Article(id=1222513213229491083, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222513210519970621, articleNumber=null, orderNo=null, doi=10.19666/j.rlfd.202304051, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1680278400000, receivedDateStr=2023-04-01, revisedDate=null, revisedDateStr=null, acceptedDate=null, acceptedDateStr=null, onlineDate=1769399463230, onlineDateStr=2026-01-26, pubDate=1700841600000, pubDateStr=2023-11-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1769399463230, onlineIssueDateStr=2026-01-26, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1769399463230, creator=13701087609, updateTime=1769399463230, updator=13701087609, issue=Issue{id=1222513210519970621, tenantId=1146029695717560320, journalId=1210938733613449225, year='2023', volume='52', issue='11', pageStart='1', pageEnd='198', issueExtLink='null', onlineDate='null', pubDate='null', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1769399462585, creator=13701087609, updateTime=1769405983425, updator=13701087609, preIssue=null, nextIssue=null, ext={EN=IssueExt(id=1222540560984957089, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222513210519970621, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1222540560984957090, tenantId=1146029695717560320, journalId=1210938733613449225, issueId=1222513210519970621, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null}, startPage=193, endPage=198, ext={EN=ArticleExt(id=1222513214772994979, articleId=1222513213229491083, tenantId=1146029695717560320, journalId=1210938733613449225, language=EN, title=Study on multi-parameter collaborative monitoring methods for hydrogen conductivity in water vapor degassing, columnId=1211002409397129992, journalTitle=Thermal Power Generation, columnName=Power generation technology forum, runingTitle=null, highlight=null, articleAbstract=

This paper proposes a multi-parameter collaborative monitoring system and method for degassed hydrogen conductivity based on the combination of double water membrane degassed method and electric regeneration ion exchange technology, which can quickly measure a number of key water quality indicators such as conductivity, hydrogen conductivity, degassed hydrogen conductivity and pH. It can make comprehensive evaluation of water quality, guide thermal equipment shutdown and startup. And it can adjust normal operating water conditions. It has a great significance for ensuring water vapor quality and thermal equipment corrosion, salt accumulation and scale formation. Double water membrane degassing technology is used to measure degassed hydrogen conductivity, which can effectively remove CO2 from water. On this basis, a method of calibration degassed hydrogen conductivity measured by standard solution is proposed, so that the accuracy of the measured value can be effectively evaluated. This method has been applied to typical gas combined cycle units and heating units for on-site supervision. It proves that the method has high measurement accuracy, can quickly and comprehensively evaluate water vapor quality, and it can assist in solving various technical problems on site. Therefore, it has strong popularization and application value.

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提出了一种基于双水膜脱气法和电再生离子交换技术相结合的水汽脱气氢电导率多参数协同监测系统及方法,可快速测量电导率、氢电导率、脱气氢电导率和pH值等多项关键水质指标,对水质做出综合评判,指导停机启动及正常运行水工况调整,对保障水汽品质及热力设备腐蚀、积盐、结垢的防控具有重要意义。其中,脱气氢电导率测量采用双水膜脱气技术,可高效脱除水中CO2,在此基础上提出标准溶液校准脱气氢电导率测量值的方法,可有效评判测量值的准确性。该方法用于典型的燃气联合循环机组、供热机组的现场监督,结果表明其测量准确性高,可快速综合评估水汽品质,能辅助解决现场出现的各类技术问题,具有很强的推广应用价值。

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张龙明(1987),男,硕士,高工,主要研究方向电厂水处理技术及电厂化学仪表,
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Energy Engineering, 2022, 42(3): 65-68., articleTitle=Application of combined determination of total organic carbon and degassing hydrogenconductivity for abnormal water and steam guality analysis in thermal power plants, refAbstract=null), Reference(id=1241137066281595307, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, doi=null, pmid=null, pmcid=null, year=2018, volume=47, issue=10, pageStart=84, pageEnd=89, url=null, language=null, rfNumber=[10], rfOrder=18, authorNames=田利, 戴鑫, 陈裕忠, journalName=热力发电, refType=null, unstructuredReference=田利,戴鑫,陈裕忠,等.一种智能型氢电导率测量方法研究及应用[J].热力发电201847(10):84-89., articleTitle=一种智能型氢电导率测量方法研究及应用, refAbstract=null), Reference(id=1241137066373870002, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, doi=null, pmid=null, pmcid=null, year=2018, volume=47, issue=10, pageStart=84, pageEnd=89, url=null, language=null, rfNumber=[10], rfOrder=19, authorNames=TIAN Li, DAI Xi, CHEN Yuzhong, journalName=Thermal Power Generation, refType=null, unstructuredReference=TIAN Li, DAI Xi, CHEN Yuzhong, et al. Research and application of an intelligent hydrogen conductivity measurement method[J]. 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Comparison of degassed hydrogen conductivity measured with different concentrations of Cl standard solutions and their theoretical hydrogen conductivity values

, figureFileSmall=null, figureFileBig=null, tableContent=
Cl质量浓度/(µg·L–1)Cl标准氢电导率/(µS·cm–1)实测脱气氢电导率/(µS·cm–1)绝对工作误差/(µS·cm–1)相对误差/%
100.134 40.147 00.012 69.38
200.242 70.249 00.006 32.60
300.356 00.367 00.011 03.09
400.470 90.454 00.016 93.59
500.586 50.599 00.012 52.13
600.702 30.683 00.019 32.75
700.818 30.779 00.039 34.80
800.934 50.934 00.000 50.05
901.050 70.982 00.068 76.54
1001.166 91.142 00.024 92.13
2002.220 92.202 00.018 90.85
), ArticleFig(id=1241137061449756890, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表1, caption=

不同质量浓度Cl标准液测量脱气氢电导率和其理论氢电导率比对

, figureFileSmall=null, figureFileBig=null, tableContent=
Cl质量浓度/(µg·L–1)Cl标准氢电导率/(µS·cm–1)实测脱气氢电导率/(µS·cm–1)绝对工作误差/(µS·cm–1)相对误差/%
100.134 40.147 00.012 69.38
200.242 70.249 00.006 32.60
300.356 00.367 00.011 03.09
400.470 90.454 00.016 93.59
500.586 50.599 00.012 52.13
600.702 30.683 00.019 32.75
700.818 30.779 00.039 34.80
800.934 50.934 00.000 50.05
901.050 70.982 00.068 76.54
1001.166 91.142 00.024 92.13
2002.220 92.202 00.018 90.85
), ArticleFig(id=1241137061567197407, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=EN, label=Tab.2, caption=

Comparison of monitoring data from multi-parameter collaborative monitoring systems such as degassed hydrogen conductivity with field instruments

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值
高压饱和蒸汽现场仪表14.0200.2830.086
协同监测系统14.1600.2750.0749.710
低压饱和蒸汽现场仪表0.280
协同监测系统14.0500.2890.0699.710
低压过热蒸汽现场仪表0.284
协同监测系统13.9900.2780.0629.700
), ArticleFig(id=1241137061672055015, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表2, caption=

协同监测系统监测数据与现场仪表数据对比

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值
高压饱和蒸汽现场仪表14.0200.2830.086
协同监测系统14.1600.2750.0749.710
低压饱和蒸汽现场仪表0.280
协同监测系统14.0500.2890.0699.710
低压过热蒸汽现场仪表0.284
协同监测系统13.9900.2780.0629.700
), ArticleFig(id=1241137061760135405, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=EN, label=Tab.3, caption=

Chromatographic analysis data

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称FACClNO2NO3SO42–PO43–
高压饱和蒸汽<0.5<0.51.66<0.5<0.5<0.5<0.5
低压饱和蒸汽<0.5<0.51.35<0.5<0.5<0.5<0.5
低压过热蒸汽<0.5<0.51.31<0.5<0.5<0.5<0.5
), ArticleFig(id=1241137061844021491, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表3, caption=

色谱分析数据

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称FACClNO2NO3SO42–PO43–
高压饱和蒸汽<0.5<0.51.66<0.5<0.5<0.5<0.5
低压饱和蒸汽<0.5<0.51.35<0.5<0.5<0.5<0.5
低压过热蒸汽<0.5<0.51.31<0.5<0.5<0.5<0.5
), ArticleFig(id=1241137061927907577, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=EN, label=Tab.4, caption=

Monitoring data of condensed water in the unit startup stage by multi-parameter collaborative monitoring system such as degassed hydrogen conductivity

, figureFileSmall=null, figureFileBig=null, tableContent=
时刻比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值Cl质量浓度/(μg·L–1)
10:10(起机)23.7802.5900.3199.922.2
11:0822.6200.5780.2889.911.5
12:3222.5900.5220.2299.910.9
13:2522.4300.4000.1899.911.0
14:3021.4200.3760.1529.890.8
15:2821.0600.1570.0909.880.6
16:0020.9800.1440.0869.880.3
), ArticleFig(id=1241137062087291137, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表4, caption=

多参数协同监测系统在机组启动阶段凝结水监测数据

, figureFileSmall=null, figureFileBig=null, tableContent=
时刻比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值Cl质量浓度/(μg·L–1)
10:10(起机)23.7802.5900.3199.922.2
11:0822.6200.5780.2889.911.5
12:3222.5900.5220.2299.910.9
13:2522.4300.4000.1899.911.0
14:3021.4200.3760.1529.890.8
15:2821.0600.1570.0909.880.6
16:0020.9800.1440.0869.880.3
), ArticleFig(id=1241137062208925961, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=EN, label=Tab.5, caption=

Comparison of measured values of degassed hydrogen conductivity and other multi-parameter collaborative monitoring systems with field tables

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值
给水现场仪表4.6770.1669.09
协同监测系统4.5890.1710.0669.20
低压饱和蒸汽现场仪表0.806
协同监测系统14.5000.8010.1429.73
低压过热蒸汽现场仪表0.756
协同监测系统14.2000.7490.1469.72
), ArticleFig(id=1241137063697903889, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表5, caption=

水汽脱气氢电导率等多参数协同监测系统测量值与现场仪表比对

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称比电导率/(µS·cm–1)氢电导率/(µS·cm–1)脱气氢电导率/(µS·cm–1)pH值
给水现场仪表4.6770.1669.09
协同监测系统4.5890.1710.0669.20
低压饱和蒸汽现场仪表0.806
协同监测系统14.5000.8010.1429.73
低压过热蒸汽现场仪表0.756
协同监测系统14.2000.7490.1469.72
), ArticleFig(id=1241137063802761495, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=EN, label=Tab.6, caption=

Chromatographic analysis data

, figureFileSmall=null, figureFileBig=null, tableContent=
样水名称FACClNO2NO3SO42–PO43–
高压饱和蒸汽<0.51.851.66<0.5<0.5<0.5<0.5
低压饱和蒸汽<0.510.201.35<0.5<0.5<0.5<0.5
低压过热蒸汽<0.511.601.31<0.5<0.5<0.5<0.5
), ArticleFig(id=1241137063953756441, tenantId=1146029695717560320, journalId=1210938733613449225, articleId=1222513213229491083, language=CN, label=表6, caption=

水样色谱分析数据

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样水名称FACClNO2NO3SO42–PO43–
高压饱和蒸汽<0.51.851.66<0.5<0.5<0.5<0.5
低压饱和蒸汽<0.510.201.35<0.5<0.5<0.5<0.5
低压过热蒸汽<0.511.601.31<0.5<0.5<0.5<0.5
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水汽脱气氢电导率多参数协同监测方法研究
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田利 1 , 谭旭南 2 , 程阳 3 , 冯向东 4 , 方湘瑜 5 , 陈丰 3 , 张龙明 1 , 冯礼奎 6 , 张国锋 1 , 曹求洋 6
热力发电 | 发电技术论坛 2023,52(11): 193-198
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热力发电 | 发电技术论坛 2023, 52(11): 193-198
水汽脱气氢电导率多参数协同监测方法研究
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田利1 , 谭旭南2, 程阳3, 冯向东4, 方湘瑜5, 陈丰3, 张龙明1 , 冯礼奎6, 张国锋1, 曹求洋6
作者信息
  • 1.浙江西热利华智能传感技术有限公司,浙江 嘉兴 314000
  • 2.广州珠江天然气发电有限公司,广东 广州 511457
  • 3.华能国际电力股份有限公司,北京 100031
  • 4.浙江省浙能技术研究院,浙江 杭州 311121
  • 5.浙江省特种设备科学研究院,浙江 杭州 310020
  • 6.国网浙江省电力公司电力科学研究院,浙江 杭州 310006
  • 田利(1970),女,硕士,研究员,主要研究方向为电厂化学监督及腐蚀监控技术,

通讯作者:

张龙明(1987),男,硕士,高工,主要研究方向电厂水处理技术及电厂化学仪表,
Study on multi-parameter collaborative monitoring methods for hydrogen conductivity in water vapor degassing
Li TIAN1 , Xunan TAN2, Yang CHENG3, Xiangdong FENG4, Xiangyu FANG5, Feng CHEN3, Longming ZHANG1 , Likui FENG6, Guofeng ZHANG1, Qiuyang CAO6
Affiliations
  • 1.Zhejiang TPRI-LH Intelligent Sensing Technology Co.,Ltd., Jiaxing 314400, China
  • 2.Guangzhou Zhujiang LNG Power Generation Co., Ltd., Guangzhou 511457,China
  • 3.Huaneng Power International, Inc. Beijing 100031, China
  • 4.Zhejiang Energy R&D Institute Co.,Ltd., Hangzhou 311121,China
  • 5.Zhejiang Academy of Special Equipment Science, Hanghzhou 310020,China
  • 6.State Grid Zhe-Jiang Electric Power Corporation Research Institute, Hanghzhou 310006, China
出版时间: 2023-11-25 doi: 10.19666/j.rlfd.202304051
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提出了一种基于双水膜脱气法和电再生离子交换技术相结合的水汽脱气氢电导率多参数协同监测系统及方法,可快速测量电导率、氢电导率、脱气氢电导率和pH值等多项关键水质指标,对水质做出综合评判,指导停机启动及正常运行水工况调整,对保障水汽品质及热力设备腐蚀、积盐、结垢的防控具有重要意义。其中,脱气氢电导率测量采用双水膜脱气技术,可高效脱除水中CO2,在此基础上提出标准溶液校准脱气氢电导率测量值的方法,可有效评判测量值的准确性。该方法用于典型的燃气联合循环机组、供热机组的现场监督,结果表明其测量准确性高,可快速综合评估水汽品质,能辅助解决现场出现的各类技术问题,具有很强的推广应用价值。

脱气  /  氢电导率  /  pH值  /  双水膜脱气

This paper proposes a multi-parameter collaborative monitoring system and method for degassed hydrogen conductivity based on the combination of double water membrane degassed method and electric regeneration ion exchange technology, which can quickly measure a number of key water quality indicators such as conductivity, hydrogen conductivity, degassed hydrogen conductivity and pH. It can make comprehensive evaluation of water quality, guide thermal equipment shutdown and startup. And it can adjust normal operating water conditions. It has a great significance for ensuring water vapor quality and thermal equipment corrosion, salt accumulation and scale formation. Double water membrane degassing technology is used to measure degassed hydrogen conductivity, which can effectively remove CO2 from water. On this basis, a method of calibration degassed hydrogen conductivity measured by standard solution is proposed, so that the accuracy of the measured value can be effectively evaluated. This method has been applied to typical gas combined cycle units and heating units for on-site supervision. It proves that the method has high measurement accuracy, can quickly and comprehensively evaluate water vapor quality, and it can assist in solving various technical problems on site. Therefore, it has strong popularization and application value.

degassed  /  hydrogen conductivity  /  pH  /  membrane degassing
田利, 谭旭南, 程阳, 冯向东, 方湘瑜, 陈丰, 张龙明, 冯礼奎, 张国锋, 曹求洋. 水汽脱气氢电导率多参数协同监测方法研究. 热力发电, 2023 , 52 (11) : 193 -198 . DOI: 10.19666/j.rlfd.202304051
Li TIAN, Xunan TAN, Yang CHENG, Xiangdong FENG, Xiangyu FANG, Feng CHEN, Longming ZHANG, Likui FENG, Guofeng ZHANG, Qiuyang CAO. Study on multi-parameter collaborative monitoring methods for hydrogen conductivity in water vapor degassing[J]. Thermal Power Generation, 2023 , 52 (11) : 193 -198 . DOI: 10.19666/j.rlfd.202304051
氢电导率是发电厂腐蚀监控的关键指标[1-2],但当水汽中有机污染物分解产生CO2,以及联合循环机组和空冷机组水汽测点漏入CO2时,CO2在氨性介质条件转化为碳酸根和碳酸氢根,从而严重影响氢电导率测量的准确性。此时,氢电导率反映的是碳酸(氢)根以及腐蚀性阴离子的总量[3],在无机碳含量不明的情况下,无法准确判断水汽样品中氯离子、硫酸根等强腐蚀性阴离子的含量,往往存在氢电导率大幅超标而腐蚀性阴离子含量合格的情况,故脱气氢电导率的测量越来越受到重视。
电厂水汽循环系统中的水样,经过阳离子交换树脂后剩下氢离子和阴离子,此时测量的电导率为氢电导率[4]。而这时水样中的阴离子包括CO2溶于水中产生的碳酸根以及碳酸氢根,如水汽系统漏入CO2含量较多时氢电导率会大幅升高,运行人员无法分辨氢电导率升高是危害较大的杂质污染物(如Cl、SO42–)引起的,还是由CO2漏入系统引起的,不能对水质做出正确判读[5]。水汽脱气氢电导率就是采用特定技术脱除水中碳酸根和碳酸氢根后的氢电导率,通过氢电导率和脱气氢电导率的对比,有效反映出机组水汽中CO2的含量[6],有助于电厂运行人员更准确的诊断机组存在的故障和问题,对机组运行状态作出更合理的判断。
脱气氢电导率作为一个关键监控指标已在水汽质量标准修订中被引入[7-9]。如《燃气—蒸汽联合循环发电厂化学监督技术导则》(DL/T 1717—2017)要求,低压饱和蒸汽和过热蒸汽这2个测点监测脱气氢电导率;在《火力发电机组及蒸汽动力设备水汽质量》(GB/T 12145—2016)中也要求多个测点使用脱气氢电导率这一监控指标。
目前,测量脱气氢电导率均是在固定测点加装脱气氢电导率表,只有测量值而无法准确有效评估测量值,导致即使安装了脱气氢电导率表也不能解决实际问题。本文提出的水汽脱气氢电导率等多参数协同监测系统和方法,通过构建基于双水膜脱气法及电再生离子交换技术的脱气氢电导率测量系统,在常温、常压下高效脱除水中痕量CO2,并建立脱气氢电导率的有效评估体系及方法,使脱气氢电导率精准反映腐蚀性阴离子的含量,并在监测脱气氢电导率的同时协同监测水汽电导率、氢电导率、铵根、pH值,便于电厂运行人员通过多指标快速诊断水汽质量。
水汽脱气氢电导率多参数协同监测系统工作原理如图1所示。待测水样经电导率传感器1测量电导率,进入电再生离子交换装置后经电导率传感器2测量氢电导率;然后,水样进入膜脱气装置去除CO2,再通过电导率传感器3测量脱气氢电导率。其中,将电再生离子交换装置替换传统树脂柱,(脱气)氢电导率实现连续准确智能化监测,即无需更换再生树脂,测量值可快速响应[10];pH值根据电导率和氢电导率测量值计算得出,测量准确性大幅提高。
脱气氢电导率是测量系统中重要的监测指标,CO2的脱除率直接影响到脱气氢电导率测量准确性。本文提出了双水膜脱气法高效脱除水中痕量CO2,即脱气膜两侧都为水介质,通过流程、流向和浓度差的设计使待测水样中µg/L级痕量CO2通过透气膜溶解于膜外高纯水中(电阻率为18.25 MΩ,CO2质量浓度为0),实现水样中痕量CO2高效去除,常温常压下脱除率大于99%。克服了传统脱气技术(沸腾法、氮气膜法等)设备庞大、脱气效果差、只能在线测量、运维量大等缺点,使脱气氢电导率值精准反映强腐蚀性阴离子含量,可在线测量也可离线测量。建立了脱气氢电导率测量准确性的有效评估体系及方法,使脱气氢电导率的测量值可与标准溶液的理论氢电导率值进行比对。
水汽脱气氢电导率等多参数协同监测系统为移动式测量系统,可协同监测不同测点的电导率、氢电导率、pH值和脱气氢电导率等指标。电导率、氢电导率等可依据相应的计量标准进行准确性评估;但脱气氢电导率尚无有效评估方法,很多电站虽购买了昂贵的国外进口在线脱气氢电导率表,只能显示监测值而无法判断其准确性,导致测量准确性参差不齐,造成对水质的误判。本文根据水汽脱气氢电导率等多参数协同监测系统建立了相应的准确性评估方法,对各指标的测量准确性进行有效评估。
参照《发电厂在线化学仪表检验规程》(DL/T 677—2018),同一水样分别经过标准表和水汽脱气氢电导率等多参数协同监测系统,比对标准表数据与系统测量数据,计算电导率、氢电导率的整机测量误差为:
δG=(KJKbB)KbB1100%
式中:δG为整机工作误差,%;KJ为系统上(氢)电导率示值,µS/cm;KbB为标准表(氢)电导率示值,µS/cm。
当电导率及氢电导率整机误差不合格时,参照DL/T 677—2018开展其他项目检验。pH值是根据电导率和氢电导率计算得出,故无需单独进行准确性评估。
测量脱气氢电导率是为了排除CO2的影响,准确反映强腐蚀性阴离子含量。由于氯离子Cl标准液配制过程会有大量CO2溶入,氢电导率无法与标物氯离子溶液的理论氢电导率值比对;另外,脱气氢电导率测量均为在线仪表,脱气效率不够高且测量需要水流量很大,无法检验脱气氢电导率的测量准确性,导致电厂即使安装了脱气氢电导率表也只有测量值而无法判断其准确性。
本文提出了双水膜脱气法高效脱除水中痕量CO2,CO2脱除率可达99%以上,测量系统可以进行在线测量也可以进行离线测量。Cl标准液可做为有效评判脱气氢电导率测量准确性的标准:配制0~200 µg/L的Cl标准液,此时由于配制过程中水样中漏入CO2,氢电导率值偏大,但测量脱气氢电导率时如能有效去除CO2,其测量值应该与标准样品的理论氢电导率值(不含CO2)吻合。根据该方法测量不同质量浓度Cl标准液的脱气氢电导率,并与其理论氢电导率值进行比较,结果见表1
表1看出,0~200 μg/L的Cl标准液测量的氢电导率值与Cl标准液的理论氢电导率值相对误差均未超过10%。为了能快速准确地评估脱气氢电导率值测量的准确性,最终确定用20 μg/L的Cl标准液,即测量值应为0.242 7±0.024 3 μS/cm,否则应对仪器各测量单元进行检查调整,直至脱气氢电导率测量准确性符合要求。
通过建立水汽脱气氢电导率等多参数协同监测系统,提出测量准确性的评估方法,对涉及多项测量参数的准确性进行有效评估测试后,在典型的燃气联合循环机组、供热机组上进行现场监督及数据分析比对。
对于调峰运行的燃气-蒸汽联合循环机组而言,由于频繁启停阶段CO2的漏入,使得机组启动阶段氢电导率“虚高”,影响机组启动进程和水汽品质监测的可靠性。水汽脱气氢电导率等多参数协同监测系统应用于该类型机组,冷态启动阶段蒸汽指标达到启动要求的边界条件所需时间会大幅度缩短,可加快余热锅炉的启动进程,同时燃气轮机在低负荷(低效率)下运转的等待时间也会随之缩短,从而降低启动成本,增加经济效益。此外,脱气氢电导率能更加灵敏地监测和反映联合循环机组调峰运行、频繁启停等运行方式对余热发电系统水汽品质的影响,还可加快机组启动进程,并有效控制危害性较大的Cl和有机物含量。联合循环机组余热锅炉水汽氢电导率和脱气氢电导率联合测试,可以实现对其中Cl等强腐蚀性阴离子和CO2含量的有效监控,真实反映水汽质量水平,提高设备运行的安全性和经济性。
浙江某联合循环机组正常运行阶段主蒸汽的氢电导率标准值不大于0.30 µS/cm,期望值不大于0.15 µS/cm,该电厂低压饱和蒸汽、低压过热蒸汽和高压饱和蒸汽等测点的氢电导率运行期间基本在0.30 µS/cm。为加快机组启动进程,提高设备运行的安全性和经济性,该电厂在高压饱和蒸汽测点加装了1台SWAN公司的在线脱气氢电导率表(现场仪表),应用水汽脱气氢电导率等多参数协同监测系统在现场实时监测各测点的电导率、氢电导率、pH值和脱气氢电导率。试验数据与现场在线仪表测量数据比对结果见表2,离子色谱测量数据见表3
表2数据可见:蒸汽氢电导率总体偏高,各测点的氢电导率均约为0.3 µS/cm,明显高于期望值;而监测的脱气氢电导率基本达标,远低于期望值水平。氢电导率与脱气氢电导率指标差异较大,表明其中有较高含量的CO2。从表3结果看出,仅检出质量浓度在2 µg/L以内的Cl,未检出其他阴离子,而据此计算出的理论氢电导率(不含CO2)应该不超过0.07 µS/cm,与测量得到的脱气氢电导率值基本相符。协同监测系统测量的氢电导率值相较SWAN的仪表更接近于理论值。另外,SWAN的在线脱气氢电导率表只能测量高压饱和蒸汽测点脱气氢电导率,低压饱和蒸汽、低压过热蒸汽氢电导率仍处于超标状态;而本文提出的协同监测系统可随时移动到任一测点进行多项水汽关键指标实时监测,对水质进行快速评估。
广东某联合循环机组正常运行阶段凝结水氢电导率小于0.30 µS/cm,但在机组启动阶段凝结水等测点的氢电导率要5 h左右才能达到0.30 µS/cm以下。氢电导率合格率异常偏低,机组启动阶段凝结水氢电导率指标基本在0.30~0.70 µS/cm内波动,但分析其中的腐蚀性阴离子含量均在合格范围内。采用水汽脱气氢电导率等多参数协同监测系统对机组启动阶段凝结水水质进行动态监测,试验结果见表4图2。从表4图2可见,虽然该机组停机启机初期凝结水氢电导率严重超标,氢电导率14:40左右才能降到控制值以下,但测量的脱气氢电导率值11:00左右就可降到0.3 µS/cm以下。检测腐蚀性阴离子Cl质量浓度均很低,表明此时氢电导率测量值超标是由于CO2导致,脱气氢电导率更能准确反映Cl等强腐蚀性阴离子总量,此时凝结水腐蚀性较小,据此就可及时进行水工况调整。
运行人员很难通过监测氢电导率指标确认水汽品质的真实水平,而脱气氢电导率指标则更能准确反映水质的腐蚀性。本文提出的水汽脱气氢电导率等多参数协同监测系统及方法,可随时移动至不同测点进行水汽品质综合评估,有效减少机组启动时间,为机组安全运行控制提供有力依据,且节能降耗经济效益显著。
江苏某热电联产、集中供热的电站,总装机容量为5.7万kW,供热能力达550 t/h。现有热网60多公里,蒸汽热力用于食品、印染、纺织、化工、采暖和制冷等行业。根据GB/T 12145—2016要求,该电厂蒸汽氢电导率值应控制在0.15 µS/cm以内。但电厂该项测量指标一直处于超标状态,最高甚至达到0.80 μS/cm以上,对供热和机组安全运行造成很大困扰。为准确分析评估水质状况,应用水汽脱气氢电导率等多参数协同监测系统在现场监测相关测点的电导率、氢电导率、pH值和脱气氢电导率等指标,同时取样进行色谱分析,试验结果见表5表6
表5试验数据可见,虽然氢电导率超标,尤其是蒸汽某些测点的氢电导率已超过0.80 µS/cm,但其脱气氢电导率小于0.15 µS/cm,符合标准要求。表6试验数据表明,蒸汽等测点水样的阴离子质量浓度对应的理论氢电导率与脱气氢电导率测量值基本吻合。证明在CO2存在的情况下,氢电导率无法准确反映水样中强腐蚀性阴离子的含量,故此时应该使用脱气氢电导率这一监测指标进行水质监督和水工况调整。
本文提出了一种水汽脱气氢电导率等多参数协同监测方法,可协同监测不同测点的电导率、氢电导率、pH值和脱气氢电导率等指标,并制定了对各关键测量指标准确性进行有效评估的方法。应用该方法在典型的联合循环电站和供热机组上协同监测多项水汽关键指标,并与离子色谱数据进行分析比对,得出以下结论。
1)在有CO2存在情况下,氢电导率无法准确反映水样中强腐蚀性阴离子的含量。标准液脱气氢电导率的测量及现场测量值与色谱值的比对结果表明,本文方法测量的脱气氢电导率值能精准反映水样强腐蚀性阴离子的含量。
2)应用本文方法可协同监测不同测点的电导率、氢电导率、pH值和脱气氢电导率等关键指标,帮助运行人员正确判断氢电导率升高的原因,对电厂的化学监督具有重要意义。
3)脱气氢电导率反映了水样中不包含CO2的侵蚀性阴离子对氢电导率的贡献,建议在供热机组、联合循环电站、空冷机组的某些关键测点采用脱气氢电导率监督和评价水汽品质,以便更好地监控水中氯离子等强腐蚀性阴离子含量,提高水汽监督水平。
  • 中国华能集团有限公司总部科技项目(HNKJ21-HF305)
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doi: 10.19666/j.rlfd.202304051
  • 接收时间:2023-04-01
  • 首发时间:2026-01-26
  • 出版时间:2023-11-25
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  • 收稿日期:2023-04-01
基金
Science and Technology Project of China Huaneng Group Co., Ltd.(HNKJ21-HF305)
中国华能集团有限公司总部科技项目(HNKJ21-HF305)
作者信息
    1.浙江西热利华智能传感技术有限公司,浙江 嘉兴 314000
    2.广州珠江天然气发电有限公司,广东 广州 511457
    3.华能国际电力股份有限公司,北京 100031
    4.浙江省浙能技术研究院,浙江 杭州 311121
    5.浙江省特种设备科学研究院,浙江 杭州 310020
    6.国网浙江省电力公司电力科学研究院,浙江 杭州 310006

通讯作者:

张龙明(1987),男,硕士,高工,主要研究方向电厂水处理技术及电厂化学仪表,
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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
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