CN108181406A - Chromatographic system and analysis method - Google Patents
Chromatographic system and analysis method Download PDFInfo
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- CN108181406A CN108181406A CN201810128452.6A CN201810128452A CN108181406A CN 108181406 A CN108181406 A CN 108181406A CN 201810128452 A CN201810128452 A CN 201810128452A CN 108181406 A CN108181406 A CN 108181406A
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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
-
- 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/40—Flow patterns using back flushing
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/46—Flow patterns using more than one column
-
- 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
- G01N30/62—Detectors specially adapted therefor
- G01N30/64—Electrical detectors
- G01N30/68—Flame ionisation detectors
-
- 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
-
- 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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
- G01N30/40—Flow patterns using back flushing
- G01N2030/402—Flow patterns using back flushing purging a device
Abstract
The present invention provides a kind of chromatographic systems, including the first ten-way valve, the second ten-way valve, the first quantitative loop, the second quantitative loop and detector, first ten-way valve is equipped with the first quantitative loop entrance, one carrier gas inlet of channel, the outlet of one column analytic unit of channel, the separation of channel one outlet, auxiliary gas entry, the outlet of one purge gass of channel, the outlet of one column analytic unit entrance of channel, the first quantitative loop, the outlet of channel a sample and channel a sample entrance, and column analytic unit is connected between one column analytic unit entrance of channel and outlet；Second ten-way valve is equipped with the second quantitative loop entrance, preanalysis column inlet, the outlet of two purge gass of channel, the auxiliary gas of channel two entrance, preanalysis column outlet, the separation of channel two outlet, the outlet of two carrier gas inlet of channel, the second quantitative loop, two sample inlet of two sample export of channel and channel, preanalysis column is connected between preanalysis column inlet and preanalysis column outlet, analytical column is equipped between the separation of channel two outlet and detector.
Description
Technical field
The present invention relates to gas chromatographic analysis field more particularly to a kind of chromatographic systems and analysis method.
Background technology
At present, the minusing that the gas chromatography analysis method of traditional non-methane total hydrocarbons is generally recommended using national standard,
I.e. by six-way valve or ten-way valve, sample introduction measures the content of the methane and total hydrocarbon in gas respectively once or twice, then uses total hydrocarbon
Content subtracts methane content, obtains the content of non-methane total hydrocarbons.If only allow single sample introduction, it is necessary to using two valves simultaneously
Measure the content of methane and total hydrocarbon.In addition, when other for needing to detect included under test gas in addition to methane simultaneously have
When machine compound composition in detail and constituent content, need additionally to increase an analysis channel, this analysis channel includes independent ten
Port valve and detector.Existing method at least needs 1 six-way valve, 2 ten-way valves, 2 detectors, 3 road-load gas and 2 tunnels auxiliary
Gas could be realized.
Invention content
In order to solve the above technical problems, the object of the present invention is to provide a kind of chromatographic system and analysis sides
Method, it is only necessary to single sample introduction, by two channels set respectively detect simultaneously non-methane total hydrocarbons content in sample gas and
Other organic constituents contents, it is only necessary to 2 ten-way valves, 1 detector, 2 road-load gas and 1 tunnel assist gas to achieve that, and
Can also blowback be carried out at the same time to the chromatographic column of two channels, enormously simplify instrument configuration demand, reduce hardware cost.
The present invention provides a kind of chromatographic system, including the first ten-way valve (100), the second ten-way valve
(200), the first quantitative loop (12), the second quantitative loop (31) and detector (18), first quantitative loop (12) and described first
Ten-way valve (100) connects, and second quantitative loop (31) connects with second ten-way valve (200), first ten-way valve
(100) there is the first quantitative loop entrance (1), one carrier gas inlet of channel (2), one column of channel that are in fluid communication being disposed thereon
Analytic unit outlet (3), the separation outlet of channel one (4), auxiliary gas entry (5), one purge gass of channel outlet (6), channel one
Column analytic unit entrance (7), the first quantitative loop outlet (8), channel a sample outlet (9) and channel a sample entrance (10) are described
Column analytic unit (15) is connected between one column analytic unit entrance (7) of channel and one column analytic unit of channel outlet (3)；It is described
Second ten-way valve (200) has the second quantitative loop entrance (21), the preanalysis column inlet that are in fluid communication being disposed thereon
(22), two purge gass of channel outlet (23), channel two assist gas entrance (24), preanalysis column outlet (25), channel two to isolate
Mouth (26), two carrier gas inlet of channel (27), the second quantitative loop outlet (28), two sample export of channel (29) and two sample of channel enter
Mouth (30), one purge gass of the channel outlet (6) assist gas entrance (24) to be in fluid communication with channel two, the preanalysis column inlet
(22) preanalysis column (33), the separation outlet of channel two (26) and detector are connected between preanalysis column outlet (25)
(18) be equipped with analytical column (34) between, the outlet of the analytical column (34) and the column analytic unit (15) respectively with the detection
Device (18) connects.
Further, column analytic unit (15) includes the first chromatographic column and the second chromatographic column parallel with one another, the channel
One column analytic unit exports (3) and passes through the first three-way connection (35) one end with first chromatographic column and the second chromatographic column respectively
Connection, the one column analytic unit entrance (7) of channel by the second three-way connection (36) respectively with first chromatographic column and the
The other end connection of two chromatographic columns, first chromatographic column include the separator tube (37), damper tube (38) and the sample introduction that are sequentially connected in series
It manages (39).
Further, analytical column (34) and channel one separation outlet (4) by three-way connection respectively with the detector
(18) it connects.
Further, the first ten-way valve (100) includes disc-shaped body, is sequentially arranged in the circumferential direction. in the disc-shaped body
First quantitative loop entrance (1), one carrier gas inlet of channel (2), one column analytic unit of channel outlet (3), the separation of channel one outlet
(4), auxiliary gas entry (5), one purge gass of channel outlet (6), one column analytic unit entrance (7) of channel, the first quantitative loop go out
Mouth (8), channel a sample outlet (9) and channel a sample entrance (10), the first quantitative loop (12) enter respectively with the first quantitative loop
Mouth (1) is connected with the first quantitative loop outlet (8).
Further, the second ten-way valve (200) includes disc-shaped body, is sequentially arranged in the circumferential direction. in the disc-shaped body
Second quantitative loop entrance (21), preanalysis column inlet (22), two purge gass of channel outlet (23), channel two assist gas entrance
(24), preanalysis column outlet (25), the separation outlet of channel two (26), two carrier gas inlet of channel (27), the outlet of the second quantitative loop
(28), two sample export of channel (29) and two sample inlet of channel (30), the second quantitative loop (31) enter respectively with the second quantitative loop
Mouth (21) is connected with the second quantitative loop outlet (28).
Further, the first ten-way valve (100) and the second ten-way valve (200) are two ten-way valves.First ten-way valve
(100) when and the second ten-way valve (200) is closed, each interface side orifice adjacent thereto；At ten-way valve
When opening, each interface opposite side orifice adjacent thereto.When first ten-way valve (100) is closed,
The first quantitative loop entrance (1) connects with channel a sample entrance (10)；First ten-way valve (100) is in unlatching
During state, the first quantitative loop entrance (1) connects with one carrier gas inlet of channel (2)；At second ten-way valve (200)
When closed state, the second quantitative loop entrance (21) connects with two sample inlet of channel (30)；Described 20th is logical
When valve (200) is in opening, the second quantitative loop entrance (21) connects with the preanalysis column inlet (22).
Further, chromatographic system further includes one carrier gas of channel (13), two carrier gas of channel (17) and auxiliary
Gas (14).
Further, under test gas enters second ten-way valve (200), warp by two sample inlet of channel (30)
The second quantitative loop outlet (28) enters channel a sample entrance (10) of first ten-way valve (100)；One carrier gas of channel
(13) first ten-way valve (100) is entered by one carrier gas inlet of channel (2)；Two carrier gas of channel (17) passes through described logical
Two carrier gas inlet of road (27) enters second ten-way valve (200)；Gas (14) is assisted to enter by the auxiliary gas entry (5)
First ten-way valve (100) enters the detector or is exported by the auxiliary gas entry (5), one purge gass of channel afterwards
(6) channel two entered on second ten-way valve (200) assists gas entrance (24).
Further, preanalysis column (33) is between preanalysis column inlet (22) and preanalysis column outlet (25)；It is described
Analytical column is located between the separation outlet of channel two (26) and detector (18).
Further, two purge gass of channel outlet (23) is connected with damper (32).
Further, quantitative loop is for quantifying the volume of under test gas, each sample size when making repeatedly to test
Unanimously；Damper can balance gas flow when ten-way valve is in two states (closed state and opening)；Detector is used
In the content for detecting the different component under test gas.
Further, detector is flame ionization ditector (FID).
Further, auxiliary gas is nitrogen.
Further, one carrier gas of channel and two carrier gas of channel are independently selected from nitrogen, helium or hydrogen.
Further, separator tube can increase the inner volume of the first chromatographic column, extend the appearance time of sample, the work of damper tube
With being to adjust the carrier gas flux by chromatographic column by changing the air damping of the first chromatographic column, by changing in sample feeding pipe
Volume-tunable section is assigned to the sample size of the first chromatographic column.Separator tube, damper tube and sample feeding pipe are blank pipe, and material is melting
Quartz capillary, stainless steel tube or PEEK pipes.
Further, the first chromatographic column is total hydrocarbon gas analysis column.Total appropriate hydrocarbon gas under test gas is through the first chromatographic column
It flows directly out.
Further, the second chromatographic column is component gas analytical column.
Further, the second chromatographic column is packed column, and it is filled with polymer carrier (Porapak Q etc.), packed columns
Shell be the high molecular polymers such as stainless steel, glass or polytetrafluoroethylene (PTFE).
The present invention also provides a kind of chromatographic method, using above-mentioned chromatographic system, including
Following steps：
(1) first ten-way valve (100) and the second ten-way valve (200) are closed, under test gas is successively through the channel two
Sample inlet (30), the second quantitative loop entrance (21), the second quantitative loop (31), the second quantitative loop outlet (28), two sample of channel
It exports (29) and flows out the second ten-way valve (200), then determine through channel a sample entrance (10), the first quantitative loop entrance (1), first
Measure ring (12), the first quantitative loop outlet (8), channel a sample outlet (9) the first ten-way valve of outflow (100)；One carrier gas of channel according to
It is secondary to be analyzed through one carrier gas inlet of channel (2), one column analytic unit of channel outlet (3), column analytic unit (15), one column of channel
The first ten-way valve (100) is flowed out in unit entrance (7), one purge gass of channel outlet (6)；Two carrier gas of channel is successively through the channel two
Carrier gas inlet (27), the separation of channel two export (26) into detector (18)；Gas is assisted through the auxiliary gas entry (5) and is led to
The separation outlet of road one (4) flows into detector (18), completes sampling process；
(2) first ten-way valve (100) is opened, the second ten-way valve (200) remains turned-off, and one carrier gas of channel is through institute
State one carrier gas inlet of channel (2), the first quantitative loop entrance (1) flows into first quantitative loop (12), first quantitative loop
(12) under test gas in is under the drive of the carrier gas successively by first quantitative loop outlet (8), the analysis of one column of channel
Unit entrance (7) then separately flows into first chromatographic column and the second chromatographic column by second three-way connection (36), stream
The gas for entering first chromatographic column enters the detector (18), the detector (18) through first three-way connection (35)
Total hydrocarbon content in detection gas；Second chromatographic column will enter gas therein and detach, described in the gas component warp after separation
First three-way connection (35) enters the detector (18), the concentration of component of the gas after detector (18) the detection separation；
At this point, channel two carrier gas inlet (27) of two carrier gas of channel through the second ten-way valve (200), channel two separation outlet (26), analysis
Column (34) enters detector (18) using three-way connection, does not interfere the work of the first ten-way valve (100) interior flow path；
(3) after detector detects the gas component concentrations of channel after a separation, first ten-way valve is closed
(100), second ten-way valve (200) is opened, two carrier gas of channel goes out through two carrier gas inlet of channel (27), the second quantitative loop
Mouthful (28) flow into second quantitative loop (31), and the under test gas in second quantitative loop (31) is under the drive of the carrier gas
The preanalysis column (33) and analysis are flowed into successively by the second quantitative loop entrance (21), preanalysis column inlet (22) successively
Column (34) and then process three-way connection enter the detector (18)；One carrier gas of channel at this time by one carrier gas inlet of channel (2),
One column analytic unit of channel outlet (3), column analytic unit (15), one column analytic unit entrance (7) of channel, one purge gass of channel go out
Mouth, (6) reach channel two and assist gas entrance (24), are vented through two purge gass of channel outlet (23) and damper (32), completion pair
The reverse blow of column analytic unit (15)；
(4) when the target components of the under test gas in the second quantitative loop (31) leave preanalysis column (33) into analytical column
(34) when, second ten-way valve (200) is closed, analytical column (34) is by the gas in it under the drive of two carrier gas of channel
In multiple components separate one by one, sequentially enter the detector (18)；The first ten-way valve (100) remains on pass at this time
Closed state, the channel two that one carrier gas of channel to come from the first ten-way valve (100) sequentially enters the second ten-way valve (200) assist gas
Entrance (24) flows through preanalysis column outlet (25) and is blown into preanalysis column (33), then through preanalysis column inlet (22) and channel two
The reverse blow of scavenging outlet (23) emptying, complete paired column analytic unit (15) and preanalysis column (33).
According to the above aspect of the present invention, the present invention has at least the following advantages：
The present invention makees the flow path in the second ten-way valve (200) using the flow path in the first ten-way valve (100) as channel one
For channel two, after single sample introduction, sample gas respectively enters channel one and channel two, passes through ingehious design flow path and analysis is flowed
Journey realizes two ten-way valves, single detector, 2 road-load gas and 1 tunnel auxiliary gas, is carried out at the same time the analysis of two channels, using logical
Road one measures the concentration of methane and total hydrocarbon, and the organic compound concentrations of multiple components, two channels are individually measured using channel two
It only uses two-way carrier gas and assists gas all the way, and pass through a three-way connection and share a detector detection, pass through ten-way valve
Open and close control makes the component to be analyzed of two channels reach detector in different time, and the component that two channels come out is being examined
It surveys on device and does not interfere so that share a detector and be possibly realized.
Entire analysis process realizes the reverse blow of the preanalysis column to the column analytic unit and channel two of channel one, fills
The interference of higher boiling ingredient that may be present to analytic process under test gas point is eliminated, while improves the use of chromatographic column
Service life reduces maintenance cost.
Channel two also carries out preanalysis column blowback using one carrier gas of channel of channel one or auxiliary gas, saves and assists all the way
Gas.
Above description is only the general introduction of technical solution of the present invention, in order to better understand the technological means of the present invention,
And can be implemented in accordance with the contents of the specification, below with presently preferred embodiments of the present invention and after attached drawing is coordinated to be described in detail such as.
Description of the drawings
Fig. 1 is that the first ten-way valve of chromatographic system of the present invention is closed, under the second ten-way valve closed state
Structure diagram；
Fig. 2 is that the first ten-way valve of chromatographic system of the present invention is opened, under the second ten-way valve closed state
Structure diagram；
Fig. 3 is that the first ten-way valve of chromatographic system of the present invention is closed, under the second ten-way valve opening
Structure diagram；
Fig. 4 is the load in column analytic unit under the first ten-way valve closed state of chromatographic system of the present invention
Air-flow is to schematic diagram；
Fig. 5 is the load in column analytic unit under the first ten-way valve opening of chromatographic system of the present invention
Air-flow is to schematic diagram；
Fig. 6 is that the present invention (contains 80.3mg/m for non-methane total hydrocarbons calibrating gas sample3Methane, 78.0mg/m3Propane, it is empty
Gas is Balance Air) detection single sample introduction spectrogram；
Fig. 7 is that the present invention (contains 20.1mg/m for benzene homologues calibrating gas sample3Benzene, 20.0mg/m3Toluene, 20.0mg/
m3Paraxylene and 20.2mg/m3Ortho-xylene, nitrogen are Balance Air) detection single sample introduction spectrogram；
Reference sign：
1- the first quantitative loop entrances；One carrier gas inlet of 2- channels；One column analytic unit of 3- channels exports；4- channels one detach
Outlet；5- auxiliary gas entries；One purge gass of 6- channels export；One column analytic unit entrance of 7- channels；The first quantitative loops of 8- go out
Mouthful；9- channels a sample exports；10- channel a sample entrances；11- under test gas；The first quantitative loops of 12-；13- channels one carry
Gas；14- assists gas；15- column analytic units；Two carrier gas of 17- channels；18- detectors；19- combustion gas；The combustion-supporting gas of 20-；21- second
Quantitative loop entrance；22- preanalysis column inlets；Two purge gass of 23- channels export；24- channels two assist gas entrance；25- preanalysis
Column outlet；The separation of 26- channels two outlet；Two carrier gas inlet of 27- channels；The second quantitative loops of 28- export；Two sample of 29- channels goes out
Mouthful；Two sample inlet of 30- channels；The second quantitative loops of 31-；32- dampers；33- preanalysis columns；34- analytical columns；35- the one or three
Pass joint；The second three-way connections of 36-；37- separator tubes；38- damper tubes；39- sample feeding pipes；40- two-way joints；The second chromatographies of 41-
Column；42- third three-way connections；The first ten-way valves of 100-；The second ten-way valves of 200-.
Specific embodiment
With reference to the accompanying drawings and examples, the specific embodiment of the present invention is described in further detail.Implement below
Example is used to illustrate the present invention, but be not limited to the scope of the present invention.
Embodiment
Referring to Fig. 1-5, a kind of chromatographic system of the invention, including two two ten-way valves, respectively
One ten-way valve 100 and the second ten-way valve 200.Ten-way valve includes disc-shaped body, wherein, on the first ten-way valve 100 circumferentially
Set gradually that the first quantitative loop entrance 1, one carrier gas inlet 2 of channel, one column analytic unit of channel outlet 3, channel one divides clockwise
Separate out mouth 4, auxiliary gas entry 5, one purge gass of channel outlet 6, one column analytic unit entrance 7 of channel, the outlet of the first quantitative loop
8th, channel a sample outlet 9 and channel a sample entrance 10.It is fixed that second is circumferentially set gradually on second ten-way valve 200 clockwise
Measure ring entrance 21, preanalysis column inlet 22, two purge gass of channel outlet 23, the auxiliary gas of channel two entrance 24, preanalysis column outlet
25th, the separation of channel two outlet 26, two carrier gas inlet 27 of channel, the second quantitative loop outlet 28, two sample export 29 of channel and channel
Two sample inlets 30.One purge gass of channel outlet 6 assists gas entrance 24 to be in fluid communication with channel two.Second quantitative loop entrance, 21 He
The second quantitative loop 31 is equipped between second quantitative loop outlet 28, is connected between preanalysis column inlet 22 and preanalysis column outlet 25
Preanalysis column 33, two purge gass of channel outlet 23 are connected with damper 32, and 26 one end of the separation of channel two outlet are connected with analytical column
34.When first ten-way valve 100 and the second ten-way valve 200 are closed, each interface side orifice adjacent thereto；
When ten-way valve is in opening, each interface opposite side orifice adjacent thereto.First ten-way valve 100, which is in, closes shape
During state, the first quantitative loop entrance 1 is connected with channel a sample entrance 10, one carrier gas inlet 2 of channel and one column analytic unit of channel
3 connection of outlet, the separation of channel one outlet 4 are connected with auxiliary gas entry 5, and one purge gass of channel outlet 6 is analyzed with one column of channel
Unit entrance 7 connects, and the first quantitative loop outlet 8 is connected with channel a sample outlet 9.First ten-way valve 100 is in opening
When, the first quantitative loop entrance 1 is connected with one carrier gas inlet 2 of channel, remaining interface is sequentially communicated two-by-two.At second ten-way valve 200
When closed state, the second quantitative loop entrance 21 is connected with two sample inlet 30 of channel, remaining interface is sequentially communicated two-by-two；Second
When ten-way valve 200 is in opening, the second quantitative loop entrance 21 is connected with preanalysis column inlet 22, remaining interface is two-by-two successively
Connection.Chromatographic system further includes detector 18, is fid detector, and detector passes through third three-way connection 42
Outlet 4 is detached with the port of export of analytical column 34 and channel one respectively to be connected, combustion gas 19 and combustion-supporting gas 20 are in 18 internal combustion of detector
It burns, detector 18 enters the concentration of gas therein for detecting.First quantitative loop, 12 inner volume 1200mL, the second quantitative loop 31
Inner volume 0.1mL.
Column analytic unit 15, column point are equipped between one column analytic unit of channel outlet 3 and one column analytic unit entrance 7 of channel
It analyses unit 15 and includes the first chromatographic column parallel with one another and the second chromatographic column 41.Wherein, one column analytic unit of channel outlet 3 passes through
The one end of one the first three-way connection 35 respectively with the first chromatographic column and the second chromatographic column 41 connects, and one column analytic unit of channel enters
Mouth 7 is connected by the other end of first three-way connection 36 respectively with the first chromatographic column and the second chromatographic column 41.First chromatography
Column includes the separator tube 37, damper tube 38 and the sample feeding pipe 39 that are sequentially connected in series, and separator tube 37, damper tube 38 and sample feeding pipe 39 are sky
Pipe, material is vitreous silica capillary, stainless steel tube or PEEK are managed.Total appropriate hydrocarbon gas is flowed directly out through the first chromatographic column.Second
Chromatographic column 41 is packed column, and for detaching the methane under test gas, it is filled with polymer carrier, the shell of packed column is
Stainless steel.
Separator tube 37, damper tube 38 and sample feeding pipe 39 are connected between any two by the two-way joint 40 with low dead volume
Come.Wherein, the outer diameter of separator tube 37 is 3mm, internal diameter 2mm, length 500mm；The outer diameter of damper tube 38 is 2mm, and internal diameter is
0.25mm, length 1000mm；The outer diameter of sample feeding pipe 39 is 2mm, internal diameter 1mm, length 500mm.Second chromatographic column 41
Outer diameter is 3mm, internal diameter 2mm, length 1200mm.The effect of separator tube 37 is to increase the inner volume of the first chromatographic column, is extended
The appearance time of total hydrocarbon changes the caliber and length of damper tube 38, thus it is possible to vary the air damping of the first chromatographic column, and then adjust
By the carrier gas flux of chromatographic column, the sample for being assigned to the first chromatographic column can be adjusted by changing the inner volume of sample feeding pipe 39
Amount.
Under test gas enters the second ten-way valve 200 by two sample inlet 30 of channel, enters through the second quantitative loop outlet 28
Channel a sample entrance 10 of first ten-way valve 100；One carrier gas 13 of channel enters the first ten-way valve by one carrier gas inlet 2 of channel
100；Two carrier gas 17 of channel enters the second ten-way valve 200 by two carrier gas inlet 27 of channel；Gas 14 is assisted by the way that gas is assisted to enter
Mouth 5 enters detector after entering the first ten-way valve 100 or enters the channel on the second ten-way valve 200 by auxiliary gas entry 5
Two auxiliary gas entrances 24.
Embodiment 2
A kind of chromatographic system using in embodiment 1 carries out the analysis method of gas-chromatography, including following
Step：
(1) referring to Fig. 1, the first ten-way valve 100 and the second ten-way valve 200 are closed, at this time the first quantitative loop entrance 1 and channel
A sample entrance 10 connects, and one carrier gas inlet 2 of channel and one column analytic unit of channel outlet 3 connect, the separation of channel one outlet 4 and
Auxiliary gas entry 5 connects, and one purge gass of channel outlet 6 is connected with one column analytic unit entrance 7 of channel, the outlet of the first quantitative loop
89 connect with the outlet of channel a sample, and the second quantitative loop entrance 21 is connected with two sample inlet 30 of channel, remaining interface two-by-two according to
Secondary connection.
Experimenter injects under test gas 11 by the injection port of gas chromatograph, and under test gas 11 is successively through two sample of channel
Product entrance 30, the second quantitative loop entrance 21, the second quantitative loop 31, the second quantitative loop outlet 28, two sample export 29 of channel flow out
Second ten-way valve 200, then through channel a sample entrance 10, the first quantitative loop entrance 1, the first quantitative loop 12, the first quantitative loop
Outlet 8,9 the first ten-way valve 100 of outflow of channel a sample outlet.At this point, one carrier gas 13 of channel is successively through one carrier gas inlet of channel
2nd, one column analytic unit of channel outlet 3, column analytic unit 15, one column analytic unit entrance 7 of channel, one purge gass of channel outlet 6
The first ten-way valve 100 is flowed out, then assists gas entrance 24, preanalysis column outlet (25) into preanalysis column (33) through channel two,
Again the second ten-way valve 200 is flowed out through preanalysis column inlet (22) and two purge gass of channel outlet (23)；Two carrier gas 17 of channel is successively
Enter detector 18 through two carrier gas inlet 27 of channel, the separation of channel two outlet 26, analytical column 34；Auxiliary gas 14 is through assisting gas to enter
Mouth 5 and the separation of channel one outlet 4 flow into detectors 18, complete sampling process.
(2) referring to Fig. 2 and Fig. 5, the first ten-way valve 100 is opened, while the second ten-way valve 200 is kept to close, at this time channel
One work：First quantitative loop entrance 1 is connected with one carrier gas inlet 2 of channel, and one column analytic unit of channel outlet 3 is detached with channel one
4 connection of outlet, auxiliary gas entry 5 are connected with one purge gass of channel outlet 6, and one column analytic unit entrance 7 and first of channel is fixed
8 connection of ring outlet is measured, channel a sample outlet 9 is connected with channel a sample entrance 10.One carrier gas 13 of channel is through one carrier gas of channel
Entrance 2, the first quantitative loop entrance 1 are by the gas in the first quantitative loop 12 through the first quantitative loop outlet 8, one column analytic unit of channel
Entrance 7 flows out the first ten-way valve 100, then separately flows into the first chromatographic column and the second chromatographic column by the first three-way connection 36
41.Total appropriate hydrocarbon gas under test gas flows directly out after entering the first chromatographic column, is then entered by the first three-way connection 35 and examined
Device 18 is surveyed, analysis obtains the concentration signal of total appropriate hydrocarbon gas.Methane gas into the second chromatographic column 41 is detached in the chromatography column
Out, detector 18 is then entered after total hydrocarbon by the first three-way connection 35, analysis obtains the concentration signal of methane gas.
The two concentration signal is subtracted each other, you can obtain the concentration of non-methane total hydrocarbons.Channel is second is that two carrier gas of channel passes through channel two at this time
Carrier gas inlet 27 enters the second ten-way valve 200, and column 34 flows into detector 18, the analysis of this process not interfering channel one by analysis
Work.
(3) referring to Fig. 3 and 4, the first ten-way valve 100 is closed after the concentration signal appearance of the methane gas of channel one, is beaten
The second ten-way valve 200 is opened, the first quantitative loop entrance 1 is connected with channel a sample entrance 10 at this time, remaining adjacent interface is two-by-two
It is sequentially communicated, the second quantitative loop entrance 21 is connected with preanalysis column inlet 22, remaining adjacent interface is sequentially communicated two-by-two.Channel
One one carrier gas 13 of channel enters column analytic unit 15 to it by one carrier gas inlet 2 of channel, one column analytic unit of channel outlet 3
Carry out blowback, in column analytic unit 15 remaining high boiling component under the drive of carrier gas 13 successively through one column analytic unit of channel
The channel two that entrance 7, one purge gass of channel outlet 6 enter the second ten-way valve 200 assists gas entrance 24, then through two purge gass of channel
Outlet 23 and damper 32 are vented, analytic process that will not be in interfering channel two.In channel two, two carrier gas 17 of channel is through channel two
Carrier gas inlet 27, the second quantitative loop outlet 28 enter the second quantitative loops 31, by gas therein through the second quantitative loop entrance 21, pre-
It analyzes column inlet 22 and is pushed into preanalysis column 33, then enter analytical column 34 through preanalysis column outlet 25, the separation of channel two outlet 26.
(4) when multiple target components in channel two, which all leave preanalysis column 33, enters analytical column 34, the 20th is closed
Port valve 200, the first ten-way valve 100 remain turned-off, the same step of connected state (1) and Fig. 1 of each interface.Two carrier gas 17 of channel at this time
Enter detector 18 through two carrier gas inlet 27 of channel, the separation of channel two outlet 26, analytical column 34 successively, by treating in analytical column 34
After the multiple components separation for analyzing component, detector 18 is then sequentially entered, carries out the analysis of multiple components.It is logical in channel one
One carrier gas 13 of road repeats the circulation path in step (1), and blowback is carried out to preanalysis column 33, is put from two purge gass of channel outlet 23
It is empty.After the last one component in analytical column 34 reaches detector 18, an analytic process is completed.
Fig. 6 is that the present invention (contains 80.3mg/m for non-methane total hydrocarbons calibrating gas sample3Methane, 78.0mg/m3Propane, it is empty
Gas is Balance Air) detection single sample introduction spectrogram.First 35 seconds in spectrogram are that non-methane total hydrocarbons calibrating gas obtains in channel one
The total hydrocarbon and methane chromatographic peak arrived, for quantitative.After 35 seconds, the peak at 112 seconds is that calibrating gas obtains in channel two
The conjunction peak of methane and propane, not as quantitative basis.
Table 1 is the precision test result of continuous six sample introductions of non-methane total hydrocarbons calibrating gas sample, can from table
Go out, the peak area relative standard deviation of total hydrocarbon and methane is 0.020% and 0.056% respectively, and being much better than 3% national standard will
It asks.Instrument noise 0.03pA, by twice of signal-to-noise ratio computation, pA detection limit=(2 × noise × concentration)/peak heights, the detection of methane
Limit is 0.014mg/m3, the detection limit of total hydrocarbon is 0.013mg/m3, more than numerical value is far below the numerical value of requirements of the national standard.
The precision test result of continuous six sample introductions of 1 non-methane total hydrocarbons calibrating gas sample of table
Fig. 7 is that the present invention (contains 20.1mg/m for benzene homologues calibrating gas sample3Benzene, 20.0mg/m3Toluene, 20.0mg/
m3Paraxylene and 20.2mg/m3Ortho-xylene, nitrogen are Balance Air) detection single sample introduction spectrogram.First 35 seconds in spectrogram,
It is that the total hydrocarbon that benzene homologues calibrating gas obtains in channel one closes peak, is that channel two detaches benzene homologues calibrating gas after 35 seconds
Obtained benzene, toluene, paraxylene and ortho-xylene chromatographic peak, for the qualitative of benzene homologues and quantitative.
Table 2 is the precision test result of continuous six sample introductions of benzene homologues calibrating gas sample, be can be seen that from table, four
Kind benzene homologues peak area relative standard deviation maximum is no more than 1.50%.
The precision test result of continuous six sample introductions of 2 benzene homologues of table
Analysis of spectra and result from the present invention for non-methane total hydrocarbons calibrating gas and benzene homologues calibrating gas can
Go out, the present invention can carry out the non-methane total hydrocarbons content (channel one) in sample gas and benzene homologues each component content (channel two)
It detects simultaneously, the chromatographic peak of two channels is not interfere with each other.Detection limit and precision are satisfied by requirements of the national standard.
The above is only the preferred embodiment of the present invention, is not intended to restrict the invention, it is noted that for this skill
For the those of ordinary skill in art field, without departing from the technical principles of the invention, can also make it is several improvement and
Modification, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a kind of chromatographic system, it is characterised in that：Including the first ten-way valve (100), the second ten-way valve (200),
First quantitative loop (12), the second quantitative loop (31) and detector (18), first quantitative loop (12) and first ten-way valve
(100) it connects, second quantitative loop (31) connects with second ten-way valve (200), and first ten-way valve (100) has
The first quantitative loop entrance (1) being in fluid communication, one carrier gas inlet of channel (2), the one column analytic unit of channel being disposed thereon
Outlet (3), the separation outlet of channel one (4), auxiliary gas entry (5), one purge gass of channel outlet (6), one column of channel analysis list
First entrance (7), the first quantitative loop outlet (8), channel a sample outlet (9) and channel a sample entrance (10) one column of channel
Column analytic unit (15) is connected between analytic unit entrance (7) and one column analytic unit of channel outlet (3)；Described 20th is logical
Valve (200) has the second quantitative loop entrance (21), preanalysis column inlet (22), the channel two that are in fluid communication being disposed thereon
Purge gass outlet (23), channel two assist gas entrance (24), preanalysis column outlet (25), the separation outlet of channel two (26), channel
Two carrier gas inlets (27), the second quantitative loop outlet (28), two sample export of channel (29) and two sample inlet of channel (30), it is described
One purge gass of channel export (6) and channel two assists gas entrance (24) to be in fluid communication, and the preanalysis column inlet (22) is divided with pre-
Preanalysis column (33) is connected between analysis column outlet (25), is equipped between the separation outlet of channel two (26) and detector (18)
Analytical column (34), the outlet of the analytical column (34) and the column analytic unit (15) are connected with the detector (18).
2. chromatographic system according to claim 1, it is characterised in that：The column analytic unit (15) includes
First chromatographic column and the second chromatographic column parallel with one another, one column analytic unit of the channel outlet (3) pass through the first three-way connection
(35) one end respectively with first chromatographic column and the second chromatographic column connects, and the one column analytic unit entrance (7) of channel is logical
It crosses the other end of the second three-way connection (36) respectively with first chromatographic column and the second chromatographic column to connect, first chromatographic column
Including the separator tube (37), damper tube (38) and sample feeding pipe (39) being sequentially connected in series.
3. chromatographic system according to claim 1, it is characterised in that：The analytical column (34) and channel one
Separation outlet (4) is connected respectively by three-way connection with the detector (18).
4. chromatographic system according to claim 1, it is characterised in that：First ten-way valve (100) packet
Disc-shaped body is included, the first quantitative loop entrance (1) is sequentially arranged in the circumferential direction. in the disc-shaped body, one carrier gas of channel enters
Mouth (2), one column analytic unit of channel outlet (3), the separation outlet of channel one (4), auxiliary gas entry (5), one purge gass of channel
(6), one column analytic unit entrance (7) of channel, the first quantitative loop outlet (8), channel a sample outlet (9) are exported as channel
Product entrance (10), first quantitative loop (12) connect respectively with the first quantitative loop entrance (1) and the first quantitative loop outlet (8).
5. chromatographic system according to claim 1, it is characterised in that：Second ten-way valve (200) packet
Disc-shaped body is included, the second quantitative loop entrance (21) is sequentially arranged in the circumferential direction. in the disc-shaped body, preanalysis column enters
Mouth (22), two purge gass of channel outlet (23), channel two assist gas entrance (24), preanalysis column outlet (25), channel two to detach
Export (26), two carrier gas inlet of channel (27), the second quantitative loop outlet (28), two sample of two sample export of channel (29) and channel
Entrance (30), second quantitative loop (31) connect respectively with the second quantitative loop entrance (21) and the second quantitative loop outlet (28).
6. chromatographic system according to claim 1, it is characterised in that：First ten-way valve (100) and
Second ten-way valve (200) is two ten-way valves；When first ten-way valve (100) is closed, described first is quantitative
Ring entrance (1) is connected with channel a sample entrance (10)；It is described when first ten-way valve (100) is in opening
First quantitative loop entrance (1) is connected with one carrier gas inlet of channel (2)；Second ten-way valve (200) is closed
When, the second quantitative loop entrance (21) connects with two sample inlet of channel (30)；Second ten-way valve (200) is in
During opening, the second quantitative loop entrance (21) connects with the preanalysis column inlet (22).
7. chromatographic system according to claim 1, it is characterised in that：The chromatographic system
Further include one carrier gas of channel (13), two carrier gas of channel (17) and auxiliary gas (14).
8. chromatographic system according to claim 7, it is characterised in that：Under test gas passes through the channel two
Sample inlet (30) enters second ten-way valve (200), and it is logical to enter the described 10th through second quantitative loop outlet (28)
Channel a sample entrance (10) of valve (100)；One carrier gas of channel (13) is by one carrier gas inlet of channel (2) into institute
State the first ten-way valve (100)；Two carrier gas of channel (17) enters the described 20th by two carrier gas inlet of channel (27)
Port valve (200)；The auxiliary gas (14) is entered afterwards by the auxiliary gas entry (5) into first ten-way valve (100)
The detector enters second ten-way valve by the auxiliary gas entry (5), one purge gass of channel outlet (6)
(200) channel two on assists gas entrance (24).
9. chromatographic system according to claim 1, it is characterised in that：Two purge gass of the channel outlet
(23) it is connected with damper (32).
A kind of 10. chromatographic method, which is characterized in that using the gas phase color described in any one of claim 1-9
Spectrometer analysis system, includes the following steps：
(1) first ten-way valve (100) and the second ten-way valve (200) are closed, under test gas is successively through two sample of channel
Entrance (30), the second quantitative loop entrance (21), the second quantitative loop (31), the second quantitative loop outlet (28), two sample export of channel
(29) the second ten-way valve of outflow (200), then through channel a sample entrance (10), the first quantitative loop entrance (1), the first quantitative loop
(12), the first ten-way valve (100) is flowed out in the first quantitative loop outlet (8), channel a sample outlet (9), completes sampling process；
(2) first ten-way valve (100) is opened, the second ten-way valve (200) remains turned-off, and one carrier gas of channel is through the channel one
Carrier gas inlet (2), the first quantitative loop entrance (1) flow into first quantitative loop (12), are treated in first quantitative loop (12)
Gas is surveyed under the drive of the carrier gas successively by first quantitative loop outlet (8), one column analytic unit entrance of channel
(7), first chromatographic column and the second chromatographic column are then separately flowed by second three-way connection (36), flows into described the
The gas of one chromatographic column enters the detector (18), detector (18) detection gas through first three-way connection (35)
Interior total hydrocarbon content；Second chromatographic column will enter gas therein and detach, and the gas component after separation is through first threeway
Connector (35) enters the detector (18), the concentration of component of the gas after detector (18) the detection separation；
(3) after gas component concentrations after detector detects separation, first ten-way valve (100) is closed, described in unlatching
Second ten-way valve (200), two carrier gas of channel is through described in two carrier gas inlet of channel (27), the second quantitative loop outlet (28) inflow
Second quantitative loop (31), under test gas in second quantitative loop (31) is under the drive of the carrier gas successively by described the
Two quantitative loop entrances (21), preanalysis column inlet (22) flow into successively the preanalysis column (33) and analytical column (34) subsequently into
The detector (18)；One carrier gas of channel at this time is exported by one carrier gas inlet of channel (2), one column analytic unit of channel
(3), column analytic unit (15), one column analytic unit entrance (7) of channel, one purge gass of channel outlet (6) reach channel two
Gas entrance (24) is assisted, through two purge gass of channel outlet (23) emptying, the reverse blow of complete paired column analytic unit (15)；
(4) when the target components in the under test gas in the second quantitative loop (31) leave preanalysis column (33) into analytical column (34)
When, second ten-way valve (200) is closed, analytical column (34) is by its interior target components under the drive of two carrier gas of channel
Multiple components separate one by one, sequentially enter the detector (18)；One carrier gas of channel to come from the first ten-way valve (100)
The channel two for sequentially entering the second ten-way valve (200) assists gas entrance (24), flows through preanalysis column outlet (25) into preanalysis
Column (33), then through preanalysis column inlet (22) and two purge gass of channel outlet (23) emptying, complete paired column analytic unit (15) and
The reverse blow of preanalysis column (33).
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| CN112213436A (en) * | 2020-08-24 | 2021-01-12 | 中国科学院微生物研究所 | Gas chromatography-mass spectrometry detection system and method |
| CN114354791A (en) * | 2021-12-29 | 2022-04-15 | 杭州谱育科技发展有限公司 | Detection system and method for non-methane total hydrocarbons |
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