JP2001099781A - Method for correcting effect of co-existing gas in gas analysis by infrared absorption method - Google Patents
Method for correcting effect of co-existing gas in gas analysis by infrared absorption methodInfo
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- JP2001099781A JP2001099781A JP27664799A JP27664799A JP2001099781A JP 2001099781 A JP2001099781 A JP 2001099781A JP 27664799 A JP27664799 A JP 27664799A JP 27664799 A JP27664799 A JP 27664799A JP 2001099781 A JP2001099781 A JP 2001099781A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、赤外吸収法によ
るガス分析における共存ガスの影響を補正する方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for correcting the influence of a coexisting gas in gas analysis by an infrared absorption method.
【０００２】[0002]
【従来の技術およびその問題点】ＮＤＩＲ法（非分散型
赤外線ガス分析法）やＦＴＩＲ法（フーリエ変換赤外
法）などの赤外吸収法によって赤外に吸収スペクトルを
もつあるガス成分（目的成分または測定対象成分）を測
定する際、同じく赤外に吸収スペクトルをもつが目的成
分とは分離できている共存成分、あるいは、赤外領域に
は吸収をもたない共存成分によって測定値（スパン感
度）が影響されてしまうことがある。2. Description of the Related Art A certain gas component (a target component) having an infrared absorption spectrum by an infrared absorption method such as an NDIR method (non-dispersive infrared gas analysis method) or an FTIR method (Fourier transform infrared method). Or the component to be measured), the coexisting component which also has an absorption spectrum in the infrared but can be separated from the target component, or the coexisting component which has no absorption in the infrared region (span sensitivity) ) May be affected.
【０００３】これは、同一ガス成分・同一ガス濃度であ
ってもベースガス組成（共存成分組成）によりスペクト
ル強度に差が生ずることがあるにもかかわらず、従来の
赤外吸収法では、成分同士の干渉は全て吸収スペクトル
の重なりが分離できてないことにに起因するという前提
になっていたためである。実際に、自動車排ガスなどの
分析において、目的成分であるＣＯおよびＣＯ2 のスパ
ン指示に対して共存成分であり、かつ濃度も一定でない
Ｈ2 ＯやＯ2 が影響を与えやすいことが確認されてい
る。[0003] This is because, although the spectral intensity may differ depending on the base gas composition (coexisting component composition) even with the same gas component and the same gas concentration, in the conventional infrared absorption method, the components are different from each other. Is presumed to be caused by the fact that the overlap of the absorption spectra cannot be separated. In fact, in the analysis of automobile exhaust gas and the like, it has been confirmed that H 2 O and O 2 , which are coexistent components and have non-constant concentrations, easily affect the span indication of the target components CO and CO 2. I have.
【０００４】しかし、Ｏ2 は赤外吸収をもたず、Ｈ2 Ｏ
は濃度校正が難しいことから、いずれも赤外吸収法での
分析は困難である。However, O 2 has no infrared absorption and H 2 O
Since it is difficult to calibrate the concentration, analysis by the infrared absorption method is difficult.
【０００５】図４（Ａ）は、種々の濃度のＣＯ2 を測定
したときにおける共存するＨ2 Ｏの濃度とＣＯ2 指示値
の誤差との関係を示すもので、この図からＨ2 Ｏ濃度が
高くなるにつれてＣＯ2 指示値の誤差がプラス側に大き
く表れることがわかる。そして、同図（Ｂ）は、２台の
ガス分析計を用いて種々の濃度のＣＯ2 を測定したとき
における共存するＯ2 の濃度とＣＯ2 指示値の誤差との
関係を示すもので、この図からＯ2 濃度が高くなるにつ
れてＣＯ2 指示値の誤差がマイナス側に大きく表れるこ
とがわかる。すなわち、これらのガス分析計の感度校正
は、Ｎ2 ガスをベースガスとして製造された標準ガスに
よって行われるため、Ｈ2 ＯやＯ2 を含む混合ガスがベ
ースガスとなる場合に感度変化を生じていることがわか
る。[0005] FIG. 4 (A), shows the relationship between the error of the of H 2 O concentration and CO 2 indicated value coexist in when measuring CO 2 at various concentrations, H 2 O concentration from FIG It can be understood that the error of the CO 2 indicated value appears larger on the positive side as the value of “” increases. FIG. 4B shows the relationship between the coexisting O 2 concentration and the error in the indicated CO 2 value when various concentrations of CO 2 are measured using two gas analyzers. From this figure, it can be seen that as the O 2 concentration increases, the error in the CO 2 indicated value appears more negatively. That is, since the sensitivity calibration of these gas analyzers is performed using a standard gas manufactured using N 2 gas as a base gas, a change in sensitivity occurs when a mixed gas containing H 2 O or O 2 is used as a base gas. You can see that it is.
【０００６】上記図４（Ａ），（Ｂ）に示したような現
象が生ずる正確な機構は不明であるが、一つには、ガス
分子同士の相互作用によるクエンチングが関係している
と考えられる。The exact mechanism that causes the phenomena shown in FIGS. 4A and 4B is unknown, but one is that quenching due to the interaction between gas molecules is involved. Conceivable.
【０００７】図５は、クエンチングによる赤外吸収量変
化モデルを示すもので、これは、目的成分Ｘと共存成分
の衝突確率および衝突の際の相互作用の大小によって、
赤外吸収量に変化が生ずるという仮説を示している。す
なわち、同図（Ａ）は、目的成分Ｘに対して共存成分Ａ
の衝突確率および衝突の際の相互作用が共に小さい場合
を示し、この場合、成分Ａは成分Ｘの基底状態・励起状
態の平衡に影響を余り与えないため、成分Ａの濃度は成
分Ｘによる赤外の吸収量に殆ど影響しない。一方、同図
（Ｂ）は、成分Ｘに対して共存成分Ｂの衝突確率および
衝突の際の相互作用が共に大きい場合を示し、この場
合、成分Ｘの平衡が基底状態側にずれるため、新たな光
吸収が起こりやすくなる。つまり、成分Ｂの存在によ
り、成分Ｘの吸収強度が大きくなり、主な共存成分、す
なわち、ベースガスが成分Ａであった場合よりも同一濃
度で強い吸収を示す。FIG. 5 shows a model of a change in the amount of infrared absorption due to quenching, which depends on the probability of collision between the target component X and the coexisting component and the magnitude of the interaction at the time of collision.
This shows a hypothesis that a change occurs in the amount of infrared absorption. That is, FIG. 3A shows that the target component X and the coexisting component A
In this case, the collision probability and the interaction at the time of collision are both small. In this case, since the component A does not significantly affect the equilibrium between the ground state and the excited state of the component X, the concentration of the component A is Almost no effect on outside absorption. On the other hand, FIG. 7B shows a case where the collision probability of the coexisting component B and the interaction at the time of the collision are both large with respect to the component X. In this case, since the equilibrium of the component X is shifted to the ground state side, Light absorption is likely to occur. That is, due to the presence of the component B, the absorption intensity of the component X is increased, and the main coexisting component, that is, stronger absorption is exhibited at the same concentration as when the base gas is the component A.
【０００８】また、上記現象の原因となりうる他の機構
としては、目的成分自身および共存成分による作用で吸
収波長が影響を受け、見かけ上、吸収線幅が広がる「衝
突広がり」というメカニズムも考えられる。As another mechanism that may cause the above phenomenon, a mechanism called "collision spread" in which the absorption wavelength is apparently widened due to the absorption wavelength being affected by the action of the target component itself and the coexisting component is also considered. .
【０００９】この発明は、上述の事柄に留意してなされ
たもので、その目的は、赤外吸収法によってガス分析を
連続的に行う場合、共存成分組成に依存する赤外吸収ス
ペクトルの強度変化に起因する感度変化を補正すること
ができる、赤外吸収法によるガス分析における共存ガス
影響の補正方法（以下、単に共存ガス影響の補正方法と
いう）を提供することである。The present invention has been made in consideration of the above-mentioned matters, and an object of the present invention is to provide a method for continuously performing gas analysis by an infrared absorption method. It is an object of the present invention to provide a method for correcting the effect of coexisting gas in gas analysis by the infrared absorption method (hereinafter, simply referred to as a method for correcting the effect of coexisting gas), which can correct the sensitivity change caused by the above.
【００１０】[0010]
【課題を解決するための手段】上記目的を達成するた
め、この発明の共存ガス影響の補正方法においては、赤
外吸収法によるガス分析計の目的成分の指示値に影響を
与えるにもかかわらず赤外吸収法では濃度測定が困難な
共存ガスの濃度および濃度変化を、赤外吸収法で測定可
能な目的成分またはそれ以外の成分の指示値から推定
し、この推定された濃度および濃度変化を用いて、目的
成分の指示値を補正するようにしている。In order to achieve the above object, in the method for correcting the influence of a coexisting gas according to the present invention, the influence of the infrared absorption method on the indicated value of the target component of the gas analyzer is reduced. The concentration and concentration change of coexisting gas, for which concentration measurement is difficult by the infrared absorption method, are estimated from the indicated values of the target component or other components that can be measured by the infrared absorption method, and the estimated concentration and the concentration change are estimated. This is used to correct the indicated value of the target component.
【００１１】[0011]
【発明の実施の形態】この発明の実施の形態を、図面を
参照しながら説明する。まず、図１は、この発明の共存
ガス影響の補正方法が適用されるガス分析装置の一例を
概略的に示すもので、例えばエンジン排ガスに含まれる
ＣＯ2 の濃度を測定するものである。すなわち、この図
において、１は自動車（例えばガソリン車）のエンジ
ン、２はエンジン１に接続される排気管、３は排気管２
を流れる排ガスＧの一部をサンプルガスＳとして採取す
るためのプローブ４を介して接続されるサンプルガス流
路である。５はサンプルガス流路３に設けられる非分散
型赤外線ガス分析計としてのＣＯ2 計である。６はこの
ＣＯ2 計５の信号ラインで、プリアンプ７およびアナロ
グ系の信号処理装置８が設けられている。Embodiments of the present invention will be described with reference to the drawings. First, FIG. 1 schematically shows an example of a gas analyzer to which the method for correcting a coexisting gas effect of the present invention is applied, for example, for measuring the concentration of CO 2 contained in an engine exhaust gas. That is, in this figure, 1 is an engine of an automobile (for example, a gasoline vehicle), 2 is an exhaust pipe connected to the engine 1, and 3 is an exhaust pipe 2.
Is a sample gas flow path connected via a probe 4 for sampling a part of the exhaust gas G flowing through the probe 4 as a sample gas S. Reference numeral 5 denotes a CO 2 meter provided as a non-dispersive infrared gas analyzer provided in the sample gas channel 3. Reference numeral 6 denotes a signal line of the CO 2 meter 5, which is provided with a preamplifier 7 and an analog signal processing device 8.
【００１２】上記構成の装置を用いた場合、エンジン排
ガスＧに含まれるＣＯ2 の濃度を測定することができる
が、エンジン排ガスＧには、同時に高濃度のＨ2 Ｏが含
まれている。つまり、この場合、Ｈ2 Ｏが共存ガスとな
り、これが測定対象成分ＣＯ 2 の濃度に影響を及ぼすこ
ととなる。しかし、このＨ2 Ｏの濃度は、前記ＣＯ2計
５で測定していない。When the apparatus having the above configuration is used, the engine exhaust
CO contained in gas GTwoCan measure the concentration of
However, the high concentration HTwoO included
It is rare. That is, in this case, HTwoO is a coexisting gas
This is the measurement target component CO TwoMay affect the concentration of
And But this HTwoThe concentration of O depends on the COTwoTotal
Not measured at 5.
【００１３】ところで、ガソリン車のエンジン１内は、
一般的に燃料とその燃焼に必要な空気の量とに過不足が
ない「理論空燃比」にコントロールされる。今仮に、通
常よく使われるように、燃料中の炭素Ｃと水素Ｈとの比
率を１：２、空気中のＯ2 とＮ2 との比率を２：８とみ
なすと、エンジン１前後の化合物の収支は、下記（１）
式のようになる。 ＣＨ2 ＋３／２・Ｏ2 ＋６・Ｎ2 ＝ＣＯ2 ＋Ｈ2 Ｏ＋６・Ｎ2 ……（１）By the way, the inside of the engine 1 of the gasoline vehicle is
Generally, the "stoichiometric air-fuel ratio" is controlled so that there is no excess or deficiency in the amount of fuel and the amount of air required for its combustion. Assuming that the ratio of carbon C and hydrogen H in fuel is 1: 2 and the ratio of O 2 to N 2 in air is 2: 8, as commonly used, the compounds around engine 1 are Is the following (1)
It looks like an expression. CH 2 + 3/2 · O 2 + 6 · N 2 = CO 2 + H 2 O + 6 · N 2 (1)
【００１４】つまり、エンジン１の下流でのＨ2 ＯとＣ
Ｏ2 の濃度比はほぼ１：１であり、この場合、Ｈ2 Ｏの
濃度は、ＣＯ2 の濃度とともに、１２．５ｖｏｌ％〔＝
１／（１＋１＋６）×１００〕であることが導き出せ
る。このような理論空燃比における燃焼では、ＣＯ2 計
５の入口では酸素濃度はゼロである。このように、Ｈ2
Ｏの濃度は、ＣＯ2 の濃度から簡単に推定することがで
きる。なお、サンプルガス流路３のＣＯ2 計５の上流側
に除湿機を設けて排ガスＧ中の水蒸気を除去しているよ
うな場合は、ＣＯ2 計５の入口におけるＨ2 Ｏの濃度
は、この除湿機の水分除去能力で決まり、また、ＣＯ2
計５の入口におけるＣＯ2 の濃度値は、除湿により失わ
れるＨ2 Ｏの分だけ高くなる。That is, H 2 O and C downstream of the engine 1
The concentration ratio of O 2 is approximately 1: 1. In this case, the concentration of H 2 O, together with the concentration of CO 2 , is 12.5 vol% [=
1 / (1 + 1 + 6) × 100]. In the combustion at such a stoichiometric air-fuel ratio, the oxygen concentration at the inlet of the CO 2 meter 5 is zero. Thus, H 2
The concentration of O can be easily estimated from the concentration of CO 2 . When a dehumidifier is provided upstream of the CO 2 meter 5 in the sample gas flow path 3 to remove water vapor in the exhaust gas G, the concentration of H 2 O at the inlet of the CO 2 meter 5 becomes determined by the dehumidifier moisture removal capability, also, CO 2
The CO 2 concentration value at the inlet of the total 5 increases by the amount of H 2 O lost by dehumidification.
【００１５】また、自動車の減速時においては、エンジ
ン１に対する燃料の供給を一時的に中断（燃料カット）
することがある。そして、仮にある時間内の燃料噴射量
が理論空燃比の１／ｎであった場合、エンジン１前後の
化合物の収支は、下記（２）式のようになる。 １／ｎ・ＣＨ2 ＋３／２・Ｏ2 ＋６・Ｎ2 ＝１／ｎ・ＣＯ2 ＋１／ｎ・Ｈ2 Ｏ ＋３（ｎ−１）／２ｎ・Ｏ2 ＋６・Ｎ2 ……（２）When the vehicle decelerates, the supply of fuel to the engine 1 is temporarily interrupted (fuel cut).
May be. If the fuel injection amount within a certain period of time is 1 / n of the stoichiometric air-fuel ratio, the balance of the compound before and after the engine 1 is expressed by the following equation (2). 1 / n · CH 2 + 3/2 · O 2 + 6 · N 2 = 1 / n · CO 2 + 1 / n · H 2 O +3 (n−1) / 2n · O 2 + 6 · N 2 (2)
【００１６】上記の場合、ＣＯ2 の実測濃度値（ｖｏｌ
％）は、２／（１５ｎ＋１）×１００ｖｏｌ％になって
いるはずであるから、 ＣＯ2 の実測濃度値＝２／（１５ｎ＋１）×１００ ……（３） とすることにより、ｎを求めることができる。そして、
このときのＣＯ2 計５の入口におけるＯ2 の濃度は、上
記（２）式から、３／（１５ｎ＋１）×１００ｖｏｌ％
と表されるので、前記（３）式を解いて得られるｎをこ
れに代入することにより、Ｏ2 濃度も推定することがで
きる。In the above case, the measured concentration of CO 2 (vol.
%) Should be 2 / (15n + 1) × 100 vol%, so that the actual measured concentration of CO 2 = 2 / (15n + 1) × 100 (3) it can. And
At this time, the concentration of O 2 at the inlet of the CO 2 meter 5 is 3 / (15n + 1) × 100 vol% from the above equation (2).
Thus, the O 2 concentration can be estimated by substituting n obtained by solving the equation (3).
【００１７】図２（Ａ）〜（Ｄ）は、測定対象成分であ
るＣＯ2 の測定値に基づいて共存するＨ2 ＯおよびＯ2
の濃度を推定し、この推定された濃度を用いて前記ＣＯ
2 の測定値を補正する例を示すもので、各図において、
横軸は時間（秒）、縦軸は濃度（ｖｏｌ％）を示してい
る。そして、同図（Ａ）はＣＯ2 計５によって測定され
たＣＯ2 の濃度値を示し、同図（Ｂ），（Ｃ）は前記Ｃ
Ｏ2 の濃度値からそれぞれ推定されたＨ2 Ｏ、Ｏ2 の濃
度値である。これらの濃度値は既に説明したような手法
を用いて推定される。そして、同図（Ｄ）は同図
（Ｂ），（Ｃ）で示されるＨ2 Ｏ、Ｏ2 の濃度値による
影響を補正した後のＣＯ2 の濃度値である。補正には、
図４に示したような影響の実測値から求められる近似式
を使用することができる。FIGS. 2A to 2D show the coexistence of H 2 O and O 2 based on the measured value of CO 2 which is the component to be measured.
Is estimated, and the CO2 is estimated using the estimated concentration.
It shows an example of correcting the measured value of 2 , in each figure,
The horizontal axis represents time (seconds), and the vertical axis represents concentration (vol%). (A) shows the concentration of CO 2 measured by the CO 2 meter 5, and (B) and (C) show the C 2 values.
O 2 concentration H 2 that is estimated from each value O, the concentration value of O 2. These density values are estimated using the method described above. FIG. 3D shows the CO 2 concentration values after the influence of the H 2 O and O 2 concentration values shown in FIGS. 2B and 2C is corrected. To correct,
An approximate expression obtained from the measured value of the influence as shown in FIG. 4 can be used.
【００１８】上述のように、エンジン排ガスＧの分析に
おいて、ＣＯ2 の濃度から、このＣＯ2 濃度に影響を与
えるＨ2 Ｏまたは／およびＯ2 の濃度を推定することが
できるため、ＣＯ2 濃度に対するＨ2 ＯまたはＯ2 の影
響度を予め調べておくことにより、それらの推定濃度を
用いてＣＯ2 濃度出力に対する影響を補正することが可
能となる。なお、推定濃度は、補正値を求めるのに用い
るだけであるから、精度自体はそれほど要求されない。
また、ガス分析計間の機差が小さければ、補正のための
近似式は代表となる装置での確認データに基づいて決定
しておけばよい。さらにこの場合、ガス分析計の校正ガ
スは通常通りＮ2 ベースのものを使用することができ
る。[0018] As described above, in the analysis of engine exhaust G, from the concentration of CO 2, it is possible to estimate the concentration of H 2 O or / and O 2 affect the CO 2 concentration, CO 2 concentration By previously examining the degree of influence of H 2 O or O 2 on the CO 2 concentration output, it is possible to correct the influence on the CO 2 concentration output using those estimated concentrations. Since the estimated density is only used for obtaining the correction value, the accuracy itself is not so required.
If the difference between the gas analyzers is small, the approximate expression for correction may be determined based on confirmation data from a representative apparatus. Furthermore, in this case, it is possible to use a calibration gas of N 2 base usual for gas analyzer.
【００１９】そして、前記補正の手法としては、近似式
を用いて補正する従来の手法のほかに、例えば、ＦＴＩ
Ｒによる場合は、この出願の出願人に係る特許出願「Ｆ
ＴＩＲ法による多成分ガス分析方法」（特願平１１−１
５８４９３号）に示されている、定量アルゴリズムによ
って混合ガススペクトルから未補正の多成分濃度を算出
した後、一部の成分についてはさらに共存ガス成分によ
るスペクトルの変化分の補正計算を行う手法を用いるこ
とができる。As the above-mentioned correction method, in addition to the conventional method of correcting using an approximate expression, for example, FTI
In the case of R, the patent application “F
Multicomponent Gas Analysis Method by TIR Method ”(Japanese Patent Application No. 11-1)
No. 58493), a method of calculating an uncorrected multi-component concentration from a mixed gas spectrum by a quantitative algorithm and then performing a correction calculation of a change in the spectrum due to a coexisting gas component for some components is used. be able to.
【００２０】上述の実施の形態におけるエンジン排ガス
分析は、エンジン１からの排ガスＧを希釈しないでガス
分析計５に導くものであったが、エンジン排ガス分析手
法としては、排ガスＧを空気またはＮ2 で希釈してガス
分析計５に導いたり、また、排ガスＧを空気またはＮ2
で希釈してバッグ内にサンプリングし、このバック内の
ガスをガス分析計５に導く手法がある。このような希釈
した排ガスをサンプルとして用いる場合にも、ＣＯ2 の
濃度実測値の理論値との比較からおおよその希釈率を求
め、この情報も加味してＨ2 ＯやＯ2 の濃度を推定し、
その後、ＣＯ2の濃度を補正すればよい。In the engine exhaust gas analysis in the above-described embodiment, the exhaust gas G from the engine 1 is led to the gas analyzer 5 without dilution, but as an engine exhaust gas analysis method, the exhaust gas G is converted to air or N 2 gas. And exhaust gas G is diluted with air or N 2.
There is a method in which the gas in the bag is sampled in the bag and the gas in the bag is guided to the gas analyzer 5. Even when such a diluted exhaust gas is used as a sample, an approximate dilution rate is obtained by comparing the actual measured value of CO 2 with the theoretical value, and the concentration of H 2 O or O 2 is estimated in consideration of this information. And
Thereafter, the concentration of CO 2 may be corrected.
【００２１】この発明は、上述の実施の形態に限られる
ものではなく、種々に変形して実施することができ、例
えばＣＯの補正を行う場合、ＣＯおよびＣＯ2 について
ほぼ同等の応答が得られるように構成したＣＯ／ＣＯ2
２成分計（あるいは、それ以上の多成分計）を使用すれ
ばよい。The present invention is not limited to the above-described embodiment, but can be implemented in various modifications. For example, when CO correction is performed, approximately equivalent responses can be obtained for CO and CO 2. CO / CO 2 configured as follows
A two-component meter (or a multi-component meter more than that) may be used.
【００２２】また、赤外吸収法によるガス分析計とし
て、図３に示すようなＦＴＩＲ１０を用いることができ
る。この図３において、１１は分析部で、平行な赤外光
を発するように構成された赤外光源１２と、ビームスプ
リッタ１３、固定ミラー１４、図外の駆動機構によって
例えばＸ−Ｙ方向に平行移動する可動ミラー１５からな
る干渉機構１６と、測定試料や比較（参照）試料等を収
容し、干渉機構１６を介して赤外光源１２からの赤外光
が照射されるセル１７と、半導体検出器１８とからな
る。そして、１９はこの分析部１１の出力であるインタ
ーフェログラムを処理するデータ処理部である。An FTIR 10 as shown in FIG. 3 can be used as a gas analyzer by the infrared absorption method. In FIG. 3, reference numeral 11 denotes an analysis unit which is parallel to, for example, the XY direction by an infrared light source 12 configured to emit parallel infrared light, a beam splitter 13, a fixed mirror 14, and a driving mechanism (not shown). An interference mechanism 16 including a movable mirror 15 that moves, a cell 17 that accommodates a measurement sample, a comparison (reference) sample, and the like, and is irradiated with infrared light from the infrared light source 12 via the interference mechanism 16; And a vessel 18. Reference numeral 19 denotes a data processing unit that processes an interferogram output from the analysis unit 11.
【００２３】上記構成のＦＴＩＲ１０を用いて例えばプ
ロセスガスの計測など、主要構成ガスが限られており、
目的成分に影響する成分の濃度が目的成分の濃度から推
定可能である試料の分析を行う場合にも、上記実施の形
態に示したのと同様の手法を適用することができる。す
なわち、成分Ｐ，Ｑ，Ｒ，Ｓからなるガス試料で、成分
Ｐ〜Ｒが目的成分であり、成分Ｓが共存成分（ベースガ
ス）でしかも校正ガスに含まれない場合、成分Ｐ〜Ｒの
濃度値から成分Ｓの濃度（＝１００−Ｐ−Ｑ−Ｒ）を求
め、この値を用いて再度、成分Ｐ〜Ｒの出力を補正する
のである。The main constituent gas is limited by using the FTIR 10 having the above structure, for example, for measuring a process gas.
The same technique as that described in the above embodiment can be applied to the case of analyzing a sample in which the concentration of the component affecting the target component can be estimated from the concentration of the target component. That is, in a gas sample composed of components P, Q, R, and S, when components P to R are target components and component S is a coexisting component (base gas) and is not included in the calibration gas, the components P to R The density of the component S (= 100-PQR) is obtained from the density value, and the output of the components P to R is corrected again using this value.
【００２４】[0024]
【発明の効果】以上説明したように、この発明の共存ガ
ス影響の補正方法においては、測定対象成分の指示値に
影響を与え、かつ赤外吸収法では濃度測定が困難な共存
ガスについて、その濃度と濃度変化とを赤外吸収法で測
定可能な目的成分またはそれ以外の成分の指示値から推
定し、目的成分の指示値に対する補正を行うようにして
いるので、ベースガス補正を確実に行うことができ、目
的成分の濃度値として信頼性の高いものが得られる。As described above, in the method of correcting the influence of a coexisting gas according to the present invention, the coexisting gas which affects the indicated value of the component to be measured and whose concentration cannot be easily measured by the infrared absorption method is described. Since the concentration and the change in concentration are estimated from the indicated values of the target component or the other components that can be measured by the infrared absorption method, and the correction is performed on the indicated value of the target component, the base gas correction is surely performed. As a result, a highly reliable concentration value of the target component can be obtained.
【００２５】特に、ベースガス成分の濃度を測定対象成
分自身から推定する場合、時間遅れによって生ずる補正
誤差を無視することができる。そして、多成分測定によ
る場合でも、セルを共用するなど成分間の応答差が生じ
ないような構成を取りやすく、時間遅れの誤差を避ける
ことができる。したがって、ガス分析計のハードおよび
ソフトをシンプルなものとすることができ、連続測定に
おいても非常に好適に適用することができる。In particular, when estimating the concentration of the base gas component from the measurement target component itself, a correction error caused by a time delay can be ignored. Even in the case of multi-component measurement, it is easy to adopt a configuration that does not cause a response difference between components, such as sharing a cell, and it is possible to avoid a time delay error. Therefore, the hardware and software of the gas analyzer can be simplified, and the gas analyzer can be suitably applied to continuous measurement.
【００２６】さらに、この発明の共存ガス影響の補正方
法によれば、Ｈ2 Ｏなどガスサンプリングの際に結露す
るなどの問題が生じやすい成分や、Ｏ2 、Ｎ2 、Ｈ2 な
ど赤外吸収をもたない成分の直接的な分析が不要であ
り、また、共存成分を全て校正ガスに混合しておく必要
もない。Further, according to the method of correcting the influence of the coexisting gas of the present invention, a component such as H 2 O, which is liable to cause a problem such as dew condensation at the time of gas sampling, or an infrared absorbing component such as O 2 , N 2 , H 2. There is no need for direct analysis of components having no components, and it is not necessary to mix all coexisting components with the calibration gas.
【図１】この発明の共存ガス影響の補正方法が適用され
るガス分析装置の一例を概略的に示す図である。FIG. 1 is a diagram schematically illustrating an example of a gas analyzer to which a method for correcting a coexisting gas effect according to the present invention is applied.
【図２】前記共存ガス影響の補正方法の一例を示す説明
図である。FIG. 2 is an explanatory diagram showing an example of a method for correcting the effect of the coexisting gas.
【図３】この発明の共存ガス影響の補正方法が適用され
るガス分析装置の他の例を概略的に示す図である。FIG. 3 is a diagram schematically showing another example of a gas analyzer to which the method of correcting a coexisting gas effect of the present invention is applied.
【図４】従来技術の問題点を説明するための図である。FIG. 4 is a diagram for explaining a problem of the related art.
【図５】クエンチングによる赤外吸収量変化モデルを示
す図である。FIG. 5 is a diagram showing a model of a change in the amount of infrared absorption due to quenching.
５，１０…赤外吸収法によるガス分析計。 5, 10 ... Gas analyzer by infrared absorption method.
フロントページの続き (72)発明者 明石 耕太郎 京都府京都市南区吉祥院宮の東町２番地 株式会社堀場製作所内 Ｆターム(参考） 2G020 BA02 BA12 CA02 CB42 2G059 AA01 BB01 CC04 EE01 HH01 NN01 Continued on the front page (72) Inventor Kotaro Akashi 2 Higashi-cho, Kichijoin-gu, Minami-ku, Kyoto, Kyoto F-term in HORIBA, Ltd. (Reference) 2G020 BA02 BA12 CA02 CB42 2G059 AA01 BB01 CC04 EE01 HH01 NN01
Claims (1)
の指示値に影響を与えるにもかかわらず赤外吸収法では
濃度測定が困難な共存ガスの濃度および濃度変化を、赤
外吸収法で測定可能な目的成分またはそれ以外の成分の
指示値から推定し、この推定された濃度および濃度変化
を用いて、目的成分の指示値を補正するようにしたこと
を特徴とする赤外吸収法によるガス分析における共存ガ
ス影響の補正方法。1. An infrared absorption method for determining the concentration of coexisting gas and a change in concentration which have an influence on an indication value of a target component of a gas analyzer by an infrared absorption method but whose concentration cannot be easily measured by the infrared absorption method. Infrared absorption method characterized by estimating from the indicated value of the target component or other components that can be measured by the method, and correcting the indicated value of the target component using the estimated concentration and the change in concentration. Of the effect of coexisting gas in gas analysis by FTIR.
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|---|---|---|---|
| JP27664799A JP4205821B2 (en) | 1999-09-29 | 1999-09-29 | Correction method for influence of coexisting gas in gas analysis by infrared absorption method and gas analyzer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP27664799A JP4205821B2 (en) | 1999-09-29 | 1999-09-29 | Correction method for influence of coexisting gas in gas analysis by infrared absorption method and gas analyzer |
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| Publication Number | Publication Date |
|---|---|
| JP2001099781A true JP2001099781A (en) | 2001-04-13 |
| JP4205821B2 JP4205821B2 (en) | 2009-01-07 |
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| CN100460858C (en) * | 2005-12-13 | 2009-02-11 | 上海神开石油化工装备股份有限公司 | Method for on-line spectral determining oily gas in drilling liquid |
| JP2010223702A (en) * | 2009-03-23 | 2010-10-07 | Toyota Motor Corp | Exhaust gas analyzer |
| JP2013120058A (en) * | 2011-12-06 | 2013-06-17 | Shimadzu Corp | Combustion exhaust gas analysis instrument |
| JP2014174054A (en) * | 2013-03-11 | 2014-09-22 | Horiba Ltd | Exhaust gas analyzer |
| EP3098592A1 (en) | 2015-05-25 | 2016-11-30 | Yokogawa Electric Corporation | Multi-component gas analysis system and multi-component gas analysis method |
| WO2022071066A1 (en) * | 2020-10-02 | 2022-04-07 | 株式会社堀場製作所 | Exhaust gas analysis device, exhaust gas analysis method, and program storage medium for exhaust gas analysis device |
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1999
- 1999-09-29 JP JP27664799A patent/JP4205821B2/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100460858C (en) * | 2005-12-13 | 2009-02-11 | 上海神开石油化工装备股份有限公司 | Method for on-line spectral determining oily gas in drilling liquid |
| JP2010223702A (en) * | 2009-03-23 | 2010-10-07 | Toyota Motor Corp | Exhaust gas analyzer |
| JP2013120058A (en) * | 2011-12-06 | 2013-06-17 | Shimadzu Corp | Combustion exhaust gas analysis instrument |
| JP2014174054A (en) * | 2013-03-11 | 2014-09-22 | Horiba Ltd | Exhaust gas analyzer |
| US9568396B2 (en) | 2013-03-11 | 2017-02-14 | Horiba, Ltd. | Exhaust gas analyzing apparatus |
| EP3098592A1 (en) | 2015-05-25 | 2016-11-30 | Yokogawa Electric Corporation | Multi-component gas analysis system and multi-component gas analysis method |
| US10605724B2 (en) | 2015-05-25 | 2020-03-31 | Yokogawa Electric Corporation | Multi-component gas analysis system and multi-component gas analysis method |
| WO2022071066A1 (en) * | 2020-10-02 | 2022-04-07 | 株式会社堀場製作所 | Exhaust gas analysis device, exhaust gas analysis method, and program storage medium for exhaust gas analysis device |
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| Publication number | Publication date |
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