Article(id=1236679389908366332, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236679384321544791, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202404077, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1713456000000, receivedDateStr=2024-04-19, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1772776942945, onlineDateStr=2026-03-06, pubDate=1735056000000, pubDateStr=2024-12-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1772776942945, onlineIssueDateStr=2026-03-06, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1772776942945, creator=13701087609, updateTime=1772776942945, updator=13701087609, issue=Issue{id=1236679384321544791, tenantId=1146029695717560320, journalId=1210938733613449225, year='2024', volume='53', issue='12', pageStart='1', pageEnd='160', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1772776941614, creator=13701087609, updateTime=1772777031740, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1236679762404504298, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236679384321544791, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1236679762404504299, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1236679384321544791, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=151, endPage=160, ext={EN=ArticleExt(id=1236679390231326724, articleId=1236679389908366332, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Probing the pyrolysis mechanism of alkylbenzene insulating oil in oil-filled cables based on ReaxFF-MD and TG-IR, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

The safe and stable operation of submarine oil-filled cables is critical, but the internal dodecylbenzene (DDB) insulating oil is subject to rapid pyrolysis and gas production at localized high temperatures due to thermal faults. Against this issue, the pyrolysis and gas production processes of dodecylbenzene insulating oil are investigated based on reactive molecular dynamics simulations (ReaxFF-MD) and thermogravimetric-infrared spectroscopy (TG-IR) experiments. The pyrolysis simulation results show that, the initial cracking reaction of the dodecylbenzene molecule is mainly the breaking of C—C bond to produce long-chain macromolecules, and then the gradual pyrolysis produces small alkyl radicals and olefinic molecules, and the DDB will eventually be pyrolyzed to the short-chain alkylbenzene molecules with the side chains of ·C2H5, ·CH3 and ·C3H7 groups. The main characteristic gases during pyrolysis are C2H4, H2, and CH4, which are the same as the results of IR experiments, and the main reaction mechanisms for the generation of the characteristic gases are: (i) the breaking of the C—C bond at the β-position, the hydrogenation reaction, and the dehydrogenation reaction; (ii) the attack of -H radicals to the H atoms on other radicals; and (iii) the reaction of the methyl radicals (·CH3) with the free hydrogen (·H) radicals, respectively. The kinetic results show that the activation energies of the TG experiment and ReaxFF-MD are 86.606 kJ/mol as well as 99.867 kJ/mol, respectively, and the similar activation energies further validate the reasonableness of the simulation results. The study conclusion provides theoretical support for deep understanding of the cracking and gas production mechanism of dodecylbenzene insulating oil.

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海底充油电缆的安全稳定运行至关重要,但内部的十二烷基苯(DDB)绝缘油在热故障导致的局部高温下会快速热解和产气。基于反应分子动力学模拟(ReaxFF-MD)和热重-红外光谱(TG-IR)实验,对十二烷基苯绝缘油的热解和产气过程进行探究。热解模拟结果表明:十二烷基苯分子初始裂解反应主要为C—C键的断裂产生长链大分子,后逐渐热解产生小烷基自由基和烯烃分子,DDB最终会热解为侧链为·C2H5、·CH3和·C3H7基团的短链烷基苯分子。热解过程中主要特征气体为C2H4、H2、CH4,与IR实验结果相同,特征气体生成的主要反应机理分别为:β位C—C键的断裂、加氢反应和脱氢反应;·H自由基攻击其他自由基上的H原子;甲基自由基(·CH3)与游离的氢(·H)自由基反应。动力学结果表明TG实验与ReaxFF-MD的活化能分别为86.606 kJ/mol以及99.867 kJ/mol,相近的活化能进一步验证了仿真结果的合理性。研究结论为深入了解十二烷基苯绝缘油的裂解和产气机理提供了理论支持。

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朱志平(1963),男,博士,教授,主要研究方向为电力化学,
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刘志峰(1995),男,硕士,工程师,主要研究方向为电力化学,

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基于ReaxFF-MD与TG-IR探究充油电缆中烷基苯绝缘油热解机理
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刘志峰 1 , 杨伟琪 2 , 廖建平 1 , 朱志平 2 , 汪红梅 2
热力发电 | 发电技术论坛 2024,53(12): 151-160
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热力发电 | 发电技术论坛 2024, 53(12): 151-160
基于ReaxFF-MD与TG-IR探究充油电缆中烷基苯绝缘油热解机理
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刘志峰1 , 杨伟琪2, 廖建平1, 朱志平2 , 汪红梅2
作者信息
  • 1.南方电网超高压输电公司电力科研院,广东 广州 510663
  • 2.长沙理工大学化学化工学院,湖南 长沙 410114
  • 刘志峰(1995),男,硕士,工程师,主要研究方向为电力化学,

通讯作者:

朱志平(1963),男,博士,教授,主要研究方向为电力化学,
Probing the pyrolysis mechanism of alkylbenzene insulating oil in oil-filled cables based on ReaxFF-MD and TG-IR
Zhifeng LIU1 , Weiqi YANG2, Jianping LIAO1, Zhiping ZHU2 , Hongmei WANG2
Affiliations
  • 1.Electric Power Research Institute of Southern Power Grid EHV Transmission Company, Guangzhou 510663, China
  • 2.College of Chemistry and Chemical Engineering, Changsha University of Science and Technology, Changsha 410114, China
出版时间: 2024-12-25 doi: 10.19666/j.rlfd.202404077
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海底充油电缆的安全稳定运行至关重要,但内部的十二烷基苯(DDB)绝缘油在热故障导致的局部高温下会快速热解和产气。基于反应分子动力学模拟(ReaxFF-MD)和热重-红外光谱(TG-IR)实验,对十二烷基苯绝缘油的热解和产气过程进行探究。热解模拟结果表明:十二烷基苯分子初始裂解反应主要为C—C键的断裂产生长链大分子,后逐渐热解产生小烷基自由基和烯烃分子,DDB最终会热解为侧链为·C2H5、·CH3和·C3H7基团的短链烷基苯分子。热解过程中主要特征气体为C2H4、H2、CH4,与IR实验结果相同,特征气体生成的主要反应机理分别为:β位C—C键的断裂、加氢反应和脱氢反应;·H自由基攻击其他自由基上的H原子;甲基自由基(·CH3)与游离的氢(·H)自由基反应。动力学结果表明TG实验与ReaxFF-MD的活化能分别为86.606 kJ/mol以及99.867 kJ/mol,相近的活化能进一步验证了仿真结果的合理性。研究结论为深入了解十二烷基苯绝缘油的裂解和产气机理提供了理论支持。

十二烷基苯  /  热解  /  产气  /  ReaxFF-MD  /  TG-IR  /  反应机理

The safe and stable operation of submarine oil-filled cables is critical, but the internal dodecylbenzene (DDB) insulating oil is subject to rapid pyrolysis and gas production at localized high temperatures due to thermal faults. Against this issue, the pyrolysis and gas production processes of dodecylbenzene insulating oil are investigated based on reactive molecular dynamics simulations (ReaxFF-MD) and thermogravimetric-infrared spectroscopy (TG-IR) experiments. The pyrolysis simulation results show that, the initial cracking reaction of the dodecylbenzene molecule is mainly the breaking of C—C bond to produce long-chain macromolecules, and then the gradual pyrolysis produces small alkyl radicals and olefinic molecules, and the DDB will eventually be pyrolyzed to the short-chain alkylbenzene molecules with the side chains of ·C2H5, ·CH3 and ·C3H7 groups. The main characteristic gases during pyrolysis are C2H4, H2, and CH4, which are the same as the results of IR experiments, and the main reaction mechanisms for the generation of the characteristic gases are: (i) the breaking of the C—C bond at the β-position, the hydrogenation reaction, and the dehydrogenation reaction; (ii) the attack of -H radicals to the H atoms on other radicals; and (iii) the reaction of the methyl radicals (·CH3) with the free hydrogen (·H) radicals, respectively. The kinetic results show that the activation energies of the TG experiment and ReaxFF-MD are 86.606 kJ/mol as well as 99.867 kJ/mol, respectively, and the similar activation energies further validate the reasonableness of the simulation results. The study conclusion provides theoretical support for deep understanding of the cracking and gas production mechanism of dodecylbenzene insulating oil.

dodecylbenzene  /  pyrolysis  /  gas production  /  ReaxFF-MD  /  TG-IR  /  reaction mechanism
刘志峰, 杨伟琪, 廖建平, 朱志平, 汪红梅. 基于ReaxFF-MD与TG-IR探究充油电缆中烷基苯绝缘油热解机理. 热力发电, 2024 , 53 (12) : 151 -160 . DOI: 10.19666/j.rlfd.202404077
Zhifeng LIU, Weiqi YANG, Jianping LIAO, Zhiping ZHU, Hongmei WANG. Probing the pyrolysis mechanism of alkylbenzene insulating oil in oil-filled cables based on ReaxFF-MD and TG-IR[J]. Thermal Power Generation, 2024 , 53 (12) : 151 -160 . DOI: 10.19666/j.rlfd.202404077
充油电缆具有耐压强度高、性能稳定、寿命长等优点,目前仍是海底电缆、过江电缆等高电压、大容量场合的首选电缆,如广东—海南联网500 kV、广州抽水蓄能4回500 kV等工程。国内充油电缆的绝缘油一般为软质十二烷基苯(DDB)[1-5]。充油电缆在运行过程中,其绝缘油会受到热[6-8]等因素的影响,加速十二烷基苯裂化和产气速率,导致绝缘性能降低,影响电力设备安全稳定运行。因此研究烷基苯在热应力下的热解过程,并分析烷基苯绝缘油特征气体的产气路径,将对充油电缆绝缘领域具有重要意义。
国内外学者从宏观角度研究了十二烷基苯绝缘油在热作用下的劣化和产气规律。英国南安普敦大学的Hosier等人[9-10]进行了十二烷基苯绝缘油在不同温度下的热老化实验,利用红外光谱证明了芳香酮和脂肪族羧酸主要是在老化的十二烷基苯上形成的。廖建平等[6]则是利用溶解气体分析(DGA)技术对十二烷基苯绝缘油在不同温度下的热解产气进行分析,研究结果表明在热场的作用下,标志性气体为C2H4、CH4和H2。目前十二烷基苯绝缘油的现有相关研究较少,并且主要是研究十二烷基苯绝缘油在老化过程中理化电气性能的变化,缺乏对其在微观结构方面的探究,不能确切地对热故障下十二烷基苯绝缘油的热解机理和产气规律进行解释。
近些年来,学科之间交叉的加深[11],计算化学备受关注。在电气用油学科中利用反应力场[12](reactive force field,ReaxFF)进行分子动力学模拟(molecular dynamics,MD)实验,其计算精度高,运算量少,现已经成为研究油类等物质热解[13-15]过程的主流方法之一。Cong等人[16]利用ReaxFF-MD模拟研究了铜对绝缘油裂化的催化机理。Arvelos等人[17]对环己酮进行热解模拟,利用模拟来证实了实验的反应路径。郑含博等[18]利用密度泛函理论(DFT)和ReaxFF-MD对棕榈油的热故障进行了微观机理研究,分析了热解过程中氢键的数量变化,揭示了天然酯绝缘油耐用性高的原因。这些成功的案例为利用ReaxFF-MD模拟对研究油类物质热解机理奠定了基础。此外还有学者利用TG-IR相结合的方法来研究物质的分子组成[19-20]以及热解路径[21]之间的关系,并结合ReaxFF-MD来研究物质的热解机理[22]
本文利用ReaxFF-MD来模拟十二烷基苯绝缘油在热场下的热解过程和产气规律,并结合TG-IR测试对其进行验证。研究温度对十二烷基苯绝缘油热解的影响,并将其模拟结果与实验热解产气规律[6]和热分析实验结果进行对比。此外,还利用DFT方法计算十二烷基苯绝缘油模型的键解离能(BDE),对十二烷基苯绝缘油初始热解进行分析。
ReaxFF反应力场最早是由Van Duin在2001年提出,其能量函数如式(1)所示,该方法综合了量子力学(QM)和分子力学(MM),依据键级(BO)的大小对2个原子之间是否成键进行判断,通常BO≥0.3[23]时,则认为原子之间形成了化学键。
Esystem=Ebond+EovEr+EundEr+Eval+EpEn+Etors+Econj+EvdWaals+EConlomb+Elp
式中:Ebond为键能;Elp为孤对电子能量项;EoverEunder分别为矫正项中的过配位和欠配位原子能量;Eval为键角能量项;Epen为修正函数;Etors为扭转角能量项;Econj为共轭效应能量项;EvdWaals为范德华相互作用;ECoulomb为库仑相互作用。ReaxFF力场通过计算当前时刻的势能来计算出下一个时刻原子键的距离和键能,进而得出下个时刻原子间化学键的断裂和生成情况[24]
本文使用DFT法对十二烷基苯结构的侧链进行键的解离能(BDE)[25]计算,由于仅是对单个分子进行计算,因此计算过程不需要添加弥散函数。计算使用应用广泛的杂化泛函B3LYP,为了保证计算的精度,最终选择6-311G基组[26],计算的原理[27]如下:
BDEA-B=H(A)+H(B)-H(A-B)
式(2)右侧3项分别对应片段的生成焓。本文中所有的量子化学计算均在Gaussian 09程序中进行。
本文选取侧烷基链不带支链的软质十二烷基苯绝缘油进行模拟,单个十二烷基苯绝缘油分子如图1所示,图中白色为H,灰色为C。具体操作如下:
1)建模 构建一个含有40个烷基苯绝缘油分子、密度为0.400 g/cm3的周期性盒子,再进行500~800 K的退火处理,然后在298 K的温度下,依次进行50 ps的100.00 MPa和0.1 MPa压强的结构弛豫,最终得到的模型边长为26.74 Å,体系密度为0.856 g/cm3,与实际密度0.859 g/cm3接近,然后通过N(粒子数)V(体积)T(温度)的正则系统,在温度298 K的条件下进行100 ps的动力学平衡,平衡后的体系如图2所示。
2)升温热解模拟 利用LAMMPS软件进行升温速率为20 K/ps非等温热解,势函数文件选择CHO2016.ff[28],升温范围为300~3 000 K,模拟过程中步长为0.20 fs,达到3 000 K后再进行10 ps的恒温热解,并利用reaxff/species和reaxff/bonds等命令对热解过程中的产物和化学键的变化进行统计分析,同时使用Auto RMA对得到的bond文件进行分析[29]
3)恒高温热解模拟 为了研究温度对十二烷基苯绝缘油裂化的影响,选择NVT系统进行2 000、2 200、2 400、2 600、2 800 K的恒高温热解动力学模拟实验,控温方法为Berendsen法,步长设为0.25 fs,模拟时长设为100 ps,每1 000步输出为1帧,其他设置与上文一致。
模拟温度高于烷基苯绝缘油过热分解的实际温度主要是因为计算能力的限制,模拟时间尺度(皮秒级)远小于实验中的反应时间(秒级)。根据阿伦尼乌斯方程和Sorensen等人[30]提出的“温度加速反应动力学”理论,提高反应温度会大大提高反应速率,特别是对于具有较高能垒的反应,并且升高温度对反应机制和反应产物的影响较小。此外,之前的ReaxFF-MD研究[19,31-32]表明,提高温度只会加快反应速率,增加分子和中间体间碰撞次数,温度的升高不会影响热解过程。因此,本文选择2 000~3 000 K区间温度进行十二烷基苯的热解过程,此区间既可以降低烷基苯热解反应体系的计算成本,又可以保证烷基苯分子热解过程中的反应可以被Auto RMA软件所追踪到。
烷基苯绝缘油的TG-IR实验中样品采用5 mg未老化的十二烷基苯绝缘油(产自英国普睿司曼公司),使用热重分析仪(TGA 8000)进行热重分析,热解过程中释放的气态产物则由FTIR(Spectrum 3)在线监测,这些仪器均是由PerkinElmer Company,USA公司生产。TG过程升温速率为20 ℃/min,升温范围为50~300 ℃,吹扫气和保护气均为氮气;FTIR过程为实时扫描,扫描波长范围为4 000~400 cm–1;设置气体传输管的温度为250 ℃,以防止挥发性产物的冷凝。
升温速率20 K/ps时十二烷基苯模型热解温度及其分子数目的变化如图3所示。由图3可知:十二烷基苯分子在84.4 ps、2 008.02 K处开始逐渐热解,84.4 ps前其分子数目并未发生变化,在129.4 ps时全部热解,此时的温度为2 858.02 K;产生的气体小分子主要为C2H4、H2、CH4、C3H6以及C3H8,而C2H6和C2H2分子出现量相对较少,且仅在末尾阶段才被观察到。由此可见十二烷基苯分子在受热分解过程中的特征气体是C2H4、H2、CH4,并且热解过程中会产生中长链的中间体如图4所示。
气体小分子的产生时间比十二烷基苯分子开始热解时间晚10 ps左右,并且C2H4分子数目在106 ps(2 433 K)之后才开始剧烈增加。因此可以得出十二烷基苯在热解过程中是先裂解成为长链分子,然后随着热解的进行再裂解成为短链分子。此外,整个热解过程,十二烷基苯的裂解速度和特征气体分子的生成速率都是随着温度的升高而逐渐加快,随着温度的升高,裂解产物迅速增加,短链分子不断积累。
观察图4可见,在20 K/ps的升温热解过程中伴随着十二烷基苯分子的逐渐裂解,热解前期逐渐产生C10—C17的长链分子,在116 ps达到峰值15,并在达到峰值之后开始逐渐减少。C6—C9则是带有苯环的分子,在热解过程中苯环在达到3 000 K之前稳定存在,说明十二烷基苯分子在热解过程中主要是烷基侧链的断裂。此外还对短链自由基进行统计,发现其中·C4H9以及·C3H7自由基的在热解的过程中先是平稳增加,随后分别稳定在17以及10,证明该自由基是热解过程中十分重要的一种中间体。
对于恒高温热解过程,主要分析十二烷基苯分子的热解以及短链气态小分子的变化。
不同温度下十二烷基苯随着时间的变化如图5所示。由图5可知,温度对十二烷基苯的热裂解速率有显著的影响,随着温度的升高十二烷基苯的裂解速度呈现出快速增长的趋势。在模拟到100 ps时,2 000 K和2 200 K温度下分别还剩余25个和11个十二烷基苯分子,而2 400、2 600、2 800 K分别在68、26、15 ps完成40个十二烷基分子的热解(在此认为当十二烷基苯分子的个数低于2个的时候已完全热解)。不同温度下短链分子C1—C4数目变化如图6所示。
图6可知:当温度范围为2 000 ~2 400 K时,在100 ps的热解过程中,气态分子都呈上升趋势,并未达到峰值,这是因为在皮秒级的时间尺度中,此范围属于中温过热范畴,分子间的碰撞以及十二烷基苯自身的热解速率都是较为缓慢的;当温度达到2 600 K和2 800 K时,分别在68.75 ps时到达峰值172和36.5 ps时达到峰值165,随后数目相对平稳。
不同温度下C2H4分子的数目变化如图7所示。从图7对C2H4的分析可以看出,在温度范围2 000~ 2 600 K时,其产气速率随温度的升高而增大,而2 800 K温度下,C2H4的气体数目达到峰值之后呈现逐渐减少的趋势,可能是因为温度过高,导致其双键的不稳定性加剧,会发生双键与自由基加成反应。对H2分子进行了统计,具体如图8所示。
图8可知,温度越高,则其分子数目越多,并都没有达到峰值,这是因为模拟的体系中还有很多游离的·H,温度越高,会加剧分子运动,增大·H基团与其他自由基的碰撞,从而加速热解反应。对C1(代表·CH3和CH4)进行统计,结果如图9所示。由图9可知,其整体变化趋势与H2的变化趋势一样,其数目与温度和时间呈现正比。对C2H2进行统计发现其仅在2 600 K以及2 800 K热解温度下出现,并且数目低于10。由此可知十二烷基苯分子在热应力的作用下产生的特征气体为CH4、H2和C2H4
此外对最终产物进行分析,发现热解到100 ps时,体系中仍存在大量的苯环,这是因为苯环自身的由于共轭效应使其C—H和其C—C键键能较大[33],不易进行脱氢以及开环反应,因此十二烷基苯绝缘油自身在热解时,主要是侧烷烃链进行解离热解以及脱氢反应,为此利用DFT法计算十二烷基苯的侧烷基链上各个C—C键的解离能(BDE)大小如图10所示,键的标号从靠近苯环开始依次是1—12,图中的十二烷基苯结构是利用B3LY/6-311G基组结构优化之后得到的,最靠近苯环的碳与苯环所处在同一个平面中,其他的碳分子则是与苯环呈一定夹角。由分析计算结果可知:在1处的C—C键的BDE达到409.572 kJ/mol,这是因为该键会受到苯环π—π键共轭效应的影响,使其更加稳定;2处和12处的BDE会略大于其他键,这是因为2处依旧会受到苯环分子的影响,而12处作为烷基链末端,受其他分子的影响比较小。
借助Auto RMA可视化软件对2 600 K温度下进行反应分子动力学得到的bond文件进行分析[34],可以得到各个阶段的反应路径,将得到的结果进行统计分析,得到特征气体C2H4、H2以及CH4的产生和消耗路径如图11所示。从图11a)可知,C2H4的生成路径可分为4类:1)烷烃类基团发生β位C—C键的断裂,如·C4H9→·C2H5+C2H4,这是产生C2H4的主要路径,占比达到67%;2)短链烷基苯分子的侧链发生断裂;3)·C2H5这一类分子的脱氢反应,如·C2H5C2H4+·H;4)·C2H3分子的加氢反应,如·C2H3+·HC2H4。C2H4的消耗路径则为上述反应的逆反应。从图11b)可知,H2的生成路径主要为·H自由基攻击气体分子与自由基上的H原子,如·H+ C2H4→·C2H3+H2,消耗路径主要是逆反应。从图11c)可知,CH4的主要产生路径是·H与·CH3自由基反应,如·H+·CH3CH4,此外还有少量的烷烃自由基以及短链烷基苯自由基的α位C-C键断裂产生CH4分子。CH4的消耗路径主要为·H自由基攻击CH4,如·H+CH4→·CH3+H2,此外还有CH4分子与其他烯烃类的自由基发生加成反应。
活化能(Ea)是决定化学反应速率的内因,利用TG过程中的失重曲线以及非等温热解中的主体反应物的质量变化曲线进行活化能的计算,据以往的研究方法,利用一级反应模型计算失重曲线的活化能[35],其动力学方程如式(3)所示:
ln[ln(1α)T2]=lnARβEa-EaRT
式中:α为转化率,%;T为温度,K;A为指数前因子,min–1R为通用气体常数,J/(K·mol);β为加热速率,K/min。
热解发生的前期以及后期热解速率都较为缓慢,因此计算活化能的转化率范围为0.20%~0.85%,即TG热解的温度范围为414.00~467.12 K,而ReaxFF MD的热解温度范围为2 152~2 611 K,计算的最终结果如图12所示,可知其计算的活化能分别为86.606 kJ/mol及99.867 kJ/mol,此外,在给定温度范围内,ReaxFF MD模拟得出的烷基苯热解失重曲线与TG实验数据非常吻合。
由此可表明尽管ReaxFF MD的模拟温度和时间尺度与热重实验中不同,但在各自的温度区间内,2个实验得到的热力学结果吻合良好,这一发现进一步验证了,升高温度仅是加速原子之间的碰撞,对反应机理的研究影响不大。
TG-IR联用过程中的热重以及红外数据如图13所示。从图13a)中可以看出,烷基苯绝缘油达到最大热解速率时对应的温度为463.12 K,该温度与图13b)中达到最大吸光度时的时间相同,此时三维红外谱图中的也出现最大透光率,对此,将该温度附近的红外光谱进行分析,如图13d)所示。图13d)中可以观察到明显的红外峰变化:在3 000 cm–1附近出现明显的双峰,分别为2 866 cm–1和2 932 cm–1,分别对应着亚甲基以及亚甲基的C—H的对称伸缩振动以及非对称伸缩振动[36];3 032 cm–1和3 072 cm–1对应与不饱和双键相连接的C—H的振动[37];而在1 586~1 456 cm–1波长范围内的峰则是对应着芳香族的C==C以及大π键振动[38];此外在698 cm-1处有一个较为强烈的峰,该峰是顺式RCH==CHR结构中的C—H振动[37]
从红外光谱可知,烷基苯绝缘油在热解过程中会产生烷烃类以及烯烃类的气态小分子,苯环峰所占的峰面积比例要远低于甲基和烯烃类的基团峰面积,由此可知烷基苯绝缘油在热解过程中其侧链以及烷烃类自由基易发生持续断键热解反应。
通过上述模拟计算以及TG-IR结果分析,得到十二烷基苯绝缘油热解的主要路径,对十二烷基苯绝缘油热解和产气机理进行阐述,十二烷基苯的热解机理如图14所示,其中红色分子为主要中间体,蓝色分子为主要产物。
十二烷基苯绝缘油在高温热故障下会发生侧链C—C键的断裂,这是因为碳氢键之间的键能要大于C—C键间的键能[39],并且苯环开环所需的能量要远大于烷基侧链断裂所需的能量。由此可知十二烷基苯分子首先生成较大的烃基(如·C10H21等)以及带有中长烷基链的烷基苯自由基(如·C13H19等);随着能量的积累,逐渐发生C—C以及C—H键的断裂,烃类自由基不断发生热解,产生·H、·CH3·C2H5以及·C3H7等自由基。依据对产物的统计发现,·C3H7以及·C4H9是裂解的过程中主要十分重要的中间体,该自由基的主要反应(图14)为:断键产生CH4、C2H4、C2H6以及C3H6;带有中长烷基链的烷基苯分子会不断发生侧链的断裂,最终形成苯环上带有·C2H5·CH3·C3H7基团的短链烷基苯分子。
1)根据模拟热解过程可知,在皮秒级别时间尺度的热解过程中,十二烷基苯分子的初始热解温度为2 000 K以上,热解过程中,先是C—C键的断裂产生长链分子,后逐渐为C—C以及C—H断键产生小分子自由基,十二烷基苯最终和逐渐热解为侧链为·C2H5·CH3·C3H7基团的短链烷基苯分子。
2)分析气体反应路径可知,·C3H7以及·C4H9是裂解的过程中主要十分重要的中间体,其会发生β位C-C键的断裂,产生气体小分子为C2H4、H2、CH4、C3H6以及C3H8。热解过程中的特征气体为C2H4、H2、CH4,其生成的主要路径分别为:β位C—C键的断裂、加氢反应和脱氢反应;·H自由基攻击其他自由基上的H原子;甲基自由基(·CH3)与游离的氢(·H)自由基反应。
3)TG-IR实验结果与ReaxFF-MD结合分析可知,热重过程以及模拟过程的活化能分别为86.606 kJ/mol及99.867 kJ/mol,红外结果与模拟计算的结果相同,相近的活化能与特征官能团进一步验证了仿真结果的合理性。本文有助于对十二烷基苯绝缘油裂解、产气过程的深入理解。
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2024年第53卷第12期
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doi: 10.19666/j.rlfd.202404077
  • 接收时间:2024-04-19
  • 首发时间:2026-03-06
  • 出版时间:2024-12-25
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出版历史
  • 收稿日期:2024-04-19
基金
Science and Technology Project of Southern Power Grid Ultra High Voltage Transmission Company(CGYKJXM20220080)
南方电网超高压输电公司科技项目(CGYKJXM20220080)
Scientific Research Key Project of Hunan Provincial Department of Education(23A0269)
湖南省教育厅科学研究重点项目(23A0269)
Research Project of Degree and Postgraduate Teaching Reform in Hunan Province(2021JGYB133)
湖南省学位与研究生教学改革研究项目(2021JGYB133)
作者信息
    1.南方电网超高压输电公司电力科研院,广东 广州 510663
    2.长沙理工大学化学化工学院,湖南 长沙 410114

通讯作者:

朱志平(1963),男,博士,教授,主要研究方向为电力化学,
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https://castjournals.cast.org.cn/joweb/rlfd/CN/10.19666/j.rlfd.202404077
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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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