HE Zhi-min. Research progress of synthesis of 5-hydroxymethylfurfural from biomass[J]. Chemical Industry and Engineering Progress, 2011, 30(9): 1937-1945.)

LESHKOV Y R,CHHEDA J N,DUMESIC J A. Phase modifiers promote efficient production of hydroxymethylfurfural from fructose[J]. Science, 2006, 312(5782): 1933-1937.

ZHAO H, HOLLADAY J E, BROWN H, ZHANG Z C. Metal chlorides in ionic liquid solvents convert sugars to 5-hydroxymethylfurfural[J]. Science, 2007, 316(5831): 1597-1600.

PAINE J B, PITHAWALLA Y B, NAWORAL J D. Carbohydrate pyrolysis mechanisms from isotopic labeling part 4. The pyrolysis of D-glucose: The formation of furans[J]. J Anal Appl Pyrol, 2008, 83(1): 37-63.

ASSARY R S, CURTISS L A. Comparison of sugar molecule decomposition through glucose and fructose: A high-level quantum chemical study[J]. Energy Fuels, 2011, 26(2): 1344-1352.

GLENN R P, GEOFFREY N R. Pyrolysis of inulin, glucose, and fructose[J]. Carbohyd Res, 1993, 24(2): 341-359.

BECKE A D. Density-functional thermochemistry III. The role of exact exchange[J]. J Chem Phys, 1993, 98(7): 5648-5652.

ZHANG X L, LI J, YANG W H, BLASIAK W. Formation mechanism of levoglucosan and formaldehyde during cellulose pyrolysis[J]. Energy Fuels, 2011, 25(8): 3739-3746.

黄金保, 刘朝, 魏顺安, 黄晓露, 李豪杰. 纤维素热解形成左旋葡聚糖机理的理论研究[J]. 燃料化学学报, 2011, 39(8): 590-594. (HUANG Jin-bao, LIU Chao, WEI Shun-an, HUANG Xiao-lu, LI Hao-jie. A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2011, 39(8): 590-594.)

ZHANG X L, YANG W H, BLASIAK W. Thermal decomposition mechanism of levoglucosan during cellulose pyrolysis[J]. J Anal Appl Pyrol, 2012, 96: 110-119.

黄金保, 刘朝, 曾桂生, 谢宇, 童红, 李伟民. 左旋葡聚糖热解机理的密度泛函理论研究[J]. 燃料化学学报, 2012, 40(7): 807-815. (HUANG Jin-bao, LIU Chao, ZENG Gui-sheng, XIE Yu, TONG Hong, LI Wei-min. A density functional theory study on the mechanism of levoglucosan pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2012, 40(7): 807-815.)

GONZALEZ C, SCHLEGEL H B. Reaction path following in mass-weighted internal coordinates[J]. J Chem Phys, 1990, 94(14): 5523-5527.

SANDERS E B, GOLDSMITH A I, SEEMAN J I. A model that distinguishes the pyrolysis of D-glucose, D-fructose, and sucrose from that of cellulose. Application to the understanding of cigarette smoke formation[J]. J Anal Appl Pyrol, 2003, 66(1-2): 29-50.

施引文献

资源附件(0)

访问统计

点击查看大图

计量

文章访问数: 1937
HTML全文浏览量: 32
PDF下载量: 885
被引次数: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

留言板

果糖低温快速热解制备5-羟甲基糠醛的机理研究

通讯作者:
陆强(1982-), 男, 江苏江阴人, 博士, 副教授, 主要从事生物质高效热解转化方面的研究, E-mail: qianglu@mail.ustc.edu.cn。

计量

Reaction mechanism of low-temperature fast pyrolysis of fructose to produce 5-hydroxymethyl furfural

计量

目录

2023年《燃料化学学报（中英文）》评优结果公布！

留言板

果糖低温快速热解制备5-羟甲基糠醛的机理研究

通讯作者: 陆强(1982-), 男, 江苏江阴人, 博士, 副教授, 主要从事生物质高效热解转化方面的研究, E-mail: qianglu@mail.ustc.edu.cn。

计量

出版历程

Reaction mechanism of low-temperature fast pyrolysis of fructose to produce 5-hydroxymethyl furfural

计量

出版历程

目录

2023年《燃料化学学报（中英文）》评优结果公布！

通讯作者:
陆强(1982-), 男, 江苏江阴人, 博士, 副教授, 主要从事生物质高效热解转化方面的研究, E-mail: qianglu@mail.ustc.edu.cn。