色谱法测定烟花爆竹用烟火药剂中有机成分的研究与应用
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摘要
烟花爆竹产品因其极具观赏性的绚烂燃放效果和对喜庆祝福的表达,受到了人们的普遍喜爱,但烟花爆竹产品的安全性和其对环境的影响也是不应忽视的问题。这些问题的根源主要在于烟火药剂的选择。近年来,国内外对于烟花爆竹产品的要求越来越严格,针对烟花爆竹用烟火药剂的成分建立快速、简单、准确的检测方法,不仅可以深入对烟火药剂研究,同时也有利于烟花爆竹生产行业的监督规范,还能为破除贸易壁垒提供技术支持。
通过查阅中外文献及资料,并根据烟火药剂中有可能添加的几种有机化合物——没食子酸、苦味酸、六氯苯及六氯乙烷的性质,建立了相应组分的高效液相色谱及毛细管气相色谱检测方法。方法简单、快速、准确,适用于烟火药剂中上述有机组分的检测分析。本论文共分为四章,主要内容如下:
第一章:概要介绍烟花爆竹用烟火药剂的组成及烟火效应的产生,对没食子酸、苦味酸、六氯苯及六氯乙烷几种有机化合物做了详细说明,并且重点介绍了烟火药剂检测分析技术。
第二章:建立了高效液相色谱测定烟火药剂中没食子酸的方法,采用Zorbax Eclipse XDB-C_(18)色谱柱(4.6×150 mm)分离,以甲醇- 0.1%冰醋酸水溶液为流动相,梯度洗脱,流速1.0 mL/min;测定温度为25℃;检测波长为274 nm。没食子酸的质量浓度在0.5~20.0μg/mL时与色谱峰面积之间线性关系良好(相关系数r=0.9999);对烟火药剂样品进行3个不同浓度水平的添加回收,回收率为87.0 ~ 104.5%,相对标准偏差(RSD)为1.2 ~ 6.4%。
第三章:建立了高效液相色谱测定烟火药剂中苦味酸的方法,在流动相V(甲醇):V (0.1%冰醋酸水溶液)=55:45时,等度洗脱,流速0.8 mL/min;测定温度为40℃;采用二极管阵列检测器检测,检测波长为355 nm。苦味酸的质量浓度在0.5~20μg/mL时与色谱峰面积之间线性关系良好(r=0.9998);加标回收率为84.0～92.0%,相对标准偏差(RSD)为2.1 ~ 5.7%。该方法简便快速,结果准确,重现性好,适用于烟火药剂中苦味酸的检测。
第四章:建立了同时测定烟火药剂中六氯苯和六氯乙烷含量的毛细管气相色谱法。烟火药剂样品经正己烷提取、浓硫酸净化后,采用氢火焰离子化检测器(FID)检测。以保留时间定性,外标法定量,六氯苯及六氯乙烷分别在5.195~207.8μg/mL和5.750~230.0μg/mL范围内线性关系良好,添加不同浓度水平的标准溶液后,测得六氯苯和六氯乙烷的添加回收率分别为79.9~101.3%和83.3~97.9%,相对标准偏差分别为1.1~5.2%和0.7~2.7%。用GC-MS进行确证,证明该方法准确、可靠。
The firework is wildly favored due to its brilliant visual enjoyment and expression for sweet wishes, however, the security and environmental problems,which are from setting off fireworks should not be neglected too. Essentially, the drawbacks of fireworks are ascribed to choice of pyrotechnic compositions. In recent years, the requirements for fireworks are getting stricter at home and abroad. The establishment of a fast, simple and accurate detection method will contribute not only to the further study of pyrotechnic compositions but also to the manufacturing supervision of fireworks industry. In addition, advanced detection methods can provide support to break technical barrier.
Through reviewing the literatures and date both home and abroad, the thesis established methods with high performance liquid chromatogram and capillary gas chromatography according to the properties of organic components which may be used in pyrotechnic compositions, such as gallic acid, picric acid, hexachlorobenzene, and hexachloroethane. These fast, simple and accurate methods are suitable to analysis the organic components aforementioned in pyrotechnic compositions. This thesis is consisted of four chapters and major contents are showed as following:
1. First, the pyrotechnic compositions used in fireworks and combustion characteristics were summarized. Second, a detailed description about gallic acid, picric acid, hexachlorobenzene and hexachloroethane was presented. Last, the analysis and detection methods of pyrotechnic compositions were mainly introduced.
2. A high performance liquid chromatography (HPLC) method was developed for the determination of gallic acid in Pyrotechnic composition. The HPLC separation was performed on a Zorbax Eclipse XDB-C_(18) column with a gradient elution program of methanol- 0.1%acetic acid solution as the mobile phase at the flow rate of 1.0 mL/min and 25℃. The detection wavelength was 274 nm. There were good linear relationships between the mass concentrations and the peak areas of gallic acid in the range of 0.5~20.0μg/mL( r=0.9999 ). The recoveries were 87.0~104.5% with the relative standard deviations of 1.2~6.4%.
3. A high performance liquid chromatography (HPLC) method was developed for the determination of picric acid in Pyrotechnic composition. With a elution program of methanol-0.1% acetic acid ( v/v = 55/45 ) solution as the mobile phase at the flow rate of 0.8 mL/min and 40℃. The detection wavelength was 355nm.There were good linear relationships between the mass concentrations and the peak areas of picric acid in the range of 0.5~20.0μg/mL(r = 0.9998).The recoveries were 84.0~92.0% with the relative standard deviations of 2.1~5.7%. The method is quick, simple and accurate. It can be used for the determination of picric acid in Pyrotechnic composition.
4. A method of simulataneous determination of Hexachlorobenzene and Hexachloroethane in Pyrotechnic composition by capillary gas chromatograph (GC) was developed. The hexachlorobenzene and hexachloroethane were extracted from the sample with n-hexane, and the extract was cleaned up using oil of vitriol. Then the determination was performed on a GC equipped with an hydrogen flame ionization detector (FID). The retention time was used for qualification and the external calibration standard was used for quantitation. The result obtained showed that there were good linear relationships in the range of 5.195~207.8μg/mL for hexachlorobenzene and 5.750~230.0μg/mL for hexachloroethane. The recoveries were 79.9%~101.3% and 83.3%~97.9%with the relative standard deviations of 1.1%~5.2% and 0.7%~2.7%in different levels. The method was corroborated by GC-MS; it’s simple, rapid and accurate.
通过查阅中外文献及资料,并根据烟火药剂中有可能添加的几种有机化合物——没食子酸、苦味酸、六氯苯及六氯乙烷的性质,建立了相应组分的高效液相色谱及毛细管气相色谱检测方法。方法简单、快速、准确,适用于烟火药剂中上述有机组分的检测分析。本论文共分为四章,主要内容如下:
第一章:概要介绍烟花爆竹用烟火药剂的组成及烟火效应的产生,对没食子酸、苦味酸、六氯苯及六氯乙烷几种有机化合物做了详细说明,并且重点介绍了烟火药剂检测分析技术。
第二章:建立了高效液相色谱测定烟火药剂中没食子酸的方法,采用Zorbax Eclipse XDB-C_(18)色谱柱(4.6×150 mm)分离,以甲醇- 0.1%冰醋酸水溶液为流动相,梯度洗脱,流速1.0 mL/min;测定温度为25℃;检测波长为274 nm。没食子酸的质量浓度在0.5~20.0μg/mL时与色谱峰面积之间线性关系良好(相关系数r=0.9999);对烟火药剂样品进行3个不同浓度水平的添加回收,回收率为87.0 ~ 104.5%,相对标准偏差(RSD)为1.2 ~ 6.4%。
第三章:建立了高效液相色谱测定烟火药剂中苦味酸的方法,在流动相V(甲醇):V (0.1%冰醋酸水溶液)=55:45时,等度洗脱,流速0.8 mL/min;测定温度为40℃;采用二极管阵列检测器检测,检测波长为355 nm。苦味酸的质量浓度在0.5~20μg/mL时与色谱峰面积之间线性关系良好(r=0.9998);加标回收率为84.0～92.0%,相对标准偏差(RSD)为2.1 ~ 5.7%。该方法简便快速,结果准确,重现性好,适用于烟火药剂中苦味酸的检测。
第四章:建立了同时测定烟火药剂中六氯苯和六氯乙烷含量的毛细管气相色谱法。烟火药剂样品经正己烷提取、浓硫酸净化后,采用氢火焰离子化检测器(FID)检测。以保留时间定性,外标法定量,六氯苯及六氯乙烷分别在5.195~207.8μg/mL和5.750~230.0μg/mL范围内线性关系良好,添加不同浓度水平的标准溶液后,测得六氯苯和六氯乙烷的添加回收率分别为79.9~101.3%和83.3~97.9%,相对标准偏差分别为1.1~5.2%和0.7~2.7%。用GC-MS进行确证,证明该方法准确、可靠。
The firework is wildly favored due to its brilliant visual enjoyment and expression for sweet wishes, however, the security and environmental problems,which are from setting off fireworks should not be neglected too. Essentially, the drawbacks of fireworks are ascribed to choice of pyrotechnic compositions. In recent years, the requirements for fireworks are getting stricter at home and abroad. The establishment of a fast, simple and accurate detection method will contribute not only to the further study of pyrotechnic compositions but also to the manufacturing supervision of fireworks industry. In addition, advanced detection methods can provide support to break technical barrier.
Through reviewing the literatures and date both home and abroad, the thesis established methods with high performance liquid chromatogram and capillary gas chromatography according to the properties of organic components which may be used in pyrotechnic compositions, such as gallic acid, picric acid, hexachlorobenzene, and hexachloroethane. These fast, simple and accurate methods are suitable to analysis the organic components aforementioned in pyrotechnic compositions. This thesis is consisted of four chapters and major contents are showed as following:
1. First, the pyrotechnic compositions used in fireworks and combustion characteristics were summarized. Second, a detailed description about gallic acid, picric acid, hexachlorobenzene and hexachloroethane was presented. Last, the analysis and detection methods of pyrotechnic compositions were mainly introduced.
2. A high performance liquid chromatography (HPLC) method was developed for the determination of gallic acid in Pyrotechnic composition. The HPLC separation was performed on a Zorbax Eclipse XDB-C_(18) column with a gradient elution program of methanol- 0.1%acetic acid solution as the mobile phase at the flow rate of 1.0 mL/min and 25℃. The detection wavelength was 274 nm. There were good linear relationships between the mass concentrations and the peak areas of gallic acid in the range of 0.5~20.0μg/mL( r=0.9999 ). The recoveries were 87.0~104.5% with the relative standard deviations of 1.2~6.4%.
3. A high performance liquid chromatography (HPLC) method was developed for the determination of picric acid in Pyrotechnic composition. With a elution program of methanol-0.1% acetic acid ( v/v = 55/45 ) solution as the mobile phase at the flow rate of 0.8 mL/min and 40℃. The detection wavelength was 355nm.There were good linear relationships between the mass concentrations and the peak areas of picric acid in the range of 0.5~20.0μg/mL(r = 0.9998).The recoveries were 84.0~92.0% with the relative standard deviations of 2.1~5.7%. The method is quick, simple and accurate. It can be used for the determination of picric acid in Pyrotechnic composition.
4. A method of simulataneous determination of Hexachlorobenzene and Hexachloroethane in Pyrotechnic composition by capillary gas chromatograph (GC) was developed. The hexachlorobenzene and hexachloroethane were extracted from the sample with n-hexane, and the extract was cleaned up using oil of vitriol. Then the determination was performed on a GC equipped with an hydrogen flame ionization detector (FID). The retention time was used for qualification and the external calibration standard was used for quantitation. The result obtained showed that there were good linear relationships in the range of 5.195~207.8μg/mL for hexachlorobenzene and 5.750~230.0μg/mL for hexachloroethane. The recoveries were 79.9%~101.3% and 83.3%~97.9%with the relative standard deviations of 1.1%~5.2% and 0.7%~2.7%in different levels. The method was corroborated by GC-MS; it’s simple, rapid and accurate.
引文
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