| 磷酸催化热解木质素模化物的反应机理研究 |
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| 引用本文： | 蒋晓燕,陆强,楚化强,胡斌,刘吉,董长青. 磷酸催化热解木质素模化物的反应机理研究[J]. 太阳能学报, 2020, 0(2): 6-12 |
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| 作者姓名： | 蒋晓燕 陆强 楚化强 胡斌 刘吉 董长青 |
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| 作者单位： | 华北电力大学生物质发电成套设备国家工程实验室;安徽工业大学能源与环境学院 |
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| 基金项目： | 国家自然科学基金(51576064);北京市科技新星(Z171100001117064);中央高校基本科研业务费(2016YQ05;2016XS54)。 |
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| 摘 要： | 采用密度泛函理论计算及快速热解-气相色谱/质谱联用(Py-GC/MS)实验相结合的方法,研究磷酸对β-O-4型木质素二聚体模型化合物苯乙基苯基醚(PPE)热解过程的影响。计算结果表明:磷酸以氢键方式与PPE结合形成复合物H3PO4-PPE,并影响PPE的热解反应。在非催化热解过程中,PPE主要发生Cβ-O键、Cα-Cβ键均裂反应和协同断裂反应(逆烯反应和Maccoll消除反应);在磷酸催化作用下,Cβ-O键、Cα-Cβ键均裂反应的能垒会升高,而上述2种协同断裂反应的能垒会降低,同时还会促进一种新协同断裂反应的发生,且其反应活性优于Cβ-O键、Cα-Cβ键均裂反应、逆烯反应和Maccoll消除反应。实验结果表明,磷酸可促进PPE协同断裂反应的发生,同时抑制均裂反应的发生,与计算结果相符。
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| 关 键 词： | 磷酸 木质素 热解 催化反应机理 密度泛函理论 |
MECHANISM STUDY ON PYROLYSIS OF LIGNIN MODEL COMPOUND CATALYZED BY PHOSPHORIC ACID |
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| Jiang Xiaoyan,Lu Qiang,Chu Huaqiang,Hu Bin,Liu Ji,Dong Changqing. MECHANISM STUDY ON PYROLYSIS OF LIGNIN MODEL COMPOUND CATALYZED BY PHOSPHORIC ACID[J]. Acta Energiae Solaris Sinica, 2020, 0(2): 6-12 |
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| Authors: | Jiang Xiaoyan Lu Qiang Chu Huaqiang Hu Bin Liu Ji Dong Changqing |
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| Affiliation: | (National Engineering Laboratory for Biomass Power Generation Equipment,North China Electric Power University,Beijing 102206,China;School of Energy and Environment,Anhui University of Technology,Maanshan 243002,China) |
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| Abstract: | Density functional theory calculations and Py-GC/MS(pyrolysis-gas chromatography/mass spectrometry)experiments are conducted to reveal the influence of phosphoric acid on the pyrolysis process of β-O-4 type lignin dimer model compound phenethyl phenyl ether(PPE). The calculation results indicate that phosphoric acid will combine with PPE through hydrogen bond to form H3PO4-PPE complex and affect its pyrolysis reactions. In the non-catalytic pyrolysis process,PPE mainly decomposes through Cβ-O bond and Cα- Cβ bond homolytic reactions and concerted decomposition reactions(retro-ene fragmentation and Maccoll elimination reactions). Under the H3PO4-catalyzed pyrolysis condition,the energy barriers of Cβ-O bond and Cα- Cβ bond homolytic reactions will increase,while the energy barriers of the above two concerted decomposition reactions will decrease. Simultaneously,a unique concerted decomposition reaction will occur,which is superior to Cβ-O bond and Cα- Cβ bond homolytic reactions,retro-ene fragmentation reaction and Maccoll elimination reaction. The experimental results verify that phosphoric acid can promote the concerted decomposition reactions of PPE while inhibit the homolytic reactions,which agrees well with the calculation results. |
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| Keywords: | phosphoric acid lignin pyrolysis catalytic reaction mechanism density functional theory |
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