WO2015083792A1 - Gas chromatograph and validation method therefor - Google Patents
Gas chromatograph and validation method therefor Download PDFInfo
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- WO2015083792A1 WO2015083792A1 PCT/JP2014/082125 JP2014082125W WO2015083792A1 WO 2015083792 A1 WO2015083792 A1 WO 2015083792A1 JP 2014082125 W JP2014082125 W JP 2014082125W WO 2015083792 A1 WO2015083792 A1 WO 2015083792A1
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- 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
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- 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
- G01N30/04—Preparation or injection of sample to be analysed
- G01N2030/042—Standards
- G01N2030/045—Standards internal
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- 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
- G01N30/84—Preparation of the fraction to be distributed
- G01N2030/8429—Preparation of the fraction to be distributed adding modificating material
- G01N2030/8435—Preparation of the fraction to be distributed adding modificating material for chemical reaction
Abstract
In order to easily measure the concentration of a target measurement component in a sample gas, even if the target measurement component is unknown, a gas chromotograph is provided that comprises: a column (10) that causes the sample gas to pass therethrough and separates each type of target measurement component included in the sample gas; a conversion unit (20) that converts a target measurement component included in the sample gas that has passed through the column (10), into a prescribed derivative having a known number of reference elements included in each molecule; a concentration measurement unit (30) that measures the concentration of the derivative; a reference element number acquisition unit (50) that obtains the number of reference elements included in each molecule in the target measurement component; and a concentration calculation unit (40) that calculates the concentration of the target measurement component included in the sample gas, on the basis of the number of reference elements included in each molecule of the derivative, the number of reference elements included in each molecule of the target measurement component, and the concentration of the derivative.
Description
本発明は、カラムに試料ガスを通過させて各測定対象成分に分離し、さらに測定対象成分を酸化・還元反応させて例えばメタン置換し、該メタンの濃度に基づいて試料ガスに含まれる前記各測定対象成分の濃度を測定する、いわゆるポストカラム反応ガスクロマトグラフ及びそのバリデーション方法に関するものである。
In the present invention, the sample gas is allowed to pass through the column to be separated into each measurement target component, and the measurement target component is further subjected to oxidation / reduction reaction, for example, methane substitution. The present invention relates to a so-called post-column reaction gas chromatograph for measuring the concentration of a measurement target component and a validation method thereof.
従来、この種の反応ガスクロマトグラフを用いて、例えば内燃機関の排ガスや光化学スモッグに含まれる各種有機化合物の成分濃度を測定することが行われている（非特許文献１）。より具体的には、下式に示すように、試料ガスに含まれる有機化合物を、酸化触媒を有した酸化反応部において酸化ガス（酸素）と反応させて二酸化炭素と水に分解し、さらにその二酸化炭素を、還元触媒を有した還元反応部において還元ガス（水素）と還元反応させてメタンに変換する。
酸化反応部・・・ＣｘＨｙＯｚ＋（ｘ＋ｙ／４－ｚ／２）Ｏ２→ｘＣＯ２＋（２／ｙ－ｚ）Ｈ２Ｏ
還元反応部・・・ｘＣＯ２＋４ｘＨ２→ｘＣＨ４＋２ｘＨ２Ｏ Conventionally, using this type of reactive gas chromatograph, for example, the concentration of various organic compounds contained in exhaust gas and photochemical smog of an internal combustion engine has been measured (Non-patent Document 1). More specifically, as shown in the following formula, an organic compound contained in the sample gas is reacted with an oxidizing gas (oxygen) in an oxidation reaction section having an oxidation catalyst to be decomposed into carbon dioxide and water. Carbon dioxide is converted into methane by a reduction reaction with a reducing gas (hydrogen) in a reduction reaction section having a reduction catalyst.
Oxidation reaction part: C x H y O z + (x + y / 4−z / 2) O 2 → xCO 2 + (2 / yz) H 2 O
Reduction reaction part: xCO 2 + 4xH 2 → xCH 4 + 2xH 2 O
酸化反応部・・・ＣｘＨｙＯｚ＋（ｘ＋ｙ／４－ｚ／２）Ｏ２→ｘＣＯ２＋（２／ｙ－ｚ）Ｈ２Ｏ
還元反応部・・・ｘＣＯ２＋４ｘＨ２→ｘＣＨ４＋２ｘＨ２Ｏ Conventionally, using this type of reactive gas chromatograph, for example, the concentration of various organic compounds contained in exhaust gas and photochemical smog of an internal combustion engine has been measured (Non-patent Document 1). More specifically, as shown in the following formula, an organic compound contained in the sample gas is reacted with an oxidizing gas (oxygen) in an oxidation reaction section having an oxidation catalyst to be decomposed into carbon dioxide and water. Carbon dioxide is converted into methane by a reduction reaction with a reducing gas (hydrogen) in a reduction reaction section having a reduction catalyst.
Oxidation reaction part: C x H y O z + (x + y / 4−z / 2) O 2 → xCO 2 + (2 / yz) H 2 O
Reduction reaction part: xCO 2 + 4xH 2 → xCH 4 + 2xH 2 O
その後、前記反応によって生成されたメタン濃度を、例えばＦＩＤによって測定し、そのメタン濃度を前記有機化合物の１分子に含まれる炭素数ｘで割ることによって、試料ガスに含まれる該有機化合物の濃度を測定する。
Thereafter, the concentration of methane produced by the reaction is measured by, for example, FID, and the concentration of the organic compound contained in the sample gas is determined by dividing the methane concentration by the number of carbons x contained in one molecule of the organic compound. taking measurement.
したがって、ポストカラム反応ガスクロマトグラフを用いる場合には、測定対象成分の１分子に含まれる基準元素（ここでは炭素）数ｘの情報が必要であり、言い換えれば、この炭素数ｘをユーザーが予め把握している必要がある。
Therefore, when using a post-column reaction gas chromatograph, information on the number x of reference elements (here, carbon) contained in one molecule of the measurement target component is necessary. In other words, the user knows the number x of carbon in advance. Need to be.
しかしながら、測定対象成分が未知の場合、該測定対象成分の炭素数ｘをユーザが把握するためには、別装置を用いたり別途調査したりする必要があり、この作業に多大な時間と労力を費やさなければならない。
However, when the component to be measured is unknown, in order for the user to know the carbon number x of the component to be measured, it is necessary to use another device or to investigate it separately, and this work takes a lot of time and effort. Have to spend.
本発明は、かかる問題点に鑑みてなされたものであって、ガスクロマトグラフにおいて、試料ガスに含まれる測定対象成分が未知であっても、当該測定対象成分の濃度を簡便に測定できるようにすることをその主たる所期課題としたものである。
The present invention has been made in view of such problems, and enables a gas chromatograph to easily measure the concentration of a measurement target component even if the measurement target component contained in the sample gas is unknown. This is the main intended issue.
すなわち、本発明に係るガスクロマトグラフは、試料ガスを通過させて該試料ガスに含まれる各種測定対象成分を分離するカラムと、該カラムを通過した試料ガスに含まれる前記測定対象成分を、１分子に含まれる基準元素の数が既知の所定の誘導体に変換する変換部と、前記誘導体の濃度を測定する濃度測定部と、前記測定対象成分１分子に含まれる前記基準元素の数を取得する基準元素数取得部と、前記誘導体１分子に含まれる基準元素の数、前記測定対象成分１分子に含まれる前記基準元素の数及び前記誘導体の濃度に基づいて前記試料ガスに含まれる測定対象成分の濃度を算定する濃度算定部とを具備することを特徴とするものである。
That is, the gas chromatograph according to the present invention includes a column that separates various measurement target components contained in the sample gas by passing the sample gas, and one molecule of the measurement target component contained in the sample gas that has passed through the column. A conversion unit that converts the number of reference elements contained in a known derivative, a concentration measurement unit that measures the concentration of the derivative, and a reference for obtaining the number of reference elements contained in one molecule of the measurement target component The number-of-elements acquisition unit, the number of reference elements contained in one molecule of the derivative, the number of reference elements contained in one molecule of the measurement target component, and the concentration of the measurement target component contained in the sample gas based on the concentration of the derivative And a concentration calculation unit for calculating the concentration.
このようなものであれば、測定対象成分が未知の試料であっても、基準元素数取得部が、この測定対象成分１分子に含まれる基準元素の数を取得するので、従来のように前記基準元素の数を予め把握すべく別装置を用いたり別途調査したりする必要がなく、その分の時間や労力を軽減することができ、測定対象成分の濃度を簡便に測定することが可能になる。
In such a case, even if the measurement target component is an unknown sample, the reference element number acquisition unit acquires the number of reference elements contained in one molecule of the measurement target component. There is no need to use a separate device or separate investigation to grasp the number of reference elements in advance, and the time and labor can be reduced and the concentration of the measurement target component can be measured easily. Become.
濃度測定部として水素炎イオン化検出器（ＦＩＤ）を具備するものを用いたときの実施態様としては、前記基準元素数取得部が、前記測定対象成分がカラムを通過する時間に基づいて、前記測定対象成分１分子に含まれる前記基準元素の数を取得するものが好ましい。
これらならば、ＦＩＤの出力に基づいてリテンションタイムを算出し、このリテンションタイムから測定対象成分１分子に含まれる基準元素の数を特定することができるので、前記基準元素の数を把握するために、わざわざ専用の装置を設ける必要がなく、測定対象成分の濃度をより簡便に測定することができる。 As an embodiment when using a hydrogen ionization detector (FID) as the concentration measurement unit, the reference element number acquisition unit is configured to perform the measurement based on the time that the measurement target component passes through the column. What acquires the number of the said reference elements contained in 1 molecule of target components is preferable.
In this case, the retention time can be calculated based on the output of the FID, and the number of reference elements contained in one molecule to be measured can be specified from the retention time, so that the number of the reference elements can be determined. Therefore, it is not necessary to provide a dedicated device, and the concentration of the measurement target component can be measured more easily.
これらならば、ＦＩＤの出力に基づいてリテンションタイムを算出し、このリテンションタイムから測定対象成分１分子に含まれる基準元素の数を特定することができるので、前記基準元素の数を把握するために、わざわざ専用の装置を設ける必要がなく、測定対象成分の濃度をより簡便に測定することができる。 As an embodiment when using a hydrogen ionization detector (FID) as the concentration measurement unit, the reference element number acquisition unit is configured to perform the measurement based on the time that the measurement target component passes through the column. What acquires the number of the said reference elements contained in 1 molecule of target components is preferable.
In this case, the retention time can be calculated based on the output of the FID, and the number of reference elements contained in one molecule to be measured can be specified from the retention time, so that the number of the reference elements can be determined. Therefore, it is not necessary to provide a dedicated device, and the concentration of the measurement target component can be measured more easily.
前記基準元素数取得部が、前記カラムに接続されて該カラムを通過した試料ガスに含まれる測定対象成分の質量を分析する質量分析部と、前記質量分析部で分析された測定対象成分の質量から該測定対象成分１分子に含まれる前記基準元素の数を算出する基準元素数算出部とを具備するものが好ましい。
これらならば、カラムの温度や試料ガスの温度等に影響されることなく、測定対象成分の質量から該測定対象成分１分子に含まれる基準元素の数を精度良く把握することができ、測定対象成分の濃度を簡便に測定するとともに、測定精度を向上させることができる。 The reference element number acquisition unit is connected to the column and analyzes the mass of the measurement target component contained in the sample gas that has passed through the column, and the mass of the measurement target component analyzed by the mass analysis unit And a reference element number calculation unit for calculating the number of the reference elements contained in one molecule of the measurement target component.
In these cases, the number of reference elements contained in one molecule of the measurement target component can be accurately grasped from the mass of the measurement target component without being affected by the temperature of the column, the temperature of the sample gas, and the like. The concentration of the component can be easily measured and the measurement accuracy can be improved.
これらならば、カラムの温度や試料ガスの温度等に影響されることなく、測定対象成分の質量から該測定対象成分１分子に含まれる基準元素の数を精度良く把握することができ、測定対象成分の濃度を簡便に測定するとともに、測定精度を向上させることができる。 The reference element number acquisition unit is connected to the column and analyzes the mass of the measurement target component contained in the sample gas that has passed through the column, and the mass of the measurement target component analyzed by the mass analysis unit And a reference element number calculation unit for calculating the number of the reference elements contained in one molecule of the measurement target component.
In these cases, the number of reference elements contained in one molecule of the measurement target component can be accurately grasped from the mass of the measurement target component without being affected by the temperature of the column, the temperature of the sample gas, and the like. The concentration of the component can be easily measured and the measurement accuracy can be improved.
本発明の効果が顕著に現れる実施態様としては、前記基準元素が炭素であり、前記測定対象成分が有機化合物であり、前記誘導体がメタンであり、前記濃度測定部がＦＩＤを具備したものが挙げられる。
As an embodiment in which the effect of the present invention is remarkably exhibited, the reference element is carbon, the measurement target component is an organic compound, the derivative is methane, and the concentration measuring unit includes FID. It is done.
また、このような構成のガスクロマトグラフの好適なバリデーション方法としては、互いに基準元素数が異なる複数の既知の測定対象成分を用いて、同一濃度にしたときの各測定対象成分から得られる前記誘導体の濃度と、対応する測定対象成分の炭素数との関係を表す検量線を作成する検量線作成ステップと、前記検量線作成ステップで用いなかった別の測定対象成分を用いた場合の、誘導体の濃度と当該測定対象成分の炭素数との関係が、前記検量線上にあるか否かによって当該ガスクロマトグラフのバリデーションを行うバリデーションステップとを有するものが挙げられることができる。
Further, as a suitable validation method of the gas chromatograph having such a configuration, a plurality of known measurement target components having different reference element numbers are used, and the derivative obtained from each measurement target component at the same concentration is used. The concentration of the derivative when using a calibration curve creating step for creating a calibration curve representing the relationship between the concentration and the carbon number of the corresponding measurement target component, and another measurement target component not used in the calibration curve creating step And a validation step for validating the gas chromatograph depending on whether the relationship between the measurement target component and the carbon number of the measurement target component is on the calibration curve.
前記基準元素が炭素であり、前記誘導体がメタンである場合において、前記検量線作成ステップにおいてはアルカンを測定対象成分として用い、前記バリデーションステップにおいては前記アルカンよりも吸着性の強い有機化合物を測定対象成分として用いるものが好ましい。
このようなものであれば、試料ガスに含まれる種々の有機化合物に対して、有機化合物の有する吸着性がどの程度の強さまでであれば、その測定に信頼性があるかを予め把握することができ、測定に無駄な時間や労力を費やすことを未然に防ぐことができる。 When the reference element is carbon and the derivative is methane, an alkane is used as a measurement target component in the calibration curve creating step, and an organic compound having a higher adsorptivity than the alkane is measured in the validation step. What is used as a component is preferable.
If this is the case, it is necessary to know in advance whether the adsorptivity of the organic compound with respect to the various organic compounds contained in the sample gas is reliable. It is possible to prevent wasteful time and labor for measurement.
このようなものであれば、試料ガスに含まれる種々の有機化合物に対して、有機化合物の有する吸着性がどの程度の強さまでであれば、その測定に信頼性があるかを予め把握することができ、測定に無駄な時間や労力を費やすことを未然に防ぐことができる。 When the reference element is carbon and the derivative is methane, an alkane is used as a measurement target component in the calibration curve creating step, and an organic compound having a higher adsorptivity than the alkane is measured in the validation step. What is used as a component is preferable.
If this is the case, it is necessary to know in advance whether the adsorptivity of the organic compound with respect to the various organic compounds contained in the sample gas is reliable. It is possible to prevent wasteful time and labor for measurement.
このように構成した本発明によれば、試料ガスに含まれる測定対象成分が未知であっても、当該測定対象成分の濃度を簡便に測定することができる。
According to the present invention configured as described above, even if the measurement target component contained in the sample gas is unknown, the concentration of the measurement target component can be easily measured.
１００・・・反応ガスクロマトグラフ
１０ ・・・カラム
２０ ・・・変換部
２１ ・・・酸化反応部
２２ ・・・還元反応部
３０ ・・・濃度測定部
４０ ・・・濃度算定部
５０ ・・・基準元素数取得部
５１ ・・・リテンションタイム測定部
５２ ・・・炭素数特定部 DESCRIPTION OFSYMBOLS 100 ... Reaction gas chromatograph 10 ... Column 20 ... Conversion part 21 ... Oxidation reaction part 22 ... Reduction reaction part 30 ... Concentration measurement part 40 ... Concentration calculation part 50 ... Reference element number acquisition unit 51 ... retention time measurement unit 52 ... carbon number identification unit
１０ ・・・カラム
２０ ・・・変換部
２１ ・・・酸化反応部
２２ ・・・還元反応部
３０ ・・・濃度測定部
４０ ・・・濃度算定部
５０ ・・・基準元素数取得部
５１ ・・・リテンションタイム測定部
５２ ・・・炭素数特定部 DESCRIPTION OF
以下、本発明の実施形態について図面を用いて説明する。なお、本発明は、以下に説明するような実施形態に限定されるものではなく、本発明の趣旨を逸脱しない範囲で種々の態様が含まれることはいうまでもない。
Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the present invention is not limited to the embodiments described below, and it goes without saying that various aspects are included without departing from the spirit of the present invention.
＜第１実施形態＞
本実施形態に係るガスクロマトグラフ（以下、反応ガスクロマトグラフと言う。）１００は、自動車から排出される排ガスや光化学スモッグなど（以下、試料ガスと言う。）に含まれる各種の有機化合物（請求項で言う測定対象成分に該当する。）の濃度を測定するためのものである。 <First Embodiment>
A gas chromatograph (hereinafter referred to as a reaction gas chromatograph) 100 according to the present embodiment is a variety of organic compounds (referred to in claims) contained in exhaust gas, photochemical smog, etc. (hereinafter referred to as sample gas) discharged from an automobile. It corresponds to the component to be measured)).
本実施形態に係るガスクロマトグラフ（以下、反応ガスクロマトグラフと言う。）１００は、自動車から排出される排ガスや光化学スモッグなど（以下、試料ガスと言う。）に含まれる各種の有機化合物（請求項で言う測定対象成分に該当する。）の濃度を測定するためのものである。 <First Embodiment>
A gas chromatograph (hereinafter referred to as a reaction gas chromatograph) 100 according to the present embodiment is a variety of organic compounds (referred to in claims) contained in exhaust gas, photochemical smog, etc. (hereinafter referred to as sample gas) discharged from an automobile. It corresponds to the component to be measured)).
そしてこのものは、図１に示すように、試料ガスを通過させて該試料ガスに含まれる各種有機化合物を分離するカラム１０と、該カラム１０を通過した試料ガスに含まれる前記有機化合物を、その１分子に含まれる基準元素（ここでは炭素Ｃ）の数が既知の所定の誘導体（ここではメタンＣＨ４）に変換する変換部２０と、前記ＣＨ４の濃度を測定する濃度測定部３０と、前記ＣＨ４１分子に含まれるＣの数、前記有機化合物１分子に含まれるＣの数及び前記ＣＨ４の濃度に基づいて当該有機化合物の濃度を算定する濃度算定部４０とを具備する。
As shown in FIG. 1, this is a column 10 that allows a sample gas to pass through and separates various organic compounds contained in the sample gas, and the organic compound contained in the sample gas that has passed through the column 10. A conversion unit 20 that converts the number of reference elements (here, carbon C) contained in one molecule into a predetermined derivative (here, methane CH 4 ), and a concentration measurement unit 30 that measures the concentration of CH 4 ; the number of C contained in the CH 4 molecule comprises a density calculation section 40 to calculate the concentration of the organic compound based on the number and concentration of the CH 4 of C contained in the organic compound molecule.
以下に、その各部の構成を説明する。
The configuration of each part will be described below.
カラム１０は、ここではその内壁に固定相を塗布したキャピラリーカラムである。この固定相としては、適宜公知のものを使用することができる。このカラム１０は、例えば所定の温度（例えば４００℃）に維持されたオーブン等の恒温槽１０１に収容されている。
Here, the column 10 is a capillary column in which a stationary phase is applied to the inner wall thereof. As this stationary phase, a well-known thing can be used suitably. The column 10 is accommodated in a thermostatic chamber 101 such as an oven maintained at a predetermined temperature (for example, 400 ° C.).
変換部２０は、カラム１０から導出された試料ガスに含まれる測定対象成分を酸化して中間体を生成する酸化反応部２１と、該酸化反応部２１を通過した試料ガスに含まれる中間体を還元する還元反応部２２とからなるものである。
The conversion unit 20 oxidizes the measurement target component contained in the sample gas derived from the column 10 to generate an intermediate, and the intermediate contained in the sample gas that has passed through the oxidation reaction unit 21. It comprises a reduction reaction part 22 for reduction.
酸化反応部２１は、ヒータによって例えば４００℃に加熱された酸化反応管（図示しない）と、酸化反応管内に収容された酸化触媒とを具備するものである。
The oxidation reaction unit 21 includes an oxidation reaction tube (not shown) heated to, for example, 400 ° C. by a heater, and an oxidation catalyst accommodated in the oxidation reaction tube.
この酸化反応管には、酸化ガスである酸素及びカラム１０を通過した試料ガスが、高温に保たれて導入される。そして、該試料ガス中の有機化合物ＣｘＨｙＯｚが、酸化触媒を介して酸素によって酸化され、ＣＯ２及びＨ２Ｏに変換されるように構成してある。酸化触媒としては、例えばパラジウム等を用いている。
すなわち、この酸化反応部２１では、以下のような反応が生じる。
ＣｘＨｙＯｚ＋（ｘ＋ｙ／４－ｚ／２）Ｏ２→ｘＣＯ２＋（２／ｙ－ｚ）Ｈ２Ｏ Oxygen, which is an oxidizing gas, and the sample gas that has passed through thecolumn 10 are introduced into the oxidation reaction tube while being kept at a high temperature. The organic compound C x H y O z in the sample gas is oxidized by oxygen through an oxidation catalyst and converted into CO 2 and H 2 O. For example, palladium or the like is used as the oxidation catalyst.
That is, the following reaction occurs in theoxidation reaction part 21.
C x H y O z + (x + y / 4−z / 2) O 2 → xCO 2 + (2 / yz) H 2 O
すなわち、この酸化反応部２１では、以下のような反応が生じる。
ＣｘＨｙＯｚ＋（ｘ＋ｙ／４－ｚ／２）Ｏ２→ｘＣＯ２＋（２／ｙ－ｚ）Ｈ２Ｏ Oxygen, which is an oxidizing gas, and the sample gas that has passed through the
That is, the following reaction occurs in the
C x H y O z + (x + y / 4−z / 2) O 2 → xCO 2 + (2 / yz) H 2 O
還元反応部２２は、ヒータによって例えば４００℃に加熱された還元反応管（図示しない）と、還元反応管内に収容された還元触媒とを具備するものである。
The reduction reaction unit 22 includes a reduction reaction tube (not shown) heated to 400 ° C. by a heater, for example, and a reduction catalyst accommodated in the reduction reaction tube.
この還元反応管は、前記酸化反応管と第１接続管Ｌ１を介して接続されており、酸化反応部２１で有機化合物が酸化され、ＣＯ２に変換された試料ガス（以下、中間ガスと言う。）が前記第１接続管Ｌ１を通じて導入される。その一方で、該還元反応管には還元ガスである水素が導入されるようにしてあり、前記ＣＯ２が、還元触媒を介して前記水素によって還元されることにより、誘導体であるＣＨ４（メタン）に変換されるように構成してある。
すなわち、この還元反応部２２では、以下のような反応が生じる。
ｘＣＯ２＋４ｘＨ２→ｘＣＨ４＋２ｘＨ２Ｏ This reduction reaction tube is connected to the oxidation reaction tube via the first connection tube L1, and a sample gas (hereinafter referred to as an intermediate gas) in which an organic compound is oxidized in theoxidation reaction unit 21 and converted to CO 2. .) Is introduced through the first connecting pipe L1. On the other hand, hydrogen, which is a reducing gas, is introduced into the reduction reaction tube, and the CO 2 is reduced by the hydrogen through a reduction catalyst, whereby a derivative CH 4 (methane). ).
That is, the following reaction occurs in thereduction reaction unit 22.
xCO 2 + 4xH 2 → xCH 4 + 2xH 2 O
すなわち、この還元反応部２２では、以下のような反応が生じる。
ｘＣＯ２＋４ｘＨ２→ｘＣＨ４＋２ｘＨ２Ｏ This reduction reaction tube is connected to the oxidation reaction tube via the first connection tube L1, and a sample gas (hereinafter referred to as an intermediate gas) in which an organic compound is oxidized in the
That is, the following reaction occurs in the
xCO 2 + 4xH 2 → xCH 4 + 2xH 2 O
なお、前記第１接続管Ｌ１は、加熱部（図示しない）により所定の温度（例えば１２０℃）に加熱されている。
The first connecting pipe L1 is heated to a predetermined temperature (for example, 120 ° C.) by a heating unit (not shown).
濃度測定部３０は、前記還元反応管と第２接続管Ｌ２を介して接続された、例えば、水素炎イオン化検出器（ＦＩＤ）を具備するものであり、還元反応部２２で還元された中間ガス（以下、最終ガスと言う。）が、前記第２接続管Ｌ２を介して導入され、その最終ガス中の誘導体（ＣＨ４）の濃度が測定される。
The concentration measurement unit 30 includes, for example, a flame ionization detector (FID) connected to the reduction reaction tube and the second connection tube L2, and is an intermediate gas reduced by the reduction reaction unit 22. (Hereinafter referred to as the final gas) is introduced through the second connecting pipe L2, and the concentration of the derivative (CH 4 ) in the final gas is measured.
濃度算定部４０は、ＣＰＵ、メモリ、Ａ／Ｄコンバータ、Ｄ／Ａコンバータ等を備えた汎用乃至専用のコンピュータに設けられたものであり、前記メモリに記憶されたプログラムにしたがってＣＰＵやその周辺機器が協働することにより、このコンピュータが濃度算定部４０として機能する。
The concentration calculation unit 40 is provided in a general purpose or dedicated computer including a CPU, a memory, an A / D converter, a D / A converter, and the like, and the CPU and its peripheral devices according to a program stored in the memory As a result of this cooperation, this computer functions as the concentration calculation unit 40.
この濃度算定部４０は、前記濃度測定部３０で測定されたＣＨ４の濃度を、前記有機化合物（ＣｘＨｙＯｚ）１分子に含まれるＣの数ｘで割ることと等価な演算をすることによって、有機化合物（ＣｘＨｙＯｚ）の濃度を算定するものである。
The concentration calculation unit 40 performs an operation equivalent to dividing the concentration of CH 4 measured by the concentration measurement unit 30 by the number x of C contained in one molecule of the organic compound (C x H y O z ). By doing so, the concentration of the organic compound (C x H y O z ) is calculated.
ところで、この実施形態に係る反応ガスクロマトグラフ１００は、図１に示すように、前記有機化合物（ＣｘＨｙＯｚ）１分子に含まれる前記Ｃの数ｘを自動取得する基準元素数取得部５０をさらに具備しており、前記濃度算定部４０は、前記有機化合物（ＣｘＨｙＯｚ）１分子に含まれるＣの数ｘを、当該基準元素数取得部５０から受け取って有機化合物（ＣｘＨｙＯｚ）の濃度を算定するように構成してある。
By the way, as shown in FIG. 1, the reaction gas chromatograph 100 according to this embodiment includes a reference element number acquisition unit that automatically acquires the number x of C contained in one molecule of the organic compound (C x H y O z ). 50, the concentration calculation unit 40 receives the number x of C contained in one molecule of the organic compound (C x H y O z ) from the reference element number acquisition unit 50 and receives the organic compound ( C x H y O z ) concentration is calculated.
前記基準元素数取得部５０は、試料ガスに含まれる測定対象成分を分析する過程で得られる分析データに基づき、該測定対象成分１分子に含まれる基準元素の数を取得するものであって、ここでは例えば、前記有機化合物がカラム１０を通過する時間、すなわちリテンションタイムに基づいて、前記有機化合物１分子に含まれるＣの数を取得するものである。より詳細にこの基準元素数取得部５０は、図２に示すように、リテンションタイムを測定するリテンションタイム測定部５１と、前記リテンションタイム測定部５１で測定したリテンションタイムに対応する有機化合物を決定し、その有機化合物の１分子に含まれるＣの数を特定する炭素数特定部５２とを具備する。
The reference element number acquisition unit 50 acquires the number of reference elements contained in one molecule of the measurement target component based on analysis data obtained in the process of analyzing the measurement target component contained in the sample gas, Here, for example, the number of C contained in one molecule of the organic compound is obtained based on the time during which the organic compound passes through the column 10, that is, the retention time. In more detail, as shown in FIG. 2, the reference element number acquiring unit 50 determines a retention time measuring unit 51 that measures a retention time and an organic compound corresponding to the retention time measured by the retention time measuring unit 51. And a carbon number specifying part 52 for specifying the number of C contained in one molecule of the organic compound.
図２を参照して、より具体的に説明する。
More specific description will be given with reference to FIG.
リテンションタイム測定部５１は、ＦＩＤが各有機化合物を検出する検出タイミングに基づいてカラム１０を通って分離された有機化合物のリテンションタイムを算出するものである。
The retention time measurement unit 51 calculates the retention time of the organic compound separated through the column 10 based on the detection timing at which the FID detects each organic compound.
炭素数特定部５２は、前記コンピュータのメモリに設定されたリテンションタイムテーブルを参照して、前記リテンションタイム測定部５１で測定されたリテンションタイムに対応する有機化合物を決定し、その有機化合物の１分子に含まれるＣの数を特定するものである。各種有機化合物がカラム１０を通過する時間は、カラム１０の種類や構造、試料ガスの圧送圧力などによってそれぞれ定まるが、ここでは、予め、予想される複数種類の既知の有機化合物のリテンションタイムを測定し、その測定した各リテンションタイムを対応する有機化合物と関連付けて、前記リテンションタイムテーブルに格納してある。
The carbon number identification unit 52 refers to a retention time table set in the memory of the computer, determines an organic compound corresponding to the retention time measured by the retention time measurement unit 51, and one molecule of the organic compound The number of C contained in is specified. The time required for various organic compounds to pass through the column 10 is determined by the type and structure of the column 10 and the pumping pressure of the sample gas. Here, the retention times of a plurality of types of known organic compounds that are expected are measured in advance. Each measured retention time is associated with the corresponding organic compound and stored in the retention time table.
しかして、このようなものであれば、有機化合物が未知の試料であっても、基準元素数取得部５０が、この有機化合物１分子に含まれるＣの数を取得するので、従来のように前記有機化合物１分子に含まれるＣの数を予め把握すべく別装置を用いたり別途調査したりする必要がなく、その分の時間や労力を軽減することができ、有機化合物の濃度を簡便に測定することが可能になる。
In such a case, even if the organic compound is an unknown sample, the reference element number acquisition unit 50 acquires the number of C contained in one molecule of the organic compound. There is no need to use a separate device or separately investigate the number of C contained in one molecule of the organic compound in advance, so that the time and labor can be reduced, and the concentration of the organic compound can be simplified. It becomes possible to measure.
また、基準元素数取得部５０が、ＦＩＤにより各有機化合物を検出する検出タイミングに基づいてリテンションタイムを算出し、このリテンションタイムに基づいて有機化合物１分子に含まれるＣの数を特定するので、Ｃの数を把握するために、わざわざ専用の装置を設ける必要がなく、有機化合物の濃度をより簡便に測定することができる。
In addition, since the reference element number acquisition unit 50 calculates the retention time based on the detection timing for detecting each organic compound by FID, and identifies the number of C contained in one molecule of the organic compound based on this retention time, In order to grasp the number of C, it is not necessary to provide a dedicated device, and the concentration of the organic compound can be measured more easily.
＜第２実施形態＞
前記基準元素数取得部５０として、以下のような構成も挙げることができる。 Second Embodiment
Examples of the reference elementnumber acquisition unit 50 include the following configurations.
前記基準元素数取得部５０として、以下のような構成も挙げることができる。 Second Embodiment
Examples of the reference element
本実施形態では、図３に示すように、カラム１０と酸化反応部２１とを接続する第３接続管Ｌ３から分岐する分岐管Ｌ４が設けられている。より詳細にこの分岐管Ｌ４は、前記第３接続管Ｌ３において、酸化ガスが流れる酸化ガス配管Ｌ５よりも上流から分岐して設けられている。
In the present embodiment, as shown in FIG. 3, a branch pipe L4 that branches from the third connection pipe L3 that connects the column 10 and the oxidation reaction unit 21 is provided. More specifically, the branch pipe L4 is provided in the third connection pipe L3 so as to branch from the upstream side of the oxidizing gas pipe L5 through which the oxidizing gas flows.
しかして、本実施形態の基準元素数取得部５０は、図３に示すように、前記分岐管Ｌ４に接続され、カラム１０を通過し、酸化ガスが混合される前の試料ガスの一部が導入されて、該試料ガスに含まれる有機化合物の質量を分析する質量分析部５３と、質量分析部５３で分析された有機化合物の質量から該有機化合物１分子に含まれる基準元素（ここでは炭素Ｃ）の数を算出する基準元素算出部５４とを具備する、いわゆる質量分析計である。
Accordingly, as shown in FIG. 3, the reference element number acquisition unit 50 of the present embodiment is connected to the branch pipe L4, passes through the column 10, and a part of the sample gas before being mixed with the oxidizing gas is obtained. The mass analyzer 53 that analyzes the mass of the organic compound contained in the sample gas and the mass of the organic compound analyzed by the mass analyzer 53 (in this case, carbon is included in one molecule of the organic compound). This is a so-called mass spectrometer including a reference element calculation unit 54 that calculates the number of C).
より具体的に説明する。
More specific explanation.
質量分析部５３は、例えば、カラム１０を通過して導入された試料ガスをイオン化して、有機化合物の質量を分析するものであり、本実施形態では、飛行時間型のものである。
なお、飛行時間型でなくとも良く、例えば、磁場型、四重極型、イオントラップ型、イオンサイクロトロン型等であっても良い。 Themass analyzer 53 is, for example, ionizing a sample gas introduced through the column 10 and analyzing the mass of the organic compound. In the present embodiment, the mass analyzer 53 is of a time-of-flight type.
The time-of-flight type may not be used, and for example, a magnetic field type, a quadrupole type, an ion trap type, an ion cyclotron type, or the like may be used.
なお、飛行時間型でなくとも良く、例えば、磁場型、四重極型、イオントラップ型、イオンサイクロトロン型等であっても良い。 The
The time-of-flight type may not be used, and for example, a magnetic field type, a quadrupole type, an ion trap type, an ion cyclotron type, or the like may be used.
基準元素算出部５４は、上述したコンピュータのメモリに設定された質量テーブルを参照して、質量分析部５３で測定された質量に対応する有機化合物を決定し、その有機化合物の１分子に含まれるＣの数を特定するものである。ここでは、予め、予想される複数種類の既知の有機化合物１分子当りの質量と、その質量に対応する有機化合物とを関連付けて、前記質量テーブルに格納してある。
The reference element calculation unit 54 refers to the mass table set in the above-described computer memory, determines an organic compound corresponding to the mass measured by the mass analysis unit 53, and is included in one molecule of the organic compound. The number of C is specified. Here, a mass per molecule of a plurality of known types of known organic compounds and an organic compound corresponding to the mass are associated in advance and stored in the mass table.
このようなものであれば、カラム１０の温度や試料ガスの温度等に影響されることなく、有機化合物の質量から有機化合物１分子に含まれるＣの数を容易に精度良く把握することができ、有機化合物の濃度を簡便に測定するとともに、測定精度を向上させることができる。
If this is the case, the number of C contained in one molecule of the organic compound can be easily and accurately grasped from the mass of the organic compound without being affected by the temperature of the column 10 or the temperature of the sample gas. The concentration of the organic compound can be easily measured and the measurement accuracy can be improved.
＜第３実施形態＞
この実施形態では、前記各実施形態で説明した反応ガスクロマトグラフ１００のバリデーション方法（動作検証方法）を図４のグラフ及び図５のフローチャートを参照して説明する。 <Third Embodiment>
In this embodiment, the validation method (operation verification method) of thereaction gas chromatograph 100 described in each of the above embodiments will be described with reference to the graph of FIG. 4 and the flowchart of FIG.
この実施形態では、前記各実施形態で説明した反応ガスクロマトグラフ１００のバリデーション方法（動作検証方法）を図４のグラフ及び図５のフローチャートを参照して説明する。 <Third Embodiment>
In this embodiment, the validation method (operation verification method) of the
まず、図４に示すように、互いに基準元素（ここでは炭素Ｃ）が異なる複数の既知の有機化合物（例えば、Ｃｘ１Ｈｙ１Ｏｚ１及びＣｘ２Ｈｙ２Ｏｚ２）を用いて、同一濃度にしたときの各有機化合物から得られるＣＨ４の濃度と、対応する有機化合物のＣの数（ｘ１及びｘ２）との関係を表す検量線を作成する（ステップＳ１）。
なお、上述したＣｘ１Ｈｙ１Ｏｚ１及びＣｘ２Ｈｙ２Ｏｚ２は、本実施形態ではいずれもアルカンである。 First, as shown in FIG. 4, a plurality of known organic compounds (for example, C x1 H y1 O z1 and C x2 H y2 O z2 ) having different reference elements (here, carbon C) are used to have the same concentration. A calibration curve representing the relationship between the concentration of CH 4 obtained from each organic compound and the number of C (x1 and x2) of the corresponding organic compound is created (step S1).
In the present embodiment, C x1 H y1 O z1 and C x2 H y2 O z2 described above are both alkanes.
なお、上述したＣｘ１Ｈｙ１Ｏｚ１及びＣｘ２Ｈｙ２Ｏｚ２は、本実施形態ではいずれもアルカンである。 First, as shown in FIG. 4, a plurality of known organic compounds (for example, C x1 H y1 O z1 and C x2 H y2 O z2 ) having different reference elements (here, carbon C) are used to have the same concentration. A calibration curve representing the relationship between the concentration of CH 4 obtained from each organic compound and the number of C (x1 and x2) of the corresponding organic compound is created (step S1).
In the present embodiment, C x1 H y1 O z1 and C x2 H y2 O z2 described above are both alkanes.
次に、ステップＳ１で用いなかった別の有機化合物（例えば、Ｃｘ３Ｈｙ３Ｏｚ３）を用いた場合の、ＣＨ４の濃度と当該有機化合物のＣの数（ｘ３）との関係が、前記検量線上にあるか否かを判定する（ステップＳ２）。
なお、上述したＣｘ３Ｈｙ３Ｏｚ３は、アルカンよりも吸着性の強い有機化合物であり、本実施形態では、例えばヒドロキシ基（－ＯＨ）を官能基として有するものである。 Next, when another organic compound not used in step S1 (for example, C x3 H y3 O z3 ) is used, the relationship between the concentration of CH 4 and the number of C in the organic compound (x3) is It is determined whether or not it is on the calibration curve (step S2).
Note that C x3 H y3 O z3 described above is an organic compound having a higher adsorptivity than alkane, and in this embodiment, for example, has a hydroxy group (—OH) as a functional group.
なお、上述したＣｘ３Ｈｙ３Ｏｚ３は、アルカンよりも吸着性の強い有機化合物であり、本実施形態では、例えばヒドロキシ基（－ＯＨ）を官能基として有するものである。 Next, when another organic compound not used in step S1 (for example, C x3 H y3 O z3 ) is used, the relationship between the concentration of CH 4 and the number of C in the organic compound (x3) is It is determined whether or not it is on the calibration curve (step S2).
Note that C x3 H y3 O z3 described above is an organic compound having a higher adsorptivity than alkane, and in this embodiment, for example, has a hydroxy group (—OH) as a functional group.
そして、ステップＳ２の判定において、Ｃｘ３Ｈｙ３Ｏｚ３を用いた場合のＣＨ４の濃度とＣの数（ｘ３）との関係が、検量線上にある場合は、－ＯＨを官能基として有する有機化合物に対しては、測定結果に信頼性がある（正常）と判定する（ステップＳ３）。
In the determination in step S2, if the relationship between the CH 4 concentration and the number of C (x3) when C x3 H y3 O z3 is used is on the calibration curve, the organic group having —OH as a functional group It is determined that the measurement result is reliable (normal) for the compound (step S3).
また、そして、ステップＳ２の判定において、Ｃｘ３Ｈｙ３Ｏｚ３を用いた場合のＣＨ４の濃度とＣの数（ｘ３）との関係が、検量線上にない場合は、－ＯＨを官能基として有する有機化合物に対しては、測定結果に信頼性がない（異常）と判定する（ステップＳ４）。
If the relationship between the CH 4 concentration and the number of C (x3) when C x3 H y3 O z3 is used in the determination of step S2 is not on the calibration curve, —OH is used as the functional group. It is determined that the measurement result is unreliable (abnormal) for the organic compound (step S4).
上述したように、例えば－ＯＨ基を有する有機化合物に対してバリデーションが終了した後は、－ＯＨ基とは異なる官能基を有する種々の有機化合物に対して次々バリデーションを行うようにする。
As described above, for example, after the validation of an organic compound having an —OH group is completed, various organic compounds having a functional group different from the —OH group are successively validated.
このようなものであれば、例えば、種々の有機化合物に対して、有機化合物の有する吸着力がどの程度の強さまでであれば測定に信頼性があるかを予め把握することができ、測定に無駄な時間や労力を費やすことを未然に防ぐことができるとともに、装置に不具合があった場合は、その異常を測定前に気づくことができる。
If this is the case, for example, for various organic compounds, it is possible to know in advance how strong the adsorptive power of the organic compound is and how reliable the measurement is. It is possible to prevent useless time and labor from being spent, and to recognize an abnormality before the measurement if there is a malfunction in the apparatus.
なお、本発明は前記各実施形態に限られるものではない。
The present invention is not limited to the above embodiments.
例えば、測定対象成分は、前記各実施形態では有機化合物であったが、窒素化合物等の有機化合物以外のものであっても良い。
For example, the component to be measured is an organic compound in each of the above embodiments, but may be other than an organic compound such as a nitrogen compound.
また、前記各実施形態の誘導体は、含まれるＣの数が１であるＣＨ４（メタン）であったが、例えば含まれるＣの数が２以上である成分を誘導体としても良い。この場合、濃度算定部は、誘導体の濃度を、有機化合物１分子に含まれるＣに数で割るとともに、誘導体１分子に含まれるＣの数を乗じることと等価な演算をすることによって、有機化合物の濃度を算定するようにすれば良い。
Further, the derivative of each of the embodiments, the number of C was CH 4 (methane) is 1, component 2008 may be a derivative in the number of C contained for example 2 or more included. In this case, the concentration calculation unit divides the concentration of the derivative by the number of C contained in one molecule of the organic compound by the number and performs an operation equivalent to multiplying the number of C contained in one molecule of the derivative by the number of C. What is necessary is just to calculate the density | concentration of.
さらに、前記第１実施形態では、基準元素数取得部５０がリテンションタイムに基づいて、有機化合物１分子に含まれるＣの数を取得するものであったが、例えば、リテンションタイムインデクスに基づいて有機化合物１分子に含まれるＣの数を取得するものであっても良い。
Furthermore, in the first embodiment, the reference element number acquisition unit 50 acquires the number of C contained in one molecule of the organic compound based on the retention time. The number of C contained in one molecule of the compound may be acquired.
加えて、前記実施形態の反応ガスクロマトグラフは、酸化反応部と還元反応部とを具備するものであったが、酸化反応部又は還元反応部のいずれか一方のみを具備するものであっても良い。
In addition, the reaction gas chromatograph of the above embodiment includes the oxidation reaction unit and the reduction reaction unit, but may include only one of the oxidation reaction unit or the reduction reaction unit. .
その他、本発明は前記実施形態に限られず、その趣旨を逸脱しない範囲で種々の変形が可能であるのは言うまでもない。
In addition, it goes without saying that the present invention is not limited to the above-described embodiment, and various modifications can be made without departing from the spirit of the present invention.
本発明によれば、試料ガスに含まれる測定対象成分が未知であっても、当該測定対象成分の濃度を簡便に測定することができる。
According to the present invention, even if the measurement target component contained in the sample gas is unknown, the concentration of the measurement target component can be easily measured.
Claims (6)
- 試料ガスを通過させて該試料ガスに含まれる各種測定対象成分を分離するカラムと、
該カラムを通過した試料ガスに含まれる前記測定対象成分を、１分子に含まれる基準元素の数が既知の所定の誘導体に変換する変換部と、
前記誘導体の濃度を測定する濃度測定部と、
前記測定対象成分１分子に含まれる前記基準元素の数を取得する基準元素数取得部と、
前記誘導体１分子に含まれる基準元素の数、前記測定対象成分１分子に含まれる前記基準元素の数及び前記誘導体の濃度に基づいて前記試料ガスに含まれる測定対象成分の濃度を算定する濃度算定部とを具備することを特徴とするガスクロマトグラフ。 A column through which a sample gas is passed to separate various components to be measured contained in the sample gas;
A conversion unit that converts the measurement target component contained in the sample gas that has passed through the column into a predetermined derivative in which the number of reference elements contained in one molecule is known;
A concentration measuring unit for measuring the concentration of the derivative;
A reference element number obtaining unit for obtaining the number of the reference elements contained in one molecule of the measurement target component;
Concentration calculation for calculating the concentration of the measurement target component contained in the sample gas based on the number of reference elements contained in one molecule of the derivative, the number of reference elements contained in one molecule of the measurement target component, and the concentration of the derivative. And a gas chromatograph. - 前記基準元素数取得部が、前記測定対象成分がカラムを通過する時間に基づいて、前記測定対象成分１分子に含まれる前記基準元素の数を取得するものである請求項１記載のガスクロマトグラフ。 The gas chromatograph according to claim 1, wherein the reference element number acquisition unit acquires the number of reference elements contained in one molecule of the measurement target component based on a time during which the measurement target component passes through the column.
- 前記基準元素数取得部が、前記カラムに接続されて該カラムを通過した試料ガスに含まれる測定対象成分の質量を分析する質量分析部と、前記質量分析部で分析された測定対象成分の質量から該測定対象成分１分子に含まれる前記基準元素の数を算出する基準元素数算出部とを具備するものである請求項１記載のガスクロマトグラフ。 The reference element number acquisition unit is connected to the column and analyzes the mass of the measurement target component contained in the sample gas that has passed through the column, and the mass of the measurement target component analyzed by the mass analysis unit The gas chromatograph according to claim 1, further comprising: a reference element number calculation unit that calculates the number of the reference elements contained in one molecule of the measurement target component.
- 前記基準元素が炭素であり、前記測定対象成分が有機化合物であり、前記誘導体がメタンであり、前記濃度測定部がＦＩＤを具備したものである請求項１記載のガスクロマトグラフ。 The gas chromatograph according to claim 1, wherein the reference element is carbon, the component to be measured is an organic compound, the derivative is methane, and the concentration measuring unit includes an FID.
- 試料ガスを通過させて該試料ガスに含まれる各種測定対象成分を分離するカラムと、
該カラムを通過した試料ガスに含まれる前記測定対象成分を、１分子に含まれる基準元素の数が既知の所定の誘導体に変換する変換部と、
前記誘導体の濃度を測定する濃度測定部と、
前記誘導体１分子に含まれる基準元素の数、前記測定対象成分１分子に含まれる前記基準元素の数及び前記誘導体の濃度に基づいて前記試料ガスに含まれる測定対象成分の濃度を算定する濃度算定部とを具備することを特徴とするガスクロマトグラフのバリデーション方法であって、
互いに基準元素数が異なる複数の既知の測定対象成分を用いて、同一濃度にしたときの各測定対象成分から得られる前記誘導体の濃度と、対応する測定対象成分の炭素数との関係を表す検量線を作成する検量線作成ステップと、
前記検量線作成ステップで用いなかった別の測定対象成分を用いた場合の、誘導体の濃度と当該測定対象成分の炭素数との関係が、前記検量線上にあるか否かによって当該ガスクロマトグラフのバリデーションを行うバリデーションステップとを有することを特徴とするガスクロマトグラフのバリデーション方法。 A column through which a sample gas is passed to separate various components to be measured contained in the sample gas;
A conversion unit that converts the measurement target component contained in the sample gas that has passed through the column into a predetermined derivative in which the number of reference elements contained in one molecule is known;
A concentration measuring unit for measuring the concentration of the derivative;
Concentration calculation for calculating the concentration of the measurement target component contained in the sample gas based on the number of reference elements contained in one molecule of the derivative, the number of reference elements contained in one molecule of the measurement target component, and the concentration of the derivative. A gas chromatograph validation method characterized by comprising:
Calibration representing the relationship between the concentration of the derivative obtained from each measurement target component when the same concentration is used using a plurality of known measurement target components having different reference element numbers and the carbon number of the corresponding measurement target component A calibration curve creation step for creating a curve;
Validation of the gas chromatograph depending on whether the relationship between the concentration of the derivative and the carbon number of the measurement target component is on the calibration curve when another measurement target component not used in the calibration curve creation step is used And a validation step for performing a gas chromatograph validation method. - 前記基準元素が炭素であり、前記誘導体がメタンである場合において、
前記検量線作成ステップにおいてはアルカンを測定対象成分として用い、前記バリデーションステップにおいては前記アルカンよりも吸着性の強い有機化合物を測定対象成分として用いる請求項５記載のガスクロマトグラフのバリデーション方法。
In the case where the reference element is carbon and the derivative is methane,
The gas chromatograph validation method according to claim 5, wherein alkane is used as a measurement target component in the calibration curve creating step, and an organic compound having a stronger adsorptivity than the alkane is used as the measurement target component in the validation step.
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