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基于组合动力学的农业残余生物质热解的热重动力学研究。

Thermogravimetric kinetic study of agricultural residue biomass pyrolysis based on combined kinetics.

机构信息

School of Environmental Science & Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.

School of Environmental Science & Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.

出版信息

Bioresour Technol. 2016 Nov;219:510-520. doi: 10.1016/j.biortech.2016.07.136. Epub 2016 Aug 3.

Abstract

Pyrolytic kinetic of an agricultural residue (AR) feedstock, a mixture of plants (cotton, wheat, rich, corn) stems, was investigated based on combined kinetics. The most suitable mechanism for AR one-step pyrolysis was f(α)=(1-α)(1.1816)α(-1.8428) with kinetic parameters of: apparent activation energy 221.7kJ/mol, pre-exponential factor 4.17E16s(-1). Pyrolysis of AR feedstock could not be described by one-step reaction attributes to heterogeneous features of pyrolysis processes. Combined kinetics three-parallel-reaction (CK-TPR) model fitted the pyrolysis experimental data very well. Reaction mechanisms for pseudo hemicelluloses, cellulose, lignin in CK-TPR model was f(α)=(1-α)(1.6244)α(-0.3371)-ln(1-α), f(α)=(1-α)(1.0597)α(-0.6909)-ln(1-α) and f(α)=(1-α)(2.9577)α(-4.7719), respectively. Apparent activation energy of three pseudo components followed the order of Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol). Mechanism of hemicelluloses pyrolysis could be further expressed as f(α)=(1-α)(1.4). The pyrolytic mechanism of cellulose met the Nucleation well. However, mechanism of lignin pyrolysis was complex, which possibly was the combined effects of Nucleation, Diffusion, Geometrical contraction, and Power law.

摘要

基于组合动力学,研究了一种农业残余物(AR)原料——棉花、小麦、玉米等植物茎秆混合物的热解动力学。AR 一步热解最适合的机理函数为 f(α)=(1-α)(1.1816)α(-1.8428),动力学参数为:表观活化能 221.7kJ/mol,指前因子 4.17E16s(-1)。由于热解过程的多相性,AR 热解不能用一步反应来描述。组合动力学三平行反应(CK-TPR)模型很好地拟合了热解实验数据。CK-TPR 模型中半纤维素、纤维素和木质素的反应机理分别为 f(α)=(1-α)(1.6244)α(-0.3371)-ln(1-α)、f(α)=(1-α)(1.0597)α(-0.6909)-ln(1-α)和 f(α)=(1-α)(2.9577)α(-4.7719)。三个伪组分的表观活化能依次为 Elignin(197.3kJ/mol)>Ecellulose(176.3kJ/mol)>Ehemicelluloses (151.1kJ/mol)。半纤维素热解的机理可以进一步表示为 f(α)=(1-α)(1.4)。纤维素的热解机理符合成核机理。然而,木质素热解的机理比较复杂,可能是成核、扩散、几何收缩和幂律的综合作用。

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