Article(id=1149769462573876181, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149769458706723113, articleNumber=null, orderNo=null, doi=10.12404/j.issn.1671-1815.2404485, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1718467200000, receivedDateStr=2024-06-16, revisedDate=1740412800000, revisedDateStr=2025-02-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1752056001561, onlineDateStr=2025-07-09, pubDate=1747497600000, pubDateStr=2025-05-18, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1752056001561, onlineIssueDateStr=2025-07-09, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1752056001561, creator=13701087609, updateTime=1752056001561, updator=13701087609, issue=Issue{id=1149769458706723113, tenantId=1146029695717560320, journalId=1146123166801305609, year='2025', volume='25', issue='14', pageStart='5705', pageEnd='6154', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=0, createTime=1752056000638, creator=13701087609, updateTime=1768456798957, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1218559392753041779, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149769458706723113, language=EN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1218559392753041780, tenantId=1146029695717560320, journalId=1146123166801305609, issueId=1149769458706723113, language=CN, specialIssueTitle=, coverIllustrator=, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=5976, endPage=5982, ext={EN=ArticleExt(id=1149769463035249627, articleId=1149769462573876181, tenantId=1146029695717560320, journalId=1146123166801305609, language=EN, title=Properties and Combustion Kinetics of Coalchar through High-Temperature Internals-Regulated Pyrolysis, columnId=1172606851066774020, journalTitle=Science Technology and Engineering, columnName=Papers·Chemical Industry, runingTitle=null, highlight=null, articleAbstract=

In order to understand the properties of char which is the main byproduct of coal pyrolysis in the reactor with internals, especially the char prepared at high temperatures, the char samples were prepared by pyrolysis of Yulin bituminous coal under vacuum condition between 1 000 ℃ and 1 500 ℃ in the fixed-bed reactor with internals. The variations of pore structure, composition, calorific value, and carbon structure of chars with pyrolysis temperature were studied. The isothermal combustion characteristic and kinetics were investigated by MFBRA(micro fluidized bed reaction analyzer). The results show that the increase in pyrolysis temperature leads to a deeper degree of pyrolysis. As the pyrolysis temperature increases, the C content and C/H molar ratio of chars gradually increase, H and O contents of chars gradually decreases, and the calorific value increases slightly. The specific surface area and pore volume of chars firstly decrease with the increase of pyrolysis temperature, and then remain essentially constant after the pyrolysis temperature exceeds 1 300 ℃, which is consistent with the trend of graphitization degree. The three-dimensional diffusion model G(x)=[1-(1-x)1/2]2 can well describe the combustion process of chars. The activation energy and pre-exponential factor increase with the increase of pyrolysis temperature, and vary in the range of 30.49~90.17 kJ/mol and 0.69~352.25 s-1, respectively. The significant decrease in combustion reactivity of char prepared above 1400 ℃ is mainly due to the sharp increase of C/H.

, correspAuthors=Xue-jing LIU, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, authorCompany=null, fund=null, authors=null, authorsList=Shuai XU, Hong ZHANG, Xue-jing LIU), CN=ArticleExt(id=1149769494987456990, articleId=1149769462573876181, tenantId=1146029695717560320, journalId=1146123166801305609, language=CN, title=内构件调控下高温热解煤焦理化性质与燃烧动力学, columnId=1172606851230351877, journalTitle=科学技术与工程, columnName=论文·化学工业, runingTitle=null, highlight=null, articleAbstract=为了认识内构件煤热解技术生成的主要副产物煤焦的性质,尤其是高温热解的煤焦,采用内构件热解反应器以榆林烟煤为原料于1 000~1 500 ℃真空条件下制备了煤焦,考察了煤焦孔结构、组成、热值、碳结构等理化性质随热解温度的变化规律,采用微型流化床反应分析仪研究了不同煤焦等温燃烧反应特性及动力学参数。结果表明,随着热解温度的增加,煤焦碳含量增加,氢和氧含量降低,C/H摩尔比升高,热值小幅度增加;煤焦比表面积和孔容先降低,但热解温度高于1 300 ℃后基本保持不变,石墨化程度与之变化趋势一致。煤焦燃烧过程可用三维扩散模型G(x)=[1-(1-x)1/2]2描述,活化能和指前因子随热解温度的增加而升高,分别在30.49~90.17 kJ/mol和0.69~352.25 s-1范围内变化,热解温度高于1 400 ℃后煤焦反应性大幅降低主要源于C/H的急剧增加。, correspAuthors=刘雪景, authorNote=null, correspAuthorsNote=
*刘雪景(1987—),女,汉族,辽宁沈阳人,博士,教授。研究方向:气固反应分析。E-mail:
, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=eCqMrUDnIBdquYgViLBMMA==, magXml=+GgCc1moyW2I57BJRSWtDg==, pdfUrl=null, pdf=dLWuSfPAhqO2EJ25zuFe1w==, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=7KGc5LzvEHbIXsWuwYVirA==, mapNumber=null, authorCompany=null, fund=null, authors=

徐帅(1999—),男,汉族,河南洛阳人,硕士研究生。研究方向:煤化工。E-mail:

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徐帅(1999—),男,汉族,河南洛阳人,硕士研究生。研究方向:煤化工。E-mail:

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language=EN, label=Fig.8, caption=Fitting curves of lnk and 1/T for different chars, figureFileSmall=LFeYEckIptZypxppfXrnZw==, figureFileBig=iBFMGhvPhCQyVIaLnEv0Mg==, tableContent=null), ArticleFig(id=1172984316939350800, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=CN, label=图8, caption=煤焦燃烧速率与温度的拟合曲线, figureFileSmall=LFeYEckIptZypxppfXrnZw==, figureFileBig=iBFMGhvPhCQyVIaLnEv0Mg==, tableContent=null), ArticleFig(id=1172984317006459666, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=EN, label=Table 1, caption=

Proximate and ultimate analysis of Yulin bituminous coal

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工业分析Wd/% 元素分析Wd/%
V A FC C H S N O
30.20 6.14 63.66 72.81 4.13 0.16 0.90 21.99
), ArticleFig(id=1172984317073568532, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=CN, label=表1, caption=

榆林烟煤的工业分析与元素分析

, figureFileSmall=null, figureFileBig=null, tableContent=
工业分析Wd/% 元素分析Wd/%
V A FC C H S N O
30.20 6.14 63.66 72.81 4.13 0.16 0.90 21.99
), ArticleFig(id=1172984317132288790, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=EN, label=Table 2, caption=

Proximate, ultimate and calorific value analysis of chars pyrolyzed at different temperatures

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样品 工业分析Wd/% 元素分析Wd/% C/H 热值/(MJ·kg-1)
V A FC C H S N O
YLC1 000 3.55 8.56 87.89 86.00 0.77 0.17 0.88 12.18 9.32 29.15
YLC1 100 3.31 8.62 88.07 86.71 0.66 0.15 0.93 11.55 10.89 29.38
YLC1 200 3.48 8.98 87.54 87.28 0.59 0.11 0.98 11.05 12.37 29.57
YLC1 300 2.98 8.87 88.24 87.03 0.49 0.14 0.90 11.45 14.74 29.47
YLC1 400 2.47 8.29 89.24 88.45 0.40 0.11 0.81 10.23 18.38 29.96
YLC1 500 2.30 8.53 89.17 89.00 0.31 0.14 0.71 9.84 23.66 30.14
), ArticleFig(id=1172984317216174872, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=CN, label=表2, caption=

不同煤焦的工业分析、元素分析和热值

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 工业分析Wd/% 元素分析Wd/% C/H 热值/(MJ·kg-1)
V A FC C H S N O
YLC1 000 3.55 8.56 87.89 86.00 0.77 0.17 0.88 12.18 9.32 29.15
YLC1 100 3.31 8.62 88.07 86.71 0.66 0.15 0.93 11.55 10.89 29.38
YLC1 200 3.48 8.98 87.54 87.28 0.59 0.11 0.98 11.05 12.37 29.57
YLC1 300 2.98 8.87 88.24 87.03 0.49 0.14 0.90 11.45 14.74 29.47
YLC1 400 2.47 8.29 89.24 88.45 0.40 0.11 0.81 10.23 18.38 29.96
YLC1 500 2.30 8.53 89.17 89.00 0.31 0.14 0.71 9.84 23.66 30.14
), ArticleFig(id=1172984317316838170, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=EN, label=Table 3, caption=

Pore structure of chars pyrolyzed at different temperatures

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 比表面积/
(m2·g-1)
孔容/
(10-2cm3·g-1)
平均孔径/nm
YLC1 000 79.10 5.250 2.656
YLC1 100 53.10 3.530 2.660
YLC1 200 35.60 3.114 3.502
YLC1 300 16.10 1.793 4.464
YLC1 400 19.90 2.362 4.744
YLC1 500 16.50 2.250 5.453
), ArticleFig(id=1172984317400724252, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=CN, label=表3, caption=

不同煤焦的孔结构

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 比表面积/
(m2·g-1)
孔容/
(10-2cm3·g-1)
平均孔径/nm
YLC1 000 79.10 5.250 2.656
YLC1 100 53.10 3.530 2.660
YLC1 200 35.60 3.114 3.502
YLC1 300 16.10 1.793 4.464
YLC1 400 19.90 2.362 4.744
YLC1 500 16.50 2.250 5.453
), ArticleFig(id=1172984317451055901, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=EN, label=Table 4, caption=

Kinetic data for combustion of chars prepared at different temperatures

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 活化能/(kJ·mol-1) 指前因子/s-1 相关系数
YLC1000 30.49 0.69 0.99
YLC1100 40.48 2.07 0.89
YLC1200 45.60 3.49 0.93
YLC1300 60.21 14.34 0.98
YLC1400 61.13 15.55 0.93
YLC1500 90.17 352.25 0.98
), ArticleFig(id=1172984317522359071, tenantId=1146029695717560320, journalId=1146123166801305609, articleId=1149769462573876181, language=CN, label=表4, caption=

不同煤焦的燃烧动力学参数

, figureFileSmall=null, figureFileBig=null, tableContent=
样品 活化能/(kJ·mol-1) 指前因子/s-1 相关系数
YLC1000 30.49 0.69 0.99
YLC1100 40.48 2.07 0.89
YLC1200 45.60 3.49 0.93
YLC1300 60.21 14.34 0.98
YLC1400 61.13 15.55 0.93
YLC1500 90.17 352.25 0.98
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内构件调控下高温热解煤焦理化性质与燃烧动力学
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徐帅 1 , 张虹 2 , 刘雪景 1, *
科学技术与工程 | 论文·化学工业 2025,25(14): 5976-5982
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科学技术与工程 | 论文·化学工业 2025, 25(14): 5976-5982
内构件调控下高温热解煤焦理化性质与燃烧动力学
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徐帅1 , 张虹2, 刘雪景1, *
作者信息
  • 1. 沈阳化工大学特色资源化工与材料教育部重点实验室, 沈阳 110142
  • 2. 沈阳工业大学材料科学与工程学院, 沈阳 110870
  • 徐帅(1999—),男,汉族,河南洛阳人,硕士研究生。研究方向:煤化工。E-mail:

通讯作者:

*刘雪景(1987—),女,汉族,辽宁沈阳人,博士,教授。研究方向:气固反应分析。E-mail:
Properties and Combustion Kinetics of Coalchar through High-Temperature Internals-Regulated Pyrolysis
Shuai XU1 , Hong ZHANG2, Xue-jing LIU1, *
Affiliations
  • 1. Key Laboratory on Resources Chemicals and Materials of Ministry of Education, Shenyang University of Chemical Technology, Shenyang 110142, China
  • 2. School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, China
出版时间: 2025-05-18 doi: 10.12404/j.issn.1671-1815.2404485
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为了认识内构件煤热解技术生成的主要副产物煤焦的性质,尤其是高温热解的煤焦,采用内构件热解反应器以榆林烟煤为原料于1 000~1 500 ℃真空条件下制备了煤焦,考察了煤焦孔结构、组成、热值、碳结构等理化性质随热解温度的变化规律,采用微型流化床反应分析仪研究了不同煤焦等温燃烧反应特性及动力学参数。结果表明,随着热解温度的增加,煤焦碳含量增加,氢和氧含量降低,C/H摩尔比升高,热值小幅度增加;煤焦比表面积和孔容先降低,但热解温度高于1 300 ℃后基本保持不变,石墨化程度与之变化趋势一致。煤焦燃烧过程可用三维扩散模型G(x)=[1-(1-x)1/2]2描述,活化能和指前因子随热解温度的增加而升高,分别在30.49~90.17 kJ/mol和0.69~352.25 s-1范围内变化,热解温度高于1 400 ℃后煤焦反应性大幅降低主要源于C/H的急剧增加。
煤焦  /  燃烧  /  内构件  /  动力学  /  微型流化床

In order to understand the properties of char which is the main byproduct of coal pyrolysis in the reactor with internals, especially the char prepared at high temperatures, the char samples were prepared by pyrolysis of Yulin bituminous coal under vacuum condition between 1 000 ℃ and 1 500 ℃ in the fixed-bed reactor with internals. The variations of pore structure, composition, calorific value, and carbon structure of chars with pyrolysis temperature were studied. The isothermal combustion characteristic and kinetics were investigated by MFBRA(micro fluidized bed reaction analyzer). The results show that the increase in pyrolysis temperature leads to a deeper degree of pyrolysis. As the pyrolysis temperature increases, the C content and C/H molar ratio of chars gradually increase, H and O contents of chars gradually decreases, and the calorific value increases slightly. The specific surface area and pore volume of chars firstly decrease with the increase of pyrolysis temperature, and then remain essentially constant after the pyrolysis temperature exceeds 1 300 ℃, which is consistent with the trend of graphitization degree. The three-dimensional diffusion model G(x)=[1-(1-x)1/2]2 can well describe the combustion process of chars. The activation energy and pre-exponential factor increase with the increase of pyrolysis temperature, and vary in the range of 30.49~90.17 kJ/mol and 0.69~352.25 s-1, respectively. The significant decrease in combustion reactivity of char prepared above 1400 ℃ is mainly due to the sharp increase of C/H.

char  /  combustion  /  internals  /  kinetics  /  micro fluidized bed
徐帅, 张虹, 刘雪景. 内构件调控下高温热解煤焦理化性质与燃烧动力学. 科学技术与工程, 2025 , 25 (14) : 5976 -5982 . DOI: 10.12404/j.issn.1671-1815.2404485
Shuai XU, Hong ZHANG, Xue-jing LIU. Properties and Combustion Kinetics of Coalchar through High-Temperature Internals-Regulated Pyrolysis[J]. Science Technology and Engineering, 2025 , 25 (14) : 5976 -5982 . DOI: 10.12404/j.issn.1671-1815.2404485
中国低阶煤资源储量丰富,约占已探明煤炭总储量的55%以上[1]。目前中国利用低阶煤的主要方式为直接燃烧和气化,然而上述方式并未使低阶煤中高价值的油气资源得到合理利用[2-3]。通过将低阶煤热解提取其中高附加值的焦油和煤气而副产品煤焦燃烧的工艺路线是实现中国低阶煤高效分级利用的重要途径[4]。了解副产品煤焦的性质及其燃烧动力学,对于实现中国煤炭的清洁高效利用具有一定的意义。
数十年来,中外开展了大量以提高煤热解焦油产率和品质为目标的研究工作,这些热解技术主要包括外热式(Toscoal技术、COED技术和Encoal技术等)和内热式(MRF技术、DG技术、LR技术和W-D技术等)工艺[5-7]。由于受限于逆向传热传质,热解制油技术只能在中低温下运行[8],此时热解气收率低,无法实现油、气的联产。为此,许光文团队提出了一种内构件调控的煤热解技术[9],通过在反应器中央设置集气内构件,调控热解挥发分由高温区向低温区流动,实现了焦油二次反应的最小化。团队最新研究结果表明,内构件调控的热解反应中,随着热解温度从600 ℃增加到1 500 ℃,热解油、气的收率保持持续增加的趋势,这表明高温热解是新技术联产油气的最佳运行温度。然而,高温热解过程中同时产生了大量煤焦,这部分煤焦利用是下一步解决的重点。由于高温下煤焦高度芳香化、石墨化,反应活性较差,燃烧是其利用的有效途径。目前,关于内构件调控下高温煤焦的燃烧特性、动力学尚未有相关报道,本文研究将对此开展系统研究。
此前大部分关于煤焦燃烧特性及动力学的研究采用热重分析仪(thermogravimetric analyzer, TGA)。TGA具有操作简便、灵敏度高、样品要求量少、原位检测和准确高效等优点,被广泛用于研究气固反应的动力学[10]。然而,受测量原理与结构的限制,TGA传热速率慢,煤焦燃烧过程中释放大量的反应热导致温度瞬间升高,从而偏离设定温度,影响实验的准确性[11-12];另一方面,样品颗粒堆积在坩埚内,坩埚的高度、样品的质量等条件均会对实验产生一定的影响,且产生的气体产物会停留在颗粒周围,不能及时随气流排出,致使反应过程中受到外扩散阻力严重。
针对TGA存在的问题,Wang等[13]设计并开发了微型流化床反应分析仪(micro fluidized bed reaction analyzer, MFBRA)。它能够利用流化床传热传质速率快、外扩散抑制最小化的优点将样品脉冲瞬时打入反应器内,与热载体颗粒快速混合加热等温化,生成的气体产物以平推流的方式进入过程质谱实时检测,依据气体产物随时间的变化求算反应速率与动力学参数,进而推测反应机理。经过十几年的发展,MFBRA已成为一项与TGA相互补充的成熟的气固反应分析手段,广泛应用于气化、热解、分解、还原等反应分析与动力学计算[14-15]
因此,现以榆林烟煤为原料,采用具有内构件的反应器于1 000~1 500 ℃范围内真空热解制备煤焦,并利用N2吸附仪、元素分析仪、共聚焦原位拉曼光谱仪等对煤焦结构进行分析,此外,采用MFBRA研究热解温度对煤焦燃烧行为的影响,并根据等温法求算燃烧动力学参数,初步揭示煤焦理化性质对煤焦燃烧反应行为及动力学的影响。为内构件调控下高温煤焦的燃烧利用提供一定的理论指导和数据支持。
实验选取陕西榆林烟煤为原料,实验前先破碎并筛分至2~3 mm,放入105 ℃烘箱内干燥12 h后备用,其工业分析和元素分析结果如表1所示。
实验用煤焦样品在如图1所示的装置中真空条件下热解生成。该装置主要分为三部分:真空系统、电加热炉、带有内构件的热解反应器。预先将约300 g榆林烟煤放入带有内构件(内径为20 mm)的热解反应器(内径为80 mm,材质为耐高温氮化硼)中,之后抽真空,使反应器内压力达到-80 kPa。加热炉达到预设温度后(1 000、1 100、1 200、1 300、1 400、1 500 ℃),迅速将处于真空状态的反应器推入电加热炉中,待反应器内中心温度与预设温度接近时,热解完成,取出反应器,冷却至室温后取出煤焦。采用四分法选取煤焦样品,研磨至75~120 μm备用,根据热解温度的不同,将煤焦分别命名为YLC1 000、YLC1 100、YLC1 200、YLC1 300、YLC1 400、YLC1 500。
全自动比表面积及孔径分布测定仪(日本麦奇克拜尔公司,BELSORP-miniX)用于测定煤焦的比表面积、孔体积和孔径分布,带有吹扫捕集技术的元素分析仪(德国Eelmentar,Vario El cube型)用于测定煤样及所制煤焦的元素组成,共聚焦原位拉曼光谱仪(日本Horiba,LabRAM HR Evolution)用于测定煤焦的碳结构,激光波长为514 nm。
煤焦燃烧实验用MFBRA的流程示意图如图2所示。详尽的仪器介绍可以参考文献[16]。实验以3 g左右、粒径范围90~160 μm的石英砂作为流化介质和热载体,以空气为载气,流速为500 mL/min,实验温度为700~850 ℃。实验时,预先将石英砂置于微型流化床反应器(石英材质,内径20 mm)内,加热至预设温度后,在稳定流化状态下采用脉冲将样品打入微型流化床反应器内,反应生成的CO2气体通过过程质谱实时在线监测其含量变化。为了保证实验结果的可靠性,每次实验重复3次。
相对于CO2,煤焦燃烧过程中生成CO的量很少,可忽略不计。因此MFBRA中煤焦在任意时刻燃烧对应的转化率xi可通过式(1)计算。
x i = S t 0 t i S t 0 t e = t 0 t i I t i d t t 0 t e I t i d t × 100 %
其中:t0为燃烧的初始反应时间时间,s;ti为反应过
程中的某一时间,s;te为反应终止时间,s;Iti为反应中某一时刻ti的CO2信号强度;   S t 0 t i S t 0 t e分别为t0tit0te的CO2信号强度积分面积。
反应速率Ri由式(2)计算获得
R i = d x i d t = k ( T ) f ( x ) = A e x p - E R T f ( x )
式(2)中:t为反应时间,s;E为活化能,kJ/(mol);A为指前因子,s-1;T为热力学温度,K;R为普适气体常量,8.314 J/(mol·K);k(T)为反应速率常数;f(x)为机理函数。
等温条件下,机理函数的积分形式为
G ( x ) = 0 x d x f ( x ) = 0 t k ( T ) d t = k ( T ) t
比较常用的燃烧反应机理函数与时间的线性度、线型范围相关系数,选择最概然机理函数。确
定机理函数 f ( x )与速率常数 k ( T )后,对阿伦乌尼斯公式取自然对数,可得
l n k ( T ) = - E R T + l n A
l n k ( T ) - 1 / T作图并进行线性拟合,根据其斜率和截距分别得到活化能E和指前因子A
表2列出了不同热解温度下高温煤焦的工业分析、元素分析、C/H摩尔比和热值结果。由表2中的工业分析可知,随着热解温度的升高,煤焦的固定碳含量逐渐增加,挥发分含量逐渐降低。煤的热解过程实际上是富碳、去氢、脱氧的过程,煤焦固定碳和挥发分含量与元素分析中C含量和H含量随热解温度变化的趋势一致,即随着热解温度的增加,煤焦中C含量逐渐增加,H和O的含量逐渐下降。比较不同热解温度下制备煤焦的C/H摩尔比发现,随着热解温度由1 000 ℃升高至1 500 ℃,C/H摩尔比从9.32增加至23.66,表明随着热解温度的增加,煤热解反应程度随温度的升高而增大。随着热解程度的加深,固体产物煤焦中的H由于裂解和缩聚脱氢释放出烃类等挥发分,O主要形成热解气体和热解水[17]。同时,煤焦热值随热解温度的升高而小幅度增加,从29.15 MJ/kg增加至30.14 MJ/kg。
采用低温N2吸附法对不同热解温度煤焦样品的孔结构进行了测试,其结果如表3所示。从表3可以明显看出,随着热解温度从1 000 ℃升高至1 300 ℃,煤焦的比表面积从79.1 m2/kg逐渐降低至16.1 m2/kg;孔容从5.25×10-2 cm3/g逐渐降低至1.793×10-2 cm3/g。进一步增加温度,煤焦的比表面积和总孔体积均不再明显变化。煤焦平均孔径则随热解温度的升高而增加,当热解温度为1 500 ℃,煤焦的平均孔径增加至5.453 nm。这主要是因为当温度超过1 300 ℃时,煤焦发生烧结现象,破坏了更多的微孔结构,微孔逐渐合并形成中孔[18]
高温热解条件下煤焦发生石墨化现象,其碳结构向有序化方向发展。通过对煤焦的拉曼光谱图分峰拟合可获得不同碳结构的参数,图3描述了煤焦YLC1 000的拉曼光谱(1000-raw)及拟合结果(1000-fit),分峰拟合的5个特征峰中,D1峰、D2峰、D4峰和G峰划分为Lorentzian峰,D3峰划分为Gaussian峰。其中G峰(1 580 cm-1)为理想石墨晶格的拉伸振动模式,通过计算G峰与总峰面积之比可获得石墨化程度[19]图4为计算的不同热解温度煤焦的石墨化程度,从图4中可知,随着热解温度的增加,石墨化程度呈现先缓慢增加后趋于稳定的趋势。
图5对比了MFBRA中反应温度为700~850 ℃时YLC1 000与700 ℃时不同煤焦的燃烧转化率随时间的变化曲线。由图5(a)可知,在较低的反应温度下,煤焦燃烧较慢,完全燃烧所需时间较长,随着反应温度的增加,反应加快,完全燃烧所需时间逐渐缩短。700 ℃时,YLC1 000完全燃烧所需时间约90 s,温度增加至850 ℃时,时间缩短至51 s。当反应温度高于800 ℃时,完全燃烧所需时间的差异性变小。YLC1000在800 ℃时完全燃烧所需时间为55 s,与850 ℃时仅相差4 s。其他热解温度制备的煤焦燃烧转化率随时间的变化曲线与图5(a)描述YLC1000的趋势一致。由图5(b)可以看出,相同反应温度下,YLC1000、YLC1100、YLC1200完全燃烧所需时间差异性较小,分别为61、76、87 s,而随着热解温度进一步增加,完全燃烧所需时间增加的幅度越来越大,YLC1300完全燃烧所需时间为107 s,YLC1400、YLC1500与之相比分别需要增加34 s和40 s才能完全燃烧。这与文献报道的趋势是一致的,即煤热处理温度越高,燃烧活性下降的幅度越大[20-21]
图6(a)进一步对比了MFBRA中反应温度范围内YLC1000的燃烧转化率随时间的变化曲线。如图6(a)所示,反应前期(x<0.1),反应温度越高,达到最大反应速率对应的转化率越低,700 ℃时,YLC1000最大反应速率对应转化率为0.2,当温度高于750 ℃时,转化率低于0.1就可达到最大反应速率,说明MFBRA具有升温速率快以及适用于等温反应的特性;反应中期,在一定转化率范围内,煤焦的燃烧均保持了较高的反应速率;反应后期(x>0.8),由于反应物浓度的降低,反应速率随反应程度的加深而逐渐变小。图6(b)描述了700 ℃时不同煤焦的转化率与反应速率的关系。相同温度下,煤焦的燃烧反应速率随热解温度的升高而降低,其最大反应速率对应的转化率也随之降低,主要源于高温热解使煤焦的部分孔结构发生塌陷,比表面积的减少,导致煤焦的燃烧性能降低。
根据文献报道的常用燃烧机理模型[22],分别为成核与生长模型G(x)=[-ln(1-x)]2/3、三维扩散模型G(x)=[1-(1-x)1/2]2、几何收缩模型G(x)=1-(1-x)1/4,通过对比不同温度下不同煤焦燃烧的G(x)与t的线性拟合度与线型范围,发现三维扩散模型G(x)=[1-(1-x)1/2]2拟合结果最佳。图7展示了YLC1 000所选三维扩散模型的积分形式与时间的拟合结果。可以发现,不同温度下,G(x)与t的线性拟合相关系数均超过0.95,说明三维扩散模型可以很好地描述煤焦燃烧过程。
应用三维扩散模型可计算得到不同温度下的反应速率常数,根据阿伦乌尼斯公式,以lnk与10 000/T作图,结果如图8所示。lnk与10 000/T呈现出良好的线性关系,线性相关系数均超过0.9,根据其斜率和截距,分别求取指前因子和活化能,其结果如表4所示。由表4可见,不同热解温度煤焦的燃烧活化能具有一定的差异性。随着热解温度从1 000 ℃升高至1 500 ℃,活化能由30.49 kJ/mol增加至90.17 kJ/mol,煤焦的燃烧反应性逐渐变差。其中,煤焦YLC1 000-YLC1 400的活化能和指前因子变化趋势与其比表面积的变化趋势相同,而YLC1500的活化能和指前因子的增幅明显增加,这可能与其C/H的增大有关。
采用内构件真空热解工艺在1 000~1 500 ℃温度范围内制备了煤焦,考察了热解温度对煤焦结构的影响,并利用MFBRA研究了煤焦的等温燃烧行为及动力学,得出以下结论。
(1)随着热解温度的升高,热解程度逐渐加深,煤焦中C含量逐渐增加,H和O的含量逐渐下降,C/H逐渐减小,热值略有增加;热解温度从1 000 ℃增加至1 300 ℃时,煤焦比表面积和孔体积逐渐降低,石墨化程度逐渐升高;当温度高于1 300 ℃后,比表面积、孔体积与石墨化程度基本保持不变,平均孔径则呈现一直增加的趋势。
(2)热解温度的增加降低了煤焦的燃烧反应性,且热解温度越高,燃烧活性下降的幅度越大,燃烧活化能和指前因子越高。
(3)内构件真空热解工艺高温所制煤焦的燃烧过程符合三维扩散模型G(x)=[1-(1-x)1/2]2
以上结果为内构件调控下高温煤焦的燃烧利用提供可靠理论指导和数据支持。
  • 辽宁省教育厅基金(JYTMS20231496)
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2025年第25卷第14期
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doi: 10.12404/j.issn.1671-1815.2404485
  • 接收时间:2024-06-16
  • 首发时间:2025-07-09
  • 出版时间:2025-05-18
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  • 收稿日期:2024-06-16
  • 修回日期:2025-02-25
基金
辽宁省教育厅基金(JYTMS20231496)
作者信息
    1. 沈阳化工大学特色资源化工与材料教育部重点实验室, 沈阳 110142
    2. 沈阳工业大学材料科学与工程学院, 沈阳 110870

通讯作者:

*刘雪景(1987—),女,汉族,辽宁沈阳人,博士,教授。研究方向:气固反应分析。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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