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    不同升温速率下绿原酸热分析动力学和热解产物研究

    Study on Thermal Analysis Kinetics and Pyrolysis Products of Chlorogenic Acid at Different Heating Rates

    • 摘要: 为深入掌握烟草中绿原酸的热解过程及热解成分释放规律,利用热重-红外-气相/质谱联用技术,结合热分析动力学弗林-沃尔-小泽Flynn-Wall-Ozawa (FWO)法,基辛格-赤平-苏诺塞Kissinger-Akahira-Sunose (KAS)法及Coats-Redfern法,研究了升温速率对绿原酸热解行为、热分析动力学及其热解产物的影响。结果显示,通过使用FWO法、KAS法及Coats-Redfern法计算不同升温速率下绿原酸热解3个阶段的活化能Ea和指前因子A,推断出绿原酸热解3个阶段可能的热解机理分别为三维扩散控制Mample单行法则,三维扩散球形对称Jander方程及三维扩散G-B方程。红外光谱显示,在氮气氛围中,绿原酸热解主要产生二氧化碳,少量的一氧化碳,以及来自水、苯酚和羧酸中典型吸收的-OH官能团。气相/质谱结果则表明,升温速率对绿原酸热解产物种类影响较小,但对热解产物含量有一定影响。绿原酸在360 ℃的主要热解产物种类为酚类、苯系物、呋喃类、酮醛类及杂环类等。本研究可为卷烟产品数值模拟提供相关热解参数,更好指导加热不燃烧及传统卷烟产品设计。

       

      Abstract: To have an in-depth understanding of the pyrolysis process and the pyrolysis product release law of chlorogenic acid in tobacco, the effects of heating rates on the pyrolysis behavior, thermal analysis kinetics, and pyrolysis products of chlorogenic acid were investigated by TG-FTIR-GC/MS, coupling with the thermal analysis kinetics methods of Flynn-Wall-Ozawa (FWO), Kissinger-Akahira-Sunose (KAS), and Coats-Redfern. The activation energy Ea and exponential factor A in three pyrolysis stages of chlorogenic acid at different heating rates were calculated by the method of FWO, KAS and Coats-Redfern. It was inferred from the calculation results that the pyrolysis mechanisms of chlorogenic acid in three pyrolysis stages were three-dimensional diffusion control Mample single line rule, the three-dimensional diffusion spherical symmetric Jander equation, and the three-dimensional diffusion G-B equation, respectively. FTIR spectroscopy showed that pyrolysis products of chlorogenic acid in a nitrogen atmosphere mainly included CO2, a small amount of CO, and typically absorbed -OH functional groups from H2O, phenol, and carboxylic acids. GC/MS results indicated that the heating rate has a little effect on the chemical categories of pyrolysis products, but has a certain impact on the content of pyrolysis products. The main categories of chlorogenic acid pyrolysis product of at 360 ℃ included phenols benzene derivatives, furans, ketones, aldehydes, heterocycles, etc. This research can provide relevant pyrolysis parameters for the numerical simulation of cigarette products, which could guide the design of “heated not burn” tobacco products and traditional cigarette products.

       

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