CN105572281A - Gas chromatography analytical device and gas chromatography analytical method for high-purity oxygen - Google Patents

Gas chromatography analytical device and gas chromatography analytical method for high-purity oxygen Download PDF

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CN105572281A
CN105572281A CN201510928845.1A CN201510928845A CN105572281A CN 105572281 A CN105572281 A CN 105572281A CN 201510928845 A CN201510928845 A CN 201510928845A CN 105572281 A CN105572281 A CN 105572281A
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gas
automatic transfer
chromatographic column
transfer valve
hydrogen
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CN105572281B (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 invention relates to a gas chromatography analytical device and a gas chromatography analytical method for high-purity oxygen. The gas chromatography analytical device comprises a sample gas sampling pipe, a carrier gas inlet pipe, automatic switching valves, chromatographic columns, a deoxidation hydrazine, exhaust pipes, a detector and the like. By switching a valve position of the automatic switching valve I, carrier gas I carries a sample gas to pass through the chromatographic column I and the chromatographic column II or carrier gas II directly flows through the chromatographic column I and enters into the automatic switching valve III; by switching a valve position of the automatic switching valve II, whether gas passing through the chromatographic column II enters into the automatic switching valve III through the deoxidation hydrazine is realized; by switching a valve position of the automatic switching valve III, gas introduced into the automatic switching valve III enters into the detector or the exhaust pipe I. According to the gas chromatography analytical device and the gas chromatography analytical method disclosed by the invention, total analysis of various components and impurities in the high-purity oxygen can be finished by one-time sampling, analysis time is shortened and use cost of carrier gases and the like is reduced.

Description

A kind of gas chromatographic analysis device of high purity oxygen gas and analytical approach thereof
Technical field
The invention belongs to analysis detection field, be specifically related to a kind of gas chromatographic analysis device and analytical approach thereof of high purity oxygen gas.
Background technology
The new standard (GB/T14599-2008 pure oxygen, high purity oxygen and ultrapure oxygen) of high purity oxygen gas was formally implemented on November 1st, 2008, and comparatively former standard (GB/T14599-1993 high purity oxygen) becomes for the kind of impurity in high purity oxygen gas the detection newly increased hydrogen impurity from original argon, nitrogen, carbon dioxide and total hydrocarbon.
At present, domestic is generally use repeatedly sample introduction repeatedly to analyze, and the various indexs in high purity oxygen gas is analyzed, and causes analytic process to use the problems such as equipment is many, method is complicated, analysis time is long, use cost is high.
Summary of the invention
Technical matters to be solved by this invention is the deficiency that exists for above-mentioned prior art and provides a kind of gas chromatographic analysis device and analytical approach thereof of high purity oxygen gas, disposable sample introduction completes the total analysis of each composition impurity in high purity oxygen gas, shortens analysis time and reduces the use costs such as carrier gas.
The technical scheme that the problem that the present invention is the above-mentioned proposition of solution adopts is:
A kind of gas chromatographic analysis device of high purity oxygen gas, comprise sample gas inlet pipe, sample gas stopple coupon, sample gas go out pipe, carrier gas one inlet pipe, carrier gas two inlet pipe, automatic transfer valve one, chromatographic column one, chromatographic column two, automatic transfer valve two, deoxidation hydrazine, gas outlet one, automatic transfer valve three, detecting device, described sample gas inlet pipe and sample gas go out between pipe to be connected with sample gas stopple coupon; Described automatic transfer valve one is all connected with sample gas stopple coupon, carrier gas one inlet pipe, carrier gas two inlet pipe, automatic transfer valve three, chromatographic column one, chromatographic column two, realize carrier gas one carry sample gas through chromatographic column one, chromatographic column two by switching the valve position of automatic transfer valve one, or realize carrier gas two and directly flow through chromatographic column one and enter automatic transfer valve three; Described automatic transfer valve two is connected with chromatographic column two, and be connected with deoxidation hydrazine, automatic transfer valve three, realize entering automatic transfer valve three through the gas of chromatographic column two through deoxidation hydrazine by the valve position switching automatic transfer valve two, or the gas realized through chromatographic column two directly enters automatic transfer valve three without deoxidation hydrazine; Described automatic transfer valve three is connected with detecting device, gas outlet one, realizes passing into the gas switching automatic transfer valve three enter detecting device or gas outlet one by the valve position switching automatic transfer valve three.
By such scheme, described automatic transfer valve two is also connected with carrier gas three inlet pipe and gas outlet two, realize carrier gas three and enter gas outlet two by switching the valve position of automatic transfer valve two by deoxidation hydrazine, or realize carrier gas three and directly do not enter gas outlet two by deoxidation hydrazine.
By such scheme, described automatic transfer valve one is ten-way valve, and described automatic transfer valve two is six-way valve, and described automatic transfer valve three is four-way valve.
A gas chromatography analysis method for high purity oxygen gas, comprises the steps:
1) high purity oxygen gas is as sample gas, wherein containing oxygen (O 2), hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2);
2) carrier gas one is by automatic transfer valve one by sample gas carry over score analysis system, and the valve position switching automatic transfer valve one makes carrier gas one carry sample gas to pass into chromatographic column one and carry out pre-separation, carbon dioxide (CO 2) be retained in chromatographic column one, the gas then through chromatographic column one comprises oxygen (O 2), hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) continue to pass into chromatographic column two with carbon monoxide (CO) and be separated;
3) switch the valve position of automatic transfer valve one, make carrier gas two flow through chromatographic column one, and then carry in chromatographic column one and retain atmospheric carbon dioxide (CO 2) enter detecting device by automatic transfer valve three, detect its response signal----peak area; As carbon dioxide (CO 2) enter detecting device after, switch the valve position of automatic transfer valve three and make CO 2component is below blown analytic system by gas outlet two;
4) control automatic transfer valve two, control the valve position of automatic transfer valve three, make directly to enter detecting device by the gas of chromatographic column two, detect wherein hydrogen (H 2) response signal----peak area; As hydrogen (H 2) enter detecting device after, switch the valve position of automatic transfer valve two, make first to flow through deoxidation hydrazine by the gas of chromatographic column two and enter detecting device again, successively detect wherein argon gas (Ar), nitrogen (N 2), methane (CH 4) response signal----peak area; As methane (CH 4) enter detecting device after, switch the valve position of automatic transfer valve two, make directly to enter detecting device by the gas of chromatographic column two, detect the response signal----peak area of wherein CO (carbon monoxide);
5) standard high purity oxygen gas sample is prepared, known wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) content be respectively C hydrogen, C argon gas, C nitrogen, C methaneand C carbon monoxide, C carbon dioxide, by step 1) and-4) measure wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) peak area be respectively S hydrogen, S argon gas, S nitrogen, S methaneand S carbon monoxide, S carbon dioxide, calculate the correction factor K of each foreign gas hydrogen, K argon gas, K nitrogen, K methaneand K carbon monoxide, K carbon dioxide, wherein K hydrogen=C hydrogen/ S hydrogen, K argon gas=C argon gas/ S argon gas, K nitrogen=C nitrogen/ S nitrogen, K methane=C methane/ S methaneand K carbon monoxide=C carbon monoxide/ S one carbonoxide, K carbon dioxide=C carbon dioxide/ S carbon dioxide;
6) high purity oxygen gas sample to be measured is chosen, by step 1)-4) measure wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) peak area be respectively S ' hydrogen, S ' argon gas, S ' nitrogen, S ' methaneand S ' carbon monoxide, S ' carbon dioxide, calculate hydrogen (H in high purity oxygen gas sample to be measured 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) content C ' hydrogen, C ' argon gas, C ' nitrogen, C ' methaneand C ' carbon monoxide, C ' carbon dioxide, wherein C ' hydrogen=K hydrogen× S ' hydrogen, C ' argon gas=K argon gas× S ' argon gas, C ' nitrogen=K nitrogen× S ' nitrogen, C ' methane=K methane× S ' methane, C ' carbon monoxide=K carbon monoxide× S ' carbon monoxide, C ' carbon dioxide=K carbon dioxide× S ' carbon dioxide.
By such scheme, described chromatographic column one is for realizing carbon dioxide (CO in sample gas 2) separation, Rt-Q-Band chromatographic column can be selected.
By such scheme, described chromatographic column two is for realizing hydrogen (H in sample gas 2), oxygen (O 2), argon gas (Ar), nitrogen (N 2), CH 4(methane) is separated with CO (carbon monoxide), can select Molsieve chromatographic column.
By such scheme, described carrier gas one, carrier gas two export with steel cylinder, and output pressure is within the scope of 0.3-0.5MPa.
By such scheme, the temperature of described detecting device is within the scope of 100-300 DEG C.
By such scheme, the temperature of described chromatographic column one adopts temperature programme, and initial temperature is 5-20 DEG C, hydrogen (H detected 2) response signal after be warming up to 80-100 DEG C.
By such scheme, the temperature of described chromatographic column two is 40-60 DEG C.
By such scheme, the temperature of described deoxidation hydrazine is within the scope of 120-200.
By such scheme, the temperature of described sample gas inlet is within the scope of 25-100 DEG C.
Compared with prior art, the invention has the beneficial effects as follows:
1) the present invention can comprise the trace impurity of hydrogen in Accurate Determining high purity oxygen gas, and ensure the product quality of high purity oxygen gas, and single sample introduction completes the total analysis of each composition impurity in high purity oxygen gas, whole analysis time is short, simple to operate; And analytical approach in the past needs repeatedly sample introduction for the analysis of composition impurity each in whole high purity oxygen gas, consume long time, and consume a lot of sample gas;
2) the present invention utilizes capillary chromatographic column to shorten analysis time, and reduces the consumption of carrier gas, reduces use cost; Used packed column to analyze impurity in the past, need to consume a large amount of carrier gas, the analyser of usual analysis high purity oxygen gas uses high-purity helium, high-purity helium cost is very high, average one bottle 1200 yuan, within one month in the past, will use 2.5-3 bottle, after choice for use capillary chromatographic column, the pure helium of a bottle height can use 2.5 months;
3) the present invention utilizes transfer valve UNICOM deoxidation hydrazine, is excised by the oxygen of high-load, reduces the deoxidation amount of high purity oxygen gas, extends the serviceable life of deoxidation hydrazine, and realizes the detection to hydrogen impurity; The analysis of high purity oxygen gas in the past, need that the sample gas of this sample introduction is carried out deoxidation to analyze again, deoxidation post uses just to be needed for 25 times to activate deoxidation post, but the present invention is only to needing the oxygen of absorption to carry out cutting process, can reduce the amount of deoxidation post adsorption of oxygen in deoxidation process significantly, such deoxidation post can use more than 100 times.
Accompanying drawing explanation
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 measures.
Wherein, 1-sample gas inlet pipe, 2-stopple coupon, 3-sample gas goes out pipe, 4-carrier gas one inlet pipe, 5-carrier gas two inlet pipe, 6-automatic transfer valve one, 7-chromatographic column one, 8-carrier gas three inlet pipe, 9-deoxidation hydrazine, 10-gas outlet two, 11-chromatographic column two, 12-automatic transfer valve two, 13-automatic transfer valve three, 14-gas outlet one, 15-detecting device.
Embodiment
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but the present invention is not only confined to the following examples.
Embodiment
(1), a kind of gas chromatographic analysis device of high purity oxygen gas, comprise sample gas inlet pipe 1, sample gas stopple coupon 2, sample gas go out pipe 3, carrier gas one inlet pipe 4, carrier gas two inlet pipe 5, automatic transfer valve 1, chromatographic column 1, chromatographic column 2 11, automatic transfer valve 2 12, deoxidation hydrazine 9, gas outlet 1, automatic transfer valve 3 13, detecting device 15, described sample gas inlet pipe 1 and sample gas go out between pipe 3 to be connected with sample gas stopple coupon 2; Described automatic transfer valve 1 is all connected with sample gas stopple coupon 2, carrier gas one inlet pipe 4, carrier gas two inlet pipe 5, automatic transfer valve 3 13, chromatographic column 1, chromatographic column 2 11, realize carrier gas one carry sample gas through chromatographic column 1, chromatographic column 2 11 by switching the valve position of automatic transfer valve 1, or realize carrier gas two and directly flow through chromatographic column 1 and enter automatic transfer valve 3 13; Described automatic transfer valve 2 12 is connected with chromatographic column 2 11, and be connected with deoxidation hydrazine 9, automatic transfer valve 3 13, realize entering automatic transfer valve 3 13 through the gas of chromatographic column two through deoxidation hydrazine 9 by the valve position switching automatic transfer valve 2 12, or the gas realized through chromatographic column two directly enters automatic transfer valve 3 13 without deoxidation hydrazine 9; Described automatic transfer valve 3 13 is connected with detecting device 15, gas outlet 1, realizes passing into the gas switching automatic transfer valve 3 13 enter detecting device 14 or gas outlet 1 by the valve position switching automatic transfer valve 3 13.
Preferably, in order to ensure the gas pressure balancing in deoxidation hydrazine, described automatic transfer valve 2 12 is also connected with carrier gas three inlet pipe 8 and gas outlet 2 10, realize carrier gas three and enter gas outlet 2 10 by switching the valve position of automatic transfer valve 2 12 by deoxidation hydrazine 9, or realize carrier gas three and directly do not enter gas outlet 2 10 by deoxidation hydrazine 9.
Preferably, described automatic transfer valve one is ten-way valve, and described automatic transfer valve two is six-way valve, and described automatic transfer valve three is four-way valve.
Preferably, described chromatographic column one is for realizing carbon dioxide (CO in sample gas 2) separation, select Rt-Q-Band chromatographic column; Described chromatographic column two is for realizing hydrogen (H in sample gas 2), oxygen (O 2), argon gas (Ar), nitrogen (N 2), CH 4(methane) is separated with CO (carbon monoxide), selects Molsieve chromatographic column.
(2), in following method, the conditional parameter of stratographic analysis is: select helium to be carrier gas (purity 99.999%), and the steel cylinder reduction valve output pressure value holding carrier gas is 0.42MPa; Injector temperature 50 DEG C; Rt-Q-Band chromatographic column adopts temperature programme, and initial temperature is 10 DEG C, hydrogen (H detected 2) response signal after be warming up to temperature 90 DEG C; Molsieve chromatographic column is placed in constant temperature clack box, and temperature is 50 DEG C; Deoxidation trap temperature is 150 DEG C, detecting device tail mouthpiece flow 36.3ml/min, detecting device base-plate temp 250 DEG C; It is as shown in table 1 that the time cut by the valve of each automatic transfer valve.
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
1, a gas chromatography analysis method for high purity oxygen gas, comprises the steps:
1) standard high purity oxygen gas sample (being called for short " sample gas " in following step) is prepared, wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2), content is as shown in table 2;
Table 2
Sequence number Title Content (ppm)
1 Carbon dioxide (CO 2) 5.0
2 Hydrogen (H 2) 5.0
3 Argon gas (Ar) 4.0
4 Nitrogen (N 2) 3.3
5 Methane (CH 4) 3.8
6 Carbon monoxide (CO) 5.0
2) carrier gas one passes through automatic transfer valve one by sample gas carry over score analysis system, switch the valve position (cutting valve time 0.01min) of automatic transfer valve one to make carrier gas one carry sample gas to pass into Rt-Q-Band chromatographic column and carry out pre-separation, carbon dioxide (CO 2) be retained in Rt-Q-Band chromatographic column, the gas then through Rt-Q-Band chromatographic column comprises oxygen (O 2), hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) continue to pass into Molsieve chromatographic column with carbon monoxide (CO) and be separated;
3) switch the valve position (cutting valve time 1.85min) of automatic transfer valve one, make carrier gas two flow through Rt-Q-Band chromatographic column, and then carry in Rt-Q-Band chromatographic column and retain atmospheric carbon dioxide (CO 2) enter detecting device by automatic transfer valve three (automatic transfer valve three switches to this state in 0.01min), detect its response signal----peak area S carbon dioxide; As carbon dioxide (CO 2) enter detecting device after, switch the valve position (cutting valve time 2.20min) of automatic transfer valve three and make CO 2component is below blown analytic system by gas outlet two;
4) switch the valve position of automatic transfer valve three, make directly to enter detecting device by the gas of Molsieve chromatographic column by automatic transfer valve two, automatic transfer valve three, detect wherein hydrogen (H 2) response signal----peak area S hydrogen; As hydrogen (H 2) enter detecting device after, switch the valve position (cutting valve time 2.90min) of automatic transfer valve two, make first to flow through deoxidation hydrazine by the gas of Molsieve chromatographic column and enter detecting device again, successively detect wherein argon gas (Ar), nitrogen (N 2), methane (CH 4) response signal----peak area is respectively S argon gas, S nitrogen, S methane; As methane (CH 4) enter detecting device after, switch the valve position (cutting valve time 9.10min) of automatic transfer valve two, make directly to enter detecting device by the gas of Molsieve chromatographic column, detect the response signal of wherein CO (carbon monoxide)----peak area S carbon monoxide, concrete data are as shown in table 3;
5) the correction factor K of each foreign gas in standard high purity oxygen gas sample is calculated hydrogen, K argon gas, K nitrogen, K methaneand K one oxidation carbon, K carbon dioxide, wherein K hydrogen=C hydrogen/ S hydrogen, K argon gas=C argon gas/ S argon gas, K nitrogen=C nitrogen/ S nitrogen, K methane=C methane/ S methaneand K one oxygen change carbon=C carbon monoxide/ S carbon monoxide, K carbon dioxide=C carbon dioxide/ S carbon dioxide, concrete 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 (CO 2) 1.78 1499860 5.0 3.33364E-06
2 Hydrogen (H 2) 2.7 221617 5.0 2.25614E-05
3 Argon gas (Ar) 4.6 832232 4.0 4.80635E-06
4 Nitrogen (N 2) 6.36 847768 3.3 3.89257E-06
5 Methane (CH 4) 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) measure wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) peak area be respectively S ' hydrogen, S ' argon gas, S ' nitrogen, S ' methaneand S ' carbon monoxide, S ' carbon dioxide, calculate hydrogen (H in high purity oxygen gas sample to be measured 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) content C ' hydrogen, C ' argon gas, C ' nitrogen, C ' methaneand C ' carbon monoxide, C ' carbon dioxide, wherein C ' hydrogen=K hydrogen× S ' hydrogen, C ' argon gas=K argon gas× S ' argon gas, C ' nitrogen=K nitrogen× S ' nitrogen, C ' methane=K methane× S ' methane, C ' carbon monoxide=K carbon monoxide× S ' carbon monoxide, C ' carbon dioxide=K carbon 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 (CO 2) 6577 3.33364E-06 0.02
2 Hydrogen (H 2) 7617 2.25614E-05 0.17
3 Argon gas (Ar) 232232 4.80635E-06 1.12
4 Nitrogen (N 2) 147768 3.89257E-06 0.58
5 Methane (CH 4) 186732 2.39486E-06 0.45
6 Carbon monoxide (CO) 2151 1.55207E-05 0.03
From Fig. 2 and table 3, table 4, the method for the invention effectively can be separated each foreign gas in high purity oxygen gas sample, and realizes qualitative and quantitative analysis.
The above is only the preferred embodiment of the present invention, it should be pointed out that for the person of ordinary skill of the art, and without departing from the concept of the premise of the invention, can also make some improvement and conversion, these all belong to protection scope of the present invention.

Claims (10)

1. the gas chromatographic analysis device of a high purity oxygen gas, it is characterized in that it comprises sample gas inlet pipe, sample gas stopple coupon, sample gas go out pipe, carrier gas one inlet pipe, carrier gas two inlet pipe, automatic transfer valve one, chromatographic column one, chromatographic column two, automatic transfer valve two, deoxidation hydrazine, gas outlet one, automatic transfer valve three, detecting device, described sample gas inlet pipe and sample gas go out between pipe to be connected with sample gas stopple coupon; Described automatic transfer valve one is all connected with sample gas stopple coupon, carrier gas one inlet pipe, carrier gas two inlet pipe, automatic transfer valve three, chromatographic column one, chromatographic column two, realize carrier gas one carry sample gas through chromatographic column one, chromatographic column two by switching the valve position of automatic transfer valve one, or realize carrier gas two and directly flow through chromatographic column one and enter automatic transfer valve three; Described automatic transfer valve two is connected with chromatographic column two, and is connected with deoxidation hydrazine, automatic transfer valve three, realizes whether entering automatic transfer valve three through deoxidation hydrazine through the gas of chromatographic column two by the valve position switching automatic transfer valve two; Described automatic transfer valve three is connected with detecting device, gas outlet one, realizes passing into the gas switching automatic transfer valve three enter detecting device or gas outlet one by the valve position switching automatic transfer valve three.
2. the gas chromatographic analysis device of a kind of high purity oxygen gas according to claim 1, it is characterized in that described automatic transfer valve two is also connected with carrier gas three inlet pipe and gas outlet two, realize carrier gas three by the valve position switching automatic transfer valve two and whether enter gas outlet two by deoxidation hydrazine.
3. the gas chromatographic analysis device of a kind of high purity oxygen gas according to claim 1, it is characterized in that described automatic transfer valve one is ten-way valve, described automatic transfer valve two is six-way valve, and described automatic transfer valve three is four-way valve.
4. a gas chromatography analysis method for high purity oxygen gas, is characterized in that comprising the steps:
1) high purity oxygen gas is as sample gas, wherein containing oxygen (O 2), hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2);
2) carrier gas one is by automatic transfer valve one by sample gas carry over score analysis system, and the valve position switching automatic transfer valve one makes carrier gas one carry sample gas to pass into chromatographic column one and carry out pre-separation, carbon dioxide (CO 2) be retained in chromatographic column one, the gas then through chromatographic column one comprises oxygen (O 2), hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) continue to pass into chromatographic column two with carbon monoxide (CO) and be separated;
3) switch the valve position of automatic transfer valve one, make carrier gas two flow through chromatographic column one, and then carry in chromatographic column one and retain atmospheric carbon dioxide (CO 2) enter detecting device by automatic transfer valve three, detect its response signal----peak area; As carbon dioxide (CO 2) enter detecting device after, switch the valve position of automatic transfer valve three and make carbon dioxide (CO 2) component is below blown analytic system by gas outlet two;
4) control automatic transfer valve two, control the valve position of automatic transfer valve three, make directly to enter detecting device by the gas of chromatographic column two, detect wherein hydrogen (H 2) response signal----peak area; As hydrogen (H 2) enter detecting device after, switch the valve position of automatic transfer valve two, make first to flow through deoxidation hydrazine by the gas of chromatographic column two and enter detecting device again, successively detect wherein argon gas (Ar), nitrogen (N 2), methane (CH 4) response signal----peak area; As methane (CH 4) enter detecting device after, switch the valve position of automatic transfer valve two, make directly to enter detecting device by the gas of chromatographic column two, detect the response signal----peak area of wherein CO (carbon monoxide);
5) standard high purity oxygen gas sample is prepared, known wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) content be respectively C hydrogen, C argon gas, C nitrogen, C methaneand C carbon monoxide, C carbon dioxide, by step 1) and-4) measure wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) peak area be respectively S hydrogen, S argon gas, S nitrogen, S methaneand S carbon monoxide, S carbon dioxide, the ratio coefficient calculating each gas composition content and peak area is respectively K hydrogen, K argon gas, K nitrogen, K methaneand K carbon monoxide, K carbon dioxide;
6) high purity oxygen gas sample to be measured is chosen, by step 1)-4) measure wherein hydrogen (H 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) 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 measured 2), argon gas (Ar), nitrogen (N 2), methane (CH 4) and carbon monoxide (CO), carbon dioxide (CO 2) content C ' hydrogen, C ' argon gas, C ' nitrogen gas, C ' methaneand C ' carbon monoxide, C ' carbon dioxide, wherein C ' hydrogen=K hydrogen× S ' hydrogen, C ' argon gas=K argon gas× S ' argon gas, C ' nitrogen=K nitrogen× S ' nitrogen gas, C ' methane=K methane× S ' methane, C ' carbon monoxide=K carbon monoxide× S ' carbon monoxide, C ' carbon dioxide=K carbon dioxide× S ' carbon dioxide.
5. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, is characterized in that described chromatographic column one selects Rt-Q-Band chromatographic column.
6. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, is characterized in that described chromatographic column two selects Molsieve chromatographic column.
7. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, it is characterized in that described carrier gas one, carrier gas two are with steel cylinder output, output pressure is 0.3-0.5MPa; The temperature of described sample gas inlet is 25-100 DEG C.
8. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, it is characterized in that the temperature of described chromatographic column one adopts temperature programme, initial temperature is 5-20 DEG C, is warming up to 80-100 DEG C after the response signal of hydrogen being detected; The temperature of described chromatographic column two is 40-60 DEG C.
9. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, is characterized in that the temperature of described deoxidation hydrazine is 120-200 DEG C.
10. the gas chromatography analysis method of a kind of high purity oxygen gas according to claim 4, is characterized in that the temperature of described detecting device is 100-300 DEG C.
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