JPH0239295B2 - GASUNOSEISEIHOHO - Google Patents
GASUNOSEISEIHOHOInfo
- Publication number
- JPH0239295B2 JPH0239295B2 JP57069307A JP6930782A JPH0239295B2 JP H0239295 B2 JPH0239295 B2 JP H0239295B2 JP 57069307 A JP57069307 A JP 57069307A JP 6930782 A JP6930782 A JP 6930782A JP H0239295 B2 JPH0239295 B2 JP H0239295B2
- Authority
- JP
- Japan
- Prior art keywords
- gas
- nitrogen
- molecular sieve
- nitrogen monoxide
- impurity
- 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.)
- Expired - Lifetime
Links
- 239000007789 gas Substances 0.000 claims description 46
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 38
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000002808 molecular sieve Substances 0.000 claims description 15
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 15
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 14
- 239000012535 impurity Substances 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 7
- 239000002826 coolant Substances 0.000 description 7
- 238000000746 purification Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- OSQPUMRCKZAIOZ-UHFFFAOYSA-N carbon dioxide;ethanol Chemical compound CCO.O=C=O OSQPUMRCKZAIOZ-UHFFFAOYSA-N 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- MWWATHDPGQKSAR-UHFFFAOYSA-N propyne Chemical group CC#C MWWATHDPGQKSAR-UHFFFAOYSA-N 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Landscapes
- Separation Of Gases By Adsorption (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Description
【発明の詳細な説明】
本発明は、ガスの精製方法に関し、もつと詳し
くは、計測機器の零点を調整するための標準ガス
いわゆる零ガスを製造するためのガスの精製方法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas purification method, and more particularly to a gas purification method for producing a standard gas, so-called zero gas, for adjusting the zero point of a measuring instrument.
従来から、大気汚染などの測定において用いら
れる一酸化窒素ガスの零ガス、すなわち高純度な
窒素ガスであつて一酸化窒素ガスを含まない窒素
ガス、を製造することは、極めて困難であつた。
市販の零ガス窒素ボンベと称する高純度窒素ガス
ボンベには、10ppb以下の一酸化窒素ガスを含む
ことが推定される。したがつて、環境基準に定め
られたたとえば20ppb前後の窒素酸化物の測定時
に、このような高純度窒素ガスボンベに充填され
た窒素ガスを校正用の零ガスとして用いること
は、窒素酸化物濃度の測定の正確さを欠くもので
ある。 BACKGROUND ART Conventionally, it has been extremely difficult to produce zero nitrogen monoxide gas, that is, highly pure nitrogen gas that does not contain nitrogen monoxide gas, which is used in measurements of air pollution and the like.
Commercially available high-purity nitrogen gas cylinders called zero-gas nitrogen cylinders are estimated to contain 10 ppb or less of nitrogen monoxide gas. Therefore, when measuring nitrogen oxides, for example around 20 ppb, as stipulated by environmental standards, using nitrogen gas filled in such a high-purity nitrogen gas cylinder as zero gas for calibration will reduce the concentration of nitrogen oxides. Measurement accuracy is lacking.
本発明の目的は、このような従来技術の問題点
を解決して、不純物ガスの含有量が極めて少ない
ガスの精製方法を提供することである。 An object of the present invention is to solve the problems of the prior art and provide a method for purifying gas with an extremely low content of impurity gases.
本発明は、不純物ガスとして一酸化窒素ガスを
含む精製されるべき窒素ガスを、高純度炭素から
形成された平均細径10Å〜20Åのモレキユラシー
ブが充填され、かつこのモレキユラシーブが一酸
化窒素の融点以下に冷却された分離管内に流過さ
せることを特徴とするガスの精製方法である。 In the present invention, a molecular sieve made of high-purity carbon and having an average diameter of 10 Å to 20 Å is filled with nitrogen gas to be purified containing nitrogen monoxide gas as an impurity gas, and the molecular sieve is below the melting point of nitrogen monoxide. This is a gas purification method characterized by passing the gas through a separation tube cooled to
第１図は、本発明に従うガスの精製装置１の簡
略化した系統図である。ガスの精製装置１は、一
定流量の精製すべきガスを供給するガス供給手段
２と、供給されたガス中の不純物ガスをトラツプ
する不純物除去手段３と、除去手段３を冷却する
冷却部４とを含む。ガス供給手段２は、一酸化窒
素ガスを1.5〜2.5ppb含む高純度窒素ガスボンベ
５と、１次減圧弁６と、２次減圧弁７と管路８と
から成る。ガス供給手段２は、ガスボンベ５の窒
素ガスを、減圧弁６，７によつて減圧して、一定
流量たとえば800ml／minの流量で管路８を介し
て不純物除去手段３に供給する。 FIG. 1 is a simplified system diagram of a gas purification apparatus 1 according to the present invention. The gas purification device 1 includes a gas supply means 2 that supplies a constant flow rate of gas to be purified, an impurity removal means 3 that traps impurity gas in the supplied gas, and a cooling unit 4 that cools the removal means 3. including. The gas supply means 2 includes a high-purity nitrogen gas cylinder 5 containing 1.5 to 2.5 ppb of nitrogen monoxide gas, a primary pressure reducing valve 6, a secondary pressure reducing valve 7, and a pipe line 8. The gas supply means 2 reduces the pressure of nitrogen gas in the gas cylinder 5 using pressure reducing valves 6 and 7, and supplies the nitrogen gas to the impurity removal means 3 via a pipe line 8 at a constant flow rate, for example, 800 ml/min.
第２図は、不純物除去手段３の一部を示す縦断
面図である。不純物除去手段３は、たとえば内径
４mmのステンレス鋼製の分離管９に後述のモレキ
ユラシーブ１０がたとえば10ml充填されて成る。
この不純物除去手段３は、冷却部４によつて冷却
される。冷却部４には、容器１１に冷却剤１２が
満たされ、前記分離管９が浸漬される。これによ
つて、ガス供給手段２から供給された不純物ガス
として一酸化窒素ガスを含む窒素ガスは、矢符１
３で示すようにモレキユラシーブ１０が充填され
た分離管９内を流過する際に、モレキユラシーブ
１０によつて一酸化窒素ガスだけがトラツプさ
れ、精製される。精製された窒素ガスは管路１４
から外部に供給される。 FIG. 2 is a longitudinal sectional view showing a part of the impurity removing means 3. FIG. The impurity removing means 3 is formed by filling a separation tube 9 made of stainless steel with an inner diameter of 4 mm, for example, with 10 ml of a molecular sieve 10, which will be described later.
This impurity removing means 3 is cooled by a cooling section 4. In the cooling section 4, a container 11 is filled with a coolant 12, and the separation tube 9 is immersed therein. As a result, the nitrogen gas containing nitrogen monoxide gas as an impurity gas supplied from the gas supply means 2 is
As shown at 3, only the nitrogen monoxide gas is trapped and purified by the molecular sieve 10 when it flows through the separation tube 9 filled with the molecular sieve 10. Purified nitrogen gas is passed through pipe 14
is supplied to the outside.
前記モレキユラシーブ１０は、特殊な表面構造
をもつた高純度炭素から成り、60〜120メツシユ
の粒状に形成され、平均細径10〜20Å、表面積
1000〜1200m2／ｇを有する可逆捕集吸着剤であ
り、好ましくは、60〜80メツシユの粒状とされ
る。このモレキユラシーブ１０には、たとえば商
品名カーボシーブＢ（米国、スペルコ社製）が選
ばれる。60〜80メツシユとされたカーボシーブＢ
をたとえば内径3.2mm、管長91.5cmのカラムに充
填する。このカラム温度を30℃／minの速度で
175℃から225℃まで昇温して窒素ガスをキヤリヤ
ガスとしたとき、炭素数１〜３の炭化水素ガスを
フレームイオン化検出器を用いて分析した結果を
第３図に示す。第３図に示すピーク３１，３２，
３３，３４，３５，３６，３７，３８は、それぞ
れメタン、アセチレン、エチレン、エタン、メチ
ルアセチレン、アレン、プロピレン、プロパンの
存在を表す。このように、モレキユラシーブ１０
は、本来無機または有機ガスの分離に用いられる
ものである。本件発明者は、このモレキユラシー
ブ１０を一酸化窒素の融点（−163.7℃）以下に
冷却することによつて、モレキユラシーブ１０間
を流過される極めて微量の一酸化窒素が選択的に
トラツプされることを見つけ出した。 The molecular sieve 10 is made of high-purity carbon with a special surface structure, and is formed into particles of 60 to 120 meshes, with an average diameter of 10 to 20 Å, and a surface area of
It is a reversible collection adsorbent having an area of 1000 to 1200 m 2 /g, preferably in the form of granules of 60 to 80 mesh. As the molecular sieve 10, for example, Carbosieve B (trade name, manufactured by Superco, USA) is selected. Carbo sheave B with 60 to 80 mesh
For example, fill a column with an inner diameter of 3.2 mm and a tube length of 91.5 cm. This column temperature was adjusted at a rate of 30℃/min.
Figure 3 shows the results of analysis of hydrocarbon gas having 1 to 3 carbon atoms using a flame ionization detector when the temperature was raised from 175°C to 225°C and nitrogen gas was used as the carrier gas. Peaks 31, 32, shown in FIG.
33, 34, 35, 36, 37, and 38 represent the presence of methane, acetylene, ethylene, ethane, methylacetylene, arene, propylene, and propane, respectively. In this way, Molecule Sieve 10
is originally used for the separation of inorganic or organic gases. The present inventor has discovered that by cooling the molecular sieve 10 below the melting point of nitric oxide (-163.7°C), an extremely small amount of nitric oxide flowing between the molecular sieves 10 is selectively trapped. I found out.
冷却剤１２としては、たとえば液体酸素が選ば
れる。液体酸素の沸点は−183.0℃であるので、
一酸化窒素の融点以下である。このように、モレ
キユラシーブ１０にカーボシーブＢを用いて冷却
剤１２に液体酸素を用いた場合において、本発明
に従えば、高純度窒素ガスボンベ５に含まれた
1.5〜2.5ppbの一酸化窒素ガスは、管路１４から
外部に供給されるとき、0.1ppb以下となる。 As the coolant 12, for example liquid oxygen is chosen. Since the boiling point of liquid oxygen is -183.0℃,
It is below the melting point of nitric oxide. As described above, in the case where Carbosieve B is used as the molecular sieve 10 and liquid oxygen is used as the coolant 12, according to the present invention, the high purity nitrogen gas contained in the high purity nitrogen gas cylinder 5
The 1.5 to 2.5 ppb nitrogen monoxide gas becomes 0.1 ppb or less when supplied to the outside from the pipe 14.
上述の実施例では、冷却剤１２として液体酸素
が用いられたけれども、本発明の他の実施例とし
ては、液体酸素に代えて、液体空気が用いられて
もよい。 Although liquid oxygen was used as the coolant 12 in the embodiments described above, other embodiments of the invention may use liquid air instead of liquid oxygen.
なお参考のために、モレキユラシーブ１０に代
えて活性炭およびシリカ系のモレキユラシーブが
用いられても、一酸化窒素ガスは、殆んどトラツ
プされない。また冷却剤１２として液体酸素が用
いられたけれども、液体酸素に代えてドライアイ
ス−エタノール系（−80℃）の冷却剤が用いられ
たとき、1.5〜2.5ppb含まれた一酸化窒素ガスは
0.3ppb程まで除去されるにすぎない。 For reference, even if activated carbon and silica-based molecular sieves are used in place of the molecular sieve 10, nitrogen monoxide gas is hardly trapped. Furthermore, although liquid oxygen was used as the coolant 12, when a dry ice-ethanol type (-80°C) coolant was used instead of liquid oxygen, the nitrogen monoxide gas contained 1.5 to 2.5 ppb.
Only about 0.3 ppb is removed.
以上のように本発明によれば不純物ガスの含有
量が極めて少ないガスを精製するとができるの
で、計測機器の零点を調整するための標準ガスを
容易に得ることができる。 As described above, according to the present invention, it is possible to purify a gas with extremely low content of impurity gases, so that a standard gas for adjusting the zero point of a measuring instrument can be easily obtained.
第１図は、本発明に従うガスの精製装置１の簡
略化した系統図、第２図は不純物除去手段３の一
部を示す縦断面図、第３図は本発明に用いるモレ
キユラシーブ１０によつて炭化水素ガスを分離し
たグラフである。
１…ガスの精製装置、２…ガス供給手段、３…
不純物除去手段、４…冷却部、５…ガスボンベ、
６，７…減圧弁、８，１４…管路、９…分離管、
１０…モレキユラシーブ、１１…容器、１２…冷
却剤。
FIG. 1 is a simplified system diagram of a gas purification device 1 according to the present invention, FIG. 2 is a vertical sectional view showing a part of the impurity removal means 3, and FIG. It is a graph in which hydrocarbon gas is separated. 1... Gas purification device, 2... Gas supply means, 3...
Impurity removal means, 4... cooling section, 5... gas cylinder,
6, 7... pressure reducing valve, 8, 14... pipe line, 9... separation pipe,
10... Molecular sieve, 11... Container, 12... Coolant.
Claims (1)
されるべき窒素ガスを、高純度炭素から形成され
た平均細径10Å〜20Åのモレキユラシーブが充填
され、かつこのモレキユラシーブが一酸化窒素の
融点以下に冷却された分離管内に流過させること
を特徴とするガスの精製方法。1 Nitrogen gas to be purified containing nitrogen monoxide gas as an impurity gas is filled with a molecular sieve made of high-purity carbon and having an average diameter of 10 Å to 20 Å, and this molecular sieve is cooled to below the melting point of nitrogen monoxide. A method for purifying a gas, characterized in that the gas is passed through a separation tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069307A JPH0239295B2 (en) | 1982-04-23 | 1982-04-23 | GASUNOSEISEIHOHO |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57069307A JPH0239295B2 (en) | 1982-04-23 | 1982-04-23 | GASUNOSEISEIHOHO |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS58186416A JPS58186416A (en) | 1983-10-31 |
| JPH0239295B2 true JPH0239295B2 (en) | 1990-09-05 |
Family
ID=13398768
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57069307A Expired - Lifetime JPH0239295B2 (en) | 1982-04-23 | 1982-04-23 | GASUNOSEISEIHOHO |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0239295B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2571176B2 (en) * | 1992-06-09 | 1997-01-16 | 株式会社荏原製作所 | Removal method of CVD exhaust gas |
| US7314506B2 (en) * | 2004-10-25 | 2008-01-01 | Matheson Tri-Gas, Inc. | Fluid purification system with low temperature purifier |
| KR101221088B1 (en) | 2012-03-30 | 2013-01-11 | (주)제니스텍 | Extensive purification cryogenic cold trap device |
| JP6680611B2 (en) * | 2016-04-28 | 2020-04-15 | 大旺新洋株式会社 | Gas separation method |
-
1982
- 1982-04-23 JP JP57069307A patent/JPH0239295B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS58186416A (en) | 1983-10-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6752852B1 (en) | Apparatus for removing moisture from fluids comprising acid gases; methods of using same, and compositions | |
| US6238636B1 (en) | Process and systems for purification of boron trichloride | |
| US5486227A (en) | Integrated process for purifying and liquefying a feed gas mixture with respect to its less strongly adsorbed component of lower volatility | |
| US20030106335A1 (en) | Process and adsorbent for the recovery of krypton and xenon from a gas or liquid stream | |
| TWI294517B (en) | System and method comprising same for measurement and/or analysis of particles in gas stream | |
| EP1316357B1 (en) | Process and adsorbent for the recovery of krypton and xenon from a gas or liquid stream | |
| JPH01160816A (en) | Method for selectively adsorpting co2 by zeolite | |
| JP2001506960A (en) | Method for purifying cryogenic fluids by filtration and adsorption | |
| JPH0239295B2 (en) | GASUNOSEISEIHOHO | |
| JPH062682B2 (en) | Acetylene purification method and apparatus used therefor | |
| JP4504184B2 (en) | Moisture-reduced composition comprising acid gas and matrix gas, product comprising the composition and method for producing the same | |
| Clemons et al. | Concentration and ultrasensitive chromatographic determination of sulfur hexafluoride for application to meteorological tracing | |
| JPH10265216A (en) | Purification of boron trichloride | |
| JP2002250722A (en) | Ultra-low concentration hydrogen sulfide analysis method and analyzer | |
| JP3103943B2 (en) | Method for analyzing carbon monoxide and / or carbon dioxide | |
| JP4909614B2 (en) | Method and apparatus for analyzing trace impurities in hydride gas | |
| JP4820596B2 (en) | Nitric oxide purification method | |
| Hanrahan et al. | Adsorption-desorption gas chromatographic-infrared determination of trace disulfur decafluoride in sulfur hexafluoride | |
| Foster et al. | Helium-Purification Unit for High-Purity Inert-Atmosphere Boxes | |
| GB805516A (en) | Improvements in or relating to the purification of gases | |
| JP2002179689A (en) | Purification of methylsilanes | |
| US3539301A (en) | Apparatus for determination of contaminants in a liquefied gas | |
| JPH0254283B2 (en) | ||
| KR19980024588A (en) | Method and apparatus for refining liquid inert fluid from impurities hydrogen (H₂) and / or carbon monoxide (CO) | |
| RU1784815C (en) | Device for deep purifying of gas from water vapors and oxygen |