CN107202851A - The sampling system and its method of a kind of head-space sampler - Google Patents
The sampling system and its method of a kind of head-space sampler Download PDFInfo
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- CN107202851A CN107202851A CN201710577845.0A CN201710577845A CN107202851A CN 107202851 A CN107202851 A CN 107202851A CN 201710577845 A CN201710577845 A CN 201710577845A CN 107202851 A CN107202851 A CN 107202851A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/16—Injection
- G01N30/20—Injection using a sampling valve
- G01N2030/201—Injection using a sampling valve multiport valves, i.e. having more than two ports
Abstract
The invention provides a kind of sampling system of head-space sampler and its method, belong to sampling system technical field.It solve in the sampling system of existing head-space sampler sampling probe can not independent temperature, there is sampling and the technical problem such as discriminate against.This sampling system includes sampling module and temperature control modules, and sampling module includes pressure/flow control unit, gas circuit switch control unit and sampling probe unit；Temperature control modules include Sample equilibration temperature conditioning unit, sampling probe temperature conditioning unit, switching valve temperature conditioning unit and sample conveying tube temperature conditioning unit, and aforementioned four temperature conditioning unit can form certain thermograde；The sampling method of the present invention includes the steps such as gradient temperature-controlled setting, without discrimination sampling, sample introduction, blowback.The present invention is integrated with without the continuous head-space sampling that pressurizes, pressurization static-head -space-sampling and pressurized dynamic head-space sampling Three models in one, can according to different analysis demands selection needed for pattern, Sample equilibration, switching valve, sampling probe and transfer tube being capable of independent accurate temperature controllers, effectively elimination sampling discrimination.
Description
Technical field
The invention belongs to sampling system technical field, the sampling system and its method of a kind of head-space sampler are refered in particular to.
Background technology
Headspace analysis techniques, are a kind of quantitative accurate, sensitivity and the high gaseous extraction detection technique of automaticity.Should
Technology does not eliminate the influence to gas chromatographic analysis of sample substrate solvent and nonvolatile element only the successfully and to instrument
Infringement, and enormously simplify the pre-treatment step of sample, saved the time, avoided the detected material during preparation of samples
The loss of matter, is quite suitable for the sample high to matrix complexity and carries out analysis detection.Headspace analysis techniques are simple and practical with its
Advantage in environment measuring, medicine organic residual solvent detection, food, forensic science, petrochemical industry, packaging material, coating
And wine-making industry analysis etc. field be widely used.
Common head-space sampling pattern mainly has static-head -space-sampling, Dynamic headspace sampling (containing purge ＆ trap).It is so-called quiet
State head-space sampling is exactly sample sealing to be stood into a period of time in a vessel, at a certain temperature to reach gas-liquid two-phase flat
Weighing apparatus, then takes gas part to enter gas chromatographic analysis.According to the analysis result of this sub-sampling, so that it may determine in original sample
The content of volatile component.Although Static Headspace analysis sensitivity it is slightly lower, be difficult to analyze higher component, its by
The interference of sample substrate such as water is minimum, instrument relatively simple, volatile samples component will not lose, can continuous sampling analysis, substantially
It can meet to the constant of tested substance, micro-analysis in sample substrate.And Dynamic headspace sampling is directed in closed ml headspace bottle
Continuous carrying stomata of the volatile component through ml headspace bottle top of the gas after inert purge gas, purging that be passed through is passed through adsorbing and trapping
Trap, volatile materials are adsorbed, and treat that all volatile materials are all purged out and the trap suction that is captured completely in ml headspace bottle
It is attached；During sample introduction, collecting trap is heated, adsorbed volatile materials desorption is separated, detected into gas-chromatography.Dynamic headspace
Analysis can all extract volatile component, and be concentrated in collecting trap, and sensitivity is higher, and can analyze higher
Component, but general instrument is complicated, it is expensive.The head space equipment that head space apparatus manufactures numerous at present is produced nearly all is adopted
With single sampling mode.The present invention is integrated with without the continuous head-space sampling that pressurizes, pressurization static-head -space-sampling and pressurized dynamic top
Sky sampling Three models in a head space equipment, can according to different analysis demands selection needed for pattern, it is convenient and swift, greatly save
About instrument configuration.
Current published head space only makes sampling probe obtain certain temperature by the heat transfer of switching valve and pipeline, therefore
Sampling probe head temperature is uncontrollable, when sampling probe penetrate ml headspace bottle sampling moment can occur needle point supercooling/superheating phenomenon, go out
Now sampling is discriminated against, and greatly affected the accuracy of sampling and the reappearance of analysis.Current published head space is not to entering
Sample pin carries out single temperature control.
The content of the invention
It is an object of the invention to provide a kind of Sample equilibration unit, sampling probe unit, switching valve cell, transmission pipe unit energy
Enough independent accurate temperature controllers, effectively eliminate sampling and discriminate against, improve the sampling system and its method of analysis repeatability.
The object of the present invention is achieved like this：
A kind of sampling system of head-space sampler, it is characterised in that：The sampling system includes sampling module and temperature control
Molding block, the sampling module includes pressure/flow control unit, gas circuit switch control unit and sampling probe unit；The temperature
Spending control module includes Sample equilibration temperature conditioning unit, sampling probe temperature conditioning unit, switching valve temperature conditioning unit and sample conveying tube temperature control
Unit, aforementioned four temperature conditioning unit can form thermograde.
In a kind of sampling system of above-mentioned head-space sampler, described pressure/flow control unit includes CPU master controls
Plate, pressure sensor/flow sensor and the proportion magnetic valve for controlling gas flow, pressure sensor/flow sensor will be examined
The pressure/flow signal measured passes to CPU master control borads, and CPU master control borads can be by the pressure/flow signal and CPU master control borads
Interior setting value is compared, and controls proportion magnetic valve to adjust the flow of gas, makes pressure sensor/flow sensor detection
The pressure/flow signal arrived is identical with the setting value in CPU master control borads.Cpu motherboard, pressure/flow sensor and ratio electricity
The close loop control circuit formed between magnet valve can be realized to the pressure/flow of gas and is more accurately controlled, and improve this head space
The accuracy of the sampling system of injector.
In a kind of sampling system of above-mentioned head-space sampler, described gas circuit switch control unit include switching valve,
First magnetic valve and the second magnetic valve, are controlled, respectively by the time series to switching valve, the first magnetic valve and the second magnetic valve
Realize that head-space sampling, sample introduction, blowback are cleaned.Above-mentioned the first magnetic valve and the second magnetic valve is two-bit triplet magnetic valve.
In a kind of sampling system of above-mentioned head-space sampler, described sampling probe unit includes sampling probe, push rod, taken off
Needle spring and ml headspace bottle, the push rod can promote ml headspace bottle sampling probe is stretched into ml headspace bottle, and the run-bake-needle fault spring is set in
The outside of the sampling probe, when the push rod thrust disappears after the completion of sampling, the run-bake-needle fault spring can restoring force work
Depart from sampling probe and ml headspace bottle under.
In a kind of sampling system of above-mentioned head-space sampler, described sampling probe temperature conditioning unit, Sample equilibration temperature control
Unit and switching valve temperature conditioning unit are heated by heating rod.
In a kind of sampling system of above-mentioned head-space sampler, described sample conveying tube temperature conditioning unit is passed including sample
Defeated pipe, the heater strip and insulating being wrapped on the outside of sample conveying tube.
A kind of sampling method of the sampling system of above-mentioned head-space sampler comprises the following steps：
A, gradient temperature-controlled are set：Corresponding Sample equilibration temperature is determined according to the difference of sample, Sample equilibration temperature control is adjusted
Unit makes the temperature of sample be above-mentioned Sample equilibration temperature；Adjust sampling probe temperature conditioning unit, make the tip temperature of sampling probe with
Above-mentioned Sample equilibration temperature is consistent；Switching valve temperature conditioning unit is adjusted, the temperature of switching valve is slightly above the temperature of sampling probe；Adjust
Sample conveying tube temperature conditioning unit is saved, the temperature of sample conveying tube is slightly above the temperature of switching valve；I.e. in Sample equilibration, sampling
The thermograde of the suitable sample system is formd between pin, switching valve and sample conveying tube.
B, without discrimination sampling：Now switching valve is closed, by setting pressure/flow control unit parameter to be passed through
Purge gass, by the first magnetic valve, the ml headspace bottle being under thermodynamic equilibrium state, purge gass band are entered from the interior pin of sampling probe
The first interface that sample gas enters switching valve from the outer pin of sampling probe, out enters trapping from the second interface of switching valve
Trap, remaining purge gass pass sequentially through the 5th interface of switching valve, the 6th interface of switching valve, the 7th interface of switching valve, switching
8th interface of valve, eventually passes the emptying of the second magnetic valve；Draw simultaneously by the pressure/flow control module on gas chromatograph
Gas chromatograph injection port is entered after 3rd interface of the 4th interface and switching valve of the carrier gas entered by switching valve, it is ensured that gas
Chromatography carrier gas is passed through.
C, sample introduction state：After above-mentioned sampling process is completed, switching valve is switched to the state of opening, while to collecting trap
Progress, which is brought rapidly up heating, makes sample desorption, and gas chromatograph carrier gas is from the 4th interface of switching valve, by the 5th of switching valve the
Interface is purged into collecting trap, is entered with sample from the second interface of switching valve, is come out from the 3rd interface of switching valve,
And enter gas chromatograph injection port along pipeline, carry out the separation analysis of gas chromatograph sample.
D, blowback state：After above-mentioned sample introduction state is completed, switching valve is switched into closed mode, collecting trap is still in adding
Hot temperature constant state；Switch the state of the first magnetic valve and the second magnetic valve so that pressure/flow controls purge gass from the first electromagnetism
Valve, by pipeline, sequentially passes through the 8th interface of switching valve, the 7th interface of switching valve, the 6th interface of switching valve, switching valve
The 5th interface, collecting trap, the second interface of switching valve, the first interface of switching valve reaches sampling probe, purging gone out from outer faller gill
Gas, completes the blowback to collecting trap, switching valve, pipeline, the first magnetic valve and the second magnetic valve and cleans；After the completion of blowback, it will catch
Collection trap cooling returns to normal temperature state.
Further, the step B is included without continuous head-space sampling state of pressurizeing：Now switching valve is closed,
The interior pin and outer pin of sampling probe are pierced into ml headspace bottle simultaneously, by setting pressure/flow control unit parameter to be passed through purge gass, warp
The first magnetic valve is crossed, the ml headspace bottle being under thermodynamic equilibrium state is entered from the interior pin of sampling probe, purge gass are with sample gas
Body enters the first interface of switching valve from the outer pin of sampling probe, comes out and enters for adsorption sample from the second interface of switching valve
Collecting trap, remaining purge gass pass sequentially through the 5th interface of switching valve, the 6th interface of switching valve, the 7th interface of switching valve,
8th interface of switching valve, eventually passes the emptying of the second magnetic valve, constitutes one without the continuous head-space sampling route that pressurizes, while through
The 3rd of fourth interface and switching valve of the carrier gas that the pressure/flow control module crossed on gas chromatograph is introduced Jing Guo switching valve
Gas chromatograph injection port is entered after interface, it is ensured that gas chromatograph carrier gas is passed through.
Further, the step B includes pressurization static-head -space-sampling state：Now switching valve is closed, and is taken
The interior pin of sample pin is penetrated in bottle, and outer pin is in outside bottle, by setting pressure/flow control module parameter to be passed through purge gass, warp
Cross the first magnetic valve and enter ml headspace bottle from the interior pin of sampling probe, pressure, pressure can be applied to ml headspace bottle by being continually fed into purge gass
Reach after certain value, stopping is passed through purge gass, while the outer pin of sampling probe enters ml headspace bottle, sample gas is in the presence of pressure differential
Enter the first interface of switching valve from outer pin, come out from the second interface of switching valve, into collecting trap, remaining purge gass are led to successively
The 5th interface, the 6th interface of switching valve, the 7th interface of switching valve, the 8th interface of switching valve of switching valve are crossed, is most passed through afterwards
The emptying of the second magnetic valve is crossed, a pressurization static-head -space-sampling route is constituted；After the completion of sampling, the thrust of pin-lift arrangement is removed,
Under the run-bake-needle fault spring effect of sampling probe unit, ml headspace bottle is unloaded, while controlling mould by the pressure/flow on gas chromatograph
Gas chromatograph injection port is entered after 3rd interface of the 4th interface and switching valve of the carrier gas that block is introduced by switching valve, is protected
Demonstrate,prove being passed through for gas chromatograph carrier gas.
Alternatively, above-mentioned collecting trap can also be replaced with quantitative loop, if during quantitative loop, then can omit
It is brought rapidly up heating this link, state that the temperature remains within the normal range, because the special tectonic of quantitative loop, in normal temperature in step C sample introduction states
The desorption of sample can be achieved under state, it is corresponding, after quantitative loop, keep heating permanent at the position in below step
Temperature and cooling etc. link can also adaptability omission.
Further, the step B includes pressurized dynamic head-space sampling state：After a static-head -space-sampling is completed,
Sample bottle after sampling is continued to implement static sampling of pressurizeing next time, every time the purge gass of static sampling with sample gas from
The outer pin of sampling probe enters the first interface of switching valve, and the trapping entered for adsorption sample is come out from the second interface of switching valve
Trap, remaining purge gass pass sequentially through the 5th interface of switching valve, the 6th interface of switching valve, the 7th interface of switching valve, switching
8th interface of valve, eventually passes the emptying of the second magnetic valve, i.e. the sample of multiplicating static state pressurization sampling, which is adsorbed on, catches
Collect trap, while fourth interface (4) of the carrier gas introduced by the pressure/flow control module on gas chromatograph Jing Guo switching valve
With after the 3rd interface (3) of switching valve gas chromatograph injection port is entered, it is ensured that gas chromatograph carrier gas is passed through, according to needing
Ask repeatedly, realize that repeatedly pressurization static-head -space-sampling is pressurized dynamic head-space sampling.
The present invention is prominent and beneficial compared with prior art to be had the technical effect that：
1st, present invention employs magnetic valve and the gas circuit switch unit and high-precision pressure/flow controlling unit of switching valve,
It can be achieved without the integrated with pressing of the continuous head-space sampling that pressurizes, pressurization static-head -space-sampling and pressurized dynamic head-space sampling Three models
Switching is needed, and gas-way inverse blow function can also be cleaned to gas piping, valve and collecting trap, it is ensured that and each sample introduction is without dirt
Dye, it is accurate repeatable.
2nd, independent temperature is carried out to Sample equilibration, sampling probe, switching valve and sample conveying tube while of the invention, can root
The temperature of modules is set according to analysis demand, and gradient temperature-controlled is formed between four modules；Usual Sample equilibration temperature can
Determined according to the specific sample of analysis, by adjusting sampling probe temperature so that sampling probe tip temperature and Sample equilibration temperature phase
Together, be thus avoided that the sampling probe of supercooling/overheat during sampling penetrate in sample bottle destroy bottle in original thermodynamical equilibrium and
Caused sampling is discriminated against.
3rd, the present invention sets switching valve and the temperature of sample conveying tube, makes the temperature of four temperature control modules by Sample equilibration
Temperature, sampling probe temperature, switching valve temperature, sample conveying tube temperature are incremented by successively, both eliminate sampling and discriminate against, also ensure that sample
Product component continues module after entering will not produce condensation.
Brief description of the drawings
Fig. 1 is the structural representation of the sampling probe unit of the present invention.
Fig. 2 is the gas flow chart of the sampling module of the present invention.
Fig. 3 is the overall structure diagram of the present invention.
Fig. 4 is the logic diagram of the pressure/flow control unit of the present invention.
Embodiment
With specific embodiment, the invention will be further described below in conjunction with the accompanying drawings, referring to Fig. 1-4：
A kind of sampling system of head-space sampler include sampling module and temperature control modules, sampling module include pressure/
Flow controlling unit, gas circuit switch control unit and sampling probe unit；Temperature control modules include Sample equilibration temperature conditioning unit, taken
Sample pin temperature conditioning unit, switching valve temperature conditioning unit and sample conveying tube temperature conditioning unit, aforementioned four temperature conditioning unit can form temperature
Gradient.The present invention makes four temperature control moulds by setting Sample equilibration, sampling probe 14, switching valve and the temperature of sample conveying tube
The temperature of block is incremented by successively by Sample equilibration temperature, the temperature of sampling probe 14, switching valve temperature, sample conveying tube temperature, both eliminates
Sampling is discriminated against, and also ensures that sample component continues module and will not produce condensation after entering.
In a kind of sampling system of above-mentioned head-space sampler, pressure/flow control unit includes CPU master control borads, pressure
The proportion magnetic valve of force snesor/flow sensor and control gas flow, pressure sensor/flow sensor will be detected
Pressure/flow signal passes to CPU master control borads, and CPU master control borads can be by the pressure/flow signal and setting in CPU master control borads
Definite value is compared, and controls the flow of proportion magnetic valve adjustment gas, the pressure for detecting pressure sensor/flow sensor
Power/flow signal is identical with the setting value in CPU master control borads.Cpu motherboard, pressure/flow sensor and proportion magnetic valve it
Between the close loop control circuit that is formed the pressure/flow of gas can be realized and more be accurately controlled, improve this head-space sampler
Sampling system accuracy.
In a kind of sampling system of above-mentioned head-space sampler, gas circuit switch control unit includes switching valve 15, first
The magnetic valve 11 of magnetic valve 10 and second, passes through the time series control to the magnetic valve 10 of switching valve 15 and first and the second magnetic valve 11
System, realizes that head-space sampling, sample introduction, blowback are cleaned respectively.Above-mentioned the first magnetic valve 10 and the second magnetic valve 11 is two three
Three-way electromagnetic valve, switching valve 15 is eight ways valve.
In a kind of sampling system of above-mentioned head-space sampler, sampling probe unit includes sampling probe 14, push rod 12, run-bake-needle fault
Spring 13 and ml headspace bottle, push rod 12 can promote ml headspace bottle sampling probe 14 is stretched into ml headspace bottle, and run-bake-needle fault spring 13, which is set in, to be taken
The outside of sample pin 14, when the thrust of push rod 12 disappears after the completion of sampling, run-bake-needle fault spring 13 can make to take in the presence of restoring force
Sample pin 14 and ml headspace bottle depart from.
In a kind of sampling system of above-mentioned head-space sampler, the first interface 1 of switching valve 15 is connected with the first threeway
Joint 16 a, interface of first three-way connection 16 also respectively with the magnetic valve 10 of sampling probe 14 and first is connected, the first electromagnetism
Another interface of valve 10 is connected with the second three-way connection 17, and the second three-way connection 17 also connects with the 8th of switching valve 15 the respectively
One orifice of the magnetic valve 11 of mouth 8 and second, the 6th interface 6 of switching valve 15 and the 7th interface 7 pass through external conduit
Connection, is connected with collecting trap 9 or quantitative loop, the 3rd interface of switching valve between the 5th interface 5 and second interface 2 of switching valve
3 and the 4th are connected with gas chromatograph between interface 4.
In a kind of sampling system of above-mentioned head-space sampler, sampling probe temperature conditioning unit, Sample equilibration temperature conditioning unit and
Switching valve temperature conditioning unit is heated by heating rod.
In a kind of sampling system of above-mentioned head-space sampler, sample conveying tube temperature conditioning unit include sample conveying tube,
It is wrapped in heater strip and insulating on the outside of sample conveying tube.
A kind of sampling method of the sampling system of above-mentioned head-space sampler comprises the following steps：
A, gradient temperature-controlled are set：Corresponding Sample equilibration temperature is determined according to the difference of sample, Sample equilibration temperature control is adjusted
Unit makes the temperature of sample be above-mentioned Sample equilibration temperature；Sampling probe temperature conditioning unit is adjusted, makes the tip temperature of sampling probe 14
It is consistent with above-mentioned Sample equilibration temperature；Switching valve temperature conditioning unit is adjusted, the temperature of switching valve is slightly above the temperature of sampling probe 14
Degree；Sample conveying tube temperature conditioning unit is adjusted, the temperature of sample conveying tube is slightly above the temperature of switching valve；I.e. Sample equilibration,
The thermograde of the suitable sample system is formd between sampling probe 14, switching valve and sample conveying tube.The step is flat to sample
Weighing apparatus, sampling probe 14, switching valve and sample conveying tube carry out independent temperature, and the temperature of modules can be set according to analysis demand
Degree, and form gradient temperature-controlled between four modules；Usual Sample equilibration temperature can be determined according to the specific sample of analysis, be passed through
Adjust the temperature of sampling probe 14 so that the tip temperature of sampling probe 14 is identical with Sample equilibration temperature, mistake when being thus avoided that sampling
The sampling probe 14 of cold/overheat, which penetrates in sample bottle to destroy to sample caused by original thermodynamical equilibrium in bottle, to be discriminated against.
B, without discrimination sampling：Now switching valve 15 is closed, by setting pressure/flow control unit parameter to lead to
Enter purge gass, by the first magnetic valve 10 and the first three-way connection 16, enter from the interior pin of sampling probe 14 and be in thermodynamical equilibrium
Ml headspace bottle under state, purge gass enter the first interface 1 of switching valve 15 with sample gas from the outer pin of sampling probe 14, from cutting
The second interface 2 for changing valve 15 out enters collecting trap 9, and remaining purge gass pass sequentially through the 5th interface 5 of switching valve 15, switching valve
15 the 6th interface 6, the 7th interface 7 of switching valve 15, the 8th interface 8 of switching valve 15, the second three-way connection 17, are eventually passed
Second magnetic valve 11 is vented；Switching valve is passed through in the carrier gas introduced simultaneously by the pressure/flow control module on gas chromatograph
Gas chromatograph injection port is entered after 15 the 4th interface 4 and the 3rd interface 3 of switching valve 15, it is ensured that gas chromatograph is carried
Gas is passed through.
C, sample introduction state：After above-mentioned sampling process is completed, switching valve 15 is switched to the state of opening, while to trapping
Trap 9 carries out being brought rapidly up heating making sample desorption, and gas chromatograph carrier gas is from the 4th interface 4 of switching valve 15, by switching valve
15 the 5th interface 5 is purged into collecting trap 9, is entered with sample from the second interface 2 of switching valve 15, from switching valve 15
The 3rd interface 3 come out, and enter gas chromatograph injection port along pipeline, carry out the separation analysis of gas chromatograph sample.
D, blowback state：After above-mentioned sample introduction state is completed, switching valve 15 is switched into closed mode, collecting trap 9 is still located
In heated constant temperature state；Switch the state of the first magnetic valve 10 and the second magnetic valve 11 so that pressure/flow control purge gass from
First magnetic valve 10 enters, by pipeline, sequentially passes through the second three-way connection 17, the 8th interface 8 of switching valve 15, switching valve 15
The 7th interface 7, the 6th interface 6 of switching valve 15, the 5th interface 5 of switching valve 15, collecting trap 9, the second of switching valve 15 connect
Mouthfuls 2, the first interface 1 of switching valve 15 reaches sampling probe 14, and purge gass are gone out from outer faller gill, complete to collecting trap 9, switching valve 15,
The blowback of pipeline, the first magnetic valve 10 and the second magnetic valve 11 is cleaned, after the completion of blowback, and the cooling of collecting trap 9 is returned into normal temperature
State.
Further, step B is included without continuous head-space sampling state of pressurizeing：Now switching valve 15 is closed, and is taken
The interior pin and outer pin of sample pin 14 are pierced into ml headspace bottle simultaneously, by setting pressure/flow control unit parameter to be passed through purge gass, warp
The first magnetic valve 10 and the first three-way connection 16 are crossed, the head space being under thermodynamic equilibrium state is entered from the interior pin of sampling probe 14
Bottle, purge gass enter the first interface 1 of switching valve 15 with sample gas from the outer pin of sampling probe 14, from the second of switching valve 15
Interface 2 comes out the collecting trap 9 entered for adsorption sample, and remaining purge gass pass sequentially through the 5th interface 5 of switching valve 15, switching
The 6th interface 6, the 7th interface 7 of switching valve 15, the 8th interface 8 of switching valve 15, the second three-way connection 17 of valve 15, are most passed through afterwards
The second magnetic valve 11 is crossed to be vented, composition one without the continuous head-space sampling route of pressurizeing, while by the pressure on gas chromatograph/
Gas is entered after 3rd interface 3 of the 4th interface 4 and switching valve 15 of the carrier gas that flow-control module is introduced by switching valve 15
Chromatography injection port, it is ensured that gas chromatograph carrier gas is passed through.
Further, step B includes pressurization static-head -space-sampling state：Now switching valve 15 is closed, sampling
The interior pin of pin 14 is penetrated in bottle, and outer pin is in outside bottle, by setting pressure/flow control module parameter to be passed through purge gass, warp
The first magnetic valve 10 and the first three-way connection 16 are crossed, enters ml headspace bottle from the interior pin of sampling probe 14, being continually fed into purge gass can be with
Apply pressure to ml headspace bottle, pressure is reached after certain value, and the outer pin of sampling probe 14 enters ml headspace bottle, work of the sample gas in pressure differential
Enter the first interface 1 of switching valve 15 from outer pin under, out enter collecting trap 9 from the second interface 2 of switching valve 15, residue is blown
Scavenging passes sequentially through the 5th interface 5 of switching valve 15, the 6th interface 6 of switching valve 15, the 7th interface 7 of switching valve 15, switching
The 8th interface 8, the second three-way connection 17 of valve 15, eventually pass the second magnetic valve 11 and are vented, and constitute a pressurization Static Headspace
Sample path；After the completion of sampling, the thrust of the device of push rod 12 is removed, in the case where the run-bake-needle fault spring 13 of sampling probe unit is acted on, unloading
Ml headspace bottle, while the carrier gas introduced by the pressure/flow control module on gas chromatograph the 4th connecing Jing Guo switching valve 15
Mouthfuls 4 and switching valve 15 the 3rd interface 3 after enter gas chromatograph injection port, it is ensured that gas chromatograph carrier gas is passed through.Make
For another scheme, above-mentioned collecting trap 9 can also be replaced with quantitative loop, if during quantitative loop, then can omit step C sample introductions
It is brought rapidly up heating this link, state that the temperature remains within the normal range, because the special tectonic of quantitative loop, under normal temperature state in state
The desorption of sample is realized, it is corresponding, after quantitative loop, heated constant temperature and cooling are kept to the position in below step
Etc. link can also adaptability omission.
Further, step B includes pressurized dynamic head-space sampling state：After a static-head -space-sampling is completed, it will take
Sample bottle after sample continues to implement static sampling of pressurizeing next time, every time the purge gass of static sampling with sample gas from sampling
The outer pin of pin 14 enters the first interface 1 of switching valve 15, comes out and enters for adsorption sample from the second interface 2 of switching valve 15
Collecting trap 9, remaining purge gass pass sequentially through the 5th interface 5, the 6th interface 6 of switching valve 15, switching valve 15 of switching valve 15
7th interface 7, the 8th interface 8 of switching valve 15, the second three-way connection 17, eventually pass the second magnetic valve 11 and are vented, i.e., repeatedly
The sample for repeating static pressurization sampling is adsorbed on collecting trap 9, while controlling mould by the pressure/flow on gas chromatograph
Gas chromatograph is entered after 3rd interface 3 of the 4th interface 4 and switching valve 15 of the carrier gas that block is introduced by switching valve 15 to enter
Sample mouthful, it is ensured that being passed through for gas chromatograph carrier gas, as desired repeatedly, realizes that repeatedly pressurization static-head -space-sampling is pressurization
Dynamic headspace is sampled.
Above-described embodiment is only presently preferred embodiments of the present invention, is not limited the scope of the invention according to this, therefore：It is all according to
The equivalence changes that structure, shape, the principle of the present invention is done, all should be covered by within protection scope of the present invention.
Claims (10)
1. a kind of sampling system of head-space sampler, it is characterised in that：The sampling system includes sampling module and temperature control
Module, the sampling module includes pressure/flow control unit, gas circuit switch control unit and sampling probe unit；The temperature
Control module includes Sample equilibration temperature conditioning unit, sampling probe temperature conditioning unit, switching valve temperature conditioning unit and sample conveying tube temperature control list
Member, aforementioned four temperature conditioning unit can form thermograde.
2. a kind of sampling system of head-space sampler according to claim 1, it is characterised in that：Described pressure/flow
Control unit includes CPU master control borads, pressure sensor/flow sensor and the proportion magnetic valve for controlling gas flow, and pressure is passed
The pressure/flow signal detected is passed to CPU master control borads by sensor/flow sensor, CPU master control borads can by the pressure/
Flow signal is compared with the setting value in CPU master control borads, and controls proportion magnetic valve to adjust the flow of gas, passes pressure
The pressure/flow signal that sensor/flow sensor is detected is identical with the setting value in CPU master control borads.
3. a kind of sampling system of head-space sampler according to claim 1, it is characterised in that：Described gas circuit switching control
Unit processed includes switching valve (15), the first magnetic valve (10) and the second magnetic valve (11), by switching valve (15) and the first electricity
The time series control of magnet valve (10) and the second magnetic valve (11), realizes that head-space sampling, sample introduction, blowback are cleaned respectively.
4. a kind of sampling system of head-space sampler according to claim 1, it is characterised in that：Described sampling probe unit
Including sampling probe (14), push rod (12), run-bake-needle fault spring (13) and ml headspace bottle, the push rod (12) can promote ml headspace bottle to make sampling
Pin (14) is stretched into ml headspace bottle, and the run-bake-needle fault spring (13) is set in the outside of the sampling probe (14), the institute after the completion of sampling
When stating the disappearance of push rod (12) thrust, the run-bake-needle fault spring (13) can make sampling probe (14) and ml headspace bottle in the presence of restoring force
Depart from.
5. a kind of sampling system of head-space sampler according to claim 1, it is characterised in that：Described sampling probe temperature control
Unit, Sample equilibration temperature conditioning unit and switching valve temperature conditioning unit are heated by heating rod, described sample conveying tube temperature control list
Member includes sample conveying tube, the heater strip and insulating that are wrapped on the outside of sample conveying tube.
6. a kind of sampling method of the sampling system of head-space sampler according to claim 1-5 any one, its feature
It is：The sampling method comprises the following steps：
A, gradient temperature-controlled are set：Corresponding Sample equilibration temperature is determined according to the difference of sample, Sample equilibration temperature conditioning unit is adjusted
It is above-mentioned Sample equilibration temperature to make its temperature；Adjust sampling probe temperature conditioning unit, make the tip temperature of sampling probe (14) with it is above-mentioned
Sample equilibration temperature it is consistent；Switching valve temperature conditioning unit is adjusted, the temperature of switching valve is slightly above the temperature of sampling probe (14)；Adjust
Sample conveying tube temperature conditioning unit is saved, the temperature of sample conveying tube is slightly above the temperature of switching valve；I.e. in Sample equilibration, sampling probe
(14) thermograde of the suitable sample system, is formd between switching valve and sample conveying tube.
B, without discrimination sampling：Switching valve (15) is closed, is blown by setting pressure/flow control unit parameter to be passed through
Scavenging, purge gass pass through the first magnetic valve (10) and the first three-way connection (16), enter from the interior pin of sampling probe (14) in heat
Ml headspace bottle under mechanical balance state, then purge gass enter switching valve (15) from the outer pin of sampling probe (14) with sample gas
First interface (1), then come out from the second interfaces (2) of switching valve (15) and enter the collecting trap for being capable of adsorption sample gas
(9), remaining purge gass pass sequentially through the 5th interface (5), the 6th interface (6) of switching valve (15), switching of switching valve (15)
The 7th interface (7), the 8th interface (8), the second three-way connection (17) of switching valve (15) of valve (15), eventually pass the second electromagnetism
Valve (11) is vented；The carrier gas introduced simultaneously by the pressure/flow control module on gas chromatograph is by switching valve (15)
Gas chromatograph injection port is entered after 4th interface (4) and the 3rd interface (3) of switching valve (15), it is ensured that gas chromatograph is carried
Gas is passed through.
C, sample introduction state：After above-mentioned sampling process is completed, switching valve (15) is switched to the state of opening, while to collecting trap
(9) carry out being brought rapidly up heating desorption sample, gas chromatograph carrier gas is from the 4th interface (4) of switching valve (15), by switching
5th interface (5) of valve (15) enters collecting trap (9) and purged, and enters with sample from the second interface (2) of switching valve (15)
Enter, come out from the 3rd interface (3) of switching valve (15), and enter gas chromatograph injection port along pipeline, carry out gas-chromatography
The separation analysis of instrument sample.
D, blowback state：After above-mentioned sample introduction state is completed, switching valve (15) is switched into closed mode, collecting trap (9) is still located
In heated constant temperature state；Switch the state of the first magnetic valve (10) and the second magnetic valve (11) so that pressure/flow control purging
Gas is from the first magnetic valve (10), by pipeline, sequentially pass through the second three-way connection (17), the 8th interface (8) of switching valve (15),
7th interface (7) of switching valve (15), the 6th interface (6) of switching valve (15), the 5th interface (5) of switching valve (15), trapping
Trap (9), the second interface (2) of switching valve (15), the first interface (1) of switching valve (15) reach sampling probe (14), from outer faller gill
Go out purge gass, complete the blowback to collecting trap (9), switching valve (15), pipeline, the first magnetic valve (10) and the second magnetic valve (11)
Clean；After the completion of blowback, collecting trap (9) cooling is returned into normal temperature state.
7. a kind of sampling method of head-space sampler according to claim 6, it is characterised in that：The step B includes nothing
Pressurize continuous head-space sampling state：Now switching valve (15) is closed, and the interior pin and outer pin of sampling probe (14) are pierced simultaneously
Enter in ml headspace bottle, by setting pressure/flow control unit parameter to be passed through purge gass, by the first magnetic valve (10) and the one or three
Pass joint (16), the ml headspace bottle being under thermodynamic equilibrium state is entered from the interior pin of sampling probe (14), purge gass are with sample
Gas enters the first interface (1) of switching valve (15) from the outer pin of sampling probe (14), goes out from the second interface (2) of switching valve (15)
To enter the collecting trap (9) for adsorption sample, remaining purge gass pass sequentially through the 5th interface (5) of switching valve (15), switching
6th interface (6) of valve (15), the 7th interface (7) of switching valve (15), the 8th interface (8) of switching valve (15), the second threeway
Joint (17), eventually passes the second magnetic valve (11) emptying, composition one is without the continuous head-space sampling route that pressurizes, while by gas
Fourth interface (4) and switching valve of the carrier gas that pressure/flow control module on chromatography is introduced Jing Guo switching valve (15)
(15) after the 3rd interface (3) gas chromatograph injection port is entered, it is ensured that gas chromatograph carrier gas is passed through.
8. a kind of sampling method of head-space sampler according to claim 6, it is characterised in that：The step B includes adding
Press static-head -space-sampling state：Now switching valve (15) is closed, and the interior pin of sampling probe (14) is penetrated in bottle, outer pin
Outside bottle, by setting pressure/flow control module parameter to be passed through purge gass, by the first magnetic valve (10) and the first threeway
Joint (16), enters ml headspace bottle from the interior pin of sampling probe (14), and pressure, pressure can be applied to ml headspace bottle by being continually fed into purge gass
Reach after certain value, stopping is passed through purge gass, while the outer pin of sampling probe (14) enters ml headspace bottle, work of the sample gas in pressure differential
Enter the first interface (1) of switching valve (15) from outer pin under, the second interface (2) of switching valve (15) entersCollecting trap(9),
Remaining purge gass pass sequentially through the 5th interface (5), the 6th interface (6) of switching valve (15), switching valve (15) of switching valve (15)
The 7th interface (7), the 8th interface (8), the second three-way connection (17) of switching valve (15), eventually pass the second magnetic valve (11)
Emptying, constitutes a pressurization static-head -space-sampling route, after the completion of sampling, the thrust of push rod (12) device is removed, in sampling probe
Under run-bake-needle fault spring (13) effect of unit, ml headspace bottle is unloaded, while drawing by the pressure/flow control module on gas chromatograph
Gas-chromatography is entered after 3rd interface (3) of the 4th interface (4) and switching valve (15) of the carrier gas entered by switching valve (15)
Instrument injection port, it is ensured that gas chromatograph carrier gas is passed through.
9. a kind of sampling method of head-space sampler according to claim 8, described collecting trap can also be quantitative loop,
If during quantitative loop, omitting and being brought rapidly up heating this link in step C sample introduction states, while being protected in below step to the position
Hold the omission of being also adapted to property of the link such as heated constant temperature and cooling.
10. a kind of sampling method of head-space sampler according to claim 8, it is characterised in that：The step B includes adding
Press state head-space sampling state：After a static-head -space-sampling is completed, the sample bottle after sampling is continued to implement next time to add
The static sampling of pressure, the purge gass of each static sampling enter switching valve (15) with sample gas from the outer pin of sampling probe (14)
First interface (1), the collecting trap (9) entered for adsorption sample, residue purging are come out from the second interface (2) of switching valve (15)
Gas passes sequentially through the 5th interface (5) of switching valve (15), the 6th interface (6) of switching valve (15), the 7th of switching valve (15) the connect
Mouth (7), the 8th interface (8), the second three-way connection (17) of switching valve (15), eventually pass the second magnetic valve (11) emptying, i.e.,
The sample that static pressurization sampling is repeated several times is adsorbed on collecting trap (9), while by the pressure/flow on gas chromatograph
Enter after 3rd interface (3) of the 4th interface (4) and switching valve (15) of the carrier gas that control module is introduced by switching valve (15)
To gas chromatograph injection port, it is ensured that gas chromatograph carrier gas is passed through；As desired repeatedly, realize that repeatedly pressurization is static
Head-space sampling is pressurized dynamic head-space sampling.
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| CN107702949A (en) * | 2017-08-15 | 2018-02-16 | 杭州臻盛科技有限公司 | Head-space sampling pin and sampling method |
| CN110095324A (en) * | 2019-04-20 | 2019-08-06 | 上海华谊检验检测技术有限公司 | A kind of sampler that distribution performance is examined |
| CN111936839A (en) * | 2018-05-10 | 2020-11-13 | 珀金埃尔默保健科学公司 | Apparatus, system and method for preparing field samples |
| CN113390995A (en) * | 2021-06-17 | 2021-09-14 | 中国烟草总公司郑州烟草研究院 | Portable gas chromatography ion mobility spectrometry GC-IMS with sample inlet |
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Application publication date: 20170926 |