CN103487543B - The analytical approach of Krypton and xenon content in krypton xenon unstripped gas - Google Patents
The analytical approach of Krypton and xenon content in krypton xenon unstripped gas Download PDFInfo
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- CN103487543B CN103487543B CN201310425255.8A CN201310425255A CN103487543B CN 103487543 B CN103487543 B CN 103487543B CN 201310425255 A CN201310425255 A CN 201310425255A CN 103487543 B CN103487543 B CN 103487543B
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- krypton
- xenon
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Abstract
The present invention relates to the analytical approach of Krypton and xenon content in a kind of krypton xenon unstripped gas, solve Krypton and the inaccurate problem of xenon content analysis in existing krypton xenon unstripped gas.The present invention, using type analysis of thermal conductivity instrument as parent, adopts capillary chromatographic column to measure, and using helium as carrier gas, uses miniature analysis of thermal conductivity instrument to measure the peak area of Krypton and xenon in krypton xenon unstripped gas, then calculates Krypton and xenon volume content.The present invention can the content of Krypton and these key components of xenon in Accurate Determining krypton xenon unstripped gas, Krypton can be met, xenon produces the requirement in earlier stage selected unstripped gas quality, detect quick and precisely, deviation ratio much smaller than 3%, within can foreshortening to 50 seconds detection time.
Description
Technical field
The utility model relates to a kind of analytical approach of krypton xenon unstripped gas, specifically the analytical approach of Krypton and xenon content in a kind of krypton xenon unstripped gas.
Background technology
Krypton and xenon are because content is in an atmosphere few, very valuable, therefore are referred to as " rare gas ", " gold gas ", and price is high; Extract difficulty, only could extract on large-scale, Extra large air separation plant.Be used in electric light source, welding and scientific research medical treatment aspect widely.
Krypton xenon unstripped gas mainly divides the liquid oxygen at main cold heat exchanger position in production run at sky, the Krypton of enriched and xenon in this place's liquid oxygen, but also containing impurity compositions such as a large amount of methane.At present for the monitoring of krypton xenon unstripped gas, main use hydrogen flame gas chromatographicanalyzer measures methane wherein, is gone out the content (ratio of namely for methane content and Krypton and xenon judges that whether unstripped gas quality is qualified) of Krypton and xenon in unstripped gas by knowhow formulae discovery.The method is too rough, cannot carry out quantitatively the exact level of Krypton in unstripped gas and xenon accurately.
Accurate quantitative analysis is carried out to Krypton in unstripped gas and xenon and there is Railway Project: 1. approximately contain 1200 × 10 according to Krypton in knowhow unstripped gas
-6(volume fraction), xenon is approximately containing 100 × 10
-6, there is the problem that component concentration difference is larger in (volume fraction).2. use gas chromatography determination, the retention time of methane and Krypton is close.Deposit separation problem in the dosing process.3. the principal ingredient of krypton xenon unstripped gas is oxygen, and oxygen exists for when measuring Krypton content the problem that chromatographic peak covers.4. the molecular mass of xenon is comparatively large, there is the problem that retention time is longer.
Summary of the invention
The object of the invention is to solve the problems of the technologies described above, provide a kind of can accurately, in Fast Measurement krypton xenon unstripped gas the content of Krypton and xenon krypton xenon unstripped gas in the analytical approach of Krypton and xenon content.
Technical scheme comprises:
1) preparation is 100 × 10 containing xenon volume content
-6(volume fraction), Krypton gas volume content is 1000 × 10
-6(volume fraction), methane gas volume content is 1000 × 10
-6the 8L Standard Gases of (volume fraction) one bottle, all the other are helium (Standard Gases); Wherein, volume fraction content deviation ± 5% of Standard Gases.
2) using miniature analysis of thermal conductivity instrument as parent, capillary chromatographic column is adopted to measure;
3) using helium as carrier gas, use miniature analysis of thermal conductivity instrument respectively determination step 1) Standard Gases in the K of Krypton and xenon
kryptonand K
xenon
4) krypton xenon unstripped gas is measured,
A, using helium as carrier gas, miniature analysis of thermal conductivity instrument is used to measure the peak area s of Krypton and xenon in krypton xenon unstripped gas
krypton; s
xenon.
B, calculating Krypton and xenon volume content, its computing formula:
V
krypton=s
krypton× K
krypton;
V
xenon=s
xenon× K
xenon;
The installation coating of described capillary chromatographic column is Porapak Q post, and column diameter is 0.32 millimeter, and length is 10 meters.
Controlling atmospheric pressure is 0.3 MPa, and described nebulizer gas pressure 0.15 MPa, controlling described krypton xenon feed gas flow rates is 30 ml/min.
The miniature analysis of thermal conductivity instrument selecting sensitivity higher is as parent, column diameter is selected to be 0.32 millimeter, length be the capillary chromatographic column of 10 meters carry out mensuration be because: 1. the conductance cell volume due to miniature thermal conductance is little, is about 1/10 (80 microlitre) of common thermal conductance analyser pond body so the very high content that can measure each component accurately of sensitivity; 2. select capillary chromatographic column to be because capillary chromatographic column has compared with packed column the feature that separation efficiency is high, retention time is short as the separating column of instrument, analysis time can be shortened while guarantee is separated each component; 3., owing to needing the content measuring Krypton and xenon, so select the capillary column of 10 meters long as separating column, allow the oxygen chromatographic peak of large content only cover methane, allow Krypton still can reach the effect be separated completely, meet and analyze requirement.
The present invention can the content of Krypton and these key components of xenon in Accurate Determining krypton xenon unstripped gas, Krypton can be met, xenon produces the requirement in earlier stage selected unstripped gas quality, detect quick and precisely, deviation ratio much smaller than 3%, within can foreshortening to 50 seconds detection time.
Accompanying drawing explanation
Fig. 1 uses helium as carrier gas, uses conventional analysis of thermal conductivity instrument bioassay standard gas spectrogram;
Fig. 2 amplifies utilization helium as carrier gas, uses xenon chromatographic peak part in conventional analysis of thermal conductivity instrument bioassay standard gas spectrogram;
Fig. 3 uses helium as carrier gas, uses conventional analysis of thermal conductivity instrument to measure krypton xenon unstripped gas spectrogram.
Fig. 4 uses helium as carrier gas, uses miniature analysis of thermal conductivity instrument bioassay standard gas spectrogram.
Fig. 5 uses helium as carrier gas, uses miniature analysis of thermal conductivity instrument to measure krypton xenon unstripped gas spectrogram.
Wherein, in Fig. 1-Fig. 5, horizontal ordinate is the time (minute); Ordinate is electric signal (millivolt), note: methane chromatographic peak is covered by oxygen chromatographic peak, and what Krypton chromatographic peak can be complete separates with oxygen chromatographic peak.
Fig. 6 uses helium as carrier gas, uses miniature analysis of thermal conductivity instrument to measure krypton xenon unstripped gas 30 histograms.
Embodiment
Embodiment:
The present invention will be further described below: described krypton xenon unstripped gas picks up from the rare production line of oxygen company.
1) preparation is 101 × 10 containing xenon volume content
-6(volume fraction), Krypton gas volume content is 1006 × 10
-6(volume fraction), methane gas volume content is 1005 × 10
-6the 8L Standard Gases of (volume fraction) one bottle, all the other are helium (Standard Gases).
2) use helium as carrier gas, use miniature analysis of thermal conductivity instrument (Varian Associates, Inc. (US) 611 Hansen Way, Palo Alto, California 94303, U.S.A. (Varian) produces, and model is CP4900) bioassay standard gas and krypton xenon unstripped gas respectively, the instrument test condition of Fig. 4 and Fig. 5:
Instrument adopts N5 level (99.999%) high-purity helium to do carrier gas.
Chromatographic column: Porapak Q post column length: 10 meters of post footpaths: 0.32 millimeter of column temperature: 80 DEG C
Control atmospheric pressure: 0.3 MPa nebulizer gas pressure: 150 kPas of (this equipment is constant-pressure type flow control) sample gas flow velocitys: 30 ml/min
Sample time: 100 milliseconds (this equipment is micropump suction sample introduction)
3) using helium as carrier gas, use miniature analysis of thermal conductivity instrument respectively determination step 1) Standard Gases in the K of Krypton and xenon
kryptonand K
xenon, wherein,
4) krypton xenon unstripped gas is measured,
A, using helium as carrier gas, miniature analysis of thermal conductivity instrument is used to measure the peak area s of Krypton and xenon in krypton xenon unstripped gas
krypton; s
xenon.
B, calculating Krypton and xenon volume content, its computing formula:
V
krypton=s
krypton× K
krypton=864138 × 1.55 × 10
-3=1339;
V
xenon=s
xenon× K
xenon=41632 × 1.99 × 10
-3=83;
3) use the instrument condition of work of Fig. 4 to carry out mensuration 10 times to Standard Gases, the Krypton of mensuration and the peak area of xenon are in table 1
| Sequence number | Krypton peak area | Xenon peak area |
| 1 | 864138 | 41632 |
| 2 | 865759 | 41453 |
| 3 | 864179 | 41567 |
| 4 | 863178 | 41654 |
| 5 | 864543 | 41546 |
| 6 | 866543 | 41493 |
| 7 | 862356 | 41549 |
| 8 | 865493 | 41736 |
| 9 | 865244 | 41458 |
| 10 | 866973 | 41421 |
According to standard deviation
relative standard deviation:
calculating the standard deviation that this instrument measures for Krypton and xenon is:
Q (Krypton)=1446.62;
cV=0.17%
Q (xenon)=100.11;
cV=0.24%
This instrument is all less than 3% for the relative standard deviation of each material, can meet the mensuration to these two kinds of materials.
4) the krypton xenon unstripped gas of the inventive method to Ke Xian rare gas production division (the rare production line of oxygen company) is used to detect, 2 times weekly, continuous 15 weeks (adding up to 30 times) sees Fig. 6 (in order to make icon more than you know, being charted xenon content × 10) to analysis result in table 2, histogram.
V can be found out by data in form and column line chart (Fig. 6) shape
methane: V
krypton: V
xenonwith the proportionate relationship of the experimental formula 10:10:1 of production division in the past.Use and measure methane content in krypton xenon unstripped gas in the past and calculate that the content of Krypton wherein and xenon is unscientific, so set up the analytical approach of Krypton and xenon content in a kind of Accurate Determining krypton xenon unstripped gas, Ke Xian rare gas production division can be helped to select accurately containing Krypton and the higher unstripped gas of these effective constituents of xenon, as raw materials for production, energy resource consumption can be reduced and improve product quality and yield.
Comparative example:
Use universal analysis of thermal conductivity instrument to analyze the Standard Gases described in above-described embodiment and krypton xenon unstripped gas, see spectrogram 1, spectrogram 2 and spectrogram 3, instrument adopts N5 level (99.999%) high-purity helium to do carrier gas.
Chromatographic column: Porapak Q post column length: 3 meters of post footpaths: 3 millimeters of column temperatures: 80 DEG C
Detector temperature: 200 DEG C control atmospheric pressure: 0.3 MPa
Nebulizer gas pressure: 0.15 MPa
Sample gas flow velocity: 30 ml/min sampling volumes: 1 milliliter
Krypton is covered by the oxygen of large content, cannot carry out quantitatively to Krypton; Xenon retention time is very long, causes in the analytic process time oversize, affects detection efficiency; The sensitivity of Krypton and xenon is very low, and impact is measured.
Claims (2)
1. the analytical approach of Krypton and xenon content in krypton xenon unstripped gas, is characterized in that, carry out according to following analysis method:
1) preparation is 100 × 10 containing xenon volume fraction
-6, Krypton volume fraction is 1000 × 10
-6, methane gas volume fraction is 1000 × 10
-68L Standard Gases one bottle, all the other are helium;
2) using miniature analysis of thermal conductivity instrument as parent, adopt capillary chromatographic column to measure, the installation coating of described capillary chromatographic column is Porapak Q post, and column diameter is 0.32 millimeter, and length is 10 meters, column temperature: 80 DEG C;
3) using helium as carrier gas, use miniature analysis of thermal conductivity instrument respectively determination step 1) Standard Gases in the K of Krypton and xenon
kryptonand K
xenon, wherein,
4) krypton xenon unstripped gas is measured,
A, using helium as carrier gas, miniature analysis of thermal conductivity instrument is used to measure the peak area s of Krypton and xenon in krypton xenon unstripped gas
krypton; s
xenon
B, calculating Krypton and xenon volume fraction, its computing formula:
V
krypton=s
krypton× K
krypton;
V
xenon=s
xenon× K
xenon.
2. the analytical approach of Krypton and xenon content in krypton xenon unstripped gas as claimed in claim 1, it is characterized in that, controlling atmospheric pressure is 0.3 MPa, and described nebulizer gas pressure 0.15 MPa, controlling described krypton xenon feed gas flow rates is 30 ml/min.
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|---|---|---|---|
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| CN112858514B (en) * | 2021-01-18 | 2022-12-13 | 中昊光明化工研究设计院有限公司 | Method for measuring krypton, xenon and methane in air separation oxygen and device for measuring krypton, xenon and methane in air separation oxygen |
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| CN101126750B (en) * | 2007-09-21 | 2010-07-28 | 武汉钢铁(集团)公司 | Xenon impurity chromatogram analysis method |
| CN102491293B (en) * | 2011-11-28 | 2013-10-30 | 西北核技术研究所 | Method and device utilizing preparative chromatograph to separate krypton and xenon |
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Effective date of registration: 20170613 Address after: 430083, Baiyu mountain, Wuhan City, Hubei province (Gate No. 20, Wuhan) Patentee after: Wuhan iron and Steel Group Gas Co Ltd Address before: 430080 Wuchang, Hubei Friendship Road, No. A, block, floor 999, 15 Patentee before: Wuhan Iron & Steel (Group) Corp. |