JPH0570107B2 - - Google Patents
Info
- Publication number
- JPH0570107B2 JPH0570107B2 JP57230088A JP23008882A JPH0570107B2 JP H0570107 B2 JPH0570107 B2 JP H0570107B2 JP 57230088 A JP57230088 A JP 57230088A JP 23008882 A JP23008882 A JP 23008882A JP H0570107 B2 JPH0570107 B2 JP H0570107B2
- Authority
- JP
- Japan
- Prior art keywords
- carrier gas
- sample
- flow path
- outer cylinder
- cylinder
- 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
- 230000008016 vaporization Effects 0.000 claims description 23
- 238000009834 vaporization Methods 0.000 claims description 20
- 239000012159 carrier gas Substances 0.000 claims description 18
- 239000007789 gas Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 239000000523 sample Substances 0.000 description 33
- 239000002904 solvent Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 9
- 239000012488 sample solution Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 210000002268 wool Anatomy 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010926 purge Methods 0.000 description 2
- 239000012472 biological sample Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 150000003431 steroids Chemical class 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
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
- G01N30/26—Conditioning of the fluid carrier; Flow patterns
- G01N30/38—Flow patterns
Description
【発明の詳細な説明】
この発明はガスクロマトグラフに関し、特に希
薄試料の短時間の分析を可能にするガスクロマト
グラフを提供するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a gas chromatograph, and in particular provides a gas chromatograph that enables analysis of dilute samples in a short time.
ガスクロマトグラフイにおいて、主カラムとし
てキヤピラリカラム（例えば0.2〜0.5mmφ）が多
用されているが、そのキヤピラリカラムの内径が
小さいためにカラム負荷の関係から通常試料（溶
液）を1/50〜1/300にして（スプリツトして）キ
ヤピラリカラムに送りこまれる。従つてその試料
が希薄溶液（低濃度成分）である場合は、検出感
度の点から分析が難しいことが多い（例えば尿中
のステロイド、有機酸などの生体試料分析）。も
ちろん溶媒を含む試料のほとんどをキヤピラリカ
ラムへ導入して分析する手法もあるが、多量の溶
媒によりキヤピラリカラムを劣化するおそれがあ
る。更に目的成分の後に溶出する不要な高沸点成
分は溶出完了までに時間がかかり、次の試料導入
ができない。すなわち分析時間が著しく長くな
り、またキヤピラリカラムにその高沸点成分が残
留して高価なカラムの劣化を起こすおそれもあ
る。 In gas chromatography, a capillary column (for example, 0.2 to 0.5 mmφ) is often used as the main column, but because the inner diameter of the capillary column is small, the sample (solution) is usually reduced to 1/50 to 1/300 due to the column load. (split) into the capillary column. Therefore, if the sample is a dilute solution (low concentration component), analysis is often difficult in terms of detection sensitivity (for example, analysis of biological samples such as steroids and organic acids in urine). Of course, there is also a method of introducing most of the sample containing a solvent into a capillary column for analysis, but there is a risk that the capillary column will deteriorate due to a large amount of solvent. Furthermore, unnecessary high-boiling components that elute after the target component take time to complete elution, making it impossible to introduce the next sample. That is, the analysis time becomes significantly longer, and there is also the risk that the high-boiling components remain in the capillary column, causing deterioration of the expensive column.
この発明はこれらの事情に鑑みなされたもの
で、その具体的構成は、プレカラムを有する試料
気化筒と、試料加熱温度制御手段と、試料気化筒
にキヤリアガスを流れ方向切換可能に供給するキ
ヤリアガス切換供給手段と、試料気化筒の一方開
口より検出器へ延びるキヤピラリカラムとを備
え、且つ
前記試料加熱制御手段及びキヤリアガス切換供
給手段を作動させることによつて、試料気化室に
注入した試料溶液中の溶媒成分を試料気化筒の他
方開口から排出除去し、その後試料溶液中の目的
成分を気化してキヤピラリカラムに導入し、次い
で試料溶液中の不要な高沸点成分を試料気化筒の
他方開口から排出除去するよう構成してなるガス
クロマトグラフである。 This invention was made in view of these circumstances, and its specific configuration includes a sample vaporization cylinder having a precolumn, a sample heating temperature control means, and a carrier gas switching supply that supplies carrier gas to the sample vaporization cylinder in a switchable flow direction. and a capillary column extending from one opening of the sample vaporization cylinder to the detector, and by operating the sample heating control means and the carrier gas switching supply means, the solvent component in the sample solution injected into the sample vaporization chamber is is discharged and removed from the other opening of the sample vaporization cylinder, then the target component in the sample solution is vaporized and introduced into the capillary column, and then unnecessary high-boiling components in the sample solution are discharged and removed from the other opening of the sample vaporization cylinder. This is a gas chromatograph made up of:
すなわち、この発明は、試料気化筒にプレカラ
ムを設け、その試料気化筒に対して加熱制御とキ
ヤリアガスの流れを経時的に切換えることによつ
て、試料溶液中の大部分を占める溶媒成分を、予
め、つまりキヤピラリカラムを通さずに、除去し
て試料溶液を濃縮し、しかも試料溶液中の目的成
分をキヤピラリカラムへ導入した後、不要な高沸
点成分をキヤピラリカラムを通さず除去するよう
にし、それによつて希薄試料の短時間の分析を可
能にするものである。 In other words, the present invention provides a precolumn in the sample vaporization column and changes over time the heating control and carrier gas flow to the sample vaporization column, thereby removing the solvent component that makes up the majority of the sample solution in advance. In other words, the sample solution is concentrated by removing it without passing it through the capillary column, and after the target components in the sample solution are introduced into the capillary column, unnecessary high-boiling components are removed without passing through the capillary column, thereby diluting the solution. This enables analysis of samples in a short time.
以下図に示す実施例に基づいてこの発明を詳述
する。なお、これによつてこの発明が限定される
ものではない。 The present invention will be described in detail below based on embodiments shown in the figures. Note that this invention is not limited to this.
まず第１図において、ガスクロマトグラフＧ
は、外筒１５と、この外筒内に同軸に内設された
試料気化内筒（又はガラスインサート）７とを備
え、１６はその内筒の支持環、１７はシール環で
ある。また１８は内筒１７の試料気化室で、６は
その気化室に充填されたシリカウール、４１はプ
レカラムを構成する充填剤（例：３％SE30、ク
ロモソルブW80〜100メツシユ２mmφ×20〜50
mm）、９は内筒の後段側開口１９より検出器１０
に延びるキヤピラリカラム（例：内径0.3mmφ、
長さ25mm）である。一方５は外筒１５の前段側開
口２０に設置されたセプタム、２１はセプタム保
持板、２２は排気部、２３は外筒１５の後段側開
口２４のシール環、２５はその開口２４附近のス
プリツト流路、２６はこの供給部とは支持環１６
及びシール環１７に対して反対側の第２キヤリア
ガス供給部である。なお、２９は調圧器、３２は
開閉弁、３３は可変高抵抗であり、３６，３７は
開閉弁、３９は可変高抵抗、４０はモニタ用検出
器、３５は流量制御器、３８は調圧器、３４は制
御弁である。３１はメイクアツプガス（又はスカ
ベンジヤガス）入口、２８はカラム槽である。 First, in Figure 1, the gas chromatograph G
comprises an outer cylinder 15 and a sample vaporizing inner cylinder (or glass insert) 7 coaxially installed inside the outer cylinder, 16 is a support ring for the inner cylinder, and 17 is a seal ring. In addition, 18 is the sample vaporization chamber of the inner cylinder 17, 6 is the silica wool filled in the vaporization chamber, and 41 is the packing material constituting the precolumn (e.g. 3% SE 30 , Chromosolve W80-100 mesh 2 mmφ x 20-50
mm), 9 is the detector 10 from the rear opening 19 of the inner cylinder.
Capillary column extending to
The length is 25mm). On the other hand, 5 is a septum installed in the front opening 20 of the outer cylinder 15, 21 is a septum holding plate, 22 is an exhaust part, 23 is a seal ring of the rear opening 24 of the outer cylinder 15, and 25 is a split near the opening 24. The flow path 26 is connected to the support ring 16 with this supply section.
and a second carrier gas supply section on the opposite side to the seal ring 17. In addition, 29 is a pressure regulator, 32 is an on-off valve, 33 is a variable high resistance, 36 and 37 are on-off valves, 39 is a variable high resistance, 40 is a monitor detector, 35 is a flow rate controller, and 38 is a pressure regulator. , 34 are control valves. 31 is a make-up gas (or scavenger gas) inlet, and 28 is a column tank.
３０は、外筒１５の周囲に胴巻きに設置された
試料加熱制御筒で、内部にはボンベから冷却器を
経て冷却された空気又は窒素などを通すことがで
き、筒外部にはヒータ８が巻設され、ヒータの制
御によつて内筒の試料気化室１８の温度を制御で
きる。 Reference numeral 30 denotes a sample heating control cylinder installed around the outer cylinder 15 in a body wrapper, through which air or nitrogen cooled from the cylinder via a cooler can pass, and a heater 8 is wound around the outside of the cylinder. The temperature of the sample vaporization chamber 18 in the inner tube can be controlled by controlling the heater.
かくしてまずマイクロシリンジ（図示省略）に
試料を一定量とり、セプタム５を通じて試料溶液
を試料気化室１８、つまり試料気化室のシリカウ
ール６に滴下する。この時試料気化室１８内の温
度は、試料溶液中の溶媒のみが蒸発できる程度の
温度（例：室温〜70℃程度、もちろん溶媒によつ
て変る）に設定されている。また開閉弁３６は
閉、開閉弁３２，３７は開とされ、キヤリアガス
は調圧器２９、開閉弁３７を通つて内筒７内部を
通り、更に開閉弁３２より外部に抜け、従つて試
料溶液中の揮発性の高い溶媒は蒸発し、排気部２
２より系外へ排出される。 Thus, first, a certain amount of sample is taken into a microsyringe (not shown), and the sample solution is dropped through the septum 5 onto the sample vaporization chamber 18, that is, the silica wool 6 of the sample vaporization chamber. At this time, the temperature in the sample vaporization chamber 18 is set to a temperature at which only the solvent in the sample solution can evaporate (for example, room temperature to about 70°C, which of course varies depending on the solvent). Also, the on-off valve 36 is closed and the on-off valves 32 and 37 are opened, and the carrier gas passes through the pressure regulator 29 and the on-off valve 37, inside the inner cylinder 7, and then escapes to the outside through the on-off valve 32, thus entering the sample solution. The highly volatile solvent evaporates and the
2, it is discharged from the system.
次いで開閉弁３２を閉とし、開閉弁３６を開と
して内筒７内のキヤリアガスの流れ方向を逆に
し、同時にヒータ８を作動させて試料気化室１８
を急速に加熱し（例：300℃）、シリカウール６に
残つている目的成分を気化し、キヤピラリカラム
９に送り込み、適宜検出器１０によつて検出す
る。このように試料の分析が大部分を占める溶媒
を除いた目的成分についてのみ行なわれ、従つて
試料が希薄試料であつても高感度の分析が可能と
なる。 Next, the on-off valve 32 is closed, the on-off valve 36 is opened to reverse the flow direction of the carrier gas in the inner cylinder 7, and at the same time, the heater 8 is activated to open the sample vaporization chamber 18.
is rapidly heated (e.g., 300° C.) to vaporize the target component remaining in the silica wool 6, and send it to the capillary column 9, where it is detected by a detector 10 as appropriate. In this way, the analysis of the sample is performed only on the target components excluding the solvent, which accounts for most of the sample, and therefore, even if the sample is a dilute sample, highly sensitive analysis is possible.
続いて開閉弁３２を開、開閉弁３６を閉とし、
ヒータ８の作動を続けて試料気化室１８内の充填
剤４１、つまりプレカラムに残つている高沸点成
分を排気部２２から系外に追い出す。従つて分析
時間が短縮され、次の試料導入が非常に早い時期
に可能になる。また高沸点成分がキヤピラリカラ
ム９に残留することによるカラムの劣化を防止で
きる。なお、これらの操作中、開閉弁３７は開状
態を維持しているので、調圧器３８によりキヤピ
ラリカラム９の流量が一定となる。また可変高抵
抗３３は、セプタムパージ用で、可変高抵抗３９
は外筒１５とキヤピラリカラム９との接続部のデ
ツドスペースをなくすと共に、モニタ用検出器４
０に接続され目的成分をモニタして流路切換を容
易にできる。制御弁３４は流量制御器３５が閉に
なつたときに圧力計が最大値になるのでリークさ
せるために設けられ、開閉弁３６と連動する。更
に溶媒の拡散が問題になる場合は溶媒除去時に開
閉弁３６を開の状態にしておいてもよい。流量制
御器３５は調圧器に代えることができる。 Subsequently, the on-off valve 32 is opened, the on-off valve 36 is closed,
The heater 8 continues to operate, and the high boiling point components remaining in the filler 41 in the sample vaporization chamber 18, that is, in the precolumn, are expelled from the system through the exhaust section 22. The analysis time is therefore shortened and the next sample can be introduced at a very early stage. Furthermore, deterioration of the column due to high boiling point components remaining in the capillary column 9 can be prevented. Note that during these operations, the on-off valve 37 remains open, so the flow rate of the capillary column 9 is kept constant by the pressure regulator 38. Also, the variable high resistance 33 is for septum purge, and the variable high resistance 39 is for septum purge.
This eliminates the dead space at the connection between the outer cylinder 15 and the capillary column 9, and also allows the monitoring detector 4 to be
0 to monitor the target component and facilitate channel switching. The control valve 34 is provided to cause leakage since the pressure gauge reaches the maximum value when the flow rate controller 35 is closed, and is interlocked with the on-off valve 36. Furthermore, if the diffusion of the solvent becomes a problem, the on-off valve 36 may be kept open during solvent removal. The flow rate controller 35 can be replaced with a pressure regulator.
なお、試料気化室１８は急速加熱後には、次の
試料導入のために冷風によつて冷却される。 Note that after the sample vaporization chamber 18 is rapidly heated, it is cooled by cold air in order to introduce the next sample.
以上の実施例において採用した試料加熱温度制
御手段のうち加熱手段は、内筒（ガラス製）の外
側に金属被膜をコーテイングするか、その内筒の
内部に常磁性金属をインサートし高周波加熱する
手段でもよく、もちろんいずれの場合も気化する
成分が金属表面に接して分解を生じないようにし
なければならない。 Among the sample heating temperature control means adopted in the above examples, the heating means is a means of coating the outside of the inner cylinder (made of glass) with a metal film, or inserting a paramagnetic metal inside the inner cylinder and performing high-frequency heating. However, in either case, care must be taken to prevent the vaporized components from coming into contact with the metal surface and causing decomposition.
本発明によれば、スプリツト流路を溶媒除去時
にキヤリアガス供給流路として使用しているた
め、キヤリアガス導入パイプを別途付設する必要
もなく、しかも、かかる簡略化した構成で、キヤ
ピラリカラム使用時に起る溶媒成分によるカラム
の劣化などの課題を解決できる。 According to the present invention, since the split flow path is used as a carrier gas supply flow path during solvent removal, there is no need to separately install a carrier gas introduction pipe.Moreover, with this simplified configuration, the solvent that occurs when using a capillary column can be removed. Problems such as column deterioration due to components can be resolved.
第１図はこの発明に係るガスクロマトグラフの
一実施例を示す縦断面図である。
７……試料気化内筒、８……ヒータ、９……キ
ヤピラリカラム、１０……検出器、２２……排気
部、２５……スプリツト流路、２６……キヤリア
ガス供給部、４１……プレカラム。
FIG. 1 is a longitudinal sectional view showing an embodiment of a gas chromatograph according to the present invention. 7...Sample vaporization inner cylinder, 8...Heater, 9...Capillary column, 10...Detector, 22...Exhaust section, 25...Split channel, 26...Carrier gas supply section, 41...Precolumn.
Claims (1)
に支持された試料気化内筒と、前記試料気化内筒
の一方開口より検出器へ延びるキヤピラリカラム
と、前記外筒のシール環を基準にして前記試料気
化内筒のキヤピラリカラム側開口側の部分に付設
されたスプリツト流路と、前記スプリツト流路に
枝分かれして接続されるモニタ検出器と、前記外
筒のシール環を基準に前記スプリツト流路と反対
側に付設されたキヤリアガス供給部と、前記キヤ
リアガス供給部およびスプリツト流路に順次キヤ
リアガスを切換可能に流すキヤリアガス切換供給
手段と、前記試料気化内筒のキヤピラリカラム側
開口と反対の開口側で外筒に付設された排気部
と、外筒の周囲に配設した試料加熱温度制御手段
とを備え、且つ 前記キヤリアガス切換供給手段は、前記モニタ
検出器の信号に基づきキヤリアガスをスプリツト
流路、キヤリアガス供給部、スプリツト流路を１
サイクルとして順に流すよう制御してなるガスク
ロマトグラフ。[Scope of Claims] 1. An outer cylinder, a sample vaporizing inner cylinder coaxially supported within the outer cylinder via a seal ring, a capillary column extending from one opening of the sample vaporizing inner cylinder to a detector, and the outer cylinder. a split flow path attached to the opening side of the capillary column side of the sample vaporization inner cylinder with reference to the seal ring of the cylinder, a monitor detector branched and connected to the split flow path, and a seal of the outer cylinder. a carrier gas supply section attached to the opposite side of the split flow path with reference to the ring; a carrier gas switching supply means for switchingably allowing carrier gas to sequentially flow through the carrier gas supply section and the split flow path; and a capillary column side of the sample vaporization inner cylinder. The carrier gas switching supply means includes an exhaust section attached to the outer cylinder on the opening side opposite to the opening, and a sample heating temperature control means disposed around the outer cylinder, and the carrier gas switching supply means Split carrier gas flow path, carrier gas supply section, split flow path
A gas chromatograph that is controlled to flow sequentially as a cycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23008882A JPS59120956A (en) | 1982-12-28 | 1982-12-28 | Gas chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP23008882A JPS59120956A (en) | 1982-12-28 | 1982-12-28 | Gas chromatograph |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59120956A JPS59120956A (en) | 1984-07-12 |
| JPH0570107B2 true JPH0570107B2 (en) | 1993-10-04 |
Family
ID=16902355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP23008882A Granted JPS59120956A (en) | 1982-12-28 | 1982-12-28 | Gas chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59120956A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6126858A (en) * | 1984-07-16 | 1986-02-06 | Shimadzu Corp | Precutting device for gas chromatograph |
| JPH087194B2 (en) * | 1984-10-09 | 1996-01-29 | 株式会社島津製作所 | Chromatographic equipment |
| JPS6486061A (en) * | 1987-08-21 | 1989-03-30 | Gasukuro Kogyo Kk | Injection port flashing back apparatus for separation column of gas chromatography |
| JPH029864U (en) * | 1988-07-04 | 1990-01-22 | ||
| JPH0289356U (en) * | 1988-12-28 | 1990-07-16 | ||
| FR2664385B1 (en) * | 1990-07-09 | 1994-04-01 | Rhone Poulenc Chimie | METHOD FOR INJECTING THE SAMPLE INTO THE SEPARATION COLUMN OF A CHROMATOGRAPHER IN THE GASEOUS PHASE AND INJECTION DEVICE FOR CARRYING OUT SAID METHOD. |
| JPH04113264A (en) * | 1990-09-03 | 1992-04-14 | Yamatake Honeywell Co Ltd | Process gas chromatograph |
| US8196450B2 (en) | 2006-08-28 | 2012-06-12 | Shimadzu Corporation | Gas chromatograph |
| JP4743270B2 (en) * | 2008-12-24 | 2011-08-10 | 株式会社島津製作所 | Gas chromatograph |
| US8152909B2 (en) * | 2009-04-01 | 2012-04-10 | Bruker Chemical Analysis B.V. | Gas chromatography check valve and system |
| JP2020118616A (en) * | 2019-01-25 | 2020-08-06 | 株式会社島津製作所 | Gas chromatograph |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5590949U (en) * | 1978-12-20 | 1980-06-23 |
-
1982
- 1982-12-28 JP JP23008882A patent/JPS59120956A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59120956A (en) | 1984-07-12 |
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