Article(id=1242756901730108008, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756895296045592, articleNumber=null, orderNo=null, doi=10.16790/j.cnki.1009-9239.im.2021.10.003, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1601308800000, receivedDateStr=2020-09-29, revisedDate=1608480000000, revisedDateStr=2020-12-21, acceptedDate=null, acceptedDateStr=null, onlineDate=1774225934679, onlineDateStr=2026-03-23, pubDate=1634659200000, pubDateStr=2021-10-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1774225934679, onlineIssueDateStr=2026-03-23, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1774225934679, creator=13701087609, updateTime=1774225934679, updator=13701087609, issue=Issue{id=1242756895296045592, tenantId=1146029695717560320, journalId=1149653034449285133, year='2021', volume='54', issue='10', pageStart='1', pageEnd='109', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1774225933134, creator=13701087609, updateTime=1774226018771, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1242757254517207738, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756895296045592, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1242757254517207739, tenantId=1146029695717560320, journalId=1149653034449285133, issueId=1242756895296045592, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=20, endPage=25, ext={EN=ArticleExt(id=1242756903323943558, articleId=1242756901730108008, tenantId=1146029695717560320, journalId=1149653034449285133, language=EN, title=Research Progress on Performance of Alkylbenzene Insulating Oil for Submarine Cable, columnId=1198667062026531195, journalTitle=Insulating Materials, columnName=Review, runingTitle=null, highlight=null, articleAbstract=

Alkylbenzene insulating oil, represented by dodecylbenzene, is a kind of liquid medium that widely used in oil-filled submarine cables. Due to the stagnation of the development of oil-filled cable technology in China, the application and research of this type of insulating oil is relatively scarce. This paper introduced the physical and chemical, electrical, ageing, and biological toxicity of dodecylbenzene insulating oil for submarine cables.

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以十二烷基苯(DDB)为代表的烷基苯合成绝缘油是一种广泛应用于充油海缆中的液体介质,目前国内受限于充油电缆技术发展的停滞,对于该类型绝缘油的应用与研究较为缺乏。本文以十二烷基苯为例,介绍了海底电缆用烷基苯绝缘油在理化、电气、老化以及生物毒性方面的性能特点。

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廖建平(1983-),男(汉族),江西赣州人,高级工程师,主要从事绝缘油的测试与分析工作。

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廖建平(1983-),男(汉族),江西赣州人,高级工程师,主要从事绝缘油的测试与分析工作。

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廖建平(1983-),男(汉族),江西赣州人,高级工程师,主要从事绝缘油的测试与分析工作。

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项目国产烷基苯矿物绝缘油
外观无色透明无色透明
密度(20℃)/(g/cm3)0.8590.895
运动黏度(40℃)/(mm2/s)3.538.50
闪点(闭口)/℃146.5140.0
倾点/℃-60-25
酸值/(mgKOH/g)0.0020.001
介质损耗因数/(×10-4)3.83.0
体积电阻率/(Ω·m)6.71×10121.00×1013
电气强度/(kV/mm)29.4424.00
), ArticleFig(id=1245097056851832990, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756901730108008, language=CN, label=表1, caption=

烷基苯与矿物绝缘油性能对比

, figureFileSmall=null, figureFileBig=null, tableContent=
项目国产烷基苯矿物绝缘油
外观无色透明无色透明
密度(20℃)/(g/cm3)0.8590.895
运动黏度(40℃)/(mm2/s)3.538.50
闪点(闭口)/℃146.5140.0
倾点/℃-60-25
酸值/(mgKOH/g)0.0020.001
介质损耗因数/(×10-4)3.83.0
体积电阻率/(Ω·m)6.71×10121.00×1013
电气强度/(kV/mm)29.4424.00
), ArticleFig(id=1245097056960884901, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756901730108008, language=EN, label=Tab.2, caption=Loss, acid value, and color of dodecylbenzene before and after ageing at 115℃, figureFileSmall=null, figureFileBig=null, tableContent=
老化时间/h介质损耗因数(100℃)酸值/(mgKOH/g)颜色
00.000 80.003 4无色透明
960.001 00.003 4无色透明
1920.001 00.003 4无色透明
2880.001 20.003 4微黄
), ArticleFig(id=1245097057032188078, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756901730108008, language=CN, label=表2, caption=

115℃下十二烷基苯老化前后介质损耗因数、酸值与颜色

, figureFileSmall=null, figureFileBig=null, tableContent=
老化时间/h介质损耗因数(100℃)酸值/(mgKOH/g)颜色
00.000 80.003 4无色透明
960.001 00.003 4无色透明
1920.001 00.003 4无色透明
2880.001 20.003 4微黄
), ArticleFig(id=1245097057103491251, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756901730108008, language=EN, label=Tab.3, caption=Test results of dodecylbenzene with different materials before and after ageing, figureFileSmall=null, figureFileBig=null, tableContent=
老化条件介质损耗因数(100℃)酸值/(mgKOH/g)颜色
老化前0.000 80.003 4无色透明
不加材料0.001 00.003 4无色透明
加铝0.000 90.003 4无色透明
加镀锡铜线0.001 10.003 0无色透明
加铜0.000 90.004 3无色透明
加钢线0.000 80.004 1无色透明
加铝及镀锡铜线0.004 40.005 6浅黄
加铝及铜0.130 30.113 0浅黄
加丁腈橡胶0.103 40.110 0红黄
), ArticleFig(id=1245097057199960253, tenantId=1146029695717560320, journalId=1149653034449285133, articleId=1242756901730108008, language=CN, label=表3, caption=

十二烷基苯与不同材料共同老化前后测试结果

, figureFileSmall=null, figureFileBig=null, tableContent=
老化条件介质损耗因数(100℃)酸值/(mgKOH/g)颜色
老化前0.000 80.003 4无色透明
不加材料0.001 00.003 4无色透明
加铝0.000 90.003 4无色透明
加镀锡铜线0.001 10.003 0无色透明
加铜0.000 90.004 3无色透明
加钢线0.000 80.004 1无色透明
加铝及镀锡铜线0.004 40.005 6浅黄
加铝及铜0.130 30.113 0浅黄
加丁腈橡胶0.103 40.110 0红黄
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海底电缆用烷基苯绝缘油的性能研究进展
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廖建平 1 , 楚金伟 1 , 高帆 1 , 陈宇飞 1 , 张晨 2 , 俞思铭 2 , 李华强 2 , 钟力生 2
绝缘材料 | 综述 2021,54(10): 20-25
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绝缘材料 | 综述 2021, 54(10): 20-25
海底电缆用烷基苯绝缘油的性能研究进展
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廖建平1, 楚金伟1, 高帆1, 陈宇飞1, 张晨2, 俞思铭2, 李华强2, 钟力生2
作者信息
  • 1南方电网公司特高压输电公司检修试验中心,广东 广州 510405
  • 2西安交通大学 电力设备电气绝缘国家重点实验室,陕西 西安 710049
  • 廖建平(1983-),男(汉族),江西赣州人,高级工程师,主要从事绝缘油的测试与分析工作。

Research Progress on Performance of Alkylbenzene Insulating Oil for Submarine Cable
Jianping LIAO1, Jinwei CHU1, Fan GAO1, Yufei CHEN1, Chen ZHANG2, Siming YU2, Huaqiang LI2, Lisheng ZHONG2
Affiliations
  • 1Maintenance and Test Center of UHV Transmission Company of China Southern Power Grid Co., Ltd., Guangzhou 510405, China
  • 2State Key Laboratory of Electrical Insulation and Power Equipment, Xi'an Jiaotong University, Xi'an 710049, China
出版时间: 2021-10-20 doi: 10.16790/j.cnki.1009-9239.im.2021.10.003
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以十二烷基苯(DDB)为代表的烷基苯合成绝缘油是一种广泛应用于充油海缆中的液体介质,目前国内受限于充油电缆技术发展的停滞,对于该类型绝缘油的应用与研究较为缺乏。本文以十二烷基苯为例,介绍了海底电缆用烷基苯绝缘油在理化、电气、老化以及生物毒性方面的性能特点。

十二烷基苯  /  海底电缆  /  老化  /  毒性

Alkylbenzene insulating oil, represented by dodecylbenzene, is a kind of liquid medium that widely used in oil-filled submarine cables. Due to the stagnation of the development of oil-filled cable technology in China, the application and research of this type of insulating oil is relatively scarce. This paper introduced the physical and chemical, electrical, ageing, and biological toxicity of dodecylbenzene insulating oil for submarine cables.

dodecylbenzene  /  submarine cable  /  ageing  /  toxicity
廖建平, 楚金伟, 高帆, 陈宇飞, 张晨, 俞思铭, 李华强, 钟力生. 海底电缆用烷基苯绝缘油的性能研究进展. 绝缘材料, 2021 , 54 (10) : 20 -25 . DOI: 10.16790/j.cnki.1009-9239.im.2021.10.003
Jianping LIAO, Jinwei CHU, Fan GAO, Yufei CHEN, Chen ZHANG, Siming YU, Huaqiang LI, Lisheng ZHONG. Research Progress on Performance of Alkylbenzene Insulating Oil for Submarine Cable[J]. Insulating Materials, 2021 , 54 (10) : 20 -25 . DOI: 10.16790/j.cnki.1009-9239.im.2021.10.003
海底电缆指敷设在海洋或河流水底的电缆,用于向海岛、海洋石油或天然气开采平台等被水域孤立的地区输送电力。1954年瑞典架设了世界上第一条商业运行的海底电缆,此后跨海输电工程有了长足发展,海底电缆的线路长度、电压等级、输送容量等提升迅速,且涵盖交、直流两种输电方式。目前国外架设的海底电缆电压等级超过500 kV,敷设长度超过40 km,水深达400 m,单回输送功率超过1 400 MW。我国跨海输电始于20世纪80年代,第一条应用长距离高压海底电缆的输电工程为1986年的珠江-虎门海底电缆工程,由日本住友公司承建。1989年我国自行建设了浙江舟山海底直流工程。2009年南方电网公司建设了广东至海南电网联网工程,电压等级为500 kV,线路长度为32 km,一期输送容量达600 MW,为国内截至目前电压等级最高、输送容量最大的海底电缆工程[1]
跨海输电工程电压等级与输送容量的提升,对海底电缆性能提出了更高要求。海底电缆的应用环境与陆缆相差很大,受到海底地形地貌,海水腐蚀、深水压强、洋流力学以及海陆线缆转换等诸多因素影响,对结构设计提出了更高要求。目前国内外已投运的海底电缆主要采用3种结构形式,分别为油浸纸绝缘电缆、充油电缆以及交联聚乙烯(XLPE)绝缘电缆,而500 kV以上的海底电缆全部采用充油电缆形式。大量工程经验表明,在长距离、超高压、大容量输电场合下,充油电缆是较为可靠的选择[2]
我国电缆技术路线主要以聚合物绝缘电缆为主,其典型代表为交联聚乙烯电缆,而国外特别是欧美国家与日本大量采用充油电缆。我国在海底电缆设计与制造领域尚存在欠缺,国内高电压等级跨海输电所用的充油电缆与绝缘油均来自国外,为掌握相关技术,有必要开展充油海缆结构与材料方面的研究。
充油电缆技术起步较早,其结构与交联聚乙烯绝缘电缆类似[3],但在绝缘层材料与线芯结构上有很大差别。充油电缆的绝缘由固体与液体共同承担,通过充入绝缘油来消除绝缘层中形成的气隙,从而达到提高工作场强的目的[4]。目前应用于海底电缆的一般是自容式充油电缆。
自容式充油电缆从内至外由线芯、绝缘层、半导电屏蔽层、护套、加强层、聚乙烯套管、防蛀蚀护层、聚丙烯塑料丝垫层、钢丝铠装组成,根据芯数不同分为单芯与三芯两种形式。单芯电缆的线芯为中空结构,在线芯中央设置供绝缘油流动的油道,油道尺寸由电缆的电压等级决定;三芯电缆的线芯为实芯,采用3根芯外绝缘层与电缆护套之间的间隙作为油道。充油电缆的绝缘层一般采用粘性浸渍纸绝缘或聚丙烯薄膜木纤维复合纸绝缘(PPLP),PPLP为新型复合材料,采用牛皮纸-聚丙烯薄膜-牛皮纸三层叠加结构,其绝缘性能与损耗相较于传统浸渍牛皮纸更具优势,但成本也更高。充油电缆通过向油道内充入绝缘油作为补充绝缘及应力释放的介质,通常充入绝缘油时会保持较高的油压,这样在护套发生破损时可以防止潮气侵入,较大的油压也能够提高绝缘层的工频电气强度。为实现绝缘油的及时补充,敷设自容式充油电缆时需要安装绝缘油补充设备,通常包括重力供油箱、压力供油箱、油泵以及油道压力监测装置等。充油海缆深处海底,其外部通常会承受较大压力,因此电缆的护套也应选取有较高机械强度的材料,一般选取铅或铝合金作为护套材料,考虑到与绝缘油的相容性,目前较多设计采用铝合金护套。
自容式充油电缆依靠浸渍纸与绝缘油配合发挥绝缘作用。当负荷发生变化时,油道温度会随之变化,温度升高时油道内的绝缘油膨胀流出,胀出的绝缘油经油道流入供油箱;温度下降时绝缘油收缩,供油箱中的绝缘油经油道又返回绝缘层,填补层间空隙。该绝缘机制能及时释放电缆内部因负荷变化引起的形变所带来的应力,避免内部压力过大造成机械老化甚至直接损坏电缆,也能消除绝缘层的气隙,提高了绝缘强度。充油海缆护套发生破损时可以不立即断电,只要不断向油道充入绝缘油,维持住油压与绝缘,电缆就可以继续工作,为调度与抢修争取时间。
烷基苯是目前海底电缆广泛采用的一种绝缘油,其结构为带有侧链的单环芳香烃,工业生产中通过化学合成制得。通常使用的烷基苯绝缘油侧链上的碳原子数为12个,称为十二烷基苯(DDB)。十二烷基苯为无色透明液体,分子量为246,目前海缆中所用绝缘油多为十二烷基苯占主要成分的烷基苯混合油,其中十二烷基苯占50%以上,其余为侧链碳原子数为10~13个的烷基苯。
烷基苯根据侧链上有无支链可分为硬质与软质两种。硬质烷基苯的侧链有支链,其红外光谱在1 380 cm-1处显示出双吸收峰;软质烷基苯侧链上无支链,又称直链烷基苯,其红外光谱在1 380 cm-1处显示单吸收峰[4]。两种烷基苯在国内外均有使用,主要差别在于生物降解性,其余性能相近,其中软质烷基苯生物降解性较好。
硬质烷基苯工业上一般制备方法:使用四聚烯烃在氟化氢催化条件下与苯进行烷基化反应,再去除氟化氢与残余的苯,其中间馏分即为硬质烷基苯,通过蒸馏去除轻馏分,提取后经白土精制即可得到绝缘用的烷基苯。软质烷基苯的合成方法主要有氯化法与烯烃法两种。氯化法是将长链正构烷烃氯化后再与苯进行烷基化反应,制得所需直链烷基苯;烯烃法以石蜡为原料经高温裂解得到α-烯烃,将α-烯烃在氧化铝催化条件下与苯进行烷基化反应,制得所需直链烷基苯。氯化法制得的产品中易残留氯元素,影响电气性能,因此一般采用烯烃法[5]。烷基苯的合成过程较之矿物绝缘油的处理过程要简便,但由于目前国内充油电缆市场较小,用作电缆绝缘的烷基苯未能形成规模生产,成本较高。
早期国外充油电缆主要使用低黏度矿物绝缘油作为液体介质,伴随石油化工领域的发展,20世纪60年代起黏度更低的烷基苯合成油受到关注。起初烷基苯仅用作改性剂与矿物绝缘油联合使用,后伴随生产成本的下降,烷基苯逐渐取代矿物油成为充油电缆用液体介质,此外烷基苯在750 kV高压电抗器套管中也有应用。
在充油海缆这一应用背景下,烷基苯绝缘油相对于矿物油具有诸多性能上的优势。表1对比了某国产750 kV充油电缆用烷基苯绝缘油与矿物绝缘油的理化性能。从表1可以看出,烷基苯具有较低的黏度、优异的电气性能,且其吸水性强于矿物绝缘油。
在选择充油海缆的液体绝缘介质时,黏度是需要重点考察的物理性能。充油海缆既依靠绝缘油流入并填充绝缘层中的空隙来提高绝缘强度,也依靠绝缘油流出来消除温差所导致的内部应力。充油海缆的绝缘层为浸渍纸包绕多层结构,层间缝隙很小,且海缆结构设计中不包含类似充油变压器中油路强迫循环的辅助流动装置,这就要求充油海缆所使用的液体绝缘介质具有较低的黏度,使其在低流速时依然能够在小间隙中顺畅流动。但黏度过低也会引起挥发性大、闪点低等问题。综合考量下,十二烷基苯在保证性能稳定的同时具有最低的黏度,满足充油海缆用绝缘液体介质的性能要求。
十二烷基苯的介电常数约为2.2,与矿物绝缘油相近,体积电阻率及介质损耗也与矿物绝缘油相当,能够与常用的牛皮纸良好配合。十二烷基苯拥有比矿物绝缘油更高的电气强度,在GB/T 507—2002所规定标准电极2.5 mm间隙下,十二烷基苯的击穿电压超过70 kV[5-6],高于大部分矿物绝缘油,意味着相同结构的充油电缆使用十二烷基苯较之矿物绝缘油能够提高工作场强。
在海底电缆正常运行工况下,十二烷基苯的析气系数为负值,且随温度升高而继续减小[6]。文献[5]报道十二烷基苯对氮、氩、水蒸气等也具有吸收性。良好的析气性使得十二烷基苯一方面能够减少油中的游离气泡,避免“气桥”的生成,从而降低损耗、提高工作场强;另一方面也能及时吸附绝缘油因局部放电或过热分解产生的各种可燃气体,避免油道中可燃气体积累,提高设备安全性。文献[6]报道硬质烷基苯的析气性优于软质烷基苯,且两种烷基苯的析气系数均为负值,远优于不加抗氧剂的矿物绝缘油。这是由于烷基苯中芳香烃的占比较矿物油高,而芳香烃能够吸附各类气体。
国内学者研究发现,十二烷基苯的吸潮与脱潮能力均强于矿物绝缘油,相同含水量下的电气强度要高于矿物绝缘油。这是由于十二烷基苯能够吸收更多因充油电缆绝缘层老化所产生的水分,减缓游离水析出导致的损耗增加,抑制电缆的老化过程[6]
十二烷基苯与矿物绝缘油的互溶性良好,研究结果表明二者能够以任何比例互溶。该特性一方面可用于添加改性,文献[10]报道了向矿物绝缘油中添加少量十二烷基苯,能够改善析气性、降低凝点;另一方面也可利用该特性进行电缆换油,十二烷基苯的电气强度优于矿物绝缘油,其密度、黏度等理化性能与矿物绝缘油近似,因此可在不改变电缆结构的情况下直接替换长期运行电缆中性能劣化的矿物绝缘油。康奈尔大学曾在修复345 kV充油电缆时使用十二烷基苯替换原本充入的矿物绝缘油,替换后电缆运行状况良好[6]。但混油目前主要在研究阶段,工程应用案例较少,这主要是出于运行维护的考量。绝缘油混合必然会改变成分,原本针对单一绝缘油制定的运行维护方案未必适用于混合后的新油,工程实际中仍需谨慎对待混油操作。
老化是所有电力设备面临的重要问题,充油海缆也不例外。电缆长期运行后,浸渍纸与绝缘油会因长期电、热应力作用发生老化分解[7],产生低分子量芳香烃、气体、水、X蜡等老化产物,这些产物积累会引起损耗上升、电缆工作场强降低、绝缘性能下降甚至失效等问题。充油海缆装设于海底,相较于陆上电缆发生故障时维修更为困难,因此掌握充油电缆材料的老化特性对于有效评估电缆寿命尤为关键。
十二烷基苯自身的理化性能与热性能较为稳定。文献[6]报道了十二烷基苯的老化试验研究,将约170 mL油样盛放于200 mL的敞口瓶中,在115℃下老化96 h,老化后油样的性能检测结果见表2。从表2可以看出,烷基苯老化前后介质损耗因数与酸值均未出现数量级变化,将老化时间延长至2倍与3倍后,油样除颜色泛黄外,介质损耗因数与酸值依然稳定,老化前后的黏度也几乎不变。文献[8]报道了老化温度为135℃、老化时长为72~336 h下烷基苯的老化实验研究,得出类似结论。
充油海缆内的绝缘油会与电缆内部多种材料接触,这就要求在选材时不仅需要考虑绝缘油本身的老化特性,还需要考察长期运行中电缆中的各种固体材料是否会加速绝缘油老化。韦华达等[6]研究了十二烷基苯与铝、铜、镀锡铜线、钢以及耐油橡胶等材料共同老化后的介质损耗因数、酸值及颜色变化,老化温度为115℃,时间为96 h,结果见表3。从表3可以看出,该老化条件下除耐油橡胶外,其余材料的加入并不会使十二烷基苯的老化程度发生明显变化,这些材料对其老化过程影响很小,且十二烷基苯中不含硫,对金属材料无腐蚀性。需要注意的是十二烷基苯与橡胶相容性很差,加入橡胶后会出现老化加速现象。文献[5]报道了十二烷基苯与聚丙烯相容性也很差,会引起聚丙烯溶解与溶胀,这都是由于烷基苯中芳香烃含量高,对聚合物的溶解能力较强。因此,在使用时应避免烷基苯与充油海缆外层聚合物接触,以免发生腐蚀。
英国学者I HOSIER等[9]通过紫外光谱与微水含量分析,研究了更高温度下十二烷基苯与铜接触后的老化情况。其老化温度为135℃,老化时间为72~336 h,油样为35 mL,置于50 mL的玻璃容器中,容器口用托盘遮挡避免过分蒸发,油样中放入厚度为0.1 mm、表面积为22.4 cm2的铜片,事先对铜片表面进行打磨以消除氧化层。结果表明,该老化条件下铜会对烷基苯的老化起到促进作用。加入铜的油样老化72 h后与不加铜的油样老化168 h后的紫外光谱吸收峰值相当,用紫外光谱分析加入铜的油样,发现进行72 h老化后其紫外光谱在波长为680 nm处出现了能够表征羧酸铜的吸收峰,证明铜与烷基苯接触后发生了老化腐蚀[9-11]。从微水含量角度来看,未加铜的烷基苯中微水含量几乎不随老化时间增加而改变,但加入铜会引起微水含量随老化时间增加而上升。研究还发现加入铜后工频下十二烷基苯的介电常数几乎不随老化时间增加而变化,与无铜时一致,但介质损耗与电导在加入铜片后会随老化时间增加而上升。十二烷基苯老化后的电气强度受铜影响很大,取老化前后油样8 mL在1 mm间隙球-球电极系统内分别进行击穿测试,烷基苯不与铜接触老化336 h后,油样的电气强度由老化前的14 kV/mm下降至老化后的9 kV/mm,分散性变化不大;油样与铜接触仅老化72 h后,油样的电气强度便下降至7 kV/mm,且分散性变大。这可能与铜老化后有固体颗粒析出有关,这些颗粒在电场牵引下会形成小桥,放电会使固体小桥发展,从而引起电气强度下降。此外铜的加入并不会影响黏度,老化前后烷基苯绝缘油的黏度没有明显变化。
除了金属的催化作用外,氧化是引起绝缘油老化的另一重要原因。充油海缆绝缘层所用的浸渍纸由纤维素构成,长期运行后在电热应力下会发生分解,产生CO、CO2、H2O等含氧副产物,从而引起绝缘油与线芯油道的氧化,导致老化加剧[12]。二苄基二硫(DBDS)是绝缘油中常用的一种抗氧化剂, I HOSIER等[9]通过紫外光谱研究了加入DBDS对烷基苯绝缘油的影响。结果表明,在接触空气与铜的情况下,未加入DBDS的油样老化72 h后在680 nm处出现了明显的表征羧酸铜的吸收峰,而加入DBDS的油样则在老化168 h后才出现该峰,说明DBDS确实能够延缓铜氧化所引发的老化现象。但另一方面DBDS会引入硫元素,硫会与铜发生硫化反应。该研究还对比了铜片参与时加入与不加入DBDS对十二烷基苯老化性能的影响,结果发现加入DBDS的油样老化后出现铜片变黑现象,且电气强度明显下降,说明加入DBDS确实会导致油中铜件的硫化[9]。日本学者H KAWARAI等[13]也发现电缆油纸上的硫化铜与油中DBDS和铜的反应有关。硫化反应同样会加速老化导致绝缘油性能下降。因此在选择抗氧剂时,应注意抗氧剂的组成成分,避免引入硫元素等影响油品。
I HOSIER等[10]研究了矿物绝缘油与十二烷基苯混合后的老化特性,老化温度为135℃,老化时间为36~288 h。该研究通过红外光谱检测烷基苯与空气接触并老化后的油样,发现在800~1 400 cm-1处出现了表征O-H键与C-O键的吸收峰,而加入10%矿物绝缘油后进行老化,油样中表征O-H键的吸收峰几乎消失,表征C-O键的吸收峰明显减弱,加入25%矿物绝缘油并老化后油样中表征氧化的峰几乎消失。该研究中添加的矿物绝缘油中不含抗氧剂,说明矿物绝缘油本身可作为氧化抑制剂添加至十二烷基苯中进行改性。研究还发现添加少量矿物绝缘油能够延缓烷基苯的老化,且不会对烷基苯的酸值、水分与介质损耗等性能造成明显影响。当烷基苯中有铜存在时,向烷基苯中添加10%矿物绝缘油,能够有效抑制绝缘油因老化引起的酸值与水分含量上升,当矿物绝缘油的添加量达25%时,还能够有效抑制老化引起的损耗上升。而更高添加量并不能起到进一步的老化抑制作用。
一种绝缘材料能否投入实际运用,既要考虑性能因素,也需要考虑安全因素。我国过去曾使用过的一些液体绝缘介质如聚氯联苯等,虽然具有优异的介电性能,但因严重毒副作用,最终还是在产业升级中被淘汰。烷基苯在制备、运输、电缆制造以及电缆维修等环节中均有可能与生产、运输或施工人员发生直接接触,有必要详细评估其安全性。此外充油海缆敷设于海底,若电缆发生破损,油道内的正压会将绝缘油挤压入海中造成污染,泄漏发生后绝缘油对海洋环境的影响特别是毒性影响,也有必要进行深入研究。因此对十二烷基苯的毒性研究应包括对人的影响以及对海洋环境的影响两个方面。
韦桂秋等[14]通过试验研究了十二烷基苯对发光细菌、海洋微藻、鱼类、对虾、多毛类以及贝类等海洋生物的急性与慢性生物毒性,结果表明十二烷基苯仅对小型甲壳类生物表现出极强毒性,对上述其余海洋生物的毒性甚微。岑贞锦等[15]研究表明十二烷基苯对海洋生物的效应浓度值介于饱和溶解浓度的17.07%~100%,水中十二烷基苯浓度在饱和溶解浓度的6.25%以下时,不会对试验生物的存活产生明显可见的毒性影响。需要注意的是实验室环境与实际环境存在一定区别,当发生海中泄漏时,需要根据泄漏源情况、泄漏范围以及扩散速度等综合评估实际毒害作用。
岑贞锦等[15]开展了小鼠14天急性经口毒性试验,研究十二烷基苯绝缘油对哺乳类生物的毒性影响。结果表明海缆绝缘油对小鼠的经口毒性计量大于5.56 mL/kg体重。小鼠给药后24 h即恢复,14天内未出现死亡,按工业化学品毒性分级属无急性毒性,按食品安全的毒性剂量分级为相对无毒。该结果与其他一些关于烷基苯低毒性的报道一致[14,16]
赵刚等[16]研究了十二烷基苯在海水中的降解率,研究表明十二烷基苯在天然海水中28天能够降解44.0%,在活性淤泥菌作用下28天降解率为75.9%,其生物降解率远高于矿物绝缘油,对环境较为友好。
综上所述,十二烷基苯对人与环境的毒性较弱,可以认为是一种较为安全的液体介质。
烷基苯绝缘油具有低黏度、高电气强度、析气性良好及凝点低等性能优势,同时具有良好的老化特性,但与铜共同使用时存在老化加速现象,需要添加抗氧剂进行调节。另外可以加入矿物绝缘油改善其老化性能。生物毒性方面,已有研究表明烷基苯对人体及海洋环境均未见明显毒性,且软质烷基苯能够有效降解,对环境友好。
我国自20世纪80年代开始探索充油电缆相关领域,学者们对包括烷基苯在内的充油电缆绝缘材料开展了大量基础研究工作,国内电缆制造与化工企业也积极推进充油电缆的国产化进程,制造出275 kV电压等级以上的充油电缆及适用于330 kV的电缆油[11]。但随着以交联聚乙烯绝缘电缆为代表的聚合物绝缘电缆技术普及,充油电缆技术路线逐渐边缘化,相关研究与生产陷入停滞。目前我国充油海缆多数为国外引进的技术与产品,而国内外的工程经验表明充油电缆未被淘汰,仍具有其独特的技术优势,特别是在高电压等级的海底电缆场合,应当予以必要的重视。
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2021年第54卷第10期
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doi: 10.16790/j.cnki.1009-9239.im.2021.10.003
  • 接收时间:2020-09-29
  • 首发时间:2026-03-23
  • 出版时间:2021-10-20
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  • 收稿日期:2020-09-29
  • 修回日期:2020-12-21
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    1南方电网公司特高压输电公司检修试验中心,广东 广州 510405
    2西安交通大学 电力设备电气绝缘国家重点实验室,陕西 西安 710049
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2种不同金属材料的力学参数

Family
属数
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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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