JPH04120463A - Gas chromatograph for analyzing hydrogen and moisture - Google Patents
Gas chromatograph for analyzing hydrogen and moistureInfo
- Publication number
- JPH04120463A JPH04120463A JP24035590A JP24035590A JPH04120463A JP H04120463 A JPH04120463 A JP H04120463A JP 24035590 A JP24035590 A JP 24035590A JP 24035590 A JP24035590 A JP 24035590A JP H04120463 A JPH04120463 A JP H04120463A
- Authority
- JP
- Japan
- Prior art keywords
- pipe
- hydrogen
- moisture
- column
- converted
- 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.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000007789 gas Substances 0.000 title claims description 9
- 239000005997 Calcium carbide Substances 0.000 claims abstract description 22
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011261 inert gas Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- 238000001514 detection method Methods 0.000 claims description 6
- 238000004458 analytical method Methods 0.000 claims description 4
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 abstract description 13
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 abstract description 11
- 150000002431 hydrogen Chemical class 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract 3
- 229910052791 calcium Inorganic materials 0.000 abstract 3
- 239000011575 calcium Substances 0.000 abstract 3
- 238000007599 discharging Methods 0.000 abstract 3
- 230000001590 oxidative effect Effects 0.000 abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 230000035945 sensitivity Effects 0.000 description 7
- 239000012159 carrier gas Substances 0.000 description 6
- 238000002347 injection Methods 0.000 description 6
- 239000007924 injection Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
Landscapes
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、微量な水素や水分をガスクロマトグラフィに
より分析する技術に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a technique for analyzing trace amounts of hydrogen and moisture by gas chromatography.
（従来の技術）
ガスクロマトグラフは、試料注入口から注入された試料
をキャリアガスにより分析用カラムへ送出し、ここで成
分毎に分離、排出されでくる各成導牲の相違を利用して
熱伝導度検出器や、＃Ａ焼性の違いを利用して水素炎イ
オン化検出器を利用して検出するものである。(Prior art) A gas chromatograph uses a carrier gas to send a sample injected from a sample injection port to an analytical column, where each component is separated and discharged. Detection is performed using a conductivity detector or a hydrogen flame ionization detector that takes advantage of the difference in #A sinterability.
ところで、水素と水分を検出対象とする場合には、水素
に対してはキャリアガスとして窒素を、カラムには分子
フルイカラムを使用し、また水分に対してはキャリアガ
スにヘリウムを、カラムにはＰｏｒａｐａｋ Ｑ ％用
い、これらカラムから排出されできた水素や水分を熱伝
導度検出器により検出することが行なわれているが、熱
伝導度検出器は、その感度が低いため、せいぜいＩＯＰ
ＰＭ以上の濃度についてしか検出てきないという問題が
ある。By the way, when hydrogen and moisture are to be detected, nitrogen is used as a carrier gas and a molecular fluoride column is used for hydrogen, and helium is used as a carrier gas and a Porapak column is used for moisture. Q%, and the hydrogen and water discharged from these columns are detected using a thermal conductivity detector, but the thermal conductivity detector has low sensitivity and can only detect IOP.
There is a problem that only concentrations higher than PM can be detected.
もとより、ガスクロマトグラフの検出器として高い感度
を備えた水素炎イオン化検出器を用いることも考えられ
るが、水素炎イオン化検出器は有機物に対しては感度を
示すものの、水素や水分に対しては全く感度を示さない
ので、水素や水分の検出には適用ができない。Of course, it is possible to use a flame ionization detector with high sensitivity as a gas chromatograph detector, but although a flame ionization detector is sensitive to organic substances, it has no sensitivity to hydrogen or moisture. Since it does not exhibit sensitivity, it cannot be applied to detect hydrogen or moisture.
（発明が解決しようとする課題）
てあって、その目的とするところは、高い検出感度を有
する水素炎イオン化検出器を用いて像量の水素や水分を
検出することができる新規なガスクロマトグラフを提供
することにある。(Problems to be Solved by the Invention) The purpose of the invention is to develop a new gas chromatograph that can detect hydrogen and water in image quantities using a hydrogen flame ionization detector with high detection sensitivity. It is about providing.
（課題を解決するための手段）
このような問題を解決するために本発明においでは、一
端か試料注入口を介して不活性ガス源に接続された分析
用カラムと、該分析用カラムの排出側に接続された酸化
触媒管と、該酸化触媒管の排出側に接続された炭化カル
シウム管と、該炭化カルシウム管の排出側に接続された
水素炎イオン化検出手段を備えるようにした。(Means for Solving the Problems) In order to solve such problems, the present invention provides an analytical column connected to an inert gas source through one end or a sample injection port, and an analytical column connected to an inert gas source through a sample injection port, and The present invention includes an oxidation catalyst pipe connected to the side, a calcium carbide pipe connected to the discharge side of the oxidation catalyst pipe, and a hydrogen flame ionization detection means connected to the discharge side of the calcium carbide pipe.
（発明の作用）
分析用カラムで分Ｎｉされた水素は、酸化触媒管により
水分に変換された後、炭化カルシウム管に流入してアセ
チレンに変換される。またカラムから分Ｍされた水分は
、酸化触媒管をそのまま通過して炭化カルシウム管に流
入してアセチレンに変換される。これら炭化カルシウム
管から排出されたアセチレンは、有機物に対しで高い感
度を示す水素炎イオン化検出器により検出されることに
なる。(Operation of the Invention) Hydrogen separated in the analytical column is converted into water by the oxidation catalyst tube, and then flows into the calcium carbide tube and converted into acetylene. Further, water separated from the column passes through the oxidation catalyst tube as it is, flows into the calcium carbide tube, and is converted into acetylene. Acetylene discharged from these calcium carbide tubes is detected by a flame ionization detector that is highly sensitive to organic matter.
（実施例）
そこで、以下に本発明の詳細を図示した実施例に基づい
て説明する。(Example) The details of the present invention will be described below based on illustrated examples.
第１図は本発明の一実施例を示すものであって、図中符
号１は水素及び水分を分離する、例えばＰｏｒａｐａｋ
Ｑ （商品名）などのガスクロマトグラフ分析用カ
ラムで、流入側には試料注入口２を介して窒素等の不活
性ガス源３から窒素ガスが供給され、また排出側には酸
化触媒管４が接続されている。酸化触媒管４は、酸化銅
等の酸化触媒粒５を収容して水素を酸化させるに足る温
度、例えば６５０℃程度に加熱され、乾燥空気源から乾
燥空気の供給を受ケている。FIG. 1 shows an embodiment of the present invention, in which reference numeral 1 indicates a device for separating hydrogen and water, such as a Porapak
A column for gas chromatography analysis such as Q (product name) is supplied with nitrogen gas from an inert gas source 3 such as nitrogen through a sample injection port 2 on the inlet side, and an oxidation catalyst tube 4 on the outlet side. It is connected. The oxidation catalyst tube 4 accommodates oxidation catalyst particles 5 such as copper oxide, is heated to a temperature sufficient to oxidize hydrogen, for example, about 650° C., and receives a supply of dry air from a dry air source.
６は、酸化触媒管５の排出側に接続された炭化カルシウ
ム管で、容器内に炭酸カルシウム粒７を収容するととも
に、水分との反応を促進する程度の温度、例えば１００
℃に加熱されている。８は水素炎イオン化検出器で、助
燃剤と水素の供給を受けて炭化カルシウム管６から排出
されるガスを検出するように構成されている。Reference numeral 6 denotes a calcium carbide pipe connected to the discharge side of the oxidation catalyst pipe 5, which accommodates calcium carbonate grains 7 in a container and is heated at a temperature that promotes the reaction with moisture, for example 100°C.
It is heated to ℃. Reference numeral 8 denotes a hydrogen flame ionization detector, which is configured to detect gas discharged from the calcium carbide pipe 6 after being supplied with a combustion improver and hydrogen.
この実施例において、試料注入口２からサンプル、例え
ば水素、及び水分がそれぞれ０．ＩＰＰＭとなるように
窒素ガスで希釈したものを注入すると、これらのガスは
キャリアガスである窒素により分析用カラム１に搬送さ
れ、水素、水分の順番に分離されてカラム１から排出さ
れる０分離排出された水素は、酸化触媒管４に流入して
、ここの流入している乾燥空気の酸素と化合して
２Ｈ２＋ＣＬＪ○ → ２Ｈ２０
なる反応により水分に変換されて炭化カルシウム管６に
流入する。炭化カルシウム管６に流入した水分は、炭化
カルシウム７と化合して
２Ｈ２０＋Ｃ２Ｃａ ４ Ｃ２Ｈ２なる反応により
アセチレンガスに変換されて水素炎イオン化検出器８に
流入する。In this example, the sample, for example hydrogen, and water are injected from the sample inlet 2 at 0. When IPPM diluted with nitrogen gas is injected, these gases are transported to analytical column 1 by nitrogen, which is a carrier gas, and hydrogen and water are separated in that order and discharged from column 1. The discharged hydrogen flows into the oxidation catalyst tube 4, combines with the oxygen of the dry air flowing into the oxidation catalyst tube 4, is converted into water by the reaction 2H2+CLJ○ → 2H20, and flows into the calcium carbide tube 6. The water that has flowed into the calcium carbide pipe 6 is combined with calcium carbide 7 and converted into acetylene gas through a reaction of 2H20+C2Ca 4 C2H2, which then flows into the hydrogen flame ionization detector 8 .
一方、分析用カラム１から排出された水分は、酸化触媒
管４をそのまま素通りして炭化カルシウム管６に流入し
て炭化カルシウム７と化合して２Ｈ２０＋Ｃ２Ｃａ
４ Ｃ；２ Ｈ２なる反応によりアセチレンに変換さ
れて水素炎イオン化検出器８に流入する。On the other hand, the water discharged from the analytical column 1 passes directly through the oxidation catalyst tube 4, flows into the calcium carbide tube 6, and combines with calcium carbide 7 to form 2H20+C2Ca.
It is converted into acetylene by the reaction 4C;2H2 and flows into the flame ionization detector 8.
いうまでもなく、水素炎イオン化検出器８は、有機物に
対して極めて高い検出感度を有するから、第２図に示し
たようにサンプル中に含まれている濃度０．ＩＰＰＭ程
度の極めて濃度の低い水素や水分が検出されることにな
る。Needless to say, the flame ionization detector 8 has extremely high detection sensitivity for organic substances, so as shown in FIG. Hydrogen and moisture at extremely low concentrations, such as IPPM, will be detected.
なお、この実施例においでは分析用カラム１から排出さ
れた成分を酸化触媒管４に直接導入するようにしている
が、第３図に示したように分析用カラム１の排出側に切
換弁９を接続し、切換弁９の一方の排出口に水分除去管
Ｉｎ、ま茫他方の排出口に水素除去管１１を接続すると
ともに、水分除去管１ｏの排出口を酸化触媒管に４、ま
た水素除去管］１の排出口を炭化カルシウム管６に接続
しても同様の作用を奏することは明らかである。In this embodiment, the components discharged from the analytical column 1 are introduced directly into the oxidation catalyst tube 4, but as shown in FIG. Connect the water removal pipe In to one outlet of the switching valve 9, and connect the hydrogen removal pipe 11 to the other outlet of the switching valve 9, and connect the water removal pipe 1o to the oxidation catalyst pipe 4, and connect the hydrogen removal pipe In to the other outlet of the switching valve 9. It is clear that the same effect can be achieved even if the outlet of the removal tube] 1 is connected to the calcium carbide tube 6.
また、この実施例においてはキャリアガスとしで窒素ガ
スを使用しているが、ヘリウム、アルゴシガス等の他の
不活性ガスを使用しても同様の作用を奏することは明ら
かである。Furthermore, although nitrogen gas is used as the carrier gas in this embodiment, it is clear that the same effect can be achieved even if other inert gases such as helium or argosi gas are used.
（発明の効果）
以上、説明したように本発明においでは、一端か試料注
入口を介して不活性ガス源に接続された分析用カラムに
直列に酸化触媒管と炭化カルシウム管とを接続するとと
もに、炭化カルシウム管の排出側に水素炎イオン化検出
手段を接続するようにしたので、分析用カラムで分離さ
れた水素を酸化触媒管により水分に変換して、ついで炭
化カルシウム管でアセチレンに変換し、分析用カラムか
ら排出された水分を炭化カルシウム管でアセチレンに変
換してから水素炎イオン化検出器に流入させて、有機物
に対して極めで高い感度を有する水素炎イオン化検出器
により微量な水素や水分を検出することができる。(Effects of the Invention) As explained above, in the present invention, an oxidation catalyst tube and a calcium carbide tube are connected in series to an analytical column connected to an inert gas source through one end or a sample injection port. Since a hydrogen flame ionization detection means was connected to the discharge side of the calcium carbide tube, the hydrogen separated in the analytical column was converted to water by the oxidation catalyst tube, and then converted to acetylene by the calcium carbide tube. Moisture discharged from the analytical column is converted into acetylene using a calcium carbide tube, and then flows into a flame ionization detector.The flame ionization detector, which has extremely high sensitivity to organic matter, collects trace amounts of hydrogen and moisture. can be detected.
第１図は本発明の一寅施例を示す装置の構成図、第２図
は同上製雪による分析結果を示すクロマトグラム、及び
第３図は本発明の他の実施例を示す装置の構成図である
。
１・・・・分析用カラム
３・・・・キャリアガス源
６・・・・炭化カルシウム管
８・・・・水素炎イオン化検出器
２・・・・試料注入口
４・・・・酸化触媒管Fig. 1 is a configuration diagram of an apparatus showing one embodiment of the present invention, Fig. 2 is a chromatogram showing the analysis results by snowmaking, and Fig. 3 is a configuration diagram of an apparatus showing another embodiment of the invention. It is a diagram. 1...Analysis column 3...Carrier gas source 6...Calcium carbide tube 8...Hydrogen flame ionization detector 2...Sample injection port 4...Oxidation catalyst tube
Claims (1)
析用カラムと、該分析用カラムの排出側に接続された酸
化触媒管と、該酸化触媒管の排出側に接続された炭化カ
ルシウム管と、該炭化カルシウム管の排出側に接続され
た水素炎イオン化検出手段を備えてなる水素、及び水分
分析用ガスクロマトグラフ。an analytical column connected at one end to an inert gas source via a sample inlet; an oxidation catalyst tube connected to the discharge side of the analytical column; and a calcium carbide connected to the discharge side of the oxidation catalyst tube. A gas chromatograph for hydrogen and moisture analysis, comprising a tube and a flame ionization detection means connected to the discharge side of the calcium carbide tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24035590A JPH04120463A (en) | 1990-09-11 | 1990-09-11 | Gas chromatograph for analyzing hydrogen and moisture |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24035590A JPH04120463A (en) | 1990-09-11 | 1990-09-11 | Gas chromatograph for analyzing hydrogen and moisture |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04120463A true JPH04120463A (en) | 1992-04-21 |
Family
ID=17058259
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24035590A Pending JPH04120463A (en) | 1990-09-11 | 1990-09-11 | Gas chromatograph for analyzing hydrogen and moisture |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04120463A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816843A3 (en) * | 1996-06-18 | 1998-08-05 | Hydro-Quebec | Process for dehydrating a mineral oil or other solvents for the preparation of moisture-in-oil or moisture-in-solvent standards |
-
1990
- 1990-09-11 JP JP24035590A patent/JPH04120463A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0816843A3 (en) * | 1996-06-18 | 1998-08-05 | Hydro-Quebec | Process for dehydrating a mineral oil or other solvents for the preparation of moisture-in-oil or moisture-in-solvent standards |
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