饮用水源中痕量二级胺检测方法及其应用的研究

发布时间：2018-05-06 22:43

本文选题：(?)量二级胺 + 气相色谱　；参考：《中南林业科技大学》2012年硕士论文

【摘要】：二级胺是一类低沸点、易挥发、易转化生成强致癌物质的有机胺类化合物,对于生态环境和人体健康都有很大的影响。快速、准确地检测痕量二级胺的分析方法对于保护环境和人类健康至关重要。本文以二甲胺、甲乙胺、二乙胺、吗啉和N-甲基苄胺物质代表物质为例,建立了使用气相色谱-氢火焰检测器和气相色谱-质谱检测器来测定饮用水源中痕量二级胺的方法,对保护环境和保障人体健康具有重要意义。使用苯磺酰氯衍生的方法,将二级胺与苯磺酰氯反应生成性质稳定的磺酰胺,通过气相色谱法测定磺酰胺的含量,间接测定二级胺的含量。并对影响衍生反应的温度、pH和搅拌时间等条件进行优化,探索出最适合衍生反应的前处理条件。使用优化后的条件进行衍生反应,再经气相色谱-氢火焰检测器(GC-FID)分析水环境中二级胺含量,色谱柱HP-5型毛细管柱(30m×0.32mm×0.25μ m)；进样口温度：280℃；检测器温度：300℃；进样量：1μL；进样模式：分流进样；分流比：1：1；载气为氮气,柱流量2mL/min,分流出口吹扫流量为3mL/min,柱前压力为79kPa；氢气和空气流量分别为45、450mL/min,升温程序：初始温度为120℃,保持3分钟；以5℃/min的速率从120℃上升至220℃,然后以10℃/分钟的速率从220℃上升至290℃,保持5分钟。结果表明：五种二级胺线性关系良好,相关系数为0.9997、0.9996、0.9996、0.9989、0.9995,相对标准偏差分别为0.46%、0.45%、0.38%、0.24%、0.16%,回收率为91%-133%。使用优化后的条件进行衍生反应,经过气相色谱-质谱检测器(GC-MS)分析水环境中的二级胺含量,使用DB-5MS型毛细管柱(30m×0.32mm×0.25μ m)；柱前压力为80kPa；氮气纯度99.99%,氮气流速1ml/min,MS检测器电离电压为70eV。升温程序：初始温度为140℃,以3℃/min的速率从140℃上升至210℃,然后以10℃/分钟的速率从210℃上升至290℃,保持5分钟。质谱检测采用离子选择模式(SIM),选择离子为77,141,185。结果表明：五种二级胺线性关系良好,相关系数为0.9987、0.9977、0.9969、0.9956、0.9969,相对标准偏差分别为0.34%、0.43%、0.46%、0.41%、0.19%,回收率为74%-136%。通过对线性关系、精密度、检出限和准确度等方法学比较,使用GC-FID比GC-MS在以上指标中有有好的表现,同时,GC-FID所需要的运行、维护成本较GC-MS也要低,更适合快速、准确测定饮用水源中二级胺的含量。使用GC-FID对某地饮用水源进行检测,使用主成分分析法对当地的二级胺污染状况进行评价,结果表明：少数地区检测出二甲胺、二乙胺,部分地区检测出甲乙胺、吗啉,大部分地区检测出N-甲基苄胺,说明该地饮用水源已受到轻微污染。
[Abstract]:Two class amine is a kind of low boiling point, volatile and easily converted to produce strong carcinogen organic amines. It has a great influence on the ecological environment and human health. Rapid, accurate detection of trace amounts of two levels of amines is essential for the protection of the environment and human health. This article is two methylamine, methylamine, two ethylamine, morpholine and N- a. A method for the determination of trace amounts of two grade amine in drinking water source by gas chromatography hydrogen flame detector and gas chromatography-mass spectrometry is established, which is of great significance in protecting the environment and protecting human health by using gas chromatography hydrogen flame detector and gas chromatography mass spectrometry detector.
Using benzsulfonyl chloride, two grade amines are reacted with benzsulfonyl chloride to produce sulfonamide with stable properties. The content of sulfonamide is determined by gas chromatography and the content of two grade amine is indirectly determined. The conditions of temperature, pH and stirring time which affect the derivative reaction are optimized, and the best preconditioning conditions for the derivative reaction are explored.
Using the optimized conditions to derive the reaction, then the gas chromatography hydrogen flame detector (GC-FID) was used to analyze the content of two grade amine in the water environment, the HP-5 capillary column of the column (30M x 0.32mm x 0.25 mu m), the inlet temperature of 280, the detector temperature, 300, 1 Mu L, the sampling mode, the diversion pattern, the shunt ratio: 1:1; The gas carrying capacity is nitrogen, the flow rate of the column flow is 2mL/min, the flow discharge flow is 3mL/min, the pre column pressure is 79kPa, and the hydrogen and air flow are 45450mL/min respectively. The initial temperature is 120 centigrade, keeping 3 minutes; at the rate of /min of 5 degrees C, it rises from 120 to 220, and then rises from 220 to 290 C at 10 C / min, keeping 5 points. The results show that the linear relationship between five kinds of two grade amines is good, the correlation coefficient is 0.9997,0.9996,0.9996,0.9989,0.9995, the relative standard deviation is 0.46%, 0.45%, 0.38%, 0.24%, 0.16%, and the recovery rate is 91%-133%.
Based on the optimized conditions, the two grade amine content in water environment was analyzed by gas chromatography-mass spectrometry (GC-MS), DB-5MS capillary column (30M x 0.32mm x 0.25 mu m), pre column pressure was 80kPa, nitrogen purity was 99.99%, nitrogen flow rate 1ml/min, MS detector ionization voltage was 70eV. heating program: initial temperature was 14. At 0 C, the rate of 3 C /min rose from 140 to 210, and then increased from 210 to 290 C at 10 C / min for 5 minutes. The ion selection mode (SIM) was used for mass spectrometry. The selection ion was 77141185., and the linear relationship of five two amines was good, the correlation coefficient was 0.9987,0.9977,0.9969,0.9956,0.9969, relative standard. The deviations were 0.34%, 0.43%, 0.46%, 0.41%, 0.19%, respectively, and the recovery rate was 74%-136%.
By comparing the linear relation, the precision, the detection limit and the accuracy, the GC-FID is better than the GC-MS in the above indexes. At the same time, the operation and maintenance cost of GC-FID are lower than that of GC-MS. It is more suitable for rapid and accurate determination of the content of two grade amine in the drinking water source.
GC-FID was used to test a drinking water source in a certain area. The status of two grade amine pollution was evaluated by principal component analysis. The results showed that two methylamine, two ethylamine were detected in a few areas, methylamine and morpholine were detected in some areas, and N- methyl benzylamine was detected in most areas, indicating that the drinking water source had been slightly polluted.

【学位授予单位】：中南林业科技大学
【学位级别】：硕士
【学位授予年份】：2012
【分类号】：R123.1

【参考文献】