CN103529115A - Directly-heated type tubular film enriching and sampling device used for online mass spectrum - Google Patents
Directly-heated type tubular film enriching and sampling device used for online mass spectrum Download PDFInfo
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- CN103529115A CN103529115A CN201210234821.2A CN201210234821A CN103529115A CN 103529115 A CN103529115 A CN 103529115A CN 201210234821 A CN201210234821 A CN 201210234821A CN 103529115 A CN103529115 A CN 103529115A
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Abstract
The invention relates to a directly-heated type tubular film enriching and sampling device used for online mass spectrum. The directly-heated type tubular film enriching and sampling device comprises a tubular film, heating wires, a film sampling cavity, a carrier gas, a sampling metal tube and an emergency switching-off solenoid valve. The tubular film is a pore-free compact polydimethylsiloxane tubular film. In the device, the tubular film is adopted to sample and quickly enrich the samples; heating wires are uniformly wound outside the film as a film heating device; a cavity outside the film is connected with mass spectrum by a metal capillary tube to form a negative-pressure state; a gas carrying device is additionally arranged outside the film. When the tubular film is under action of stretching, heating, pressure difference and carrier gas, samples can be quickly enriched through the tubular film. Penetration rate and penetration velocity of samples in the film sampling device are improved.
Description
Technical field
The invention belongs to mass spectrometer, particularly a kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy.This device can be realized the on-line preconcentration of volatile organic contaminant in fluid sample and gaseous sample.Under the effect of stretching, pressure reduction, heating and carrier gas, make analytic sample see through fast film enrichment in film outboard chambers, and by carrier gas, be brought into mass spectrum ionized region and ionize.Improved transmitance and the transmission rates of sample in film sampling device.
Background technology
Volatilizable and although half volatile organic contaminant concentration is low in water and atmosphere, mostly there are pathogenic, teratogenesis and carcinogenesis.So the online detection to organic contaminant in environment gets more and more people's extensive concerning always.After conventional detection method is generally on-the-spot sample collection, in laboratory, the sample collecting is carried out to pre-service and enrichment, re-use gas phase and liquid phase chromatography-mass spectroscopy (GC/LC-MS) analysis.Although the method is highly sensitive, spent time long (general a few minutes are to dozens of minutes).Thereby from sample laboratory treatment sample process, analyze the component impact analysis result that may change.Can not realize the on-line continuous of environmental sample is detected.So the online detection method fast of exploration is extremely important for the analysis of organic pollutant in magnanimity environmental sample.
Film sample introduction utilize pervaporation effect realized mass spectrographic directly, continuous sample introduction, in conjunction with mass spectrum, become one of the most effective technology of online express-analysis volatile organic matter.Meanwhile, due to the selection permeability of semi-permeable diaphragm, the inorganicss such as the nitrogen in water and air, oxygen are more difficult sees through film, and volatility and semi-volatile organic matter are easy to see through film by enrichment.Yet common laminar film sampling device requires and makes membrane area little in order to meet mass spectrum vacuum, and film is very thin easily breaks.Membrane area is little to be contacted with sample less, causes film sampling preconcentration Efficiency Decreasing.Although common tubular film specific surface area is larger, wall thickness is few compared with making greatly sample transmitance, and bioaccumulation efficiency is low, and penetration speed is slower, and the response time of film is longer, and is not suitable as method for quick.
Thus, the present invention has designed a kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy, and sample can see through rapidly film under the effect of film stretching, pressure reduction, heating and carrier gas, to improve transmitance and the transmission rates of sample in film sampling device.
Summary of the invention
The object of the present invention is to provide a kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy.
A kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy, comprise film sample introduction cavity, tubular film is placed in film sample introduction cavity, and tubular film can be stretched vertically after 1-5 length doubly and use, and the tubular film after stretching can effectively reduce tubular film wall thickness.Film two ends connection metal kapillary, as sampling import and outlet, is provided with particle filtering net in sampling import metal capillary, and heater strip is evenly centered around film outside, on the sidewall at film sample introduction cavity near outlet, offers through hole as carrier gas inlet; On sidewall at film sample introduction cavity near sampling import, offer through hole as connecting mass spectrum ionized region interface, interface is provided with the second metal capillary, on the second metal capillary of interface, emergency cut-off magnetic valve is housed.
When sample introduction is fluid sample, sampling import front end arranges peristaltic pump fluid sample is sent in tubular film, from adopting outlet to discharge; When sample introduction is gaseous sample, sampling import front end arranges aspiration pump gaseous sample is sent in tubular film, from adopting outlet to discharge, when sampling analysis sample is less, circulation sample introduction can be set.
Tubular film material is PDMS membrane, and this film is semi-permeable diaphragm, and uses after the 1-5 length doubly that can be stretched vertically.Heater strip is nichrome wire, by wire, connects DC voltage.Carrier gas interface is Capillary restrictor, and carrier gas is: helium (He) or nitrogen (N
2).
Film sample introduction cavity is connected with mass spectrum ionized region by metal capillary, utilizes mass spectrum vacuum condition to maintain film outboard chambers and forms negative pressure state.The sample that sees through film enters mass spectrum ionized region and is ionized under carrier gas effect.
In sampling process, liquid or gaseous sample enter in tubular film from sampling import, have promoted the diffusion of sample molecule in film under the differential pressure action inside and outside film, have improved transmitance and the penetration speed speed of sample.Outside film, the heater strip of uniform winding is tubular film heating, can accelerate sample desorption from film surface, improves sample by the speed of film.Carrier gas is taken the analyte on film outside in mass spectrum ionized region to and is ionized rapidly.Advantage of the present invention:
Tubular film is stretched vertically after 1-5 length doubly and used, effectively reduced tubular film wall thickness.And utilizing mass spectrum vacuum condition to make tubular film outboard chambers form condition of negative pressure, in film, the pressure reduction in outside has been accelerated the diffusion of sample molecule in film, has improved transmitance and the transmission rates of sample.
Uniform winding heater strip outside tubular film, for the heating of tubular film outside surface is accelerated sample from the desorption on film surface.
Carrier gas can purge the sample on tubular film outside surface desorption and be brought into rapidly mass spectrum ionized region and be ionized detection.The effect of stretching, pressure reduction, heating and carrier gas can increase speed and the penetration speed rate that sample sees through film.
Directly-heated type tubular film enrichment sampling device, can realize the continuous on-line detection to environmental sample.
Accompanying drawing explanation
Fig. 1 is a kind of directly-heated type tubular film enrichment sampling device structural representation for on-line mass spectroscopy of the present invention.
Embodiment
In order to improve transmitance and the transmission rates of sample in film sampling device.The invention provides a kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy.
As shown in Figure 1, the present invention is applied to mass spectrometer, and wherein 1 is tubular film, 2 is heater strip, 3 is film sample introduction cavity, and 4 is particle filtering net, and 5 is sampling import, 6 is sampling outlet, 7 is sampling metal capillary, and 8 is film outboard chambers, and 9 is carrier gas inlet, 10 is the second metal capillary the direct mass spectrum ionized region that connects, and 11 is emergency cut-off magnetic valve.Wherein during fluid sample, sampling import 5 front ends arrange peristaltic pump fluid sample are sent in tubular film 1, from sampling outlet 6, discharge; During gaseous sample, sampling import 5 front ends arrange aspiration pump gaseous sample are sent in tubular film 1, from sampling outlet 6, discharge, and when sampling analysis sample is less, circulation sample introduction can be set.
A kind of directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy, comprise airtight film sample introduction cavity, tubular film is placed in film sample introduction cavity, tubular film two ends are connection metal kapillary respectively, metal capillary is external from extending out to film sample cavity in film sample introduction cavity, and the metal capillary at film two ends is respectively as sampling import and outlet.In metal capillary in sampling inflow point, be provided with particle filtering net, heater strip is evenly centered around the outside of tubular film, on sidewall at film sample introduction cavity near outlet, offer through hole as carrier gas inlet, on sidewall at film sample introduction cavity near sampling import, offer through hole as connecting mass spectrum ionized region interface, interface is provided with the second metal capillary, on the second metal capillary of interface, emergency cut-off magnetic valve is housed.
Directly-heated type tubular film enrichment sampling device is connected and can realizes the on-line preconcentration of environmental sample and fast detecting with mass spectrum.In directly-heated type tubular film enrichment sampling device of the present invention, utilize peristaltic pump or aspiration pump that environmental sample is delivered in tubular film, before sampling injection port, add particulate matter in a particle filtering net removal sample and carry out diaphragm device.
The tubular film that the present invention adopts is PDMS membrane, and uses after the 3 times of length that stretched.During detection, analytic sample continues to enter in tubular film by sampling import through particle filtering net filtration.When analytic sample is less, can use circulation sample introduction.Film outboard chambers maintains negative pressure state by mass spectrum vacuum system, and volatility and half volatile organic contaminant see through rapidly film under membrane inside and outside pressure difference effect, in film outboard chambers by enrichment.Outside film under the effect of the heater strip of uniform winding heating and carrier gas, make organism can be rapidly attached from film surface desorption and be brought into also analyzed detection of mass spectrum ionized region ionization by carrier gas.
On between sample introduction metal capillary between directly-heated type tubular film enrichment sampling device and mass spectrum, emergency cut-off magnetic valve is housed.When film rupture, mass spectrum vacuum tightness can change rapidly, and now emergency cut-off magnetic valve can be closed rapidly, to protect mass spectrometer.
Claims (6)
1. for a directly-heated type tubular film enrichment sampling device for on-line mass spectroscopy, it is characterized in that:
Comprise airtight film sample introduction cavity (3), tubular film (1) is placed in film sample introduction cavity (3), tubular film two ends are connection metal kapillary (7) respectively, metal capillary (7) extend out to film sample introduction cavity (3) in film sample introduction cavity (3), and the metal capillary at film two ends (7) is respectively as sampling import (5) and outlet (6);
In the metal capillary (7) of locating in sampling import (5), be provided with particle filtering net (4), heater strip (2) is evenly centered around the outside of tubular film (1), on sidewall at film sample introduction cavity (3) near outlet (6), offer through hole as carrier gas (9) import, on sidewall at film sample introduction cavity (3) near sampling import (5), offer through hole as connecting mass spectrum ionized region interface, interface is provided with the second metal capillary (10), on second metal capillary (10) of interface, emergency cut-off magnetic valve (11) is housed.
2. directly-heated type tubular film enrichment sampling device according to claim 1, is characterized in that:
When sample introduction is fluid sample, described sampling import (5) front end arranges peristaltic pump fluid sample is sent in tubular film (1), from outlet (6), discharges;
When sample introduction is gaseous sample, described sampling import (5) front end arranges aspiration pump gaseous sample is sent in tubular film (1), from outlet (6), discharges.
3. directly-heated type tubular film enrichment sampling device according to claim 1, is characterized in that: described tubular film (1) material is PDMS membrane.
4. directly-heated type tubular film enrichment sampling device according to claim 3, it is characterized in that: PDMS membrane is semi-permeable diaphragm, the tubular film that business is bought can be stretched vertically after 1-5 length doubly and use, and the tubular film after stretching can effectively reduce tubular film wall thickness.
5. directly-heated type tubular film enrichment sampling device according to claim 1, is characterized in that: described heater strip (2) is nichrome wire, and it connects DC voltage by wire.
6. directly-heated type tubular film enrichment sampling device according to claim 1, is characterized in that: described carrier gas (9) import adopts Capillary restrictor, and carrier gas is: helium (He) or nitrogen (N
2).
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| CN201210234821.2A CN103529115B (en) | 2012-07-05 | 2012-07-05 | A kind of directly-heated type tubular film for on-line mass spectroscopy is enriched with sampling device |
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| CN105372357A (en) * | 2015-12-17 | 2016-03-02 | 吕梁学院 | Ionization, adsorption and enrichment device |
| CN105590827A (en) * | 2014-11-13 | 2016-05-18 | 中国科学院大连化学物理研究所 | Mass spectrum low-temperature enrichment high-temperature thermal analysis sweeping type membrane sample feeding apparatus and application |
| CN105655225A (en) * | 2014-11-13 | 2016-06-08 | 中国科学院大连化学物理研究所 | Mass spectrum rapid enrichment-thermal analysis membrane sample introduction apparatus and application |
| CN105719934A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Double film sample introduction apparatus |
| CN109841482A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | The Concentration Sampling and ionization device of volatile organic matter in a kind of fluid sample |
| CN109839421A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method quickly detected for the direct mass spectrography of semi-volatile organic matter in liquid |
| CN110144566A (en) * | 2019-06-20 | 2019-08-20 | 高炬 | A kind of physical vapour deposition (PVD) sample heating device |
| CN110169600A (en) * | 2014-03-19 | 2019-08-27 | 菲利普莫里斯生产公司 | Aerosol generates system and manufacturing method |
| CN111199861A (en) * | 2018-11-20 | 2020-05-26 | 中国科学院大连化学物理研究所 | Capillary micro-reaction ionization source |
| CN111220694A (en) * | 2018-11-27 | 2020-06-02 | 中国科学院大连化学物理研究所 | Mass spectrometry device and method for wide concentration range online monitoring |
| CN113607800A (en) * | 2021-07-27 | 2021-11-05 | 中国计量科学研究院 | Rapid mass spectrometry detection device and detection method for detecting rubber content in plant |
| CN114002306A (en) * | 2021-11-12 | 2022-02-01 | 暨南大学 | Membrane sample injection structure for extracting volatile organic compounds in water through bubble enrichment |
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| US11700889B2 (en) | 2014-03-19 | 2023-07-18 | Philip Morris Products S.A. | Aerosol-generating devices incorporating an intertwined wick and heating element |
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| CN105655225B (en) * | 2014-11-13 | 2017-09-15 | 中国科学院大连化学物理研究所 | A kind of film sampling device of mass spectrum fast enriching Thermal desorption and application |
| CN105719934A (en) * | 2014-12-05 | 2016-06-29 | 中国科学院大连化学物理研究所 | Double film sample introduction apparatus |
| CN105181419B (en) * | 2015-10-22 | 2017-11-17 | 中国科学院合肥物质科学研究院 | The online and offline detection means and detection method of volatile organic matter in a kind of ultrasonic atomizatio extraction water body |
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| CN105372357A (en) * | 2015-12-17 | 2016-03-02 | 吕梁学院 | Ionization, adsorption and enrichment device |
| CN105372357B (en) * | 2015-12-17 | 2017-04-05 | 吕梁学院 | A kind of ionization adsorption and enrichment device |
| CN109839421A (en) * | 2017-11-27 | 2019-06-04 | 中国科学院大连化学物理研究所 | The method quickly detected for the direct mass spectrography of semi-volatile organic matter in liquid |
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| CN114002306A (en) * | 2021-11-12 | 2022-02-01 | 暨南大学 | Membrane sample injection structure for extracting volatile organic compounds in water through bubble enrichment |
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