JP2010105825A - Method for purifying nitrogen trifluoride containing halogen or halogen compound as impurity - Google Patents
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Abstract
Description
本発明は、ハロゲンまたはハロゲン化合物を不純物として含む三フッ化窒素の精製方法に関するものである。 The present invention relates to a method for purifying nitrogen trifluoride containing halogen or a halogen compound as an impurity.
半導体製造プロセスなどで使用されるガスは、一般的にはガスボンベなどの容器に充填された形態で供給されるが、これらの原料ガスには通常、５ ｖｏｌ．ｐｐｍ程度またはそれ以上のハロゲン化水素などが不純物として含有されている場合が多く、ガス供給配管など製造装置の腐食によるトラブルや半導体薄膜の食刻などによる不良製品発生の原因ともなっている。そのため半導体製造プロセスなどで使用されるガス中のハロゲン不純物のコンタミは非常に深刻な問題であり、上記の腐食や不良品発生防止の目的と合わせて不純物であるハロゲン化水素を低濃度になるまで除去することが望まれている。また、塩素またはフッ素などのハロゲン、フッ化塩素または三フッ化塩素などのハロゲン化合物を不純物として含む原料ガスを水と反応させるとハロゲン酸化物が発生し精製ガス中へのハロゲン酸化物のコンタミが発生するという問題がある。 A gas used in a semiconductor manufacturing process or the like is generally supplied in a form filled in a container such as a gas cylinder, but usually 5 vol. In many cases, hydrogen halide of about ppm or more is contained as an impurity, which causes troubles due to corrosion of manufacturing equipment such as gas supply pipes and defective products due to etching of semiconductor thin films. For this reason, contamination of halogen impurities in gases used in semiconductor manufacturing processes is a very serious problem, and it is necessary to reduce the concentration of hydrogen halide, which is an impurity, together with the purpose of preventing corrosion and defective products described above. It is desired to be removed. In addition, when a raw material gas containing a halogen compound such as chlorine or fluorine, or a halogen compound such as chlorine fluoride or chlorine trifluoride as an impurity is reacted with water, halogen oxide is generated, and contamination of the halogen oxide in the purified gas is caused. There is a problem that occurs.
これまで一般にガス中の不純物の除去方法としては、例えば半導体のクリーニングガスに用いられる三フッ化窒素の精製にゼオライトなどの精製薬剤を用いた方法が報告されている（非特許文献１）。 Conventionally, as a method for removing impurities in a gas, for example, a method using a purification agent such as zeolite for purification of nitrogen trifluoride used in a semiconductor cleaning gas has been reported (Non-patent Document 1).
その他、湿式の精製方法としてフッ素系化合物を含む塩化水素の精製方法に塩酸水溶液、水を用いた方法（特許文献１）、ＮＯＸを除去する方法として還元剤水溶液を用いた方法が報告されている（特許文献２）。 Other, aqueous hydrochloric acid in the purification process of the hydrogen chloride containing a fluorine-based compound as a purification method of a wet method using water (Patent Document 1), is reported a method of using a reducing agent aqueous solution as a method of removing NO X (Patent Document 2).
しかし以上の方法では非常に反応活性なハロゲンまたはハロゲン化合物の除去は困難である。
本発明の目的は、ハロゲンまたはハロゲン化合物を不純物に含んだ三フッ化窒素の精製において、ハロゲン酸化物の発生を抑えて不純物を除去できる、安価な精製方法を提供することにある。 An object of the present invention is to provide an inexpensive purification method capable of removing impurities by suppressing generation of halogen oxides in the purification of nitrogen trifluoride containing halogen or a halogen compound as an impurity.
本発明者らは、ハロゲンまたはハロゲン化合物を不純物に含んだ三フッ化窒素を水、塩基水溶液、および還元剤水溶液と反応させることで三フッ化窒素を精製できることを見出した。 The present inventors have found that nitrogen trifluoride can be purified by reacting nitrogen trifluoride containing halogen or a halogen compound as an impurity with water, an aqueous base solution, and an aqueous reducing agent solution.
すなわち本発明は、ハロゲンまたはハロゲン化合物を不純物として含む三フッ化窒素の精製方法において、該三フッ化窒素を、水と接触させる工程、塩基水溶液と接触させる工程、および還元剤水溶液と接触させる工程を有することを特徴とする三フッ化窒素の精製方法を提供するものである。さらに、該ハロゲンがフッ素または塩素、該ハロゲン化合物がフッ化塩素または三フッ化塩素であることを特徴とする上記に記載の三フッ化窒素の精製方法を提供するものである。
また、第一に水と接触させる工程、第二に塩基水溶液と接触させる工程、第三に還元剤水溶液と接触させる工程を用いることを特徴とする上記に記載の三フッ化窒素の精製方法、該還元剤水溶液として、水溶液中の標準電極電位が−０．０９２Ｖ以下である還元剤を溶解した還元剤水溶液を用いることを特徴とする上記に記載の三フッ化窒素の精製方法、または、還元剤水溶液に塩基を共存させることを特徴とする上記に記載の三フッ化窒素の精製方法を提供するものである。
That is, the present invention relates to a method for purifying nitrogen trifluoride containing halogen or a halogen compound as an impurity, the step of bringing the nitrogen trifluoride into contact with water, the step of bringing into contact with an aqueous base solution, and the step of bringing into contact with an aqueous reducing agent solution. The present invention provides a method for purifying nitrogen trifluoride characterized by comprising: Furthermore, the present invention provides the method for purifying nitrogen trifluoride as described above, wherein the halogen is fluorine or chlorine, and the halogen compound is chlorine fluoride or chlorine trifluoride.
The method for purifying nitrogen trifluoride according to the above, characterized by using a step of first contacting with water, a second contacting with an aqueous base solution, and a third contacting with an aqueous reducing agent solution, As the reducing agent aqueous solution, a reducing agent aqueous solution in which a reducing agent in which the standard electrode potential in the aqueous solution is −0.092 V or less is used, or the nitrogen trifluoride purification method or the reduction described above, The present invention provides a method for purifying nitrogen trifluoride as described above, wherein a base is allowed to coexist in the aqueous agent solution.
本発明により、ハロゲンまたはハロゲン化合物を不純物として含む三フッ化窒素を精製することが可能となる。 According to the present invention, nitrogen trifluoride containing halogen or a halogen compound as an impurity can be purified.
以下、本発明の内容を詳細に説明する。 Hereinafter, the contents of the present invention will be described in detail.
まず精製に使用する水、塩基水溶液、還元剤水溶液の三種の水溶液とそれぞれ反応させるために、水溶液と精製対象のガスとが接触可能であれば、ガス精製器、洗浄装置等の装置を、それぞれ任意の装置に使用することができる。例えば、バブラー装置、スクラバー装置等を用いることができる。また、精製対象ガスと水溶液との接触の方式については、向流接触、又は並流接触を用いることができる。しかし、気液の接触効率を考えると、向流接触の方が好ましい。 First, if the aqueous solution and the gas to be purified can be contacted with each other in order to react with water, base aqueous solution, and reducing agent aqueous solution used for purification, respectively, a gas purifier, a cleaning device, etc. Can be used for any device. For example, a bubbler device, a scrubber device or the like can be used. Moreover, countercurrent contact or cocurrent contact can be used for the contact method between the gas to be purified and the aqueous solution. However, in consideration of the gas-liquid contact efficiency, countercurrent contact is preferred.
精製による除去対象物としては、フッ素、塩素、臭素、沃素等のハロゲン、フッ化塩素、三フッ化塩素、五フッ化塩素、フッ化臭素、三フッ化臭素、五フッ化臭素、フッ化沃素、五フッ化沃素、七フッ化沃素等のハロゲン化合物が挙げられる。その中でもフッ素、塩素、フッ化塩素、三フッ化塩素に対して特に有効である。 Items to be removed by purification include halogens such as fluorine, chlorine, bromine and iodine, chlorine fluoride, chlorine trifluoride, chlorine pentafluoride, bromine fluoride, bromine trifluoride, bromine pentafluoride and iodine fluoride. And halogen compounds such as iodine pentafluoride and iodine heptafluoride. Among them, it is particularly effective for fluorine, chlorine, chlorine fluoride, and chlorine trifluoride.
さらに、精製対象のガスを接触させる順番は、特に限定されないが、水との接触および塩基水溶液との接触において発生するハロゲン酸化物の除去が可能なこと、更には精製の効率を考慮すると第三に還元剤水溶液と接触させることが好ましい。この場合、水との接触および塩基水溶液との接触の順番については、水との接触において水素化ハロゲンが発生するが、これを後の工程の還元剤水溶液との接触により除去できるため、順不同でどちらを第一に行っても効果が得られる。より好ましくは、水よりも塩基水溶液との接触の方が、塩素の除去効率が良好なこと及び水素化ハロゲンの除去が可能なため、第二に塩基水溶液と接触させる方がより好ましい。尚、本発明の工程中に、ハロゲン酸化物または水素化ハロゲンが発生するものの、ハロゲンまたはハロゲン化合物の吸収の効果のほうが大きいため、精製対象のガスを接触させる水溶液の順番によらず本発明により得られる三フッ化窒素の純度向上の効果は十分得られる。 Furthermore, the order in which the gas to be purified is brought into contact is not particularly limited, but it is possible to remove the halogen oxide generated in contact with water and in contact with the aqueous base solution, and further considering the efficiency of purification, the third order. It is preferable to contact with a reducing agent aqueous solution. In this case, with regard to the order of contact with water and contact with the aqueous base solution, halogen hydride is generated in contact with water, but since this can be removed by contact with the reducing agent aqueous solution in a later step, the order is not limited. The effect is obtained regardless of which one is performed first. More preferably, contact with an aqueous base solution is more preferable than contact with an aqueous base solution, because contact with an aqueous base solution has better chlorine removal efficiency and can remove halogen hydride. In addition, although halogen oxide or hydrogen hydride is generated during the process of the present invention, the effect of absorption of halogen or halogen compound is greater, so the present invention does not depend on the order of the aqueous solution in contact with the gas to be purified. The effect of improving the purity of the obtained nitrogen trifluoride is sufficiently obtained.
また、塩基水溶液に使用する塩基は、無機塩基で三フッ化窒素と反応しないものが好ましい。その中でも反応後に生成するフッ化物塩の溶解度を考慮するとカリウム塩が特に好ましい。塩基水溶液のｐＨについては８以上が好ましく、より好ましくは９〜１１、更に好ましくは１１超である。一定の温度下での精製効率はｐＨの上昇で向上するためである。また塩基水溶液との接触反応温度については特に指定されない。 The base used in the aqueous base solution is preferably an inorganic base that does not react with nitrogen trifluoride. Among these, potassium salt is particularly preferable in consideration of the solubility of the fluoride salt formed after the reaction. The pH of the aqueous base solution is preferably 8 or more, more preferably 9 to 11, and still more preferably 11. This is because the purification efficiency under a certain temperature is improved by increasing the pH. The contact reaction temperature with the aqueous base solution is not particularly specified.
次に還元剤水溶液に使用する還元剤は、水溶液中における標準電極電位が−０．０９２Ｖ以下で三フッ化窒素と反応しないものが好ましい。該標準電極電位が低いものほどより高い効果が得られる。例えば、化学大辞典（東京化学同人 第四版 ＩＩ−４６５）に記載されている化合物が挙げられる。その中でも亜二チオン酸カリウムが特に好ましく、その他に好ましくは亜硫酸カリウムである。より好ましくは使用する際に還元剤水溶液に塩基を共存させることが望ましい。また共存させる塩基の効果について還元後に発生する酸による還元剤の劣化を防ぐ役割があり、塩基の種類としては三フッ化窒素及び、還元剤と直接反応しないものが好ましい。その中でも反応後に生成するフッ化物塩の溶解度を考慮するとカリウム塩が特に好ましい。また、共存させる塩基と還元剤との混合比については特に限定しない。 Next, the reducing agent used in the reducing agent aqueous solution is preferably one that does not react with nitrogen trifluoride when the standard electrode potential in the aqueous solution is −0.092 V or less. The lower the standard electrode potential, the higher the effect. For example, the compounds described in the Dictionary of Chemistry (Tokyo Kagaku Dojin 4th Edition II-465) can be mentioned. Of these, potassium dithionite is particularly preferred, and potassium sulfite is particularly preferred. More preferably, a base is allowed to coexist in the reducing agent aqueous solution when used. Further, the effect of the coexisting base has a role of preventing deterioration of the reducing agent due to the acid generated after the reduction, and as the kind of base, those that do not directly react with nitrogen trifluoride and the reducing agent are preferable. Among these, potassium salt is particularly preferable in consideration of the solubility of the fluoride salt formed after the reaction. Further, the mixing ratio of the coexisting base and reducing agent is not particularly limited.
還元剤水溶液との接触反応温度については特に指定しない。還元剤が分解する温度以上では、精製能力が低下すると考えられるので、還元剤が分解する温度以下での使用が好ましい。例えば、亜二チオン酸カリウムの場合は６０℃以下での使用が望ましい。還元剤の濃度は例えば、亜二チオン酸カリウムを用いる場合で濃度下限としては０．２９ｍｏｌ／ｌ以上が好ましくそれ以下では十分な精製能力が発揮されない。また還元剤の濃度上限は、飽和溶液である１．６３ｍｏｌ／ｌにおいても十分な精製能力を発揮するため限定されない。 There is no particular specification for the temperature of the contact reaction with the reducing agent aqueous solution. Since it is considered that the purification capacity is lowered above the temperature at which the reducing agent decomposes, use at a temperature below the temperature at which the reducing agent decomposes is preferred. For example, in the case of potassium dithionite, the use at 60 ° C. or lower is desirable. The concentration of the reducing agent is, for example, when potassium dithionite is used, and the lower limit of concentration is preferably 0.29 mol / l or less, and if it is less than that, sufficient purification ability cannot be exhibited. Further, the upper limit of the concentration of the reducing agent is not limited because a sufficient purification ability is exhibited even at 1.63 mol / l which is a saturated solution.
以下、実施例により本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail by way of examples.
図１に、本実施例に用いた概略系統図を示す。ハロゲンまたはハロゲン化合物を不純物として含む精製処理対象の三フッ化窒素は、ハロゲンまたはハロゲン化合物の不純物として、塩素とフッ化塩素を含有した三フッ化窒素（実施例１）、フッ素、塩素、フッ化塩素、三フッ化塩素を含有した三フッ化窒素（実施例２、３、７、８、９、１０、１１、比較例１、２）、三フッ化塩素を含有した三フッ化窒素（実施例４）、フッ素、フッ化塩素、三フッ化塩素を含有した三フッ化窒素（実施例５）、またはフッ素を含有した三フッ化窒素（実施例６）を使用する。 FIG. 1 shows a schematic system diagram used in this embodiment. Nitrogen trifluoride to be refined containing halogen or a halogen compound as an impurity is nitrogen trifluoride (Example 1) containing chlorine and chlorine fluoride as an impurity of a halogen or a halogen compound, fluorine, chlorine, fluoride. Nitrogen trifluoride containing chlorine and chlorine trifluoride (Examples 2, 3, 7, 8, 9, 10, 11, Comparative Examples 1 and 2), nitrogen trifluoride containing chlorine trifluoride (implemented) Example 4), nitrogen, trifluoride containing fluorine, chlorine fluoride, chlorine trifluoride (Example 5) or nitrogen trifluoride containing fluorine (Example 6) is used.
湿式精製装置５、１０、１５は、充填材を充填した充填塔７、１２、１７と、導入される精製処理の対象ガスと反応させる反応液４、９、１４と、反応液４、９、１４を溜める液釜３、８、１３と、液釜３、８、１３内の反応液４、９、１４を充填材の上方に液送する液送ポンプ６、１１、１６を備えており、充填塔７、１２、１７下部より導入される精製処理の対象となるガスは、充填塔７、１２、１７内で反応液４、９、１４と向流接触し、充填塔７、１２、１７上部より放出される。 Wet purification apparatuses 5, 10, and 15 are packed towers 7, 12, and 17 filled with a filler, reaction liquids 4, 9, and 14 that are reacted with a target gas to be purified, and reaction liquids 4, 9, and Liquid tanks 3, 8, 13 for storing 14, and liquid feed pumps 6, 11, 16 for feeding the reaction liquids 4, 9, 14 in the liquid pots 3, 8, 13 above the filler, The gas to be purified introduced from the lower part of the packed towers 7, 12, 17 is in countercurrent contact with the reaction liquids 4, 9, 14 in the packed towers 7, 12, 17, and the packed towers 7, 12, 17 are in contact. Released from the top.
精製処理の対象となる三フッ化窒素が充填されたボンベ１から精製処理の対象となる三フッ化窒素を、マスフローコントローラー２にて所定の流量に制御し、湿式精製装置５に導入し、反応液４と向流接触させた後、湿式精製装置１０に導入し反応液９と向流接触させ、さらに、湿式精製装置１５に導入し反応液１４と向流接触させる。その後、湿式精製装置１５から放出されるガスを空容器１８に捕集する。 The nitrogen trifluoride subject to purification treatment is controlled from the cylinder 1 filled with nitrogen trifluoride subject to purification treatment to a predetermined flow rate by the mass flow controller 2, introduced into the wet purification apparatus 5, and reacted. After being brought into countercurrent contact with the liquid 4, it is introduced into the wet purification apparatus 10 and brought into countercurrent contact with the reaction liquid 9, and further introduced into the wet purification apparatus 15 and brought into contact with the reaction liquid 14. Thereafter, the gas released from the wet purification apparatus 15 is collected in the empty container 18.
空容器１８に捕集されたガスを赤外分光光度計（大塚電子社製 ＩＧ−１０００）、イオンクロマトグラフィー（島津製作所製）で分析し精製された三フッ化窒素の純度を測定する。 The purity of the nitrogen trifluoride which is analyzed by analyzing the gas collected in the empty container 18 with an infrared spectrophotometer (IG-1000 manufactured by Otsuka Electronics Co., Ltd.) and ion chromatography (manufactured by Shimadzu Corporation) is measured.
表１に、実施例１〜１１及び比較例１、２にて行った湿式精製装置の主な条件を記載する。 Table 1 describes the main conditions of the wet purification apparatus performed in Examples 1 to 11 and Comparative Examples 1 and 2.
［実施例１］
長さ ７５０ｃｍ、内径２５ｍｍのポリテトラフルオロエチレンライニングされたＳＵＳ３１６製の充填塔７に充填剤として２φのポリテトラフルオロエチレン製のラシヒリングを充填し、反応液４として水を用いた湿式精製装置５にフッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝０ ｖｏｌ．％：１．０ ｖｏｌ．％：２１．０ ｖｏｌ．％：０ ｖｏｌ．％：７８．０ ｖｏｌ．％に調整した混合ガスをマスフローコントローラー２にて２７４ ｍｌ／ｍｉｎで導入した。その後、湿式精製装置５から放出されるガスを長さ ７５０ｃｍ、内径５０ｍｍの塩ビ製の充填塔１２に充填剤として６ｍｍのＳＵＳ３０４製のヘリパックを充填し、反応液９として水酸化カリウム濃度が０．５ｍｏｌ／ｌ（ｐＨ＝１３）の水酸化カリウム水溶液を用いた湿式精製装置１０に導入した。その後、湿式精製装置１０から放出されるガスを長さ １５００ｃｍ、内径５０ｍｍの塩ビ製の充填塔１２に充填剤として６ｍｍのＳＵＳ３０４製のヘリパックを充填し、反応液１４として亜二チオン酸カリウムの濃度が１．５ｍｏｌ／ｌ、水酸化カリウム濃度が０．１５ｍｏｌ／ｌの水溶液を用いた湿式精製装置１５に導入した。その後、湿式精製装置１５から排出されるガスを空容器１８に捕集した。
[Example 1]
A SUS316 packed tower 7 made of SUS316 having a length of 750 cm and an inner diameter of 25 mm is filled with a 2φ polytetrafluoroethylene Raschig ring as a filler, and a wet purification apparatus 5 using water as a reaction solution 4 is used. Fluorine: Chlorine: Chlorine fluoride: Chlorine trifluoride: Nitrogen trifluoride = 0 vol. %: 1.0 vol. %: 21.0 vol. %: 0 vol. %: 78.0 vol. The mixed gas adjusted to% was introduced at 274 ml / min by the mass flow controller 2. After that, the gas released from the wet purification apparatus 5 is filled with a 6-mm SUS304 helipack as a packing material in a packed column 12 made of polyvinyl chloride having a length of 750 cm and an inner diameter of 50 mm. The solution was introduced into the wet purification apparatus 10 using a 5 mol / l (pH = 13) aqueous potassium hydroxide solution. Thereafter, the gas released from the wet purification apparatus 10 is filled with a 6 mm SUS304 helipack as a packing material in a packed column 12 made of polyvinyl chloride having a length of 1500 cm and an inner diameter of 50 mm, and the concentration of potassium dithionite as the reaction solution 14 Was introduced into the wet purification apparatus 15 using an aqueous solution having a concentration of 1.5 mol / l and a potassium hydroxide concentration of 0.15 mol / l. Thereafter, the gas discharged from the wet purification apparatus 15 was collected in the empty container 18.
空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１ 質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 The gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ion, fluoride ion, Chlorate ion and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), and infrared spectrophotometry As a result of the total analysis, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例２］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝０．５ ｖｏｌ．％：０．４ ｖｏｌ．％：１８．０ｖｏｌ．％：０．５ ｖｏｌ．％：８０．６ ｖｏｌ．％に調整した混合ガスを使用する以外は、実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 2]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 0.5 vol. %: 0.4 vol. %: 18.0 vol. %: 0.5 vol. %: 80.6 vol. The same conditions as in Example 1 were used except that a mixed gas adjusted to% was used.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。 It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
［実施例３］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝０．５ ｖｏｌ．％：０．４ ｖｏｌ．％：１８．０ｖｏｌ．％：０．５ ｖｏｌ．％：８０．６ ｖｏｌ．％に調整した混合ガスを使用し、反応液９として炭酸カリウム濃度が０．５ｍｏｌ／ｌ（ｐＨ＝９．７）の炭酸カリウム水溶液、反応液１４として、亜二チオン酸カリウム濃度が１．５ ｍｏｌ／ｌ、炭酸カリウム濃度が０．１５ ｍｏｌ／ｌの水溶液を使用し、それ以外は実施例１と同条件で行った。
[Example 3]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 0.5 vol. %: 0.4 vol. %: 18.0 vol. %: 0.5 vol. %: 80.6 vol. %, A potassium carbonate aqueous solution having a potassium carbonate concentration of 0.5 mol / l (pH = 9.7) as the reaction solution 9, and a potassium dithionite concentration of 1.5 as the reaction solution 14. An aqueous solution having a mol / l and potassium carbonate concentration of 0.15 mol / l was used, and the other conditions were the same as in Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例４］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝０ ｖｏｌ．％：０ ｖｏｌ．％：０ ｖｏｌ．％：５．７ ｖｏｌ．％：９４．３ ｖｏｌ．％に調整した混合ガスを使用し、反応液１４として、亜二チオン酸カリウムの濃度が溶解度量である１．６３ ｍｏｌ／ｌ、水酸化カリウム濃度が ０．１５ ｍｏｌ／ｌの水溶液を使用し、それ以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 4]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 0 vol. %: 0 vol. %: 0 vol. %: 5.7 vol. %: 94.3 vol. %, And the reaction solution 14 is an aqueous solution having a potassium dithionite concentration of 1.63 mol / l in terms of solubility and a potassium hydroxide concentration of 0.15 mol / l. The other conditions were the same as in Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例５］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝５．１ ｖｏｌ．％：０ ｖｏｌ．％：４．１ ｖｏｌ．％：２．５ ｖｏｌ．％：８８．３ ｖｏｌ．％に調整した混合ガスを使用し、反応液９として水酸化カリウム濃度が１．５ｍｏｌ／ｌ（ｐＨ＝１３）の水酸化カリウム水溶液、反応液１４として、亜二チオン酸カリウムの濃度が０．４５ ｍｏｌ／ｌ、水酸化カリウム濃度が ０．１５ ｍｏｌ／ｌの水溶液を使用し、それ以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 5]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 5.1 vol. %: 0 vol. %: 4.1 vol. %: 2.5 vol. %: 88.3 vol. %, A potassium hydroxide aqueous solution having a potassium hydroxide concentration of 1.5 mol / l (pH = 13) as the reaction solution 9, and a potassium dithionite concentration of 0.1 as the reaction solution 14. An aqueous solution having a concentration of 45 mol / l and a potassium hydroxide concentration of 0.15 mol / l was used, and the other conditions were the same as in Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例６］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝６．２ ｖｏｌ．％：０ ｖｏｌ．％：０ ｖｏｌ．％：０ ｖｏｌ．％：９３．８ ｖｏｌ．％に調整した混合ガスを使用し、反応液９として水酸化カリウム濃度が１．５ｍｏｌ／ｌ（ｐＨ＝１３）の水酸化カリウム水溶液、反応液１４として、亜二チオン酸カリウムの濃度が０．４５ ｍｏｌ／ｌ、水酸化カリウム濃度が０．１５ ｍｏｌ／ｌの水溶液を使用し、それ以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 6]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 6.2 vol. %: 0 vol. %: 0 vol. %: 0 vol. %: 93.8 vol. %, A potassium hydroxide aqueous solution having a potassium hydroxide concentration of 1.5 mol / l (pH = 13) as the reaction solution 9, and a potassium dithionite concentration of 0.1 as the reaction solution 14. An aqueous solution with 45 mol / l and a potassium hydroxide concentration of 0.15 mol / l was used, and the other conditions were the same as in Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例７］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％に調整した混合ガスを使用し、反応液９として水酸化カリウム濃度が１．５ｍｏｌ／ｌ（ｐＨ＝１３）の水酸化カリウム水溶液、反応液１４として、亜硫酸カリウムの濃度が１．０ ｍｏｌ／ｌ、水酸化カリウム濃度が０．１５ ｍｏｌ／ｌの水溶液を使用し、それ以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 7]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. %, A potassium hydroxide aqueous solution having a potassium hydroxide concentration of 1.5 mol / l (pH = 13) as the reaction solution 9, and a potassium sulfite concentration of 1.0 mol / l as the reaction solution 14. 1 and an aqueous solution having a potassium hydroxide concentration of 0.15 mol / l was used, and the other conditions were the same as in Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例８］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝０．５ ｖｏｌ．％：０．４ ｖｏｌ．％：１８．０ｖｏｌ．％：０．５ ｖｏｌ．％：８０．６ ｖｏｌ．％ に調整した混合ガスを使用、１．０９６ｌ／ｍｉｎ（空塔線速度 ３．７２×１０−２ｍ／ｓｅｃ）で導入する以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 8]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 0.5 vol. %: 0.4 vol. %: 18.0 vol. %: 0.5 vol. %: 80.6 vol. % Was used under the same conditions as in Example 1 except that a mixed gas adjusted to% was used and introduced at 1.096 l / min (superficial linear velocity 3.72 × 10 −2 m / sec).
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例９］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％ に調整した混合ガスを使用し、湿式精製装置５の反応液４として塩基水溶液、湿式精製装置１０の反応液９として水、湿式精製装置１５の反応液１４として還元剤水溶液を通過させる以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 9]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. %, A base aqueous solution is used as the reaction solution 4 of the wet purification device 5, water is used as the reaction solution 9 of the wet purification device 10, and a reducing agent aqueous solution is passed as the reaction solution 14 of the wet purification device 15. It carried out on the same conditions as Example 1.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［実施例１０］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％ に調整した混合ガスを使用し湿式精製装置５の反応液４として水、湿式精製装置１０の反応液９として還元剤水溶液、湿式精製装置１５の反応液１４として塩基水溶液を通過させる以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Example 10]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. %, Using water as the reaction solution 4 of the wet purification device 5, passing the reducing agent aqueous solution as the reaction solution 9 of the wet purification device 10, and passing the base aqueous solution as the reaction solution 14 of the wet purification device 15. The same conditions as in Example 1 were used.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であったが、赤外分光光度計で分析した結果、不純物としてＣｌＯ３Ｆが３６ ｖｏｌ．ｐｐｍ含まれていることを確認した。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion were below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less) However, as a result of analysis with an infrared spectrophotometer, it was confirmed that 36 vol.ppm of ClO 3 F was contained as an impurity.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９質量％まで精製出来ることを確認した。
［実施例１１］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％ に調整した混合ガスを使用し、反応液１４として、亜二チオン酸ナトリウムの濃度が溶解度量である１．６３ ｍｏｌ／ｌ、水酸化カリウム濃度が ０．１５ ｍｏｌ／ｌの水溶液を使用する以外は、実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.99% by mass.
[Example 11]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. %, And the reaction solution 14 is an aqueous solution having a sodium dithionite concentration of 1.63 mol / l in terms of solubility and a potassium hydroxide concentration of 0.15 mol / l. The conditions were the same as in Example 1 except for the above.
実施例１と同様、空容器１８に捕集したガスを、赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオン、フッ化物イオン、亜塩素酸イオン、および塩素酸イオンは、検出下限（塩化物、フッ化物イオン：１質量ｐｐｍ以下、亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であり、また、赤外分光光度計で分析した結果、三フッ化窒素の以外のピークは確認されなかった。 As in Example 1, the gas collected in the empty container 18 was analyzed by an infrared spectrophotometer (manufactured by Otsuka Electronics Co., Ltd. (IG-1000), ion chromatography. As a result of analysis by ion chromatography, chloride ions were analyzed. , Fluoride ion, chlorite ion, and chlorate ion are below the detection limit (chloride, fluoride ion: 1 mass ppm or less, chlorite, chlorate ion: 0.2 mass ppm or less), As a result of analysis with an infrared spectrophotometer, no peaks other than those of nitrogen trifluoride were confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９．９９９質量％まで精製出来ることを確認した。
［比較例１］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％ に調整した混合ガスを使用し、湿式精製装置５、１０、１５の反応液４、９、１４を全て水とする以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 99.999% by mass.
[Comparative Example 1]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. % Was used under the same conditions as in Example 1 except that all the reaction liquids 4, 9, and 14 of the wet purification apparatuses 5, 10, and 15 were water.
実施例１と同様、空容器１８に捕集したガス中の精製ガス中のハロゲン成分（塩化物イオン、フッ化物イオン、亜塩素酸イオン、塩素酸イオン）を赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクロマトグラフィーで分析した結果、塩化物イオンを１５９２０質量ｐｐｍ、フッ素イオンを８２６質量ｐｐｍ、亜塩素酸イオンを１２．７質量ｐｐｍ、塩素酸イオンを１．８質量ｐｐｍ確認し、また、赤外分光光度計で分析した結果、不純物としてＣｌＯ３Ｆが３１２８ ｖｏｌ．ｐｐｍ含まれていることを確認した。 As in Example 1, the halogen components (chloride ions, fluoride ions, chlorite ions, chlorate ions) in the purified gas in the gas collected in the empty container 18 were analyzed with an infrared spectrophotometer (Otsuka Electronics Co., Ltd.). (IG-1000), analyzed by ion chromatography As a result of analysis by ion chromatography, 15920 mass ppm of chloride ions, 826 mass ppm of fluorine ions, 12.7 mass ppm of chlorite ions, chloric acid As a result of confirming 1.8 mass ppm of ions and analyzing with an infrared spectrophotometer, it was confirmed that 3128 vol.ppm of ClO 3 F was contained as an impurity.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９５質量％まで精製出来ることを確認した。
［比較例２］
精製処理の対象となる三フッ化窒素として、フッ素：塩素：フッ化塩素：三フッ化塩素：三フッ化窒素＝２．３ ｖｏｌ．％：６．１ ｖｏｌ．％：１．５ ｖｏｌ．％：２．３ ｖｏｌ．％：８７．８ ｖｏｌ．％ に調整した混合ガスを使用し、湿式精製装置５、１０のみを通過させ、湿式精製装置１５を通過させない工程で精製し、湿式精製装置１０から排出されるガスを空容器１８に捕集する以外は実施例１と同条件で行った。
It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity could be purified to a purity of at least 95% by mass.
[Comparative Example 2]
As nitrogen trifluoride to be purified, fluorine: chlorine: chlorine fluoride: chlorine trifluoride: nitrogen trifluoride = 2.3 vol. %: 6.1 vol. %: 1.5 vol. %: 2.3 vol. %: 87.8 vol. %, Using only the wet refining devices 5 and 10 and purifying in a process not allowing the wet refining device 15 to pass through, and collecting the gas discharged from the wet refining device 10 in the empty container 18. The conditions were the same as in Example 1 except for the above.
実施例１と同様、空容器１８に捕集したガス中の精製ガス中のハロゲン成分（塩化物イオン、フッ化物イオン、亜塩素酸イオン、塩素酸イオン）を赤外分光光度計（大塚電子社製（ＩＧ−１０００）、イオンクロマトグラフィーで分析した。イオンクトマトグラフィーで分析した結果、塩化物イオンを５．３質量ｐｐｍ、フッ素イオンを６．１質量ｐｐｍ確認し、亜塩素酸イオンと塩素酸イオンについては検出下限（亜塩素酸、塩素酸イオン：０．２質量ｐｐｍ以下）以下であることを確認した。また、赤外分光光度計で分析した結果、不純物としてＣｌＯ３Ｆが２８１６ ｖｏｌ．ｐｐｍ含まれていることを確認した。 As in Example 1, the halogen components (chloride ions, fluoride ions, chlorite ions, chlorate ions) in the purified gas in the gas collected in the empty container 18 were analyzed with an infrared spectrophotometer (Otsuka Electronics Co., Ltd.). (IG-1000), analyzed by ion chromatography, and analyzed by ion chromatography, as a result, 5.3 mass ppm of chloride ions and 6.1 mass ppm of fluorine ions were confirmed, chlorite ions and chlorine It was confirmed that the acid ion was below the lower limit of detection (chlorous acid, chlorate ion: 0.2 mass ppm or less), and as a result of analysis with an infrared spectrophotometer, ClO 3 F was 2816 vol as an impurity. .Ppm was confirmed.
不純物としてハロゲンまたはハロゲン化合物を含有する三フッ化窒素を、少なくとも純度９９質量％まで精製出来ることを確認した。 It was confirmed that nitrogen trifluoride containing halogen or a halogen compound as an impurity can be purified to a purity of at least 99% by mass.
上記の分析結果を表２に示す。 The analysis results are shown in Table 2.
本発明は、三フッ化窒素の精製のほかに、例えば塩化物ガス、フッ化物ガスの製造時の精製手段として、または塩化物ガス、フッ化物ガスを使用する半導体工場や化学工場などの排出ガスの除害手段として利用可能である。 In addition to the purification of nitrogen trifluoride, the present invention, for example, as a purification means in the production of chloride gas or fluoride gas, or exhaust gas from semiconductor factories or chemical factories using chloride gas or fluoride gas. It can be used as an abatement means.
１：ボンベ
２：マスフローコントローラ
３：液釜
４：反応液
５：湿式精製装置
６：送液ポンプ
７：充填塔
８：液釜
９：反応液
１０：湿式精製装置
１１：送液ポンプ
１２：充填塔
１３：液釜
１４：反応液
１５：湿式精製装置
１６：送液ポンプ
１７：充填塔
１８：空容器
1: cylinder 2: mass flow controller 3: liquid kettle 4: reaction liquid 5: wet purification apparatus 6: liquid feed pump 7: packed tower 8: liquid kettle 9: reaction liquid 10: wet purification apparatus 11: liquid feed pump 12: filling Tower 13: Liquid kettle 14: Reaction liquid 15: Wet purification device 16: Liquid feed pump 17: Packing tower 18: Empty container
Claims (5)
The method for purifying nitrogen trifluoride according to any one of claims 1 to 4, wherein a base is allowed to coexist in the reducing agent aqueous solution.
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| PCT/JP2009/067399 WO2010050342A1 (en) | 2008-10-28 | 2009-10-06 | Method and system for purifying nitrogen trifluoride containing halogen or halogen compound as impurity |
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