亚/超临界乙醇液化玉米秸秆反应路径与机理

    Liquefaction reaction pathway and mechanism of cornstalk in sub-and super-critical ethanol

    • 摘要: 为了建立玉米秸秆在亚/超临界乙醇中进行液化各集总组分之间的主要反应路径图,考查反应过程中乙醇对产物的影响机理。该文利用集总的方法,根据产物和原料的性质将产物与原料分为气体、易挥发物、轻油、重油、固体物5个集总,考查了液化过程(升温过程和反应过程)和乙醇量对各集总产物的分布规律的影响,建立了5集总组分之间的主要液化反应路径图。结果表明,玉米秸秆在反应温度到达180℃之前主要是水溶性有机物参加反应,主要生成了挥发物、气体与少量的重油;当反应温度达到180℃之后玉米秸秆3种主要成分(纤维素、半纤维素、木质素)开始液化,主要产物是挥发物、轻油、重油和气体;液化过程中挥发物与重油之间存在着可逆反应,轻油在液化过程中发生二次反应主要生成气体。乙醇在液化过程中除了起到了传热作用和充当反应溶剂外还为反应过程提供自由基,对产物起到了重整作用。

       

      Abstract: The aim of this paper is to establish the main reaction pathway chart when the cornstalk is liquefied in the sub-and super-critical ethanol, and research the mechanism how the ethanol exert an influence on the products in the reaction. With the principle of lump, five lumps were defined based on the characteristics of the material and products, and they were gas, organic dissolved, heavy oil, volatile organic compounds and residue. According to the study of products yield of a series of liquefaction (a series of calefaction and a series of reaction) and effect of the content of ethanol on products yield, the lumped components of complex reaction system were defined and a reaction network was proposed. The results showed that the main reactant was cornstalk water soluble extracts before the reaction temperature came to 180℃ and the main products were gas, volatile organic compounds and a little heavy oil. Then the three main components of cornstalk (cellulose, hemicellulose, lignin) began to react after the reaction had came to 180℃, and the main products were gas, volatile organic compounds, heavy oil and organic dissolved. In the liquefaction process there was reversible reaction between the heavy oil and volatile organic compounds; organic dissolved was mainly transformed into gas in the secondary reaction. In the liquefaction process ethanol not only transferred heat, acted as the solvent of the reaction, but also supplied radicals for the reaction, and these radicals restructured the products of the liquefaction.

       

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