Engineering Research Centre of Oil Shale Comprehensive Utilization, Ministry of Education, Northeast Electric Power University, Jilin City, Jilin, 132012, China.
Sci Rep. 2020 Feb 27;10(1):3626. doi: 10.1038/s41598-020-60095-2.
In this paper, analytical pyrolyzer coupled with a gas chromatography-mass spectrometry set-up (Py-GC/MS) and density functional theory(DFT) theory was used to reveal the initial pyrolysis mechanism and product formation mechanism of cellulose pyrolysis. We demonstrated an experimentally benchmarked molecular simulation approach that delineates pyrolysis process of cellulose. Experimental results indicated that the cellulose pyrolysis products mostly incorporate levoglucosan (LG), glycolaldehyde (HAA), 5-hydroxyfurfural (5-HMF), and the like. The constituents of fast pyrolysis products of cellulose and cellobiose demonstrated the identical trend, although the contents of certain products are different. Laying the foundation of experimental analysis, the reaction pathways of four categories of cellulose pyrolysis were outlined using DFT theory; the pathways are those of generating LG, HAA, and 5-HMF and the dehydration reaction in the process of cellulose pyrolysis. Also, by comparing the energy barriers of various reactions, the optimal pathway of different reactions were summarized. The deduced cellulose pyrolysis reaction pathway opened up new ideas for studying the pyrolysis behavior of cellulose.
本文采用热解气相色谱-质谱联用仪（Py-GC/MS）和密度泛函理论（DFT）研究了纤维素热解的初始热解机制和产物形成机制。我们提出了一种经过实验验证的分子模拟方法，可以详细描述纤维素的热解过程。实验结果表明，纤维素热解产物主要包括左旋葡聚糖（LG）、乙二醇醛（HAA）、5-羟甲基糠醛（5-HMF）等。纤维素和纤维二糖快速热解产物的组成具有相同的趋势，尽管某些产物的含量不同。通过 DFT 理论，我们为纤维素的四类热解反应途径奠定了实验分析的基础，分别是生成 LG、HAA 和 5-HMF 以及纤维素热解过程中的脱水反应。此外，通过比较各种反应的能垒，总结了不同反应的最佳途径。推断出的纤维素热解反应途径为研究纤维素的热解行为开辟了新思路。
