磷酸催化β-D-吡喃葡萄糖热解脱水反应的密度泛函理论研究

doi:10.3969/j.issn.0253-2417.2017.01.006

摘要/Abstract

摘要： 为揭示磷酸催化纤维素热解时可以显著促进脱水反应发生的催化机理，以β-D-吡喃葡萄糖为纤维素模型化合物，利用密度泛函理论方法研究了磷酸对其热解脱水反应的作用机理。结果表明：催化热解过程中β-D-吡喃葡萄糖和磷酸通过氢键作用形成多个可能的反应复合物，氢键能够稳定反应复合物结构，不同反应复合物引发β-D-吡喃葡萄糖不同位点的1，2-脱水反应和1，3-脱水反应。与非催化相比，磷酸催化作用下β-D-吡喃葡萄糖的脱水反应活化能显著降低，其中8个位点的1，2-脱水反应活化能降低了79~129 kJ/mol，2个位点的1，3-脱水反应活化能降低了28~60 kJ/mol。β-D-吡喃葡萄糖发生1，2-脱水反应的活化能更低，比1，3-脱水反应更容易发生，且以4-OH+3-H、1-OH+2-H、3-OH+2-H和3-OH+4-H这4个位点的1，2-脱水反应为主。

关键词: 催化热解, 磷酸, 脱水反应, 纤维素, 葡萄糖, 密度泛函理论

Abstract: In order to investigate the catalytic mechanism that the dehydration reactions will be promoted by phosphoric acid in pyrolysis process, β-D-glucopyranose is selected as the model compound of cellulose, and the mechanism of pyrolytic dehydration reactions catalyzed by phosphoric acid is investigated using density functional theory method. The results indicate that during catalytic pyrolysis process, β-D-glucopyranose and phosphoric acid will interact to form several possible reaction complexes through hydrogen bonds. Different reaction complexes can initiate different 1,2-dehydration and 1,3-dehydration reactions of β-D-glucopyranose. Compared with the non-catalytic process, the activation energies of dehydration reactions decrease greatly in the phosphoric acid catalyzed process. The activation energies decrease by 79-129 kJ/mol for the eight 1,2-dehydration reactions, and 28~60 kJ/mol for the two 1,3-dehydration reactions. In addition, 1,2-dehydration is easier to occur than 1,3-dehydration in the catalytic process. And the 1,2-dehydration at 4-OH+3-H, 1-OH+2-H and 3-OH+2-H/4-H sites are predominant in the catalytic pyrolysis process.

Key words: catalytic pyrolysis, phosphoric acid, dehydration reactions, cellulose, glucose, density functional theory

中图分类号:

TQ35
TK6

胡斌, 陆强, 蒋晓燕, 张镇西, 董长青. 磷酸催化β-D-吡喃葡萄糖热解脱水反应的密度泛函理论研究[J]. 林产化学与工业, 2017, 37(1): 43-53.

HU Bin, LU Qiang, JIANG Xiaoyan, ZHANG Zhenxi, DONG Changqing. Pyrolytic Dehydration Reactions of β-D-Glucopyranose Catalyzed by Phosphoric Acid Using Density Functional Theory[J]. Chemistry and Industry of Forest Products, 2017, 37(1): 43-53.

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