CN103487543A - Method for analyzing content of krypton and xenon in krypton and xenon feed gas - Google Patents

Method for analyzing content of krypton and xenon in krypton and xenon feed gas Download PDF

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Publication number
CN103487543A
CN103487543A CN201310425255.8A CN201310425255A CN103487543A CN 103487543 A CN103487543 A CN 103487543A CN 201310425255 A CN201310425255 A CN 201310425255A CN 103487543 A CN103487543 A CN 103487543A
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krypton
xenon
gas
content
feed gas
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CN201310425255.8A
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CN103487543B (en
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谢程
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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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Abstract

The invention relates to a method for analyzing content of krypton and xenon in krypton and xenon feed gas, and the problem that the content of krypton and xenon in existing krypton and xenon feed gas can not be analyzed accurately is solved. According to the method, a mini-type thermal conductance analyzer serves as a main body, measurement is carried out by a capillary chromatographic column, helium serves as carrier gas, the mini-type thermal conductance analyzer is used for measuring the peak area of the krypton and the peak area of the xenon in the krypton and xenon feed gas, and then the volume content of the krypton and the volume content of the xenon are calculated. The method can accurately measure the content of the main components such as the krypton and the xenon in the krypton and xenon feed gas, can meet the requirement for selecting the mass of the feed gas in the early stage of production of the krypton and the xenon, and is fast and accurate in detection, the deviation ratio is far less than 3%, and the detection time can be shortened to be within 50 seconds.

Description

The analytical approach of Krypton and xenon content in krypton xenon unstripped gas
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 the content in atmosphere is few, very valuable, therefore be referred to as " rare gas ", " gold gas ", price is high; Extract difficulty, only could extract on large-scale, Extra large air separation plant.Be used in widely electric light source, welding and scientific research medical treatment aspect.
Krypton xenon unstripped gas is mainly to divide the liquid oxygen at main cold heat exchanger position in the production process at sky, Krypton and the xenon of enriched in this place's liquid oxygen, but also contain a large amount of impurity compositions such as methane.The current monitoring for krypton xenon unstripped gas, the main hydrogen flame gas chromatographicanalyzer that uses is measured methane wherein, calculates the content (ratio of namely for methane content and Krypton and xenon judges that whether the unstripped gas quality is qualified) of Krypton and xenon in unstripped gas by the knowhow formula.The method is too rough, can't be accurately the accurate content of Krypton in unstripped gas and xenon be carried out quantitatively.
Krypton in unstripped gas and xenon are carried out to accurate quantitative analysis and have several problems: 1. approximately contain 1200 * 10 according to Krypton in the knowhow unstripped gas -6(volume fraction), xenon approximately contains 100 * 10 -6, there is the problem that the component concentration difference is larger in (volume fraction).2. utilization gas chromatography determination, the retention time of methane and Krypton is close.There is the separation problem in quantitative process.3. the principal ingredient of krypton xenon unstripped gas is oxygen, the problem that oxygen exists chromatographic peak to cover when measuring Krypton content.4. the molecular mass of xenon is larger, has the problem that retention time is longer.
Summary of the invention
The objective of the invention is in order to solve the problems of the technologies described above, provide a kind of can be accurately, the analytical approach of Krypton and xenon content in the krypton xenon unstripped gas of the content of Krypton and xenon in Fast Measurement krypton xenon unstripped gas.
Technical scheme comprises:
1) preparation is 100 * 10 containing the xenon volume content -6(volume fraction), Krypton gas volume content is 1000 * 10 -6(volume fraction), methane gas volume content is 1000 * 10 -6one bottle of the 8L Standard Gases of (volume fraction), all the other are helium (Standard Gases); Wherein, the volume fraction content deviation of Standard Gases ± 5%.
2) using miniature analysis of thermal conductivity instrument as parent, adopt capillary chromatographic column to be measured;
3) using helium as carrier gas, use miniature analysis of thermal conductivity instrument determination step 1 respectively) 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, use miniature analysis of thermal conductivity instrument 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 Propark Q post, and column diameter is 0.32 millimeter, and length is 10 meters.
Controlling atmospheric pressure is 0.3 MPa, described nebulizer gas pressure 0.15 MPa, and controlling described krypton xenon feed gas flow rates is 30 ml/min.
Select the higher miniature analysis of thermal conductivity instrument of sensitivity as parent, selecting column diameter is 0.32 millimeter, the capillary chromatographic column that length is 10 meters measure be because: 1. the conductance cell volume due to miniature thermal conductance is little, is about the 1/10(80 microlitre of common thermal conductance analyser pond body) so the very high content that can measure accurately each component of sensitivity; 2. selecting capillary chromatographic column is because capillary chromatographic column has than packed column the characteristics that separation efficiency is high, retention time is short as the separating column of instrument, can when guaranteeing to separate each component, shorten analysis time; 3. measure the content of Krypton and xenon due to needs, so select 10 meters long capillary columns as separating column, allow the oxygen chromatographic peak of large content only cover methane, allow Krypton still can reach the effect of separating fully, meet and analyze requirement.
The present invention can Accurate Determining krypton xenon unstripped gas in the content of Krypton and these key components of xenon, can meet Krypton, xenon and produce the requirement of early stage the unstripped gas quality being selected, detect quick and precisely, deviation ratio is much smaller than 3%, and can foreshorten in 50 seconds detection time.
The accompanying drawing explanation
Fig. 1 uses helium as carrier gas, uses conventional analysis of thermal conductivity instrument bioassay standard gas spectrogram;
Fig. 2 amplifies the 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 be the time (minute); Ordinate is electric signal (millivolt), and annotate: the oxygen chromatographic peak is covered the methane chromatographic peak, and what the Krypton chromatographic peak can be complete separates with the oxygen chromatographic peak.
Fig. 6 uses helium as carrier gas, uses miniature analysis of thermal conductivity instrument to measure 30 histograms of krypton xenon unstripped gas.
Embodiment
Embodiment:
Below the present invention will be further described: described krypton xenon unstripped gas picks up from the rare production line of oxygen company.
1) preparation is 101 * 10 containing the xenon volume content -6(volume fraction), Krypton gas volume content is 1006 * 10 -6(volume fraction), methane gas volume content is 1005 * 10 -6one bottle of the 8L Standard Gases of (volume fraction), 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 the high-purity helium of N5 level (99.999%) to do carrier gas.
Chromatographic column: Propark Q post column length: 10 meters post footpaths: 0.32 millimeter column temperature: 80 ℃
Control atmospheric pressure: 0.3 MPa nebulizer gas pressure: 150 kPas (this equipment is constant voltage
The type flow control) sample gas flow velocity: 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 determination step 1 respectively)
The K of Krypton and xenon in Standard Gases kryptonand K xenon, wherein,
4) krypton xenon unstripped gas is measured,
A, using helium as carrier gas, use miniature analysis of thermal conductivity instrument 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 be measured 10 times Standard Gases, the Krypton of mensuration and the peak area of xenon are in Table 1
Sequence number The Krypton peak area The 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:
The Q(Krypton)=1446.62; cV=0.17%
The Q(xenon)=100.11; cV=0.24%
This instrument all is less than 3% for the relative standard deviation of each material, can meet the mensuration to these two kinds of materials.
4) use the inventive method to be detected the krypton xenon unstripped gas of krypton xenon rare gas production division (the rare production line of oxygen company), 2 times weekly, continuous 15 weeks (adding up to 30 times) to analysis result in Table 2, histogram is shown in Fig. 6 (in order to make icon more than you know, being charted in xenon content * 10).
In form, data and column line chart (Fig. 6) shape can be found out V methane: V krypton: V xenonwith the proportionate relationship of the experimental formula 10:10:1 of production division in the past.Use and to measure methane content in krypton xenon unstripped gas in the past and calculate that Krypton wherein and the content of xenon are unscientific, so set up the analytical approach of Krypton and xenon content in a kind of Accurate Determining krypton xenon unstripped gas, can help krypton xenon rare gas production division to select accurately to contain Krypton and the higher unstripped gas of these effective constituents of xenon as raw materials for production, can reduce energy resource consumption and improve product quality and yield.
Comparative example:
Use universal analysis of thermal conductivity instrument to be analyzed the described Standard Gases of above-described embodiment and krypton xenon unstripped gas, see spectrogram 1, spectrogram 2 and spectrogram 3, instrument adopts the high-purity helium of N5 level (99.999%) to do carrier gas.
Chromatographic column: Propark Q post column length: 3 meters post footpaths: 3 millimeters column temperatures: 80 ℃
Detector temperature: control atmospheric pressure for 200 ℃: 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, can't carry out quantitatively Krypton; The xenon retention time is very long, causes in the analytic process time oversizely, affects detection efficiency; The sensitivity of Krypton and xenon is very low, and impact is measured.

Claims (3)

1. the analytical approach of Krypton and xenon content in a krypton xenon unstripped gas, is characterized in that, according to the following analysis method, carries out:
1) preparation is 100 * 10 containing the xenon volume content -6, Krypton gas volume content is 1000 * 10 -6, methane gas volume content is 1000 * 10 -6one bottle of 8L Standard Gases, all the other are helium;
2) using miniature analysis of thermal conductivity instrument as parent, adopt capillary chromatographic column to be measured;
3) using helium as carrier gas, use miniature analysis of thermal conductivity instrument determination step 1 respectively) 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, use miniature analysis of thermal conductivity instrument 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;
2. the analytical approach of Krypton and xenon content in krypton xenon unstripped gas as claimed in claim 1, is characterized in that, the installation coating of described capillary chromatographic column is Propark Q post, and column diameter is 0.32 millimeter, and length is 10 meters.
3. the analytical approach of Krypton and xenon content in krypton xenon unstripped gas as claimed in claim 1 or 2, is characterized in that, controlling atmospheric pressure is 0.3 MPa, described nebulizer gas pressure 0.15 MPa, and controlling described krypton xenon feed gas flow rates is 30 ml/min.
CN201310425255.8A 2013-09-17 2013-09-17 The analytical approach of Krypton and xenon content in krypton xenon unstripped gas Active CN103487543B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN107132303A (en) * 2016-02-26 2017-09-05 中国辐射防护研究院 Use Dynamic Adsorption coefficient method of the gas chromatographic measurement activated carbon to inert gas

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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.