CN101206204B - Device for on-line enrichment of minitype flight time mass spectrum sample - Google Patents
Device for on-line enrichment of minitype flight time mass spectrum sample Download PDFInfo
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- CN101206204B CN101206204B CN2006101349477A CN200610134947A CN101206204B CN 101206204 B CN101206204 B CN 101206204B CN 2006101349477 A CN2006101349477 A CN 2006101349477A CN 200610134947 A CN200610134947 A CN 200610134947A CN 101206204 B CN101206204 B CN 101206204B
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Abstract
The invention discloses a membrane sampling device for direct sampling and online enrichment of sample in micro mass spectrum. The device, which adopts nonporous compact dimethyl silicone polymer lamellar membrane, can effectively limit the quantity of gas entering into mass spectrum and can also be used as the intermediate interface between the mass spectrum and the atmosphere. The inside of the device adopts a single-layer ultrathin membrane to complete quick enrichment of sample; moreover, a vacuum difference cavity is arranged behind the membrane and is used to carry out the buffering and storage of enrichment sample; because the cavity is under low vacuum condition, the area of the membrane can be enlarged to enlarge the contact area between the sample and the membrane, thereby increasing enrichment efficiency; a difference port is provided with an electromagnetic valve, therefore, a gas extraction port can be closed off before gas enrichment and gas can enter into a buffering cavity through the membrane for enrichment; after sample analysis is finished, the electromagnetic valve is opened to carry out difference gas extraction, thereby enriched sample is extracted quickly to prevent memory effect.
Description
Technical field
The invention belongs to mass spectrometer, the miniature on-line analysis time of-flight mass spectrometer of volatile organic contaminant example enrichment device in particularly a kind of air, this device in conjunction with processing, enrichment and the mass spectrometer interface various piece of gaseous sample in one.
Background technology
Volatilizable organism and half volatile organic contaminant content in atmospheric environment is very low, but has pathogenic, carcinogenesis mostly, so the organic pollutant monitoring is subjected to paying close attention to widely always.(organism measuring method: EPA 601～612 in the water, toxic organic compound assay method: TO-1 in the surrounding air～TO-17) middle key step is the organic method of measurement that U.S. environment general administration is recommended: sample collecting → pre-service and enrichment → GC/HPLC → mass spectrum.Though this method is very accurate, but the analytic process of chromatogram (many minutes a few minutes to 10) consuming time many, cost is high, can't satisfy present needs to the air continuous monitoring, tediously long in addition off-line analysis process may make some component of sample change, thus impact analysis result's accuracy.Therefore development fast, sample treatment will have very important significance for on-the site analysis in real time.
Sampling system mostly is to adopt pulse valve, kapillary direct injected or multi-stage vacuum difference sample introduction in the present gas detection mass spectrum.But these input modes all can not be realized sample enrichment, and this often surveys the mass signal less than it for the organic pollutant molecule of concentration in the air in the ppb level.The film sample introduction that adopts in the document has been realized sample direct injected and enrichment function, but the film sampling system all adopts film directly to press close to the design of ionized region, this design makes that the vacuum gap of film both sides is big, the gas that sees through film is many, so film must adopt very little area can guarantee vacuum requirement in the mass analyzer, the area of film is little and film thin, so brought very big inconvenience to installation, the little area that contacts with sample of the area of film is little, so the also corresponding reduction of film sample introduction bioaccumulation efficiency.
Vacuum buffer district film direct injected and enriching apparatus have been designed according to above shortcoming the present invention, this method has effectively strengthened the area of film, improved the bioaccumulation efficiency of film, can realize complex sample direct injected on-line preconcentration, sample need not pre-treatment, and enriched sample is extracted out does not rapidly have the memory effect of analysis.The enrichment time of sample in film only has 1 minute, can directly carry out the quick sample analysis.
Summary of the invention
It is good to the purpose of this invention is to provide a kind of maneuverability, can measure the film sampling device of sample direct injected on-line preconcentration in the miniature mass spectrum of organic contaminant in the air fast, with the coupling of miniature time of flight mass analyzer, can realize that concentration in the air is low to moderate the fast detecting of the volatile organic contaminant of 50ppb.
The present invention specifically provides a kind of device for enrichment of minitype flight time mass spectrum sample on-line, it is characterized in that described example enrichment device mainly by sampling section (1), example enrichment part (2), go out sample part (3) formation that is linked in sequence;
Described example enrichment part is made of gas separation membrane (21), vacuum difference cavity (22), gas piping (23), and vacuum difference cavity (22) is provided with gas feed (221), gas vent (222), difference bleeding point (223); Gas separation membrane (21) places vacuum difference cavity gas feed (221) to locate, gas piping (23) places in the vacuum difference cavity (22), the rear end of gas separation membrane (21), and cause vacuum difference cavity gas vent (222) and locate, difference bleeding point (223) is connected to side and takes out valve (224);
The sampler chamber front end of described sampling section (1) is connected to injection port (11), and the side is provided with ebullator bleeding point (12);
Describedly go out sample part (3) and be connected to kapillary (31).
In the device for enrichment of minitype flight time mass spectrum sample on-line of the present invention, described injection port (11) has particle screen pack (111).
In the device for enrichment of minitype flight time mass spectrum sample on-line of the present invention, described gas separation membrane (21) material is chosen as the dimethyl silicone polymer ultrathin membrane, and thickness is 20～100 μ m.
In the device for enrichment of minitype flight time mass spectrum sample on-line of the present invention, described gas separation membrane (21) is supported by stainless steel cloth (24).
In the device for enrichment of minitype flight time mass spectrum sample on-line of the present invention, described device for enrichment of minitype flight time mass spectrum sample on-line places in the well heater (4).
The course of work of device for enrichment of minitype flight time mass spectrum sample on-line of the present invention is that the gaseous sample under the normal pressure directly enters into vacuum difference cavity by gas separation membrane and obtains enrichment after particle filters; Use the prime mechanical pump to obtain black vacuum in this vacuum difference cavity and make the gas separation membrane area increase, bioaccumulation efficiency improves.At vacuum difference cavity side mask the difference bleeding point is arranged, the difference bleeding point leads under the normal condition, and the enriched sample major part that enter in the vacuum difference cavity this moment is taken away.In the time will carrying out sample detection, the instantaneous difference bleeding point of closing, enriched gas enter to accumulate in the vacuum difference cavity and make its pressure raise gradually, and the sample gas after the enrichment carries out ionization through arriving ionized region after the capillary.
Device for enrichment of minitype flight time mass spectrum sample on-line of the present invention adopts the fine and close dimethyl silicone polymer laminar film of atresia as gas separation membrane, can effectively limit entering mass spectral gas flow, simultaneously can be as the intermediary interface of mass spectrum and atmosphere.Adopted the individual layer ultrathin membrane that sample is carried out fast enriching in the device, had a vacuum difference cavity behind the gas separation membrane, this cavity is used for carrying out the buffering and the storage of enriched sample; This cavity is under the low vacuum condition, thus allow to strengthen the area of gas separation membrane, thus adding the contact area of large sample film separated from the gas, bioaccumulation efficiency improves.Difference mouth place is equipped with solenoid valve, closes bleeding point in the time will carrying out the gas enrichment, and gas enters the buffering cavity through gas separation membrane and carries out enrichment; Open electromagnetic valve after sample analysis finishes and carry out difference and bleed, can prevent memory effect to the rapid extraction of the sample after the enrichment; Open the valve on the difference cavity when carrying out next sample analysis, the gas in the difference cavity can be drawn out of in 10 seconds fast, thereby had also guaranteed memory-less effect in the sample analysis process.Device for enrichment of minitype flight time mass spectrum sample on-line of the present invention by the valve switch on the control difference cavity can realize to sample carry out fast, efficiently concentrating, enrichment time only needs 1 minute, because be 50s miniature mass spectrometric analysis time, make the portable minisize time of-flight mass spectrometer can detect in 2 minutes that content is low to moderate the volatile organic contaminant of 50ppb in the air, thereby realized fast detecting, the analysis of the volatile organic contaminant of content 50ppb (benzene series thing, iodomethane etc.) in the air.
Description of drawings
Fig. 1 is the structural representation of device for enrichment of minitype flight time mass spectrum sample on-line;
Fig. 2 is a portable minisize time of-flight mass spectrometer structural representation;
The sample spectrogram that Fig. 3 obtains during for capillary sample inlet;
Fig. 4 is the sample signal that the benzene,toluene,xylene film enrichment of 10ppm obtains;
Fig. 5 film sample introduction the time 10ppm benzene,toluene,xylene at response time and signal intensity synoptic diagram.
Embodiment
As shown in Figure 1, device for enrichment of minitype flight time mass spectrum sample on-line mainly by sampling section (1), example enrichment part (2), go out sample part (3) formation that is linked in sequence; The example enrichment part is made of gas separation membrane (21), vacuum difference cavity (22), gas piping (23), and vacuum difference cavity (22) is provided with gas feed (221), gas vent (222), difference bleeding point (223); Gas separation membrane (21) places vacuum difference cavity gas feed (221) to locate, gas piping (23) places in the vacuum difference cavity (22), the rear end of gas separation membrane (21), and cause vacuum difference cavity gas vent (222) and locate, difference bleeding point (223) is connected to side and takes out valve (224); The sampler chamber front end of sampling section (1) is connected to injection port (11), and injection port (11) has particle screen pack (111), and the sampler chamber side is provided with ebullator bleeding point (12); Go out sample part (3) and be connected to kapillary (31).Sampling section (1), example enrichment part (2), go out between the sample part (3) and seal by the O RunddichtringO.
As shown in Figure 2, device for enrichment of minitype flight time mass spectrum sample on-line and the coupling of minitype flight time mass spectrum instrument have just constituted the portable minisize time of-flight mass spectrometer.
In the design of device for enrichment of minitype flight time mass spectrum sample on-line of the present invention, in order to allow more gas absorption to the surface of gas separation membrane, need to accelerate the circulation of sample gas, add the air circulation pump at the side of sampler chamber gas separation membrane.The air circulation pump that sampler chamber is used is the continuously adjustable micropump of 0-1L/min.For the pollution of the inevitable accelerating gas separation membrane surface of complicated gas componant quickening gas circulation, and the large particulate matter in the filtered air (as sandstone) also can damage gas separation membrane.Adopt the particulate matter of removing in the sample introduction gas as the particle screen pack with common sub-sieve net at air circulation pump front end to come the blanket gas diffusion barrier among the present invention.
The gas separation membrane that the present invention adopts is the thick poly dimethyl silicone rubber membranes of 20～100 μ m.Thereby this film mainly is by the different relative enrichments that realize compound of the infiltration rate of different material molecule in film.The characteristic of this film is: under the pressure differential expulsive force of film both sides gas, thereby in the mixed gas because gas with various molecular shape, size and different solubility infiltration rate generation difference in film in film, the gas that permeability is big obtains enrichment in per-meate side, be difficult for infiltration gas and then obtain enrichment, separate purpose thereby reach gas in the unstripped gas side.For the inorganic molecule (N that accounts for the airborne overwhelming majority
2, O
2Deng) transmitance is very low, for organic contaminant transmitance very good (referring to table 1) then.Compare with traditional transformation absorption, absorption, low-temperature liquefaction technology, gas separation membrane technical equipment of the present invention is simple, energy consumption is low, sample preparation is simple, analysis speed is fast, do not have additional organic solvent (helping portable instrument), and with highly sensitive detecting device (as gas chromatography, mass spectrum etc.) coupling, can realize on-the site analysis and process monitoring.
(the cm sec.cm of the infiltration rate unit of table 1. gas
2CmHg)
The thickness of dimethyl silicone polymer enrichment film has only 20～100um, intensity difference, cracky, the time standby O type circle that vacuum is cut off is pushed down gas separation membrane, gas separation membrane is under pressure and must be out of shape so that breaks in the time of sample introduction, and the present invention has adopted stainless aperture plate to do circular supporter in design.For the feasible sample gas desorb fast that is adsorbed in the gas separation membrane, at whole device skin heating arrangement is arranged, the control temperature remains on about 50～80 degrees centigrade, can improve the analysis speed of sample like this.And the heating can effectively prevent the absorption of sample at wall, reduced memory effect.As vacuum interface, must keep the vacuum tightness in the time of flight mass analyzer simultaneously, this can regulate the air inflow of sample by the area of gas separation membrane, according to the convenience of desired vacuum tightness of vacuum UV lamp ionization chamber and film processing, the membrane area that can adopt is 25～80mm in design
2, the membrane area that adopts among the design is 80mm
2, this area is obviously greater than the 12.6mm that adopts in the document
2And 7mm
2
The gas that obtains from the gas separation membrane enrichment enters into the high vacuum environment at ionization chamber place under atmospheric pressure, there is supersonic jet in gas, if the gas that enters is not used restraint, it will be diffused in whole ionization chamber space rapidly so, thereby cause the dilution of sample gas.In order effectively to prevent, to have adopted the film rear end to add internal diameter 0.2～1mm kapillary 6 in the design and directly sample has been incorporated into ionized region and carries out ionization by the sample gas of enrichment diffusion.
The vacuum system of portable minisize time of-flight mass spectrometer adopts the molecular pump of a 110L/s to keep, and vacuum tightness maintains 1 * 10
-5Torr, the forepump of molecular pump are the mechanical pump of 4L/s, utilize threeway to tell a bleeding point from forepump and are directly used in vacuum difference cavity.
Sample is sucked by the sample ebullator, directly be adsorbed on the film, sample molecule spreads in 50～80 degrees centigrade gas separation membrane, other one side at gas separation membrane adds thermal desorption then, organic contaminant is because rate of diffusion obtains relatively rich collection soon, sample enters into ionization chamber through internal diameter 0.2～1mm kapillary then, ion vertically enters the pulse accelerating electrode of time of flight mass analyzer, under the impulse electric field effect, all ions have all obtained identical energy, in flight cavity, it is fast that the ion that quality is little flies, wanting that the ion that quality is big flies relatively is slow, after the ion mirror reflection, arrives detector.The little ion of quality arrives detector earlier, arrives detector behind the big ion of quality, from detector simulating signal is received on the high-speed data acquisition card, obtains the composition and the content of pollutant through Data Management Analysis.
The sample that adopts in the experiment is the benzene of 10ppm, and the hybrid standard sample of toluene and dimethylbenzene adopts spectrogram that direct capillary sample inlet obtains as shown in Figure 3, weak output signal.When adopting the film sample introduction, closed difference bleeding point process film enrichment time 1 minute, 50 seconds analysis times of minitype flight time mass spectrum instrument, the signal that obtains is compared bioaccumulation efficiency and has been reached 500 times as shown in Figure 4 with the kapillary direct injected, be that 3 detections that can draw benzene are limited to 25ppb with signal to noise ratio (S/N ratio).0.5ppm, 10ppm detectability that the employing monofilm electron impact ionization that this detectability also obviously is better than reporting in the document obtains.Practice shows that this device for the volatile organic pollutant enrichment fast and effectively.And the spectrogram contrast that kapillary direct injected and film sample introduction obtain can see significantly that the film sample introduction has effectively been eliminated the assorted peak of water vapor and nitrogen.
The response time of sample in film is unusual important parameters for express-analysis, sees Fig. 5.The benzene,toluene,xylene signal intensity rise time is approximately 60 seconds (the so-called rise time is that signal intensity was 10～90% o'clock needed time), and signal intensity returned to the background state in 10 seconds after the valve open that side is taken out, and did not have memory effect to exist.
Claims (5)
1. device for enrichment of minitype flight time mass spectrum sample on-line, it is characterized in that described example enrichment device mainly by sampling section (1), example enrichment part (2), go out sample part (3) formation that is linked in sequence;
Described example enrichment part is made of gas separation membrane (21), vacuum difference cavity (22), gas piping (23), and vacuum difference cavity (22) is provided with gas feed (221), gas vent (222), difference bleeding point (223); Gas separation membrane (21) places vacuum difference cavity gas feed (221) to locate, gas piping (23) places in the vacuum difference cavity (22), the rear end of gas separation membrane (21), and cause vacuum difference cavity gas vent (222) and locate, difference bleeding point (223) is connected to side and takes out valve (224);
The sampler chamber front end of described sampling section (1) is connected to injection port (11), and the side is provided with ebullator bleeding point (12);
Describedly go out sample part (3) and be connected to kapillary (31).
2. according to the described device for enrichment of minitype flight time mass spectrum sample on-line of claim 1, it is characterized in that: described injection port (11) has particle screen pack (111).
3. according to the described device for enrichment of minitype flight time mass spectrum sample on-line of claim 1, it is characterized in that: described gas separation membrane (21) material is the dimethyl silicone polymer ultrathin membrane, and thickness is 20～100 μ m.
4. according to the described device for enrichment of minitype flight time mass spectrum sample on-line of claim 3, it is characterized in that: described gas separation membrane (21) is supported by stainless steel cloth (24).
5. according to the described device for enrichment of minitype flight time mass spectrum sample on-line of one of claim 1-4, it is characterized in that: described device for enrichment of minitype flight time mass spectrum sample on-line places in the well heater (4).
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| CN101206204B true CN101206204B (en) | 2011-08-31 |
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| CN111220694B (en) * | 2018-11-27 | 2021-09-28 | 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 |
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