JP7189730B2 - Hydrogen isotope ratio measurement method and apparatus - Google Patents

Hydrogen isotope ratio measurement method and apparatus Download PDF

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JP7189730B2
JP7189730B2 JP2018204930A JP2018204930A JP7189730B2 JP 7189730 B2 JP7189730 B2 JP 7189730B2 JP 2018204930 A JP2018204930 A JP 2018204930A JP 2018204930 A JP2018204930 A JP 2018204930A JP 7189730 B2 JP7189730 B2 JP 7189730B2
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智 高柳
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Taiyo Nippon Sanso Corp
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本発明は、水素同位体比測定方法及び装置に関し、詳しくは、重水素化化合物の水素同位体比を測定する方法及び装置に関する。 TECHNICAL FIELD The present invention relates to a method and apparatus for measuring hydrogen isotope ratios, and more particularly to a method and apparatus for measuring hydrogen isotope ratios of deuterated compounds.

様々な化合物にて重水素化した化合物の有効性が確認されている。例えばアンモニアの構成元素である水素を重水素化した重水素化アンモニアを、半導体製膜工程などに使用することで半導体製品の性能向上に寄与することが知られている（特許文献１参照。）。このため、前記重水素化アンモニアなどの重水素化化合物の品質を評価するため、重水素化化合物における水素同位体比を測定することが行われており、安定同位体比質量分析計（ＩＲＭＳ）を用いることで高精度に測定することが可能となっている。さらに、測定時の前処理として、重水素化化合物を燃焼させ、発生したガス中の水素同位体比を測定する手法が知られている（例えば、特許文献２参照。）。また、天然存在比付近の水素同位体比を高精度かつ簡便に測定できるキャビティーリングダウン分光法（ＣＲＤＳ）も知られている（例えば、非特許文献１参照。）。 The effectiveness of deuterated compounds has been confirmed in various compounds. For example, it is known that the use of deuterated ammonia, which is obtained by deuterating hydrogen, which is a constituent element of ammonia, in a semiconductor film forming process or the like contributes to improving the performance of semiconductor products (see Patent Document 1). . For this reason, in order to evaluate the quality of deuterated compounds such as deuterated ammonia, the hydrogen isotope ratio in deuterated compounds is measured, and stable isotope ratio mass spectrometer (IRMS) is used. It is possible to measure with high accuracy by using Furthermore, as a pretreatment for measurement, a method of burning a deuterated compound and measuring the hydrogen isotope ratio in the generated gas is known (see, for example, Patent Document 2). Also known is cavity ring-down spectroscopy (CRDS), which allows highly accurate and simple measurement of hydrogen isotope ratios near natural abundances (see, for example, Non-Patent Document 1).

特開平１１－８７７１２号公報JP-A-11-87712 特開２０１７－２１９４２８号公報Japanese Unexamined Patent Application Publication No. 2017-219428

Ｐｉｃａｒｒｏ社、Ｂ２２２１－ｉデーターシート、米国、２０１３年５月７日Picarro, B2221-i datasheet, USA, May 7, 2013

しかし、前記ＩＲＭＳは、高精度に水素同位体比を測定可能であるが、装置が大型かつ高価であることが課題となっている。また、従来の前処理方法は、密閉容器内にて重水素化化合物を燃焼させ、燃焼によって発生したガスを測定する方法であることから、燃焼できていない残留物があると、その後の水素同位体比測定の誤差に直結するという問題がある。残留物を確認するには、重水素化化合物及び発生ガスを測定する必要があり、一般には、測定で重水素化化合物及び発生ガスを消費するため、前処理が不十分であると判断した場合、最初の工程から、前処理及び測定をやり直す必要がある。一方、前記ＣＲＤＳは、天然存在比付近の水素同位体比を測定する仕様であり、天然存在比付近から大きく逸脱する化合物の同位体比測定には適していない。 However, although the IRMS can measure the hydrogen isotope ratio with high accuracy, the problem is that the apparatus is large and expensive. In addition, the conventional pretreatment method burns deuterated compounds in a closed container and measures the gas generated by the combustion. There is a problem that it is directly linked to an error in body ratio measurement. Confirmation of residues requires measurement of deuterated compounds and evolved gases, generally if deuterated compounds and evolved gases are consumed in the measurement and pretreatment is determined to be inadequate. , the pretreatment and measurement must be redone from the first step. On the other hand, the CRDS is designed to measure the hydrogen isotope ratio near the natural abundance ratio, and is not suitable for measuring the isotope ratio of compounds that greatly deviate from the natural abundance ratio.

そこで本発明は、天然存在比より大きく逸脱する高い重水素化率の重水素化化合物であっても、重水素化化合物における水素同位体比を安価な装置で簡便に測定できる水素同位体比測定方法及び装置を提供することを目的としている。 Therefore, the present invention is a hydrogen isotope ratio measurement that can easily measure the hydrogen isotope ratio in a deuterated compound even if it is a deuterated compound with a high deuteration rate that greatly deviates from the natural abundance ratio with an inexpensive device. It is an object to provide a method and apparatus.

上記目的を達成するため、本発明の水素同位体比測定方法は、重水素化化合物を前処理し、前処理で発生したガスの水素同位体を測定することで前記重水素化化合物における水素同位体比を測定する水素同位体比測定方法であって、前記重水素化化合物を前処理する前処理工程と、該前処理工程を行った後の残留重水素化化合物の量を測定する残留量測定工程と、重水素化化合物の残留量があらかじめ設定された量未満になったときに、前記前処理工程で発生したガス成分を測定して水素同位体比を算出するガス成分測定工程とを循環経路内で循環させながら連続して行うことを特徴としている。 In order to achieve the above object, the hydrogen isotope ratio measuring method of the present invention comprises pretreating a deuterated compound and measuring the hydrogen isotope of the gas generated by the pretreatment. A hydrogen isotope ratio measuring method for measuring a volume ratio, comprising a pretreatment step of pretreating the deuterated compound, and a residual amount for measuring the amount of the residual deuterated compound after the pretreatment step. and a gas component measuring step of measuring the gas component generated in the pretreatment step and calculating the hydrogen isotope ratio when the residual amount of the deuterated compound is less than a preset amount. It is characterized by performing continuously while circulating in the circulation path.

また、本発明の水素同位体比測定方法では、前記重水素化化合物は、窒素元素及び炭素元素の少なくともいずれか一方と、水素元素及び水素元素の同位体とからなる化合物であること、前記ガス成分測定工程は、前記前処理工程で発生した水蒸気における水素同位体比（Ｈ／Ｄ）を測定することで水素同位体比を測定することを特徴としている。 Further, in the hydrogen isotope ratio measuring method of the present invention, the deuterated compound is a compound composed of at least one of a nitrogen element and a carbon element, and a hydrogen element and an isotope of the hydrogen element, and the gas The component measurement step is characterized by measuring the hydrogen isotope ratio (H/D) in the water vapor generated in the pretreatment step.

さらに、前記ガス成分測定工程は、フーリエ変換赤外分光光度計（ＦＴＩＲ）又は非分散型赤外分光計（ＮＤＩＲ）で行うこと、前記循環経路は、該循環経路内のガスを循環させるためのダイヤフラムポンプ又はスクロールポンプを備えていることを特徴とし、前記循環経路は、該循環経路内に前記重水素化化合物を導入する導入経路を備えるとともに、該導入経路は、前記重水素化化合物に含まれる水分を除去する水分除去手段を備えていることを特徴としている。また、前記循環経路は、該循環経路内に、前記前処理工程で使用する酸素又はオゾンを添加する酸素添加手段を備えていること、前記前処理工程は、該前処理における反応を促進する光照射手段又は触媒を有していることを特徴としている。 Furthermore, the gas component measurement step is performed with a Fourier transform infrared spectrophotometer (FTIR) or a non-dispersive infrared spectrophotometer (NDIR), and the circulation path is for circulating the gas in the circulation path. characterized by comprising a diaphragm pump or a scroll pump, wherein the circulation path includes an introduction path for introducing the deuterated compound into the circulation path, and the introduction path includes a deuterated compound contained in the deuterated compound. It is characterized by comprising a moisture removing means for removing moisture that is extracted. Further, the circulation path is provided with oxygen adding means for adding oxygen or ozone used in the pretreatment step in the circulation path, and the pretreatment step includes light that accelerates the reaction in the pretreatment. It is characterized by having irradiation means or a catalyst.

本発明の水素同位体比測定装置は、重水素化化合物を前処理し、前処理で発生したガスの水素同位体を測定することで前記重水素化化合物における水素同位体比を測定する水素同位体比測定方法であって、前記重水素化化合物を前処理する前処理手段と、該前処理手段で前処理を行った後の残留重水素化化合物の量を測定するとともに、前記前処理手段での前処理で発生したガス成分を測定して水素同位体比を算出するガス成分測定手段と、ガスを循環させるガス循環手段とを有する循環経路を備えていることを特徴としている。 The hydrogen isotope ratio measuring apparatus of the present invention preprocesses a deuterated compound and measures the hydrogen isotope of the gas generated by the pretreatment, thereby measuring the hydrogen isotope ratio in the deuterated compound. A volume ratio measuring method comprising: pretreatment means for pretreating the deuterated compound; measuring the amount of the residual deuterated compound after pretreatment by the pretreatment means; and a circulation path having a gas component measuring means for measuring the gas components generated in the pretreatment and calculating the hydrogen isotope ratio, and a gas circulation means for circulating the gas.

さらに、本発明の水素同位体比測定装置は、前記重水素化化合物は、窒素元素及び炭素元素の少なくともいずれか一方と、水素元素及び水素元素の同位体とからなる化合物であることを特徴とし、前記ガス成分測定手段は、前記前処理手段での前処理で発生した水蒸気における水素同位体比（Ｈ／Ｄ）を測定することで水素同位体比を測定すること、前記ガス成分測定手段は、フーリエ変換赤外分光光度計（ＦＴＩＲ）又は非分散型赤外分光計（ＮＤＩＲ）であることを特徴としている。 Further, in the hydrogen isotope ratio measuring apparatus of the present invention, the deuterated compound is a compound composed of at least one of nitrogen element and carbon element, and hydrogen element and isotope of hydrogen element. , the gas component measuring means measures the hydrogen isotope ratio (H/D) of the water vapor generated in the pretreatment by the pretreatment means to measure the hydrogen isotope ratio, and the gas component measuring means measures , Fourier transform infrared spectrophotometer (FTIR) or non-dispersive infrared spectrometer (NDIR).

また、前記ガス循環手段は、ダイヤフラムポンプ又はスクロールポンプであること、前記循環経路は、該循環経路内に前記重水素化化合物を導入する導入経路を備えるとともに、該導入経路は、前記重水素化化合物に含まれる水分を除去する水分除去手段を備えていること、前記循環経路は、該循環経路内に、前記前処理手段で使用する酸素又はオゾンを添加する酸素添加手段を備えていること、前記前処理手段は、該前処理手段での反応を促進する光照射手段又は触媒を有していることを特徴としている。
In addition, the gas circulation means is a diaphragm pump or a scroll pump, the circulation path includes an introduction path for introducing the deuterated compound into the circulation path, and the introduction path includes the deuterated compound. comprising moisture removing means for removing moisture contained in the compound; said circulation path comprising, within said circulation path, oxygen adding means for adding oxygen or ozone used in said pretreatment means; The pretreatment means is characterized by having light irradiation means or a catalyst for promoting the reaction in the pretreatment means.

本発明によれば、重水素化化合物を循環経路で循環させながら測定を行うので、前処理及び測定を同時かつ連続的に実施できる。このため、前処理、前処理完了確認、水素同位体比測定を同時に実施可能な簡便な測定法であり、かつ比較的安価な装置にてこれを実現できる。 According to the present invention, since the measurement is performed while the deuterated compound is circulated in the circulation path, pretreatment and measurement can be performed simultaneously and continuously. Therefore, it is a simple measurement method that can simultaneously perform pretreatment, confirmation of pretreatment completion, and hydrogen isotope ratio measurement, and can be realized with a relatively inexpensive apparatus.

本発明の水素同位体比測定方法を実施可能な本発明の水素同位体比測定装置の一形態例を示す系統図である。BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a system diagram showing one embodiment of a hydrogen isotope ratio measuring apparatus of the present invention capable of implementing the hydrogen isotope ratio measuring method of the present invention.

図１は、本発明の水素同位体比測定装置の一形態例を示す系統図であって、本形態例に示す水素同位体比測定装置は、測定対象となる試料である重水素化化合物を循環させるための循環経路１１を有している。この循環経路１１は、前記重水素化化合物を前処理し、前処理で発生したガスの水素同位体を測定することで前記重水素化化合物における水素同位体比を測定するためのものであって、前記重水素化化合物を前処理する前処理手段１２と、該前処理手段１２で前処理を行った後の残留重水素化化合物及び前記前処理手段１２で発生したガス成分を測定するガス成分測定手段１３と、循環経路１１内でガスを循環させるためのガス循環手段１４とを備えている。 FIG. 1 is a system diagram showing one embodiment of the hydrogen isotope ratio measuring device of the present invention. It has a circulation path 11 for circulation. This circulation path 11 is for pretreating the deuterated compound and measuring the hydrogen isotope of the gas generated by the pretreatment to measure the hydrogen isotope ratio in the deuterated compound. , a pretreatment means 12 for pretreating the deuterated compound, and a gas component for measuring the residual deuterated compound after pretreatment by the pretreatment means 12 and the gas component generated by the pretreatment means 12. A measuring means 13 and a gas circulation means 14 for circulating gas in the circulation path 11 are provided.

さらに、循環経路１１には、該循環経路１１に測定対象となる試料ガスを、試料ガス源１５から循環経路１１内に導入するための試料ガス導入経路１６が設けられるとともに、測定済みのガスを循環経路１１からパージするためのパージガスをパージガス源１７から導入するためのパージガス導入経路１８及びパージガスの導入に伴って循環経路１１内のガスを外部に排出するための排気経路１９が設けられている。さらに、循環経路１１内を真空排気するための真空ポンプ２０を備えた真空排気経路２１が設けられている。また、試料ガス導入経路１６とパージガス導入経路１８とが合流した合流導入経路２２には、試料ガスやパージガスに含まれていて測定に悪影響を与える成分、例えば水分を除去する水分除去手段２３が設けられている。 Further, the circulation path 11 is provided with a sample gas introduction path 16 for introducing a sample gas to be measured into the circulation path 11 from a sample gas source 15 into the circulation path 11, and the measured gas is introduced into the circulation path 11. A purge gas introduction path 18 for introducing a purge gas for purging the circulation path 11 from a purge gas source 17 and an exhaust path 19 for discharging the gas in the circulation path 11 to the outside along with the introduction of the purge gas are provided. . Furthermore, an evacuation path 21 having a vacuum pump 20 for evacuating the inside of the circulation path 11 is provided. In addition, a water removing means 23 for removing components, such as water, contained in the sample gas and the purge gas that adversely affect the measurement is provided in the joint introduction path 22 where the sample gas introduction path 16 and the purge gas introduction path 18 join. It is

また、循環経路１１における前処理手段１２のガス流れ方向の上流側には、前処理を行う際に使用するガスとして、酸素又はオゾンを添加する酸素添加手段２４が設けられている。さらに、循環経路１１には、該循環経路１１内のガス量を検出するための圧力計２５が設けられている。 Further, an oxygen addition means 24 for adding oxygen or ozone as a gas used for pretreatment is provided on the upstream side in the gas flow direction of the pretreatment means 12 in the circulation path 11 . Furthermore, the circulation path 11 is provided with a pressure gauge 25 for detecting the amount of gas in the circulation path 11 .

本発明での測定対象となる前記重水素化化合物は、窒素元素及び炭素元素の少なくともいずれか一方と、水素元素及び水素元素の同位体とからなる化合物であって、例えば、ＮＨ３、Ｎ２Ｈ２、Ｎ２Ｈ４、（ＣＨ３）ＮＨ２、（ＣＨ３）２ＮＨ、ＣＨ３-ＮＨ-ＮＨ２であり、これらの化合物の水素の一部又は全部が水素の同位体である重水素（Ｄ）となっている化合物である。 The deuterated compound to be measured in the present invention is a compound composed of at least one of a nitrogen element and a carbon element , and a hydrogen element and an isotope of the hydrogen element. H 2 , N 2 H 4 , (CH 3 )NH 2 , (CH 3 ) 2 NH, CH 3 —NH—NH 2 and some or all of the hydrogens in these compounds are isotopes of hydrogen; It is a compound that is hydrogen (D).

前記ガス成分測定手段１３は、前記前処理手段１２で発生したガス成分、通常は、水蒸気における水素同位体比（Ｈ／Ｄ）を測定するもので、例えば、フーリエ変換赤外分光光度計（ＦＴＩＲ）や非分散型赤外分光計（ＮＤＩＲ）を好適に用いることができる。また、ガス成分測定手段１３では、前処理手段１２で未反応の残留重水素化化合物も同時に測定し、残留重水素化化合物が測定されなくなったときに、重水素化化合物の全量が前処理手段１２で反応したと判断する。 The gas component measuring means 13 measures the hydrogen isotope ratio (H/D) in the gas component generated by the pretreatment means 12, usually water vapor. ) and a non-dispersive infrared spectrometer (NDIR) can be preferably used. Further, the gas component measuring means 13 simultaneously measures the unreacted residual deuterated compounds in the pretreatment means 12, and when the residual deuterated compounds are no longer measured, the total amount of the deuterated compounds reaches the level of the pretreatment means. 12 is judged to have responded.

また、前記ガス循環手段１４は、前記重水素化化合物や前記前処理手段１２で発生したガス成分との反応性がない材料を使用したものが選択され、通常は、ダイヤフラムポンプやスクロールポンプを使用することが好ましい。 In addition, the gas circulation means 14 is selected from materials that are not reactive with the deuterated compound and the gas components generated in the pretreatment means 12, and usually a diaphragm pump or a scroll pump is used. preferably.

次に、前記構成の水素同位体比測定装置を使用して重水素化化合物における水素同位体比を測定する手順の一例を説明する。なお、各弁についての開閉操作、切替操作についての詳細な説明は省略する。 Next, an example of the procedure for measuring the hydrogen isotope ratio in a deuterated compound using the hydrogen isotope ratio measuring apparatus having the above configuration will be described. A detailed description of the opening/closing operation and switching operation of each valve will be omitted.

まず、第１の段階として、測定誤差の要因となる不要成分を循環経路１１から排除する。例えば、パージガス導入経路１８からパージガス、通常は窒素を導入して排気経路１９から排出する流通パージや、真空ポンプ２０によって循環経路１１のガスを吸引排気する真空パージを行う。そして、循環経路１１内に試料ガスを導入するため、循環経路１１内のガスを、例えば圧力が１００Ｐａ未満になるまで排出する。 First, as a first step, unnecessary components that cause measurement errors are eliminated from the circulation path 11 . For example, a flow purge in which a purge gas, usually nitrogen, is introduced from the purge gas introduction path 18 and discharged from the exhaust path 19, or a vacuum purge in which the gas in the circulation path 11 is sucked and exhausted by the vacuum pump 20 is performed. Then, in order to introduce the sample gas into the circulation path 11, the gas in the circulation path 11 is discharged until the pressure becomes less than 100 Pa, for example.

次に、第２段階として、循環経路１１に試料ガスを導入する。このとき、合流導入経路２２に設けた水分除去手段２３、例えば、モレキュラーシーブスなどの吸着剤やフロン冷媒などの低温を利用した水分捕集部などの水分除去手段２３により、測定誤差が発生する要因となる水分を除去し、水分除去後の試料ガスを循環経路１１に導入する。また、試料ガスの導入量は、圧力計２５によって測定する。 Next, as a second step, the sample gas is introduced into the circulation path 11 . At this time, the moisture removing means 23 provided in the confluence introduction path 22, for example, the moisture removing means 23 such as an adsorbent such as molecular sieves or a moisture collecting portion using low temperature such as Freon refrigerant is a factor that causes measurement errors. After removing the moisture, the sample gas from which moisture has been removed is introduced into the circulation path 11 . Also, the introduction amount of the sample gas is measured by the pressure gauge 25 .

第３の段階では、ガス成分測定手段１３、例えばＦＴＩＲによって試料ガスである重水素化化合物の赤外吸収スペクトルを取得する。 In the third step, the infrared absorption spectrum of the deuterated compound, which is the sample gas, is obtained by the gas component measuring means 13, such as FTIR.

第４の段階では、酸素添加手段２４から一定量の酸素を導入する。酸素又はオゾンの導入量は、試料ガスの種類や導入量などの条件に応じてあらかじめ設定しておく。 In the fourth stage, a certain amount of oxygen is introduced from the oxygen adding means 24 . The introduction amount of oxygen or ozone is set in advance according to conditions such as the type and introduction amount of the sample gas.

第５の段階で、ガス循環手段１４を起動し、循環経路１１内のガスを循環させる。同時に、前処理手段１２で重水素化化合物と酸素とを反応（酸化反応）させて重水素化化合物中の水素と酸素とによって水を生成させる（本願発明方法の前処理工程）。重水素化化合物中の他の成分は、通常、二酸化炭素や二酸化窒素になる。また、特定の波長の光を照射したり、触媒を加熱することによって酸化反応を促進させる。 At the fifth stage, the gas circulation means 14 is activated to circulate the gas in the circulation path 11 . At the same time, the deuterated compound and oxygen are reacted (oxidized) in the pretreatment means 12 to produce water from the hydrogen and oxygen in the deuterated compound (pretreatment step of the method of the present invention). Other constituents in deuterated compounds are typically carbon dioxide and nitrogen dioxide. Further, the oxidation reaction is accelerated by irradiating light of a specific wavelength or heating the catalyst.

第６の段階では、前処理手段１２での酸化反応と同時に重水素化化合物の赤外吸収スペクトルを取得し、第３の段階で取得した赤外吸収スペクトルと比較して酸化反応処理率、残留重水素化化合物の量を確認する（本願発明方法の残留量測定工程）。 In the sixth stage, the infrared absorption spectrum of the deuterated compound is acquired simultaneously with the oxidation reaction in the pretreatment means 12, and compared with the infrared absorption spectrum acquired in the third stage, the oxidation reaction treatment rate, the residual The amount of deuterated compounds is confirmed (residual amount measurement step of the method of the present invention).

重水素化化合物の残留量があらかじめ設定された量未満になった第７の段階で、第５の段階での酸化処理で発生したガスの赤外吸収スペクトルをＦＴＩＲにて連続的に取得し、発生したガス、通常は水分（水蒸気）におけるＨ／Ｄを算出し、重水素化化合物の水素同位体比を測定する（本願発明方法のガス成分測定工程）。測定終了後は、前記第１の段階に戻って次の測定に対する準備を行う。 In the seventh stage when the residual amount of the deuterated compound is less than the preset amount, the infrared absorption spectrum of the gas generated in the oxidation treatment in the fifth stage is continuously acquired by FTIR, H/D in the generated gas, usually moisture (water vapor) is calculated, and the hydrogen isotope ratio of the deuterated compound is measured (gas component measurement step of the method of the present invention). After the measurement is completed, the process returns to the first step to prepare for the next measurement.

このように、循環経路１１を使用することにより、重水素化化合物の前処理と、前処理の際に残留する重水素化化合物の測定と、前処理によって発生したガスにおけるＨ／Ｄの測定とを同時かつ連続的に実施できることから、重水素化化合物中の水素同位体の比率、すなわち、水素同位体比を容易かつ確実に測定することができる。また、簡単な装置構成で実施できることから、水素同位体比の測定を低コストで実施することができる。 Thus, by using the circulation path 11, pretreatment of the deuterated compound, measurement of the deuterated compound remaining during the pretreatment, and measurement of H/D in the gas generated by the pretreatment can be performed. can be performed simultaneously and continuously, the ratio of hydrogen isotopes in the deuterated compound, that is, the hydrogen isotope ratio can be measured easily and reliably. Moreover, since it can be performed with a simple device configuration, the hydrogen isotope ratio can be measured at low cost.

なお、各種構成要素は、同種の機器を任意に選択して使用することができ、循環経路における各機器の順番も特に限定されるものではない。 It should be noted that devices of the same type can be arbitrarily selected and used as various components, and the order of each device in the circulation route is not particularly limited.

１１…循環経路、１２…前処理手段、１３…ガス成分測定手段、１４…ガス循環手段、１５…試料ガス源、１６…試料ガス導入経路、１７…パージガス源、１８…パージガス導入経路、１９…排気経路、２０…真空ポンプ、２１…真空排気経路、２２…合流導入経路、２３…水分除去手段、２４…酸素添加手段、２５…圧力計 DESCRIPTION OF SYMBOLS 11... Circulation path, 12... Pretreatment means, 13... Gas component measuring means, 14... Gas circulation means, 15... Sample gas source, 16... Sample gas introduction path, 17... Purge gas source, 18... Purge gas introduction path, 19... Exhaust route 20 Vacuum pump 21 Evacuation route 22 Merging introduction route 23 Moisture removing means 24 Oxygen adding means 25 Pressure gauge

Claims (16)

重水素化化合物を前処理し、前処理で発生したガスの水素同位体を測定することで前記重水素化化合物における水素同位体比を測定する水素同位体比測定方法であって、前記重水素化化合物を前処理する前処理工程と、該前処理工程を行った後の残留重水素化化合物の量を測定する残留量測定工程と、重水素化化合物の残留量があらかじめ設定された量未満になったときに、前記前処理工程で発生したガス成分を測定して水素同位体比を算出するガス成分測定工程とを循環経路内で循環させながら連続して行うことを特徴とする水素同位体比測定方法。 A hydrogen isotope ratio measuring method for pretreating a deuterated compound and measuring the hydrogen isotope of the gas generated by the pretreatment to measure the hydrogen isotope ratio in the deuterated compound, wherein the deuterium a pretreatment step of pretreating the deuterated compound; a residual amount measuring step of measuring the amount of the residual deuterated compound after the pretreatment step; and a residual amount of the deuterated compound less than a preset amount. When it becomes, the gas component measurement step of measuring the gas component generated in the pretreatment step and calculating the hydrogen isotope ratio is continuously performed while circulating in the circulation path Hydrogen isotopes Body ratio measurement method. 前記重水素化化合物は、窒素元素及び炭素元素の少なくともいずれか一方と、水素元素及び水素元素の同位体とからなる化合物であることを特徴とする請求項１記載の水素同位体比測定方法。 2. The hydrogen isotope ratio measuring method according to claim 1, wherein said deuterated compound is a compound comprising at least one of nitrogen element and carbon element, hydrogen element and an isotope of hydrogen element. 前記ガス成分測定工程は、前記前処理工程で発生した水蒸気における水素同位体比（Ｈ／Ｄ）を測定することで水素同位体比を測定することを特徴とする請求項１又は２記載の水素同位体比測定方法。 3. Hydrogen according to claim 1 or 2, wherein the gas component measuring step measures the hydrogen isotope ratio (H/D) in the water vapor generated in the pretreatment step. Isotope ratio measurement method. 前記ガス成分測定工程は、フーリエ変換赤外分光光度計（ＦＴＩＲ）又は非分散型赤外分光計（ＮＤＩＲ）で行うことを特徴とする請求項１乃至３のいずれか１項記載の水素同位体比測定方法。 4. The hydrogen isotope according to any one of claims 1 to 3, wherein the gas component measurement step is performed with a Fourier transform infrared spectrophotometer (FTIR) or a non-dispersive infrared spectrometer (NDIR). Ratio measurement method. 前記循環経路は、該循環経路内のガスを循環させるためのダイヤフラムポンプ又はスクロールポンプを備えていることを特徴とする請求項１乃至４のいずれか１項記載の水素同位体比測定方法。 5. The hydrogen isotope ratio measuring method according to any one of claims 1 to 4, wherein the circulation path includes a diaphragm pump or a scroll pump for circulating gas in the circulation path. 前記循環経路は、該循環経路内に前記重水素化化合物を導入する導入経路を備えるとともに、該導入経路は、前記重水素化化合物に含まれる水分を除去する水分除去手段を備えていることを特徴とする請求項１乃至５のいずれか１項記載の水素同位体比測定方法。 The circulation path includes an introduction path for introducing the deuterated compound into the circulation path, and the introduction path includes moisture removal means for removing moisture contained in the deuterated compound. 6. The hydrogen isotope ratio measuring method according to any one of claims 1 to 5. 前記循環経路は、該循環経路内に、前記前処理工程で使用する酸素又はオゾンを添加する酸素添加手段を備えていることを特徴とする請求項１乃至６のいずれか１項記載の水素同位体比測定方法。 7. The hydrogen isotope according to any one of claims 1 to 6, wherein the circulation path is provided with oxygen adding means for adding oxygen or ozone used in the pretreatment step. Body ratio measurement method. 前記前処理工程は、該前処理における反応を促進する光照射手段又は触媒を有していることを特徴とする請求項１乃至７のいずれか１項記載の水素同位体比測定方法。 8. The hydrogen isotope ratio measuring method according to any one of claims 1 to 7, wherein the pretreatment step includes a light irradiation means or a catalyst that promotes the reaction in the pretreatment. 重水素化化合物を前処理し、前処理で発生したガスの水素同位体を測定することで前記重水素化化合物における水素同位体比を測定する水素同位体比測定方法であって、前記重水素化化合物を前処理する前処理手段と、該前処理手段で前処理を行った後の残留重水素化化合物の量を測定するとともに、前記前処理手段での前処理で発生したガス成分を測定して水素同位体比を算出するガス成分測定手段と、ガスを循環させるガス循環手段とを有する循環経路を備えていることを特徴とする水素同位体比測定装置。 A hydrogen isotope ratio measuring method for pretreating a deuterated compound and measuring the hydrogen isotope of the gas generated by the pretreatment to measure the hydrogen isotope ratio in the deuterated compound, wherein the deuterium a pretreatment means for pretreating a deuterated compound, measuring the amount of the residual deuterated compound after pretreatment by the pretreatment means, and measuring the gas component generated by the pretreatment by the pretreatment means; 1. A hydrogen isotope ratio measuring apparatus, comprising: a gas component measuring means for calculating the hydrogen isotope ratio by means of a gas component measuring means; and a gas circulation means for circulating the gas. 前記重水素化化合物は、窒素元素及び炭素元素の少なくともいずれか一方と、水素元素及び水素元素の同位体とからなる化合物であることを特徴とする請求項９記載の水素同位体比測定装置。 10. The hydrogen isotope ratio measuring apparatus according to claim 9, wherein said deuterated compound is a compound comprising at least one of nitrogen element and carbon element, hydrogen element and isotope of hydrogen element. 前記ガス成分測定手段は、前記前処理手段での前処理で発生した水蒸気における水素同
位体比（Ｈ／Ｄ）を測定することで水素同位体比を測定することを特徴とする請求項９又は１０記載の水素同位体比測定装置。 10. The gas component measuring means measures the hydrogen isotope ratio by measuring the hydrogen isotope ratio (H/D) in the water vapor generated in the pretreatment by the pretreatment means. 11. The hydrogen isotope ratio measuring device according to 10. 前記ガス成分測定手段は、フーリエ変換赤外分光光度計（ＦＴＩＲ）又は非分散型赤外分光計（ＮＤＩＲ）であることを特徴とする請求項９乃至１１のいずれか１項記載の水素同位体比測定装置。 The hydrogen isotope according to any one of claims 9 to 11, wherein the gas component measuring means is a Fourier transform infrared spectrophotometer (FTIR) or a non-dispersive infrared spectrometer (NDIR). Ratio measuring device. 前記ガス循環手段は、ダイヤフラムポンプ又はスクロールポンプであることを特徴とする請求項９乃至１２のいずれか１項記載の水素同位体比測定装置。 13. The hydrogen isotope ratio measuring apparatus according to claim 9, wherein said gas circulation means is a diaphragm pump or a scroll pump. 前記循環経路は、該循環経路内に前記重水素化化合物を導入する導入経路を備えるとともに、該導入経路は、前記重水素化化合物に含まれる水分を除去する水分除去手段を備えていることを特徴とする請求項９乃至１３のいずれか１項記載の水素同位体比測定装置。 The circulation path includes an introduction path for introducing the deuterated compound into the circulation path, and the introduction path includes moisture removal means for removing moisture contained in the deuterated compound. 14. The hydrogen isotope ratio measuring device according to any one of claims 9 to 13. 前記循環経路は、該循環経路内に、前記前処理手段で使用する酸素又はオゾンを添加する酸素添加手段を備えていることを特徴とする請求項９乃至１４のいずれか１項記載の水素同位体比測定装置。 15. The hydrogen isotope according to any one of claims 9 to 14, wherein the circulation path is provided with oxygen adding means for adding oxygen or ozone used in the pretreatment means in the circulation path. Body ratio measuring device. 前記前処理手段は、該前処理手段での反応を促進する光照射手段又は触媒を有していることを特徴とする請求項９乃至１５のいずれか１項記載の水素同位体比測定装置。 16. The hydrogen isotope ratio measuring apparatus according to any one of claims 9 to 15, wherein said pretreatment means has light irradiation means or a catalyst for promoting the reaction in said pretreatment means.
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