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Article(id=1209928455408448474, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2024.06.015, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1686067200000, receivedDateStr=2023-06-07, revisedDate=1688572800000, revisedDateStr=2023-07-06, acceptedDate=null, acceptedDateStr=null, onlineDate=1766399023153, onlineDateStr=2025-12-22, pubDate=1718812800000, pubDateStr=2024-06-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766399023153, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766399023153, creator=13701087609, updateTime=1766399023153, updator=13701087609, issue=Issue{id=1209928452547933122, tenantId=1146029695717560320, journalId=1149653034449285133, year='2024', volume='57', issue='6', pageStart='1', pageEnd='120', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766399022471, creator=13701087609, updateTime=1766563931405, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210620130816561673, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210620130816561674, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209928452547933122, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=102, endPage=107, ext={EN=ArticleExt(id=1209928455664301027, articleId=1209928455408448474, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research on preparation and detection of new environmentally friendly insulating gas C4F7N/CO2, columnId=1192878364340924664, journalTitle=Insulating Materials, columnName=Test and Analysis, runingTitle=null, highlight=null, articleAbstract=

In order to further explore the application potential of C4F7N/CO2 mixed gas in high-voltage electrical equipment, a preparation system for C4F7N/CO2 mixed gas was established and mixed gas with different volume fraction of C4F7N was prepared by partial pressure method. A gas chromatograph-hydrogen flame ionization detector (GC-FID) detection method was established, in view of the difficulty in controlling the testing quality during the preparation of C4F7N/CO2 mixture system, the thermal driven diffusion simulation experiments of different C4F7N/CO2 mixed gas was carried out based on fluid mechanics and finite element analysis. The results show that when the volume fraction of C4F7N is 2%, 5%, and 10%, the diffusion equilibrium time of C4F7N/CO2 concentration is 4 775 s, 6 600 s, and 8 800 s, respectively; the concentration diffusion equilibrium time of C4F7N gas is 94 min, 122 min, and 158 min, respectively. The three C4F7N/CO2 mixed gas can achieve good quality control effect in the quality detection and application after preparing for 100 min, 125 min, and 160 min, respectively.

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为了进一步探究C4F7N/CO2混合气体在高压电气设备中的应用潜能，本研究搭建C4F7N/CO2混合气体制备系统，采用分压法制备了C4F7N体积分数不同的C4F7N/CO2混合气体。建立了气相色谱-氢火焰离子化检测器（GC-FID）检测方法，针对C4F7N/CO2混合气体制备过程中检测质量难以控制的问题，基于流体力学及有限元分析，开展不同C4F7N/CO2混合气体的热驱动扩散模拟实验。结果表明：C4F7N体积分数为2%、5%、10%时C4F7N/CO2气体浓度扩散平衡的时间分别为4 775、6 600、8 800 s，C4F7N气体浓度扩散平衡的时间分别为94、122、158 min。3种C4F7N/CO2混合气体分别在配制100、125、160 min后进行质量检测及应用，可达到良好的质量控制效果。

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曾晓哲（1984-），男（汉族），河南邓州人，工程师，主要从事气体传感技术及高压绝缘气体化学的研究。
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唐晓杰（1994-），男（汉族），浙江宁波人，高级工程师，主要从事高压绝缘气体化学及电气工程的研究。

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唐晓杰（1994-），男（汉族），浙江宁波人，高级工程师，主要从事高压绝缘气体化学及电气工程的研究。

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唐晓杰（1994-），男（汉族），浙江宁波人，高级工程师，主要从事高压绝缘气体化学及电气工程的研究。

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caption=C4F7N气体摩尔分数随时间的分布云图, figureFileSmall=2Rc9QbIyumR0sQ6de8IPMQ==, figureFileBig=wT9gpKj+MmseBpjqDQ/YIQ==, tableContent=null), ArticleFig(id=1217749116403241101, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Fig.8, caption=Variation of volume fraction of C4F7N in different mixed gas with time, figureFileSmall=2aS7tm3Z5DO763LDyvxY4w==, figureFileBig=WW8dn4z2I61II9P7txfIvQ==, tableContent=null), ArticleFig(id=1217749116482932880, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=图8, caption=不同混合气体中C4F7N体积分数气体随时间的变化, figureFileSmall=2aS7tm3Z5DO763LDyvxY4w==, figureFileBig=WW8dn4z2I61II9P7txfIvQ==, tableContent=null), ArticleFig(id=1217749116550041747, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Tab.1, caption=Physical parameters of C4F7N and SF6, figureFileSmall=null, figureFileBig=null, tableContent=
特性名称C4F7NSF6
沸点/℃-4.7-68.3
蒸气压/kPa2522 149
气体密度/(kg/m3)7.95.9
介电强度/kV27.514
大气中代谢寿命/年353 200
全球温室效应值(GWP)2 21023 500
臭氧破坏潜能值(ODP)00
), ArticleFig(id=1217749116633927828, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=表1, caption=

C4F7N与SF6的物理量参数

, figureFileSmall=null, figureFileBig=null, tableContent=
特性名称C4F7NSF6
沸点/℃-4.7-68.3
蒸气压/kPa2522 149
气体密度/(kg/m3)7.95.9
介电强度/kV27.514
大气中代谢寿命/年353 200
全球温室效应值(GWP)2 21023 500
臭氧破坏潜能值(ODP)00
), ArticleFig(id=1217749116709425303, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Tab.2, caption=Partial pressure of each gas in different C4F7N/CO2 mixed gas, figureFileSmall=null, figureFileBig=null, tableContent=
C4F7N体积分数/%C4F7N分压/kPaCO2分压/kPaC4F7N/CO2总压力/kPa
212588600
530570600
1060540600
), ArticleFig(id=1217749116780728472, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=表2, caption=

不同C4F7N/CO2混合气体中各气体的分压

, figureFileSmall=null, figureFileBig=null, tableContent=
C4F7N体积分数/%C4F7N分压/kPaCO2分压/kPaC4F7N/CO2总压力/kPa
212588600
530570600
1060540600
), ArticleFig(id=1217749116847837338, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Tab.3, caption=The diffusion of different C4F7N/CO2 gas with time, figureFileSmall=null, figureFileBig=null, tableContent=
C4F7N的体积分数/%扩散时间/s各部位C4F7N的体积分数/%
钢瓶底部中部顶部
25010—0.10
2 450320.75
4 7751.982.011.99
55015—0.60
3 440852
6 6005.074.964.95
105020.10——
4 4005.00913.50
8 80010.1010.0710.02
), ArticleFig(id=1217749116944306334, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=表3, caption=

钢瓶内不同C4F7N/CO2气体随时间的扩散情况

, figureFileSmall=null, figureFileBig=null, tableContent=
C4F7N的体积分数/%扩散时间/s各部位C4F7N的体积分数/%
钢瓶底部中部顶部
25010—0.10
2 450320.75
4 7751.982.011.99
55015—0.60
3 440852
6 6005.074.964.95
105020.10——
4 4005.00913.50
8 80010.1010.0710.02
), ArticleFig(id=1217749117003026592, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Tab.4, caption=C4F7N/CO2 mixed gas release pressure test data, figureFileSmall=null, figureFileBig=null, tableContent=
混合气体压力/kPa600400200
Cij/%10.0810.1210.08
10.1010.0910.07
10.0610.1110.04
), ArticleFig(id=1217749117070135459, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=表4, caption=

C4F7N/CO2混合气体放压试验数据

, figureFileSmall=null, figureFileBig=null, tableContent=
混合气体压力/kPa600400200
Cij/%10.0810.1210.08
10.1010.0910.07
10.0610.1110.04
), ArticleFig(id=1217749117141438629, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=EN, label=Tab.5, caption=C4F7N/CO2 mixed gas release pressure test data calculation results, figureFileSmall=null, figureFileBig=null, tableContent=
参数MS内MS间FF0.95(v1,v2)
数值3.67×10-41.47×10-34.015.14
), ArticleFig(id=1217749117225324711, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209928455408448474, language=CN, label=表5, caption=

C4F7N/CO2混合气体放压试验数据计算结果

, figureFileSmall=null, figureFileBig=null, tableContent=
参数MS内MS间FF0.95(v1,v2)
数值3.67×10-41.47×10-34.015.14
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新型环保绝缘气体C4F7N/CO2的制备及检测研究
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唐晓杰 1 , 张荣伟 2 , 李龙 2 , 戴坚宇 2 , 何涛 3 , 曾晓哲 3 , 宁帅官 3 , 王腾辉 4
绝缘材料 | 测试与分析 2024,57(6): 102-107
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绝缘材料 | 测试与分析 2024, 57(6): 102-107
新型环保绝缘气体C4F7N/CO2的制备及检测研究
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唐晓杰1, 张荣伟2, 李龙2, 戴坚宇2, 何涛3, 曾晓哲3, 宁帅官3, 王腾辉4
作者信息
  • 1宁波送变电建设有限公司，浙江 宁波 315000
  • 2宁波永耀电力投资集团有限公司， 浙江 宁波 315000
  • 3河南省日立信股份有限公司，河南 郑州 450001
  • 4郑州大学 物理学院，河南 郑州 450001

    • 唐晓杰（1994-），男（汉族），浙江宁波人，高级工程师，主要从事高压绝缘气体化学及电气工程的研究。

通讯作者:

曾晓哲（1984-），男（汉族），河南邓州人，工程师，主要从事气体传感技术及高压绝缘气体化学的研究。
Research on preparation and detection of new environmentally friendly insulating gas C4F7N/CO2
Xiaojie TANG1, Rongwei ZHANG2, Long LI2, Jianyu DAI2, Tao HE3, Xiaozhe ZENG3, Shuaiguan NING3, Tenghui WANG4
Affiliations
  • 1Ningbo Power Transmission and Transformation Construction Co., Ltd., Ningbo 315000, China
  • 2Ningbo Yongyao Electric Power Investment Group Co., Ltd., Ningbo 315000, China
  • 3Henan Relations Co., Ltd., Zhengzhou 450001, China
  • 4School of Physics, Zhengzhou University, Zhengzhou 450001, China
出版时间: 2024-06-20 doi: 10.16790/j.cnki.1009-9239.im.2024.06.015
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摘要
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为了进一步探究C4F7N/CO2混合气体在高压电气设备中的应用潜能，本研究搭建C4F7N/CO2混合气体制备系统，采用分压法制备了C4F7N体积分数不同的C4F7N/CO2混合气体。建立了气相色谱-氢火焰离子化检测器（GC-FID）检测方法，针对C4F7N/CO2混合气体制备过程中检测质量难以控制的问题，基于流体力学及有限元分析，开展不同C4F7N/CO2混合气体的热驱动扩散模拟实验。结果表明：C4F7N体积分数为2%、5%、10%时C4F7N/CO2气体浓度扩散平衡的时间分别为4 775、6 600、8 800 s，C4F7N气体浓度扩散平衡的时间分别为94、122、158 min。3种C4F7N/CO2混合气体分别在配制100、125、160 min后进行质量检测及应用，可达到良好的质量控制效果。

物理特性  /  分压法  /  GC-FID  /  C4F7N/CO2  /  流体力学  /  扩散特性

In order to further explore the application potential of C4F7N/CO2 mixed gas in high-voltage electrical equipment, a preparation system for C4F7N/CO2 mixed gas was established and mixed gas with different volume fraction of C4F7N was prepared by partial pressure method. A gas chromatograph-hydrogen flame ionization detector (GC-FID) detection method was established, in view of the difficulty in controlling the testing quality during the preparation of C4F7N/CO2 mixture system, the thermal driven diffusion simulation experiments of different C4F7N/CO2 mixed gas was carried out based on fluid mechanics and finite element analysis. The results show that when the volume fraction of C4F7N is 2%, 5%, and 10%, the diffusion equilibrium time of C4F7N/CO2 concentration is 4 775 s, 6 600 s, and 8 800 s, respectively; the concentration diffusion equilibrium time of C4F7N gas is 94 min, 122 min, and 158 min, respectively. The three C4F7N/CO2 mixed gas can achieve good quality control effect in the quality detection and application after preparing for 100 min, 125 min, and 160 min, respectively.

physical characteristics  /  partial pressure method  /  GC-FID  /  C4F7N/CO2  /  fluid mechanics  /  diffusion characteristics
唐晓杰, 张荣伟, 李龙, 戴坚宇, 何涛, 曾晓哲, 宁帅官, 王腾辉. 新型环保绝缘气体C4F7N/CO2的制备及检测研究. 绝缘材料, 2024 , 57 (6) : 102 -107 . DOI: 10.16790/j.cnki.1009-9239.im.2024.06.015
Xiaojie TANG, Rongwei ZHANG, Long LI, Jianyu DAI, Tao HE, Xiaozhe ZENG, Shuaiguan NING, Tenghui WANG. Research on preparation and detection of new environmentally friendly insulating gas C4F7N/CO2[J]. Insulating Materials, 2024 , 57 (6) : 102 -107 . DOI: 10.16790/j.cnki.1009-9239.im.2024.06.015
正文
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0 引言
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SF6作为优异的绝缘和灭弧介质而被广泛应用于高压电气设备，但SF6具有强温室效应而被要求限制排放。因此，寻找环境友好型的SF6替代气体的研究日趋火热[1-4]。目前的研究中，SF6替代气体包括二元SF6混合气体（SF6-N2、SF6-CO2等）和新型环保绝缘气体如氟代烃类（PFC）、全氟酮（PFK）及全氟异丁腈等得到了广泛的关注[5-6]。其中由3M公司研发的全氟异丁腈（C4F7N）混合气体因其在绝缘强度、环保特性等方面的优势，已成为国内外环保替代气体的首选[7]。绝缘性能方面，李兴文等[8]研究表明20%C4F7N/80%CO2混合气体的绝缘水平可达到相同条件下SF6气体的95%。开断性能方面，宋宇等[9]通过仿真模拟与试验等手段开展燃弧及灭弧特性研究来对C4F7N/CO2混合气体的隔离开关开断能力进行分析。此外，诸多高校、科研院所和制造业企业已开展该气体的应用验证，并成功开发以C4F7N/CO2为绝缘介质的气体绝缘金属封闭开关设备产品[10-11]。虽然C4F7N混合气体作为绝缘介质在高压开关设备中得到了广泛应用，但其性能研究仍处于理论与试验探索阶段，而针对C4F7N/CO2混合气体制备技术的研究尚无报道。
本文结合C4F7N气体的理化性质研究，根据不同摩尔分数、温度下C4F7N气体的饱和蒸气压曲线，开展C4F7N/CO2混合气体制备方法及系统的研究，建立气相色谱氢火焰离子化检测器（GC-FID）溯源校准方法。针对工业制备C4F7N/CO2混合气体检测及质量难以控制问题，基于流体力学及有限元分析，开展常温条件下40 L钢瓶模型内不同混合比的C4F7N/CO2混合气体热驱动扩散模拟实验，通过不同混合比下C4F7N气体的浓度云图随时间的分布变化情况，进一步优化C4F7N/CO2混合气体制备过程中的检测策略，以满足市场对C4F7N/CO2混合气体的科研及应用需求。
1 实验系统的建立
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1.1 C4F7N气体的理化性质
在25℃、1个标准大气压下，新型环保绝缘气体C4F7N与SF6气体的理化参数如表1所示。
从表1可以看出，C4F7N气体的介电强度为27.5 kV，约为SF6气体的2倍；大气中代谢寿命为35年，仅为SF6气体的1.1%；全球温室效应值（GWP）为2 210，为SF6气体的9.4%；不可燃、臭氧破坏潜能值（ODP）为0。C4F7N分子结构式如图1所示。不同温度及C4F7N摩尔分数下C4F7N/CO2混合气体的饱和蒸气压曲线如图2所示。从图2可以看出，一定温度下，混合气体的饱和蒸气压随着C4F7N摩尔分数的增大而呈现非线性降低的趋势；在C4F7N摩尔分数一定的条件下，饱和蒸气压随着温度的升高而呈现非线性增大趋势。针对高压电气设备应用的典型工作温度（-15℃和-25℃）及高压电气设备气室内的典型工作压力（0.6 MPa）的要求[8]，-15℃时C4F7N气体的饱和蒸气压为64.8 kPa，-25℃时C4F7N气体的饱和蒸气压为40.2 kPa。饱和蒸气压为0.1 MPa时，C4F7N和SF6的液化温度分别为-4.7℃和-68.3℃，因此C4F7N在SF6典型的工作压力0.6 MPa下会发生液化，导致无法使用，难以起到绝缘效果。而在实际投运时，C4F7N/CO2混合气体满足设备绝缘强度所需的气压一般高于SF6的典型工作压力，如国内某厂家126 kV高压开关设备的试验设计压力为0.8 MPa。因此，必须充入大量缓冲气体以降低液化温度，并使其在相应的大气压下达到SF6的绝缘强度[11]。不同摩尔分数、不同温度下C4F7N/CO2混合气体的饱和蒸气压曲线，可为C4F7N/CO2混合气体制备及检测策略研究提供参考。
1.2 C4F7N/CO2混合气体制备系统的建立
基于C4F7N气体的理化性质，对C4F7N/CO2混合气体制备方法及系统进行研究。分别对混合气体制备应用的称重法及分压法进行分析。称重法是目前标准气体制备的经典方法，气体称量装置采用不同感量的高精密天平，但它存在气体制备速度慢的问题，难以满足工业过程中较大规模C4F7N/CO2混合气体制备的需求，且C4F7N/CO2混合气体中两者物质的量之比较大时，C4F7N充注钢瓶瞬间会汽化吸热，导致钢瓶外壁的水汽遇冷凝固，得到的C4F7N气体质量包含钢瓶外壁水蒸气的质量，进一步加剧配气的误差。针对称重法的弊端，本研究采用分压法进行C4F7N/CO2混合气体制备，其中C4F7N气体（摩尔分数为99.3%）由3M公司提供，制备系统包括数字压力表、热换器、双级旋片真空泵、减压及稳压阀、三通阀等，如图3所示。整个制备过程在电力仪表校验方舱实验室中进行，首先打开真空泵，将管路及钢瓶抽真空，绝对压力可抽至2 Pa，对配气精度的影响可忽略不计。另外钢瓶内壁面有特殊涂层，防止气体吸附，做抽真空处理后，可保证气体纯度。然后通过阀路控制，先向钢瓶内充注C4F7N气体，通过热换器温度调节，确保让a、b钢瓶的C4F7N及CO2气体充分气化，防止充注时气化吸热管路结冰。根据配制的混合气体混合比确定C4F7N气体分压，通过数字压力表显示，分别制备C4F7N体积分数为2%、5%、10%的C4F7N/CO2混合气体，各气体分压如表2所示。
1.3 C4F7N/CO2混合气体检测方法的建立
采用气相色谱-氢火焰离子化检测器（Panna-A91型，常州磐诺仪器有限公司）对C4F7N/CO2混合气体进行检测，设置检测器温度为250℃，氢气流量为60 mL/min，尾吹氮气流量为20 mL/min，柱箱温度为60℃，分流比为100∶1，分流流量为90 mL/min，进样口温度为150℃。基于上述条件，选择中国计量院配制的C4F7N体积分数为4.24%、6.95%、14.9%、19.8%的标准C4F7N/CO2样品，采用外标法从低到高依次进样，套取任意组分样品的保留时间作为定性定量分析的依据，建立标准曲线，如图4所示，并对建标实验数据进行拟合，拟合系数R2为0.999 8，可满足C4F7N/CO2混合气体的检测需求。为了进一步验证该方法的准确性，分别以6.95%、14.9%及19.8% 3种标准C4F7N/CO2样品为试样，分析结果如图5所示。从图5可以看出，当进样C4F7N体积分数标准值为19.8%时，存在最大示值误差0.58%。该方法的建立可为C4F7N/CO2混合气体的制备提供可靠的溯源校准方法。
2 基于流体力学的C4F7N/CO2混合气体热驱动扩散模拟
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采用上述方法在实际制备C4F7N/CO2混合气体的过程中，分析测试结果显示运用GC-FID检测的体积分数结果往往在静止一段时间后才能与混合气体制备系统配制的理论值相吻合，制备的不同C4F7N/CO2混合气体在不同的时间段，钢瓶内C4F7N体积分数难以确定，不仅制约了工业过程中高质量C4F7N/CO2混合气体的制备效率及下游的应用时效性，也在一定程度上造成高精度检测仪器资源及人力资源的浪费。鉴于此，本文进一步基于流体力学及有限元分析，开展常温条件下40 L钢瓶模型内C4F7N/CO2混合气体的热驱动扩散模拟实验，通过C4F7N气体的体积分数云图随时间的分布变化情况，进一步优化C4F7N/CO2混合气体制备过程中的检测策略。
2.1 模型方程
C4F7N/CO2混合气体中两种气体在钢瓶壁面热源的热流驱动下产生对流扩散，因此求解考虑动量与能量控制方程，同时考虑壁面热源的辐射影响。
质量守恒方程如式（1）所示。
∂ρ∂t+∇ρU=0
式（1）中：ρ为密度；t为时间；U为气体速度。
动量守恒方程如式（2）所示。
∂ρU∂t+∇ρUU=-∇P+ρg+∇μ∇U+UT+Fs
式（2）中：P为压力；▽P表示单位面积的表面力；g为重力加速度；μ为黏度；Fs为表面张力源项；T为温度。
能量守恒方程如式（3）所示。
∂∂tρE+∇UρE+ρ=∇ke∇T+Sh
式（3）中：E为能量；ke为有效传热系数；T为温度；Sh为辐射源项。
采用Rosseland辐射模型，模拟辐射作用对流-热耦合过程的影响，辐射引起的能量源方程如式（4）所示。
dIr, sds+α+σsIr, s=an2σT4π+σs4π∫04πIr, s'φr, s'dΩ'
式（4）中：r为位置向量；s为方向向量；α为吸收系数；σs为散射系数；I为辐射强度；n为折射系数；s′为散射方向；φ为相位函数；Ω′为空间立体角。
组分输运方程如式（5）所示。
∂ρYi∂t+∇ρUYi=-∇Ji
式（5）中：Yi为组分i的浓度；Ji为组分i的扩散速率。
2.2 网格划分
C4F7N/CO2混合气体钢瓶物理模型直径为220 mm，高度为1 300 mm。采用Ansys Meshing将计算区域离散划分为结构化网格，经过独立性检验后，确定最终划分的网格数为9 125个，网格质量良好，满足要求，网格分布如图6所示。
2.3 模拟结果及实验分析
为了得到总压一定时不同C4F7N/CO2混合气体在室温条件下的扩散特性，基于表2仿真模拟得到不同C4F7N/CO2混合气体扩散结果，C4F7N气体摩尔分数随时间的分布云图如图7所示。由图7可以看出，在封闭的钢瓶模型体系内，当C4F7N的体积分数为2%时，充入钢瓶内C4F7N气体的分压为12 kPa，在扩散初期即扩散时间为50 s时，C4F7N气体在钢瓶内浓度梯度较大，其中底部C4F7N气体浓度分布最大，摩尔分数约为10%，钢瓶顶部存在最小浓度，摩尔分数为0.1%，浓度梯度带对比明显。扩散至2 450 s时即扩散中期，钢瓶底部浓度低至3%，中部及顶部摩尔分数分别扩散至2%及0.75%；扩散时间至4 775 s时，钢瓶中不同部位C4F7N气体摩尔分数为2%，认为混合气体中C4F7N扩散至平衡状态。当C4F7N体积分数为5%及10%时，其他条件不变，扩散均匀的时间分别为6 600 s及8 800 s，其中不同C4F7N/CO2气体在不同时间段不同部位C4F7N体积分数分布情况如表3所示。
3 C4F7N/CO2混合气体制备实验验证及检测策略简析
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3.1 C4F7N/CO2混合气体制备扩散实验验证
基于上述第2节流体力学仿真模拟的基础上，为了进一步验证C4F7N/CO2混合气体在制备后不同时间段的扩散情况及C4F7N气体的实际浓度，采用1.2中分压法制备系统，分别配制C4F7N体积分数为2%、5%、10%的C4F7N/CO2混合气体作为样品气，混合气体总压为600 kPa。配制完成后在不同的时间内用气体采样袋进行采样，采样时钢瓶取气口减压阀出口压力较大，故采样时间可忽略不计。在不同时间段对不同样气分别采样8次，采用1.3中建立的GC-FID检测方法进行色谱测试，测试结果如图8所示。从图8可以看出，C4F7N体积分数2%、5%、10%的混合气体中C4F7N组分扩散的平衡时间分别为94 min（5 640 s）、122 min（7 320 s）及158 min（9 480 s），均比模拟扩散平衡时间长，但差异不大，该结果进一步验证了模拟的合理性。差异的产生是由于实际配气过程中C4F7N气体沸点较高，在钢瓶中以液态形式存在，经过热换器充分气化充入钢瓶的过程中，增加了C4F7N/CO2混合气体的扩散平衡时间。
3.2 C4F7N/CO2混合气体的均匀性评估
对上述分压法制备系统、GC-FID检测方法、模拟及实验测试扩散平衡时间下制备的C4F7N/CO2混合气体均匀性进行评估验证。采用样气C4F7N的体积分数为10%，制备后静置158 min后，对混合气体进行GC-FID分析，结果显示，混合气体浓度的相对标准偏差（RSD）为0.56%，均匀性良好。
将混合气体缓慢释放并用采样袋回收，使钢瓶内压力逐渐降低，记录初始压力为600 kPa及压力降低至400 kPa、200 kPa时GC的信号响应值，每一压力下的浓度值重复测定3次，采用F检验法对量值的稳定性进行考察[12]，如式（6）～（8）所示。
F=M间M内
M内=∑i=1n∑j=1kCij-C¯j2ν2
M间=n∑j=1kCj¯-C¯2ν1
式（6）～（8）中：Cij为每一压力下单次测定的浓度数据；Cj¯为各压力下检测的浓度数据；自由度v1=2，v2=6；M间为不同压力下测量结果的均方值；M内为同一压力下重复测量结果的均方值；n为重复测定次数；C¯为一定压力下的浓度平均值。
混合气体随压力的稳定性数据及计算结果如表4和5所示。结果表明，混合气体放压试验的F值为4.01，小于查表值F0.95(v1,v2)，即C4F7N/CO2混合气体在200、400、600 kPa情况下稳定性良好。
综上，采用分压法及GC-FID技术制备的3种典型C4F7N体积分数的C4F7N/CO2混合气体分别在配制100、125、160 min后进行质量检测及应用，可达到良好的质量控制效果，混合气体的均匀性满足工程应用要求。
4 结论
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（1）分压法可满足C4F7N/CO2混合气体的制备需求；建立了气相色谱-氢火焰离子化检测器（GC-FID）检测方法，标准曲线拟合系数R2为0.999 8，可满足C4F7N/CO2混合气体的检测需求。
（2）基于流体力学及有限元分析，开展常温条件下40 L钢瓶模型内不同混合比的C4F7N/CO2混合气体热驱动扩散模拟实验，通过不同混合比下C4F7N气体的浓度云图随时间的分布变化情况，进一步优化C4F7N/CO2混合气体制备过程中的检测策略。结合GC实验测试，确定工业常用的C4F7N体积分数为2%、5%及10%的C4F7N混合气体分别在配制100、125、160 min后进行质量检测及应用，可达到良好的质量控制效果。
基金
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  • 国家重点研发计划项目(2020YFB2008605)
  • 中国南方电网重点科技项目(GDKJXM20222223)
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[1]
ZHANGB, XIONGJ, CHENL, et al. Fundamental physicochemical properties of SF6-alternative gases: A review of recent progress[J]. Journal of Physics D: Applied Physics,2020,53(17):173001.
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ZHAOH, LIX, ZHUK, et al. Study of the arc interruption performance of SF6-CO2 mixtures as a substitute for SF6[J]. IEEE Transactions on Dielectrics and Electrical Insulation,2016,23(5):2657-2667.
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STOCKERT. Climate change 2013-The physical science basis[M]. Cambridge: Cambridge University Press,2014.
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曾炼,黄青丹,王勇,等.C3F7CN/CO2混合气体在极不均匀场下的局部放电特性[J].绝缘材料,2020,53(7):62-67.
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李兴文,赵虎.SF6替代气体的研究进展综述[J]. 高电压技术,2016,42(6):1695-1701.
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周文俊,郑宇,高克利,等.环保型绝缘气体电气特性研究进展[J].高电压技术,2018,44(10):3114-3124.
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杨圆,高克利,王宝山,等.C4F7N/CO2/O2混合气体交流电晕放电分解特性[J].高电压技术,2023,49(3):955-961.
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李兴文,邓云坤,姜旭,等.环保气体C4F7N和C5F10O与CO2混合气体的绝缘性能及其应用[J].高电压技术,2017,43(3):708-714.
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宋宇,林莘,徐建源,等.高压断路器中C4F7N/CO2混合气体的开断性能[J].高电压技术,2023,49(3):971-981.
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史荣斌,秦炜淇,张猛,等.特高压C4F7N/CO2混合气体GIL温度分布[J].高电压技术,2022,48(2):698-705.
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2024年第57卷第6期
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doi: 10.16790/j.cnki.1009-9239.im.2024.06.015
  • 接收时间：2023-06-07
  • 首发时间：2025-12-22
  • 出版时间：2024-06-20
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  • 收稿日期：2023-06-07
  • 修回日期：2023-07-06
基金
国家重点研发计划项目(2020YFB2008605)
中国南方电网重点科技项目(GDKJXM20222223)
作者信息
    1宁波送变电建设有限公司，浙江 宁波 315000
    2宁波永耀电力投资集团有限公司， 浙江 宁波 315000
    3河南省日立信股份有限公司，河南 郑州 450001
    4郑州大学 物理学院，河南 郑州 450001

通讯作者:

曾晓哲（1984-），男（汉族），河南邓州人，工程师，主要从事气体传感技术及高压绝缘气体化学的研究。
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https://castjournals.cast.org.cn/joweb/jycl/CN/10.16790/j.cnki.1009-9239.im.2024.06.015
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2种不同金属材料的力学参数
科
Family		 属数
Number of
genus		 种数
Number of
species		 占总种数比例
Percentage of
total species (%)		 属
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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