CN108088895A - A kind of quick online apparatus and method for differentiating amine isomer - Google Patents
A kind of quick online apparatus and method for differentiating amine isomer Download PDFInfo
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- 150000001412 amines Chemical class 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 13
- 239000007789 gas Substances 0.000 claims abstract description 133
- 239000012159 carrier gas Substances 0.000 claims abstract description 75
- 238000001514 detection method Methods 0.000 claims abstract description 27
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000004458 analytical method Methods 0.000 claims abstract description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000005070 sampling Methods 0.000 claims description 28
- 150000002500 ions Chemical class 0.000 claims description 26
- 238000001228 spectrum Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 239000012634 fragment Substances 0.000 claims description 5
- 150000001793 charged compounds Chemical class 0.000 claims description 4
- 238000005485 electric heating Methods 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 238000000752 ionisation method Methods 0.000 claims description 3
- 229920000620 organic polymer Polymers 0.000 claims description 3
- 239000002861 polymer material Substances 0.000 claims description 3
- 238000009795 derivation Methods 0.000 abstract 1
- 238000005259 measurement Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 4
- -1 amine compounds Chemical class 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000004094 preconcentration Methods 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供了一种快速在线鉴别胺类同分异构体的装置和方法，所用在线分析系统包括样品气产生装置、供气装置和气体检测装置。所述在线分析方法是利用上述在线分析系统，将装有胺类样品的液体样品瓶置于样品气产生装置内，由供气装置提供含有氧气的载气气氛携带胺类的样品气流出装置，流出气的一部分直接进入气体检测装置进行分析，其余作为尾气排出。改变载气的流速以及液体样品瓶的瓶盖开口状态可以获得不同浓度的样品气，胺类样品气随载气直接进入气体检测装置而不需要任何离线浓缩、衍生等步骤，操作简单，分析准确，测定精度高。
The invention provides a device and method for fast on-line identification of amine isomers. The on-line analysis system used includes a sample gas generating device, a gas supply device and a gas detection device. The on-line analysis method is to use the above-mentioned on-line analysis system to place the liquid sample bottle containing the amine sample in the sample gas generating device, and the gas supply device provides a carrier gas atmosphere containing oxygen to carry the amine sample gas out of the device, A part of the effluent gas directly enters the gas detection device for analysis, and the rest is discharged as tail gas. Sample gases with different concentrations can be obtained by changing the flow rate of the carrier gas and the opening state of the cap of the liquid sample bottle. The amine sample gas directly enters the gas detection device with the carrier gas without any off-line concentration and derivation steps. The operation is simple and the analysis is accurate. , high measurement accuracy.
Description
技术领域technical field
本发明涉及一种快速在线鉴别胺类同分异构体的装置和方法，具体来说就是利用该在线分析装置将一定浓度的胺类样品气与含有氧气的载气混合，一起快速通过气体进样管进入气体检测装置，获得胺类的特征谱图，根据其特征谱图实现在线鉴别胺类同分异构体的目的。The present invention relates to a device and method for fast on-line identification of amine isomers. Specifically, the on-line analysis device is used to mix a certain concentration of amine sample gas with a carrier gas containing oxygen, and quickly pass through the gas together. The sample tube enters the gas detection device to obtain the characteristic spectrum of amines, and realizes the purpose of online identification of amine isomers according to the characteristic spectrum.
背景技术Background technique
随着经济的发展和生活水平的提高，人们向环境中输入的有机污染物越来越多，其中胺类就是环境中一种常见的有机污染物，它们广泛存在于水环境、大气环境甚至土壤环境中，如各种水产品中，对人们的身体健康造成了严重危害。因此，有必要发展先进的检测技术和方法对胺类化合物进行全面而高灵敏的检测。其中，对胺类同分异构体的准确鉴别可以帮助我们更全面、准确了解环境中的胺类污染物。目前，用于分析胺类化合物的传统方法主要是气相色谱法(GC)和气相色谱-质谱联用法(GC-MS)。但是这些方法为离线操作，容易造成样品的污染和变质，而且耗时很长，操作复杂，还容易对其中的胺类同分异构体造成假阳性检测。因此，需要发展一种可以快速准确鉴别胺类同分异构体的技术和方法。With the development of the economy and the improvement of living standards, people import more and more organic pollutants into the environment, among which amines are a common organic pollutant in the environment, which widely exist in the water environment, atmospheric environment and even soil In the environment, such as various aquatic products, it has caused serious harm to people's health. Therefore, it is necessary to develop advanced detection techniques and methods for comprehensive and highly sensitive detection of amine compounds. Among them, the accurate identification of amine isomers can help us understand the amine pollutants in the environment more comprehensively and accurately. At present, the traditional methods for analyzing amine compounds are mainly gas chromatography (GC) and gas chromatography-mass spectrometry (GC-MS). However, these methods are offline operations, which are easy to cause contamination and deterioration of samples, and are time-consuming and complicated to operate, and are also prone to false positive detection of amine isomers. Therefore, it is necessary to develop a technology and method that can quickly and accurately identify amine isomers.
本文的目的在于提供一种快速在线鉴别胺类同分异构体的装置和新方法。该方法以样品气产生装置获得一定浓度的胺类样品气，一定浓度的胺类样品气和一定流量的含有氧气的载气混合，然后两者一起进入气体检测装置即真空紫外灯为离子源的正电离质谱仪中进行电离分析。该方法有效解决了上述分析方法的不足，实现了快速在线鉴别胺类同分异构体的目的，不需要任何预浓缩、衍生化或洗脱步骤，提供了一种简单快速、准确高效的检测手段和可靠数据。另外，该装置气路简单，成本低廉，便于操作。The purpose of this article is to provide a device and new method for rapid online identification of amine isomers. In this method, a sample gas generating device is used to obtain a certain concentration of amine sample gas, a certain concentration of amine sample gas is mixed with a certain flow rate of carrier gas containing oxygen, and then the two enter the gas detection device together, that is, the vacuum ultraviolet lamp as the ion source. Ionization analysis was performed in a positive ionization mass spectrometer. This method effectively solves the deficiencies of the above analysis methods, realizes the purpose of rapid online identification of amine isomers, does not require any pre-concentration, derivatization or elution steps, and provides a simple, fast, accurate and efficient detection means and reliable data. In addition, the gas circuit of the device is simple, the cost is low, and the operation is convenient.
发明内容Contents of the invention
本发明的目的是提供一种快速在线鉴别胺类同分异构体的装置和方法。The purpose of the present invention is to provide a device and method for fast on-line identification of amine isomers.
一种快速在线鉴别胺类同分异构体的装置，其特征在于：包括密闭的样品气产生装置、供气装置、载气导入管、载气导出管和气体检测装置；A device for rapidly on-line identification of amine isomers, characterized in that it includes a closed sample gas generating device, a gas supply device, a carrier gas inlet tube, a carrier gas outlet tube, and a gas detection device;
所述样品气产生装置为一中空密闭腔体，中空密闭腔体包括一上端开口、下端密闭的样品杯和一可开启和关闭的盖体；盖体与样品杯的开口端密封连接，样品杯用于盛装液体样品瓶；于样品杯上设有载气流入口、载气流出口；The sample gas generating device is a hollow airtight cavity, the hollow airtight cavity includes a sample cup with an open upper end and a closed lower end, and an openable and closable cover; the cover is sealed and connected to the open end of the sample cup, and the sample cup Used to hold liquid sample bottles; the sample cup is provided with a carrier gas inlet and a carrier gas outlet;
所述供气装置包括载气气源和质量流量控制器，载气气源的气体经质量流量控制器由载气导入管通入样品气产生装置内；载气导入管的气体出口端与样品杯的载气流入口密封连接；The gas supply device includes a carrier gas source and a mass flow controller, the gas of the carrier gas source passes through the mass flow controller into the sample gas generating device through the carrier gas introduction pipe; the gas outlet end of the carrier gas introduction pipe is connected to the sample gas The carrier gas inlet of the cup is sealed and connected;
样品杯的载气流出口与载气导出管密封连接，载气导出管与气体检测装置的气体进样管密封相连。The carrier gas outlet of the sample cup is sealed and connected with the carrier gas outlet tube, and the carrier gas outlet tube is sealed and connected with the gas sampling tube of the gas detection device.
所述盖体为一端开口、另一端密闭的中空管，开口端内壁设有内螺纹，所述样品杯为一端开口、另一端密闭的中空管，开口端为液体样品瓶的取出和放入口，样品杯的开口端外壁上设有外螺纹，样品杯与盖体通过密封O圈密封螺合。The cover body is a hollow tube with one end open and the other end closed. The inner wall of the open end is provided with internal threads. The sample cup is a hollow tube with one end open and the other end closed. In the inlet, the outer wall of the open end of the sample cup is provided with external threads, and the sample cup and the cover body are sealed and screwed together by a sealing O ring.
所述样品气产生装置的中空腔体大小与液体样品瓶的大小匹配，保证液体样品瓶能够放入样品气产生装置中。The size of the hollow cavity of the sample gas generating device matches the size of the liquid sample bottle to ensure that the liquid sample bottle can be put into the sample gas generating device.
载气气源为装有氧气的钢瓶或净化后的干燥空气，载气导入管上设有质量流量控制器，载气流量可控。The source of the carrier gas is a steel cylinder filled with oxygen or purified dry air. A mass flow controller is installed on the carrier gas inlet tube, and the flow rate of the carrier gas is controllable.
所述气体检测装置为直接气体进样的分析装置，主要为气体进样的正离子模式在线质谱仪，通过气体进样管和载气导出管与样品气产生装置相连，对样品气的一部分采样分析，其余作为尾气排出。气体进样管外设有电加热装置，可对其加热到一定温度。The gas detection device is an analysis device for direct gas sampling, mainly a positive ion mode online mass spectrometer for gas sampling, connected to the sample gas generating device through a gas sampling tube and a carrier gas outlet tube, and sampling a part of the sample gas analysis, and the rest are discharged as tail gas. There is an electric heating device outside the gas sampling tube, which can be heated to a certain temperature.
所述样品气产生装置为不锈钢材质，可以对其加热至一定温度。The sample gas generating device is made of stainless steel and can be heated to a certain temperature.
采用权利要求1-6中任一所述装置进行操作，包括如下步骤：Adopt any described device among the claims 1-6 to operate, comprising the steps of:
A.将盛有胺的液体样品瓶的瓶盖打开或瓶盖上插入一段毛细管供样品气溢出，同时设定好气体进样管的加热温度并开始加热；A. Open the bottle cap of the liquid sample bottle containing amine or insert a section of capillary on the bottle cap to allow the sample gas to overflow, and set the heating temperature of the gas sampling tube at the same time and start heating;
B.将液体样品瓶放入样品气产生装置内，拧紧盖体；B. Put the liquid sample bottle into the sample gas generating device, and tighten the cover;
C.将载气导入管与气体流入口密封连接，载气导出管一端与气体流出口密封连接，载气导出管另一端与气体进样管连接；C. Connect the carrier gas inlet pipe to the gas inflow port, one end of the carrier gas outlet pipe is connected to the gas outflow port, and the other end of the carrier gas outlet pipe is connected to the gas sampling pipe;
D.打开质量流量控制器，设定好流量，通入载气，同时利用气体检测装置对流出气在线采样，获得胺类的特征谱图。D. Turn on the mass flow controller, set the flow rate, feed the carrier gas, and use the gas detection device to sample the effluent gas online to obtain the characteristic spectrum of amines.
所述气体导入管和气体导出管为有机聚合物材料管或不锈钢管。The gas inlet pipe and the gas outlet pipe are organic polymer material pipes or stainless steel pipes.
气体检测装置为气体进样的正离子模式在线质谱仪，采用真空紫外灯离子源对胺的样品挥发气进行电离分析，该电离方法可对绝大多数有机物实现有效电离，特征离子主要为物质的分子离子或准分子离子，碎片离子较少，便于对物质实现准确鉴别。The gas detection device is a positive ion mode online mass spectrometer for gas sampling. The vacuum ultraviolet lamp ion source is used to ionize and analyze the volatile gas of the amine sample. This ionization method can effectively ionize most organic substances, and the characteristic ions are mainly substances. Molecular ions or quasi-molecular ions have fewer fragment ions, which are convenient for accurate identification of substances.
采用真空紫外灯为离子源，其发射的光子能量为10.6eV，可以对绝大多数胺类有效电离，且得到的特征谱图简单，主要为物质的分子离子，碎片离子很少。采用的载气为含有氧气的气体，如干净空气，高纯氧气等。The vacuum ultraviolet lamp is used as the ion source, and the photon energy emitted by it is 10.6eV, which can effectively ionize most amines, and the characteristic spectrum obtained is simple, mainly molecular ions of substances, and fragment ions are few. The carrier gas used is a gas containing oxygen, such as clean air, high-purity oxygen, etc.
附图说明Description of drawings
图1为快速在线鉴别胺类同分异构体的装置示意图：1-样品气产生装置；2-盖体；3-载气流出口；4-载气流入口；5-样品杯；6-载气气源；7-质量流量控制器；8-供气装置；9-载气导入管；10-载气导出管；11-气体进样管；12-气体检测装置。Figure 1 is a schematic diagram of the device for rapid online identification of amine isomers: 1-sample gas generator; 2-cover; 3-carrier gas outlet; 4-carrier gas inlet; 5-sample cup; 6-carrier gas Gas source; 7-mass flow controller; 8-gas supply device; 9-carrier gas inlet tube; 10-carrier gas outlet tube; 11-gas sampling tube; 12-gas detection device.
图2为相同条件下正己胺与其同分异构体三乙胺的特征谱图。Figure 2 is the characteristic spectrum of n-hexylamine and its isomer triethylamine under the same conditions.
具体实施方式Detailed ways
首先，图1为一种快速在线鉴别胺类同分异构体的装置，其特征在于：包括密闭的样品气产生装置1、供气装置8、载气导入管9、载气导出管10和气体检测装置12；First of all, Fig. 1 is a device for rapid online identification of amine isomers, which is characterized in that it includes a closed sample gas generating device 1, a gas supply device 8, a carrier gas inlet pipe 9, a carrier gas outlet pipe 10 and Gas detection device 12;
所述样品气产生装置1为一中空密闭腔体，中空密闭腔体包括一上端开口、下端密闭的样品杯5和一可开启和关闭的盖体2；盖体2与样品杯5的开口端密封连接，样品杯5用于盛装液体样品瓶；于样品杯5上设有载气流入口4、载气流出口3；The sample gas generating device 1 is a hollow airtight cavity, the hollow airtight cavity includes a sample cup 5 with an open upper end and a closed lower end and an openable and closable cover 2; the open end of the cover 2 and the sample cup 5 Sealed connection, the sample cup 5 is used to hold the liquid sample bottle; the sample cup 5 is provided with a carrier gas inlet 4 and a carrier gas outlet 3;
所述供气装置8包括载气气源6和质量流量控制器7，载气气源6的气体经质量流量控制器7由载气导入管9通入样品气产生装置1内；载气导入管9的气体出口端与样品杯5的载气流入口4密封连接；The gas supply device 8 includes a carrier gas source 6 and a mass flow controller 7, and the gas of the carrier gas source 6 is passed into the sample gas generating device 1 by the carrier gas introduction pipe 9 through the mass flow controller 7; The gas outlet end of the tube 9 is in sealing connection with the carrier gas inlet 4 of the sample cup 5;
样品杯5的载气流出口3与载气导出管10密封连接，载气导出管10与气体检测装置12的气体进样管11密封相连。The carrier gas outlet 3 of the sample cup 5 is sealed and connected with the carrier gas outlet tube 10 , and the carrier gas outlet tube 10 is sealed and connected with the gas sampling tube 11 of the gas detection device 12 .
所述盖体2为一端开口、另一端密闭的中空管，开口端内壁设有内螺纹，所述样品杯5为一端开口、另一端密闭的中空管，开口端为液体样品瓶的取出和放入口，样品杯5的开口端外壁上设有外螺纹，样品杯5与盖体2通过密封O圈密封螺合。The cover body 2 is a hollow tube with one end open and the other end closed. The inner wall of the open end is provided with an internal thread. The sample cup 5 is a hollow tube with one end open and the other end closed. The open end is used for taking out the liquid sample bottle. and the insertion port, the outer wall of the opening end of the sample cup 5 is provided with an external thread, and the sample cup 5 and the cover body 2 are sealed and screwed together by a sealing O ring.
所述样品气产生装置1的中空腔体大小与液体样品瓶的大小匹配，保证液体样品瓶能够放入样品气产生装置1中。The size of the hollow cavity of the sample gas generating device 1 matches the size of the liquid sample bottle to ensure that the liquid sample bottle can be put into the sample gas generating device 1 .
载气气源6为装有氧气的钢瓶或净化后的干燥空气，载气导入管9上设有质量流量控制器7，载气流量可控。The carrier gas source 6 is a steel cylinder filled with oxygen or purified dry air, and a mass flow controller 7 is provided on the carrier gas introduction pipe 9, so that the flow rate of the carrier gas is controllable.
所述气体检测装置12为直接气体进样的分析装置，主要为气体进样的正离子模式在线质谱仪，通过气体进样管11和载气导出管10与样品气产生装置1相连，对样品气的一部分采样分析，其余作为尾气排出。气体进样管11外设有电加热装置，可对其加热到一定温度。The gas detection device 12 is an analysis device for direct gas sampling, mainly a positive ion mode online mass spectrometer for gas sampling, which is connected to the sample gas generating device 1 through a gas sampling tube 11 and a carrier gas outlet tube 10. A part of the gas is sampled and analyzed, and the rest is discharged as tail gas. The gas sampling tube 11 is provided with an electric heating device outside, which can be heated to a certain temperature.
所述样品气产生装置1为不锈钢材质，可以对其加热至一定温度。The sample gas generating device 1 is made of stainless steel and can be heated to a certain temperature.
采用权利要求1-6中任一所述装置进行操作，包括如下步骤：Adopt any described device among the claims 1-6 to operate, comprising the steps of:
A.将盛有胺的液体样品瓶的瓶盖打开或瓶盖上插入一段毛细管供样品气溢出，同时设定好气体进样管的加热温度并开始加热；A. Open the bottle cap of the liquid sample bottle containing amine or insert a section of capillary on the bottle cap to allow the sample gas to overflow, and set the heating temperature of the gas sampling tube at the same time and start heating;
B.将液体样品瓶放入样品气产生装置1内，拧紧盖体2；B. Put the liquid sample bottle into the sample gas generating device 1, and tighten the cover 2;
C.将载气导入管9与气体流入口4密封连接，载气导出管10一端与气体流出口(3)密封连接，载气导出管10另一端与气体进样管11连接；C. The carrier gas inlet tube 9 is sealed and connected to the gas inlet 4, one end of the carrier gas outlet tube 10 is sealed and connected to the gas outlet (3), and the other end of the carrier gas outlet tube 10 is connected to the gas sampling tube 11;
D.打开质量流量控制器7，设定好流量，通入载气，同时利用气体检测装置12对流出气在线采样，获得胺类的特征谱图。D. Turn on the mass flow controller 7, set the flow rate, feed the carrier gas, and use the gas detection device 12 to sample the effluent gas online to obtain the characteristic spectrum of amines.
所述气体导入管9和气体导出管10为有机聚合物材料管或不锈钢管。The gas inlet pipe 9 and the gas outlet pipe 10 are organic polymer material pipes or stainless steel pipes.
气体检测装置12为气体进样的正离子模式在线质谱仪，采用真空紫外灯离子源对胺的样品挥发气进行电离分析，该电离方法可对绝大多数有机物实现有效电离，特征离子主要为物质的分子离子或准分子离子，碎片离子较少，便于对物质实现准确鉴别。The gas detection device 12 is a positive ion mode online mass spectrometer for gas sampling, and uses a vacuum ultraviolet lamp ion source to perform ionization analysis on the volatile gas of the amine sample. This ionization method can effectively ionize most organic substances, and the characteristic ions are mainly substance Molecular ions or quasi-molecular ions have fewer fragment ions, which is convenient for accurate identification of substances.
其中，所用液体样品瓶为安捷伦生产的1.5ml棕色玻璃瓶，内装约0.5ml的胺类标准样品。气体进样管采用内径250μm、长度约1m的金属毛细管，外设有一定电阻的电加热带。另外，载气导入管和载气导出管采用外径4mm的聚四氟乙烯管，气体检测装置采用真空紫外灯为离子源电离的飞行时间质谱仪，该质谱仪采用正交加速设计，以MCP探测器检测，胺类样品气的一部分随含有氧气的载气通过金属毛细管进入质谱仪进行分析，其余作为废气排出。实验中电离区总气压维持在400Pa左右。Wherein, the liquid sample bottle used is a 1.5ml brown glass bottle produced by Agilent, which contains about 0.5ml of amine standard samples. The gas sampling tube is a metal capillary with an inner diameter of 250 μm and a length of about 1 m, and an electric heating band with a certain resistance is installed outside. In addition, the carrier gas inlet tube and the carrier gas outlet tube adopt polytetrafluoroethylene tubes with an outer diameter of 4mm, and the gas detection device adopts a time-of-flight mass spectrometer ionized by a vacuum ultraviolet lamp as an ion source. Detector detection, a part of the amine sample gas enters the mass spectrometer through the metal capillary with the carrier gas containing oxygen for analysis, and the rest is discharged as waste gas. In the experiment, the total air pressure in the ionization zone was maintained at about 400Pa.
实施例1Example 1
针对本发明所述一种快速在线鉴别胺类同分异构体的装置和方法性能的考查，实验以正己胺和其同分异构体三乙胺为对象，利用该在线分析装置在线分析它们的特征谱图，利用特征谱图实现两种同分异构体的快速在线鉴别。实验中载气采用干燥的干净空气，设定进入样品气产生装置的高纯干燥空气的流量为1L/min，金属毛细管的加热温度为150℃。所用胺类液体标准品的体积均为0.5ml，液体样品瓶的瓶盖完全拧开但是不拿掉，仍然覆盖在瓶口。实验中电离源的电离方式采用真空紫外灯离子源，电离区气压维持在400Pa左右。先是在无胺类样品的情况下进行空白试验，采样时间为1min。之后，将上述液体样品瓶放入样品气产生装置，连接好载体管路，然后通入载气并立即利用质谱仪进行采样分析。图2是正己胺及其同分异构体三乙胺的特征谱图。可以发现，三乙胺的特征离子主要为其质子化离子(C2H5)3N·H+(m/z＝102)和主碎片离子(C2H5)2CH2N+(m/z＝86)，而正己胺除了这两种离子外，还检测到相对强度较高的其他加合离子，包括CH3(CH2)5NH2·CH3 +(m/z＝116)、CH3(CH2)5NH2·O2 +(m/z＝133)、2CH3(CH2)5NH2·H+(m/z＝203)、2CH3(CH2)5NH2·CH3 +(m/z＝217)和2CH3(CH2)5NH2·O2 +(m/z＝234)。利用这些三乙胺谱图中没有的加合离子可以实现这两种同分异构体胺类的快速在线鉴别。Aiming at the examination of the performance of a device and method for quickly on-line identification of amine isomers described in the present invention, n-hexylamine and its isomer triethylamine were used as objects in the experiment, and the online analysis device was used to analyze them online. The characteristic spectrum, using the characteristic spectrum to realize the rapid online identification of two isomers. In the experiment, dry clean air was used as the carrier gas, the flow rate of high-purity dry air entering the sample gas generator was set at 1L/min, and the heating temperature of the metal capillary was 150°C. The volume of the amine liquid standard used is 0.5ml, and the bottle cap of the liquid sample bottle is completely unscrewed but not removed, and still covers the bottle mouth. The ionization mode of the ionization source in the experiment adopts the vacuum ultraviolet lamp ion source, and the air pressure in the ionization area is maintained at about 400Pa. First, a blank test was carried out without amine samples, and the sampling time was 1 min. After that, put the above-mentioned liquid sample bottle into the sample gas generating device, connect the carrier pipeline, then feed the carrier gas and immediately use the mass spectrometer for sampling and analysis. Fig. 2 is the characteristic spectrogram of n-hexylamine and its isomer triethylamine. It can be found that the characteristic ions of triethylamine are mainly its protonated ion (C 2 H 5 ) 3 N H + (m/z=102) and the main fragment ion (C 2 H 5 ) 2 CH 2 N + (m /z=86), and n-hexylamine, in addition to these two ions, also detected other adduct ions with relatively high intensity, including CH 3 (CH 2 ) 5 NH 2 ·CH 3 + (m/z=116) , CH 3 (CH 2 ) 5 NH 2 ·O 2 + (m/z=133), 2CH 3 (CH 2 ) 5 NH 2 ·H + (m/z=203), 2CH 3 (CH 2 ) 5 NH 2 ·CH 3 + (m/z=217) and 2CH 3 (CH 2 ) 5 NH 2 ·O 2 + (m/z=234). The use of adduct ions not found in these triethylamine spectra allowed rapid on-line identification of these two isomeric amines.
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