Article(id=1209926726184997159, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209926723278336734, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2022.03.015, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1618761600000, receivedDateStr=2021-04-19, revisedDate=1624550400000, revisedDateStr=2021-06-25, acceptedDate=null, acceptedDateStr=null, onlineDate=1766398610873, onlineDateStr=2025-12-22, pubDate=1647705600000, pubDateStr=2022-03-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1766398610873, onlineIssueDateStr=2025-12-22, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1766398610873, creator=13701087609, updateTime=1766398610873, updator=13701087609, issue=Issue{id=1209926723278336734, tenantId=1146029695717560320, journalId=1149653034449285133, year='2022', volume='55', issue='3', pageStart='1', pageEnd='118', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1766398610181, creator=13701087609, updateTime=1766563016675, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1210616294165049744, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209926723278336734, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1210616294165049745, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1209926723278336734, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=107, endPage=111, ext={EN=ArticleExt(id=1209926726516347183, articleId=1209926726184997159, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Determination and Analysis on Ostwald Coefficient of Natural Ester and Modified Ester Insulating Oil, columnId=1192878364340924664, journalTitle=Insulating Materials, columnName=Test and Analysis, runingTitle=null, highlight=null, articleAbstract=

Gas chromatography is a common way to determine the dissolved gas content in insulating oils, but there is many types of natural insulating oil, and the Ostwald coefficient is not clear. In order to be able to accurately calculate the dissolved gas content in natural insulating oils, the Ostwald coefficient of seven typical dissolved gases in four natural ester insulating oils was measured using double equilibrium method and compared with the Ostwald coefficient in mineral oil. The results show that there is little difference on Ostwald coefficient of the seven dissolved gases in the three natural esters, while the Ostwald coefficient of dissolved gas in the modified esters is slightly greater than that in the natural esters. The Ostwald coefficient of dissolved gas in FR3 has little relative error compared with the available data, which proves that the data obtained by the method has good credibility.

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气相色谱法是测定绝缘油中溶解气体含量最常用的手段,但植物绝缘油种类众多,其气体平衡常数尚不明确。为了能够准确测定常见植物绝缘油中的溶解气体含量,本文利用二次平衡法,对7种典型油中溶解气体分别在4种植物绝缘油中的平衡常数进行测定,并与矿物绝缘油的气体平衡常数进行对比分析。结果表明:7种气体的平衡常数在3种天然酯中差别不大,而在改性酯中的平衡常数均略大于天然酯。将所测植物绝缘油FR3的气体平衡常数与现有数据对比,发现其相对误差总体比较小,证明所采用方法以及所得数据可信度较高。

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黄慧红(1976-),女(汉族),广东顺德人,工程师,研究方向为一次设备高压电气试验、化学试验。

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黄慧红(1976-),女(汉族),广东顺德人,工程师,研究方向为一次设备高压电气试验、化学试验。

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黄慧红(1976-),女(汉族),广东顺德人,工程师,研究方向为一次设备高压电气试验、化学试验。

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San Juan, USA: IEEE,2012., articleTitle=Gassing behavior of various alternative insulating liquids under thermal and electrical stress, refAbstract=null), Reference(id=1210892076661731883, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, doi=null, pmid=null, pmcid=null, year=2017, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[8], rfOrder=7, authorNames=全国电气化学标准化技术委员会, journalName=null, refType=null, unstructuredReference=全国电气化学标准化技术委员会. 绝缘油中溶解气体组分含量的气相色谱测定法:GB/T 17623—2017[S].北京:中国标准出版社,2017., articleTitle=null, refAbstract=null), Reference(id=1210892076787561009, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, doi=null, pmid=null, pmcid=null, year=2018, volume=51, issue=3, pageStart=70, pageEnd=73,78, url=null, language=null, rfNumber=[9], rfOrder=8, authorNames=何清, 鲁莽, 王瑞珍, journalName=绝缘材料, refType=null, unstructuredReference=何清,鲁莽,王瑞珍,等.FR3植物绝缘油中溶解气体奥斯特瓦尔德系数的测定[J].绝缘材料,2018,51(3):70-73,78., articleTitle=FR3植物绝缘油中溶解气体奥斯特瓦尔德系数的测定, refAbstract=null), Reference(id=1210892076879835700, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, doi=null, pmid=null, pmcid=null, year=2017, volume=null, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[10], rfOrder=9, authorNames=余辉, journalName=null, refType=null, unstructuredReference=余辉.植物基绝缘油的制备以及相关性能的研究[D].武汉:武汉大学,2017., articleTitle=植物基绝缘油的制备以及相关性能的研究, refAbstract=null)], funds=null, companyList=[AuthorCompany(id=1210892071926362485, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, xref=null, ext=[AuthorCompanyExt(id=1210892071938945399, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, companyId=1210892071926362485, language=EN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=Guangzhou Power Supply Bureau, Guangdong Power Grid Co., Ltd., Guangzhou 510000, China), AuthorCompanyExt(id=1210892071947334007, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, companyId=1210892071926362485, language=CN, country=null, province=null, city=null, postcode=null, companyName=null, departmentName=null, remark=广东电网有限责任公司广州供电局,广东 广州 510000)])], figs=[ArticleFig(id=1210892074426167749, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.1, caption=Performance comparison between vegetable insulating oil and mineral insulating oil, figureFileSmall=null, figureFileBig=null, tableContent=
参数RAPOFR3RDBPFAE矿物油
工频击穿电压/kV78(2.5 mm)73(2.5 mm)69(2.5 mm)81(2.5 mm)60(2.5 mm)
相对介电常数(25℃)3.13.22.82.952.2
体积电阻率/(Ω·m)1011(90℃)1012(90℃)1011(90℃)7.1×1010(80℃)1013(90℃)
介质损耗因数0.4×10-3(90℃)0.03(90℃)0.02(90℃)0.003 1(80℃)0.1×10-3(90℃)
黏度(40℃)/(mm2/s)35.833.639.95.06≤11.0
酸值/(mgKOH/g)0.030.040.030.01≤0.03
闪点/℃322316325176>145
密度(20℃)/(kg·dm-3)0.9190.920.900.860.83~0.89
表面张力/(mN·m-1)302430>40
21d生物降解率/%9899989830
), ArticleFig(id=1210892074564579786, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表1, caption=

植物绝缘油与矿物绝缘油性能对比

, figureFileSmall=null, figureFileBig=null, tableContent=
参数RAPOFR3RDBPFAE矿物油
工频击穿电压/kV78(2.5 mm)73(2.5 mm)69(2.5 mm)81(2.5 mm)60(2.5 mm)
相对介电常数(25℃)3.13.22.82.952.2
体积电阻率/(Ω·m)1011(90℃)1012(90℃)1011(90℃)7.1×1010(80℃)1013(90℃)
介质损耗因数0.4×10-3(90℃)0.03(90℃)0.02(90℃)0.003 1(80℃)0.1×10-3(90℃)
黏度(40℃)/(mm2/s)35.833.639.95.06≤11.0
酸值/(mgKOH/g)0.030.040.030.01≤0.03
闪点/℃322316325176>145
密度(20℃)/(kg·dm-3)0.9190.920.900.860.83~0.89
表面张力/(mN·m-1)302430>40
21d生物降解率/%9899989830
), ArticleFig(id=1210892074673631693, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.2, caption=Concentration of standard mixing gas, figureFileSmall=null, figureFileBig=null, tableContent=
气体组分配制浓度/(μL/L)
H2980.10
O29 844.1
N220 228.27
CO985.29
CO22 480.4
CH497.42
C2H6100.59
C2H4101.79
C2H250.27
Ar2平衡
), ArticleFig(id=1210892074774294992, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表2, caption=

标准混合气体浓度

, figureFileSmall=null, figureFileBig=null, tableContent=
气体组分配制浓度/(μL/L)
H2980.10
O29 844.1
N220 228.27
CO985.29
CO22 480.4
CH497.42
C2H6100.59
C2H4101.79
C2H250.27
Ar2平衡
), ArticleFig(id=1210892074883346898, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.3, caption=Concentrations of gas components after first oscillation equilibrium, figureFileSmall=null, figureFileBig=null, tableContent=
特征气体样品名称H2COCO2CH4C2H6C2H4C2H2
FR31#气样970.66924.381346.9575.3226.6432.733.29
2#气样986.43896.291166.3770.6128.3332.953.57
3#气样1027.55911.341337.9970.5828.0433.533.52
平均值994.88910.671283.7772.1727.6733.073.46
RAPO1#气样844.88843.651432.3571.2227.1133.383.77
2#气样858.61818.021240.3266.7628.8333.614.09
3#气样894.40831.751422.8266.7428.5434.204.03
平均值865.96831.141365.1668.2428.1633.733.96
RDB1#气样805.55895.081130.5568.0024.4829.715.31
2#气样715.21794.691003.7660.3721.7426.384.71
3#气样737.79819.791035.4662.2822.4227.214.86
平均值752.85836.521056.5963.5522.8827.774.96
PFAE1#气样684.31784.761184.6160.6820.0225.673.43
2#气样695.43760.911025.7956.8821.2925.853.72
3#气样724.42773.691176.7256.8621.0726.303.67
平均值701.39773.121129.0458.1420.7925.943.61
), ArticleFig(id=1210892074984010198, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表3, caption=

一次振荡平衡后气体各组分浓度

, figureFileSmall=null, figureFileBig=null, tableContent=
特征气体样品名称H2COCO2CH4C2H6C2H4C2H2
FR31#气样970.66924.381346.9575.3226.6432.733.29
2#气样986.43896.291166.3770.6128.3332.953.57
3#气样1027.55911.341337.9970.5828.0433.533.52
平均值994.88910.671283.7772.1727.6733.073.46
RAPO1#气样844.88843.651432.3571.2227.1133.383.77
2#气样858.61818.021240.3266.7628.8333.614.09
3#气样894.40831.751422.8266.7428.5434.204.03
平均值865.96831.141365.1668.2428.1633.733.96
RDB1#气样805.55895.081130.5568.0024.4829.715.31
2#气样715.21794.691003.7660.3721.7426.384.71
3#气样737.79819.791035.4662.2822.4227.214.86
平均值752.85836.521056.5963.5522.8827.774.96
PFAE1#气样684.31784.761184.6160.6820.0225.673.43
2#气样695.43760.911025.7956.8821.2925.853.72
3#气样724.42773.691176.7256.8621.0726.303.67
平均值701.39773.121129.0458.1420.7925.943.61
), ArticleFig(id=1210892075076284889, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.4, caption=Concentrations of gas components after second oscillation equilibrium, figureFileSmall=null, figureFileBig=null, tableContent=
特征气体样品名称H2COCO2CH4C2H6C2H4C2H2
FR31#气样70.36106.91735.1419.4718.3221.772.26
2#气样75.29107.44749.8320.8520.6118.892.49
3#气样75.21110.55760.4622.0218.8222.192.57
平均值73.62108.3748.4820.7819.2520.952.44
RAPO1#气样53.0493.62771.0817.8616.8120.832.51
2#气样56.7694.09786.4919.1218.9118.082.77
3#气样56.7096.81797.6420.2017.2721.242.85
平均值55.594.84785.0719.0617.6620.052.71
RDB1#气样47.8291.12632.6316.7115.0016.723.41
2#气样42.4680.90561.6814.8413.3214.853.03
3#气样43.8083.46579.4215.3113.7415.323.13
平均值44.6985.16591.2415.6214.0215.633.19
PFAE1#气样55.81110.10697.0518.3314.7718.532.52
2#气样59.72110.64710.9819.6316.6216.082.78
3#气样59.66113.85721.0620.7315.1718.892.86
平均值58.4111.53709.719.5615.5217.832.72
), ArticleFig(id=1210892075227279838, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表4, caption=

二次振荡平衡后油样各组分浓度

, figureFileSmall=null, figureFileBig=null, tableContent=
特征气体样品名称H2COCO2CH4C2H6C2H4C2H2
FR31#气样70.36106.91735.1419.4718.3221.772.26
2#气样75.29107.44749.8320.8520.6118.892.49
3#气样75.21110.55760.4622.0218.8222.192.57
平均值73.62108.3748.4820.7819.2520.952.44
RAPO1#气样53.0493.62771.0817.8616.8120.832.51
2#气样56.7694.09786.4919.1218.9118.082.77
3#气样56.7096.81797.6420.2017.2721.242.85
平均值55.594.84785.0719.0617.6620.052.71
RDB1#气样47.8291.12632.6316.7115.0016.723.41
2#气样42.4680.90561.6814.8413.3214.853.03
3#气样43.8083.46579.4215.3113.7415.323.13
平均值44.6985.16591.2415.6214.0215.633.19
PFAE1#气样55.81110.10697.0518.3314.7718.532.52
2#气样59.72110.64710.9819.6316.6216.082.78
3#气样59.66113.85721.0620.7315.1718.892.86
平均值58.4111.53709.719.5615.5217.832.72
), ArticleFig(id=1210892075332137442, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.5, caption=Degassing volume after the second oscillation balance, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称FR3RAPORDBPFAE
1#气样15161918
2#气样18172019
3#气样15181817
平均值16171918
), ArticleFig(id=1210892075441189350, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表5, caption=

二次振荡后脱气体积

, figureFileSmall=null, figureFileBig=null, tableContent=
样品名称FR3RAPORDBPFAE
1#气样15161918
2#气样18172019
3#气样15181817
平均值16171918
), ArticleFig(id=1210892075567018476, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=EN, label=Tab.6, caption=Equilibrium constant of dissolved gas in vegetable insulating oil at 50, figureFileSmall=null, figureFileBig=null, tableContent=
绝缘油H2COCO2CH4C2H6C2H4C2H2
FR30.0680.1151.1880.3431.9421.4682.032
RAPO0.0620.1161.2220.3501.5191.3231.958
RDB0.0690.1241.3870.3561.7281.4061.968
PFAE0.0870.1621.6280.4882.8322.1142.939
矿物油0.0600.1200.9200.3902.3001.4601.020
), ArticleFig(id=1210892075684458995, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1209926726184997159, language=CN, label=表6, caption=

50℃下植物绝缘油中溶解气体平衡常数

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绝缘油H2COCO2CH4C2H6C2H4C2H2
FR30.0680.1151.1880.3431.9421.4682.032
RAPO0.0620.1161.2220.3501.5191.3231.958
RDB0.0690.1241.3870.3561.7281.4061.968
PFAE0.0870.1621.6280.4882.8322.1142.939
矿物油0.0600.1200.9200.3902.3001.4601.020
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天然酯与改性酯植物绝缘油气体平衡常数的测定和分析
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黄慧红 , 王炜 , 宋浩永 , 黄青丹
绝缘材料 | 测试与分析 2022,55(3): 107-111
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绝缘材料 | 测试与分析 2022, 55(3): 107-111
天然酯与改性酯植物绝缘油气体平衡常数的测定和分析
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黄慧红, 王炜, 宋浩永, 黄青丹
作者信息
  • 广东电网有限责任公司广州供电局,广东 广州 510000
  • 黄慧红(1976-),女(汉族),广东顺德人,工程师,研究方向为一次设备高压电气试验、化学试验。

Determination and Analysis on Ostwald Coefficient of Natural Ester and Modified Ester Insulating Oil
Huihong HUANG, Wei WANG, Haoyong SONG, Qingdan HUANG
Affiliations
  • Guangzhou Power Supply Bureau, Guangdong Power Grid Co., Ltd., Guangzhou 510000, China
出版时间: 2022-03-20 doi: 10.16790/j.cnki.1009-9239.im.2022.03.015
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气相色谱法是测定绝缘油中溶解气体含量最常用的手段,但植物绝缘油种类众多,其气体平衡常数尚不明确。为了能够准确测定常见植物绝缘油中的溶解气体含量,本文利用二次平衡法,对7种典型油中溶解气体分别在4种植物绝缘油中的平衡常数进行测定,并与矿物绝缘油的气体平衡常数进行对比分析。结果表明:7种气体的平衡常数在3种天然酯中差别不大,而在改性酯中的平衡常数均略大于天然酯。将所测植物绝缘油FR3的气体平衡常数与现有数据对比,发现其相对误差总体比较小,证明所采用方法以及所得数据可信度较高。

天然酯绝缘油  /  改性酯绝缘油  /  气体平衡常数  /  二次平衡法

Gas chromatography is a common way to determine the dissolved gas content in insulating oils, but there is many types of natural insulating oil, and the Ostwald coefficient is not clear. In order to be able to accurately calculate the dissolved gas content in natural insulating oils, the Ostwald coefficient of seven typical dissolved gases in four natural ester insulating oils was measured using double equilibrium method and compared with the Ostwald coefficient in mineral oil. The results show that there is little difference on Ostwald coefficient of the seven dissolved gases in the three natural esters, while the Ostwald coefficient of dissolved gas in the modified esters is slightly greater than that in the natural esters. The Ostwald coefficient of dissolved gas in FR3 has little relative error compared with the available data, which proves that the data obtained by the method has good credibility.

natural ester insulating oil  /  modified ester insulating oil  /  Ostwald coefficient  /  double equilibrium method
黄慧红, 王炜, 宋浩永, 黄青丹. 天然酯与改性酯植物绝缘油气体平衡常数的测定和分析. 绝缘材料, 2022 , 55 (3) : 107 -111 . DOI: 10.16790/j.cnki.1009-9239.im.2022.03.015
Huihong HUANG, Wei WANG, Haoyong SONG, Qingdan HUANG. Determination and Analysis on Ostwald Coefficient of Natural Ester and Modified Ester Insulating Oil[J]. Insulating Materials, 2022 , 55 (3) : 107 -111 . DOI: 10.16790/j.cnki.1009-9239.im.2022.03.015
矿物绝缘油是目前电力变压器中主要的绝缘介质,其燃点为160℃左右,在变压器发生一些故障时,因其燃点比较低可能会引起电力变压器发生火灾甚至爆炸事故。并且矿物绝缘油的生物降解率较低,通常低于30%,属于一种非环保型绝缘油,如果发生事故泄漏可能会引起严重的环境污染情况。植物绝缘油燃点较高并且生物降解率可达95%以上[1-2],如果发生变压器油泄漏,植物绝缘油能够快速而彻底地被微生物降解。表1给出了几种植物绝缘油与矿物绝缘油的性能对比[3-5],可以发现,总体上植物绝缘油具有和矿物绝缘油相当的电气绝缘和理化性能,此外植物绝缘油还有高燃点、高闪点、易降解等优点,具有更为广阔的应用前景。目前植物绝缘油已经在国内的配电变压器和110 kV及220 kV电力变压器中得到了较广泛的应用,而国外已有420 kV电压等级的植物绝缘油变压器挂网运行。随着应用技术和工艺的日渐成熟,未来植物绝缘油有望成为矿物绝缘油的替代品。
对于油浸式电力设备,油中溶解气体分析(dissolved gas analysis, DGA)是目前判断设备运行状态最为可靠的手段之一,已经在工程实际中应用多年。现有针对矿物油变压器故障的DGA诊断技术建立在现场运行变压器大量的故障数据之上,已形成了较完备的DGA故障判断体系。利用DGA技术进行矿物油变压器的故障判定时,首先采用气相色谱法测定气相中DGA气体含量,然后利用矿物油中气体溶解平衡常数计算出油中溶解气体含量,再结合DGA判据进行故障诊断[6-7]。天然酯绝缘油的主要成分为甘油三酸酯,改性酯绝缘油PFAE为棕榈油与醇进行酯交换反应得到的单酯结构绝缘油,而矿物油的主要成分为烷烃和环烷烃构成的混合物,植物油和矿物油之间存在显著的分子组成和结构差异,因此典型DGA故障气体在植物油中的溶解能力与矿物油也有所区别。由于植物绝缘油的应用历史较短,缺乏运行数据和研究文献的积累,植物绝缘油中气体溶解平衡常数的测定研究鲜见报道,这为植物绝缘油变压器故障时的DGA分析带来了困难。
本研究对典型天然酯绝缘油和改性酯绝缘油的气体溶解平衡常数进行测定。针对3种常见基质的天然酯绝缘油和改性酯绝缘油,利用标准浓度气体配置了溶有典型DGA故障气体的油样,利用气相色谱仪测定油气两相平衡状态时气相中的气体浓度,采用二次平衡法计算得到油相中的气体浓度,进一步得到不同气体在植物绝缘油中的平衡常数。计算过程中根据热力学定律对温度的影响进行修正,并将计算结果与矿物油中气体溶解平衡常数进行对比。
气体平衡常数是指平衡时液相中气体浓度与平衡时气相中气体浓度的比值,又称为奥斯特瓦尔德(Ostwald)系数,如式(1)所示。
Ki=ci1cig
式(1)中:Ki为试验温度下气、液两相平衡后溶解气体i组分的平衡常数;ci1为平衡条件下溶解气体i组分在液体中的浓度,μL/Lcig为平衡条件下溶解气体i组分在气体中的浓度,μL/L
当油中溶解气体在气、液两相达到分配平衡时,可以通过式(2)计算得到油样溶解气体中各组分的浓度。
Xi=cig(Ki+VgV1)
式(2)中:Xi为油样溶解气体中i组分的浓度,μL/LVg为平衡条件下气体体积,mLV1为平衡条件下液体体积,mL
通常采用二次平衡法来测定某气体的平衡常数,具体操作如下:在一密闭容器内放入一定体积的空白油和一定体积的含被测组分的气体(不必测定其准确的起始浓度值)。在恒温下经气液溶解平衡后,测定该组分在气相中的浓度。然后排出全部气体,再充入一定体积的空白气体(如色谱分析用载气),在同样的恒定温度下进行第二次平衡,然后测定该组分在气相中的浓度。根据分配定律和物料平衡原理,按式(3)可求出该组分在测定温度下的气体平衡常数Ki
Ki=c'igcig-c'ig×VgV1
式(3)中:Kii组分在温度为T时的平衡常数(或称气体溶解系数);cig为第一次平衡后溶解气体i组分在气体中的浓度,μL/Lc'ig为第二次平衡后溶解气体i组分在气体中的浓度,μL/LVgV1分别为第二次平衡后温度T时的气体、液体体积,mL。
检验试品:检测油样为4种植物绝缘油,分别为大豆基天然酯绝缘油FR3(美国Cargill公司)、天然酯绝缘油RAPO(广东卓原新材料有限公司)、山茶籽基绝缘油RDB(重庆大学)、棕榈脂肪酸酯绝缘油PFAE(日本AE帕瓦株式会社和狮王公司)。
检验设备:安捷伦GC7890A气相色谱仪,配置2个氢火焰(FID)检测器和1个热导(TCD)检测器;恒温定时振荡器;标准气体,各个组分浓度见表2,载气为高纯度氩气。
取12支玻璃注射器,每3个分为一组,每组对应一种植物油。对每组玻璃注射器每支取5 mL植物绝缘油,冲洗玻璃注射器筒内壁1~2次后,吸入约0.5 mL油样,套上橡胶封帽,插入双头针头,针头垂直向上。将注射器内的空气和试油慢慢排出,使油样充满注射器内壁缝隙而避免残存空气。
首先对待测油样进行脱水脱气处理。利用真空干燥箱将4种油样在90℃真空条件下静置12 h,以脱去油样中可能存在的水分和气体。对每组植物油的100 mL玻璃注射器分别注入4种待测植物绝缘油20 mL,向其注射器中缓慢注入20 mL氩气,注入完成后立即用胶封帽将注射器出口密封。然后将处理过的油样分组放入恒温定时振荡器内的振荡盘上,连续振荡20 min,静置10 min,重复5次,得到4种植物绝缘油空白油样。
在已制备好的12支20 mL空白植物绝缘油玻璃注射器中密封充入20 mL表2中已知浓度的混合标准气体;利用恒温定时机械振荡器在50℃下连续振荡60 min,再放入50℃恒温箱中静置12 h以保证植物绝缘油与混合标准气体充分平衡,制得标准气体油样。
现有的国内外标准中给出了50℃下矿物绝缘油溶解气体中各个组分的气体平衡常数,因此植物绝缘油中溶解气体平衡常数的测定在50℃下进行,便于将测试结果与矿物油进行对比。
色谱条件:柱流量为15 mL/min;辅助加热375℃;阀箱100℃,阀开时间为1.75 min,阀关时间为3.8 min;柱温箱40℃保持5 min,以24℃/min升至130℃;热导检测器加热器温度为250℃,参比气体流量为20 mL/min,尾吹5 mL/min;氢火焰离子化检测器加热器温度为250℃,氢气40 mL/min,空气400 mL/min,尾吹5 mL/min。
实验室环境条件:大气压力为99 kPa;室温为17℃。
将4组标准气体油样取出,用玻璃注射器分别从每支油样中取出全部的溶解平衡后的气体,按照每种植物绝缘油分组情况在气相色谱仪中进行气体浓度检测。表3为第一次振荡平衡后4组油样中各个溶解气体组分浓度情况。
向第一次振荡取样处理后的每组油样注射器中加入20 mL的氩气,在50℃恒温条件下放置于机械振荡器中进行第二次振荡平衡;然后取出此时溶解平衡后的全部平衡气体,在室温下准确读出第二次振荡后的脱气体积,将所取气体按组在气相色谱仪中进行气体浓度检测。表4为第二次振荡平衡后4组油样中各个溶解气体组分浓度情况。表5为所有油样第二次振荡后的脱气体积。
通过式(4)式(5)将在室温、试验压力下平衡气样体积和油样体积分别校正为50℃、标准大气压下(101 kPa)的体积。
V'g=Vg×323273+t×P101.3
V'1=V1[1+γ×(50-t)]
式(4)~(5)中:V'g为50℃、标准大气压下的平衡气体体积,mL;Vg为室温t、试验压力下的平衡气体体积,mL;P为试验时的大气压力,kPa;V'1为50℃油样体积,mL;V1为室温t时所取油样体积,mL;t为试验时的室温,℃;γ为油样的热膨胀系数,℃-1
通过计算分析,第一次和第二次振荡后的数据之间误差均不超过5%,标准差很小,数据一致性较好,重复性和再现性均能满足要求,故认为数据可靠。将各组分浓度的4组测试结果取平均值来计算气体平衡常数。
将脱气后的气体体积和油样体积校正到50℃、标准大气压下。脱气气体体积由于数据之间误差较小,满足一致性要求,故也取每种植物油的脱气气体体积平均值作为校正数据,经过校正可以得到FR3、RAPO、RDB、PFAE 4种植物油脱气气体体积分别为17.47、18.56、20.68、19.66 mL。对每种植物绝缘油的油样体积,取其相应的热膨胀系数进行校正,经过校正可以得到FR3、RAPO、RDB、PFAE 4种植物油油样气体体积分别为20.57、20.56、20.83、20.44 mL。
根据式(3)可以计算得到50℃下4种植物绝缘油溶解气体组分的气体平衡常数,由于每个油样计算的气体平衡常数之间平行性较好,误差较小在3%以内,故仅列出每种植物油气体平衡常数的平均值。将得到的植物绝缘油气体平衡常数的平均值与GB/T 17623—2017中50℃下矿物绝缘油的气体平衡常数进行对比,结果如表6所示。从表6可以看出,H2、CO、CH4在4种植物油与矿物油中的气体平衡常数相差不大,而其余特征气体(CO2、C2H6、C2H4、C2H2)的溶解平衡常数差异较大。通过对比天然酯和改性酯两种植物绝缘油可以发现,特征气体在改性酯PFAE中的溶解能力均略大于3种天然酯。天然酯主要成分为甘油酸三脂;而改性酯由棕榈脂肪酸通过交换反应得到,是一种单酯结构的绝缘油。绝缘油分子结构的差异会导致特征气体溶解能力存在不同,从而导致改性酯绝缘油中溶解气体含量可能会大于天然酯。另外,乙烷在矿物油中的溶解能力大于植物油;而乙炔和二氧化碳在植物油中的溶解能力远大于矿物油。其中乙炔在植物油中溶解能力从大到小依次为PFAE、FR3、RDB、RAPO。二氧化碳在植物油中的溶解能力从大到小依次为PFAE、RDB、RAPO、FR3。因此,这可能会导致植物绝缘油中溶解较多的乙炔和二氧化碳。
目前对大豆基天然酯FR3植物油的平衡常数测定比较多,其中文献[9-10]中对FR3油中溶解气体的平衡常数进行了测定。将本研究所得FR3油中溶解气体平衡系数与其进行对比分析,相对误差大部分都在10%以内,其中C2H6与文献[9]中的误差最大,相对误差达17%,而与文献[10]中的误差为 -6%,这可能是植物绝缘油本身的差异以及气相色谱仪本身造成的。总体来说,本研究测得的数据以及采用的方法具有可靠性,对后续植物绝缘油制定相应标准具有一定参考价值。
通过测定和计算得到50℃下4种植物绝缘油中溶解气体组分气体平衡常数的平均值,将其与现行标准中给出的50℃下矿物绝缘油溶解气体组分的气体平衡常数进行对比,得到以下结论:
(1)H2、CO、CH4等分子量较小或碳数较少的气体的平衡常数较小,且在不同植物油和矿物油中的平衡常数十分相近,而CO2、C2H6、C2H4、C2H4等分子量较大或碳数较多的平衡常数较大,且在不同油中平衡常数差异较大。
(2)7种DGA气体在改性酯PFAE中的平衡常数均大于其余3种天然酯和矿物油,而特征气体溶解能力在3种天然酯之间的差异较小。
(3)在烃类气体中,C2H2在4种植物绝缘油中的平衡常数较大,其溶解能力远大于矿物油;而C2H6在植物油中的平衡常数小于矿物油。
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2022年第55卷第3期
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doi: 10.16790/j.cnki.1009-9239.im.2022.03.015
  • 接收时间:2021-04-19
  • 首发时间:2025-12-22
  • 出版时间:2022-03-20
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  • 收稿日期:2021-04-19
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2种不同金属材料的力学参数

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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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