JP3240574B2 - Process gas chromatograph - Google Patents
Process gas chromatographInfo
- Publication number
- JP3240574B2 JP3240574B2 JP03439594A JP3439594A JP3240574B2 JP 3240574 B2 JP3240574 B2 JP 3240574B2 JP 03439594 A JP03439594 A JP 03439594A JP 3439594 A JP3439594 A JP 3439594A JP 3240574 B2 JP3240574 B2 JP 3240574B2
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- Japan
- Prior art keywords
- sample
- separation column
- temperature
- analysis
- component
- Prior art date
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Description
【０００１】[0001]
【産業上の利用分野】本発明は，試料に含まれる成分の
量を分析するプロセスガスクロマトグラフ（以下，単に
プロセスガスクロという）に関し，分析時間の短縮化を
図ったプロセスガスクロに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process gas chromatograph (hereinafter simply referred to as "process gas chromatograph") for analyzing the amount of a component contained in a sample, and to a process gas chromatograph which shortens the analysis time.
【０００２】[0002]
【従来の技術】プロセスガスクロはプロセスの試料がサ
ンプリングバルブにより採取され，その採取された試料
が分析ユニットにおいてガス状態で分離カラム中を移動
し，その移動速度の差を利用して試料の成分が分離さ
れ，その成分および含有量に応じた出力信号，いわゆる
クロマトグラム信号を得るものである。2. Description of the Related Art In a process gas chromatograph, a sample of a process is collected by a sampling valve, and the collected sample moves through a separation column in a gas state in an analysis unit. It separates and obtains an output signal corresponding to its component and content, a so-called chromatogram signal.
【０００３】図３（ａ）はプロセスガスクロの従来例を
示す構成図である。図において１は試料の一定量を計量
管１’により採取するサンプリングバルブであり，２は
採取した試料をキャリアガスとともに導入する分離カラ
ムである。３は分離カラムが配置された恒温槽で低温〜
高温領域までの温度設定（例えば５５〜２２５℃の範囲
で１℃単位で温度設定）が可能である。４は検出器で例
えば熱伝導度検出器（ＴＣＤ）や水素炎イオン化検出器
（ＦＩＤ），炎光光度検出器（ＦＰＤ）等のいずれかで
構成され，分離カラムから所定の時間遅れで順次溶出す
る特定のガス成分を電気信号に変換する。FIG. 3A is a configuration diagram showing a conventional example of process gas chromatography. In the figure, reference numeral 1 denotes a sampling valve for collecting a fixed amount of a sample by a measuring tube 1 ', and 2 denotes a separation column for introducing the collected sample together with a carrier gas. No. 3 is a constant temperature bath in which a separation column is arranged.
It is possible to set a temperature up to a high-temperature region (for example, set a temperature in a range of 55 to 225 ° C. in 1 ° C. units). Reference numeral 4 denotes a detector, which comprises, for example, a thermal conductivity detector (TCD), a flame ionization detector (FID), or a flame photometric detector (FPD), and elutes sequentially from the separation column with a predetermined time delay. The specific gas component is converted into an electric signal.
【０００４】図３（ｂ）は恒温槽３内の所定時間（ｔ）
における温度パターンを示し，初期温度（ａ点…例えば
６０℃）〜終点温度（ｂ点…例えば２００℃）まで上昇
させた後初期温度（ａ点）まで降下させた状態を示して
いる。図３（ｃ）はサンプリングバルブの動作を示し初
期温度に同期して試料を取り込んでいるいる状態を示し
ている。図３（ｄ）は検出器の出力信号を示し，比較的
低い温度から高い温度に渡って成分が流出している状態
を示している。FIG. 3B shows a predetermined time (t) in the thermostat 3.
5 shows a state in which the temperature is increased from the initial temperature (point a: for example, 60 ° C.) to the end point temperature (point b, for example, 200 ° C.) and then lowered to the initial temperature (point a). FIG. 3C shows the operation of the sampling valve and a state in which a sample is being taken in synchronization with the initial temperature. FIG. 3D shows an output signal of the detector, and shows a state where components are flowing out from a relatively low temperature to a high temperature.
【０００５】[0005]
【発明が解決しようとする課題】ところで，上記従来の
ガスクロマトグラフでは多数成分よりなる試料について
分離カラム１台で各成分の完全個別分離を行っており，
そのために例えばナフサの様な１００〜２５０またはそ
れ以上の成分から構成される試料の測定には長時間（例
えば６０〜９０分）を要する。By the way, in the conventional gas chromatograph described above, for a sample composed of a large number of components, each component is completely individually separated by one separation column.
Therefore, it takes a long time (for example, 60 to 90 minutes) to measure a sample composed of 100 to 250 or more components such as naphtha.
【０００６】しかしながら，石油精製プロセスでオンラ
インでナフサの分析を行う場合，長時間の測定を行って
いたのでは試料組成に変化が生じた場合，迅速な対応が
出来ないという問題がある。本発明は上記従来技術の問
題を解決するためになされたもので，採取した試料を２
系統以上に分岐し低温領域と高温領域を分別して分析す
ることにより分析時間の短縮化を図ったプロセスガスク
ロを提供することを目的とする。However, when performing naphtha analysis online in a petroleum refining process, there is a problem that if the measurement is performed for a long time, if a change occurs in the sample composition, it is not possible to respond quickly. The present invention has been made in order to solve the above-mentioned problems of the prior art.
It is an object of the present invention to provide a process gas chromatograph which is branched into more than one system and separates a low-temperature region and a high-temperature region for analysis, thereby shortening the analysis time.
【０００７】[0007]
【課題を解決するための手段】上記課題を解決する為に
本発明は，試料を一定量採取するサンプリングバルブ
と，該サンプリングバルブにより採取された試料を２以
上に分岐する分岐手段と，前記試料から分析成分を分離
するための比較的低い温度から高い温度範囲を２以上の
温度分布範囲に分割する２以上の恒温槽と，該２以上の
恒温槽のそれぞれに配置され前記２以上に分岐した試料
のそれぞれを導入する分離カラムと，前記恒温槽のうち
最も高い温度分布範囲を担当する恒温槽以外に配置され
た分離カラムの入口側と出口側に設けられた流路切換バ
ルブと，前記分離カラムの後段にそれぞれ配置された分
析ユニットと，得られた結果（クロマトグラム信号）を
解析手段により解析して表示或いは記録する表示手段を
有し，前記試料に含まれる分析成分のうち所定の成分が
分離した段階で分離カラムに残留する分析成分を前記流
路切換バルブを介して排除するように構成したことを特
徴とするものである。SUMMARY OF THE INVENTION In order to solve the above-mentioned problems, the present invention provides a sampling valve for collecting a fixed amount of a sample, a branching means for branching the sample collected by the sampling valve into two or more samples, Two or more thermostats that divide a relatively low temperature to a high temperature range into two or more temperature distribution ranges for separating an analytical component from the water, and are arranged in each of the two or more thermostats and branched into two or more. A separation column for introducing each of the samples, a flow path switching valve provided on an inlet side and an outlet side of a separation column arranged in a thermostatic chamber other than a thermostat chamber in charge of the highest temperature distribution range; It has an analysis unit arranged at the subsequent stage of the column, and a display means for analyzing and displaying or recording the obtained result (chromatogram signal) by the analysis means. Given component of the analysis component is characterized in that the analysis components remaining in the separation column at a stage which was separated and configured to eliminate through the flow channel switching valve.
【０００８】[0008]
【作用】各分離カラムは所定の温度範囲の成分を明確に
分離する。検出器は分離カラムから溶出した分析成分の
検出信号を解析手段に送る。最も高い温度分布範囲を担
当する恒温槽以外に配置された分離カラムの入口側と出
口側に設けられた流路切換バルブは所定の成分が分離し
た時点で分離カラムの出口側からキャリアガスを吹き込
んで分離カラム中に残っている高沸点成分を排除する。Each separation column clearly separates components within a predetermined temperature range. The detector sends a detection signal of the analysis component eluted from the separation column to the analysis means. The flow path switching valves provided on the inlet side and the outlet side of the separation column, which are arranged other than the thermostat that is in charge of the highest temperature distribution range, blow carrier gas from the outlet side of the separation column when a predetermined component is separated. The high boiling point components remaining in the separation column are eliminated with.
【０００９】[0009]
【実施例】図１は本発明によるプロセスガスクロの一実
施例を示す要部構成図である。なお，ここでは試料を２
系統に分岐し，高温側を担当する恒温槽の温度を一定に
維持し，低温側を担当する恒温槽の温度を中程度の温度
まで上昇させる例について説明する。FIG. 1 is a schematic diagram showing a main part of an embodiment of a process gas chromatography according to the present invention. Here, the sample was 2
An example of branching into a system, maintaining the temperature of a constant-temperature bath in charge of the high-temperature side constant, and raising the temperature of the constant-temperature bath in charge of the low-temperature side to a medium temperature will be described.
【００１０】図１において，１は計量管１’を有するサ
ンプリングバルブ，７は試料を２方向に分岐するチー，
２ａは第１分離カラムであり，第１恒温槽３ａ内に配置
されている。２ｂは第２分離カラムであり，第２恒温槽
３ｂ内に配置されている。４ａ，４ｂは分離カラムの後
段に配置された検出器，５ａ，５ｂは第２分離カラム２
ｂの入口側と出口側に設けられた流路切換バルブで，こ
れらの切換バルブは同時に切り換わる。In FIG. 1, 1 is a sampling valve having a measuring tube 1 ', 7 is a tee for branching a sample in two directions,
Reference numeral 2a denotes a first separation column, which is arranged in the first constant temperature bath 3a. Reference numeral 2b denotes a second separation column, which is arranged in the second constant temperature bath 3b. Reference numerals 4a and 4b denote detectors arranged downstream of the separation column, and reference numerals 5a and 5b denote second separation columns 2
These switching valves are switched at the same time by the flow path switching valves provided on the inlet side and the outlet side of b.
【００１１】即ち，切換バルブ５ａが切り換わると検出
器４ｂ側への流路が閉となり矢印イ，ロ側からキャリア
ガスが流入する。同時にチー７側への流路が閉となり矢
印ハ，ニ側からキャリアガスが第２分離カラム２ｂ内に
残った試料とともに流出する。なお，検出器４ａ，４ｂ
の後段には，その検出器の出力信号に基づいて成分量を
演算し，表示あるいは記録する手段が配置されている。
また，図では省略するがサンプリングバルブ１の前段に
は試料を採取してガス化するための前処理装置が接続さ
れているものとする。That is, when the switching valve 5a is switched, the flow path to the detector 4b side is closed, and the carrier gas flows from the side indicated by arrows A and B. At the same time, the flow path to the Q7 side is closed, and the carrier gas flows from the arrow C and D sides together with the sample remaining in the second separation column 2b. The detectors 4a, 4b
In the subsequent stage, means for calculating the component amount based on the output signal of the detector and displaying or recording the component amount is arranged.
Although not shown in the figure, it is assumed that a pretreatment device for collecting a sample and gasifying the sample is connected in front of the sampling valve 1.
【００１２】上記の構成において，例えば石油精製プラ
ントの原油の成分を分析する場合，第１恒温槽の温度を
例えば２００℃に維持し，第２恒温槽の温度を例えば６
０→１００℃に変化させる。図２（ａ）は分離カラムの
温度パターンを示し２ａ’は第１分離カラムがｂの温度
（２００℃）に維持されており，２ｂ’は第２分離カラ
ムがａの温度（６０℃）から所定の時間でｃの温度（１
００℃）まで加熱され，再びａの温度に降温している状
態を示している。In the above arrangement, for example, when analyzing the components of crude oil in a petroleum refining plant, the temperature of the first constant temperature bath is maintained at, for example, 200 ° C., and the temperature of the second constant temperature bath is, for example, 6 ° C.
Change from 0 to 100 ° C. FIG. 2 (a) shows the temperature pattern of the separation column, 2a 'indicates that the first separation column is maintained at the temperature of b (200 ° C.), and 2b' indicates that the second separation column is maintained at the temperature of a (60 ° C.). The temperature of c (1
00 ° C.) and the temperature is again lowered to the temperature a.
【００１３】図２（ｂ）はサンプリングバルブ１の試料
取り込みのタイミングで第２分離カラムの温度がａの温
度になったときに試料を採取している状態を示してい
る。採取された試料はチー７により２方向に分岐され，
分岐した一方の試料は第１分離カラム２ａに導入され，
他方の試料は第２分離カラム２ｂに導入される。その場
合，第１カラム２ａに導入された試料は図２（ｄ）に示
すように直ちに２００℃に加熱されるので低沸点の成分
（ｆの範囲）は多くの成分が短時間で溶出し高沸点の成
分（ｇの範囲）が所定の時間をかけて比較的長時間で溶
出する。また，第２分離カラム２ｂに導入した試料は低
沸点の成分（ｈの範囲）が比較的長時間で溶出する（ｉ
の範囲は１００℃以上に加熱しないと溶出しない）。FIG. 2B shows a state in which a sample is being taken when the temperature of the second separation column reaches the temperature a at the timing of taking in the sample by the sampling valve 1. The collected sample is branched in two directions by Qi7,
One branched sample is introduced into the first separation column 2a,
The other sample is introduced into the second separation column 2b. In this case, since the sample introduced into the first column 2a is immediately heated to 200 ° C. as shown in FIG. 2 (d), many of the components having a low boiling point (range f) elute in a short time, Boiling point components (range g) elute over a relatively long period of time. Further, in the sample introduced into the second separation column 2b, components having a low boiling point (range h) are eluted in a relatively long time (i.
Does not elute unless heated above 100 ° C.).
【００１４】図２（ｃ）は切換えバルブ５ａ，５ｂの切
換えのタイミングを示すもので，これらの切換えバルブ
はサンプリングバルブが試料を取り込んだと同時に閉と
なり第２分離カラムの温度が１００℃になって温度が下
降しはじめたときに開となる。上記の構成によれば２つ
の分離カラムを用いて低沸点で溶出する成分と高沸点で
溶出する成分を平行して検出することが出来るので，試
料に含まれる多くの成分を短時間で検出することが出来
る。FIG. 2C shows the switching timing of the switching valves 5a and 5b. These switching valves are closed at the same time as the sampling valve takes in the sample, and the temperature of the second separation column becomes 100 ° C. It opens when the temperature begins to drop. According to the above configuration, components eluting at a low boiling point and components eluting at a high boiling point can be detected in parallel using two separation columns, so that many components contained in a sample can be detected in a short time. I can do it.
【００１５】なお，上記実施例においては恒温槽と分離
カラムの数を２とし，高い温度分布範囲を担当する恒温
槽の温度を一定にした例について説明したが，恒温槽の
数を３とし，低温〜高温までを３つの範囲に分け，最も
高い温度分布範囲を担当する恒温槽以外に配置された分
離カラムの入口側と出口側に流路切換バルブを設けて所
定の温度になった段階で切り換えて出口側からキャリア
ガスを流すことにより更に短時間での分析が可能とな
る。In the above embodiment, an example was described in which the number of the thermostats and the number of the separation columns were two and the temperature of the thermostat in charge of a high temperature distribution range was constant. The range from low temperature to high temperature is divided into three ranges, and at the stage where the temperature reaches a predetermined level by providing flow path switching valves on the inlet side and outlet side of the separation column arranged other than the thermostat that is in charge of the highest temperature distribution range. By switching the flow of the carrier gas from the outlet side, the analysis can be performed in a shorter time.
【００１６】[0016]
【発明の効果】以上実施例とともに具体的に説明した様
に本発明によれば，試料から分析成分を分離するための
比較的低い温度から高い温度範囲を２以上の温度分布範
囲に分割する２以上の恒温槽と，その２以上の恒温槽の
それぞれに配置され２以上に分岐した試料のそれぞれを
導入する分離カラムと，恒温槽のうち最も高い温度分布
範囲を担当する恒温槽以外に配置された分離カラムの入
口側と出口側に設けられた流路切換バルブと，分離カラ
ムの後段にそれぞれ配置された分析ユニットと，得られ
た結果を解析手段により解析して表示或いは記録する表
示手段を有し，試料に含まれる分析成分のうち所定の成
分が分離した段階で分離カラムに残留する分析成分を流
路切換バルブを介して排除するように構成したので，分
析時間の短縮化を図ったプロセスガスクロを実現するこ
とが出来る。According to the present invention, as described above in detail with the embodiments, the range from a relatively low temperature to a high temperature for separating an analytical component from a sample is divided into two or more temperature distribution ranges. The above-mentioned constant temperature bath, the separation column arranged in each of the two or more constant temperature baths and introducing each of the two or more branched samples, and the constant temperature bath which is disposed in the constant temperature bath which is in charge of the highest temperature distribution range. Flow path switching valves provided on the inlet side and the outlet side of the separation column, an analysis unit disposed at a subsequent stage of the separation column, and a display means for analyzing and displaying or recording an obtained result by the analysis means. As a result, the analysis component remaining in the separation column at the stage when the predetermined component among the analysis components contained in the sample is separated is eliminated via the flow path switching valve, so that the analysis time can be reduced. It is possible to realize the process gas chromatograph that Tsu.
【図１】本発明の一実施例を示すプロセスガスクロマト
グラフの要部構成図である。FIG. 1 is a main part configuration diagram of a process gas chromatograph showing one embodiment of the present invention.
【図２】２系統分離カラムの温度制御と出力の状態及び
切換えバルブの切換えのタイミングを示す図である。FIG. 2 is a diagram showing a temperature control and output state of a two-system separation column and a switching timing of a switching valve.
【図３】従来例を示す要部構成図である。FIG. 3 is a main part configuration diagram showing a conventional example.
１ サンプルバルブ ２ａ，２ｂ 分離カラム ３ａ，３ｂ 恒温槽 ４ａ，４ｂ 検出器 ５ａ，５ｂ 切換バルブ ７ チー 1 Sample valve 2a, 2b Separation column 3a, 3b Thermostat 4a, 4b Detector 5a, 5b Switching valve 7 Q
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.7，ＤＢ名) G01N 30/02 G01N 30/04 G01N 30/40 G01N 30/46 G01N 30/54 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int.Cl. 7 , DB name) G01N 30/02 G01N 30/04 G01N 30/40 G01N 30/46 G01N 30/54
Claims (1)
と，該サンプリングバルブにより採取された試料を２以
上に分岐する分岐手段と，前記試料から分析成分を分離
するための比較的低い温度から高い温度範囲を２以上の
温度分布範囲に分割する２以上の恒温槽と，該２以上の
恒温槽のそれぞれに配置され前記２以上に分岐した試料
のそれぞれを導入する分離カラムと，前記恒温槽のうち
最も高い温度分布範囲を担当する恒温槽以外に配置され
た分離カラムの入口側と出口側に設けられた流路切換バ
ルブと，前記分離カラムの後段にそれぞれ配置された分
析ユニットと，得られた結果（クロマトグラム信号）を
解析手段により解析して表示或いは記録する表示手段を
有し，前記試料に含まれる分析成分のうち所定の成分が
分離した段階で分離カラムに残留する分析成分を前記流
路切換バルブを介して排除するように構成したことを特
徴とするプロセスガスクロマトグラフ。1. A sampling valve for collecting a predetermined amount of a sample, a branching means for branching the sample collected by the sampling valve into two or more, and a relatively low to high temperature for separating an analytical component from the sample. Two or more thermostats for dividing the range into two or more temperature distribution ranges, a separation column arranged in each of the two or more thermostats and introducing each of the two or more branched samples; Flow path switching valves provided on the inlet side and the outlet side of the separation column arranged other than the thermostat bath in charge of the highest temperature distribution range, and the analysis units respectively arranged at the subsequent stage of the separation column. It has display means for analyzing and displaying or recording the result (chromatogram signal) by the analysis means, and separates when a predetermined component among the analysis components contained in the sample is separated. Process gas chromatograph, characterized in that the analysis component remaining on the column was configured to eliminate through the flow channel switching valve.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03439594A JP3240574B2 (en) | 1994-03-04 | 1994-03-04 | Process gas chromatograph |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP03439594A JP3240574B2 (en) | 1994-03-04 | 1994-03-04 | Process gas chromatograph |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07244034A JPH07244034A (en) | 1995-09-19 |
| JP3240574B2 true JP3240574B2 (en) | 2001-12-17 |
Family
ID=12413000
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP03439594A Expired - Lifetime JP3240574B2 (en) | 1994-03-04 | 1994-03-04 | Process gas chromatograph |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3240574B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022224540A1 (en) * | 2021-04-23 | 2022-10-27 | 株式会社日立ハイテク | Analysis device and method for controlling analysis device |
-
1994
- 1994-03-04 JP JP03439594A patent/JP3240574B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH07244034A (en) | 1995-09-19 |
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