Detailed chemical kinetic modeling as an innovative approach for understanding complex reactions included in thermochemical conversions of carbon resources

研究了纤维素等碳资源热化学转化过程中的反应化学。采用两级管式反应器对初生热解产物的二次气相反应动力学进行了评价。实验还通过一个详细的化学动力学模型进行了数值验证，该模型由8000多个基本步反应组成，涉及500多种化学物质。动力学模型在预测产物浓度分布方面的可接受能力使我们能够评估通过纤维素初级热解产物中的炔和二烯导致苯和萘的反应途径。在低温下，C3炔和二烯是苯的初级前体，而乙烯和乙烯乙炔的结合在高温下主要生成苯。环戊二烯是萘的重要前体。乙炔与丙基或烯丙基结合生成环戊二烯。

The reaction chemistries included in the thermochemical conversion of carbon resources such as cellulose were studied. A two-stage tubular reactor was used for evaluating the reaction kinetics of secondary vapor phase reactions of the nascent pyrolysates. Experiments were also numerically validated by a detailed chemical kinetic model consisting of more than 8000 elementary step like reactions with over 500 chemical species. Acceptable capabilities of the kinetic model in predicting concentration profiles of the products enabled us to assess reaction pathways leading to benzene and naphthalene via the alkyne and diene from primary pyrolysates of cellulose. C3 alkyne and diene are primary precursors of benzene at low temperature, while combination of ethylene and vinylacetylene produces benzene dominantly at high temperature. Cyclopentadiene is a prominent precursor of naphthalene. Combination of acetylene with propyne or allyl radical leads to the formation of cyclopentadiene.