高温裂解-离子色谱法测定煤中卤素的含量
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摘要
建立高温裂解-离子色谱联用技术检测煤中卤素含量的方法。煤样30.0~40.0 mg在350 mL·min~(-1)富氧条件下经1 100℃高温裂解处理后,含卤素组分转化成气体形式被20 mmol·L~(-1)氢氧化钠溶液5 mL吸收后,采用离子色谱电导检测器和IonPac AS18柱测定吸收液中氟、氯和溴的含量,采用离子色谱安培检测器和Ionpac AS11-HC柱测定吸收液中碘离子的含量。结果表明,氟、氯、溴和碘的质量浓度在一定范围内与其峰面积呈线性关系,检出限(3s)分别为3.03,2.47,0.80,8.85 mg·kg~(-1)。精密度试验结果显示测定值的相对标准偏差(n=9)均小于5.0%。按标准加入法对煤样进行回收试验,回收率在83.6%~105%之间。
A method was proposed for determination of the halogens in coal using high temperature pyrolysis pretreatment and ion chromatography. The coal sample( 30. 0-40. 0 mg) was treated by pyrolysis at 1 100 ℃ in the oxygen of 350 mL·min~(-1),and then the gas products of pyrolysis were absorbed in 5 mL of 20 mmol·L~(-1) Na OH solution.F~- ,Cl~- and Br~- in the absorption solution were determined by ion chromatography with suppressed conductivity detector and IonPac AS18 column,and I-in the absorption solution was determined by ion chromatography with integrated amperometric detector and Ionpac AS11-HC column. As shown by the results,linear relationships between values of peak area and mass concentration of F~- ,Cl~- ,Br~- and I-were found in definite ranges,with detection limts(3 s) of 3. 03 mg·kg~(-1) for F~- ,2. 47 mg·kg~(-1) for Cl~- ,0. 80 mg·kg~(-1) for Br~- and 8. 85 mg·kg~(-1) for I-. Values of RSD( n = 9) for precision test were all less than 5. 0% . Test for recovery was made by standard addition method for the coal sample,giving results in the range of 83. 6% -105% .
A method was proposed for determination of the halogens in coal using high temperature pyrolysis pretreatment and ion chromatography. The coal sample( 30. 0-40. 0 mg) was treated by pyrolysis at 1 100 ℃ in the oxygen of 350 mL·min~(-1),and then the gas products of pyrolysis were absorbed in 5 mL of 20 mmol·L~(-1) Na OH solution.F~- ,Cl~- and Br~- in the absorption solution were determined by ion chromatography with suppressed conductivity detector and IonPac AS18 column,and I-in the absorption solution was determined by ion chromatography with integrated amperometric detector and Ionpac AS11-HC column. As shown by the results,linear relationships between values of peak area and mass concentration of F~- ,Cl~- ,Br~- and I-were found in definite ranges,with detection limts(3 s) of 3. 03 mg·kg~(-1) for F~- ,2. 47 mg·kg~(-1) for Cl~- ,0. 80 mg·kg~(-1) for Br~- and 8. 85 mg·kg~(-1) for I-. Values of RSD( n = 9) for precision test were all less than 5. 0% . Test for recovery was made by standard addition method for the coal sample,giving results in the range of 83. 6% -105% .
引文
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[9]FUNG Y S,DAO K L.Elemental analysis of chemical wastes by oxygen bomb combustion-ion chromatography[J].Analytica Chimica Acta,1996,334:51-56.
[10]任飞,邬蓓蕾,叶佳楣,等.氧弹燃烧-离子色谱法测定原油中氯和溴[J].理化检验-化学分册,2012,48(11):1350-1352.
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[12]刘雪锋,刘晶,宋党育,等.用高温水解-离子色谱法研究贵州煤中氟质量分数[J].华中科技大学学报(自然科学版),2008,36(4):84-87.
[13]GB/T 4633-2014煤中氟的测定方法[S].
[14]GB/T 3558-2014煤中氯的测定方法[S].
[15]MIYAKE Y,KATO M,URANO K.A method for measuring semi-and non-volatile organic halogens by combustion ion chromatography[J].Journal of Chromatography A,2007,1139(1):63-69.
[16]KRISTIANA I,MCDONALD S,TAN J,et al.Analysis of halogen-specific TOX revisited:Method improvement and application[J].Talanta,2015,139:104-110.
[17]王碗,刘肖,蔡亚岐,等.自动快速燃烧炉-离子色谱联用技术检测水泥等建材中的氯[J].分析试验室,2007,26(12):10-13.
[18]葛立新,秦荣林,毛芝旺,等.燃烧吸收-离子色谱法测定乙酸中总碘的研究[J].化学工程与装备,2011(12):186-187.
[19]李春雄,林海,蔡润斌,等.用燃烧炉及离子色谱仪测定原油中总氯、有机氯、无机氯含量的方法研究[J].分析测试技术与仪器,2014,20(1):25-30.
[2]CLARKE L B.The fate of trace elements during coal combustion and gasification:An overview[J].Fuel,1993,72(6):731-736.
[3]齐庆杰,刘建忠,周俊虎,等.煤中微量元素氟测定方法的研究进展[J].煤炭转化,2000,23(2):7-11.
[4]王珲,宋蔷,姚强,等.ICP-OES/ICP-MS测定煤中多种元素的微波消解方法研究[J].光谱学与光谱分析,2012,32(6):1662-1665.
[5]冯广林,李力,朱立军,等.微波消解样品-离子色谱法测定卷烟纸中钠、钾、镁、钙的含量[J].理化检验-化学分册,2012,48(4):449-451.
[6]吕鑫磊.ICP-OES法同时测定煤中11种微量元素[J].洁净煤技术,2015,21(5):107-109.
[7]刘建权,赵峰华,刘璟,等.氧弹燃烧-离子色谱法测定煤中氯含量[J].分析化学,2009,37(8):1152-1156.
[8]蒋每雄,戴厚益.氧弹燃烧处理试样-离子色谱法测定聚苯硫醚中总氯含量[J].理化检验-化学分册,2011,47(2):221-222.
[9]FUNG Y S,DAO K L.Elemental analysis of chemical wastes by oxygen bomb combustion-ion chromatography[J].Analytica Chimica Acta,1996,334:51-56.
[10]任飞,邬蓓蕾,叶佳楣,等.氧弹燃烧-离子色谱法测定原油中氯和溴[J].理化检验-化学分册,2012,48(11):1350-1352.
[11]SOUZA G B,CARRILHO E N V M,OLIVEIRA C V,et al.Oxygen bomb combustion of biological samples for inductively coupled plasma optical emission spectrometry[J].Spectrochimica Acta Part B:Atomic Spectroscopy,2002,57(12):2195-2201.
[12]刘雪锋,刘晶,宋党育,等.用高温水解-离子色谱法研究贵州煤中氟质量分数[J].华中科技大学学报(自然科学版),2008,36(4):84-87.
[13]GB/T 4633-2014煤中氟的测定方法[S].
[14]GB/T 3558-2014煤中氯的测定方法[S].
[15]MIYAKE Y,KATO M,URANO K.A method for measuring semi-and non-volatile organic halogens by combustion ion chromatography[J].Journal of Chromatography A,2007,1139(1):63-69.
[16]KRISTIANA I,MCDONALD S,TAN J,et al.Analysis of halogen-specific TOX revisited:Method improvement and application[J].Talanta,2015,139:104-110.
[17]王碗,刘肖,蔡亚岐,等.自动快速燃烧炉-离子色谱联用技术检测水泥等建材中的氯[J].分析试验室,2007,26(12):10-13.
[18]葛立新,秦荣林,毛芝旺,等.燃烧吸收-离子色谱法测定乙酸中总碘的研究[J].化学工程与装备,2011(12):186-187.
[19]李春雄,林海,蔡润斌,等.用燃烧炉及离子色谱仪测定原油中总氯、有机氯、无机氯含量的方法研究[J].分析测试技术与仪器,2014,20(1):25-30.