CN105572281B - The gas chromatographic analysis device and its analysis method of a kind of high purity oxygen gas - Google Patents

The gas chromatographic analysis device and its analysis method of a kind of high purity oxygen gas Download PDF

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CN105572281B
CN105572281B CN201510928845.1A CN201510928845A CN105572281B CN 105572281 B CN105572281 B CN 105572281B CN 201510928845 A CN201510928845 A CN 201510928845A CN 105572281 B CN105572281 B CN 105572281B
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gas
automatic transfer
transfer valve
valve
chromatographic column
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CN105572281A (en
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谢程
路家兵
谢欣
熊万红
杨艳
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Wuhan Iron And Steel Group Gas Co Ltd
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Wuhan Iron and Steel Group Corp
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8804Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 automated systems
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02Column chromatography
    • G01N30/88Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86
    • G01N2030/8809Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample
    • G01N2030/8872Integrated analysis systems specially adapted therefor, not covered by a single one of the groups G01N30/04 - G01N30/86 analysis specially adapted for the sample impurities

Abstract

The present invention relates to the gas chromatographic analysis device and its analysis method of a kind of high purity oxygen gas, it is including sample gas probe tube, carrier gas inlet pipe, automatic transfer valve, chromatographic column, deoxidation hydrazine, blast pipe, detector etc., realize that carrier gas one carries sample gas by chromatographic column one, chromatographic column two by the valve position for switching automatic transfer valve one, or realize that carrier gas two enters automatic transfer valve three directly through chromatographic column one;Realize the gas by chromatographic column two whether by deoxidation hydrazine into automatic transfer valve three by the valve position for switching automatic transfer valve two;Realize that the gas for being passed through switching automatic transfer valve three enters detector or blast pipe one by the valve position for switching automatic transfer valve three.The present invention can disposably sample introduction complete high purity oxygen gas in each component impurity complete analysis, shorten analysis time and reduce the use costs such as carrier gas.

Description

The gas chromatographic analysis device and its analysis method of a kind of high purity oxygen gas
Technical field
The invention belongs to analyze detection field, and in particular to a kind of gas chromatographic analysis device of high purity oxygen gas and its analysis Method.
Background technology
The new standard (GB/T 14599-2008 pure oxygens, pure oxygen high and ultrapure oxygen) of high purity oxygen gas on November 1st, 2008 just Formula implement, older standard (GB/T 14599-1993 pure oxygens high) for impurity in high purity oxygen gas species from original argon, nitrogen, Carbon dioxide and total hydrocarbon become the detection newly increased to hydrogen impurity.
At present, domestic is usually repeatedly to be analyzed using multiple sample introduction, and the various indexs in high purity oxygen gas are analyzed, and is made The problems such as equipment is more, method is complicated, analysis time is long, use cost is high are used into analysis process.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiency of above-mentioned prior art presence and provide a kind of pure oxygen high The gas chromatographic analysis device and its analysis method of gas, disposable sample introduction complete the complete analysis of each component impurity in high purity oxygen gas, Shorten analysis time and reduce the use costs such as carrier gas.
The present invention is to solve the problems, such as that used technical scheme set forth above is:
A kind of gas chromatographic analysis device of high purity oxygen gas, including sample gas inlet pipe, sample gas probe tube, sample gas go out Pipe, the inlet pipe of carrier gas one, the inlet pipe of carrier gas two, automatic transfer valve one, chromatographic column one, chromatographic column two, automatic transfer valve two, deoxidation hydrazine, Blast pipe one, automatic transfer valve three, detector, are connected with sample gas sampling between the sample gas inlet pipe and sample gas outlet pipe Pipe;The automatic transfer valve one and sample gas probe tube, the inlet pipe of carrier gas one, the inlet pipe of carrier gas two, automatic transfer valve three, chromatographic column First, chromatographic column two is connected, and realizes that carrier gas one carries sample gas by chromatographic column by the valve position for switching automatic transfer valve one First, chromatographic column two, or realize that carrier gas two enters automatic transfer valve three directly through chromatographic column one;The automatic transfer valve two with Chromatographic column two is connected, and is connected with deoxidation hydrazine, automatic transfer valve three, is realized by the valve position for switching automatic transfer valve two By chromatographic column two gas by deoxidation hydrazine enter automatic transfer valve three, or realize by chromatographic column two gas without Deoxidation hydrazine and be directly entered automatic transfer valve three;The automatic transfer valve three is connected with detector, blast pipe one, by switching Realize that the gas for being passed through switching automatic transfer valve three enters detector or blast pipe one in the valve position of automatic transfer valve three.
By such scheme, the automatic transfer valve two is also associated with the inlet pipe of carrier gas three and blast pipe two, automatic by switching The valve position of switching valve two realizes that carrier gas three enters blast pipe two by deoxidation hydrazine, or realizes that carrier gas three is not straight by deoxidation hydrazine Tap into blast pipe two.
By such scheme, the automatic transfer valve one is ten-way valve, and the automatic transfer valve two is six-way valve, described automatic Switching valve three is four-way valve.
A kind of gas chromatography analysis method of high purity oxygen gas, comprises the following steps:
1) high purity oxygen gas are used as sample gas, wherein containing oxygen (O2), hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2);
2) carrier gas one brings sample gas into analysis system by automatic transfer valve one, and the valve position for switching automatic transfer valve one makes The carrying sample gas of carrier gas one are passed through chromatographic column one carries out pre-separation, carbon dioxide (CO2) be retained in chromatographic column one, then pass through The gas of chromatographic column one includes oxygen (O2), hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO) Continue to be passed through chromatographic column two and separated;
3) the valve position of switching automatic transfer valve one, makes carrier gas two flow through chromatographic column one, and then carry reservation in chromatographic column one Atmospheric carbon dioxide (CO2) detector is entered by automatic transfer valve three, detect its response signal ----peak area;Work as titanium dioxide Carbon (CO2) enter detector after, switch automatic transfer valve three valve position make CO2Component below is blown point by blast pipe two Analysis system;
4) the valve position of control automatic transfer valve two, control automatic transfer valve three, makes directly to enter by the gas of chromatographic column two Enter detector, detect wherein hydrogen (H2) response signal ----peak area;As hydrogen (H2) enter detector after, switching is automatic The valve position of switching valve two, makes first to flow through deoxidation hydrazine by the gas of chromatographic column two and enters back into detector, successively detects wherein argon gas (Ar), nitrogen (N2), methane (CH4) response signal ----peak area;As methane (CH4) enter detector after, switching cut automatically The valve position of valve two is changed, makes to be directly entered detector, the response letter of detection wherein CO (carbon monoxide) by the gas of chromatographic column two Number ----peak area;
5) standard high purity oxygen gas sample is prepared, it is known that wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and Carbon monoxide (CO), carbon dioxide (CO2) content be respectively CHydrogen、CArgon gas、CNitrogen、CMethaneAnd CCarbon monoxide、CCarbon dioxide, by step 1) wherein hydrogen (H -4) is determined2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) Peak area be respectively SHydrogen、SArgon gas、SNitrogen、SMethaneAnd SCarbon monoxide、SCarbon dioxide, calculate the correction factor K of each foreign gasHydrogen、KArgon gas、 KNitrogen、KMethaneAnd KCarbon monoxide、KCarbon dioxide, wherein KHydrogen=CHydrogen/SHydrogen、KArgon gas=CArgon gas/SArgon gas、KNitrogen=CNitrogen/SNitrogen、KMethane=CMethane/SMethane And KCarbon monoxide=CCarbon monoxide/SCarbon monoxide、KCarbon dioxide=CCarbon dioxide/SCarbon dioxide
6) high purity oxygen gas sample to be measured is chosen, by step 1) -4) determine wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) peak area be respectively S 'Hydrogen、S’Argon gas、S’Nitrogen、S’MethaneWith S’Carbon monoxide、S’Carbon dioxide, calculate hydrogen (H in high purity oxygen gas sample to be measured2), argon gas (Ar), nitrogen (N2), methane (CH4) and an oxygen Change carbon (CO), carbon dioxide (CO2) content C 'Hydrogen、C’Argon gas、C’Nitrogen、C’MethaneAnd C 'Carbon monoxide、C’Carbon dioxide, wherein C 'Hydrogen=KHydrogen ×S’Hydrogen、C’Argon gas=KArgon gas×S’Argon gas、C’Nitrogen=KNitrogen×S’Nitrogen、C’Methane=KMethane×S’Methane、C’Carbon monoxide=KCarbon monoxide×S’Carbon monoxide、 C’Carbon dioxide=KCarbon dioxide×S’Carbon dioxide
By such scheme, the chromatographic column one is used to realize carbon dioxide (CO in sample gas2) separation, can select Rt-Q-Band chromatographic columns.
By such scheme, the chromatographic column two is used to realize hydrogen (H in sample gas2), oxygen (O2), argon gas (Ar), nitrogen (N2)、CH4The separation of (methane) and CO (carbon monoxide), can select Molsieve chromatographic columns.
By such scheme, the carrier gas one, carrier gas two are exported with steel cylinder, and output pressure is in the range of 0.3-0.5MPa.
By such scheme, the temperature of the detector is in the range of 100-300 DEG C.
By such scheme, the temperature of the chromatographic column one uses temperature programming, and initial temperature is 5-20 DEG C, detects hydrogen (H2) response signal after be warming up to 80-100 DEG C.
By such scheme, the temperature of the chromatographic column two is 40-60 DEG C.
By such scheme, the temperature of the deoxidation hydrazine is in the range of 120-200.
By such scheme, the temperature of the sample gas inlet is in the range of 25-100 DEG C.
Compared with prior art, the beneficial effects of the invention are as follows:
1) present invention being capable of the trace impurity comprising hydrogen in Accurate Determining high purity oxygen gas, it is ensured that the product of high purity oxygen gas Quality, and single sample introduction completes the complete analysis of each component impurity in high purity oxygen gas, and whole analysis time is short, simple to operate; And conventional analysis method needs multiple sample introduction for the analysis of each component impurity in whole high purity oxygen gas, when consumption is very long Between, and consume many sample gas;
2) present invention shortens analysis time using capillary chromatographic column, and reduces the consumption of carrier gas, and reduction is used into This;Impurity is analyzed using packed column in the past, it is necessary to consume substantial amounts of carrier gas, the analyzer of generally analysis high purity oxygen gas makes It is high-purity helium, high-purity helium cost is very high, average one bottle 1200 yuan, uses 2.5-3 bottles within conventional one month, selection makes After with capillary chromatographic column, one bottle of high-purity helium can be used 2.5 months;
3) present invention is cut off the oxygen of high content using switching valve UNICOM deoxidation hydrazine, reduces the deoxidation amount of high purity oxygen gas, The service life of deoxidation hydrazine is extended, and realizes the detection to hydrogen impurity;The analysis of conventional high purity oxygen gas is, it is necessary to this The sample gas of sample introduction carry out deoxidation and analyze again, and deoxidation post is accomplished by activating deoxidation post using 25 times, but the present invention is only Oxygen to needing absorption carries out cutting process, can significantly reduce the amount of deoxidation post adsorption of oxygen in deoxidation process, So deoxidation post can be used more than 100 times.
Brief description of the drawings
Fig. 1 is the structural representation of the gas chromatographic analysis device of high purity oxygen gas of the present invention.
Fig. 2 is the chromatogram of the standard high purity oxygen gas sample that the present invention is determined.
Wherein, 1- sample gas inlet pipe, 2- probe tubes, 3- sample gas outlet pipes, the inlet pipe of 4- carrier gas one, the inlet pipe of 5- carrier gas two, 6- Automatic transfer valve one, 7- chromatographic columns one, the inlet pipe of 8- carrier gas three, 9- deoxidation hydrazines, 10- blast pipes two, 11- chromatographic columns two, 12- is automatic Switching valve two, 13- automatic transfer valves three, 14- blast pipes one, 15- detectors.
Specific embodiment
For a better understanding of the present invention, with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not It is limited only to the following examples.
Embodiment
(1) a kind of, gas chromatographic analysis device of high purity oxygen gas, including sample gas inlet pipe 1, sample gas probe tube 2, sample Product gas outlet pipe 3, the inlet pipe 4 of carrier gas one, the inlet pipe 5 of carrier gas two, automatic transfer valve 1, chromatographic column 1, chromatographic column 2 11, automatic switchover Valve 2 12, deoxidation hydrazine 9, blast pipe 1, automatic transfer valve 3 13, detector 15, the sample gas inlet pipe 1 and sample gas outlet pipe Sample gas probe tube 2 is connected between 3;The automatic transfer valve 1 and sample gas probe tube 2, the inlet pipe 4 of carrier gas one, carrier gas two Inlet pipe 5, automatic transfer valve 3 13, chromatographic column 1, chromatographic column 2 11 are connected, by the valve position for switching automatic transfer valve 1 Realize that carrier gas one carries sample gas by chromatographic column 1, chromatographic column 2 11, or realize carrier gas two directly through chromatographic column 1 Into automatic transfer valve 3 13;The automatic transfer valve 2 12 is connected with chromatographic column 2 11, and with deoxidation hydrazine 9, automatically cut Change valve 3 13 to be connected, realized by the gas of chromatographic column two by deoxidation hydrazine 9 by the valve position for switching automatic transfer valve 2 12 Into automatic transfer valve 3 13, or realization automatic switchover is directly entered by the gas of chromatographic column two without deoxidation hydrazine 9 Valve 3 13;The automatic transfer valve 3 13 is connected with detector 15, blast pipe 1, by switching automatic transfer valve 3 13 Realize that the gas for being passed through switching automatic transfer valve 3 13 enters detector 14 or blast pipe 1 in valve position.
Preferably, in order to ensure the gas pressure balancing in deoxidation hydrazine, the automatic transfer valve 2 12 is also associated with carrier gas Three inlet pipes 8 and blast pipe 2 10, realize that carrier gas three enters exhaust by deoxidation hydrazine 9 by the valve position for switching automatic transfer valve 2 12 Pipe 2 10, or realize that carrier gas three is not directly entered blast pipe 2 10 by deoxidation hydrazine 9.
Preferably, the automatic transfer valve one is ten-way valve, and the automatic transfer valve two is six-way valve, the automatic switchover Valve three is four-way valve.
Preferably, the chromatographic column one is used to realize carbon dioxide (CO in sample gas2) separation, from Rt-Q-Band Chromatographic column;The chromatographic column two is used to realize hydrogen (H in sample gas2), oxygen (O2), argon gas (Ar), nitrogen (N2)、CH4(first Alkane) and CO (carbon monoxide) separation, from Molsieve chromatographic columns.
(2), in following methods, the conditional parameter of chromatography is:It is carrier gas (purity 99.999%) from helium, contains The steel cylinder pressure-reducing valve output pressure value for putting carrier gas is 0.42MPa;50 DEG C of injector temperature;Rt-Q-Band chromatographic columns use program Heat up, initial temperature is 10 DEG C, detects hydrogen (H2) response signal after be warming up to 90 DEG C of temperature;Molsieve chromatographic columns are put In constant temperature clack box, temperature is 50 DEG C;Deoxidation trap temperature is 150 DEG C, detector tail mouthpiece flow 36.3ml/min, detector base 250 DEG C of temperature of seat;It is as shown in table 1 that the valve of each automatic transfer valve cuts the time.
Table 1
Valve is cut the time (min) Valve number
0.01 Automatic transfer valve one
1.85 Automatic transfer valve one
2.90 Automatic transfer valve two
9.10 Automatic transfer valve two
0.01 Automatic transfer valve three
2.20 Automatic transfer valve three
1st, a kind of gas chromatography analysis method of high purity oxygen gas, comprises the following steps:
1) standard high purity oxygen gas sample (in following step referred to as " sample gas "), wherein hydrogen (H are prepared2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2), content is as shown in table 2;
Table 2
Sequence number Title Content (ppm)
1 Carbon dioxide (CO2) 5.0
2 Hydrogen (H2) 5.0
3 Argon gas (Ar) 4.0
4 Nitrogen (N2) 3.3
5 Methane (CH4) 3.8
6 Carbon monoxide (CO) 5.0
2) carrier gas one brings sample gas into analysis system by automatic transfer valve one, switches the valve position of automatic transfer valve one (cutting valve time 0.01min) makes the carrying sample gas of carrier gas one be passed through Rt-Q-Band chromatographic columns carries out pre-separation, carbon dioxide (CO2) be retained in Rt-Q-Band chromatographic columns, then include oxygen (O by the gas of Rt-Q-Band chromatographic columns2), hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO) continue to be passed through Molsieve chromatographic columns and separated;
3) valve position (cutting valve time 1.85min) of switching automatic transfer valve one, makes carrier gas two flow through Rt-Q-Band chromatograms Post, and then carry reservation atmospheric carbon dioxide (CO in Rt-Q-Band chromatographic columns2) pass through (automatic transfer valve of automatic transfer valve three Three switch to the state in 0.01min) enter detector, detect its response signal ----peak area SCarbon dioxide;Work as titanium dioxide Carbon (CO2) enter detector after, switch automatic transfer valve three valve position (cutting valve time 2.20min) make CO2Component below passes through Blast pipe two is blown analysis system;
4) the valve position of switching automatic transfer valve three, make by the gas of Molsieve chromatographic columns by automatic transfer valve two, Automatic transfer valve three is directly entered detector, detects wherein hydrogen (H2) response signal ----peak area SHydrogen;As hydrogen (H2) Into after detector, switch valve position (cutting valve time 2.90min) of automatic transfer valve two, make the gas by Molsieve chromatographic columns Body first flows through deoxidation hydrazine and enters back into detector, successively detects wherein argon gas (Ar), nitrogen (N2), methane (CH4) response letter Number ----peak area is respectively SArgon gas、SNitrogen、SMethane;As methane (CH4) enter detector after, switch automatic transfer valve two valve position (cutting valve time 9.10min), makes to be directly entered detector, a detection wherein CO (oxidations by the gas of Molsieve chromatographic columns Carbon) response signal ----peak area SCarbon monoxide, specific data are as shown in table 3;
5) the correction factor K of each foreign gas in standard high purity oxygen gas sample is calculatedHydrogen、KArgon gas、KNitrogen、KMethaneAnd KCarbon monoxide、 KCarbon dioxide, wherein KHydrogen=CHydrogen/SHydrogen、KArgon gas=CArgon gas/SArgon gas、KNitrogen=CNitrogen/SNitrogen、KMethane=CMethane/SMethaneAnd KCarbon monoxide=CCarbon monoxide/ SCarbon monoxide、KCarbon dioxide=CCarbon dioxide/SCarbon dioxide, specific data are as shown in table 3.
Table 3
Sequence number Title Retention time (min) Peak area Content (ppm) Correction factor K
1 Carbon dioxide (CO2) 1.78 1499860 5.0 3.33364E-06
2 Hydrogen (H2) 2.7 221617 5.0 2.25614E-05
3 Argon gas (Ar) 4.6 832232 4.0 4.80635E-06
4 Nitrogen (N2) 6.36 847768 3.3 3.89257E-06
5 Methane (CH4) 8.13 1586732 3.8 2.39486E-06
6 Carbon monoxide (CO) 15.2 322151 5.0 1.55207E-05
6) high purity oxygen gas sample to be measured is chosen, by step 1) -4) determine wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) peak area be respectively S 'Hydrogen、S’Argon gas、S’Nitrogen、S’MethaneWith S’Carbon monoxide、S’Carbon dioxide, calculate hydrogen (H in high purity oxygen gas sample to be measured2), argon gas (Ar), nitrogen (N2), methane (CH4) and an oxygen Change carbon (CO), carbon dioxide (CO2) content C 'Hydrogen、C’Argon gas、C’Nitrogen、C’MethaneAnd C 'Carbon monoxide、C’Carbon dioxide, wherein C 'Hydrogen=KHydrogen ×S’Hydrogen、C’Argon gas=KArgon gas×S’Argon gas、C’Nitrogen=KNitrogen×S’Nitrogen、C’Methane=KMethane×S’Methane、C’Carbon monoxide=KCarbon monoxide×S’Carbon monoxide、 C’Carbon dioxide=KCarbon dioxide×S’Carbon dioxide, concrete outcome is as shown in table 4.
Table 4
Sequence number Title Peak area S ' Correction factor K Content (ppm)
1 Carbon dioxide (CO2) 6577 3.33364E-06 0.02
2 Hydrogen (H2) 7617 2.25614E-05 0.17
3 Argon gas (Ar) 232232 4.80635E-06 1.12
4 Nitrogen (N2) 147768 3.89257E-06 0.58
5 Methane (CH4) 186732 2.39486E-06 0.45
6 Carbon monoxide (CO) 2151 1.55207E-05 0.03
From Fig. 2 and Biao 3, table 4, the method for the invention can to high purity oxygen gas sample in each foreign gas carry out Efficiently separate, and realize qualitative and quantitative analysis.
The above is only the preferred embodiment of the present invention, it is noted that come for one of ordinary skill in the art Say, without departing from the concept of the premise of the invention, can also make some modifications and variations, these belong to of the invention Protection domain.

Claims (7)

1. a kind of gas chromatography analysis method of high purity oxygen gas, it is characterised in that comprise the following steps:
1) high purity oxygen gas are used as sample gas, wherein containing oxygen (O2), hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) With carbon monoxide (CO), carbon dioxide (CO2);
2) carrier gas one brings sample gas into analysis system by automatic transfer valve one, and the valve position for switching automatic transfer valve one makes carrier gas One carrying sample gas are passed through chromatographic column one carries out pre-separation, carbon dioxide (CO2) be retained in chromatographic column one, then by chromatogram The gas of post one includes oxygen (O2), hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO) continuation Chromatographic column two is passed through to be separated;
3) the valve position of switching automatic transfer valve one, makes carrier gas two flow through in chromatographic column one, and then carrying chromatographic column one and retains gas Carbon dioxide (CO2) detector is entered by automatic transfer valve three, detect its response signal ----peak area;Work as carbon dioxide (CO2) enter detector after, switch automatic transfer valve three valve position make carbon dioxide (CO2) behind component pass through blast pipe two It is blown analysis system;
4) the valve position of control automatic transfer valve two, control automatic transfer valve three, makes to be directly entered inspection by the gas of chromatographic column two Device is surveyed, wherein hydrogen (H is detected2) response signal ----peak area;As hydrogen (H2) enter detector after, switching automatically switch The valve position of valve two, makes first to flow through deoxidation hydrazine by the gas of chromatographic column two and enters back into detector, successively detect wherein argon gas (Ar), Nitrogen (N2), methane (CH4) response signal ----peak area;As methane (CH4) enter detector after, switch automatic transfer valve Two valve position, makes to be directly entered detector, the response letter of detection wherein CO (carbon monoxide) by the gas of chromatographic column two Number ----peak area;
5) standard high purity oxygen gas sample is prepared, it is known that wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and an oxygen Change carbon (CO), carbon dioxide (CO2) content be respectively CHydrogen、CArgon gas、CNitrogen、CMethaneAnd CCarbon monoxide、CCarbon dioxide, by step 1) and -4) Determine wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) peak face Product is respectively SHydrogen、SArgon gas、SNitrogen、SMethaneAnd SCarbon monoxide、SCarbon dioxide, it is calculated the ratio coefficient of each gas component content and peak area Respectively KHydrogen、KArgon gas、KNitrogen、KMethaneAnd KCarbon monoxide、KCarbon dioxide
6) high purity oxygen gas sample to be measured is chosen, by step 1) -4) determine wherein hydrogen (H2), argon gas (Ar), nitrogen (N2), first Alkane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) peak area be respectively S 'Hydrogen、S’Argon gas、S’Nitrogen、S’MethaneAnd S 'Carbon monoxide、 S’Carbon dioxide, calculate oxygen hydrogen (H in high purity oxygen gas sample to be measured2), argon gas (Ar), nitrogen (N2), methane (CH4) and carbon monoxide (CO), carbon dioxide (CO2) content C 'Hydrogen、C’Argon gas、C’Nitrogen、C’MethaneAnd C 'Carbon monoxide、C’Carbon dioxide, wherein C 'Hydrogen=KHydrogen× S’Hydrogen、C’Argon gas=KArgon gas×S’Argon gas、C’Nitrogen=KNitrogen×S’Nitrogen、C’Methane=KMethane×S’Methane、C’Carbon monoxide=KCarbon monoxide×S’Carbon monoxide、 C’Carbon dioxide=KCarbon dioxide×S’Carbon dioxide
The gas chromatographic analysis device that the gas chromatography analysis method of the high purity oxygen gas is used, it include sample gas inlet pipe, Sample gas probe tube, sample gas outlet pipe, the inlet pipe of carrier gas one, the inlet pipe of carrier gas two, automatic transfer valve one, chromatographic column one, chromatographic column two, Automatic transfer valve two, deoxidation hydrazine, blast pipe one, automatic transfer valve three, detector, the sample gas inlet pipe and sample gas outlet pipe it Between be connected with sample gas probe tube;The automatic transfer valve one and sample gas probe tube, the inlet pipe of carrier gas one, the inlet pipe of carrier gas two, from Dynamic switching valve three, chromatographic column one, chromatographic column two are connected, and the carrying of carrier gas one is realized by the valve position for switching automatic transfer valve one Sample gas are by chromatographic column one, chromatographic column two, or realize that carrier gas two enters automatic transfer valve three directly through chromatographic column one;Institute State automatic transfer valve two to be connected with chromatographic column two, and be connected with deoxidation hydrazine, automatic transfer valve three, cut automatically by switching Realize the gas by chromatographic column two whether by deoxidation hydrazine into automatic transfer valve three in the valve position for changing valve two;The automatic switchover Valve three is connected with detector, blast pipe one, realizes being passed through switching automatic transfer valve by the valve position for switching automatic transfer valve three Three gas enters detector or blast pipe one;The automatic transfer valve two is also associated with the inlet pipe of carrier gas three and blast pipe two, Realize carrier gas three whether by deoxidation hydrazine into blast pipe two by the valve position for switching automatic transfer valve two;The automatic transfer valve One is ten-way valve, and the automatic transfer valve two is six-way valve, and the automatic transfer valve three is four-way valve.
2. a kind of gas chromatography analysis method of high purity oxygen gas according to claim 1, it is characterised in that the chromatographic column One selects Rt-Q-Bond chromatographic columns.
3. a kind of gas chromatography analysis method of high purity oxygen gas according to claim 1, it is characterised in that the chromatographic column Two select Molsieve chromatographic columns.
4. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 1, it is characterised in that the carrier gas one, Carrier gas two is exported with steel cylinder, and output pressure is 0.3-0.5MPa;The temperature of the sample gas inlet is 25-100 DEG C.
5. a kind of gas chromatography analysis method of high purity oxygen gas according to claim 1, it is characterised in that the chromatographic column One temperature uses temperature programming, and initial temperature is 5-20 DEG C, and 80-100 DEG C is warming up to after the response signal for detecting hydrogen;Institute The temperature for stating chromatographic column two is 40-60 DEG C.
6. a kind of gas chromatography analysis method of high purity oxygen gas according to claim 1, it is characterised in that the deoxidation hydrazine Temperature be 120-200 DEG C.
7. a kind of gas chromatography analysis method of high purity oxygen gas according to claim 1, it is characterised in that the detector Temperature be 100-300 DEG C.
CN201510928845.1A 2015-12-15 2015-12-15 The gas chromatographic analysis device and its analysis method of a kind of high purity oxygen gas Active CN105572281B (en)

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