JP4758510B6 - Organic elemental analysis measurement method and system - Google Patents
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
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Description
本発明は、有機元素分析測定装置及びその情報処理方法に関する The present invention relates to an organic element analysis measurement device and an information processing method thereof.
従来、有機元素分析測定は測定物の重量をミクロ天びんで正確に量り、炭素、水素、
窒素各元素の重量に対する含有量(w／w％)を測定するものであり、測定物の純度の確
認や医薬品の構造決定に用いられている。
Conventionally, organic elemental analysis measures the weight of a measured object accurately with a micro balance, and carbon, hydrogen,
It measures the content (w / w%) of each nitrogen element with respect to the weight, and is used for confirming the purity of a measurement object and determining the structure of a pharmaceutical product.
また、産業界においては土壌や堆肥中のC／N比測定及び産業廃棄物中の可燃分の元素組成（炭素、水素、窒素の割合）の測定やゴミ焼却用高温ガス炉の安定化と制御のために可燃分中の水素と炭素のモル比の測定、及び水質浄化のための高効率なC／N比の測定、さらに大気粉塵中の炭素の定量など環境分野の利用や、食品原材料、石油、石炭、海洋浮遊物など非常に広い利用の分野を挙げることができる。 Also, in industry, C / N ratio measurement in soil and compost, elemental composition (carbon, hydrogen, nitrogen ratio) of combustibles in industrial waste and stabilization and control of HTGR for waste incineration Measurement of hydrogen and carbon molar ratio in combustibles, high-efficiency C / N ratio measurement for water purification, use of environmental fields such as determination of carbon in atmospheric dust, food raw materials, The fields of very wide use such as oil, coal and marine suspended matter can be listed.
有機元素分析装置の構成の例として一般に普及している国産機の原理を図１に示して実際の測定の手順を以下に示す。測定には図１に示す分析装置の他にミクロ天びんを使用する。 FIG. 1 shows the principle of a domestic machine that is widely used as an example of the configuration of the organic element analyzer, and the actual measurement procedure is shown below. For the measurement, a microbalance is used in addition to the analyzer shown in FIG.
１．測定系にキャリアガスとして高純度ヘリウムを一定速度で流す。
２．ミクロ天びんを用いて試料化合物の重さ２mg程度を正確に計る。
３．950oCの分解炉及び850oCの酸化炉に入れた酸化銅を充填した石英燃焼管の中で試料化合物を完全に燃焼し気体にする。このときキャリアガスの１０％程度の純酸素を燃焼管内に流している。この過程で炭素はCO2に、窒素はNO2に、水素はH2Oになる。NO2は次の還元炉の中の石英還元管に充填された還元銅によりN2に還元される。余分な酸素は同じく還元管の還元銅により酸化銅として除く。試料中にハロゲンと硫黄が含まれる場合は還元管先端に充填された銀粒によりハロゲン化銀、硫化銀としてそれぞれトラップする。
４．残った気体はCO2とN2とH2O、およびキャリアガスの混合気体である。
５．150mlの容量の金属ポンプにキャリアガスで送り込んで希釈した後、混合燃焼気体を一定の流量で測定系に送り込む。
６．混合気体は３つの計測セルを順次通してそれぞれの濃度をTCD検出器により電気信号で検出し、電気信号は信号処理手段により演算処理されて計数値countとして出力される。さらにTCD検出器について説明する。TCD検出器の計測セルにはフィラメントがある。ヘリウムは熱伝導度の良い気体であるが、そこに他の気体が不純物として混じると熱伝導度が下がり、セルのフィラメントの温度が高くなり、抵抗値が上がる。抵抗値の大きさが計数値countとして記録計に出力される。
７．混合気体はH2Oの吸収剤を充填した吸収管をまず通り、H2Oが取り除かれる。その前後の計測セルによる抵抗値の差をすでに説明した方法で計数値countに変換する。
８．つぎに、残りの混合気体はCO2の吸収剤を充填した吸収管を通りCO2が除かれる。その前後の抵抗値の差を同じように計数値countに変換する。
９．最後に、残りの気体N2の抵抗値とヘリウムの抵抗値の差を同じように計数値countに変換する。
１０．以上の計数値countについて測定当日の気圧補正を行う。これは検出器における気体のモル分率による大気圧補正を行うものである。
１１．あらかじめCHN含有率（w/w％）が既知の元素分析用標準試料を用いてCHN元素ごとの感度係数（μｇ／count）を決定する。これはファクターとも呼ばれる。決められた感度係数（μｇ／count）即ちファクターを用い未知試料化合物のCHN含有率（w/w％）を計算する。以後本発明においては感度係数をファクターと表す。
１２．元素分析値はC: □％、H: □％、N: □％と表示される。
1. High purity helium is supplied as a carrier gas to the measurement system at a constant speed.
2. Using a micro balance, weigh about 2 mg of the sample compound accurately.
3. Completely burn the sample compound into a gas in a quartz combustion tube filled with copper oxide in a 950 o C decomposition furnace and an 850 o C oxidation furnace. At this time, pure oxygen of about 10% of the carrier gas is allowed to flow into the combustion tube. In this process, carbon becomes CO 2 , nitrogen becomes NO 2 , and hydrogen becomes H 2 O. NO 2 is reduced to N 2 by the reduced copper filled in the quartz reduction tube in the next reduction furnace. Excess oxygen is also removed as copper oxide by reduced copper in the reducing tube. When halogen and sulfur are contained in the sample, they are trapped as silver halide and silver sulfide, respectively, by the silver grains filled at the tip of the reducing tube.
4). The remaining gas is a mixed gas of CO 2 , N 2 , H 2 O, and carrier gas.
5. After feeding and diluting the metal pump with a capacity of 150 ml with a carrier gas, the mixed combustion gas is sent to the measurement system at a constant flow rate.
6). The mixed gas passes through the three measurement cells in sequence, and the concentration of each gas is detected by an electric signal by the TCD detector. The electric signal is processed by the signal processing means and output as a count value count. Further, a TCD detector will be described. The measuring cell of the TCD detector has a filament. Helium is a gas with good thermal conductivity. However, when other gases are mixed as impurities, the thermal conductivity is lowered, the temperature of the cell filament is increased, and the resistance value is increased. The magnitude of the resistance value is output to the recorder as a count value count.
7). The mixed gas first passes through the absorption tube filled with the H2O absorbent, and H2O is removed. The difference in resistance value between the measurement cells before and after that is converted into a count value count by the method already described.
8). Next, the remaining gas mixture passes through an absorption tube filled with a CO2 absorbent, and CO2 is removed. The difference between the resistance values before and after is converted into the count value count in the same manner.
9. Finally, the difference between the resistance value of the remaining gas N2 and the resistance value of helium is converted into the count value count in the same manner.
10. The atmospheric pressure correction on the measurement day is performed for the above count value count. This is to perform atmospheric pressure correction by the mole fraction of gas in the detector.
11. The sensitivity coefficient (μg / count) for each CHN element is determined using a standard sample for elemental analysis whose CHN content (w / w%) is known in advance. This is also called a factor. The CHN content (w / w%) of the unknown sample compound is calculated using the determined sensitivity coefficient (μg / count) or factor. Hereinafter, in the present invention, the sensitivity coefficient is expressed as a factor.
12 Elemental analysis values are displayed as C: □%, H: □%, N: □%.
次に上記測定における演算処理方法について説明する。
はじめに、元素分析用標準試料を用いて、分析装置のファクターSH、SC、SN（μg／count）を以下にして求める。同じ標準試料で通常４回程度測定し、その平均値を用いる。または標準試料の各量を測定してｙ＝aXまたはy＝aX＋ｂの検量線式を用いる。
ここではファクターの計算方法を説明する。
YH：水素の計数値count、 YC：炭素の計数値count、 YN：窒素の計数値countとする。元素分析標準試料の重さWμg、含有％をC、H、N％とするとファクター SH、SC SNは各成分重量μgと装置計数値countから以下に示す関係式より求められる。
SH： W×H（％）/100＝H（μｇ）＝ FactorH×YH
SC： W×C（％）/100＝C（μｇ）＝ FactorC×YC
SN： W×N（％）/100＝N（μｇ）＝ FactorN×YN
ただし、上述のように装置の原理より計数値YH 、YC 、YNの気圧補正が必要であるが、次の項で説明する。
Next, an arithmetic processing method in the measurement will be described.
First, using the standard sample for elemental analysis, the factors S H , S C , and S N (μg / count) of the analyzer are determined as follows. Measure about 4 times with the same standard sample and use the average value. Alternatively, each amount of the standard sample is measured, and a calibration curve formula of y = aX or y = aX + b is used.
Here, a method for calculating the factor will be described.
Y H : hydrogen count value, Y C : carbon count value, Y N : nitrogen count value. Assuming that the weight of the elemental analysis standard sample is W μg and the content% is C, H, and N%, the factors S H and S C S N can be obtained from the respective component weights μg and the device count value count by the following relational expression.
S H : W × H (%) / 100 = H (μg) = Factor H × Y H
S C : W × C (%) / 100 = C (μg) = Factor C × Y C
S N : W × N (%) / 100 = N (μg) = Factor N × Y N
However, as described above, the atmospheric pressure correction of the count values Y H , Y C , and Y N is necessary based on the principle of the apparatus, which will be described in the next section.
気圧補正について、C、H、N各測定セルでは体積あたりの気体分子数は測定時の気圧により変化するため以下のように補正される。補正された計数値とファクターSH 、SC 、SNと成分含有量との関係式を数１の3式のように示す。
FH＝1.005＋Cμｇ×10-5 （７）
FC＝1.000176−（Cμｇ×9.968×10-5−Nμｇ×6.934×10-6）
（８）
FN＝0.99977−（Hμｇ×10-４×Cμｇ×1.642×10-5）
（９）
Regarding the atmospheric pressure correction, the number of gas molecules per volume in each of the C, H, and N measurement cells varies depending on the atmospheric pressure at the time of measurement, and is corrected as follows. A relational expression between the corrected count value, the factors S H , S C , S N and the component content is shown as the following three formulas.
F H = 1.005 + Cμg × 10 -5 (7)
F C = 1.000176− ( C μg × 9.968 × 10 −5 −N μg × 6.934 × 10 −6 )
(8)
F N = 0.99977− (H μg × 10 −4 × C μg × 1.642 × 10 −5 )
(9)
しかしながら、有機元素分析測定は天びんと元素分析装置によって行われる分析方法であり、試料を正確に測りとることと標準試料を用いて検量線を作成することが求められるため、作業場の空調管理や秤量技術の熟練と毎回の作業工程が困難であり、普及が限られている。 However, organic elemental analysis is an analytical method performed by a balance and an elemental analyzer, and it is required to accurately measure the sample and create a calibration curve using the standard sample. Technical skill and every work process are difficult, and the spread is limited.
同じく、測定物の成分含有w/w％を求めるという原理に基づいているために、産業界で利用しているような炭素、水素、窒素各元素の成分ひを求めたい場合にも炭素、水素、窒素の含有重量％を計算してからその比を出すという不合理な面があった。 Similarly, since it is based on the principle of obtaining the component content w / w% of the measured object, carbon, hydrogen, and nitrogen can be obtained when it is desired to obtain the components of carbon, hydrogen, and nitrogen elements used in the industry. There was an unreasonable aspect of calculating the nitrogen content weight% and then calculating the ratio.
さらに有機元素分析装置は高温炉をもち室温の上昇が大きいので、検量線作成と試料の測定とを同じ環境条件でしなければならないために常時エアコンによる測定環境の調整が必要であった。 Furthermore, since the organic element analyzer has a high temperature furnace and a large increase in room temperature, the calibration environment and the measurement of the sample must be performed under the same environmental conditions. Therefore, it is necessary to constantly adjust the measurement environment using an air conditioner.
本発明は有機元素分析測定における上記記述の不合理を解決し、元素分析測定の現状の目的にあう簡素なシステムを構成し、産業界への普及を目的としている。 The present invention solves the above-mentioned unreasonableness in organic elemental analysis measurement, constitutes a simple system that meets the current purpose of elemental analysis measurement, and aims to spread it to the industry.
さらに本発明は、秤量工程中や分析計動作中の装置出力信号安定化のための精密な環境管理（室温、湿度）から開放されることと作業時間の短縮で不必要な電気エネルギーの損失を抑え炭酸ガス排出軽減効果をえることを目的としている。 Furthermore, the present invention eliminates unnecessary electrical energy loss by eliminating the need for precise environmental management (room temperature, humidity) to stabilize the device output signal during the weighing process and during analyzer operation, and shortening the work time. The purpose is to suppress carbon dioxide emissions and to reduce the emission.
上記目的を解決する本発明の有機元素分析方法は、燃焼した測定物に含有された炭素、水素、および窒素の中から選んだ所定の第１の元素の含有量を表す値を出力するとともに、該測定物に含有された炭素、水素、および窒素の中から選んだ、該第１の元素とは異なる所定の第２の元素の含有量を表す値を出力する分析装置を用いた有機元素分析測定方法において
前記第１の元素の含有量と第２の元素の含有量との比が既知の第１標準物質における該第１の元素の既知の含有量と第２の元素の既知の含有量との比に対応する関係を求めるファクター導出ステップと、
前記分析装置から出力される、燃焼した測定物における前記第１の元素の含有量を表す第１計測測定値および前記第２の元素の含有量を表す第２計測測定値を求める測定値計測ステップと、
第１計測測定値を分母とし前記第２計測測定値を分子とした比率を算出する比率算出ステップと、
前記比率算出ステップで算出した比率を前記ファクター導出ステップで求めたファクターに基づいて換算する換算ステップと、
前記換算ステップで算出した比率に大気圧補正を行うステップとを有することを特徴とする。
The organic element analysis method of the present invention that solves the above object outputs a value representing the content of a predetermined first element selected from carbon, hydrogen, and nitrogen contained in a combusted measurement object, Organic elemental analysis using an analyzer that outputs a value representing the content of a predetermined second element different from the first element, selected from carbon, hydrogen, and nitrogen contained in the measurement object In the measurement method, the known content of the first element and the known content of the second element in the first standard substance whose ratio between the content of the first element and the content of the second element is known. A factor derivation step for obtaining a relationship corresponding to the ratio of
A measurement value measurement step for obtaining a first measurement measurement value representing the content of the first element in the burned measurement object and a second measurement measurement value representing the content of the second element outputted from the analyzer When,
A ratio calculating step for calculating a ratio using the first measurement measurement value as a denominator and the second measurement measurement value as a numerator;
A conversion step for converting the ratio calculated in the ratio calculation step based on the factor obtained in the factor derivation step;
And a step of performing atmospheric pressure correction on the ratio calculated in the conversion step.
なお、上記第1標準物質と上記第2標準物質は同じもの、即ち、上記ファクター導出ステップでは、前記第1の元素及び前記第2の元素それぞれの含有量が既知の標準物質を用いてよい。 The first standard substance and the second standard substance are the same, that is, in the factor deriving step, a standard substance in which the contents of the first element and the second element are known may be used.
また、本発明の有機元素分析測定方法において、
前記分析装置から出力される、前記第１の元素の含有量および第２の元素の含有量それぞれが理論値として既に求められている燃焼したサンプルにおける前記第１の元素の含有量を表す第１理論測定値および前記第２の元素の含有量を表す第２理論測定値を求める理論出力値計測ステップと、
前記第１理論測定値から所定の許容誤差を引いた値を分母とし前記第２理論測定値から該許容誤差を加えた値を分子とした最大値と、該第１理論測定値から該許容誤差を加えた値を分母とし該第２理論測定値から所定の許容誤差を引いた値を分子とした最小値との間に前記換算ステップおよび大気圧補正ステップで補正した比率が属するか否かを判定する判定ステップとを有することが好ましい。
Further, in the organic element analysis measurement method of the present invention,
The first element representing the content of the first element in the burned sample in which the content of the first element and the content of the second element, which are output from the analysis device, are already determined as theoretical values, respectively. A theoretical output value measurement step for obtaining a theoretical measurement value and a second theoretical measurement value representing the content of the second element;
A maximum value with a value obtained by subtracting a predetermined allowable error from the first theoretical measurement value as a denominator and a value obtained by adding the allowable error from the second theoretical measurement value, and the allowable error from the first theoretical measurement value. Whether or not the ratio corrected in the conversion step and the atmospheric pressure correction step belongs to the minimum value with the value obtained by subtracting a predetermined tolerance from the second theoretical measurement value as the denominator And a determination step for determining.
上記目的を解決する本発明の有機元素分析測定システムは、
燃焼した測定物に含有された炭素、水素、窒素の中から選んだ所定の第１の元素の含有量をあらわす値を出力するとともに、該測定物に含有された炭素、水素、及び窒素の中から選んだ、該第１の元素とは異なる所定の第２の元素の含有量をあらわす値を出力する分析装置を有する有機元素分析測定システムにおいて、
前記第１の元素の含有量と第２の元素の含有量との比が既知の第１標準物質における該第１の元素の既知の含有量と第２標準物質における該第２元素の既知の含有量を表す値との比に対応する関係を求めるファクター導出手段を有し、
前記分析装置は、燃焼した測定物における前記第１の元素の含有量を表す第１計測測定値および前記第２の元素の含有量を表す第２計測測定値を出力するものであり、
さらにこの有機元素分析測定システムが、
前記、第１計測測定値を分母とし前記第２計測測定値を分子とした比率を算出する比率算出手段と、
前記比率算出ステップで算出した比率を、前記ファクター導出ステップで求めたファクターに基づいて換算する換算手段と、
前記換算ステップで算出した値に大気圧補正を行う手段とを有することを特徴とする。
The organic element analysis measurement system of the present invention that solves the above-mentioned object is
A value representing the content of the predetermined first element selected from the carbon, hydrogen, and nitrogen contained in the burned measurement object is output, and the carbon, hydrogen, and nitrogen contained in the measurement object are output. In the organic element analysis measurement system having an analyzer that outputs a value representing the content of the predetermined second element different from the first element selected from
The known content of the first element in the first reference material having a known ratio of the content of the first element and the content of the second element and the known content of the second element in the second standard material A factor deriving means for obtaining a relationship corresponding to a ratio with a value representing content;
The analyzer outputs a first measurement measurement value representing the content of the first element and a second measurement measurement value representing the content of the second element in the burned measurement object,
Furthermore, this organic element analysis measurement system
A ratio calculating means for calculating a ratio using the first measurement measurement value as a denominator and the second measurement measurement value as a numerator;
Conversion means for converting the ratio calculated in the ratio calculation step based on the factor obtained in the factor derivation step;
And means for performing atmospheric pressure correction on the value calculated in the conversion step.
なお、上記第1標準物質と上記第2標準物質は同じもの、即ち、上記ファクター導出手段は、前記第1の元素及び前記第2の元素それぞれの含有量が既知の標準物質を用いる手段であっても良い。 The first standard substance and the second standard substance are the same, that is, the factor deriving means is a means using a standard substance whose contents of the first element and the second element are known. May be.
また、本発明の有機元素分析測定システムにおいて、前記分析装置は、前記第１の元素の含有量および第２の元素の含有量それぞれが理論値として既に求められている燃焼したサンプルにおける前記第１の元素の含有量を表す第１理論測定値および前記第２の元素の含有量を表す第２理論測定値を出力するものであり、
さらにこの有機元素分析測定システムが、
前記第１理論測定値から所定の許容誤差を引いた値を分母とし前記第２理論測定値から該許容誤差を加えた値を分子とした最大値と、該第１理論測定値から該許容誤差を加えた値を分母とし該第２理論測定値から所定の許容誤差を引いた値を分子とした最小値との間に前記換算ステップおよび大気圧補正ステップで補正した比率が属するか否かを判定する判定手段とを有することが好ましい。
Further, in the organic element analysis measurement system according to the present invention, the analyzer includes the first element in the burned sample in which the content of the first element and the content of the second element are already obtained as theoretical values. Outputting a first theoretical measurement value representing the content of the element and a second theoretical measurement value representing the content of the second element,
Furthermore, this organic element analysis measurement system
A maximum value with a value obtained by subtracting a predetermined allowable error from the first theoretical measurement value as a denominator and a value obtained by adding the allowable error from the second theoretical measurement value, and the allowable error from the first theoretical measurement value. Whether or not the ratio corrected in the conversion step and the atmospheric pressure correction step belongs to the minimum value with the value obtained by subtracting a predetermined tolerance from the second theoretical measurement value as the denominator It is preferable to have determination means for determining.
有機元素分析は重さを基準にその測定物の含有する炭素、水素、窒素の各成分の含有率w/w％を求め組成比から分子式を導くための手段であったため、近年利用の仕方が多様化しているにもかかわらず専門技術者による秤量は必然であったが、本発明では秤量を行わないで合理的に成分比を求めることができ、誰にでも使える機器として再開発することができる。 Organic elemental analysis has been used in recent years because it is a means to derive the molecular formula from the composition ratio by determining the content w / w% of each component of carbon, hydrogen, and nitrogen contained in the measurement object based on weight. Despite diversification, weighing by professional engineers was inevitable, but in the present invention, the component ratio can be obtained reasonably without weighing, and it can be redeveloped as a device that can be used by anyone. it can.
本発明の効果は測定を成分単位ではなく成分比を用いて行い、新しい発想である成分比のファクターを利用することによるものである。 The effect of the present invention is due to the fact that the measurement is performed using the component ratio instead of the component unit and the factor of the component ratio, which is a new idea, is used.
上述したように本発明により検量線の作成又は複数個のファクターを求めることなく純度の確認をすることができるため測定作業工程を大きく改善し、迅速な計測を実現するものである。 As described above, according to the present invention, it is possible to confirm the purity without preparing a calibration curve or obtaining a plurality of factors, so that the measurement work process is greatly improved and rapid measurement is realized.
また、本発明は分析作業工程の軽減と作業時間中を通して厳密に空調設備による調整を必要としないため電気エネルギーの損失をおさえることができる。 In addition, the present invention can reduce the loss of electrical energy because the analysis work process is reduced and the adjustment by the air conditioning equipment is not strictly required throughout the work time.
また秤量を関せず、装置の高性能な検出能力を直接利用できるためこれまで秤量誤差の大きい検量域でも目的を達成でき、燃焼により回収できない測定物の損失を少なくする効果がある。 Moreover, since the high-performance detection capability of the apparatus can be directly used regardless of the weighing, the object can be achieved even in the calibration range where the weighing error has been large so far, and there is an effect of reducing the loss of the measurement object that cannot be recovered by combustion.
また、本発明によれば、土壌や堆肥その他の産業界で必要とするＣ／Ｎ比の測定や医薬品やその他の品質管理などに測定物を量ることなく、利用できる利点がありこの方面の普及拡大も図れる。 In addition, according to the present invention, there is an advantage that it can be used without measuring a measurement object for measurement of C / N ratio required for the industry such as soil, compost, and other pharmaceuticals, and other quality control. It can also be spread and expanded.
さらに本発明によれば、重さの計れない不安定な化合物の純度のチェックもでき、その結果正しい分子式の確認もできる利点がある。近年医薬品製造のための有機化合物の合成において極微量で純度を調べる意義はきわめて大きくNMR,HRMSなどの他機器では代用できない重要な役割を持つ元素分析の利用の向上により医薬業界にはきわめて重要な発明効果を与えることになる。 Furthermore, according to the present invention, it is possible to check the purity of an unstable compound which cannot be weighed, and as a result, there is an advantage that a correct molecular formula can be confirmed. In recent years, the significance of purifying purity in the synthesis of organic compounds for the manufacture of pharmaceuticals is extremely significant, and it is extremely important for the pharmaceutical industry by improving the use of elemental analysis that has an important role that cannot be substituted by other instruments such as NMR and HRMS The invention effect will be given.
本発明はすべての計算を成分ではなく成分比を用いて行うことを特徴とする。
上述した数２の（４）〜（６）の式は成分比にすると以下のように重さWの項が消えることを利用する。
以下本発明の実施の形態を図１−図４に基づいて説明する。
The present invention is characterized in that all calculations are performed using component ratios rather than components.
The formulas (4) to (6) in the
Embodiments of the present invention will be described below with reference to FIGS.
本発明のシステムにおける、ファクター導出手段、比率算出手段、換算手段、大気圧補正手段、および判定手段はパーソナルコンピューター（PC）によって行われるもの、すなわち、有機元素分析測定アプリケーションソフトがインストールされたPCにおいて、当該ソフトに従ってファクター導出処理、比率算出処理、ファクター換算処理、大気圧補正処理それぞれを実行するCPUがこれら各手段に相当する。 In the system of the present invention, the factor deriving means, the ratio calculating means, the converting means, the atmospheric pressure correcting means, and the judging means are performed by a personal computer (PC), that is, in the PC on which the organic element analysis measurement application software is installed. The CPU that executes the factor derivation process, the ratio calculation process, the factor conversion process, and the atmospheric pressure correction process according to the software corresponds to each of these means.
本発明における元素分析装置１４はＰＣ１３（パーソナルコンピューター、以下PCと省略する。）に接続されている。元素分析装置の原理図は従来法と同じ図１に示す。上述分析装置の情報処理装置はＰＣ１３である。また、情報処理装置は有機元素分析装置内の一部の機器であってもよい。
The
図２は、本発明を実行する情報処理装置のハードウェア構成図であり、有機元素分析装置１４とＰＣ１３はＩ／ＯバスＡ、Ｂを経由して各機能部がデータを授受する。１５，１６はＲＡＭであり、ＰＣのＯＳ等制御系のプログラム等を格納する。１７，１８はＣＰＵであり、情報処理Ａ，Ｂを実行するメモリであり、結果をプリンター１９へ出力する。
FIG. 2 is a hardware configuration diagram of an information processing apparatus that implements the present invention. In the
本発明の理論値入力部と情報処理部Ａはプログラムを含む処理機能であり、ＰＣで作動する。また、装置出力信号は装置格納部からＰＣの制御機構内に転送され、情報処理部Ｂにて処理される。当該ＰＣの手入力による情報処理部Ａと交流して情報処理部Bにより合否の判断処理を行う。 The theoretical value input unit and the information processing unit A of the present invention are processing functions including a program and operate on a PC. The device output signal is transferred from the device storage unit to the control mechanism of the PC and processed by the information processing unit B. The information processing unit B performs pass / fail judgment processing by interacting with the information processing unit A manually input by the PC.
ＰＣ１３のキーボード１より測定化合物の推定理論値を入力し情報がＲＡＭ１５に記憶される。次に情報処理Ａにより後述の方法で誤差を処理する。一方、分析装置よりの出力信号強度即ち計数値（count）はＲＡＭ１６に記憶される。情報処理部Ａよりの情報に基づいて情報処理部Ｂは情報処理する。純度の判定はC／N、C／H、N／Hと順次誤差処理情報に基づいて判別され、ＮＯであれば“許容誤差範囲外“と出力され、プリンター８で印字される。ＹＥＳの場合は次に進み最終は”許容誤差範囲内“と出力され、プリンター８に印字される。このようにして純度が認証され判定されたことになる。
The estimated theoretical value of the measured compound is input from the keyboard 1 of the
本発明では 標準試料で１回C、H、N質量構成比C／N％、C／H％、N／H％と装置信号からの計数値C/Ncount、C/Hcount、N/Hcountとの相関から求めたファクターを用いて、以後はすべての分析は装置出力信号からの計数値C／Ncount、C／Hcount、H／Ncountをそのファクターで演算することにより通常の測定によって得られる質量％比、C／N％、C／H％、N／H％と同じ意味を持つ数値が得られる。理論値入力ステップはファクター算出ステップの前に行ってもよくこのステップを行うタイミングは限定されない。 In the present invention, C, H, and N mass composition ratio C / N%, C / H%, N / H% and the count values C / Ncount, C / Hcount, and N / Hcount from the instrument signal once in the standard sample. Using the factor obtained from the correlation, all analyzes are performed in the following steps, and the mass% ratio obtained by normal measurement by calculating the count values C / Ncount, C / Hcount, and H / Ncount from the device output signal. , C / N%, C / H%, and N / H% have the same meaning. The theoretical value input step may be performed before the factor calculation step, and the timing of performing this step is not limited.
本発明による計数値countの各成分比によるファクターを求めるには有機微量分析標準試料の各成分の理論値w／w％の比とその装置出力信号強度即ち計数値countの比から以下に示す式により求める。
検出感度（μ／count）
FactorC／N （成分比換算係数） 理論値C／N(％)＝FactorC／N×C／N(count)
FactorC／H （成分比換算係数） 理論値C／H(％)＝FactorC／H×C／H(count)
FactorH／N （成分比換算係数） 理論値H／N(％)＝FactorH／N×H／N(count)
The factor according to the ratio of each component of the count value count according to the present invention is obtained from the ratio of the theoretical value w / w% of each component of the organic microanalysis standard sample and the ratio of the device output signal intensity, that is, the count value count. Ask for.
Detection sensitivity (μ / count)
Factor C / N (component ratio conversion factor) Theoretical value C / N (%) = Factor C / N x C / N (count)
Factor C / H (component ratio conversion factor) Theoretical value C / H (%) = Factor C / H x C / H (count)
Factor H / N (component ratio conversion factor) Theoretical value H / N (%) = Factor H / N x H / N (count)
本発明ではすべての情報処理を有機元素分析装置内の一部の機器に任せても良い。 In the present invention, all information processing may be left to some devices in the organic element analyzer.
本発明は、有機化合物の純度を所定の誤差で確認するために、試料をはかり取ることなく分析し、装置の出力信号を用いて情報処理装置に任せる点に特徴がある。この場合、利用する情報処理装置にあらかじめ被測定有機化合物の推定理論値より所定の誤差％に外れた場合の測定の幅をシミュレーションし、其の値から求めたC／N値、C／H値、N／H値の各誤差幅を情報処理して測定値と比較する必要がある。本発明では其の対比を当該情報処理装置によりチェックすることにより認証するものである。 The present invention is characterized in that in order to confirm the purity of an organic compound with a predetermined error, a sample is analyzed without weighing and left to an information processing device using an output signal of the device. In this case, the information processing device to be used simulates the width of measurement when it deviates by a predetermined error% from the estimated theoretical value of the organic compound to be measured in advance, and the C / N value and C / H value obtained from that value are simulated. Therefore, it is necessary to process each error width of the N / H value and compare it with the measured value. In this invention, it authenticates by checking the contrast with the said information processing apparatus.
即ち、有機化合物の純度が低く分析値が其の推定理論値と
所定の誤差％以上外れるような化合物の場合、当該情報処理装置により“許容誤差範囲外”と判定される。同様に、純度が 所定の誤差％内に確定される化合物については当該情報処理装置により“許容誤差範囲内”と判定される。分析利用者は測定値を理論値と対比して其の差を計算し純度の判定をする代わりに自動的に前述の判定を与えられることになる。
That is, when the purity of the organic compound is low and the analytical value deviates from the estimated theoretical value by a predetermined error% or more, the information processing apparatus determines that the compound is “outside the allowable error range”. Similarly, a compound whose purity is determined within a predetermined error% is determined to be “within an allowable error range” by the information processing apparatus. The analysis user is automatically given the above-mentioned determination instead of calculating the difference between the measured value and the theoretical value and determining the purity.
さらに、装置出力信号比より装置固有のファクターを用いてＣ／Ｎ値が求められる。特にはかりにくい医薬品や天秤上安定しない医薬品は、従来法に比較してより信頼のある純度の確認の判定ができる。秤量から開放されれば利用者は測定環境管理することなく、分析作業が従来法にくらべてはるかに容易になる。 Further, the C / N value is obtained from the device output signal ratio using a factor specific to the device. Especially for drugs that are difficult to measure and drugs that are not stable on the balance, it is possible to make a more reliable determination of purity confirmation compared to the conventional method. When free from weighing, the user can perform analysis work much easier than the conventional method without managing the measurement environment.
上述の所定の誤差というのは元素分析装置の実測精度で置き換えて判断する方が合理的である場合について述べたものであり、従来の許容誤差０．３％とどちらも発明の方法で実施できる。 The above-mentioned predetermined error is a case where it is more reasonable to replace the judgment with the actual measurement accuracy of the elemental analyzer, and the conventional allowable error of 0.3% can be implemented by the method of the invention. .
図３は、本発明における上記情報処理の工程を説明するフローチャートである。有機元素分析装置からの出力信号と手入力した試料の情報をパソコンが記憶、誤差判定アプリケーションによって判断した結果の”許容誤差範囲内“または”許容誤差範囲外”を提供するフローチャートである。以下、その処理の流れを図３に沿って説明する。情報処理部Ａは理論値を入力し、その許容誤差範囲の限界数値を演算する。その演算方法を以下に示す。 FIG. 3 is a flowchart for explaining the information processing steps in the present invention. 7 is a flowchart for providing “within allowable error range” or “outside of allowable error range” as a result of a personal computer storing an output signal from an organic element analyzer and manually input sample information and judging by an error determination application. The processing flow will be described below with reference to FIG. The information processing unit A inputs a theoretical value and calculates a limit value of the allowable error range. The calculation method is shown below.
許容誤差範囲の限界数値の計算法
許容誤差範囲の限界数値は±０．３％の誤差とすると
例えばC：71.09％ H：6.71％ N：10.36％の化合物の場合
C％について
最小値71.09−0.3＝70.79
最大値71.09＋0.3＝71.39である。
同様にNについては
最小値10.36−0.3＝10.06
最大値10.36＋0.3＝10.66
然るに成分比C／Nの最小値は（C-0.3）/（N＋0.3）＝70.79/10.66＝6.640
成分比C／Nの最大値は（C＋0.3）/（N―0.3）＝71.39/10.06＝7.096
つまりC／Nの限界数値は上述最小値と最大値でありこの範囲外であれば純度が許容誤差を外れると判断する。以下同様にC／N、Ｃ／H、N／Hの計算をする
Calculating the limit value of the allowable error range If the limit value of the allowable error range is ± 0.3%, for example, C: 71.09% H: 6.71% N: 10.36%
Minimum value for C% 71.09−0.3 = 70.79
The maximum value is 71.09 + 0.3 = 71.39.
Similarly, for N, the minimum value is 10.36−0.3 = 1.06
Maximum value 10.36 + 0.3 = 10.66
However, the minimum value of the component ratio C / N is (C-0.3) / (N + 0.3) = 70.79 / 10.66 = 6.640
The maximum value of the component ratio C / N is (C + 0.3) / (N-0.3) = 71.39 / 10.06 = 7.096
That is, the C / N limit values are the above-mentioned minimum and maximum values, and if it is outside this range, it is determined that the purity is out of the allowable error. Similarly, calculate C / N, C / H, and N / H.
情報処理部Ｂは分析装置よりの信号を演算し情報処理部Ａと比較しながらC／N、C／H、N／Hと順次“許容誤差範囲内”“許容誤差範囲外“の判定をしながら進む。最後の判定が”許容誤差範囲内“であれば試料は
所定の誤差％ないに元素分析が合うことを示す。”許容誤差範囲外”であれば不純物が相当数含むことを示す。以上のように本実施形態によれば試料の重さを計ることなく純度の確認や各成分比の測定値を得られるのである。以下に実験により数値的に確かめた例を示す。
The information processing unit B calculates the signal from the analyzer and compares it with the information processing unit A to determine “within the allowable error range” and “out of the allowable error range” sequentially with C / N, C / H, N / H. Go forward. If the final judgment is “within an allowable error range”, the sample indicates that the elemental analysis is suitable without a predetermined error%. “Out of tolerance” indicates that a substantial number of impurities are included. As described above, according to the present embodiment, the purity can be confirmed and the measured values of each component ratio can be obtained without measuring the weight of the sample. The following is an example that has been confirmed numerically by experiment.
従来の方法と発明の方法で測定物の純度の確認を行い両方法の判定結果を比較する
（実験）
Confirm the purity of the measured product using the conventional method and the method of the invention, and compare the judgment results of both methods (experiment)
試料12個について上述した従来方法で元素分析を行う。以下の実験試料の分子式より得られる理論値との測定誤差を分析誤差として表１に示す。
次に発明の方法で許容誤差範囲の限界数値を計算する。計算方法は図3に基づき以下に示す
以上のG,H,I,J,K,Lを以下の表に作成し、分析成分比による許容誤差内に合否判断の基準を示す。
以上の計算により成分比による許容誤差判定の基準が求められたので、つぎに測定試料の成分比を計算する。計算方法は同じく図３に基づき以下に示す。
発明の方法による成分比の測定値を表２の基準値で許容誤差範囲内であるか判定する。
表３はその判定結果と従来法による判定結果を比較したものである。
Table 3 compares the determination results with the determination results obtained by the conventional method.
次に本発明の方法を用いて各成分比を求める方法について示す。
１．測定物を適量燃焼炉に投入する
２．従来法で説明したとおりに生成する炭酸ガス、水、窒素酸化物は還元炉へ送られ、還元銅で還元されて窒素酸化物は窒素になる。
３．ヘリウムガスと３つの気体はポンプに集められ検出系へ送られる。
つぎに装置の検出系から出力された計数値（COUNT）は各成分比を演算される。
その結果に上述の標準試料によって得られた成分比のファクターを乗じた各成分比をプリンターに自動出力する。
なお、以上、本発明は通常の元素分析測定に必要な測定物をはかり取るという作業を必要としないで、成分比や純度の判定ができることを説明した。さらに産業界で行われるC／N比、C／H／N比、H／C比の測定も同様の方法で可能になることを付け加える。
Next, a method for obtaining each component ratio using the method of the present invention will be described.
1. 1. Put an appropriate amount of the sample into the combustion furnace. Carbon dioxide gas, water, and nitrogen oxides generated as described in the conventional method are sent to a reduction furnace and reduced with reduced copper to turn nitrogen oxides into nitrogen.
3. Helium gas and three gases are collected in a pump and sent to a detection system.
Next, each component ratio is calculated from the count value (COUNT) output from the detection system of the apparatus.
Each component ratio obtained by multiplying the result by the component ratio factor obtained from the standard sample is automatically output to the printer.
As described above, it has been explained that the present invention can determine the component ratio and the purity without requiring the work of measuring a measurement object necessary for normal elemental analysis measurement. Furthermore, it is added that the C / N ratio, C / H / N ratio, and H / C ratio measurement performed in the industry can be performed in the same way.
本発明の方法は医薬品やその他産業用試料の純度の判定や品質検査用として利用できる。またC/N値の測定は土壌改良や堆肥やいわゆるゴミの中の可燃分の元素組成（炭素、水素、窒素の割合い）の調査や、ごみ焼却の際の高温ガス炉の安定化と制御のために可燃分中の水素と炭素のモル比の測定、また水質浄化のための高効率なC/N比測定など環境分野の利用や食品原材料、石油、石炭、海洋浮遊物など非常に広い分野に応用できる。 The method of the present invention can be used for determining the purity of pharmaceutical products and other industrial samples and for quality inspection. In addition, C / N values are measured for soil improvement, investigation of combustible elements in compost and so-called garbage (ratio of carbon, hydrogen and nitrogen), and stabilization and control of HTGR during incineration of garbage. For measurement of hydrogen and carbon in the combustible component, and highly efficient C / N ratio measurement for water purification, use in environmental fields, food raw materials, petroleum, coal, marine suspended matter, etc. Applicable to fields.
本発明は検量線を作成する１時間ほどの手間を省き、電源消費電力を１日８時間稼動する場合約１２．５％削減できる。さらに、装置の安定のための環境調整に要する消費電力を削減し、環境負荷を大きく軽減する。特に有機元素分析装置は複数の電気炉を装備し長時間の放熱により室温が上昇するのを空冷により抑えなければならないため、本発明による合理的な測定システムは設置環境の二酸化炭素削減効果に少なからず貢献するとともに産業振興のために広く普及をはかれる効果を有する。 The present invention saves about 1 hour of creating a calibration curve, and can reduce power consumption by about 12.5% when operating for 8 hours per day. Furthermore, the power consumption required for environmental adjustment for the stability of the apparatus is reduced, and the environmental load is greatly reduced. In particular, since the organic element analyzer must be equipped with multiple electric furnaces and the room temperature rise due to long-term heat dissipation must be suppressed by air cooling, the rational measurement system according to the present invention has little effect on the reduction of carbon dioxide in the installation environment. And contributes widely to the promotion of industry.
１．試料分解炉
２．酸化炉
３．還元炉
４．燃焼管
５．試料導入棒
６．ポンプ
７．H:TCD検出器
８．C:TCD検出器
９．N:TCD検出器
１０．H２０吸収管
１１．CO２吸収管
１２．パソコンキーボード
１３．パソコン
１４．元素分析装置
１５．情報記憶装置A RAM
１６．情報記憶装置B RAM
１７．１７．情報処理装置A CPU
１８．情報処理装置B CPU
１９．プリンター
1.
16. Information storage device B RAM
17.17. Information processor A CPU
18. Information processor B CPU
19. printer
Claims (4)
前記第１の元素の含有量と第２の元素の含有量との比が既知の第１標準物質における該第１の元素の既知の含有量と第２の元素の既知の含有量との比に対応する関係を求めるファクター導出ステップと、
前記分析装置から出力される、燃焼した測定物における前記第１の元素の含有量を表す第１計測測定値および前記第２の元素の含有量を表す第２計測測定値を求める測定値計測ステップと、
第１計測測定値を分母とし前記第２計測測定値を分子とした比率を算出する比率算出ステップと、
前記比率算出ステップで算出した比率を前記ファクター導出ステップで求めたファクターに基づいて換算する換算ステップと、
前記換算ステップで算出した比率に大気圧補正を行うステップとを有することを特徴とする有機元素分析測定方法。 A value representing the content of a predetermined first element selected from the carbon, hydrogen, and nitrogen contained in the burned measurement object is output, and the carbon, hydrogen, and nitrogen contained in the measurement object are output. In the organic element analysis measurement method using an analyzer that outputs a value representing the content of a predetermined second element different from the first element selected from the above, the content of the first element and the second content A factor deriving step for obtaining a relationship corresponding to the ratio between the known content of the first element and the known content of the second element in the first reference material whose ratio to the content of the element is known;
A measurement value measurement step for obtaining a first measurement measurement value representing the content of the first element in the burned measurement object and a second measurement measurement value representing the content of the second element outputted from the analyzer When,
A ratio calculating step for calculating a ratio using the first measurement measurement value as a denominator and the second measurement measurement value as a numerator;
A conversion step for converting the ratio calculated in the ratio calculation step based on the factor obtained in the factor derivation step;
And a step of correcting atmospheric pressure to the ratio calculated in the conversion step.
前記第１理論測定値から所定の許容誤差を引いた値を分母とし前記第２理論測定値から該許容誤差を加えた値を分子とした最大値と、該第１理論測定値から該許容誤差を加えた値を分母とし該第２理論測定値から所定の許容誤差を引いた値を分子とした最小値との間に前記換算ステップおよび大気圧補正ステップで補正した比率が属するか否かを判定する判定ステップとを有することを特徴とする請求項１記載の有機元素分析測定方法。 The first element representing the content of the first element in the burned sample in which the content of the first element and the content of the second element, which are output from the analysis device, are already determined as theoretical values, respectively. A theoretical output value measurement step for obtaining a theoretical measurement value and a second theoretical measurement value representing the content of the second element;
A maximum value with a value obtained by subtracting a predetermined allowable error from the first theoretical measurement value as a denominator and a value obtained by adding the allowable error from the second theoretical measurement value, and the allowable error from the first theoretical measurement value. Whether or not the ratio corrected in the conversion step and the atmospheric pressure correction step belongs to the minimum value with the value obtained by subtracting a predetermined tolerance from the second theoretical measurement value as the denominator The organic element analysis measurement method according to claim 1, further comprising a determination step of determining.
前記第１の元素の含有量と第２の元素の含有量との比が既知の第１標準物質における該第１の元素の既知の含有量と第２標準物質における該第２元素の既知の含有量を表す値との比に対応する関係を求めるファクター導出手段を有し、
前記分析装置は、燃焼した測定物における前記第１の元素の含有量を表す第１計測測定値および前記第２の元素の含有量を表す第２計測測定値を出力するものであり、
さらにこの有機元素分析測定システムが、
前記、第１計測測定値を分母とし前記第２計測測定値を分子とした比率を算出する比率算出手段と、
前記比率算出ステップで算出した比率を、前記ファクター導出ステップで求めたファクターに基づいて換算する換算手段と、
前記換算ステップで算出した値に大気圧補正を行う手段とを有することを特徴とする有機元素分析測定システム。 A value representing the content of the predetermined first element selected from the carbon, hydrogen, and nitrogen contained in the burned measurement object is output, and the carbon, hydrogen, and nitrogen contained in the measurement object are output. In the organic element analysis measurement system having an analyzer that outputs a value representing the content of the predetermined second element different from the first element selected from
The known content of the first element in the first reference material having a known ratio of the content of the first element and the content of the second element and the known content of the second element in the second standard material A factor deriving means for obtaining a relationship corresponding to a ratio with a value representing content;
The analyzer outputs a first measurement measurement value representing the content of the first element and a second measurement measurement value representing the content of the second element in the burned measurement object,
Furthermore, this organic element analysis measurement system
A ratio calculating means for calculating a ratio using the first measurement measurement value as a denominator and the second measurement measurement value as a numerator;
Conversion means for converting the ratio calculated in the ratio calculation step based on the factor obtained in the factor derivation step;
An organic element analysis measurement system comprising: means for performing atmospheric pressure correction on the value calculated in the conversion step.
さらにこの有機元素分析測定システムが、
前記第１理論測定値から所定の許容誤差を引いた値を分母とし前記第２理論測定値から該許容誤差を加えた値を分子とした最大値と、該第１理論測定値から該許容誤差を加えた値を分母とし該第２理論測定値から所定の許容誤差を引いた値を分子とした最小値との間に前記換算ステップおよび大気圧補正ステップで補正した比率が属するか否かを判定する判定手段を有することを特徴とする請求項３記載の有機元素分析測定システム。
The analysis device includes a first theoretical measurement value representing a content of the first element in a burned sample in which each of the content of the first element and the content of the second element is already obtained as a theoretical value. And outputting a second theoretical measurement value representing the content of the second element,
Furthermore, this organic element analysis measurement system
A maximum value with a value obtained by subtracting a predetermined allowable error from the first theoretical measurement value as a denominator and a value obtained by adding the allowable error from the second theoretical measurement value, and the allowable error from the first theoretical measurement value. Whether or not the ratio corrected in the conversion step and the atmospheric pressure correction step belongs to the minimum value with the value obtained by subtracting a predetermined tolerance from the second theoretical measurement value as the denominator 4. The organic element analysis measurement system according to claim 3, further comprising determination means for determining.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010029003A JP4758510B6 (en) | 2010-02-12 | Organic elemental analysis measurement method and system |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2010029003A JP4758510B6 (en) | 2010-02-12 | Organic elemental analysis measurement method and system |
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| Publication Number | Publication Date |
|---|---|
| JP2011164020A JP2011164020A (en) | 2011-08-25 |
| JP4758510B2 JP4758510B2 (en) | 2011-08-31 |
| JP4758510B6 true JP4758510B6 (en) | 2011-10-19 |
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