静态顶空-气质联用法测定企业环境水中丙烯酸丁酯残留量
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摘要
建立静态顶空-气相色谱-质谱联用(HS-GC-MS)测定水样中丙烯酸正丁酯残留量的方法.通过优化顶空进样过程中的平衡温度、平衡时间、盐离子浓度等前处理条件,确定连续测定水样中丙烯酸正丁酯含量的测试方法.水样中丙烯酸正丁酯在顶空平衡温度为50℃、盐离子的质量分数为30%、平衡15 min的条件下,经过毛细管色谱柱进行分离,采用气相色谱-质谱联用仪进行分析,以目标化合物的保留时间和选择离子进行定性,通过氘代乙苯作内标法定量.丙烯酸正丁酯在5～250 mg/L的质量浓度范围内相关系数r2为0.999 8,具有良好的线性关系,通过低、中、高(5、25、100 mg/L)不同质量浓度的加标试验,对方法进行质控,回收率在85.7%～94.6%之间,精密度(RSD)为1.81%～2.79%,方法检出限为0.109 mg/L.方法操作简便,灵敏度和准确度高,稳定性好,适用于水样中丙烯酸正丁酯的残留量测定.
A method has been set up to the determination of n-butyl acrylate in water samples by automated static headspace sampling with gas chromatography-mass spectrometry( GC-MS). The pre-treatment conditions such as equilibrium temperature,equilibrium time and salt ion concentration in the headspace injection process were optimized for the continuous determination. The compound in the water samples was extracted by the headspace at 50 ℃ after 15 min of equilibration,with the addition of the mass fraction of Na Cl of 30%,then separated by a capillary column and analyzed by GC-MS. The retention time of the compound and the selected ions were characterized and quantified by deuterated ethylbenzene used as an internal standard. The correlation coefficient r2 of n-butyl acrylate was 0.999 8 in the concentration range from 5 to 250 mg/L,with a good linear relationship. The method was quality controlled by different concentrations( 5,25,100 mg/L),the recoveries were between 85.7% and 94.6%,and the RSD were between 1.81% and 2.79%,the detection of limit was 0.109 mg/L. The method is simple in operation,highly sensitive and accurate,and good in stability,and is suitable for the determination of the residual amount of n-butyl acrylate in water samples.
A method has been set up to the determination of n-butyl acrylate in water samples by automated static headspace sampling with gas chromatography-mass spectrometry( GC-MS). The pre-treatment conditions such as equilibrium temperature,equilibrium time and salt ion concentration in the headspace injection process were optimized for the continuous determination. The compound in the water samples was extracted by the headspace at 50 ℃ after 15 min of equilibration,with the addition of the mass fraction of Na Cl of 30%,then separated by a capillary column and analyzed by GC-MS. The retention time of the compound and the selected ions were characterized and quantified by deuterated ethylbenzene used as an internal standard. The correlation coefficient r2 of n-butyl acrylate was 0.999 8 in the concentration range from 5 to 250 mg/L,with a good linear relationship. The method was quality controlled by different concentrations( 5,25,100 mg/L),the recoveries were between 85.7% and 94.6%,and the RSD were between 1.81% and 2.79%,the detection of limit was 0.109 mg/L. The method is simple in operation,highly sensitive and accurate,and good in stability,and is suitable for the determination of the residual amount of n-butyl acrylate in water samples.
引文
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[13]饶竹,李松,佟柏龄,等.顶空气相色谱法测定地层水中的苯系物[J].岩矿测试,2004,23(2):97-101.[RAO Zhu,LI Song,TONG Bo-lin,et al.Determination of BTEXs in stratum water by headspace-gas chromatography[J].Roch and Mineral Analysis,2004,23(2):97-101.]
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[2]耿强,王鑫泉,马立国.丙烯酸乙酯与丁酯的生产工艺差异化分析[J].石油化工设计,2016,33(4):46-49.[GENG Qiang,WANG Xin-quan,MA Li-guo.Differentiation analysis of production process of ethyl acrylate and butyl ester[J].Petrochemical Design,2016,33(4):46-49.]
[3]邵敬铭.丙烯酸丁酯生产工艺及催化体系的改进[J].上海化工,2002(1):20-23.[SHAO Jing-ming.The improvement of Butye Acrylate production technology and catalysis system[J].Shanghai Chemical,2002(1):20-23.]
[4]祝海珍.溶剂解吸气相色谱同时测定工作场所中甲基丙烯酸甲酯和丙烯酸正丁酯的方法研究[J].职业与健康,2009,25(23):2484-2486.[ZHU Haizhen.Study on method for simultaneous determination of methyl methacrylate and butyl acrylate in air of work place by gas chromatography with dissolvent desorption[J].Occup and Health,2009,25(23):2484-2486.]
[5]张文儒.气相色谱法测定大气中的丙烯酸丁酯[J].黑龙江环境通报,2012,36(4):76-77.[ZHANGWen-ru.Determining butyl acrylate in air with gas chromatographic[J].Heilongjiang Environmental Journal,2012,36(4):76-77.]
[6]孙立芳,荀其宁,张泉,等.热解析进样气相色谱法测定车间空气中的丙烯酸正丁酯[J].化学分析计量,2015,24(3):83-85.[SUN Li-fang,XUN Qining,ZHANG Quan,et al.Determination of n-butyl acrylate in the workshop air by gas chromatography with thermal desorption[J].Chemical Analysis And Meterage,2015,24(3):83-85.]
[7]祝海珍,成文东,黄伟莉,等.工作场所空气中甲基丙烯酸正丁酯溶剂解吸气相色谱测定方法的研究[J].中国卫生检验杂志,2010(5):1011-1013.[ZHU Hai-zhen,CHENG Wen-dong,HUANG Weili,et al.Study on method for determination of n-butyl methacrylate in air in a work place by gas Chromatography[J].Chinese Journal of Health Laboratory Technology,2010(5):1011-1013.]
[8]张琛,李成发,刘冬春,等.溶解沉淀-顶空气相色谱/质谱法测定丙烯酸树脂中残余单体[J].分析试验室,2015,34(1):81-86.[ZHANG Chen,LICheng-fa,LIU Dong-chun,et al.Determination of residual monomers in acrylic resin by dissolution precipitation-headspace-gas chromatography-mass spectrometry[J].Chinese Journal of Analysis Laboratory,2015,34(1):81-86.]
[9]刘丹,陈晓青,吴名剑,等.顶空气相色谱-质谱联用法测定胶黏剂中的丙烯酸酯类残余单体[J].色谱,2011,29(12):1179-1182.[LIU Dan,CHENXiao-qing,WU Ming-jian,et al.Determination of residual acrylate monomers in adhesives by headspace gas chromatography-mass spectrometry[J].Chinese Journal of Chromatography,2011,29(12):1179-1182.]
[10]赖莺,林睿,蔡鹭欣,等.微波辅助萃取-气相色谱-质谱法测定丙烯酸树脂中9种残余单体[J].色谱,2012,30(1):21-26.[LAI Ying,LIN Rui,CAI Luxin,et al.Determination of 9 residual acrylic monomers in acrylic resins by gas chromatography-mass spectrometry[J].Chinese Journal of Chromatography,2012,30(1):21-26.]
[11]高玲,杨元,宋红焕,等.水中54种挥发性有机物的顶空-气相色谱法研究[J].中国卫生检验杂志,2010,20(7):1645-1648.[GAO Ling,YANG Yuan,SONG Hong-huan,et al.Study on method for 54 kinds of volatile organic compounds-VOCs in water using static headspace analysis in gas chromatography/mass spectrometry[J].Chinese Journal of Health Laboratory Technology,2010,20(7):1645-1648.]
[12]普学伟,邵应春,施艳峰,等.顶空-气相色谱-质谱法测定水中25种挥发性有机物的含量[J].理化检验-化学分册,2015,51(8):1194-1198.[PU Xuewei,SHAO Ying-chun,SHI Yan-feng,et al.Headspace-GC-MS determination of 25 volatile organic compounds in water[J].PTCA(PART B:CHEM.ANAL.),2015,51(8):1194-1198.]
[13]饶竹,李松,佟柏龄,等.顶空气相色谱法测定地层水中的苯系物[J].岩矿测试,2004,23(2):97-101.[RAO Zhu,LI Song,TONG Bo-lin,et al.Determination of BTEXs in stratum water by headspace-gas chromatography[J].Roch and Mineral Analysis,2004,23(2):97-101.]
[14]梁定鸿.顶空毛细管柱气相色谱法测定水中苯系物的研究[J].广东化工,2007,34(7):122-125.[LIANG Ding-hong.Study on the analysis of BTEX in water by headspace gas chromatography[J].Guangdong Chemical Engineering,2007,34(7):12-125.]
[15]国家质量监督检验检疫总局.JJG1164-2006台式气相色谱-质谱联用仪校准规范[M].北京:中国计量出版社,2010.
[16]环境保护部.HJ 168-2010环境监测分析方法标准制修订技术导则[S].2010.