Article(id=1154429043068887368, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154429037721146272, articleNumber=null, orderNo=null, doi=null, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1657036800000, receivedDateStr=2022-07-06, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1753166932121, onlineDateStr=2025-07-22, pubDate=1710864000000, pubDateStr=2024-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1753166932121, onlineIssueDateStr=2025-07-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1753166932121, creator=13701087609, updateTime=1753166932121, updator=13701087609, issue=Issue{id=1154429037721146272, tenantId=1146029695717560320, journalId=1146119893612605453, year='2024', volume='42', issue='3', pageStart='284', pageEnd='426', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1753166930847, creator=13701087609, updateTime=1753694626061, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1156642351918469663, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154429037721146272, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1156642351918469664, tenantId=1146029695717560320, journalId=1146119893612605453, issueId=1154429037721146272, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=292, endPage=299, ext={EN=ArticleExt(id=1154429043744170314, articleId=1154429043068887368, tenantId=1146029695717560320, journalId=1146119893612605453, language=EN, title=Pyrolysis characteristics of naked oats straw in Bashang area, columnId=null, journalTitle=Renewable Energy Resources, columnName=null, runingTitle=null, highlight=null, articleAbstract=

In order to achieve high efficiency and clean combustion of crop straw in Bashang area, typical naked oats straw was selected as the research object to analyze the pyrolysis characteristics. The pyrolysis atmosphere environment in the combustion process was created by simulating flue gas with mixed gases. The thermogravimetric analyzer was used to study the thermogravimetric characteristics and the influence of temperature rise rate on the mixed gas atmosphere composed of air and N2, CO2, and O2 in different proportions. The AKTS software was used for kinetic analysis. The results showed that: the pyrolysis process of naked oats straw was divided into three stages, which were drying stages (30~140 °C), volatilization stages (140~370 °C), carbonization stages (370~900℃). Gas atmosphere mainly affected the pyrolysis of carbonization stage, drying and volatilization stage had little effect, heating rate affects volatilization and carbonization stage, the faster the heating rate, the greater the reaction rate. When the pyrolysis atmosphere was 15%O25% CO280% N2 mixed gas (gas 2), the activation energy required for pyrolysis process was the least, and the average activation energy was 139.86 kJ/mol. The results provided a certain theoretical basis for the energy utilization of biomass straw in the alpine Bashang area.

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为实现高寒坝上地区农作物秸秆高效清洁燃烧,文章选取典型莜麦秸秆作为研究对象,通过混合气体模拟烟气燃烧过程中的热解气氛环境,采用热重分析仪研究空气和 N2, CO2,02 不同比例组成的混合气体氛围下热失重特性以及升温速率对其影响,采用 AKTS 软件进行动力学分析。结果表明:莜麦秸秆热解过程可分为干燥(30~140℃)、挥发(140~370℃)、炭化(370~900℃)3个阶段;气体氛围主要影响热解的炭化阶段,对干燥和挥发阶段影响较小;升温速率影响挥发和炭化阶段,升温速率越快,反应速率越大;当热解气氛为15%025%CO280%N2混合气体(气体2)时,热解过程所需活化能最少,平均活化能为139.86 kJ/mol。研究结果可为高寒坝上地区生物质秸秆能源化利用提供一定理论依据。

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王冬计(1990-),男,博士,讲师,研究方向为农村建筑清洁供能。E-mail:
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刘联胜(1970-),男,博士,教授,研究方向为清洁燃烧技术与装备。E-mail:

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刘联胜(1970-),男,博士,教授,研究方向为清洁燃烧技术与装备。E-mail:

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刘联胜(1970-),男,博士,教授,研究方向为清洁燃烧技术与装备。E-mail:

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秸秆种类 地区 元素分析/% 工业分析/%
C H 0 S M V A FC
莜麦秸秆 张北坝上 48.42 5.54 42.91 1.33 0.07 7.38 75.05 6.30 11.27
水稻秸秆 [ 12 ] 广东某厂 40.10 5.09 40.93 0.44 0.00 11.23 66.74 13.44 8.59
玉米秸秆[ 13 ] 河南某田 45.26 6.31 47.51 1.04 0.14 5.09 66.77 10.72 16.78
), ArticleFig(id=1154429084772852319, tenantId=1146029695717560320, journalId=1146119893612605453, articleId=1154429043068887368, language=CN, label=表 1, caption=元素分析与工业分析结果, figureFileSmall=null, figureFileBig=null, tableContent=
秸秆种类 地区 元素分析/% 工业分析/%
C H 0 S M V A FC
莜麦秸秆 张北坝上 48.42 5.54 42.91 1.33 0.07 7.38 75.05 6.30 11.27
水稻秸秆 [ 12 ] 广东某厂 40.10 5.09 40.93 0.44 0.00 11.23 66.74 13.44 8.59
玉米秸秆[ 13 ] 河南某田 45.26 6.31 47.51 1.04 0.14 5.09 66.77 10.72 16.78
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坝上地区莜麦秸秆热解特性研究
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刘联胜 1, 2 , 梁小虎 1, 2 , 王冬计 3 , 张晓宇 1, 2 , 黄亚龙 3
可再生能源 | 2024,42(3): 292-299
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可再生能源 | 2024, 42(3): 292-299
坝上地区莜麦秸秆热解特性研究
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刘联胜1, 2 , 梁小虎1, 2, 王冬计3 , 张晓宇1, 2, 黄亚龙3
作者信息
  • 1 河北工业大学 能源与环境工程学院 天津 300401
  • 2 河北省热科学与能源清洁利用技术重点实验室 天津 300401
  • 3 天津城建大学 能源与安全工程学院 天津 300384
  • 刘联胜(1970-),男,博士,教授,研究方向为清洁燃烧技术与装备。E-mail:

通讯作者:

王冬计(1990-),男,博士,讲师,研究方向为农村建筑清洁供能。E-mail:
Pyrolysis characteristics of naked oats straw in Bashang area
Liansheng Liu1, 2 , Xiaohu Liang1, 2, Dongji Wang3 , Xiaoyu Zhang1, 2, Yalong Huang3
Affiliations
  • 1 School of Energy and Environmental Engineering Hebei University of Technology Tianjin 300401 China
  • 2 Key Laboratory of Thermal Science and Clean Energy Utilization Technology of Hebei Province Tianjin 300401 China
  • 3 School of Energy and Safety Engineering Tianjin Chengjian University Tianjin 300384 China
出版时间: 2024-03-20
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为实现高寒坝上地区农作物秸秆高效清洁燃烧,文章选取典型莜麦秸秆作为研究对象,通过混合气体模拟烟气燃烧过程中的热解气氛环境,采用热重分析仪研究空气和 N2, CO2,02 不同比例组成的混合气体氛围下热失重特性以及升温速率对其影响,采用 AKTS 软件进行动力学分析。结果表明:莜麦秸秆热解过程可分为干燥(30~140℃)、挥发(140~370℃)、炭化(370~900℃)3个阶段;气体氛围主要影响热解的炭化阶段,对干燥和挥发阶段影响较小;升温速率影响挥发和炭化阶段,升温速率越快,反应速率越大;当热解气氛为15%025%CO280%N2混合气体(气体2)时,热解过程所需活化能最少,平均活化能为139.86 kJ/mol。研究结果可为高寒坝上地区生物质秸秆能源化利用提供一定理论依据。

坝上地区  /  莜麦秸秆  /  热解特性  /  活化能

In order to achieve high efficiency and clean combustion of crop straw in Bashang area, typical naked oats straw was selected as the research object to analyze the pyrolysis characteristics. The pyrolysis atmosphere environment in the combustion process was created by simulating flue gas with mixed gases. The thermogravimetric analyzer was used to study the thermogravimetric characteristics and the influence of temperature rise rate on the mixed gas atmosphere composed of air and N2, CO2, and O2 in different proportions. The AKTS software was used for kinetic analysis. The results showed that: the pyrolysis process of naked oats straw was divided into three stages, which were drying stages (30~140 °C), volatilization stages (140~370 °C), carbonization stages (370~900℃). Gas atmosphere mainly affected the pyrolysis of carbonization stage, drying and volatilization stage had little effect, heating rate affects volatilization and carbonization stage, the faster the heating rate, the greater the reaction rate. When the pyrolysis atmosphere was 15%O25% CO280% N2 mixed gas (gas 2), the activation energy required for pyrolysis process was the least, and the average activation energy was 139.86 kJ/mol. The results provided a certain theoretical basis for the energy utilization of biomass straw in the alpine Bashang area.

Bashang area  /  naked oats straw  /  pyrolysis characteristics  /  activation energy
刘联胜, 梁小虎, 王冬计, 张晓宇, 黄亚龙. 坝上地区莜麦秸秆热解特性研究. 可再生能源, 2024 , 42 (3) : 292 -299 .
Liansheng Liu, Xiaohu Liang, Dongji Wang, Xiaoyu Zhang, Yalong Huang. Pyrolysis characteristics of naked oats straw in Bashang area[J]. Renewable Energy Resources, 2024 , 42 (3) : 292 -299 .
据统计,我国每年秸秆产量高达 10 亿 ${\mathrm{t}}$ [ 1 ] ,然而离田利用总量却不足 ${50}{\%}$ [ 2 ] ,大量秸秆被直接焚烧, 不仅造成能源浪费, 还对环境产生严重污染 [ 3 ] 。目前,国家已出台多项政策支持生物质能源发展,明确要求全国各县区结合当地实际情况,进一步加大农作物秸秆的综合利用 [ 4 ] 。秸秆可通过生物化学法 [ 5 ] 和热化学法 [ 6 ] 转化为高品质能源,生物化学法主要利用发酵技术产生沼气, 其缺点是产生大量的废渣, 热化学法主要包括燃烧、气化、 热解等方法,其中热解是较好的方法之一。
针对秸秆热解特性方面的研究, 张喜坤 [ 7 ]利用热重分析仪研究了空气氛围和 ${\mathrm{N}}_{2}$ 氛围下玉米秸秆和水稻秸秆的热解特性,结果表明,空气氛围下所需能量较少,容易进行热解。但对于不同种类混合气体氛围下的秸秆热解特性并未深入研究。秸秆在炉内燃烧时产生的烟气主要由 ${\mathrm{N}}_{2}$ , ${\mathrm{{CO}}}_{2},{\mathrm{O}}_{2}$ 等组分混合而成,由于烟气不能及时排出,导致热解氛围发生改变,因此可通过选取不同比例的混合气体模拟烟气燃烧过程的气氛环境, 探究烟气氛围下的热解特性。Kartal Furkan [ 8 ] 采用不同升温速率对小麦秸秆进行了热解特性分析, 利用 Flynn-Wall-Ozawa(FWO)模型方法 [ 9 ] 得到了动力学参数。
目前对农作物秸秆的热解研究主要集中在平原地区, 对于较高海拔的坝上地区农作物秸秆热解特性研究较少, 高寒气候使得生物质秸秆在元素组成和热解温度方面与平原地区有所不同。张北县位于河北省西北部、内蒙古高原南麓的坝上地区,平均海拔在 ${1400}\mathrm{\;m}$ 左右,农作物主要为莜麦 [ 10 ] ,受光照时间影响,昼夜温差较大,有利于植物进行光合作用,使其有机质增多 [ 11 ] 。本文选取典型的莜麦秸秆作为研究对象, 分析不同气体氛围和不同升温速率下的热解特性, 并利用 FWO 动力学模型进行活化能计算, 以期为张北坝上地区的生物质秸秆利用提供一定的理论依据。
本实验选取张北坝上地区典型农作物莜麦秸秆作为实验样品, 秸秆经晾晒、粉碎、研磨后过 80 目筛,在 ${105}^{\circ }\mathrm{C}$ 鼓风干燥箱中干燥至恒重,装进密封袋备用。利用元素分析仪和工业分析仪对莜麦秸秆空气干燥基的元素和成分组成进行测试,结果如 表 1 所示。与广东某厂水稻秸秆和河南某田玉米秸秆对比可知:张北坝上地区莜麦秸秆的 $\mathrm{H}$ , $0,\mathrm{\;S}$ 含量低于玉米秸秆、高于水稻秸秆, $\mathrm{C},\mathrm{N}$ 含量高于二者, $\mathrm{C}$ 含量的增多有助于改善高温热熔融结焦, 0 含量的降低会提高燃料的热值; 莜麦秸秆的固定碳高于水稻、低于玉米,挥发分均高于二者, 灰分均低于二者, 挥发分含量高、灰分含量低有助于维持热解反应温度, 具有较高的热利用价值。元素分析和工业分析结果表明,莜麦秸秆是热化学转化的理想原料之一。
热解实验设备采用美国 PerkinElmer 公司生产的 STA-6000 型同步 TG-DSC 热分析仪。载气分别为空气 (气体 1)、 ${15}\%{\mathrm{O}}_{2}- 5\%{\mathrm{{CO}}}_{2}- {80}\%{\mathrm{\;N}}_{2}$ 混合气体 (气体 2)、 ${10}\%{\mathrm{O}}_{2}- {10}\%{\mathrm{{CO}}}_{2}- {80}\%{\mathrm{\;N}}_{2}$ 混合气体 (气体 3 )、 $5\%{\mathrm{O}}_{2}- {15}\%{\mathrm{{CO}}}_{2}- {80}\%{\mathrm{\;N}}_{2}$ 混合气体(气体 4),4 种气体独立存放在高压气瓶中。实验系统如 图 1 所示。
将装有气体 1 的高压气瓶阀门打开, 控制压力表为 ${0.2}\mathrm{{MPa}}$ ,数据采集及控制系统流量显示为 ${19.8}\mathrm{\;{mL}}/\mathrm{{min}}$ ,待气体稳定后,在 STA-6000 中加入空坩埚进行动态校准, 样品质量控制在 11 $\mathrm{{mg}}$ 左右,以保证样品占坩埚容积的 $1/2 \sim 2/3$ 。考虑到较低升温速率下样品的失重分区较为明显,分别采用 ${10},{20},{30}{}^{\circ }\mathrm{C}/\mathrm{{min}}$${40}{}^{\circ }\mathrm{C}/\mathrm{{min}}4$ 种升温速率。为保证样品充分反应,升温设定为 30~900 C。每做完一个实验,待实验设备温度降至室温再进行下一个实验, 4 种不同升温速率实验完成后, 更换高压气瓶为气体 2、气体 3、气体 4,重复上述实验,得到不同气体氛围的热解过程。将最终得到的热失重数据以 ASCII 格式输出, 导入 AKTS-Thermokinetics 模块中生成 TG 曲线, 对该曲线进行微分可得相应的 DTG 曲线, 并进一步修正与优化得到模拟结果。
本文利用 FWO 方法对莜麦秸秆进行动力学分析。FWO 方法是一种等转化率方法, 通过选取不同升温速率、相同转化率下的温度,做出散点图,然后通过拟合方程做出相应的直线,求出不同转化率下的活化能。相比于 Vyazovkin 方法、改进的 Coats-Redfern 方法, 该方法能够从拟合图像中直接求出活化能, 可避免因为不同的反应机理函数假设带来的误差。FWO 方法的函数方程如下所示:
$ X =\frac{{m}_{0}- m}{{m}_{0}}$
$\frac{\mathrm{d}X}{\mathrm{\;d}t}= k\left( T\right) f\left( X\right){P}_{{\mathrm{O}}_{2}}^{n}$
$ k\left( T\right)= {k}_{0}\exp \left({-\frac{E}{RT}}\right)$
式中: $X$ 为转化程度; ${m}_{0}$$m$ 分别为样品的初始质量和瞬时质量, $\mathrm{{mg}};T$ 为温度, $\mathrm{C};f\left( X\right)$ 为结构性因素; ${P}_{{O}_{2}}$ 为混合物中氧气分压力, $\mathrm{{Pa}};n$${P}_{{O}_{2}}$ 的反应级数; ${k}_{0}$ 为指前常数; $E$ 为活化能, $\mathrm{{kJ}}/\mathrm{{mol}}$
${P}_{{\mathrm{O}}_{2}}$ 固定情况下,可认为 ${P}_{{\mathrm{O}}_{2}}^{n}$ 是常数,令 ${k}_{0}^{\prime }=$ ${k}_{0}{P}_{{\mathrm{O}}_{2}}^{n}$ ,式(2)可转化为
$\frac{\mathrm{d}X}{\mathrm{\;d}t}= {k}_{0}{P}_{{\mathrm{O}}_{2}}^{n}f\left( X\right)\exp \left({-\frac{E}{RT}}\right)= {k}_{0}f\left( X\right)\exp \left({-\frac{E}{RT}}\right)$
对于线性升温速率的热重实验,式(4)可进一步转化为
$\frac{\mathrm{d}X}{\mathrm{\;d}T}\beta ={k}_{0}^{\prime }f\left( X\right)\exp \left({-\frac{E}{RT}}\right)$
式中: $\beta$ 为升温速率, $℃/\mathrm{{min}}$
对式(5)两边取对数可得:
$\operatorname{In}\left(\frac{\mathrm{d}X}{\mathrm{\;d}t}\right)= \operatorname{In}\left\lbrack {{k}_{0}^{\prime }f\left( X\right)}\right\rbrack -\frac{E}{R{T}_{\mathrm{f}}}$
式中: ${T}_{\mathrm{f}}$$X$ 阶段对应的温度, ${}^{\circ }\mathrm{C}$
对式(6)积分可得:
${\int }_{0}^{X}\frac{\mathrm{d}X}{f\left( X\right)} =\frac{{k}_{0}^{\prime }}{\beta }{\int }_{0}^{{T}_{\mathrm{f}}}\exp \left({-\frac{E}{RT}}\right)\mathrm{d}T =\\\frac{{k}_{0}E}{\beta R}{\int }_{{y}_{i}}^{\infty }\frac{\exp \left({-y}\right)}{{y}^{2}}\mathrm{\;d}y $
式中: $y = E/\left({RT}\right);{y}_{\mathrm{f}}= E/\left({R{T}_{\mathrm{f}}}\right)$
令:
$ p\left( y\right)= {\int }_{{y}_{\mathrm{f}}}^{\infty }\frac{\exp \left({-y}\right)}{{y}^{2}}\mathrm{\;d}y $
式(8)又可近似为
$ p\left( y\right)\cong \frac{\exp \left({-{Ay}+ B}\right)}{{y}^{d}}$
式中: $A, B, d$ 为与每个近似相关的特定值。
等转化的一般形式为
$\operatorname{In}\frac{\beta }{{T}_{\mathrm{f}}^{d}}= - A\frac{E}{RT}+ {C}_{1}$
式中: ${C}_{1}$ 为常数。
$p\left( y\right)$ 的近似值可写为
$ p\left( y\right)\cong \exp \left({-{1.0518y}- {5.330}}\right)$
通过以上等式可导出最终方程:
$\operatorname{In}\beta =- {1.0518}\frac{E}{R{T}_{\mathrm{f}}}+ {C}_{2}$
式中: ${C}_{2}$ 为常数。
根据式 (12),以 $1/{T}_{\mathrm{f}}$ 为横坐标, $\operatorname{In}\beta$ 为纵坐标进行线性拟合,即可得到直线,直线的斜率 $k$ 和活化能 $E$ 的关系可表示为
$ k =- {1.0518}\frac{E}{R}$
图 2 为不同升温速率下 4 种气体氛围的 DTG 曲线。DTG 曲线代表样品的失重率,根据失重率的变化规律,可以将热解分为 3 个主要阶段: 第一阶段温度为 ${30}\sim {140}^{\circ }\mathrm{C}$ ,样品进行干燥吸热, 随着温度的升高, 样品中残留的表面水和结晶水吸收热量,以水蒸气的形式散失掉;第二阶段温度为 ${140}\sim {370}^{\circ }\mathrm{C}$ ,该阶段主要是样品中挥发分的析出, 纤维素、半纤维素和木质素在对应的温度范围内挥发成气体,然后在高温条件下进行反应,样品的大部分重量会在此阶段失去; 第三阶段温度为 370~900 ${}^{\circ }\mathrm{C}$ ,主要进行炭化过程,此阶段内样品仍存在失重现象,但失重率远小于挥发阶段。
样品在不同气氛下的热解特性虽有所区别, 但规律大致相同。在同一升温速率图中可以看到, 干燥阶段 4 种气体氛围在 75 ℃附近均会出现一个肩状峰,随着气体中氧气含量的减少,肩峰越明显失重率越大,且出现峰值后移的现象。这是因为气体 1 为空气, 空气本身含有的水蒸气会吸收部分热量,氧气含量的减少使气体氧化性减弱,有利于结晶水析出。整个干燥阶段曲线规律一致,气体氛围对样品干燥阶段的影响较小。
在挥发阶段, 4 种气体氛围的热解曲线重合度较高,同一升温速率下不同气体氛围样品失重率先增大后减小,最大失重峰值对应的温度为 300 °C左右,不同气体氛围仅造成最大失重率微小变化。然而,不同升温速率下不同气体氛围的最大失重规律并不相同,10°C/min 时最大失重率为气体 $1 <$ 气体 2 $<$ 气体 4 $<$ 气体 3,20 ${}^{\circ }\mathrm{C}/\mathrm{{min}}$ 时最大失重率为气体 3<气体 2<气体 1<气体 4。这是因为在二氧化碳氧化性气氛中, 部分可挥发碱金属气态化合物会与硅(铝)酸盐发生反应生成不可挥发性物质, 使得挥发阶段失重率有所变化。由于此阶段大分子物质裂解为小分子物质, 温度是影响失重率的主要原因, 并且同一升温速率下曲线重合度较高。综合得出, 气体中的二氧化碳会影响样品的挥发阶段失重,但并不是主要原因。
在炭化阶段,曲线几乎不重合,气体氛围影响较大,氧气含量越多越容易发生反应。在同一升温速率图中比较不同气体氛围的曲线, 随着气体中氧气含量的减少失重峰值存在明显滞后现象,氧气含量越多,第三阶段内失重越快,炭化过程越早完成。这是由于热解过程中氧气参与炭化反应,局部出现燃烧现象,氧气含量越多燃烧现象越明显, 炭化越快, 气体氛围对样品炭化阶段产生了较大影响。
升温速率是影响热解过程的重要因素之一。 图 3 为不同气体氛围下, 4 种升温速率的反应进程和反应速率曲线。其中反应进程曲线中, 实线为实验得到的曲线, 虚线为热动力学软件模拟得到的曲线, 两条曲线相关系数较高, 平行度较强, 吻合性较好, 实验数据真实可靠, 同时也表明 AKTS 软件热动力学分析具有一定的可行性。对比不同升温速率的热解过程, 反应进程与反应速率曲线形状基本相同,但对各个阶段影响程度略有区别。
在较低升温速率下,4 种气体氛围的干燥阶段曲线完全重合, 热解起始温度相差不大, 升温速率对干燥阶段无影响。在挥发和炭化阶段,曲线急剧变化,升温速率越高反应速率越大。随着升温速率的升高, 热解的终止温度有所上升, 曲线出现向高温区偏移的现象。这主要是因为低升温速率下热解传热均匀, 样品的挥发和炭化阶段大分子物质有足够的时间充分反应; 升温速率增大时样品内部的温度来不及改变, 传热受到一定的影响, 使挥发分不易析出, 影响热解及炭化过程, 出现挥发炭化滞后现象。低升温速率有利于促使更多碳质结构暴露,改善热解过程,适当加快升温速率,可减少热解时间, 但升温速率过快会导致表面灰分熔融产生较大热阻,不利于热解进行。因此结合以上因素,选取 ${20}^{\circ }\mathrm{C}/\mathrm{{min}}$ 为最佳升温速率。
图 4 为不同气体氛围下整个反应进程中的活化能曲线。当氛围为气体 1 和气体 2 时, 活化能的变化趋势相同,自反应开始至反应进程 0.5 左右时活化能呈现上升趋势, 然后开始下降, 反应进程在 0.65 左右时活化能又开始上升, 反应进程在 0.7 以后逐渐下降, 气体 2 相对气体 1 存在滞后现象, 且气体 1 的波动幅度大于气体 2 。当氛围为气体 3 和气体 4 时, 活化能在反应刚开始时有一个先下降后上升的波动,反应进程在 0.6 左右时,活化能突然增加再降低, 气体 4 相对气体 3 存在滞后现象。氧气含量能够提高活化性能,在反应开始阶段空气气氛所需活化能较小,随着反应进行氧气不断消耗,所需活化能呈上升趋势。气体 1 和气体 2 反应过程中出现波动主要是由于氧气使局部出现燃烧, 导致温度迅速提升, 降低了所需活化能。反应即将结束时, 所有气氛下活化能均低于 ${80}\mathrm{\;{kJ}}/\mathrm{{mol}}$ ,这是由于样品已基本热解完,剩余的物质几乎不会再参与反应。
4 种气体氛围在整个反应进程中所需活化能平均值分别为162.44,139.86,164.09,164.55 $\mathrm{{kJ}}/\mathrm{{mol}}$ ,随着气体氛围中氧气含量的减小,活化能先降低后升高, 其中在气体 2 氛围下热解所需的活化能较少。
由于不同秸秆组成成分相差较大,不同产地对热解特性也会产生一定影响, 因此本文选取我国 3 个不同产地 (东北平原-黑龙江、华北平原- 北京、珠江三角洲平原-广州)的生物质秸秆与高寒坝上地区秸秆作对比, 讨论各地区秸秆的独特性。利用软件对秸秆的热解特性进行模拟,以期获得快速升温速率下的热解规律。
根据现有文献, 选取我国不同地区的生物质秸秆进行热解对比, 图 5 为黑龙江玉米和水稻秸秆 [ 7 ] 、张北莜麦秸秆、北京玉米秸秆 [ 14 ] 、广州水稻秸秆 [ 12 ] 热解的 TG 曲线。 图 6 为上述 4 种秸秆热解的 DTG 曲线, 其中, 黑龙江、北京、广州秸秆热解氛围均为高纯度 ${\mathrm{N}}_{2}$ ,张北莜麦秸秆选取 ${15}\%{\mathrm{O}}_{2}- 5\%$ ${\mathrm{{CO}}}_{2}- {80}\%{\mathrm{\;N}}_{2}$ 混合气体 (气体 2) 热解氛围,升温速率均为 ${20}^{\circ }\mathrm{C}/\mathrm{{min}}$ 。对比结果表明,张北莜麦秸秆和黑龙江秸秆热解比北京和广州地区更加充分, 黑龙江地区秸秆热解主要集中在 ${130}\sim {500}{}^{\circ }\mathrm{C}$ ,张北地区秸秆热解主要集中在 ${140}\sim {370}{}^{\circ }\mathrm{C}$ ,北京地区秸秆热解主要集中在 ${205}\sim {385}^{\circ }\mathrm{C}$ ,广州地区秸秆热解主要集中在 ${250}\sim {400}{}^{\circ }\mathrm{C}$ 。每个地区秸秆的热解特性各有特点,热解所需活化能相差较大,这与植物生长环境息息相关, 因此针对不同地区秸秆进行热解特性分析, 可对秸秆能源化利用起到事半功倍的效果。
现有热解实验中升温速率一般选择 5~40 ${}^{o}$ C/min,而对于较快升温速率并未进行研究。为此, 本文利用 AKTS 软件模拟莜麦秸秆在混合气体 2 氛围下的热解曲线, 探讨较快升温速率下的热解特性, 结果如 图 7 所示。由图可以看出: 升温速率越快热解反应速率峰值越大; 干燥阶段, 4 种升温速率几乎完全重合,升温速率对干燥过程无影响; 与较慢反应速率实验相同,较快升温速率下挥发和炭化阶段峰值仍存在向高温区偏移现象, 升温速率越快传热越不均匀,导致偏移现象越明显。
本文针对高寒坝上地区典型农作物秸秆进行热解特性分析, 得到了不同升温速率和不同气体氛围下的热解特性曲线, 并通过 FWO 模型方法计算其活化能,得到如下结论。
①在 4 种气体氛围下莜麦秸秆热解均可以分为 3 个阶段,第一干燥阶段温度为 ${30}\sim {140}^{\circ }\mathrm{C}$ , 生物质内水分散失; 第二挥发阶段温度为 140~ 370°C,此阶段挥发分析出,纤维素、半纤维素、 木质素分解为相应的小分子气体;第三炭化阶段温度为 ${370}\sim {900}{}^{\circ }\mathrm{C}$ ,这个阶段主要进行焦炭的形成反应。
②莜麦秸秆热解过程中,气体氛围对干燥阶段和挥发阶段影响较小,对炭化过程影响较大,气体中氧气含量越多炭化过程越容易发生反应。
③升温速率对干燥过程无影响,在挥发和炭化阶段会产生滞后现象,升温速率越大,反应速率越快, 反应结束时温度越高, 最佳升温速率为 20 °C/min。
④ 4 种气体氛围中, ${15}\%{\mathrm{O}}_{2}- 5\%{\mathrm{{CO}}}_{2}- {80}\%{\mathrm{\;N}}_{2}$ 混合气体(气体 2)热解过程所需的活化能最少,平均活化能为 139.86 kJ/mol。
  • 天津市教委科研计划项目(2023KJ218)
  • 天津市科技计划项目(19ZXBTSN00220)
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2024年第42卷第3期
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  • 接收时间:2022-07-06
  • 首发时间:2025-07-22
  • 出版时间:2024-03-20
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  • 收稿日期:2022-07-06
基金
天津市教委科研计划项目(2023KJ218)
天津市科技计划项目(19ZXBTSN00220)
作者信息
    1 河北工业大学 能源与环境工程学院 天津 300401
    2 河北省热科学与能源清洁利用技术重点实验室 天津 300401
    3 天津城建大学 能源与安全工程学院 天津 300384

通讯作者:

王冬计(1990-),男,博士,讲师,研究方向为农村建筑清洁供能。E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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