火电机组水汽中痕量阴离子的毛细管离子色谱法测定
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摘要
提出了一种采用毛细管离子色谱法同时测定火电机组水汽中痕量无机阴离子(F-,Cl-,SO2-4,Br-,NO-3,NO-2,PO3-4)和小分子有机酸根(CH3COO-,HCOO-,C2O2-4)的方法:直接进样10μL;采用IonPac AS18(250 mm×0.4 mm)毛细管离子色谱分析柱;流速为0.010mL/min的KOH淋洗液进行梯度淋洗。采用该方法对上述10种痕量阴离子进行测定。结果表明:采用毛细管离子色谱法检测的10种离子标准曲线线性关系良好,相关系数均大于99.9%,以信噪比S/N=3计算,所测离子检出限在0.04~0.80μg/L之间;连续运行96h后相对标准偏差仍在0.03~5.81%,加标回收率81%~116%。检测结果准确可靠,该方法适用于火电机组水汽检测。
A capillary ion chromatography method was proposed,which can detect trace inorganic anions(F-,Cl-,SO2-4,Br-,NO-3,NO-2,PO3-4)and low-molecular-weight organic acids(CH3COO-,HCOO-,C2O2-4)in water and steam from boilers in power plants.The separation was achieved on IonPac AS18(250mm×0.4mm)capillary anions analytical column with optimized KOH gradient elution and 10μL injection at 0.010mL/min,and then each component's concentration was detected by suppressed conductivity.The results show that,under the chosen condition,the linear correlation coefficients of the above 10 anions were greater than 99.9%,the detection of limit with signal-to-noise ratio of 3were between 0.04μg/L and 0.8μg/L.After running for 96 hours,the relative standard deviations(RSDs)were still between0.03% and 5.81%,and the average recoveries ranged from 81%to 116%,indicating this method has better repeatability and accuracy.This detection method can be applied in numbers determination of trace anions and low-molecular-weight organic acids in water and steam of boilers in power plants.
A capillary ion chromatography method was proposed,which can detect trace inorganic anions(F-,Cl-,SO2-4,Br-,NO-3,NO-2,PO3-4)and low-molecular-weight organic acids(CH3COO-,HCOO-,C2O2-4)in water and steam from boilers in power plants.The separation was achieved on IonPac AS18(250mm×0.4mm)capillary anions analytical column with optimized KOH gradient elution and 10μL injection at 0.010mL/min,and then each component's concentration was detected by suppressed conductivity.The results show that,under the chosen condition,the linear correlation coefficients of the above 10 anions were greater than 99.9%,the detection of limit with signal-to-noise ratio of 3were between 0.04μg/L and 0.8μg/L.After running for 96 hours,the relative standard deviations(RSDs)were still between0.03% and 5.81%,and the average recoveries ranged from 81%to 116%,indicating this method has better repeatability and accuracy.This detection method can be applied in numbers determination of trace anions and low-molecular-weight organic acids in water and steam of boilers in power plants.
引文
[1]曹顺安,谢学军,许金莹,等.离子色谱测试技术在火电厂水汽化学监督中的应用与进展[J].华中电力,2001,14(2):29-32.CAO Shun'an,XIE Xuejun,XU Jinying,et al.The application and progress of ion chromatography used for pure-high water and steam monitoring in thermal power plant[J].Central China Electric Power,2001,14(2):29-32.
[2]曹松彦,常旭红.离子色谱测试技术在电厂凝结水精处理系统中的应用[J].热力发电,2011,40(10):81-83.CAO Songyan,CHANG Xuhong.Application of ion chromatographic test technology in condensate polishing system[J].Thermal Power Generation,2011,40(10):81-83.
[3]高扬,曹顺安,梁沁沁,等.大体积进样离子色谱法对电厂水汽中痕量阴离子测定中两种分离柱的分离效果[J].理化检验-化学分册,2014,50(1):101-104.GAO Yang,CAO Shunan,LIANG Qinqin,et al.Efficiency of 2different separation columns in IC determination of traces of anions in steam of power generating unit with large volume sample introducution[J].Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2014,50(1):101-104.
[4]胡静,曹顺安.梯度离子色谱法在火电厂水汽监督中的应用[J].分析仪器,2003(4):23-26.HU Jing,CAO Shun'an.Application of gradient ion chromatography for monitoring quality of water and steam in thermal power plant[J].Analytical Instrumentation,2003(4):23-26.
[5]Vladana N,Rajakovic O,Dragana Z Z,et al.Improvement of chemical control in the water-steam cycle of thermal power plants[J].Applied Thermal Engineering,2011,31:119-128.
[6]常燕.离子色谱测试技术在电力行业化学分析中的综合运用[J].分析实验室,2007,26(增刊1):278-280.CHANG Yan.Applications of ion chromatography for chemical analysis in electric power industry[J].Chinese Journal of Analysis Laboratory,2007,26(Suppl.1):278-280.
[7]杨丙成,刁雪芳.毛细管离子色谱分析系统研究进展[J].色谱,2012,30(4):333-339.YANG Bingcheng,DIAO Xuefang.Recent advances in capillary scale ion chromatography technology[J].Chinese Journal of Chromatography,2012,30(4):333-339.
[8]石先哲,李攻科,梁振,等.色谱研究最新进展[J].化学通报,2014,77(7):720-730.SHI Xianzhe,LI Gongke,LIANG Zhen,et al.Recent development of chromatographic research[J].Chemistry,2014,77(7):720-730.
[9]牟世芬,刘克纳.离子色谱方法及应用[M].北京:化学工业出版社,2004:57-61.MU Shifen,LIU Kenan.The ion chromatographic method and its applications[M].Beijing:Chemistry Industry Press,2004:57-61(in Chinese).
[10]Phani M,Efthimios L,Leonidas K S,et al.Data quality in water analysis:validation of ion chromatographic method for the determinationof routine ions in potable water[J].Desalination,2007,213:182-188.
[11]Cristina L M,Isabel V,Ana M.Validation of an ion chromatographic method for the quantification of anions in water[J].Desalination,2010,261:111-116.
[12]Zhong Y,Zhou W,Zhu H,et al.A single pump column-switching technique coupled with polystyrene-divinylbenzene-carbon nanotubes column for the determination of trace anions in different concentrated organic matrices by ion chromatography[J].Analytica Chimica Acta,2011,686:1-8.
[13]Vermeiren K.Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography:II.Method performance study with a hydroxide eluent and a low noise suppressor[J].Journal of Chromatography A,2005,1085(1):66-73.
[14]Ying Y Z,Wen F Z,Xue L Z,et al.Trace analysis of anions in organic matrices by ion chromatography coupled with a novel reversed-phase column for on-line sample pretreatment[J].Chinese Chemical Letters,2011,22(4):461-464.
[15]Vanatta E L,Woodruff A,Coleman D E.Comparison of two cryptand separator columns for the determination of trace chloride in semiconductor-grade nitric acid[J].Journal of Chromatography A,2005,1085(1):33-36.
[16]Santoyo E,Vermaa S P,Sandoval F,et al.Suppressed ion chromatography for monitoring chemical impurities in steam for geothermal power plants[J].Journal of Chromatography A,2002,949(1/2):281-289.
[17]Dragana ZLjubinka V R.Application and validation of ion chromatography for the analysis of power plants water:Analysis of corrosive anions in conditioned water-steam cycles[J].Desalination,2011,275:17-25.
[18]Zhong Q L,Yan L,Victor B,et al.Determination of anions at trace levels in power plant water samples by ion chromatography with electrolytic eluent generation and suppression[J].Journal of Chromatography A,2002,956(1/2):129-138.
[19]DL/T 954-2005,火力发电厂水汽试验方法-痕量氟离子、乙酸根离子、甲酸根离子、氯离子、亚硝酸根离子、硝酸根离子、磷酸根离子和硫酸根离子的测定离子色谱法[S].DL/T 954-2005,Analysis of water and steam in fossil fuel power plant determination of fluoride,acetate,formate,chloride,nitrite,nitrate phosphate and sulfate by ion chromatography[S].
[20]杨丙成,刁雪芳.毛细管离子色谱分析系统研究进展[J].色谱,2012,30(4):333-339.YANG Bingcheng,DIAO Xuefang.Recent advances in capillary scale ion chromatography technology[J].Chinese Journal of Chromatography,2012,30(4):333-339.
[21]Hans F N,Kvitvang,Kre A K,et al.Assessment of capillary anion exchange ion chromatography tandem mass spectrometry for the quantitative profiling of the phosphometabolome and organic acids in biological extracts[J].Journal of Chromatography A,2014,1370:70-79.
[22]顾文奎,赵风仙,王雨,等.矿泉水中常见阴离子的毛细管离子色谱测定法[J].环境与健康杂志,2010,27(12):1109-1110.GU Wenkui,ZHAO Fengxian,WANG Yu,et al.Determination of common anions by capillary ion chromatography in mineral water[J].Journal of Environment and Health,2010,27(12):1109-1110.
[23]王慕华,谢佩谨,叶明立,等.毛细管离子色谱法测定爆炸残留物中的无机阴离子[J].浙江大学学报(理学版),2012,39(4):425-427.WANG Muhua,XIE Peijin,YE Mingli et al.Determination of inorganic anions in explosive residue by capillary ion chromatography[J].Journal of Zhejiang University(Science Edition),2012,39(4):425-427.
[24]叶明立,胡忠阳,潘广文.毛细管离子色谱法同时测定饮用水中痕量碘离子、硫氰酸根和草甘膦[J].分析化学,2011,39(11):1762-1765.YE Mingli,HU Zhongyang,PAN Guangwen.Determination of trace iodide,thiocyanate and glyphosate in drinking water by capillary ion chromatography[J].Chinese Journal of Analytical Chemistry,2011,39(11):1762-1765.
[25]王成,程军喜.毛细管级离子色谱检测水中的阳离子[J].环境卫生学杂志,2012,2(4):187-188.WANG Cheng,CHENG Junxi.Capillary ion chromatographic method in the detection of cations in water[J].Journal of Environmental Hygiene,2012,2(4):187-188.
[26]李静,李仁勇,梁立娜.毛细管型离子色谱-脉冲安培法检测枸杞多糖的单糖组成[J].分析化学,2012,40(9):1415-1420.LI Jing,LI Renyong,LIANG Lina.Determination of monosaccharide constituents in lycium barbarum polysaccharide using capillary ion chromatography with pulsed amperometric detection[J].Chinese Journal of Analytical Chemistry,2012,40(9):1415-1420.
[27]马继平,丁明玉.毛细管离子色谱进展[J].分析化学,2006,34(增刊1):272-277.MA Jiping,DING Mingyu.Progress in capillary ion chromatography[J].Chinese Journal of Analytical Chemistry,2006,34(Suppl.1):272-277.
[28]谭和平,周黎黎,徐文平,等.强疏水性AS-15色谱柱测定茶叶中F-、Cl-、NO-3、PO3-4、SO2-4、BrO-3、Br-、NO-2的研究[J].中国测试,2011,37(6):49-52.TAN Heping,ZHOU Lili,XU Wenping,et al.Simultaneous determination of F-、Cl-、NO-3、PO3-4、SO2-4、BrO-3、Br-and NO-2in tea by IC with hydrophobic column AS-15[J].China Measurement&Test,2011,37(6):49-52.
[29]李义,禹海清,董建芳,等.加标回收在水质分析中的应用及回收率计算方法[J].岩矿测试,2010,29(5):597-600.LI Yi,YU Haiqing,DONG Jianfang,et al.Application of standard addition in water quality analysis and calculation methods for recovery rates[J].Rock and Mineral Analysis,2010,29(5):597-600.
[2]曹松彦,常旭红.离子色谱测试技术在电厂凝结水精处理系统中的应用[J].热力发电,2011,40(10):81-83.CAO Songyan,CHANG Xuhong.Application of ion chromatographic test technology in condensate polishing system[J].Thermal Power Generation,2011,40(10):81-83.
[3]高扬,曹顺安,梁沁沁,等.大体积进样离子色谱法对电厂水汽中痕量阴离子测定中两种分离柱的分离效果[J].理化检验-化学分册,2014,50(1):101-104.GAO Yang,CAO Shunan,LIANG Qinqin,et al.Efficiency of 2different separation columns in IC determination of traces of anions in steam of power generating unit with large volume sample introducution[J].Physical Testing and Chemical Analysis(Part B:Chemical Analysis),2014,50(1):101-104.
[4]胡静,曹顺安.梯度离子色谱法在火电厂水汽监督中的应用[J].分析仪器,2003(4):23-26.HU Jing,CAO Shun'an.Application of gradient ion chromatography for monitoring quality of water and steam in thermal power plant[J].Analytical Instrumentation,2003(4):23-26.
[5]Vladana N,Rajakovic O,Dragana Z Z,et al.Improvement of chemical control in the water-steam cycle of thermal power plants[J].Applied Thermal Engineering,2011,31:119-128.
[6]常燕.离子色谱测试技术在电力行业化学分析中的综合运用[J].分析实验室,2007,26(增刊1):278-280.CHANG Yan.Applications of ion chromatography for chemical analysis in electric power industry[J].Chinese Journal of Analysis Laboratory,2007,26(Suppl.1):278-280.
[7]杨丙成,刁雪芳.毛细管离子色谱分析系统研究进展[J].色谱,2012,30(4):333-339.YANG Bingcheng,DIAO Xuefang.Recent advances in capillary scale ion chromatography technology[J].Chinese Journal of Chromatography,2012,30(4):333-339.
[8]石先哲,李攻科,梁振,等.色谱研究最新进展[J].化学通报,2014,77(7):720-730.SHI Xianzhe,LI Gongke,LIANG Zhen,et al.Recent development of chromatographic research[J].Chemistry,2014,77(7):720-730.
[9]牟世芬,刘克纳.离子色谱方法及应用[M].北京:化学工业出版社,2004:57-61.MU Shifen,LIU Kenan.The ion chromatographic method and its applications[M].Beijing:Chemistry Industry Press,2004:57-61(in Chinese).
[10]Phani M,Efthimios L,Leonidas K S,et al.Data quality in water analysis:validation of ion chromatographic method for the determinationof routine ions in potable water[J].Desalination,2007,213:182-188.
[11]Cristina L M,Isabel V,Ana M.Validation of an ion chromatographic method for the quantification of anions in water[J].Desalination,2010,261:111-116.
[12]Zhong Y,Zhou W,Zhu H,et al.A single pump column-switching technique coupled with polystyrene-divinylbenzene-carbon nanotubes column for the determination of trace anions in different concentrated organic matrices by ion chromatography[J].Analytica Chimica Acta,2011,686:1-8.
[13]Vermeiren K.Trace anion determination in concentrated hydrofluoric acid solutions by two-dimensional ion chromatography:II.Method performance study with a hydroxide eluent and a low noise suppressor[J].Journal of Chromatography A,2005,1085(1):66-73.
[14]Ying Y Z,Wen F Z,Xue L Z,et al.Trace analysis of anions in organic matrices by ion chromatography coupled with a novel reversed-phase column for on-line sample pretreatment[J].Chinese Chemical Letters,2011,22(4):461-464.
[15]Vanatta E L,Woodruff A,Coleman D E.Comparison of two cryptand separator columns for the determination of trace chloride in semiconductor-grade nitric acid[J].Journal of Chromatography A,2005,1085(1):33-36.
[16]Santoyo E,Vermaa S P,Sandoval F,et al.Suppressed ion chromatography for monitoring chemical impurities in steam for geothermal power plants[J].Journal of Chromatography A,2002,949(1/2):281-289.
[17]Dragana ZLjubinka V R.Application and validation of ion chromatography for the analysis of power plants water:Analysis of corrosive anions in conditioned water-steam cycles[J].Desalination,2011,275:17-25.
[18]Zhong Q L,Yan L,Victor B,et al.Determination of anions at trace levels in power plant water samples by ion chromatography with electrolytic eluent generation and suppression[J].Journal of Chromatography A,2002,956(1/2):129-138.
[19]DL/T 954-2005,火力发电厂水汽试验方法-痕量氟离子、乙酸根离子、甲酸根离子、氯离子、亚硝酸根离子、硝酸根离子、磷酸根离子和硫酸根离子的测定离子色谱法[S].DL/T 954-2005,Analysis of water and steam in fossil fuel power plant determination of fluoride,acetate,formate,chloride,nitrite,nitrate phosphate and sulfate by ion chromatography[S].
[20]杨丙成,刁雪芳.毛细管离子色谱分析系统研究进展[J].色谱,2012,30(4):333-339.YANG Bingcheng,DIAO Xuefang.Recent advances in capillary scale ion chromatography technology[J].Chinese Journal of Chromatography,2012,30(4):333-339.
[21]Hans F N,Kvitvang,Kre A K,et al.Assessment of capillary anion exchange ion chromatography tandem mass spectrometry for the quantitative profiling of the phosphometabolome and organic acids in biological extracts[J].Journal of Chromatography A,2014,1370:70-79.
[22]顾文奎,赵风仙,王雨,等.矿泉水中常见阴离子的毛细管离子色谱测定法[J].环境与健康杂志,2010,27(12):1109-1110.GU Wenkui,ZHAO Fengxian,WANG Yu,et al.Determination of common anions by capillary ion chromatography in mineral water[J].Journal of Environment and Health,2010,27(12):1109-1110.
[23]王慕华,谢佩谨,叶明立,等.毛细管离子色谱法测定爆炸残留物中的无机阴离子[J].浙江大学学报(理学版),2012,39(4):425-427.WANG Muhua,XIE Peijin,YE Mingli et al.Determination of inorganic anions in explosive residue by capillary ion chromatography[J].Journal of Zhejiang University(Science Edition),2012,39(4):425-427.
[24]叶明立,胡忠阳,潘广文.毛细管离子色谱法同时测定饮用水中痕量碘离子、硫氰酸根和草甘膦[J].分析化学,2011,39(11):1762-1765.YE Mingli,HU Zhongyang,PAN Guangwen.Determination of trace iodide,thiocyanate and glyphosate in drinking water by capillary ion chromatography[J].Chinese Journal of Analytical Chemistry,2011,39(11):1762-1765.
[25]王成,程军喜.毛细管级离子色谱检测水中的阳离子[J].环境卫生学杂志,2012,2(4):187-188.WANG Cheng,CHENG Junxi.Capillary ion chromatographic method in the detection of cations in water[J].Journal of Environmental Hygiene,2012,2(4):187-188.
[26]李静,李仁勇,梁立娜.毛细管型离子色谱-脉冲安培法检测枸杞多糖的单糖组成[J].分析化学,2012,40(9):1415-1420.LI Jing,LI Renyong,LIANG Lina.Determination of monosaccharide constituents in lycium barbarum polysaccharide using capillary ion chromatography with pulsed amperometric detection[J].Chinese Journal of Analytical Chemistry,2012,40(9):1415-1420.
[27]马继平,丁明玉.毛细管离子色谱进展[J].分析化学,2006,34(增刊1):272-277.MA Jiping,DING Mingyu.Progress in capillary ion chromatography[J].Chinese Journal of Analytical Chemistry,2006,34(Suppl.1):272-277.
[28]谭和平,周黎黎,徐文平,等.强疏水性AS-15色谱柱测定茶叶中F-、Cl-、NO-3、PO3-4、SO2-4、BrO-3、Br-、NO-2的研究[J].中国测试,2011,37(6):49-52.TAN Heping,ZHOU Lili,XU Wenping,et al.Simultaneous determination of F-、Cl-、NO-3、PO3-4、SO2-4、BrO-3、Br-and NO-2in tea by IC with hydrophobic column AS-15[J].China Measurement&Test,2011,37(6):49-52.
[29]李义,禹海清,董建芳,等.加标回收在水质分析中的应用及回收率计算方法[J].岩矿测试,2010,29(5):597-600.LI Yi,YU Haiqing,DONG Jianfang,et al.Application of standard addition in water quality analysis and calculation methods for recovery rates[J].Rock and Mineral Analysis,2010,29(5):597-600.