JPH0734008B2 - Gas chromatographic analysis method using thermal conductivity detector - Google Patents
Gas chromatographic analysis method using thermal conductivity detectorInfo
- Publication number
- JPH0734008B2 JPH0734008B2 JP63163638A JP16363888A JPH0734008B2 JP H0734008 B2 JPH0734008 B2 JP H0734008B2 JP 63163638 A JP63163638 A JP 63163638A JP 16363888 A JP16363888 A JP 16363888A JP H0734008 B2 JPH0734008 B2 JP H0734008B2
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- Prior art keywords
- helium
- gas
- analysis method
- hydrogen
- detector
- Prior art date
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Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は検出器として熱伝導度検出器（以下「TCD検出
器」という）を用いるガスクロマトグラフ（以下「GC＞
という）分析法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention is a gas chromatograph (hereinafter “GC>”) that uses a thermal conductivity detector (hereinafter, “TCD detector”) as a detector.
Say) analytical method.
（従来の技術） TDC検出器の感度は，キャリヤガスと試料ガスの熱伝導
度の差が大きいほど高くなるから，試料ガスに比べて熱
伝導度の非常に大きな水素やヘリウムがキャリヤガスと
して使用される。特に安全性の観点よりヘリウムがキャ
リヤガスとしてよく使用されている。(Prior Art) The sensitivity of the TDC detector increases as the difference in thermal conductivity between the carrier gas and the sample gas increases, so hydrogen or helium, which has a much higher thermal conductivity than the sample gas, is used as the carrier gas. To be done. In particular, helium is often used as a carrier gas from the viewpoint of safety.
（発明が解決しようとする課題） キャリアガスとしてヘリウムを用い，検出器にTDC検出
器を用いるGC分析時に,1）成分の溶出中にベースライン
が負側に下がり，分析対象化合物によっては定量値に信
頼がおけなくなったり，定量が不可能になる。２）ノイ
ズレベルが高くなる，などの問題点があった。(Problems to be solved by the invention) During GC analysis using helium as a carrier gas and a TDC detector as a detector, 1) the baseline dropped to the negative side during the elution of the component, and a quantitative value depending on the analyte compound. It becomes unreliable and quantifiable. 2) There were problems such as high noise level.
本発明の発明者は，空気を含む試料をカラムに導入した
ときに上記ベースラインの変動が顕著なこと，有機溶媒
溶液試料をカラムに導入したときに上記ベースライン変
動が少ないこと並びにキャリアガスとして水素を用い，
検出器にTCD検出器を用いるGC分析時には，ベースライ
ンの変動がほぼ観察されないことを注意深く考察した結
果，このベースライン変動がTCD検出器に使用されてい
るフィラメントやセル部材の酸化に起因することを見出
し，本発明をなすに至った。The inventor of the present invention has found that the baseline fluctuation is remarkable when a sample containing air is introduced into the column, the baseline fluctuation is small when the organic solvent solution sample is introduced into the column, and the carrier gas is used as a carrier gas. Using hydrogen,
As a result of careful consideration that almost no baseline fluctuation was observed during GC analysis using a TCD detector as the detector, it was found that this baseline fluctuation was caused by the oxidation of filaments or cell members used in the TCD detector. The present invention has been completed and the present invention has been completed.
（課題を解決するための手段） 本発明は，キャリアガスとしてヘリウムを用いるGC分析
法において,TCD検出器のセルに導かれる被検出気体流
に，常時水素ガスが混合されているGC分析法を提供す
る。(Means for Solving the Problems) The present invention provides a GC analysis method using helium as a carrier gas, in which hydrogen gas is constantly mixed with a gas flow to be detected introduced into a cell of a TCD detector. provide.
本発明において，ヘリウムと水素の混合位置はTCD検出
器の上流であればGC流路のどの流路部分でもよい。ま
た，ヘリウムガスに予め水素ガスを混合した気体を充て
んしたボンベをキャリアガス源として用いるGC分析法も
本発明に包含される。In the present invention, the mixing position of helium and hydrogen may be any flow path portion of the GC flow path as long as it is upstream of the TCD detector. The present invention also includes a GC analysis method using a cylinder filled with a gas in which helium gas is mixed with hydrogen gas in advance as a carrier gas source.
（作 用） 本発明のGC分析法にあっては,TCD検出器のセル部材やフ
ィラメント等は，水素を含む気体流に曝されるから常時
還元的雰囲気に置かれている。従って，酸素ガスを含む
試料（例えば空気）をカラムに導入して分析を行って
も，セル部材やフィラメント等が酸化されることがなく
TCD検出器のベースライン変動が防がれる。(Operation) In the GC analysis method of the present invention, the cell members, filaments, etc. of the TCD detector are exposed to a gas flow containing hydrogen, and thus are always placed in a reducing atmosphere. Therefore, even if a sample containing oxygen gas (for example, air) is introduced into the column for analysis, the cell members and filaments are not oxidized.
The baseline fluctuation of the TCD detector is prevented.
（実 施 例） 第１図は本発明の一実施例であるGC分析法を実施するた
めのGC流路を示す流路図である。本例は気化室1,2の上
流側でキャリアガスであるヘリウムに水素を混合する分
析法を示している。第１図中の３ヘリウムガスボンベよ
り供給されるキャリアガスであるヘリウムは１次調圧弁
４で調圧された後２つの流路5,6に分岐される。ここで
流路５は分析用であって流路６はレファランス用であ
る。水素は水素ガスボンベ７より供給され,1次調圧弁８
で調圧された後２つの流路9,10に分岐される。分析用流
路５に入ったヘリウムは流量制御弁11で流量が制御され
抵抗12を通過した後に，流路9,流量制御弁13,抵抗14を
通った水素と合流し,30〜60メッシュ程度の粒度のケイ
ソウ土粒が充てんされたSUS製管より成るガス混合器15
で均一に混合され，気化室1,分離カラム16,TCD検出器17
の分析用セル18に導かれる。TCD検出器17のレファレン
ス用セル19には分析用流路と同様にして水素が混合され
たヘリウムが導かれる。(Example) FIG. 1 is a flow path diagram showing a GC flow path for carrying out a GC analysis method according to an embodiment of the present invention. This example shows an analysis method in which hydrogen is mixed with helium, which is a carrier gas, on the upstream side of the vaporization chambers 1 and 2. Helium, which is the carrier gas supplied from the 3 helium gas cylinder in FIG. 1, is pressure-regulated by the primary pressure regulating valve 4 and then branched into two flow paths 5, 6. Here, the channel 5 is for analysis and the channel 6 is for reference. Hydrogen is supplied from the hydrogen gas cylinder 7, and the primary pressure regulating valve 8
After the pressure is adjusted by, it is branched into two flow paths 9 and 10. The flow rate of the helium entering the analysis flow path 5 is controlled by the flow rate control valve 11 and passes through the resistance 12, and then merges with hydrogen that has passed through the flow path 9, the flow rate control valve 13, and the resistance 14 to obtain about 30 to 60 mesh. Mixer consisting of SUS tube filled with diatomaceous earth particles of different particle size 15
Evenly mixed in the vaporization chamber 1, separation column 16, TCD detector 17
To the analysis cell 18 of. Helium mixed with hydrogen is introduced into the reference cell 19 of the TCD detector 17 in the same manner as in the analysis channel.
レファレンスカラム20を分離カラム16と分離特性の異な
るカラムにしておけば，上に述べたレファレンス流路系
（気化室2,レファレンスカラム20,レファレンス用セル1
9）を分析用流路として使用することができる。また，
レファレンス用流路には水素を混合する必要はないの
で，キャリアガスであるヘリウムだけが流れるようにし
て流路構成を簡略化することもできる。If the reference column 20 has a separation characteristic different from that of the separation column 16, the reference flow path system (vaporization chamber 2, reference column 20, reference cell 1
9) can be used as a flow path for analysis. Also,
Since it is not necessary to mix hydrogen in the reference channel, it is possible to simplify the channel structure by allowing only helium, which is the carrier gas, to flow.
TCD検出器17は半拡散型TCD検出器であり，セル18,19は
ステンレスティール製の容器とタングステンレニウム合
金もしくはタングステンで作られたフィラメントより構
成されている。The TCD detector 17 is a semi-diffusion type TCD detector, and the cells 18 and 19 are composed of a container made of stainless steel and a filament made of tungsten rhenium alloy or tungsten.
第１図中21はヒータを有するカラムオーブンであってGC
分析中は通常ヒータに通電される。水素ガスは可燃性だ
からヘリウム・水素の混合比によってはカラムオーブン
21内で混合ガスが漏れた場合に発火することも起こり得
る。In FIG. 1, 21 is a column oven having a heater, which is a GC.
The heater is normally energized during analysis. Since hydrogen gas is flammable, depending on the mixing ratio of helium and hydrogen, the column oven
Ignition can also occur if the gas mixture leaks in 21.
本発明にかかるGC分析法の実施にはヘリウムに混合する
水素の濃度を制限することが安全上より望ましい。In carrying out the GC analysis method according to the present invention, it is more desirable for safety to limit the concentration of hydrogen mixed with helium.
N2−H2−Air系のH2の発火下限濃度はN2が０〜75％の領
域で４％と一定値を示す。N2,He−メタン−空気系の発
火限界組成を参考としてHeを希釈ガスとしたときのH2−
AIRでの発火限界濃度を求めると,Heが０〜約77％の範囲
でH2の発火下限濃度が４％と推定できる。H2とHeの混合
ガスがカラムオーブン内にもれた場合を想定して許容さ
れるH2の上限濃度は,Heが77％H2が４％（AIRが19％）時
のHe−H2混合気体中のH2濃度即ち である。The lower ignition limit concentration of H 2 in the N 2 -H 2 -Air system shows a constant value of 4% in the region where N 2 is 0 to 75%. N 2 , He − H 2 − when He is used as a diluent gas with reference to the ignition limit composition of the methane-air system
When the ignition limit concentration in AIR is calculated, it can be estimated that the lower ignition limit concentration of H 2 is 4% in the range of He of 0 to about 77%. The upper limit concentration of H 2 mixed gas of H 2 and He is permitted on the assumption that the leakage in the column oven, He is 77% H 2 is 4% (AIR 19%) when He-H 2 H 2 concentration in mixed gas Is.
以上の計算にあたてはLewis−von Elbe“Combustion",l
oc cit（化学便覧より）の報告を基準とした。ヘリウム
と水素の混合比は流量制御弁11と13を調整することによ
り変更することができる。また水素はヘリウム中に１％
以上の場合にベースラインの安定化に効果があった。尚
ヘリウムからH2含有ヘリウムにキャリアガスが変わるこ
とにより感度変化が生じるので定量分析ではH2−ヘリウ
ムの混合比を一定にすることが必要であった。For the above calculation, Lewis-von Elbe “Combustion”, l
Based on the report of oc cit (from Chemical Handbook). The mixing ratio of helium and hydrogen can be changed by adjusting the flow rate control valves 11 and 13. Hydrogen is 1% in helium
In the above cases, it was effective in stabilizing the baseline. Since the sensitivity changes due to the change of the carrier gas from helium to H 2 -containing helium, it was necessary to keep the H 2 -helium mixing ratio constant in the quantitative analysis.
第２図は本発明の分析法と従来の分析法により塩化アリ
ルを分析したクロマトグラムである。従来の分析法，第
２図Ｂでは3.5分付近よりベースラインの変動が生じた
が，本発明に係る分析法第2A（ヘリウムに３％の水素を
混合）ではベースラインの変動が生じなかった。FIG. 2 is a chromatogram obtained by analyzing allyl chloride by the analysis method of the present invention and the conventional analysis method. In the conventional analysis method, FIG. 2B, the baseline fluctuated from around 3.5 minutes, but in the analytical method 2A (helium mixed with 3% hydrogen), the baseline fluctuated. .
分析条件は以下の通りである。The analysis conditions are as follows.
カラム：化学結合型メチルシリコン0.53mmI.D×25mL カラム温度:60℃ 注入口温度:150℃ 検出器温度:150℃ 試 料 塩化アリル 試料注入量:0,5μ（全量注入法） 電流値:120mA キャリアガス：第２図Ａ ３％水素含有ヘリウム50ml/m
in。Column: Chemically bonded methyl silicon 0.53mm I.D × 25mL Column temperature: 60 ℃ Injection temperature: 150 ℃ Detector temperature: 150 ℃ Sample allyl chloride Sample injection amount: 0,5μ (total injection method) Current value: 120mA Carrier gas: Fig. 2A Helium containing 3% hydrogen 50ml / m
in.
第２図Ｂ ヘリウム50ml/min。Fig. 2 B Helium 50 ml / min.
第３図は本発明の他の実施例であるGC分析法を実施する
ためのGC流路を示す流路図である。本例はカラムの下流
側で水素を混合する分析法を示している。第３図中22は
ヘリウムガスボンベであってキャリアガスであるヘリウ
ムは気化室23分離カラム24を通り,TCD検出器25の分析用
セル26に導かれる。また，ヘリウムはレファレンスカラ
ム27を通りTCD検出器25のレファレンス用セル28に導か
れる。FIG. 3 is a flow path diagram showing a GC flow path for carrying out a GC analysis method which is another embodiment of the present invention. This example shows an analytical method in which hydrogen is mixed on the downstream side of the column. In FIG. 3, reference numeral 22 denotes a helium gas cylinder, and helium as a carrier gas passes through a vaporization chamber 23 separation column 24 and is introduced into an analysis cell 26 of a TCD detector 25. Further, helium is guided to the reference cell 28 of the TCD detector 25 through the reference column 27.
水素は流量制御弁29,流路抵抗30を通り分析用流路のヘ
リウムガスに混合される。分離カラム24の下流側に流路
抵抗31が取り付けられており，水素がカラムオーブン32
内の流路に逆流することがないので，水素とヘリウムの
混合比を発火下限値を越えて設定しても安全性は保たれ
得る。Hydrogen passes through the flow control valve 29 and the flow path resistance 30 and is mixed with the helium gas in the analysis flow path. A flow path resistor 31 is installed on the downstream side of the separation column 24, and hydrogen is stored in the column oven 32.
Since it does not flow back into the internal flow path, safety can be maintained even if the mixing ratio of hydrogen and helium is set above the lower ignition limit.
本発明は予め水素を混合したヘリウムガスボンベをキャ
リアガス供給源として使用して実施することができる。
この場合は第１図の実施例について説明したようにカラ
ムオーブン内でキャリアガスの漏れがあっても発火の危
険性がないように予め混合する水素を4.9％以下の濃度
とすることがより望ましい。The present invention can be carried out by using a helium gas cylinder previously mixed with hydrogen as a carrier gas supply source.
In this case, as described in the embodiment of FIG. 1, it is more preferable to pre-mix hydrogen with a concentration of 4.9% or less so that there is no risk of ignition even if carrier gas leaks in the column oven. .
本発明の分析法はセル構造が半拡散型以外に直通型，拡
散型等の他のTCD検出器に使用することが可能であり，
またデュアルカラム流路に使用するTCD検出器のみなら
ず，シングル流路で使用するTCD検出器にも使用でき
る。The analysis method of the present invention can be used for other TCD detectors having a cell structure other than a semi-diffusion type, such as a direct type and a diffusion type.
It can be used not only for the TCD detector used in the dual column flow channel, but also for the TCD detector used in the single flow channel.
（効 果） 本発明の分析法を使用すれば，酸素を含む試料を導入し
てもTCD検出器の出力するベースラインは安定に保たれ
る。また,TCD検出器のフィラメントが酸化されないので
フィラメントの寿命が延びる。(Effect) By using the analysis method of the present invention, the baseline output from the TCD detector can be kept stable even when a sample containing oxygen is introduced. Moreover, since the filament of the TCD detector is not oxidized, the life of the filament is extended.
第１図は本発明の一実施例であるGC分析法を実施するた
めのGC流路を示す流路図であり，第２図は本発明の分析
法と従来の分析法により塩化アリルを分析したクロマト
グラムであり，第３図は本発明の他の実施例であるGC分
析法を実施するためのGC流路を示す流路図である。 図中,1,2は気化室,3はヘリウムガスボンベ,7は水素ガス
ボンベ,16は分離カラム,17はTCD検出器,20はレファレン
スカラム,22はヘリウムガスボンベ,24は分離カラム,25
はTCD検出器,27はレファレンスカラムである。FIG. 1 is a flow path diagram showing a GC flow path for carrying out a GC analysis method according to an embodiment of the present invention, and FIG. 2 is a method for analyzing allyl chloride by the analysis method of the present invention and a conventional analysis method. FIG. 3 is a flow chart showing a GC flow path for carrying out a GC analysis method which is another embodiment of the present invention. In the figure, 1 and 2 are vaporization chambers, 3 is a helium gas cylinder, 7 is a hydrogen gas cylinder, 16 is a separation column, 17 is a TCD detector, 20 is a reference column, 22 is a helium gas cylinder, 24 is a separation column, 25
Is a TCD detector and 27 is a reference column.
Claims (1)
器に熱伝導度検出器を用いるガスクロマトグラフ分析法
において，水素ガスを予めキャリヤガスに混合するかあ
るいはガスクロマトグラフ流路中のキャリヤガス導入路
から熱伝導度検出器の流入側流路までの間のいずれかの
位置に水素ガス導入路を設けることを特徴とするガスク
ロマトグラフ分析法。1. In a gas chromatographic analysis method using helium as a carrier gas and a thermal conductivity detector as a detector, hydrogen gas is mixed with the carrier gas in advance or from a carrier gas introduction passage in the gas chromatograph passage. A gas chromatograph analysis method, characterized in that a hydrogen gas introduction passage is provided at any position between the thermal conductivity detector and the inflow side passage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63163638A JPH0734008B2 (en) | 1988-06-30 | 1988-06-30 | Gas chromatographic analysis method using thermal conductivity detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63163638A JPH0734008B2 (en) | 1988-06-30 | 1988-06-30 | Gas chromatographic analysis method using thermal conductivity detector |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0212058A JPH0212058A (en) | 1990-01-17 |
| JPH0734008B2 true JPH0734008B2 (en) | 1995-04-12 |
Family
ID=15777743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63163638A Expired - Lifetime JPH0734008B2 (en) | 1988-06-30 | 1988-06-30 | Gas chromatographic analysis method using thermal conductivity detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0734008B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2570938B2 (en) * | 1991-12-20 | 1997-01-16 | 株式会社島津製作所 | Gas chromatograph Ar analysis system |
| JP4306129B2 (en) * | 2001-01-31 | 2009-07-29 | 株式会社島津製作所 | Gas chromatograph |
| CN100561217C (en) | 2006-06-29 | 2009-11-18 | 上海神开石油化工装备股份有限公司 | A Method for Analyzing Oil and Gas Components Only Needing Air and Hydrogen |
| CN114414705B (en) * | 2022-03-29 | 2022-07-01 | 南京霍普斯科技有限公司 | Gas chromatography detection system and method for constant nitrogen and hydrogen in synthetic ammonia |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58172544A (en) * | 1982-04-02 | 1983-10-11 | Shimadzu Corp | Helium ionization detector |
| JPH0233985B2 (en) * | 1982-08-11 | 1990-07-31 | Hitachi Ltd | KEIKOKENSHUTSUAMINOSANBUNSEKIKEI |
| JPS6342467A (en) * | 1986-08-08 | 1988-02-23 | Shimadzu Corp | Gas chromatograph |
-
1988
- 1988-06-30 JP JP63163638A patent/JPH0734008B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0212058A (en) | 1990-01-17 |
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