玉米秸秆主要共价键含量及热解过程中自由基生成特征研究

赵晓胜; 李笑莹; 陈赞; 肖博恩; 张怡菲; 张美婷; 回文龙; 闫玉新

doi:10.12434/j.issn.2097-2547.20250147

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玉米秸秆主要共价键含量及热解过程中自由基生成特征研究

碳资源转化利用 | 更新时间：2026-02-13

- 玉米秸秆主要共价键含量及热解过程中自由基生成特征研究
- Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis
- 低碳化学与化工 2026, 51(2): 91-98.
- 作者机构：
  
  1.沧州师范学院河北省环渤海生物质材料重点实验室，河北沧州 061001
  2.北京化工大学化学工程学院，北京 100029
- 作者简介：
  
  赵晓胜（1990—），博士，副教授，研究方向为生物质及油页岩的热转化，E-mail：zhaoxs@caztc.edu.cn。
  闫玉新（1991—），博士，副教授，硕士研究生导师，研究方向为重质有机资源高效清洁利用，E-mail：yanyx@buct.edu.cn。
- 基金信息：
  
  河北省自然科学基金(B2022110004);大学生科技创新能力培育项目(DXSZDL2023001)
- DOI：10.12434/j.issn.2097-2547.20250147
  中图分类号： TK6
- 收稿：2025-03-31，
  
  修回：2025-05-17，
  
  纸质出版：2026-02-25
- 稿件说明：
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赵晓胜,李笑莹,陈赞等.玉米秸秆主要共价键含量及热解过程中自由基生成特征研究[J].低碳化学与化工,2026,51(2):91-98.

ZHAO Xiaosheng,LI Xiaoying,CHEN Zan,et al.Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):91-98.
赵晓胜,李笑莹,陈赞等.玉米秸秆主要共价键含量及热解过程中自由基生成特征研究[J].低碳化学与化工,2026,51(2):91-98. DOI： 10.12434/j.issn.2097-2547.20250147.

ZHAO Xiaosheng,LI Xiaoying,CHEN Zan,et al.Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis[J].Low-Carbon Chemistry and Chemical Engineering,2026,51(2):91-98. DOI： 10.12434/j.issn.2097-2547.20250147.

摘要

热解作为玉米秸秆（以下简称“秸秆”）综合利用的重要技术，该过程遵循自由基反应机理。明确秸秆中共价键的组成及热解过程中自由基的生成特征，对于揭示自由基反应的内在机制及其与有机结构之间的关系，进而优化热解工艺具有重要意义。基于元素分析和

C NMR表征获得的碳骨架结构参数，计算了秸秆中主要共价键含量。采用9

10-二氢蒽作为分子探针，间接测定了热解过程中活性自由基生成量，并通过电子自旋共振（ESR）技术对热解后产生的稳定自由基数量及其

值进行了检测。结果表明，秸秆中C

—C

和C

—C

含量分别为28.47 mmol/g和4.95 mmol/g，C—O中主要以C

—O为主（含量高达28.57 mmol/g）。秸秆热解过程中生成的活性自由基浓度（

R-A

）随着温度升高和时间延长而逐渐增大，300~420 ℃下热解12 min时，

R-A

达到4.60~29.44 mmol/g。热解过程中，秸秆可能主要发生

-O—C

、

-C

—C

等弱键断裂，生成的活性自由基主要为脂肪碳自由基、与芳香碳相连的氧自由基以及与芳香碳相连的脂肪碳自由基。随秸秆热解反应进行，稳定自由基浓度呈现先快速增大后缓慢减小再缓慢增大的趋势。含芳香结构的大尺寸活性自由基（尤其是·C

—C

）在耦合过程中更容易转变为稳定自由基，新形成的稳定自由基的

值随热解时间延长逐渐降低，其含有较多的含氧自由基。

Abstract

As pyrolysis serves as the important technology for the comprehensive utilization of corn stalks (hereinafter referred to as “stalks”)

the process follows a free radical reaction mechanism. Understanding the compositions of covalent bonds in stalks and the generation characteristics of free radicals during pyrolysis is of great significance for elucidating the underlying mechanisms of free radical reactions and their relationships with organic structures

thereby contributing to the optimization of pyrolysis processes. The contents of major covalent bonds in stalks were calculated based on elemental analysis and carbon skeleton structural parameters derived from

C NMR characterization. 9

10-dihydroanthracene

was employed as a molecular probe to indirectly quantify the formation of active free radicals during pyrolysis. Additionally

the numbers and

-values of stable free radicals formed after pyrolysis were determined using electron spin resonance (ESR) spectroscopy. The results show that the contents of C

—C

and C

—C

in stalks are 28.47 mmol/g and 4.95 mmol/g

respectively

with C

—O (with a content of up to 28.57 mmol/g) as the dominant C—O type. The concentration of active free radicals (

R-A

) gradually increases with higher temperature and longer residence time

reaching 4.60 mmol/g to 29.44 mmol/g after 12 min of pyrolysis at 300 ℃ to 420 °C. During pyrolysis of stalks

weak bonds such as

-O—C

and

-C

—C

are likely to be cleaved

generating active free radicals primarily consisting of aliphatic carbon radicals

oxygen radicals bonded to aromatic carbons

and aliphatic carbon radicals bonded to aromatic carbons. As the pyrolysis of stalks proceeds

the concentration of stable free radicals first increases rapidly

then decreases slowly

and finally increases slightly again. Large-sized active radicals of aromatic structures (especially ·C

—C

) are more likely to transform into stable free radicals during coupling. The

-value of newly formed stable free radicals gradually decreases with the extension of pyrolysis time

with more oxygen-containing radicals.

关键词

Keywords

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