JPH11153579A - Electron capture detector - Google Patents
Electron capture detectorInfo
- Publication number
- JPH11153579A JPH11153579A JP9319947A JP31994797A JPH11153579A JP H11153579 A JPH11153579 A JP H11153579A JP 9319947 A JP9319947 A JP 9319947A JP 31994797 A JP31994797 A JP 31994797A JP H11153579 A JPH11153579 A JP H11153579A
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- Prior art keywords
- collector electrode
- cell
- electrode
- gas
- gas inlet
- Prior art date
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ガスク口マトグ
ラフ用の検出器、特に親電子性化合物を含有する物質を
検出する場合に適するエレクトロンキャプチャ検出器
（電子捕獲形検出器）（以下ＥＣＤという）に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a detector for a gas chromatograph, and more particularly, to an electron capture detector (hereinafter referred to as ECD) suitable for detecting a substance containing an electrophilic compound. About.
【０００２】[0002]
【従来の技術】ガスクロマトグラフ用検出器の一種であ
るＥＣＤは、ハロゲン化合物やニトロ化合物等の分析に
適している検出器である。2. Description of the Related Art ECD, which is a kind of detector for gas chromatography, is a detector suitable for analyzing halogen compounds, nitro compounds and the like.
【０００３】従来のＥＣＤの構造例としては図２に示す
ように、63Ｎｉなどの放射性同位元素の線源２１を陰
極、棒状コレクタ電極２２を陽極として封入した小容積
のセル２３の下部にあるガス入口２４にカラム２７の端
部を位置させて該カラム２７からセル２３内に流入する
試料が上方へ送られるような構造のものが知られてい
る。As an example of the structure of a conventional ECD, as shown in FIG. 2, a radioactive isotope source such as 63 Ni is provided at a lower portion of a small volume cell 23 in which a source 21 and a bar-shaped collector electrode 22 are sealed as a cathode and an anode, respectively. There is known a structure in which an end of a column 27 is positioned at a gas inlet 24 and a sample flowing into the cell 23 from the column 27 is sent upward.
【０００４】この例ではセル２３内にはパージガス流入
路２５から窒素ガスが送られ、線源２１からのβ線によ
って、該窒素ガス等が電離し、セル２３内に電子が生成
する。この電子は陽極である棒状コレクタ電極２２に引
き寄せられるので、棒状コレクタ電極２２と線源２１の
間に定常電流が流れる。In this example, nitrogen gas is sent from the purge gas inflow passage 25 into the cell 23, and the nitrogen gas and the like is ionized by β-rays from the radiation source 21 to generate electrons in the cell 23. Since the electrons are attracted to the rod-shaped collector electrode 22 serving as the anode, a steady current flows between the rod-shaped collector electrode 22 and the radiation source 21.
【０００５】カラム流出ガス中に電子親和性物質がある
場合、当該電子親和性物質は電子と衝突して負イオンを
形成する。当該負イオンは棒状コレクタ電極２２に引き
寄せられて動くが、電子に比べ移動速度が遅いため結果
的に、定常電流の流れが小さくなる。この場合、棒状コ
レクタ電極２２に流れる電流を一定に保つための電圧変
化を記録して負イオン濃度、すなわち、カラム２７から
流出する電子親和性物質の濃度に比例した信号が得られ
るようになっている。[0005] When an electron-affinity substance is present in a column effluent gas, the electron-affinity substance collides with an electron to form a negative ion. The negative ions are attracted to the rod-shaped collector electrode 22 and move, but since the moving speed is slower than the electrons, the flow of the steady current is reduced as a result. In this case, a voltage change for keeping the current flowing through the rod-shaped collector electrode 22 constant is recorded, and a signal proportional to the negative ion concentration, that is, the concentration of the electron affinity substance flowing out of the column 27 can be obtained. I have.
【０００６】ここで、２６は排出流路であり、セル２３
内に流入したガスが排出流路を通って排出される。ま
た、セル２３は、図示しない検出器恒温槽の中に入れら
れているか、または、セルの外側に図示しないヒータ線
が巻かれていて、セル２３は一定の高温に保たれてい
る。Here, reference numeral 26 denotes a discharge channel, and the cell 23
The gas flowing into the inside is discharged through the discharge passage. The cell 23 is placed in a detector thermostat (not shown) or a heater wire (not shown) is wound around the outside of the cell, and the cell 23 is kept at a constant high temperature.
【０００７】[0007]
【発明が解決しようとする課題】従来のＥＣＤはコレク
タ電極が汚れることがあり、このため感度の低下やクロ
マトグラム上にゴーストピークが出現し、精度のよい検
出が出来なくなるという問題点があった。A problem with the conventional ECD is that the collector electrode may be contaminated, which causes a reduction in sensitivity and the appearance of a ghost peak on a chromatogram, making accurate detection impossible. .
【０００８】更に、線源として63Ｎｉのような放射性同
位元素を使用しているため安全性や法規制の面から、コ
レクタ電極を取出し洗浄する場合には相当の専用設備を
必要とする。従って自由に分解・洗浄することが出来な
いため、電極の汚染は深刻な問題となる。Furthermore, from the standpoint of safety and regulatory due to the use of radioactive isotopes, such as 63 Ni as a radiation source, which requires considerable private facilities in the case of washing extraction collector electrode. Therefore, since the electrode cannot be freely disassembled and washed, contamination of the electrode becomes a serious problem.
【０００９】発明者は、この汚れの原因について鋭意検
討を重ねた結果、コレクタ電極の温度及びコレクタ電極
とガス入口の位置関係が問題であることに思い至った。As a result of diligent studies on the cause of the contamination, the inventors have found that the temperature of the collector electrode and the positional relationship between the collector electrode and the gas inlet are problems.
【００１０】すなわち、従来のＥＣＤのコレクタ電極
は、特別の加熱手段を持たずに受動的に検出器恒温層か
ら熱をもらう構造になっている。しかし、コレクタ電極
とセルとの接点は、電気的な絶縁の必要性からセラミッ
ク等で絶縁されている結果、熱的に良好に接続されてい
るとは言い難い。またコレクタ電極は中空セル内部に位
置するために、セルの壁面からの熱伝導性も良くない。
従って、セル内の温度に比較して、コレクタ電極の温度
が低い状態が起こりうる。That is, the conventional ECD collector electrode has a structure in which heat is passively received from the detector constant temperature layer without special heating means. However, the contact between the collector electrode and the cell is insulated by ceramics or the like due to the necessity of electrical insulation, so that it cannot be said that the connection is thermally excellent. In addition, since the collector electrode is located inside the hollow cell, thermal conductivity from the wall surface of the cell is not good.
Therefore, a state in which the temperature of the collector electrode is lower than the temperature in the cell may occur.
【００１１】また、従来のＥＣＤのコレクタ電極は、セ
ル内のガス流路の中に位置しているので、コレクタ電極
に、カラムから出た試料ガスが直接吹き付けられること
になる。このため、試料ガス中の不純物がコレクタ電極
に付着する原因となりうるものであった。In addition, since the collector electrode of the conventional ECD is located in the gas flow path in the cell, the sample gas from the column is directly blown onto the collector electrode. For this reason, the impurities in the sample gas may cause the adhesion to the collector electrode.
【００１２】[0012]
【課題を解決するための手段】このような課題を解決す
るために、本願発明のＥＣＤにあっては、コレクタ電極
を中空柱状として、当該電極の中心軸を略垂直方向に配
置して、かつ、当該電極の中心軸をガス入口の中心と略
一致した配置とすることにより、前記ガス入口からセル
内に導入された気体が前記コレクタ電極の中空部分を通
過するように構成した。In order to solve such a problem, in the ECD of the present invention, the collector electrode is formed as a hollow column, and the center axis of the electrode is arranged in a substantially vertical direction. By arranging the center axis of the electrode substantially coincident with the center of the gas inlet, the gas introduced into the cell from the gas inlet passes through the hollow portion of the collector electrode.
【００１３】本発明において、コレクタ電極の中空柱状
形状とは中空の柱状を意味し、その両端面は、多角形、
正多角形、円形、楕円形を含む。ただし、加工の容易性
やセル内への収納性から、円筒形状がふさわしい。ま
た、柱状形状の底面と高さの関係については、特に制限
は無く、例えば、円筒状の場合に高さよりも底面直径が
大きくてもなんら差し支えない。In the present invention, the hollow columnar shape of the collector electrode means a hollow columnar shape, and both end surfaces thereof are polygonal,
Including regular polygons, circles, and ellipses. However, a cylindrical shape is suitable for ease of processing and storability in a cell. There is no particular limitation on the relationship between the bottom surface of the columnar shape and the height. For example, in the case of a cylindrical shape, the diameter of the bottom surface may be larger than the height.
【００１４】また、中空柱状コレクタの空間配置は、上
方に流れる試料ガスが柱状体の中空部分を通過すればよ
く、ふさわしくは中空柱状コレクタの中心軸を垂直に配
置するのが望ましいが、必ずしも、垂直にする必要はな
く、略垂直に配置すれば本願発明は達成される。The spatial arrangement of the hollow columnar collector may be such that the sample gas flowing upward passes through the hollow portion of the columnar body, and it is desirable that the central axis of the hollow columnar collector be vertically arranged. It is not necessary to be vertical, and the present invention can be achieved if they are disposed substantially vertically.
【００１５】さらに、コレクタ電極の中心軸とガス流の
空間配置については、ガス入口の中心とコレクタ電極の
中心軸を略一致させることが望ましい。これは、セル内
のガス流が、コレクタ壁面に直接吹きあたることなく、
コレクタ電極の中空部分を通過することを目的とするも
のであるが、気体流体の流れを完全に制御したり、ま
た、測定することは困難であり、当該目的を達成できれ
ば、ガス入口の中心と中空柱状コレクタ電極の中心軸を
必ずしも一致させる必要はない。Further, with respect to the spatial arrangement of the central axis of the collector electrode and the gas flow, it is desirable that the center of the gas inlet and the central axis of the collector electrode substantially coincide with each other. This is because the gas flow in the cell does not blow directly to the collector wall,
Although the purpose is to pass through the hollow part of the collector electrode, it is difficult to completely control the flow of the gaseous fluid, and it is difficult to measure the gaseous fluid. It is not necessary that the central axes of the hollow columnar collector electrodes coincide.
【００１６】[0016]
【発明の実施の形態】以下、実施例に基づいて本願発明
を説明するが、本願発明は上述の課題解決手段によって
定義されるものを全て含んでおり、以下の実施例に限定
されるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described based on embodiments. However, the present invention includes all of those defined by the above-mentioned means for solving the problems, and is not limited to the following embodiments. Absent.
【００１７】第1 図は本発明にかかるＥＣＤの説明図で
ある。FIG. 1 is an explanatory diagram of an ECD according to the present invention.
【００１８】図中２３はセルであり、このセル２３の中
にニッケル６３（63Ｎｉ）の円筒状の線源２１が収めら
れている。セル２３の上部は電極室２となっていて、こ
の中に中空柱状コレクタ電極１が収められている。中空
柱状コレクタ電極１には電極引出線３がついている。セ
ル２３の下部には、ガス入口２４が開口し、ここにはカ
ラム２７の出口端部が接続され、また、パージガス流路
２５の出口端が取り付けられている。パージガス流路２
５からはセル２３に窒素ガスが導入される。さらに、セ
ル２３の上部には、排出流路２６が取り付けられてい
る。また、図示しない直流電源が、線源２１は陰極、中
空柱状コレクタ電極１は陽極となる電位でつながれてい
る。[0018] figure 23 is a cell, cylindrical source 21 nickel 63 (63 Ni) is housed in the cell 23. The upper part of the cell 23 is an electrode chamber 2 in which the hollow columnar collector electrode 1 is housed. The hollow columnar collector electrode 1 is provided with an electrode lead wire 3. In the lower part of the cell 23, a gas inlet 24 is opened, where the outlet end of the column 27 is connected, and the outlet end of the purge gas flow path 25 is attached. Purge gas flow path 2
From 5, nitrogen gas is introduced into the cell 23. Further, a discharge channel 26 is attached to the upper part of the cell 23. A DC power supply (not shown) is connected to the line source 21 at a potential to be a cathode and the hollow columnar collector electrode 1 to be an anode.
【００１９】中空柱状コレクタ電極１はその端面が上下
に位置するように配置されている。また、ガス入口２４
の中心と中空柱状コレクタ電極１の中心軸が一致するよ
うに配置されている。The hollow columnar collector electrode 1 is arranged so that the end faces thereof are positioned vertically. Gas inlet 24
And the center axis of the hollow columnar collector electrode 1 is aligned.
【００２０】ガス入口２４からセル内に流入するカラム
流出気体とパージガス流路２５から流入する窒素ガスは
ガス入口２４からセル２３内に入って上昇し、円筒状の
線源２１の中空部を通過し、さらに上昇して中空柱状コ
レクタ電極１の中空部を通過して、排出流路２６からセ
ル２３の外に流出する。The column effluent gas flowing into the cell from the gas inlet 24 and the nitrogen gas flowing from the purge gas passage 25 enter the cell 23 from the gas inlet 24 and rise, and pass through the hollow portion of the cylindrical source 21. Then, it rises further, passes through the hollow portion of the hollow columnar collector electrode 1, and flows out of the cell 23 from the discharge channel 26.
【００２１】さらにセル２３の外側には、図示しないヒ
ータ線が巻かれている。このヒータ線の発熱によって、
セル２３は被分析対象成分のガスクロマトグラフ分析に
適する一定の高温状態に保たれる。本実施例にあって
は、中空柱状コレクタ電極１は直接の加熱手段をもたな
いが、当該電極はセル２３の壁面に近接して配置されて
おり、かつ、円筒状の外壁面全体でセル２３の内壁面か
らの熱を受けるので、十分な高熱状態に保たれる。Further, a heater wire (not shown) is wound outside the cell 23. Due to the heat generated by this heater wire,
The cell 23 is kept at a constant high temperature suitable for gas chromatographic analysis of the component to be analyzed. In this embodiment, the hollow columnar collector electrode 1 does not have a direct heating means, but the electrode is arranged close to the wall surface of the cell 23, and the entire outer wall surface of the cell forms a cell. Since it receives heat from the inner wall surface of 23, it is maintained in a sufficiently high heat state.
【００２２】続いて、本発明に係るＥＣＤ検出器の動作
を説明する。Next, the operation of the ECD detector according to the present invention will be described.
【００２３】パージガス流入路２５からセル２３内に送
られた窒素ガスは、線源２１からのβ線によって、その
一部分が電離し、セル２３内に電子が生成する。この電
子は陽極である中空柱状コレクタ電極１に引き寄せられ
るので、中空柱状コレクタ電極１と線源２１の間に定常
電流が流れる。The nitrogen gas sent from the purge gas inflow passage 25 into the cell 23 is partially ionized by the β-rays from the radiation source 21 to generate electrons in the cell 23. Since these electrons are attracted to the hollow columnar collector electrode 1 serving as the anode, a steady current flows between the hollow columnar collector electrode 1 and the radiation source 21.
【００２４】カラム流出ガス中に電子親和性物質がある
場合、当該電子親和性物質は電子と衝突して負イオンを
形成する。当該負イオンは中空柱状コレクタ電極１に引
き寄せられて動くが、電子に比べ移動速度が遅いため結
果的に、定常電流の流れが小さくなる。この場合、中空
柱状コレクタ電極１に流れる電流を一定に保つための電
圧変化を測定して負イオン濃度、すなわち、カラム２７
から流出する電子親和性物質の濃度に比例した信号が得
られる。When an electron-affinity substance is present in the gas discharged from the column, the electron-affinity substance collides with an electron to form a negative ion. The negative ions are attracted to the hollow columnar collector electrode 1 and move. However, since the moving speed is slower than that of the electrons, the flow of the steady current is reduced. In this case, a voltage change for keeping the current flowing through the hollow columnar collector electrode 1 constant is measured to determine the negative ion concentration, that is, the column 27.
A signal proportional to the concentration of the electron-affinity substance flowing out of the device is obtained.
【００２５】[0025]
【発明の効果】本発明にかかるＥＣＤ検出器は、そのコ
レクタ電極が、一定の高温状態に保たれているセルの壁
面からの温度を効率よく受けるので、当該コレクタ電極
が高温に保たれること、また、カラム流出気体が直接コ
レクタ電極に吹き当たらないから、当該コレクタ電極の
汚染が少ない。According to the ECD detector of the present invention, since the collector electrode thereof efficiently receives the temperature from the wall surface of the cell maintained at a constant high temperature, the collector electrode can be maintained at a high temperature. Also, since the gas flowing out of the column does not directly blow on the collector electrode, the collector electrode is less contaminated.
【図１】本発明にかかるＥＣＤの説明図である。FIG. 1 is an explanatory diagram of an ECD according to the present invention.
【図２】従来の棒状コレクタ電極を有するＥＣＤの説明
図である。FIG. 2 is an explanatory view of a conventional ECD having a rod-shaped collector electrode.
１ 中空柱状コレクタ電極 ２ 電極室 ３ 電極引出線 ２１ 線源 ２２ 棒状コレクタ電極 ２３ セル ２４ ガス入口 ２５ パージガス流路 ２６ 排出流路 ２７ カラム DESCRIPTION OF SYMBOLS 1 Hollow pillar-shaped collector electrode 2 Electrode chamber 3 Electrode lead-out line 21 Source 22 Bar-shaped collector electrode 23 Cell 24 Gas inlet 25 Purge gas flow path 26 Discharge flow path 27 Column
Claims (1)
用電極（コレクタ電極）を有し、かつセル下部にカラム
出口から導かれるガス入口を有し、セルを負極、コレク
タ電極を正極として電圧を印加して、放射性同位元素の
線源から放射される放射線によってガス入口からセル内
に導入された気体分子を電離し生じた電子等に起因する
コレクタ電流の変化を検出するガスクロマトグラフ用エ
レクトロンキャプチャ検出器において、 コレクタ電極を中空柱状として、当該電極の中心軸を略
垂直方向に配置して、かつ、当該電極の中心軸を前記ガ
ス入口の中心と略一致させて配置することにより、前記
ガス入口からセル内に導入された気体が前記コレクタ電
極の中空部分を通過するように構成したことを特徴とす
るエレクトロンキャプチャ検出器。1. A cell having a radioisotope radiation source and an electron capturing electrode (collector electrode) in a cell, a gas inlet led from a column outlet below the cell, a cell as a negative electrode, and a collector electrode as a positive electrode. A gas chromatograph that detects changes in collector current caused by electrons generated by ionizing gas molecules introduced into the cell from the gas inlet by radiation emitted from a radioisotope source by applying a voltage as In the electron capture detector, the collector electrode is formed as a hollow column, the center axis of the electrode is arranged in a substantially vertical direction, and the center axis of the electrode is arranged so as to substantially coincide with the center of the gas inlet. An electron capture detector, wherein the gas introduced into the cell from the gas inlet passes through a hollow portion of the collector electrode. .
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9319947A JPH11153579A (en) | 1997-11-20 | 1997-11-20 | Electron capture detector |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9319947A JPH11153579A (en) | 1997-11-20 | 1997-11-20 | Electron capture detector |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11153579A true JPH11153579A (en) | 1999-06-08 |
Family
ID=18116026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9319947A Pending JPH11153579A (en) | 1997-11-20 | 1997-11-20 | Electron capture detector |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11153579A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339709C (en) * | 2004-10-09 | 2007-09-26 | 安捷伦科技有限公司 | Method and device for preventing wall polluting in collector of N-P detector |
| JP2008232783A (en) * | 2007-03-20 | 2008-10-02 | Shimadzu Corp | Electron capture detector |
| JP2009236928A (en) * | 2009-07-15 | 2009-10-15 | Shimadzu Corp | Electron capture detector |
| JP2011128171A (en) * | 2011-03-30 | 2011-06-30 | Shimadzu Corp | Electron capture detector |
| WO2015159463A1 (en) * | 2014-04-17 | 2015-10-22 | 株式会社島津製作所 | Electron capture detector |
| CN105229457A (en) * | 2013-05-17 | 2016-01-06 | 株式会社岛津制作所 | Electron capture detector |
| CN107907621A (en) * | 2017-12-28 | 2018-04-13 | 浙江福立分析仪器股份有限公司 | The automatically cleaning electron capture detector and its application process of a kind of gas chromatograph |
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| JPS6161459U (en) * | 1984-09-28 | 1986-04-25 | ||
| JPS62115657U (en) * | 1986-01-16 | 1987-07-23 | ||
| JPH01118764A (en) * | 1987-11-02 | 1989-05-11 | Hitachi Ltd | Electron capturing ionization detector |
| JPH09265935A (en) * | 1996-03-29 | 1997-10-07 | Hitachi Ltd | Analyser |
-
1997
- 1997-11-20 JP JP9319947A patent/JPH11153579A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6079657A (en) * | 1983-10-07 | 1985-05-07 | Hitachi Ltd | Ion source for atmospheric pressure ionization mass spectrometer |
| JPS6161459U (en) * | 1984-09-28 | 1986-04-25 | ||
| JPS62115657U (en) * | 1986-01-16 | 1987-07-23 | ||
| JPH01118764A (en) * | 1987-11-02 | 1989-05-11 | Hitachi Ltd | Electron capturing ionization detector |
| JPH09265935A (en) * | 1996-03-29 | 1997-10-07 | Hitachi Ltd | Analyser |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100339709C (en) * | 2004-10-09 | 2007-09-26 | 安捷伦科技有限公司 | Method and device for preventing wall polluting in collector of N-P detector |
| JP2008232783A (en) * | 2007-03-20 | 2008-10-02 | Shimadzu Corp | Electron capture detector |
| JP2009236928A (en) * | 2009-07-15 | 2009-10-15 | Shimadzu Corp | Electron capture detector |
| JP2011128171A (en) * | 2011-03-30 | 2011-06-30 | Shimadzu Corp | Electron capture detector |
| CN105229457A (en) * | 2013-05-17 | 2016-01-06 | 株式会社岛津制作所 | Electron capture detector |
| WO2015159463A1 (en) * | 2014-04-17 | 2015-10-22 | 株式会社島津製作所 | Electron capture detector |
| CN107907621A (en) * | 2017-12-28 | 2018-04-13 | 浙江福立分析仪器股份有限公司 | The automatically cleaning electron capture detector and its application process of a kind of gas chromatograph |
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