CN109841482B - Enrichment sampling and ionization device for volatile organic compounds in liquid sample - Google Patents
Enrichment sampling and ionization device for volatile organic compounds in liquid sample Download PDFInfo
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- CN109841482B CN109841482B CN201711203622.4A CN201711203622A CN109841482B CN 109841482 B CN109841482 B CN 109841482B CN 201711203622 A CN201711203622 A CN 201711203622A CN 109841482 B CN109841482 B CN 109841482B
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Abstract
The invention relates to a mass spectrometer, in particular to an enrichment sampling and ionization device for volatile organic compounds in a liquid sample, which comprises: a venturi tube, a membrane enrichment sampling tube and an atmospheric pressure ionization source. The Venturi tube comprises a gas transmission tube, a contraction tube, a throat tube and an expansion tube which are coaxially arranged in sequence; the inlet end of the gas delivery pipe is connected with an external high-pressure carrier gas source; the membrane enrichment sampling pipe is a tubular membrane and penetrates through the liquid sampling pipe; a through hole is arranged on the outer wall surface of the throat of the Venturi tube, and the outlet end of the membrane enrichment sampling tube is hermetically connected with the through hole; a mass spectrum sample introduction Skimmer electrode is arranged at the rear end of the outlet of the expansion pipe, and an ionization region of the atmospheric pressure ionization source is arranged in a region between the Venturi tube and the mass spectrum sample introduction Skimmer electrode. The invention adopts the technologies of tubular membrane enrichment, Venturi sampling and atmospheric pressure soft ionization, and can realize high-flux, rapid and on-line detection of VOCs in the liquid sample without sample pretreatment.
Description
Technical Field
The invention relates to a mass spectrometer, in particular to a sampling and ionization device of a mass spectrometer, and specifically relates to an enrichment sampling and ionization device of volatile organic compounds in a liquid sample.
Background
With the continuous acceleration of urbanization and industrialization, the water environment in which human beings depend on living is facing a serious pollution problem. Volatile Organic Compounds (VOCs) are organic compounds with saturated vapor pressure of more than 133.322Pa at room temperature and boiling point of 50-260 ℃. In general, the VOCs exist in water environment at trace or trace levels, but most of the VOCs have toxicity and irritation, and some of the VOCs even generate biological toxicity such as carcinogenesis and teratogenesis, thereby causing serious damage to human health. Therefore, the research of a high-throughput, rapid and on-line detection method for detecting a large amount of samples in the environmental water body is receiving wide attention. At present, in a standard detection method of organic matters in water, for example, in national standard GB/T5750.8-2006 'standard inspection method for domestic drinking water-organic matter index', an off-line analysis method based on gas chromatography is adopted, and complex sample pretreatment processes such as headspace balance, solvent extraction and the like are needed. Although the method has high accuracy of analysis results, the detection speed is slow, the cost is high, and the rapid online analysis and screening of a large amount of samples to be detected are difficult to realize.
The mass spectrometry has the advantages of high analysis speed, high resolution and sensitivity and strong qualitative capability, particularly combines mass spectrometry with various soft ionization technologies, such as electrospray ionization, atmospheric pressure chemical ionization and the like, and is suitable for quick and online analysis of organic samples. However, the mass spectrum needs to work in a high vacuum environment, a liquid sample is difficult to directly enter a mass spectrum cavity for ionization and analysis, the VOCs to be detected in the liquid sample are usually extracted by means of headspace, extraction and the like, and then ionization and detection are performed, but the pretreatment method is long in time consumption; electrospray ionization can directly ionize an object to be detected in a liquid sample, and gas-phase ions are formed through desolvation and enter mass spectrometry for analysis, but the detection sensitivity of direct electrospray ionization on trace VOCs in the liquid sample is not high due to the limitation of the concentration of the object to be detected in the liquid sample.
Therefore, the invention designs an enrichment sampling and ionization device for volatile organic compounds in a liquid sample, which adopts a tubular membrane enrichment and venturi sampling technology to carry out direct online extraction, enrichment sampling, solvent redissolution desorption and sufficient atomization on VOCs in the liquid sample, and then the VOCs are subjected to high-efficiency ionization by an atmospheric pressure soft ionization source to enter a mass spectrum to realize high-flux, rapid and online analysis.
Disclosure of Invention
The invention aims to provide an enrichment sampling and ionization device for volatile organic compounds in a liquid sample, which utilizes the technologies of tubular membrane enrichment, Venturi sampling and atmospheric pressure soft ionization to realize high-flux, quick and online detection of VOCs in the liquid sample without sample pretreatment. In order to achieve the purpose, the invention adopts the technical scheme that:
an enrichment sampling and ionization device for volatile organic compounds in a liquid sample, comprising: the device comprises a Venturi tube, a membrane enrichment sampling tube and an atmospheric pressure ionization source;
the Venturi tube comprises a gas transmission tube, a contraction tube, a throat tube and an expansion tube which are coaxially arranged in sequence; the inner diameter of the throat pipe is smaller than that of the gas transmission pipe; the inlet end of the gas delivery pipe is connected with an external high-pressure carrier gas source;
the membrane enrichment sampling pipe is a tubular membrane and penetrates through the liquid sampling pipe; a through hole is arranged on the outer wall surface of the throat of the Venturi tube, the outlet end of the membrane enrichment sampling tube is hermetically connected with the through hole, and the inlet end of the membrane enrichment sampling tube extends into the position below the liquid level of the spray solvent in the spray solvent storage tank;
a mass spectrum sample introduction Skimmer electrode is arranged at the rear end of the outlet of the expansion pipe, and the middle part of the mass spectrum sample introduction Skimmer electrode is provided with a through hole; an included angle theta between the axis of the Venturi tube and the axis of the mass spectrum sample introduction Skimmer electrode through hole is set to be 0-90 degrees; the ionization region of an atmospheric pressure ionization source is arranged in a venturi tube) and the region between the Skimmer electrodes for mass spectrum sampling.
The membrane enrichment sampling pipe and the liquid sampling pipe are coaxially arranged, or the membrane enrichment sampling pipe is spirally arranged in the liquid sampling pipe.
Two ends of the liquid sample inlet pipe are respectively provided with a liquid sample inlet and a liquid sample outlet; the liquid sample to be detected enters the liquid sample inlet pipe from the liquid sample inlet and flows through the outer surface of the membrane enrichment sampling pipe, and then generated waste liquid is discharged from the liquid sample outlet.
The axial section of the inner surface of the contraction pipe is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the contraction pipe is gradually reduced from the gas transmission pipe to the throat pipe;
the axial section of the inner surface of the expansion pipe is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the expansion pipe gradually increases from the throat pipe to the outlet end.
The air pressure of the high-pressure carrier gas source is 0.1-20 MPa.
The atmospheric pressure ionization source is an electrospray ionization source, an atmospheric pressure chemical ionization source or an atmospheric pressure photoionization source; the high-pressure carrier gas generates sample spray at the outlet end of the expansion pipe after passing through the Venturi tube, the sample spray generates sample ions after being ionized by an atmospheric pressure ionization source, and the sample ions enter a mass spectrometer at the rear end through a through hole in the middle of a mass spectrum sample introduction Skimmer electrode) for detection.
The membrane enrichment sampling tube is a tubular membrane capable of adsorbing volatile organic compounds, and the material of the membrane enrichment sampling tube comprises but is not limited to polydimethylsiloxane, polyurethane, polydimethylsiloxane-polycarbonate copolymer and the like;
the spraying solvent is used for carrying the volatile organic compound sample enriched by the membrane enrichment sampling tube, and comprises but is not limited to one or a mixed solution of more than two of solvents such as water, methanol or acetonitrile.
The enrichment sampling and ionization device provided by the invention adopts the tubular membrane to perform online extraction and enrichment on VOCs in the liquid sample flowing through the outer surface of the membrane, and simultaneously, the spray solvent is introduced into the inner surface of the tubular membrane to accelerate the analysis and desorption of the VOCs. The venturi atomization tube designed based on the venturi effect can fully atomize a spray solvent carrying VOCs components to be detected in a liquid sample, and then the atomized spray solvent enters a rear-end mass spectrum for detection through efficient ionization of an atmospheric pressure soft ionization source, so that high-flux, quick and online analysis of the VOCs in the liquid sample is realized.
Drawings
Fig. 1 is a schematic structural diagram of an enrichment sampling and ionization device for volatile organic compounds in a liquid sample according to the present invention.
FIG. 2 is a schematic structural diagram of an enrichment sampling and ionization device which adopts a coaxial tubular membrane and is provided with an included angle theta of 0 degree between the axis of a Venturi atomizing tube and the axis of a Skimmer electrode for mass spectrum sampling.
FIG. 3 is a schematic structural diagram of an enrichment sampling and ionization device which adopts a spiral tubular membrane and is provided with an included angle theta of 90 degrees between the axis of a Venturi atomizing tube and the axis of a Skimmer electrode for mass spectrum sampling.
Detailed Description
Fig. 1 is a schematic structural diagram of the present invention. The invention relates to an enrichment sampling and ionization device for volatile organic compounds in a liquid sample, which consists of a Venturi tube 1, a membrane enrichment sampling tube 6 and an atmospheric pressure ionization source 8;
the Venturi tube 1 comprises a gas transmission tube 2, a contraction tube 3, a throat tube 4 and an expansion tube 5 which are coaxially arranged in sequence; the inner diameter of the throat pipe 4 is smaller than that of the gas transmission pipe 2; the inlet end of the gas delivery pipe 2 is connected with an external high-pressure carrier gas source 13;
the membrane enrichment sampling tube 6 is a tubular membrane, and the membrane enrichment sampling tube 6 penetrates through the interior of the liquid sampling tube 7; a through hole is arranged on the outer wall surface of the throat 4 of the Venturi tube 1, the outlet end of the membrane enrichment sampling tube 6 is hermetically connected with the through hole, and the inlet end of the membrane enrichment sampling tube 6 extends into a position below the liquid level of a spray solvent 10 in a spray solvent storage tank;
a mass spectrum sample introduction Skimmer electrode 9 is arranged at the rear end of the outlet of the expansion pipe 5, and the middle part of the mass spectrum sample introduction Skimmer electrode 9 is provided with a through hole; an included angle theta between the axis of the Venturi tube 1 and the axis of the through hole of the Skimmer electrode 9 for mass spectrum sampling is 0-90 degrees; the ionization region of the atmospheric pressure ionization source 8 is arranged in the region between the venturi tube 1 and the Skimmer electrode 9 for mass spectrum sampling.
The membrane enrichment sampling pipe 6 and the liquid sampling pipe 7 are coaxially arranged, or the membrane enrichment sampling pipe 6 is spirally arranged inside the liquid sampling pipe 7.
The axial section of the inner surface of the contraction pipe 3 is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the contraction pipe gradually reduces from the gas transmission pipe 2 to the throat pipe 4;
the axial section of the inner surface of the expanding pipe 5 is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the expanding pipe gradually increases from the throat pipe 4 to the outlet end.
When the device is used, a liquid sample enters the liquid sampling pipe 7 from the liquid sample inlet 11, the liquid sample flows through the outer surface of the membrane enrichment sampling pipe 6 in the liquid sampling pipe 7, VOCs in the liquid sample are desorbed on the inner surface of the tubular membrane after membrane extraction and enrichment under the action of concentration gradient, and the generated waste liquid is discharged from the liquid sample outlet 12; meanwhile, spraying solvent 10 is introduced into the inner surface of the membrane enrichment sampling tube 6 to accelerate the desorption and desorption of VOCs. Under the action of an external high-pressure carrier gas source 13, a certain negative pressure is generated at the throat 4 of the venturi atomizing pipe 1, the spraying solvent 10 is driven by the pressure to carry VOCs to be detected into the venturi atomizing pipe 1, and a sample spray 14 of tiny droplets is generated at the rear end of the expansion pipe 5. The sample spray 14 reaches the atmospheric pressure ionization source 8 to obtain high-efficiency soft ionization, finally VOCs ions to be detected are generated, and enter a mass spectrometer 16 at the rear end through a middle through hole of a mass spectrum sampling Skimmer electrode 9 to realize high-flux, rapid and on-line detection. The pressure of the high-pressure carrier gas source 13 is 0.1-20 MPa. The atmospheric pressure ionization source 8 is an electrospray ionization source, an atmospheric pressure chemical ionization source or an atmospheric pressure photoionization source. The membrane enrichment sampling tube 6 is a tubular membrane capable of adsorbing volatile organic compounds, and the material of the membrane enrichment sampling tube includes but is not limited to polydimethylsiloxane, polyurethane, polydimethylsiloxane-polycarbonate copolymer and the like; the spray solvent 10 is used for carrying the volatile organic compound sample enriched by the membrane enrichment sampling tube 6, and includes but is not limited to solvents such as water, methanol, acetonitrile and the like, or a mixed solution of two or more solvents.
Example 1
As shown in fig. 2. The invention relates to an enrichment sampling and ionization device for volatile organic compounds in a liquid sample. The pressure of an external high-pressure carrier gas source connected with the inlet end of the gas delivery pipe is 1 MPa. The membrane enrichment sampling pipe and the liquid sampling pipe are coaxially arranged, and the membrane enrichment sampling pipe is made of polydimethylsiloxane material. The spraying solvent is acetonitrile and is used for carrying the volatile organic compound sample enriched by the membrane enrichment sampling tube. An included angle theta between the axis of the Venturi atomizing pipe and the axis of the Skimmer electrode through hole for mass spectrum sampling is set to be 0 degree, and an electrospray ionization source is adopted as an atmospheric pressure ionization source.
Example 2
As shown in fig. 3. The invention relates to an enrichment sampling and ionization device for volatile organic compounds in a liquid sample. The pressure of an external high-pressure carrier gas source connected with the inlet end of the gas delivery pipe is 2 MPa. The membrane enrichment sampling tube is arranged in a spiral tube shape in the liquid sample injection tube, and is made of polydimethylsiloxane-polycarbonate copolymer. The spraying solvent is a mixed solution of water and methanol in a ratio of 1:1 and is used for carrying the volatile organic compound sample enriched by the membrane enrichment sampling tube. An included angle theta between the axis of the Venturi atomizing pipe and the axis of the mass spectrum sample introduction Skimmer electrode through hole is 90 degrees, and the atmospheric pressure ionization source adopts an atmospheric pressure photoionization source.
The foregoing is merely a preferred embodiment of this invention and all changes and modifications that come within the spirit, construction and principles of the invention are desired to be protected.
Claims (7)
1. An enrichment sampling and ionization device for volatile organic compounds in a liquid sample, comprising: venturi (1), membrane enrichment sampling pipe (6) and atmospheric pressure ionization source (8), its characterized in that:
the Venturi tube (1) comprises a gas transmission tube (2), a contraction tube (3), a throat tube (4) and an expansion tube (5) which are coaxially arranged in sequence; the inner diameter of the throat pipe (4) is smaller than that of the gas transmission pipe (2); the inlet end of the gas delivery pipe (2) is connected with an external high-pressure carrier gas source (13);
the membrane enrichment sampling tube (6) is a tubular membrane, and the membrane enrichment sampling tube (6) penetrates through the interior of the liquid sampling tube (7); a through hole is arranged on the outer wall surface of the throat (4) of the Venturi tube (1), the outlet end of the membrane enrichment sampling tube (6) is hermetically connected with the through hole, and the inlet end of the membrane enrichment sampling tube (6) extends into the position below the liquid level of the spray solvent (10) in the spray solvent storage tank;
a mass spectrum sample introduction Skimmer electrode (9) is arranged at the rear end of the outlet of the expansion pipe (5), and a through hole is formed in the middle of the mass spectrum sample introduction Skimmer electrode (9); an included angle theta between the axis of the Venturi tube (1) and the axis of the through hole of the mass spectrum sample introduction Skimmer electrode (9) is set to be 0-90 degrees; an ionization region of the atmospheric pressure ionization source (8) is arranged in a region between the Venturi tube (1) and the Skimmer electrode (9) for mass spectrum sampling.
2. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
the membrane enrichment sampling pipe (6) and the liquid sampling pipe (7) are coaxially arranged, or the membrane enrichment sampling pipe (6) is spirally arranged in the liquid sampling pipe (7).
3. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
two ends of the liquid sample inlet pipe (7) are respectively provided with a liquid sample inlet (11) and a liquid sample outlet (12); the liquid sample to be measured enters the liquid sample inlet pipe (7) from the liquid sample inlet (11) and flows through the outer surface of the membrane enrichment sampling pipe (6), and then generated waste liquid is discharged from the liquid sample outlet (12).
4. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
the axial section of the inner surface of the contraction pipe (3) is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the contraction pipe gradually reduces from the gas transmission pipe (2) to the throat pipe (4);
the axial section of the inner surface of the expansion pipe (5) is a symmetrical straight line segment or a symmetrical curve segment, and the radial section area of the expansion pipe gradually increases from the throat pipe (4) to the outlet end.
5. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
the air pressure of the high-pressure carrier gas source (13) is 0.1-20 MPa.
6. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
the atmospheric pressure ionization source (8) is an electrospray ionization source, an atmospheric pressure chemical ionization source or an atmospheric pressure photoionization source; high-pressure carrier gas generates sample spray (14) at the outlet end of the expansion pipe (5) after passing through the Venturi pipe (1), the sample spray (14) generates sample ions (15) after being ionized by the atmospheric pressure ionization source (8), and the sample ions (15) enter a mass spectrometer (16) at the rear end through a through hole in the middle of a mass spectrum sample introduction Skimmer electrode (9) for detection.
7. The apparatus for sampling and ionizing volatile organic compounds in a liquid sample according to claim 1, wherein:
the membrane enrichment sampling tube (6) is a tubular membrane capable of adsorbing volatile organic compounds, and is made of polydimethylsiloxane, polyurethane or polydimethylsiloxane-polycarbonate copolymer;
the spray solvent (10) is used for carrying the volatile organic compound sample enriched by the membrane enrichment sampling tube (6), and comprises a mixed solution of one or more than two solvents of water, methanol or acetonitrile.
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| CN201711203622.4A CN109841482B (en) | 2017-11-27 | 2017-11-27 | Enrichment sampling and ionization device for volatile organic compounds in liquid sample |
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| US5412208A (en) * | 1994-01-13 | 1995-05-02 | Mds Health Group Limited | Ion spray with intersecting flow |
| WO2010136887A1 (en) * | 2009-05-27 | 2010-12-02 | Zoltan Takats | System and method for identification of biological tissues |
| CN103529115B (en) * | 2012-07-05 | 2016-12-21 | 中国科学院大连化学物理研究所 | A kind of directly-heated type tubular film for on-line mass spectroscopy is enriched with sampling device |
| CN103794463B (en) * | 2013-11-18 | 2016-07-06 | 韩梅 | A kind of pneumoelectric coupled ion aggregation apparatus |
| CN104867806B (en) * | 2014-02-24 | 2018-05-01 | 岛津分析技术研发（上海）有限公司 | Sample injection method and device for desorption sample |
| CN204028046U (en) * | 2014-09-04 | 2014-12-17 | 吉林市光大分析技术有限责任公司 | Film Concentration Sampling device |
| KR101639573B1 (en) * | 2014-10-07 | 2016-07-14 | 주식회사 부림이엔씨 | The skimmer for the aquarium |
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