Sun Baizhong, Liang Honglin, Che Deyong, Liu Hongpeng, Guo Shuai
School of Energy and Power Engineering, Northeast Electric Power University Jilin 132000 China
RSC Adv. 2019 Mar 19;9(16):9099-9105. doi: 10.1039/c8ra10106j. eCollection 2019 Mar 15.
A large amount of furan and its derivatives are contained in the biomass pyrolysis products, which mainly lead to the formation of combustible CO with an increase in the pyrolysis temperature; in this study, to illuminate the reaction mechanisms involved in the evolution of CO during the pyrolysis of furan and its main derivatives, quantum chemical theory has been adopted with the GGA-RPBE method, and nine possible reaction pathways have been investigated for the pyrolysis of furan, furfural (FF), furfuryl alcohol (FA) and 5-hydroxymethylfurfural (5-HMF) to generate CO. According to the calculation results, the optimal path for the pyrolysis of furan and its main derivatives to generate CO is as follows: at first, a ring opening reaction of furan occurs to form an aldehyde group, and then, decarbonylation occurs to form CO. Furthermore, the side chain functional groups on the furan ring can promote the ring opening reaction of the furan ring. In addition, the reaction energy barriers of the rate-determining step for the pyrolysis of furan, furfural, furfuryl alcohol and 5-hydroxymethylfurfural (5-HMF) to form CO have been determined as 343 kJ mol, 330 kJ mol, 317 kJ mol and 363 kJ mol, respectively.
生物质热解产物中含有大量的呋喃及其衍生物，随着热解温度的升高，这些物质主要导致可燃一氧化碳的生成；在本研究中，为阐明呋喃及其主要衍生物热解过程中一氧化碳生成所涉及的反应机理，采用了量子化学理论和GGA-RPBE方法，研究了呋喃、糠醛（FF）、糠醇（FA）和5-羟甲基糠醛（5-HMF）热解生成一氧化碳的九条可能反应途径。根据计算结果，呋喃及其主要衍生物热解生成一氧化碳的最佳路径如下：首先，呋喃发生开环反应形成醛基，然后发生脱羰反应生成一氧化碳。此外，呋喃环上的侧链官能团可促进呋喃环的开环反应。另外，已确定呋喃、糠醛、糠醇和5-羟甲基糠醛（5-HMF）热解生成一氧化碳的速率决定步骤的反应能垒分别为343 kJ/mol、330 kJ/mol、317 kJ/mol和363 kJ/mol。
