CN106596811B - For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas - Google Patents
For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas Download PDFInfo
- Publication number
- CN106596811B CN106596811B CN201611256690.2A CN201611256690A CN106596811B CN 106596811 B CN106596811 B CN 106596811B CN 201611256690 A CN201611256690 A CN 201611256690A CN 106596811 B CN106596811 B CN 106596811B
- Authority
- CN
- China
- Prior art keywords
- oxygen
- argon
- column tube
- column
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/60—Construction of the column
- G01N30/6052—Construction of the column body
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N30/04—Preparation or injection of sample to be analysed
- G01N30/06—Preparation
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
- G01N30/02—Column chromatography
- G01N2030/022—Column chromatography characterised by the kind of separation mechanism
- G01N2030/025—Gas chromatography
Abstract
The present invention relates to a kind of chromatography columns and preparation method thereof analyzed for Traces of Oxygen in Gases, argon, and micro amount of oxygen, the analysis method of argon, belong to gas chromatographic analysis technique application field in high-purity gas.The chromatography column of the present invention analyzed for Traces of Oxygen in Gases, argon, including gc column tube and it is sequentially filled the 5A molecular sieves, Pd catalyst, porous polymer bead being arranged in gc column tube；The Pd catalyst is Pd/C, Pd/Al2O3, one kind in Pd/ zeolites；The porous polymer bead is one kind in Porapak Q, Porapak N, GDX 502.Chromatography column using the present invention can realize the simplicity quickly analysis to oxygen, argon under higher temperature (70~120 DEG C), and analysis result is repeatable, and accuracy, high sensitivity, disclosure satisfy that quickly analysis testing requirements.
Description
Technical field
The present invention relates to a kind of chromatography column and preparation method thereof analyzed for Traces of Oxygen in Gases, argon, high-purity gas
Micro amount of oxygen, the analysis method of argon, belong to gas chromatographic analysis technique application field in body.
Background technology
The separation of oxygen, argon gas is the big technical barrier in gas analysis, using gas chromatographic technique to high-purity gas
Oxygen, argon component interfere with each other when analysis, but are required to detection oxygen, micro group of argon in related high-purity gas detects national standard
The content divided.
In the prior art, when using chromatography column to the analysis of oxygen, argon, frequently with the molecular sieve filled chromatographies of 5A or 13X
Column, and need to use cold-trap (dry ice+acetone) sub-cooled, separating degree requirement necessary to Analysis of Gases of High Purity could be met；
This method is higher to cold-trap equipment and instrument requirements, and actual analysis is not easily accomplished, and stainless steel gc column tube is easy by third
The corrosion of ketone, dry ice；In addition, when lower temperature carries out oxygen, argon analysis, 5A molecular sieves stationary phase has oxygen, argon certain
Suction-operated, to can on concentration of component detect accuracy have certain influence.Using 5A PLOT quartz capillary chromatographic columns
Can also realize the separation of oxygen, argon gas in room temperature (35 DEG C), but capillary chromatographic column column capacity is smaller, sensitivity for analysis by
To certain influence；Complicated for operation although can improve the sensitivity of detection according to heartcut technology, equipment is expensive,
It is not suitable for the actual analysis detection of high-purity gas.
GB/T3634.2-2011 (hydrogen part 2s：Pure hydrogen, High Purity Hydrogen and ultra-pure hydrogen) in also provide a kind of analysis side
Method, the process employs deoxy technologies, by sample introduction twice, determine oxygen, the total content of argon component and argon component respectively and contain
Amount finds out the content of each component by calculating；This method is cumbersome, simultaneously because the analysis result that sample introduction error band comes twice
Error is more apparent.
In addition, granted patent CN203688513U discloses the micro- packing chromatography for measuring micro and trace oxygen, argon in gas
Column, the chromatographic column use 5A molecular sieve chromatography fillers to prepare internal diameter and fill out chromatographic column for 1 millimeter micro-, can be realized at 50 DEG C
The separation of oxygen argon component, but there is a problem of that chromatographic column column capacity is low as capillary chromatographic column, and also analysis time is longer
(4 minutes).
Invention content
The object of the present invention is to provide a kind of chromatography columns analyzed for Traces of Oxygen in Gases, argon, can realize
To the simplicity quickly analysis of oxygen, argon under higher temperature.
The present invention also provides a kind of preparation methods and one kind of the chromatography column analyzed for Traces of Oxygen in Gases, argon
Micro amount of oxygen, the analysis method of argon in high-purity gas.
In order to achieve the goal above, used by the chromatography column of the present invention analyzed for Traces of Oxygen in Gases, argon
Technical solution is：
A kind of Traces of Oxygen in Gases, argon analysis chromatography column, including gc column tube and being sequentially filled is arranged in chromatography
5A molecular sieves, Pd catalyst, porous polymer bead in column tube；The Pd catalyst is Pd/C, Pd/Al2O3, in Pd/ zeolites
One kind；The porous polymer bead is one kind in Porapak Q, Porapak N, GDX-502.
The chromatography column of the present invention analyzed for Traces of Oxygen in Gases, argon, Pd catalyst can convert the oxygen to
Water, to realize oxygen, argon separating at high temperature, reactional equation is：The carrier that Pd catalyst uses is different,
It is different to the transformation efficiency of oxygen, oxygen (water) can be caused to trail or adsorb, to the sensitivity and accuracy of impact analysis.
The present invention for Traces of Oxygen in Gases, argon analyze chromatography column, in high-purity gas micro amount of oxygen, argon into
Row analysis when, only need single injected sampling, and can be realized under higher temperature (70~120 DEG C) oxygen, argon gas it is simple and efficient
Analysis；Its analysis result is repeatable, accuracy, high sensitivity, disclosure satisfy that micro amount of oxygen in high-purity gas, the quick of argon component are divided
Analyse testing requirements.
Preferably, the filling length ratio of the 5A molecular sieves in the gc column tube, Pd catalyst and polymer microsphere is
1.0~1.5:0.2~0.5:0.3~0.6.
Preferably, the both ends of the gc column tube are equipped with the silica wool for blocking gc column tube.
Preferably, the internal diameter of the gc column tube is 2~3mm, and outer diameter is 3~4mm.It is further preferred that 5A molecular sieves
Filling length be 1.0~1.5m, the filling length of Pd catalyst is 0.2~0.5m, the length of the filling of porous polymer bead
Degree is 0.3~0.6m.
Preferably, the length of the gc column tube is 2m.
Separation of the filling length of 5A molecular sieves, Pd catalyst and porous polymer bead in gc column tube to oxygen, argon
Degree and analysis time influence apparent；High pure nitrogen, helium, hydrogen, oxygen, argon gas can be realized by changing the filling length of filler
The analysis detection of middle oxygen, argon.
Preferably, the grain size of the 5A molecular sieves is 60~100 mesh；The grain size of the polymer microsphere is 60~100 mesh；
The grain size of the catalyst is 60~100 mesh.
Preferably, the mass percent of Pd is 0.5~3% in the Pd catalyst.The color of Pd catalyst is taupe
Or black.The Pd catalyst is the Pd catalyst by activation process.The activation be use hydrogen volume score for 5~
10% hydrogen and the mixed gas of nitrogen are reducing gas, and gas flow is 5~10ml/min, by Pd catalyst with 2 DEG C/
The heating rate of min rises to 220~260 DEG C, is kept for 5 hours.
Technical solution used by the preparation method for the chromatography column of the present invention analyzed for Traces of Oxygen in Gases, argon
For：
A kind of preparation method of the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, includes the following steps：
Porous polymer bead, Pd catalyst and 5A molecular sieves are sequentially filled in gc column tube, then aging to get.
It is simple for process provided by the present invention for the preparation method of Traces of Oxygen in Gases, the chromatography column of argon analysis, easily
In implementation, prepared chromatographic column is high to the separating degree of oxygen, argon, is suitable for the analysis detection of micro amount of oxygen in high-purity gas, argon component.
Preferably, the filling length ratio of the 5A molecular sieves in the gc column tube, Pd catalyst and polymer microsphere is
1.0~1.5:0.2~0.5:0.3~0.6.
Preferably, the internal diameter of the gc column tube is 2~3mm, and outer diameter is 3~4mm.It is further preferred that 5A molecular sieves
Filling length be 1.0~1.5m, the filling length of Pd catalyst is 0.2~0.5m, the length of the filling of porous polymer bead
Degree is 0.3~0.6m.
Preferably, the length of the gc column tube is 2m.
Preferably, the grain size of the 5A molecular sieves is 60~100 mesh；The grain size of the polymer microsphere is 60~100 mesh；
The grain size of the catalyst is 60~100 mesh.
Preferably, the mass percent of Pd is 0.5~3% in the Pd catalyst.The color of Pd catalyst is taupe
Or black.Pd catalyst will pass through activation process before filling.It is described activation be use hydrogen volume score for 5~10% hydrogen
The mixed gas of gas and nitrogen is reducing gas, and gas flow is 5~10ml/min, by Pd catalyst with the heating of 2 DEG C/min
Rate rises to 220~260 DEG C, is kept for 5 hours.
Preferably, the gc column tube is stainless steel gc column tube；Stainless steel gc column tube passes through following place before filling
Reason：First stainless steel gc column tube inner wall is polished, it is that 25~35% hydrogen peroxide impregnates 1 at 70~80 DEG C then to use mass concentration
~3h then rinses gc column tube with deionized water, cooling then in 180~240 DEG C of dry 1~3h, then with dichlorosilane with
The mixed solution of toluene is cleaned, and high pure nitrogen is passed through, and 1~3h is kept the temperature at 100~150 DEG C；The dichlorosilane and toluene
Mixed solution in, the volume ratio of dichlorosilane and toluene is 1~5:100.The mixed solution of dichlorosilane and toluene is by stainless
Steel gc column tube one end is injected.The processing method can be passivated stainless steel column pipe internal surface, to improve oxygen, argon point
Analyse the sensitivity of detection；Existing treatment technology only carries out simple acid, alkali process to stainless steel, to remove stainless steel tube processing
The chaff interferents such as caused greasy dirt and iron rust in the process, not to stainless steel inner wall without Passivation Treatment process, sensitivity
It is low.
Preferably, using pump when being sequentially filled porous polymer bead, Pd catalyst and 5A molecular sieves in gc column tube
Take out completion method.Pumping completion method is specially：Silica wool and it is connected to vacuum pump beyond the Great Wall in one end of gc column tube, other end connection
Funnel equipped with filler vibrates chromatographic column under the suction of vacuum pump, loads porous polymer bead, Pd catalysis successively
Agent and 5A molecular sieves, after the completion of filling, silica wool beyond the Great Wall.Pressure when vacuum pump is aspirated is 0.5~0.7MPa.
The aging is at 200~240 DEG C, with the carrier gas flux of 8~12ml/min in filled gc column tube
It is passed through hydrogen, ageing time is 8~10h.
Technical solution used by micro amount of oxygen, the analysis method of argon is in the high-purity gas of the present invention：A kind of use is above-mentioned
The chromatography column analyzed for Traces of Oxygen in Gases, argon is to carry with hydrogen to micro amount of oxygen, the analysis method of argon in high-purity gas
Gas carries out separation detection under 70~120 DEG C of column temperature to the micro amount of oxygen in high-purity gas, argon.
Micro amount of oxygen, the analysis method of argon in the high-purity gas of the present invention are analyzed using above-mentioned for Traces of Oxygen in Gases, argon
Chromatography column, simple and efficient analysis is carried out to oxygen, argon gas at 70~120 DEG C, it is fixed when can reduce low temperature analysis
The suction-operated that opposite oxygen, argon have improves sensitivity and the accuracy of analysis detection.
Description of the drawings
Fig. 1 is the chromatogram to micro amount of oxygen in high pure nitrogen, argon analysis of embodiment 1；
Fig. 2 is the chromatogram to micro amount of oxygen in high pure nitrogen, argon analysis of embodiment 2；
Fig. 3 is the chromatogram to micro amount of oxygen in high pure nitrogen, argon analysis of embodiment 3；
Fig. 4 is the chromatogram to micro amount of oxygen in high pure nitrogen, argon analysis of embodiment 4；
Fig. 5 is the chromatogram to micro amount of oxygen in high pure nitrogen, argon analysis of embodiment 5.
Specific implementation mode
Below in conjunction with specific implementation mode, the following further describes the technical solution of the present invention.
Pd catalyst in specific implementation mode before filling, use hydrogen volume score for 5% hydrogen and nitrogen
Mixed gas is reducing gas, and gas flow is 5~10ml/min, rises to 240 DEG C with the heating rate of 2 DEG C/min, holding 5 is small
When.
Embodiment 1
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 60/80 mesh, and filling length is 1.2m；Pd catalyst is Pd/C, and grain size is 60/80 mesh, loads length
For 0.3m, the mass percent of Pd is 0.5% in Pd catalyst；Porous polymer bead is Porapak Q, grain size 60/80
Mesh, filling length are 0.5m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, includes the following steps：
Porous polymer bead, Pd catalyst and 5A molecular sieves are sequentially filled in gc column tube, then aging to get；It specifically includes
Following steps：
1) first the inner wall of stainless steel gc column tube is polished, it is that 30% hydrogen peroxide is impregnated at 75 DEG C then to use mass concentration
2h then rinses gc column tube with deionized water, and 2h is then dehydrated at 200 DEG C, cooling, then with the mixing of dichlorosilane and toluene
Solution from one end, cleaned by injection, is passed through high pure nitrogen, 2h is kept the temperature at 120 DEG C；The mixing of the dichlorosilane and toluene is molten
In liquid, the volume ratio of dichlorosilane and toluene is 1:100；
2) silica wool and it is connected to vacuum pump beyond the Great Wall in one end of stainless steel gc column tube, other end connection is filled out equipped with chromatography
The funnel of material vibrates chromatographic column under the suction of vacuum pump, loads porous polymer bead, Pd catalyst and 5A molecules successively
Sieve, silica wool beyond the Great Wall after filling；The pressure of vacuum pumping is 0.5MPa；
3) by filled chromatographic column at 200 DEG C, with the flow of 10ml/min be passed through hydrogen carry out aging 10h to get.
Micro amount of oxygen, the analysis method of argon are divided micro amount of oxygen, argon in high pure nitrogen in the high-purity gas of the present embodiment
Analysis, using the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, analysis condition is that sample size is 1ml, and gasify room temperature
80 DEG C of degree, 80 DEG C of TCD detector temperatures, bridge stream 180,70 DEG C of column temperature, carrier gas flux 10ml/min.The present embodiment to High Purity Nitrogen
The chromatogram that micro amount of oxygen, argon are analyzed in gas is shown in Fig. 1.
Embodiment 2
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 80/100 mesh, and filling length is 1.0m；Pd catalyst is Pd/Al2O3, grain size is 80/100 mesh, filling
Length is 0.4m, and the mass percent of Pd is 3% in Pd catalyst；Porous polymer bead is GDX-502, grain size 60/80
Mesh, filling length are 0.6m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, includes the following steps：
Porous polymer bead, Pd catalyst and 5A molecular sieves are sequentially filled in gc column tube, then aging to get；It specifically includes
Following steps：
1) first the inner wall of stainless steel gc column tube is polished, it is that 25% hydrogen peroxide is impregnated at 70 DEG C then to use mass concentration
3h then rinses gc column tube with deionized water, and 3h is then dehydrated at 180 DEG C, cooling, then with the mixing of dichlorosilane and toluene
Solution from one end, cleaned by injection, is passed through high pure nitrogen, 3h is kept the temperature at 100 DEG C；The mixing of the dichlorosilane and toluene is molten
In liquid, the volume ratio of dichlorosilane and toluene is 5:100；
2) silica wool and it is connected to vacuum pump beyond the Great Wall in one end of stainless steel gc column tube, other end connection is filled out equipped with chromatography
The funnel of material vibrates chromatographic column under the suction of vacuum pump, loads porous polymer bead, Pd catalyst and 5A molecules successively
Sieve, silica wool beyond the Great Wall after filling；The pressure of vacuum pumping is 0.7MPa；
3) by filled chromatographic column at 240 DEG C, with the flow of 10ml/min be passed through hydrogen carry out aging 8h to get.
Micro amount of oxygen, the analysis method of argon are divided micro amount of oxygen, argon in high pure nitrogen in the high-purity gas of the present embodiment
Analysis, using the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, analysis condition is that sample size is 1ml, and gasify room temperature
80 DEG C of degree, 80 DEG C of TCD detector temperatures, bridge stream 180,70 DEG C of column temperature, carrier gas flux 20ml/min.The present embodiment to High Purity Nitrogen
The chromatogram that micro amount of oxygen, argon are analyzed in gas is shown in Fig. 2.
Embodiment 3
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 60/80 mesh, and filling length is 1.2m；Pd catalyst is Pd/ zeolites, and grain size is 60/80 mesh, filling length
It is 0.3m to spend, and the mass percent of Pd is 1.5% in Pd catalyst；Porous polymer bead is Porapak N, grain size 60/
80 mesh, filling length are 0.5m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, includes the following steps：
Porous polymer bead, Pd catalyst and 5A molecular sieves are sequentially filled in gc column tube, then aging to get；It specifically includes
Following steps：
1) first the inner wall of stainless steel gc column tube is polished, it is that 35% hydrogen peroxide is impregnated at 80 DEG C then to use mass concentration
1h then rinses gc column tube with deionized water, and 1h is then dehydrated at 240 DEG C, cooling, then with the mixing of dichlorosilane and toluene
Solution from one end, cleaned by injection, is passed through high pure nitrogen, 1h is kept the temperature at 150 DEG C；The mixing of the dichlorosilane and toluene is molten
In liquid, the volume ratio of dichlorosilane and toluene is 3:100；
2) silica wool and it is connected to vacuum pump beyond the Great Wall in one end of stainless steel gc column tube, other end connection is filled out equipped with chromatography
The funnel of material vibrates chromatographic column under the suction of vacuum pump, loads porous polymer bead, Pd catalyst and 5A molecules successively
Sieve, silica wool beyond the Great Wall after filling；The pressure of vacuum pumping is 0.6MPa；
3) by filled chromatographic column at 240 DEG C, with the flow of 10ml/min be passed through hydrogen carry out aging 8h to get.
Micro amount of oxygen, the analysis method of argon are divided micro amount of oxygen, argon in high pure nitrogen in the high-purity gas of the present embodiment
Analysis, using the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, analysis condition is that sample size is 1ml, and gasify room temperature
80 DEG C of degree, 80 DEG C of TCD detector temperatures, bridge stream 180,80 DEG C of column temperature, carrier gas flux 30ml/min.The present embodiment to High Purity Nitrogen
The chromatogram that micro amount of oxygen, argon are analyzed in gas is shown in Fig. 3.
Embodiment 4
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 80/100 mesh, and filling length is 1.3m；Pd catalyst is Pd/ zeolites, and grain size is 60/80 mesh, filling
Length is 0.2m, and the mass percent of Pd is 2% in Pd catalyst；Porous polymer bead is Porapak Q, grain size 80/
100 mesh, filling length are 0.5m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, with embodiment 1.
Micro amount of oxygen, the analysis method of argon are divided micro amount of oxygen, argon in high pure nitrogen in the high-purity gas of the present embodiment
Analysis, using the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, analysis condition is that sample size is 1ml, and gasify room temperature
80 DEG C of degree, 80 DEG C of TCD detector temperatures, bridge stream 180,80 DEG C of column temperature, carrier gas flux 40ml/min.The present embodiment to High Purity Nitrogen
The chromatogram that micro amount of oxygen, argon are analyzed in gas is shown in Fig. 4.
Embodiment 5
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 60/80 mesh, and filling length is 1.2m；Pd catalyst is Pd/ zeolites, and grain size is 60/80 mesh, filling length
It is 0.4m to spend, and the mass percent of Pd is 2.5% in Pd catalyst；Porous polymer bead is GDX-502, grain size 60/80
Mesh, filling length are 0.4m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, with embodiment 2.
Micro amount of oxygen, the analysis method of argon are divided micro amount of oxygen, argon in high pure nitrogen in the high-purity gas of the present embodiment
Analysis, using the above-mentioned chromatography column analyzed for Traces of Oxygen in Gases, argon, analysis condition is that sample size is 1ml, and gasify room temperature
80 DEG C of degree, 80 DEG C of TCD detector temperatures, bridge stream 180,120 DEG C of column temperature, carrier gas flux 40ml/min.The present embodiment to high-purity
The chromatogram that micro amount of oxygen, argon are analyzed in nitrogen is shown in Fig. 5.
From the chromatography column that Fig. 1~5 can be seen that the Traces of Oxygen in Gases of Examples 1 to 5, argon is analyzed to High Purity Nitrogen
Oxygen, the separating degree of argon are high in gas, disclosure satisfy that micro amount of oxygen in high-purity gas, the quick analysis testing requirements of argon component.
Embodiment 6
The chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, including gc column tube and be sequentially filled
5A molecular sieves, Pd catalyst, the porous polymer bead being arranged in gc column tube.5A molecular sieves, Pd catalyst, macromolecule are more
Hole microballoon is filled in along the length direction of gc column tube in pipe respectively, forms the 5A molecules set gradually along column tube length direction
Sieve section, Pd catalyst sections, porous polymer bead section.The both ends of gc column tube are equipped with the silica wool for blocking gc column tube；
The grain size of 5A molecular sieves is 60/80 mesh, and filling length is 1.5m；Pd catalyst is Pd/ zeolites, and grain size is 60/80 mesh, filling length
It is 0.2m to spend, and the mass percent of Pd is 2.5% in Pd catalyst；Porous polymer bead is GDX-502, grain size 60/80
Mesh, filling length are 0.3m；Gc column tube is stainless steel gc column tube, and the internal diameter of gc column tube is 2mm, outer diameter 3mm.
The preparation method of the chromatography column analyzed for Traces of Oxygen in Gases, argon of the present embodiment, with embodiment 2.
Claims (4)
1. a kind of chromatography column analyzed for Traces of Oxygen in Gases, argon, it is characterised in that：It fills out including gc column tube and successively
Fill the 5A molecular sieves, Pd catalyst, porous polymer bead being arranged in gc column tube；The Pd catalyst is Pd/C, Pd/
Al2O3, one kind in Pd/ zeolites；The porous polymer bead is one kind in Porapak Q, Porapak N, GDX-502；
The internal diameter of the gc column tube is 2 ~ 3mm, and outer diameter is 3 ~ 4mm；The filling length of the 5A molecular sieves is 1.0 ~ 1.5m, Pd catalysis
The filling length of agent is 0.2 ~ 0.5m, and the filling length of porous polymer bead is 0.3 ~ 0.6m；The grain size of the 5A molecular sieves
For 60 ~ 100 mesh；The grain size of the porous polymer bead is 60 ~ 100 mesh；The grain size of the Pd catalyst is 60 ~ 100 mesh；Institute
It is stainless steel gc column tube to state gc column tube；Stainless steel gc column tube passes through following processing before filling：First by stainless steel chromatography
Column tube inner wall polishes, and it is that 25 ~ 35% hydrogen peroxide impregnates 1 ~ 3h at 70 ~ 80 DEG C then to use mass concentration, is then rushed with deionized water
Gc column tube is washed, it is cooling then in 180 ~ 240 DEG C of dry 1 ~ 3h, then cleaned with the mixed solution of dichlorosilane and toluene,
It is passed through high pure nitrogen, 1 ~ 3h is kept the temperature at 100 ~ 150 DEG C；In the mixed solution of the dichlorosilane and toluene, dichlorosilane and first
The volume ratio of benzene is 1 ~ 5:100.
2. a kind of preparation method of the chromatography column as described in claim 1 analyzed for Traces of Oxygen in Gases, argon, special
Sign is：Include the following steps：Porous polymer bead, Pd catalyst and 5A molecular sieves are sequentially filled in gc column tube, so
Afterwards aging to get.
3. the preparation method of the chromatography column according to claim 2 analyzed for Traces of Oxygen in Gases, argon, feature
It is：The aging is to be passed through hydrogen in filled gc column tube with the flow of 8 ~ 12ml/min at 200 ~ 240 DEG C,
Ageing time is 8 ~ 10h.
4. a kind of use the chromatography column analyzed as described in claim 1 for Traces of Oxygen in Gases, argon to high-purity gas
Middle micro amount of oxygen, the analysis method of argon, it is characterised in that：Using hydrogen as carrier gas, in high-purity gas under 70 ~ 120 DEG C of column temperature
Micro amount of oxygen, argon carry out separation detection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611256690.2A CN106596811B (en) | 2016-12-30 | 2016-12-30 | For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611256690.2A CN106596811B (en) | 2016-12-30 | 2016-12-30 | For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106596811A CN106596811A (en) | 2017-04-26 |
| CN106596811B true CN106596811B (en) | 2018-09-25 |
Family
ID=58582994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611256690.2A Active CN106596811B (en) | 2016-12-30 | 2016-12-30 | For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106596811B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| PL240677B1 (en) * | 2017-12-27 | 2022-05-16 | Akademia Gorniczo Hutnicza Im Stanislawa Staszica W Krakowie | Packed chromatography column |
| CN108195980B (en) * | 2018-01-03 | 2020-10-02 | 甘肃政法大学 | Trace COx analysis gas chromatography packed column for FID detector and preparation method thereof |
| CN114062540A (en) * | 2021-11-05 | 2022-02-18 | 中国测试技术研究院化学研究所 | Method for rapidly measuring impurity gases of oxygen and argon in pure gas |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6011163A (en) * | 1983-06-30 | 1985-01-21 | Kyodo Sanso Kk | Analyzing method of gaseous mixture composed of oxygen, nitrogen and argon |
| SU1385794A1 (en) * | 1986-06-24 | 1991-06-30 | Предприятие П/Я М-5301 | Method of method of preparing sorbent for chromatography separation of argon and oxygen |
| CN101865897A (en) * | 2009-04-14 | 2010-10-20 | 上海神开石油化工装备股份有限公司 | Gas phase chromatography separation detection device and method thereof |
| CN203688513U (en) * | 2013-12-31 | 2014-07-02 | 大连大特气体有限公司 | Micro-packed chromatographic column for detecting micro and trace oxygen and argon in gas |
-
2016
- 2016-12-30 CN CN201611256690.2A patent/CN106596811B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN106596811A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106596811B (en) | For the chromatography column and preparation method thereof that Traces of Oxygen in Gases, argon are analyzed, micro amount of oxygen, the analysis method of argon in high-purity gas | |
| CN102183610B (en) | Method for analyzing 7N electronic grade ultrapure ammonia | |
| CN106841490B (en) | A kind of method of contained polycyclic aromatic hydrocarbon in detection surrounding air | |
| CN102937627B (en) | Online analysis method for gas components in natural gas hydrogen production process | |
| CN205374391U (en) | Toxin detects uses solid phase extraction column | |
| JP2010112761A5 (en) | ||
| CN105699478A (en) | Method for quickly identifying sugar | |
| CN111948327B (en) | Analysis method for trace oxygen, argon, nitrogen, carbon monoxide, methane and carbon dioxide in industrial hydrogen | |
| CN104198601A (en) | Chromatographic column parallel-connection analysis device and method thereof | |
| CN101968466B (en) | Method for analyzing nitrous oxide and carbon dioxide in atmosphere by adopting gas chromatography through one sampling | |
| CN104297382A (en) | Gas chromatograph for analyzing trace impurities in electronic grade hexafluoroethane | |
| CN107607644B (en) | A kind of chromatographic column of modified high-molecular porous microsphere and preparation method thereof and measurement sulfur hexafluoride decomposition product | |
| CN203758978U (en) | Automatic continuous determination device for volume content of greenhouse gases in atmosphere | |
| CN104101671B (en) | Dissolved gas analysis chromatographic column specially and preparation method thereof in a kind of transformer oil | |
| CN103823012A (en) | Method for analyzing argon mass number abundance value and specific value in argon by GC-MS (gas chromatography-mass spectrometry) method | |
| CN204116290U (en) | For the gas chromatograph of Analysis of Micro-amount Impurities In Liquid in electron level perfluoroethane | |
| CN101907612A (en) | Method for carrying out gas chromatography on minor components contained in finished hydrogen | |
| CN103926343B (en) | Silica gel material chromatographic column is used for the application of high-purity gas gas chromatographic detection | |
| CN101893614B (en) | Method for detecting impurities in corrosive gas | |
| CN111991981A (en) | Chromatographic column oxygen-argon separation process and temperature control method and device thereof | |
| CN203811584U (en) | Pure oxygen gas chromatography detection universal device | |
| JP3097031B2 (en) | Method and apparatus for analyzing impurities in gas | |
| CN203379635U (en) | Solid-phase microextraction device | |
| CN108195980A (en) | Trace amounts of CO x analysis gas-chromatography packed columns for fid detector and preparation method thereof | |
| CN204346990U (en) | Microamounts of Hydrogen in gas and oxygen chromatographic device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |