Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis

ZHAO Xiaosheng; LI Xiaoying; CHEN Zan; XIAO Boen; ZHANG Yifei; ZHANG Meiting; HUI Wenlong; YAN Yuxin

doi:10.12434/j.issn.2097-2547.20250147

您当前的位置：

首页 >

文章列表页 >

Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis

更新时间：2026-02-13

- Study on contents of major covalent bonds of corn stalks and generation characteristics of free radicals during their pyrolysis
- Vol. 51, Issue 2, Pages: 91-98(2026)
- 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：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20250147
  CLC： TK6
- Received：31 March 2025，
  
  Revised：2025-05-17，
  
  Published：25 February 2026
- 稿件说明：
移动端阅览
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

references

GUO Y P , ZHANG Q Q , FENG W J , et al . Coadsorption of tetracycline and copper(II) by KOH-modified biomass and biochar derived from corn straw in aqueous solution [J ] . Water , 2025 , 17 ( 2 ): 284 .

XU H , LV S H , WU W W , et al . Catalytic conversion of the heavy fraction of bio-oil into phenol-rich oils using an Fe-carbon catalyst during straw pyrolysis [J ] . Journal of Analytical and Applied Pyrolysis , 2025 , 186 : 106902 .

刘乐桐 , 王雯 , 代建军 , 等 . 玉米秸秆催化热解制取富氢气体 [J ] . 可再生能源 , 2023 , 41 ( 11 ): 1421 - 1429 .

LIU L T , WANG W , DAI J J , et al . Catalytic pyrolysis of corn straw for hydrogen-rich syngas generation [J ] . Renewable Energy Resources , 2023 , 41 ( 11 ): 1421 - 1429 .

刘振宇 . 重质有机资源热解过程中的自由基化学 [J ] . 北京化工大学学报（自然科学版） , 2018 , 45 ( 5 ): 8 - 24 .

LIU Z Y . Radical chemistry in the pyrolysis of heavy organics [J ] . Journal of Beijing University of Chemical Technology (Natural Science) , 2018 , 45 ( 5 ): 8 - 24 .

XIANG C , LIU Q Y , SHI L , et al . A study on the new type of radicals in corncob derived biochars [J ] . Fuel , 2020 , 277 : 118163 .

TAO W M , YANG X W , LI Y , et al . Components and persistent free radicals in the volatiles during pyrolysis of lignocellulose biomass [J ] . Environmental Science Technology , 2020 , 54 : 13274 - 13281 .

张梦垚 , 汪家乐 , 张源 , 等 . 基于等转化率法和生物炭性质揭示稻草秸秆的热解特性 [J ] . 环境化学 , 2024 , 43 ( 9 ): 2978 - 2987 .

ZHANG M Y , WANG J L , ZHANG Y , et al . Pyrolytic behavior of rice straw based on the detailed analysis of iso-conversional method and biochar characterization [J ] . Environmental Chemistry , 2024 , 43 ( 9 ): 2978 - 2987 .

ZHAO X S , LIU Z Y , LU Z H , et al . A study on average molecular structure of eight oil shale organic matters and radical information during pyrolysis [J ] . Fuel , 2018 , 219 : 399 - 405 .

LEI M , WU S B , LIANG J J , et al . Comprehensive understanding the chemical structure evolution and crucial intermediate radical in situ observation in enzymatic hydrolysis/mild acidolysis lignin pyrolysis [J ] . Journal of Analytical and Applied Pyrolysis , 2019 , 138 : 249 - 260 .

LI G X , LUO Z Y , WANG W B , et al . A study of the mechanisms of guaiacol pyrolysis based on free radicals detection technology [J ] . Catalysts , 2020 , 10 ( 3 ): 295 .

MA L Q , SYED-HASSAN S , TONG Y X , et al . Interactions of cellulose- and lignin-derived radicals during pyrolysis: An in situ Electron Paramagnetic Resonance (EPR) study [J ] . Fuel Processing Technology , 2023 , 239 : 107536 .

SHEN T , HU Z W , LIU Q Y , et al . A method to evaluate hydrogen donation ability of hydrogen-storage solvent in hydrogenation process by radical-precursor compounds [J ] . Fuel , 2022 , 314 : 122741 .

FENG Y F , WANG Q , ZHAO X S , et al . Covalent bond concentration and pyrolysis free radical reaction of kerogens in oil shale with different densities from the same mining area [J ] . Chemical Engineering Journal , 2025 , 505 : 159172 .

WANG X Y , MA T , LIU H X , et al . Experimental and molecular dynamics of corn straw char high-temperature steam gasification: Effects on char structure, temperature and steam mass concentration [J ] . Chemical Engineering Journal , 2025 , 506 : 160035 .

JIANG S Y , LOU C H , ZHOU Y L , et al . Biobased epoxy composites reinforced with acetylated corn straw [J ] . ACS Omega , 2023 , 8 ( 14 ): 12644 - 12652 .

LE M , NIELSEN D , SORENSEN R , et al . Characterisation of authentic lignin biorefinery samples by fourier transform infrared spectroscopy and determination of the chemical formula for lignin [J ] . BioEnergy Research , 2017 , 10 ( 4 ): 1025 - 1035 .

李亚平 . 超微粉碎预处理和酶解对玉米秸秆结构的影响 [J ] . 陕西农业科学 , 2024 , 70 ( 12 ): 21 - 26 .

LI Y P . Effects of ultrafine grinding pretreatment and enzymatic hydrolysis on structure of corn straw [J ] . Shaanxi Journal of Agricultural Sciences , 2024 , 70 ( 12 ): 21 - 26 .

ZHAO X S , FENG Y F , FAN X Z , et al . Covalent bonding structures of eight oil shales and the characteristics of bond cleavage during the pyrolysis process [J ] . Fuel , 2024 , 370 : 131821 .

赵晓胜 . 油页岩有机质的结构与热解断键研究 [D ] . 北京 : 北京化工大学 , 2019 .

ZHAO X S . Study on structure of oil shale organic matter and bond cleavage during pyrolysis [D ] . Beijing : Beijing University of Chemical Technology , 2019 .

王林洋 , 张育维 , 李亚丽 , 等 . 基于 13 C-NMR偶极去相技术的有机肥料中有机组分特征研究 [J ] . 植物营养与肥料学报 , 2024 , 30 ( 8 ): 1630 - 1638 .

WANG L Y , ZHANG Y W , LI Y L , et al . Structures of components in different organic fertilizers analyzed through 13 C-NMR dipolar dephasing technology [J ] . Journal of Plant Nutrition and Fertilizers , 2024 , 30 ( 8 ): 1630 - 1638 .

QIAO W C , LIU H , ZHANG Y H , et al . Structural characterization of the biogas fermentation residue from wheat straw [J ] . Journal of Biobased Materials and Bioenergy , 2019 , 13 ( 2 ): 188 - 194 .

陶用珍 , 管映亭 . 木质素的化学结构及其应用 [J ] . 纤维素科学与技术 , 2003 , 11 ( 1 ): 42 - 55 .

TAO Y Z , GUAN Y T . Study of chemical composition of lignin and its application [J ] . Journal of Cellulose Science and Technology , 2003 , 11 ( 1 ): 42 - 55 .

罗渝然 . 化学键能数据手册 [M ] . 北京 : 科学出版社 , 2005 : 100 - 211 .

LUO Y R . Handbook of chemical bond energies [M ] . Beijing : Science Press , 2005 : 100 - 211 .

HE W J , LIU Z Y , LIU Q Y , et al . Behavior of radicals during solvent extraction of three low rank bituminous coals [ J ] . Fuel Processing Technology , 2017 , 156 : 221 - 227 .

LIU M X , YANG J L , YANG Y , et al . The radical and bond cleavage behaviors of 14 coals during pyrolysis with 9,10-dihydrophenanthrene [J ] . Fuel , 2016 , 182 : 480 - 486 .

WANG W , MA Y , LI S Y , et al . Effect of temperature on the EPR properties of oil shale pyrolysates [J ] . Energy Fuels , 2016 , 30 : 830 - 834 .

ZHOU Q Q , LIU Q Y , SHI L , et al . Behaviors of coking and radicals during reaction of volatiles generated from fixed-bed pyrolysis of a lignite and a subbituminous coal [J ] . Fuel Processing Technology , 2017 , 161 : 304 - 310 .

PETRAKIS L , GRANDY D . Electron spin resonance spectrometric study of free radicals in coals [J ] . Analytical Chemistry , 1978 , 50 : 303 - 308 .

Views

下载量

CNKI被引量

Alert me when the article has been cited

提交

Tools

Publicity Resources

Research hotspots and development trends of biomass thermochemical conversion in China

Mechanism study of pyrolysis process and characteristics analysis of energy conversion of Gannan navel orange peel

Research progress on biomass torrefaction pre-conditioning and optimization of pyrolysis product quality

Research progress of biomass-based carbon materials for supercapacitors

Comparative Analysis on the Linetype Mechanical Performances of Two Railway Transition Curves

Related Author

YAN Yuxin

HUI Wenlong

ZHANG Meiting

ZHANG Yifei

XIAO Boen

CHEN Zan

LI Xiaoying

ZHAO Xiaosheng

Related Institution

College of Chemistry and Chemical Engineering, Cangzhou Normal University

University of Chinese Academy of Sciences

State Key Laboratory of Coal Conversion, Institute of Engineering Thermophysics, Chinese Academy of Sciences

Xinfeng Xunjiexing Circuit Technology Co., Ltd.

Jiangxi Tongyi Polymer Material Technology Co., Ltd.

Postal code：610225
Tel：028-85964717 Email：236764603@qq.com
Technical support is provided by Beijing Founder electronics co., LTD 蜀ICP备12008600号-10 蜀公网安备51012202001533
It is recommended to read the content of this site in Chrome&IE9+. Please switch to extreme mode in browser 360.
Cookies We use cookies to help provide and enhance our service and tailor content. By continuing, you agree to the use of cookies.
Total Visits：378882 Visits Today：30

⁰