棕榈壳酶解-温和酸解木质素的结构及热解特性研究

Structure and pyrolysis characteristics of enzymatic/mild acidolysis lignin isolated from palm kernel shell

  • 摘要: 采用酶解/温和酸解法提取了棕榈壳和麦秆的木质素(EMALs),利用傅里叶红外光谱(FT-IR)、裂解器-气相色谱质谱联用(Py-GC/MS)和热重-红外联用(TG-FTIR)技术,对两种EMALs的化学结构和热解特性进行了对比研究,并采用Ozawa-Flynn-Wall方法计算了其热解反应的活化能。结果表明,棕榈壳EMAL和麦秆EMAL均为HGS型木质素。500℃下,两种EMALs的热解产物主要包括酚类、酸类和少量的醇类、醛酮类等化合物;棕榈壳EMAL热解酚类产物中H、G、S型单体酚类的比例分别为47.61%、25.64%和17.18%,而麦秆EMAL分别为23.66%、51.90%和15.50%。在热解反应主失重区(200-380℃),棕榈壳EMAL的主失重速率(50.80%/min)低于麦秆EMAL(78.63%/min);但棕榈壳EMAL热解同时存在肩状失重峰(265℃,27.40%/min),这与其较多H结构产物的释放相关。H型结构产物释放的放热效应降低了棕榈壳EMAL热解初期的活化能(20%,127.92 kJ/mol),同时使其热解过程(20%-80%)的平均活化能(152.32 kJ/mol)低于麦秆EMAL(161.75 kJ/mol)。

     

    Abstract: Firstly, lignin of palm kernel shell (PKS) and wheat straw (WS) were isolated by enzymatic/mild acidolysis method (EMAL). Then the functional groups and thermal decomposition characteristics of the two EMALs were analyzed with Fourier transform infrared spectroscopy (FT-IR), pyrolysis-gas chromatography/mass spectrometry (Py-GC/MS) and TG-FTIR. At last, the Ozawa-Flynn-Wall method was used to calculate the activation energy of pyrolysis of the two EMALs. FT-IR result show that both PKS-EMAL and WS-EMAL are Type HGS. Phenols, acids, few of alcohols, aldehydes and ketones are detected in volatile products from 500℃ pyrolysis of the two EMALs. Meanwhile, H-type, G-type and S-type phenols with proportions of 47.61%, 25.64% and 17.18% are obtained in phenolic products from PKS-EMAL pyrolysis; while they are 23.66%, 51.90% and 15.50%, respectively, in phenolic products of WS-EMAL. During 200-380℃, the main weight loss rate of PKS-EMAL pyrolysis is 50.80%/min, which is obviously lower than that (78.63%/min) of WS-EMAL. A shoulder peak of 27.40%/min at 265℃ is also observed in PKS-EMAL pyrolysis, which is closely related to release of H-derivatives during PKS-EMAL pyrolysis. The activation energy (127.92 kJ/mol) of PKS-EMAL pyrolysis at a conversion of 20% reduced by the exothermic effect corresponding torelease of H-derivatives, which was the main reason that the average activation energy (152.32 kJ/mol) of PKS-EMAL pyrolysis (20%-80%) was lower than that (161.75 kJ/mol) for WS-EMAL pyrolysis.

     

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