CN112858514B - Method for measuring krypton, xenon and methane in air separation oxygen and device for measuring krypton, xenon and methane in air separation oxygen - Google Patents
Method for measuring krypton, xenon and methane in air separation oxygen and device for measuring krypton, xenon and methane in air separation oxygen Download PDFInfo
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Abstract
The invention relates to the technical field of gas measurement, in particular to a method for measuring krypton, xenon and methane in air separation oxygen and equipment for measuring krypton, xenon and methane in air separation oxygen. According to the invention, by removing methane, the interference of methane on krypton detection is avoided, and simultaneously, the methane is converted into carbon dioxide, and the carbon dioxide is tested, so that the purpose of accurately measuring the content of methane is further realized, oxygen is removed, the krypton peak is prevented from being covered by an oxygen peak, the damage of oxygen on a detector is also prevented, and the detection precision of krypton, xenon and methane is improved.
Description
Technical Field
The invention relates to the technical field of gas measurement, in particular to a method for measuring krypton, xenon and methane in air separation oxygen and equipment for measuring krypton, xenon and methane in air separation oxygen.
Background
Rare gases, also known as noble gases, are rare in nature, expensive and versatile as their name suggests. Wherein krypton and xenon are noble in noble gases. Thus, many specialized enterprises have emerged that produce purified krypton and xenon. As is well known, in raw material gas required by rare gas production, the content of rare gas impurities directly determines the price of the raw material gas, and plays a decisive role in the production process flow, so that the technical requirements of analysis and detection of krypton and xenon raw material gas are increased.
In the gas detection and analysis industry, the detection of the content of krypton, xenon and methane in air separation oxygen has certain troubles. The separation and quantification of krypton and methane, the interference of a pure oxygen main body and the damage to an instrument are always targets of attack and research of a plurality of enterprises. Numerous attempts have been made to reduce the temperature, reduce the flow rate of the carrier gas, and to cut the exhaust, all without significant effect.
In the chinese patent publication No. CN103487543A, "method for analyzing the content of krypton and xenon in krypton-xenon feed gas", the separation of krypton, xenon and methane by using a long capillary column instead is disclosed. However, oxygen in the equipment cannot be discharged, so that the oxygen enters the detector, and the thermal conductivity element is oxidized to cause irreversible damage to the instrument, so that the equipment cannot be used for a long time; furthermore, when the device is used for measurement, the oxygen peak can cover the methane peak, and the methane cannot be accurately and quantitatively analyzed.
Disclosure of Invention
The invention aims to provide a method for measuring krypton, xenon and methane in air separation oxygen and equipment for measuring krypton, xenon and methane in air separation oxygen, wherein the measuring method avoids the damage of oxygen to a detection device, and can accurately and quantitatively analyze methane while accurately measuring the content of krypton and xenon.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a method for measuring krypton, xenon and methane in air separation oxygen, which comprises the following steps:
carrying out catalytic dealkylation and catalytic deoxidation on the standard gas in sequence, and then carrying out gas chromatography test to obtain peak areas of krypton, xenon and carbon dioxide respectively, and recording the peak areas as S Label 1 、S Label 2 And S Label 3 (ii) a The volume contents of krypton, xenon and methane in the standard gas are respectively marked as C Label 1 、C Label 2 And C Label 3 ；
Repeating the processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test on the air separation oxygen to be tested to respectively obtain peak areas of krypton, xenon and carbon dioxide, and respectively marking as S Sample 1 、S Sample 2 And S Sample 3 ；
According to the formula C Sample (A) /C Sign ＝S Sample (A) /S Sign board Obtaining the volume contents of krypton and xenon in the air separation oxygen to be detected, and respectively recording the volume contents as C Sample 1 And C Sample 2 And the total volume content of methane and carbon dioxide background is C Sample 3 '；
When the content of methane is determined, the determination method further includes:
performing catalytic deoxidation on air to be detected, and performing gas chromatography test to obtain peak area of carbon dioxide background, which is marked as S Sample 4 ；
According to formula C Sample (II) /C Sign board ＝S Sample (A) /S Sign board Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected, and marking as C Sample 4 ；
The content of methane in the air separation oxygen to be detected is C Sample 3 ＝C Sample 3 '-C Sample 4 。
Preferably, the hydrocarbon removing catalyst for catalytic hydrocarbon removing is a noble metal catalyst;
the particle size of the noble metal catalyst is 15-25 mu m.
Preferably, the temperature for catalytic hydrocarbon removal is 300-450 ℃.
Preferably, the deoxidation catalyst used for catalytic deoxidation is a palladium catalyst and/or a zeolite catalyst;
the particle size of the palladium catalyst and the particle size of the zeolite catalyst are independently 15-25 mu m.
Preferably, the temperature of the catalytic deoxidation is 100-350 ℃.
Preferably, the chromatographic column adopted by the gas chromatography test is a GDX-104 packed column with the outer diameter of 3mm and the length of 3 m;
the carrier gas is hydrogen, and the flow rate of the carrier gas is 25-35 mL/min;
the flow rate of the standard gas or the air separation oxygen to be detected is 30-120 mL/min;
the bridge current is 110-160 mA;
the temperature programming process of the column box is as follows: keeping at 80 deg.C for 1min, continuing to heat to 150 deg.C for 1min, and cooling to 80 deg.C;
the temperature of the detector is 130-150 ℃.
The invention also provides equipment for measuring krypton, xenon and methane in air separation oxygen, which comprises a catalytic dealkylation device, a sample injection valve, a catalytic deoxidation device and a gas chromatography test device which are sequentially arranged.
Preferably, the sampling valve is a six-way sampling valve.
Preferably, the gas chromatography test device comprises a gas chromatograph consisting of a chromatographic column and a thermal conductivity detector.
Preferably, the chromatographic column is a GDX-104 packed column with the outer diameter of 3mm and the length of 3 m.
The invention provides a method for measuring krypton, xenon and methane in air separation oxygen, which comprises the following steps: carrying out catalytic dealkylation and catalytic deoxidation on the standard gas in sequence, and then carrying out gas chromatography test to obtain peak areas of krypton, xenon and carbon dioxide respectively, and recording the peak areas as S Label 1 、S Label 2 And S Label 3 (ii) a The volume contents of krypton, xenon and methane in the standard gas are respectively marked as C Label 1 、C Label 2 And C Label 3 (ii) a Repeating the processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test on the air separation oxygen to be tested to respectively obtain peak areas of krypton, xenon and carbon dioxide, and respectively marking as S Sample 1 、S Sample 2 And S Sample 3 (ii) a According to formula C Sample (A) /C Sign ＝S Sample (A) /S Sign board Obtaining the volume contents of krypton and xenon in the air separation oxygen to be detected, and respectively marking as C Sample 1 And C Sample 2 And the total volume content of methane and carbon dioxide background is C Sample 3 '; when the content of methane is determined, the determination method further includes: performing catalytic deoxidation on air to be detected, and performing gas chromatography test to obtain peak area of carbon dioxide background, which is marked as S Sample 4 (ii) a According to formula C Sample (A) /C Sign board ＝S Sample (A) /S Sign Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected, and marking as C Sample 4 (ii) a The content of methane in the air separation oxygen to be detected is C Sample 3 ＝C Sample 3 '-C Sample 4 . According to the invention, by removing methane, the interference of methane on krypton detection is avoided, and simultaneously, the methane is converted into carbon dioxide, and the carbon dioxide is tested, so that the purpose of accurately measuring the content of methane is further ensured, oxygen is removed, the krypton peak is prevented from being covered by an oxygen peak, the damage of oxygen on a detector is also prevented, and the detection precision of krypton, xenon and methane is improved.
The invention also provides equipment for measuring krypton, xenon and methane in air separation oxygen, which comprises a catalytic dealkylation device, a sample injection valve, a catalytic deoxidation device and a gas chromatography testing device which are sequentially arranged. The measuring equipment overcomes the problems that the detection of the content of krypton, xenon and methane in air separation oxygen can not be finished on one instrument in the prior art, which brings cost and inconvenience for the detection, even if the detection of the content of methane, the peak interference of krypton and methane, the interference of oxygen main peaks to krypton peaks and xenon peaks and the damage to the instrument are not needed. The catalytic dealkylation device can convert methane in air separation oxygen into carbon dioxide through the catalytic dealkylation device, so that the detection interference of methane on krypton is avoided; the catalytic deoxidation device is used for deoxidation and conversion, so that the oxygen peak is prevented from covering the krypton peak, the damage of oxygen to the detector is also prevented, and the effect of killing two birds with one stone is achieved. And because the measuring equipment removes the interference of methane and oxygen in advance, the conditions such as changing a chromatographic column or reducing the flow rate of carrier gas, the temperature of the column and the like are not needed, and the problem of sensitivity reduction is avoided. The purpose of direct rapid detection can be carried out, and the method also has the advantages of wide detection range, high applicability, high detection speed, no damage to instruments and the like.
Drawings
FIG. 1 is a diagram of equipment for measuring krypton, xenon and methane in air separation, where 1 is a catalytic dealkylation device, 2 is a sample injection valve, 3 is a catalytic deoxidation device, 4 is a chromatographic column, 5 is a thermal conductivity detector, and 6 is a gas fine adjustment valve;
a is a carrier gas inlet joint, f is a carrier gas outlet joint, c is a sample outlet joint, d is a sample inlet joint, b and e are two joints connected with a quantitative tube, and g is the quantitative tube;
FIG. 2 is a gas chromatogram of high purity oxygen measured in an apparatus for measuring krypton, xenon, and methane in air separation oxygen according to the present invention;
FIG. 3 is a gas chromatogram of a standard gas measured in an apparatus for measuring krypton, xenon and methane in air separation oxygen according to the present invention;
FIG. 4 is a gas chromatogram for determining krypton, xenon and methane in air separation oxygen in the device for determining air separation oxygen according to the present invention after air separation oxygen to be determined is subjected to catalytic de-hydrocarbon and catalytic de-oxidation;
FIG. 5 is a gas chromatogram for measuring krypton, xenon and methane in the air separation oxygen measuring device according to the present invention after catalytic deoxidation of the air separation oxygen to be measured.
Detailed Description
The invention provides a method for measuring krypton, xenon and methane in air separation oxygen, which comprises the following steps:
after catalytic dealkylation and catalytic deoxidation are sequentially carried out on the standard gas, gas chromatography test is carried out to respectively obtain peak areas of krypton, xenon and carbon dioxide which are respectively marked asS Label 1 、S Label 2 And S Label 3 (ii) a The volume contents of krypton, xenon and methane in the standard gas are respectively marked as C Label 1 、C Label 2 And C Label 3 ；
Repeating the processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test on the air separation oxygen to be tested to respectively obtain peak areas of krypton, xenon and carbon dioxide, and respectively marking as S Sample 1 、S Sample 2 And S Sample 3 ；
According to the formula C Sample (A) /C Sign board ＝S Sample (II) /S Sign board Obtaining the volume contents of krypton and xenon in the air separation oxygen to be detected, and respectively recording the volume contents as C Sample 1 And C Sample 2 And the total volume content of methane and carbon dioxide background is C Sample 3 '；
When the content of methane is determined, the determination method further includes:
performing catalytic deoxidation on air to be detected, and performing gas chromatography test to obtain peak area of carbon dioxide background, which is marked as S Sample 4 ；
According to the formula C Sample (II) /C Sign ＝S Sample (II) /S Sign board Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected, and marking as C Sample 4 ；
The content of methane in the air separation oxygen to be detected is C Sample 3 ＝C Sample 3 '-C Sample 4 。
In the present invention, all the raw materials are commercially available products well known to those skilled in the art unless otherwise specified.
The method comprises the steps of sequentially carrying out catalytic dealkylation and catalytic deoxidation on standard gas, and then carrying out gas chromatography test to respectively obtain peak areas of krypton, xenon and carbon dioxide, wherein the peak areas are respectively marked as S Label 1 、S Label 2 And S Label 3 (ii) a The volume contents of krypton, xenon and methane in the standard gas are respectively marked as C Label 1 、C Label 2 And C Label 3 。
In the invention, the hydrocarbon removing catalyst used for catalytic hydrocarbon removing is preferably a noble metal catalyst; the particle size of the noble metal catalyst is preferably 15 to 25 μm, more preferably 18 to 22 μm. In the present invention, the noble metal catalyst is preferably palladium and/or platinum.
In the catalytic dealkylation, it is preferable to conduct the catalytic dealkylation by passing a standard gas into the dealkylation catalyst. In the present invention, the ratio of the flow rate of the standard gas to the mass of the dealkylation catalyst is preferably (30 to 120) mL/min: (10 to 50) g, and more preferably (40 to 100) mL/min (20 to 30) g.
In the present invention, the temperature for catalytic dealkylation is preferably 300 to 450 ℃, more preferably 350 to 400 ℃.
In the invention, the catalytic hydrocarbon removal process can convert methane in air separation oxygen into carbon dioxide, and the content of the methane is determined by measuring the content of the carbon dioxide subsequently; and simultaneously, the influence of methane on the content determination of krypton is also avoided.
In the present invention, the deoxidation catalyst used for the catalytic deoxidation is preferably a palladium-based catalyst and/or a zeolite catalyst. The particle size of the palladium catalyst and the particle size of the zeolite catalyst are independently preferably 15 to 25 μm, and more preferably 18 to 22 μm. In the present invention, the kind of the palladium-based catalyst and the zeolite catalyst is not particularly limited, and those known to those skilled in the art may be used.
In the catalytic deoxidation, it is preferable to introduce the gas subjected to catalytic dealkylation into the deoxidation catalyst to perform catalytic deoxidation. In the present invention, the ratio of the flow rate of the gas after catalytic dealkylation to the mass of the deoxygenation catalyst is preferably (30 to 120) mL/min: (10-50) g, more preferably (40-100) mL/min (20-30).
In the present invention, the temperature of the catalytic deoxidation is preferably 100 to 350 ℃, more preferably 150 to 300 ℃, and most preferably 200 to 250 ℃.
In the invention, the chromatographic column adopted by the gas chromatography test is preferably a GDX-104 packed column with the outer diameter of 3mm and the length of 3 m; the carrier gas is preferably hydrogen, and the flow rate of the carrier gas is preferably 25-35 mL/min, and more preferably 28-35 mL/min; the flow rate of the standard gas or the air to be detected is preferably 30-120 mL/min, and more preferably 50-100 mL/min; the bridge current is preferably 110 to 160mA, more preferably 120 to 130mA; the temperature programming process of the column box is preferably as follows: keeping at 80 deg.C for 1min, continuing to heat to 150 deg.C for 1min, and cooling to 80 deg.C; the rate of temperature rise is preferably 30 ℃/min. The detector temperature is preferably 130 to 150 deg.C, more preferably 135 to 145 deg.C.
After the peak areas of krypton, xenon and carbon dioxide are obtained, the air separation oxygen to be tested is subjected to the processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test, and the peak areas of krypton, xenon and carbon dioxide are respectively obtained and are respectively marked as S Sample 1 、S Sample 2 And S Sample 3 (ii) a According to formula C Sample (II) /C Sign board ＝S Sample (A) /S Sign board Obtaining the volume contents of krypton and xenon in the air separation oxygen to be detected, and respectively recording the volume contents as C Sample 1 And C Sample 2 And the total volume content of methane and carbon dioxide background is C Sample 3 '. In the present invention, the above processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test are preferably repeated by referring to the above processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test in the process of determining standard gas, and no further description is provided herein.
When the content of methane is determined, the determination method further includes: performing catalytic deoxidation on air separation oxygen to be detected, and performing gas chromatography test to obtain a peak area of a carbon dioxide background, which is recorded as S Sample 4 (ii) a According to formula C Sample (II) /C Sign ＝S Sample (A) /S Sign Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected, and marking as C Sample 4 (ii) a The content of methane in the air separation oxygen to be detected is C Sample 3 ＝C Sample 3 '-C Sample 4 . In the present invention, the processes of catalytic deoxygenation and gas chromatography are preferably referred to the processes of catalytic deoxygenation, catalytic deoxygenation and gas chromatography in the process of determining standard gas, and are not described herein again.
The invention also provides equipment for measuring krypton, xenon and methane in air separation oxygen, which comprises a catalytic dealkylation device, a sample injection valve, a catalytic deoxidation device and a gas chromatography test device which are sequentially arranged.
As a specific embodiment of the invention, the sample injection valve is a six-way sample injection valve. In the invention, the six-way sample injection valve comprises six connecting points, namely a carrier gas inlet connecting point, a carrier gas outlet connecting point, a sample inlet connecting point, a sample outlet connecting point and two connecting points connected with a quantitative tube.
As a specific embodiment of the invention, the gas chromatography test device comprises a gas chromatograph consisting of a chromatographic column and a thermal conductivity detector.
As a specific embodiment of the invention, the chromatographic column is a GDX-104 packed column with an outer diameter of 3mm and a length of 3 m.
As a specific embodiment of the invention, 10-50 g of the dealkylation catalyst is arranged in the catalytic dealkylation device. In the present invention, the dealkylation catalyst is preferably a noble metal catalyst; the particle size of the noble metal catalyst is preferably 15 to 25 μm, more preferably 18 to 22 μm. In the present invention, the noble metal catalyst is preferably a palladium catalyst and/or platinum.
As a specific embodiment of the invention, 10-50 g of deoxygenation catalyst is arranged in the catalytic deoxygenation device. In the present invention, the deoxidation catalyst is preferably a palladium-based catalyst and/or a zeolite catalyst. The particle size of the palladium catalyst and the particle size of the zeolite catalyst are independently preferably 15 to 25 μm, and more preferably 18 to 22 μm. In the present invention, the kind of the palladium-based catalyst and the zeolite catalyst is not particularly limited, and those known to those skilled in the art may be used. In an embodiment of the present invention, the catalytic deoxygenation catalyst is a palladium catalyst.
As a specific embodiment of the invention, the catalytic hydrocarbon removal device further comprises a sample inlet, wherein the sample inlet is connected with a sample pipeline, and a gas fine-tuning valve is arranged in the sample pipeline.
In the present invention, the method for using the apparatus for determining krypton, xenon and methane in air separation oxygen preferably comprises the following steps:
controlling the gas to be detected to enter the catalytic dealkylation device through the sample inlet at a certain flow speed through a gas fine-adjustment valve for catalytic dealkylation, rotating the sample inlet valve to a sampling position (a sample inlet joint is communicated with a quantitative pipe joint) for more than 30 seconds, then rotating the sample inlet valve to the sample inlet position (a carrier gas inlet joint is communicated with the quantitative pipe joint), simultaneously starting the detection work of the gas chromatography detection device, sequentially entering a catalytic deoxidation device and a thermal conductivity detector gas chromatograph for catalytic deoxidation and gas chromatography detection, stopping the test after the last xenon peak is discharged, and performing data processing.
When the background content of carbon dioxide in air separation oxygen is measured, a catalytic de-hydrocarbon device is closed, a six-way sampling valve is rotated to a sampling position (a sample inlet joint is communicated with a quantitative tube joint), a quantitative tube is fully replaced and then rotated to a sampling position (a carrier gas inlet joint is communicated with the quantitative tube joint), meanwhile, the detection work of a gas chromatography detection device is started, and the air separation oxygen to be measured sequentially enters a catalytic de-oxidation device and a thermal conductivity detector gas chromatograph to be subjected to catalytic de-oxidation and gas chromatography detection.
The following will describe in detail the method for measuring krypton, xenon and methane in air separation oxygen and the device for measuring krypton, xenon and methane in air separation oxygen provided by the present invention with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
By using the device shown in fig. 1, a standard gas containing 2000ppm of krypton, 200ppm of xenon and 2000ppm of methane is controlled by a gas micro-valve to enter a catalytic dehydrocarbon device through an injection port at a flow rate of 50mL/min (a catalyst in the catalytic dehydrocarbon device is a palladium catalyst, the particle size is 20 μm, and the filling amount is 25 g), after a catalytic dehydrocarbon reaction is performed at a temperature of 380 ℃, an injection valve is rotated to an injection position, and simultaneously a thermal conductivity detector gas chromatograph is started and subjected to temperature programming (after the temperature is raised to 80 ℃ and maintained for 1min, the temperature is continuously raised to 150 ℃ and maintained for 1min, and then is reduced to 80 ℃) for confirmation, so that the gas after catalytic dehydrocarbon enters the catalytic dehydrocarbon device through a six-way injection valve (the catalyst in the catalytic dehydrocarbon device is a palladium catalyst, the particle size is 20 μm, and the filling amount is 30 g), after a catalytic dehydrocarbon reaction is performed at a temperature of 220 ℃, the gas chromatography is performed in the thermal conductivity detector gas chromatograph, and the test conditions are as follows: the chromatographic column is a GDX-104 packed column with the outer diameter of 3mm and the length of 3 m; the carrier gas is hydrogen, and the flow rate of the carrier gas is 30mL/min; the flow rate of the standard gas is 50mL/min; bridge current is 120mA; the temperature of the detector is 140 ℃, the obtained gas chromatogram is shown in figure 3, the peak area of a krypton peak is 11434, the peak area of a xenon peak is 1383, and the peak area of carbon dioxide is 5804;
measuring oxygen of the air to be measured according to the steps, and obtaining a gas chromatogram with a peak area of 7556 for a krypton peak, 704 for a xenon peak and 3100 for a carbon dioxide peak as shown in fig. 4; according to formula C Sample (A) /C Sign board ＝S Sample (A) /S Sign Obtaining the volume content C of krypton in the air separation oxygen to be detected Sample 1 =7556/11434 × 2000=1321.7ppm, volume content of xenon C Sample 2 =704/1383 × 200=101.8ppm, total volume content of carbon dioxide and methane C Sample 3 '＝3100/5804*2000＝1068.2ppm
When the content of methane in the air separation oxygen to be detected is measured, the steps are referred, the difference is only that the catalytic dealkylation process is omitted, the obtained gas chromatogram is shown in figure 5, and the obtained peak area of the carbon dioxide background is 608; according to formula C Sample (A) /C Sign board ＝S Sample (A) /S Sign board Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected as C Sample 4 ＝608/5804*2000＝209.5ppm
The content C of methane in the air separation oxygen to be detected Sample 3 ＝1068.2-209.5＝858.7ppm。
Verification example
The high purity oxygen was measured according to the procedure of example 1, and the resulting gas chromatogram is shown in FIG. 2. From FIG. 2, it can be seen that the main body of high purity oxygen was completely removed, and the small peak at 0.537min may be an air peak that has not been completely replaced or a nitrogen argon impurity peak in the high purity oxygen.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (6)
1. A method for measuring krypton, xenon and methane in air separation oxygen is characterized by comprising the following steps:
carrying out catalytic dealkylation and catalytic deoxidation on the standard gas in sequence, and then carrying out gas chromatography test to obtain peak areas of krypton, xenon and carbon dioxide respectively, and recording the peak areas as S Label 1 、S Label 2 And S Label 3 (ii) a The volume contents of krypton, xenon and methane in the standard gas are respectively marked as C Label 1 、C Label 2 And C Label 3 ；
Repeating the processes of catalytic dealkylation, catalytic deoxidation and gas chromatography test on the air separation oxygen to be tested to respectively obtain peak areas of krypton, xenon and carbon dioxide, and respectively marking as S Sample 1 、S Sample 2 And S Sample 3 ；
According to formula C Sample (II) /C Sign board ＝S Sample (A) /S Sign Obtaining the volume contents of krypton and xenon in the air separation oxygen to be detected, and respectively marking as C Sample 1 And C Sample 2 And the total volume content of methane and carbon dioxide background is C Sample (II) 3'；
When the content of methane is determined, the determination method further includes:
performing catalytic deoxidation on air to be detected, and performing gas chromatography test to obtain peak area of carbon dioxide background, which is marked as S Sample 4 ；
According to formula C Sample (II) /C Sign board ＝S Sample (A) /S Sign board Obtaining the volume content of the carbon dioxide background in the air separation oxygen to be detected, and marking as C Sample 4 ；
The content of methane in the air separation oxygen to be detected is C Sample 3 ＝C Sample 3' -C Sample 4 。
2. The method according to claim 1, wherein the catalyst for catalytic dealkylation is a noble metal catalyst;
the particle size of the noble metal catalyst is 15-25 mu m.
3. The method according to claim 1 or 2, wherein the temperature for catalytic dealkylation is 300 to 450 ℃.
4. The method according to claim 1, wherein the deoxidation catalyst used in the catalytic deoxidation is a palladium-based catalyst and/or a zeolite catalyst;
the particle size of the palladium catalyst and the particle size of the zeolite catalyst are independently 15-25 mu m.
5. The method according to claim 1 or 4, wherein the temperature for catalytic deoxidation is in the range of 100 to 350 ℃.
6. The assay method according to claim 1, wherein the gas chromatography test uses a GDX-104 packed column having an outer diameter of 3mm and a length of 3 m;
the carrier gas is hydrogen, and the flow rate of the carrier gas is 25-35 mL/min;
the flow rate of the standard gas or the air separation oxygen to be detected is 30-120 mL/min;
the bridge current is 110-160 mA;
the temperature programming process of the column box comprises the following steps: keeping at 80 deg.C for 1min, continuing heating to 150 deg.C for 1min, and cooling to 80 deg.C; the heating rate of the heating is 30 ℃/min;
the temperature of the detector is 130-150 ℃.
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| US3609983A (en) * | 1968-05-16 | 1971-10-05 | Air Reduction | Krypton-xenon recovery system and process |
| JP4400973B2 (en) * | 1999-01-25 | 2010-01-20 | 大陽日酸株式会社 | Method and apparatus for analyzing trace impurities in gas |
| CN101126750B (en) * | 2007-09-21 | 2010-07-28 | 武汉钢铁(集团)公司 | Xenon impurity chromatogram analysis method |
| TW201100795A (en) * | 2009-06-25 | 2011-01-01 | China Steel Corp | System and method for performing quantitative analysis of argon composition in oxygen |
| CN102243219A (en) * | 2011-03-29 | 2011-11-16 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | Method for analyzing nitrous oxide, methane and carbon dioxide in atmosphere by injecting sample once |
| CN102495158A (en) * | 2011-11-22 | 2012-06-13 | 中国科学院地质与地球物理研究所兰州油气资源研究中心 | Method for analyzing N2O, CO, CH4 and CO2 in atmosphere with one injection by gas chromatography |
| CN103487543B (en) * | 2013-09-17 | 2015-08-05 | 武汉钢铁(集团)公司 | The analytical approach of Krypton and xenon content in krypton xenon unstripped gas |
| CN107399718A (en) * | 2017-07-25 | 2017-11-28 | 大连中鼎化学有限公司 | A kind of ultra-pure oxygen, nitrogen purification method |
| CN212060095U (en) * | 2020-01-14 | 2020-12-01 | 中广核研究院有限公司 | Separation and purification device for ultralow radioactivity krypton and xenon in gaseous effluent of nuclear power station |
| CN111257475B (en) * | 2020-03-31 | 2022-07-12 | 西北核技术研究院 | Chromatographic detection method capable of simultaneously detecting contents of various rare gases and chromatograph |
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