Abstract: In order to explore the influence of pyrolysis temperature on the distribution of pyrolysis products of lignin, the theoretical calculations of two main pyrolysis reactions in the pyrolysis process of β-O-4 lignin dimer were carried out for each step at different pyrolysis temperatures by density functional theory B3LYP/6-31G (d,p). The energy gradients of reactants, products, intermediates and transition states for each reaction pathway were optimized, and vibration frequencies of which were calculated at different temperatures. The influence of pyrolysis temperature on the distribution of pyrolysis products was analyzed based on the variation of kinetics and thermodynamics parameters. The calculation results showed that the reaction after the cleavage of Cβ-O bond was the main reaction. When the pyrolysis temperature was below 700 K, the main products of the reaction were compounds 4, 7, 15 and small molecules including formaldehyde and ethylene, while the proportions of compounds 10, 11, 13, 14 and CO in the product were relatively low. When the pyrolysis temperature was higher than 700 K, the proportions of compound 15 and ethylene increased continuously, which were still the main products. At the same time, the proportions of compound 7 and formaldehyde decreased, while the proportions of compounds 10, 11 and CO increased. The cleavage reaction of Cα-Cβ bond was the main competing reaction. With the increasing pyrolysis temperature, the proportions of the main products including compound 4 and acetaldehyde increased continuously, the proportions of chemical 20 and CO decreased obviously, and the proportions of compound 25 and formaldehyde in the products changed a little.
何正文, 田红, 黄章俊, 胡章茂, 刘威. 基于量子化学理论的热解温度对木质素二聚体热解产物分布的影响[J]. 材料导报, 2020, 34(6): 6180-6185.
HE Zhengwen, TIAN Hong, HUANG Zhangjun, HU Zhangmao, LIU Wei. Influence of Pyrolysis Temperature on the Distribution of Pyrolysis Products of Lignin Dimer Based on Quantum Chemistry Theory. Materials Reports, 2020, 34(6): 6180-6185.
1 Roberto G, Consuelo, Antonio G L, et al. Fuel, 2017, 195, 182. 2 Ragauskas A J, Beckham G T, Biddy M J, et al. Science, 2014, 344, 709. 3 Tian J, Yang Y Q, Song J L.Journal of Cellulose Science and Technology, 2018, 26 (4), 76 (in Chinese). 田静, 杨益琴, 宋君龙. 纤维素科学与技术, 2018, 26 (4), 76. 4 Juhyon Kang, Sibel Irmak, Mark Wilkins.Renewable Energy,2019,135, 951. 5 Wang S, Ru B, Lin H, et al. Bioresource Technology, 2015, 182, 120. 6 Gu J, Liu B, Zhang Q S. Biomass Chemical Engineering, 2015, 49 (4), 7 (in Chinese). 顾洁, 刘斌, 张齐生. 生物质化学工程, 2015, 49 (4), 7. 7 Bai T T, Ren X Y, Zhang Z T. China Forest Products Industry, 2014,41 (5), 7 (in Chinese). 白甜甜, 任学勇, 张忠涛. 林产工业, 2014,41 (5), 7. 8 Li J L, Qu C T, Zhu S D. Materials Review A: Review Papers, 2018,32 (9),3023 (in Chinese). 李金灵, 屈撑囤, 朱世东.材料导报:综述篇, 2018, 32 (9), 3023. 9 Tian H, Yao C, Yin Y S, et al. Materials Review B: Research Papers, 2016, 30 (11), 152 (in Chinese). 田红, 姚灿, 尹艳山, 等.材料导报:研究篇, 2016, 30 (11), 152. 10 Jiang G, Nowakowski D J, Bridgwater A V. Energy and Fuels, 2010, 24 (8), 4470. 11 Custodis V B, Bahrle C, Vogel F,et al. Journal of Analytical and Applied Pyrolysis, 2015, 115, 214. 12 Lou R, Wu S, Yu G L. Journal of Analytical and Applied Pyrolysis, 2015, 111, 27. 13 Zhang J J, Jiang X Y, Ye X N, et al. Thermal Analysis and Calorimetry, 2016, 123 (1), 501. 14 Huang J B, Wu S B, Lei M, et al. Journal of Fule Chemistry and Technology, 2015, 43 (11), 1334 (in Chinese). 黄金保, 武书彬, 雷鸣, 等.燃料化学学报, 2015, 43 (11), 1334. 15 Tao K, Strezov V, Evans T J. Renewable and Sustainable Energy Reviews, 2016, 57, 1126. 16 Dhyani V, Thallada B. Renewable Energy, 2018, 129, 695. 17 Burhenne L, Marco D, Thomas A. Fuel, 2013, 107,836. 18 Park S W, Jang C H. Energy, 2012, 39 (1), 187. 19 Tan Y, Ma C F.Biomass Chemical Engineering, 2018, 52 (2), 35 (in Chinese). 谭扬, 马春富. 生物质化学工程,2018,52 (2),35. 20 Che D Y, Sun Y X, Sun B Z.Chinese Society for Electrical Engineering, 2015, 35 (24), 6439 (in Chinese). 车德勇, 孙艳雪, 孙佰仲.中国电机工程学报, 2015, 35 (24), 6439. 21 Nakamura T, Kawamoto H, Saka S. Analytical and Applied Pyrolysis, 2008, 81, 173. 22 Beste A, Buchanan III A C. The Journal of Organic Chemistry, 2009, 74 (7), 2837. 23 Huang J, Liu C, Wu D, et al. Analytical and Applied Pyrolysis, 2014,109, 98. 24 Wang G Q, Li N, Shen J L. Journal of Capital Normal University, 2007, 28 (3), 27 (in Chinese). 王光琴, 李宁, 沈京玲. 首都师范大学学报, 2007, 28 (3), 27. 25 Fan K N. Physical chemistry, Higher Education Press, China, 2005 (in Chinese). 范康年. 物理化学, 高等教育出版社,2005.
渝公网安备50019002502923号 版权所有：《材料导报》编辑部
2020, Vol. 34 
