JP3567058B2 - Detecting agent - Google Patents
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Description
【０００１】
【発明の属する技術分野】
本発明はハロゲンガスおよび酸性ガスの検知剤に関し、さらに詳細には、窒素、水素、アルゴン、ヘリウムなどのガス中に含まれるフッ素、塩素、臭素、フッ化水素、六フッ化タングステン、四フッ化珪素、三フッ化硼素、塩化水素、四塩化珪素、三塩化硼素、フッ化塩素、三フッ化塩素等のハロゲンガスおよび酸性ガスの検知剤に関する。
【０００２】
近年、半導体工業やオプトエレクトロニクス工業の発展に伴い各種のハロゲンガスおよび酸性ガスが使用されているとともに、その使用量が増加している。
これらのハロゲンガスおよび酸性ガスはシリコン半導体や化合物半導体製造工程などにおいて、結晶性シリコン、アモルファスシリコンあるいは酸化シリコン膜の膜成長用ガス、あるいは、エッチング用ガスとして不可欠な物質である。
【０００３】
しかし、これらのガスはいずれも極めて毒性が高く、特に毒性の高い塩素やフッ素の時間加重平均許容濃度は１ｐｐｍとされている。従って、これらのガスの取り扱いに際しては絶えず作業環境の測定を行わなくてはならず、万一これらのガスが漏れた場合には的確に検知し、危害を生じないような処置を講ずる必要がある。
また、半導体製造プロセス等から排出されるガスにはこれらのハロゲンガスおよび酸性ガスが含有されているため、除害装置等を用いて浄化した後、外部に放出する際には、これらのハロゲンガスおよび酸性ガスの有無を確認する必要がある。
【０００４】
【従来の技術】
従来、ハロゲンガスの検知方法としては、▲１▼オルトトリジン法を利用したもの、▲２▼ハロゲンガスの脱色作用を利用したものなどがある。また、酸性ガスの検知方法としては、▲３▼変色成分にｐＨ指示薬を用いたもの、▲４▼酸性ガスと水からハロゲン化水素を生成させ、そのｐＨ変化を利用したものなどがある。
これらの検知方法を利用した検知剤をガラス管や容器に充填して検知管や検知器として構成し、被測定ガスと接触させて、検知剤が変色することを利用したものが多数知られている。
【０００５】
【発明が解決しようとする課題】
しかしながら、▲１▼オルトトリジン法を利用したもの、▲２▼ハロゲンガスの脱色作用を利用したもの、あるいは▲４▼酸性ガスと水からハロゲン化水素を生成させ、そのｐＨ変化を利用したものではいずれも湿式あるいは湿度の高い反応条件が必要であり、ガス中のハロゲンガスあるいは酸性ガスの検出には加湿を要すること、および応答性が遅い点などの不都合があり、乾燥条件下では実際上使用できないという問題点があった。
一方、▲３▼変色成分にｐＨ指示薬を用いたものでは、乾式法で行うことができるものの、何れもその変色の差が小さく、高感度で検出できないほか、検知成分が乾燥するとさらに感度が低下する等の不都合があった。 これらのことから、ハロゲンガスおよび酸性ガスに対して、乾燥条件下でも、高感度で検出しうるとともに、長期間にわたり安定した検出能を有する検知剤の開発が強く望まれていた。
【０００６】
【課題を解決するための手段】
本発明者らはこれらの問題点を解決し、希薄なハロゲンガスおよび酸性ガスに対しても高感度で、かつ迅速に変色する検知剤を得るべく検討を重ねた結果、変色成分として遷移金属の水酸化物とコンゴーレッドを組み合わせることにより優れた検知剤を得ることができることを見いだし、本発明を完成した。
すなわち、本発明は、遷移金属の水酸化物とコンゴーレッドを変色成分とした、ハロゲンガスおよび酸性ガスから選ばれる少なくとも一種を含有するガスの検知剤である。
【０００７】
【発明の実施の態様】
本発明の検知剤は、窒素、水素、アルゴン、およびヘリウムなどに含まれるハロゲンガスおよび酸性ガスから選ばれる少なくとも一種を含むガスの検知に適用することができる。
本発明におけるハロゲンガスとはフッ素、塩素または臭素である。また酸性ガスとは、そのもの自体酸性を有するほか、水と接触して加水分解により酸性を示すものをいい、具体的にはフッ化水素、六フッ化タングステン、四フッ化珪素、三フッ化硼素、塩化水素、四塩化珪素、三塩化硼素、フッ化塩素、三フッ化塩素などである。
【０００８】
本発明の検知剤は、遷移金属の水酸化物とｐＨ指示薬コンゴーレッドとの混合物を変色成分とした、ハロゲンガスと酸性ガスの検知剤であり、ハロゲンガスおよびフッ化塩素、三フッ化塩素など一部の酸性ガスと接触することにより柿色〜紅色から黒色に変色し、フッ化塩素、三フッ化塩素を除く他の酸性ガスと接触することにより柿色〜紅色から青色〜紺色へと鋭敏に変色する。
【０００９】
本発明において検知剤の変色成分の一成分として遷移金属の水酸化物が用いられる。遷移金属としてはニッケル（ＩＩ）、コバルト（ＩＩ）又はマンガン（ＩＩ）等が挙げられ、その水酸化物は水酸化ニッケル（Ｎｉ（ＯＨ）２ ）、水酸化コバルト（Ｃｏ（ＯＨ）２ ）、水酸化マンガン（Ｍｎ（ＯＨ）２ ）であり、これらの水酸化物の１種を用いてもよく、また２種以上を併用して用いてもよい。
水酸化ニッケル（ＩＩ）は淡緑色の結晶であり、硝酸ニッケル（ＩＩ）等の水溶液に水酸化カリウム溶液を加えることによって調製することもできるが、市販品があり、それらを用いることもできる。水酸化ニッケル（ＩＩ）に少量の水酸化ニッケル（Ｉ）および水酸化ニッケル（ＩＩＩ）を含有する場合があるが、水酸化ニッケル（ＩＩ）の色調を著しく損なうものでなければ、本発明の検知剤に用いることができる。
【００１０】
水酸化コバルト（ＩＩ）は淡青色またはバラ色の結晶であり、水酸化カリウム水溶液に硝酸コバルト（ＩＩ）溶液を加えることによって調製することができる。水酸化コバルト（ＩＩ）は空気中で比較的容易に酸化されて緑色から暗緑色に変色することから、不活性気体中で取り扱うことが好ましい。
【００１１】
水酸化マンガン（ＩＩ）は白色結晶であり、水酸化カリウム水溶液に硝酸マンガン（ＩＩ）溶液を加えることによって調製することができる。水酸化マンガン（ＩＩ）は空気中で比較的容易に酸化されて褐色に変色することから、不活性気体中で取り扱うことが好ましい。
本発明の一方の変色成分であるコンゴーレッドはｐＨ指示薬として広く用いられているものであり、市販品があることから、それを用いると好都合である。
【００１２】
本発明において、変色成分である遷移金属の水酸化物とコンゴーレッドとの混合物を粉末状のまま、またはペレット状などに成型して検知剤としてもよく、または無機担体などに担持させて検知剤とすることもできる。
遷移金属の水酸化物とコンゴーレッドとの混合物を粉末状のまま、又はペレット状などに成型して検知剤として用いる場合の混合割合は、コンゴーレットの割合が少ない場合は変色感度が得られず、また多すぎる場合は変色が不明瞭となることから重量比（水酸化物：コンゴーレッド）で通常は１：０．０１〜０．００００１、好ましくは１：０．００５〜０．０００１である。これらの混合物を通常の乾式あるいは湿式の成型方法によってペレット状、あるいは粒状などに成型して用いることができる。また成型の際に、成型を容易にするために、遷移金属の水酸化物およびコンゴーレッドに不活性な少量の滑剤、成形剤を用いることもできる。
【００１３】
変色成分である遷移金属の水酸化物とコンゴーレッドとの混合物を担体に担持させて用いることもできる。特に水酸化コバルトは安定的に取扱いにくいことから、担体に担持させて用いることが好ましい。
遷移金属の水酸化物とコンゴーレッドの混合物を無機担体に担持させる場合の担体としては、広い範囲から選択することができるが、例えばシリカゲル、シリカアルミナ、アルミナ、ジルコニア、チタニアなどの触媒担体、中でも白色ないしは無色のものが好適に使用され、これらの内でもシリカゲルが特に好ましい。シリカゲルとしては、乾燥剤用として一般に市販されているものは４５０〜８００ｍ２ ／ｇ程度の比表面積を有するものであり、これらを用いてもよいが本発明の目的をより高度に達成するためには水熱合成法などで得られる比表面積５０〜４００ｍ２ ／ｇの範囲のものが好ましい。比表面積が小さくなりすぎると変色速度が小さくなることがある。
【００１４】
担体を用いる場合の変色成分の担持方法としては、例えば変色成分を水や各種の有機溶媒などに溶解またはけん濁させた液に担体を浸漬させてもよく、もしくは担体をかき混ぜながら変色成分の溶液あるいはけん濁液を担体表面に散布して担持させてもよい。
【００１５】
無機担体に対する遷移金属の水酸化物とコンゴーレッドの担持量は重量比（無機担体：水酸化物：コンゴーレッド）で通常は１：０．１５〜０．０００１：０．１〜０．００００１、好ましくは１：０．０５〜０．００５：０．０１〜０．０００１である。
無機担体に対する遷移金属水酸化物の担持量が上記範囲よりも少ない場合は感度が得られず、また多すぎる場合、遷移金属の種類によっては（コバルトの場合）変色前後の色の変化が判別しにくくなる。
また、無機担体に対するコンゴーレッドの担持量が上記範囲よりも少ない場合には感度が得られず、また多すぎる場合には変色前後の色の変化が判別しにくくなる。
検知剤調製時における遷移金属水酸化物の酸化を防止するため、担持操作および乾燥は、窒素雰囲気中で行うことが好ましい。また、得られた検知剤は酸素との接触をさけて保存することが好ましい。
【００１６】
検知剤と接触させるガスの速度に特に制限はないが、半導体製造プロセスの装置内や排ガス処理装置内では、通常、空筒基準線速度で０．０１〜１００ｃｍ／ｓｅｃ程度とされる。ただし、これらの装置のパージの時などでは１００ｃｍ／ｓｅｃを越える線速度となる場合がある。通常、空筒基準線速度が上記範囲より低い場合は変色が遅くなり、高い場合は圧力損失が大きくなるおそれがある。
接触時のガスの温度は通常は−２０〜１００℃、また、圧力は０．００１〜２０ｋｇ／ｃｍ２ ａｂｓ程度である。
【００１７】
本発明の検知剤は固体であり、通常はガラス製の検知管や透明プラスチック製などの透明な容器またはガスの浄化筒などに設けられた透明な覗き窓部に充填して使用され、ガス中に含有されるハロゲンおよび酸性ガスの存在を検知剤の変色により知ることができる。また、本発明の検知剤を浄化剤などとともに使用する場合には浄化筒内の浄化剤の層の下流側または複数の浄化剤層の間に充填したり、検知剤を充填した検知筒を浄化筒の後ろに接続した形態などで使用される。
【００１８】
このように本発明の検知剤を用いることによって、検知剤がハロゲンガスおよびフッ化塩素、三フッ化塩素など一部の酸性ガスに接触することにより柿色〜紅色から黒色に鋭敏に変色し、検知剤がフッ化塩素、三フッ化塩素を除く他の酸性ガスに接触した場合には柿色〜紅色から青色〜紺色に鋭敏に変色することにより容易に検知することができる。
【００１９】
【実施例】
次に本発明を実施例により具体的に説明するが、本発明はこれらに限定されるものではない。
実施例１〜９
（検知剤の調製１）
粒の大きさが５〜１０ｍｅｓｈ、比表面積３２５ｍ２ ／ｇ、細孔容積０．９９ｍｌ／ｇ、充填密度０．４２０ｇ／ｍｌの粒状シリカゲル（富士シリシア化学（株）製、キャリアクト−１０）１００ｇに、硝酸コバルト６水和物５．０ｇを水１５３ｍｌに溶解した溶液を含浸させた後、１Ｎの水酸化ナトリウム水溶液５０ｍｌを加えてかき混ぜたのち、ロータリーエバポレーターで５０℃の温度で減圧乾燥させた。これにコンゴーレッド０．１ｇを水１００ｍｌに溶解した溶液を加えてかき混ぜ、再びロータリーエバポレーターで完全に減圧乾燥させて検知剤を調製した。
【００２０】
（検知能力の測定１）
この検知剤２．０ｇを内径１９ｍｍのガラス管に充填したものを多数作製し、これに１０ｐｐｍおよび１ｐｐｍの塩素、５０ｐｐｍおよび５ｐｐｍの塩化水素、１０ｐｐｍの臭素、１０ｐｐｍのフッ素、５０ｐｐｍの三塩化ほう素、５０ｐｐｍの六フッ化タングステン、１０ｐｐｍの三フッ化塩素を含有する窒素ガスをそれぞれ空筒基準線速度５．９ｃｍ／ｓｅｃで接触させ、変色し始めるまでの時間を測定した。
結果を表１に示す。
【００２１】
【表１】
実施例１０、１１
（検知剤の調製２）
実施例１と同様の粒状シリカゲル１００ｇに、硫酸ニッケル６水和物２０．０ｇを水１５３ｍｌに溶解した溶液を含浸させた後、１Ｎの水酸化ナトリウム水溶液２５０ｍｌを加えかき混ぜた。次に時々かき混ぜながら１２時間放置して反応させた後上澄みを捨て、ロータリーエバポレーターで５０℃の温度で減圧乾燥させた。これにコンゴーレッド０．０２ｇを水１００ｍｌに溶解した溶液を加え、再びロータリーエバポレーターで完全に乾燥させて検知剤を調製した。
【００２３】
（検知能力の測定２）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含有する窒素ガスをそれぞれ空筒基準線速度５．９ｃｍ／ｓｅｃで接触させ、変色し始めるまでの時間を測定した。
結果を表２に示す。
【００２４】
【表２】
実施例１２、１３
（検知剤の調製３）
実施例１と同様の粒状シリカゲル１００ｇに、硫酸マンガン４〜５水和物２０．０ｇを水１５３ｍｌに溶解した溶液を含浸させた後、１Ｎの水酸化ナトリウム水溶液２５０ｍｌを加えてかき混ぜた。次に時々かき混ぜながら１２時間放置して反応させた後上澄みを捨て、ロータリーエバポレーターで５０℃の温度で減圧乾燥させた。これにコンゴーレッド０．０２ｇを水１００ｍｌに溶解した溶液を加え、再びロータリーエバポレーターで完全に乾燥させて検知剤を調製した。
【００２６】
（検知能力の測定３）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含有する窒素ガスをそれぞれ空筒基準線速度５．９ｃｍ／ｓｅｃで通して接触させ、変色し始めるまでの時間を測定した。
結果を表３に示す。
【００２７】
【表３】
実施例１４、１５
（検知剤の調製４）
粒の大きさが８〜１６ｍｅｓｈ、比表面積２１０ｍ２ ／ｇ、細孔容積０．９９ｇ、平均細孔径１００Å、充填密度０．６８ｇ／ｍｌの活性アルミナ（水沢化学工業（株）製、Ｎｅｏｂｅａｄｓ ＧＢ８〜１６）１５０ｇ、硝酸コバルト６水和物５．０ｇを水１５３ｍｌに溶解した溶液を含浸させた後、１Ｎの水酸化ナトリウム水溶液５０ｍｌを加えてかき混ぜた。次に時々かき混ぜながら１２時間放置して反応させた後上澄みを捨て、ロータリーエバポレーターで５０℃の温度で減圧乾燥させた。これにコンゴーレッド０．１ｇを水１００ｍｌに溶解した溶液を加え、再びロータリーエバポレーターで完全に乾燥させて検知剤を調製した。
【００２９】
（検知能力の測定４）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含有する窒素ガスをそれぞれ空筒基準線速度５．９ｃｍ／ｓｅｃで通して接触させ、変色し始めるまでの時間を測定した。
結果を表４に示す。
【００３０】
【表４】
実施例１６、１７
（検知剤の調製５）
水酸化ニッケル１．５水和物１００ｇに、コンゴーレッド０．０４ｇを水２２ｇに溶かした溶液を加え、更に１Ｎの水酸化ナトリウム水溶液２ｍｌを加え、そのペーストを型に入れ、窒素ガス雰囲気下５０℃で乾燥させたのち、それを６〜１０ｍｅｓｈに砕いて検知剤を調製した。
【００３２】
（検知能力の測定５）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含有する窒素ガスをそれぞれ空筒基準線速度５．９ｃｍ／ｓｅｃで通して接触させ、変色し始めるまでの時間を測定した。
結果を表４に示す。
【００３３】
【表５】
実施例１８
（窒素ガスによる影響の確認）
次に、実施例１で使用した検知剤２．０ｇを内径１９ｍｍのガラス管に充填し、これに１００％の窒素ガスを空筒基準線速度６．４ｃｍ／ｓｅｃで通して接触させ、変化の有無を観察した。その結果、７２００分経過後も変色は認められなかった。
【００３５】
実施例１９、２０
（検知能力の測定６）
実施例１８で使用した検知剤に１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含有する窒素ガスをそれぞれ線速度５．９ｃｍ／ｓｅｃで通して接触させ、変色し始めるまでの時間を測定した。
結果を表６に示す。
【００３６】
【表６】
実施例２１〜２４
（検知剤能力の測定７）
実施例１〜９で用いたものと同種類の検知剤２．０ｇを内径１９ｍｍのガラス管に充填し、これに弗化水素、四弗化珪素、三弗化硼素、四塩化珪素を５０ｐｐｍ含む窒素ガスをそれぞれ線速５．９ｃｍ／ｓｅｃで通して接触させ、変色しはじめるまでの時間を測定した。
結果を表７に示す。
【００３８】
【表７】
実施例２５、２６
（検知剤の調製６）
担体として、８〜１６ｍｅｓｈ、比表面積２１０ｍ２ ／ｇ、細孔容積０．９９ｍｌ／ｇ、充填密度０．６８ｇ／ｍｌの活性アルミナ（水澤化学（株）Ｎｅｏｂｅａｄｓ ＧＢ８ 〜１６）１５０ｇを用い、これに硝酸コバルト６水和物５．０ｇを水１５３ｍｌに溶解した溶液を含浸させた。次に、これに１Ｎの水酸化ナトリウムを５０ｍｌ加えてかき混ぜた。次いで時々かき混ぜながら１２時間放置して反応させた後上澄みを捨て、ロータリーエバポレーターで５０℃の温度で余分な水分を減圧乾燥させた。さらに、コンゴーレット０．１ｇを水１００ｍｌに溶解した溶液を加え、再びロータリーエバポレーターで完全に乾燥させて検知剤を調製した。
【００４０】
（検知剤能力の測定８）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素、５０ｐｐｍの塩化水素を含む窒素ガスを通気して変色しはじめる迄の時間を測定した。
結果を表８に示す。
【００４１】
実施例２７、２８
（検知剤の調製７）
担体として、直径５ｍｍの球状、比表面積３９ｍ２ ／ｇ、細孔容積０．３３ｍｌ／ｇ、のチタニア（日産ガードラー（株）製、ＣＳ−３００−４６ ）１５０ｇを用いたほかは、実施例２５、２６と同様にして検知剤を調製した。
（検知剤能力の測定９）
この検知剤について実施例２５、２６と同様の方法で，塩素、塩化水素を含む窒素ガスについて変色しはじめる迄の時間を測定した。
結果を表８に示す。
【００４２】
実施例２９、３０
（検知剤の調製８）
担体として、直径２〜３ｍｍ、長さ約５ｍｍ、比表面積９０ｍ２ ／ｇ、細孔容積０．３１ｍｌ／ｇ、のジルコニア（ノートン社製、ＸＺ−１６０５２）１５０ｇを用いたほかは、実施例２５、２６と同様にして検知剤を調製した。
（検知剤能力の測定１０）
この検知剤について実施例２５、２６と同様の方法で、塩素、塩化水素を含む窒素ガスについて変色しはじめる迄の時間を測定した。
結果を表８に示す。
【００４３】
実施例３１、３２
（検知剤の調製９）
担体として、直径５ｍｍの球状、比表面積８０ｍ２ ／ｇ、のシリカアルミナ（ノートン社製、ＳＡ３７７ ）１５０ｇを用いたほかは、実施例２５、２６と同様にして検知剤を調製した。
（検知剤能力の測定１１）
この検知剤について実施例２５，２６と同様の方法で、塩素、塩化水素を含む窒素ガスについて変色しはじめる迄の時間を測定した。
結果を表８に示す。
【００４４】
【表８】
比較例１
（検知剤の調製１０）
実施例１で用いたものと同じ粒状のシリカゲル１００ｇに、コンゴーレッド０．１ｇを水２００ｍｌに溶解した溶液を加え、ロータリーエバポレーターで５０℃の温度で余分な水を減圧乾燥させて検知剤を調製した。
（検知剤能力の測定１２）
この検知剤２．０ｇを実施例１と同様にガラス管に充填し、これに１０ｐｐｍの塩素を含む窒素ガスをそれぞれ線速５．９ｃｍ／ｓｅｃで通気して接触させ、変色しはじめるまでの時間を測定した。
結果を表９に示したが、通気後１分以内に検知剤が脱色してしまった。
【００４６】
【表９】
【発明の効果】
本発明の検知剤は以下のような優れた特長を有している。
▲１▼ハロゲンガスおよび酸性ガスの検知に水分を必要としないため、測定対象ガスおよび検知剤の水分量に関係なく、常に高感度で検知することができる。
▲２▼検知剤がハロゲンガスまたは酸性ガスと接触すると明るい色から暗い色に変色するため、変色差が大きく極めて容易に、かつ高感度で検知することができる。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a detection agent for halogen gas and acid gas, and more specifically, fluorine, chlorine, bromine, hydrogen fluoride, tungsten hexafluoride, and tungsten tetrafluoride contained in gases such as nitrogen, hydrogen, argon, and helium. The present invention relates to an agent for detecting a halogen gas and an acid gas such as silicon, boron trifluoride, hydrogen chloride, silicon tetrachloride, boron trichloride, chlorine fluoride, and chlorine trifluoride.
[0002]
In recent years, along with the development of the semiconductor industry and the optoelectronics industry, various halogen gases and acid gases have been used, and their usage has been increasing.
These halogen gas and acid gas are indispensable substances as a gas for growing a crystalline silicon, an amorphous silicon or a silicon oxide film, or as an etching gas in a process of manufacturing a silicon semiconductor or a compound semiconductor.
[0003]
However, all of these gases are extremely toxic, and the time-weighted average allowable concentration of particularly toxic chlorine or fluorine is 1 ppm. Therefore, when handling these gases, it is necessary to constantly measure the working environment, and in the event that these gases leak, it is necessary to accurately detect them and take measures to prevent harm. .
In addition, since gases discharged from a semiconductor manufacturing process and the like contain these halogen gases and acid gases, these gases are required to be released to the outside after purification using a detoxification device or the like. It is necessary to confirm the presence of acid gas.
[0004]
[Prior art]
Conventionally, methods for detecting halogen gas include (1) a method utilizing the ortho-tolidine method, and (2) a method utilizing the decolorizing action of the halogen gas. As a method for detecting an acid gas, there are (3) a method using a pH indicator as a color change component, and (4) a method using a pH change of hydrogen halide generated from an acid gas and water.
A glass tube or a container is filled with a detecting agent using these detection methods to constitute a detecting tube or a detector, and a number of known methods utilizing contact with a gas to be measured and discoloration of the detecting agent are known. I have.
[0005]
[Problems to be solved by the invention]
However, any of (1) a method utilizing the ortho-tolidine method, (2) a method utilizing the decolorizing action of a halogen gas, or (4) a method utilizing the change in pH of hydrogen halide generated from an acidic gas and water. Also requires reaction conditions of wet or high humidity, detection of halogen gas or acid gas in the gas requires humidification, and has the disadvantage of slow response, and cannot be practically used under dry conditions. There was a problem.
On the other hand, in the case of using (3) a pH indicator for the discoloration component, the drying method can be used, but the difference in discoloration is small and cannot be detected with high sensitivity, and the sensitivity further decreases when the detection component is dried. There were inconveniences such as doing. For these reasons, there has been a strong demand for the development of a detection agent that can detect halogen gas and acid gas with high sensitivity even under dry conditions and has stable detection ability for a long period of time.
[0006]
[Means for Solving the Problems]
The present inventors have solved the above problems, and have studied repeatedly to obtain a detection agent that is highly sensitive to a dilute halogen gas and an acidic gas and that rapidly changes color. It has been found that an excellent detector can be obtained by combining hydroxide and Congo Red, and the present invention has been completed.
That is, the present invention is a detection agent for a gas containing at least one selected from a halogen gas and an acid gas, using a transition metal hydroxide and Congo Red as discoloring components.
[0007]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The detection agent of the present invention can be applied to detection of a gas containing at least one selected from a halogen gas and an acidic gas contained in nitrogen, hydrogen, argon, helium and the like.
The halogen gas in the present invention is fluorine, chlorine or bromine. In addition, the acidic gas refers to a gas which itself has acidity and shows acidity by hydrolysis upon contact with water, specifically, hydrogen fluoride, tungsten hexafluoride, silicon tetrafluoride, boron trifluoride. , Hydrogen chloride, silicon tetrachloride, boron trichloride, chlorine fluoride, chlorine trifluoride and the like.
[0008]
The detection agent of the present invention is a detection agent for a halogen gas and an acid gas containing a mixture of a transition metal hydroxide and a pH indicator Congo Red as a discoloration component, such as a halogen gas and chlorine fluoride or chlorine trifluoride. The color changes from persimmon to red to black when it comes in contact with some acid gases, and sharply changes from persimmon to red to blue to dark blue when it comes in contact with other acid gases except chlorine fluoride and chlorine trifluoride. I do.
[0009]
In the present invention, a transition metal hydroxide is used as one component of the discoloring component of the detecting agent. Examples of the transition metal include nickel (II), cobalt (II), and manganese (II), and the hydroxide thereof is nickel hydroxide (Ni (OH) 2 ), cobalt hydroxide (Co (OH) 2 ), Manganese hydroxide (Mn (OH) 2 ), one of these hydroxides may be used, or two or more may be used in combination.
Nickel (II) hydroxide is a pale green crystal and can be prepared by adding a potassium hydroxide solution to an aqueous solution of nickel (II) nitrate or the like, but there are commercially available products and these can also be used. Nickel (II) hydroxide may contain a small amount of nickel hydroxide (I) and nickel hydroxide (III), but if the color tone of nickel hydroxide (II) is not significantly impaired, the detection of the present invention is performed. Agent.
[0010]
Cobalt (II) hydroxide is a pale blue or rose-colored crystal and can be prepared by adding a cobalt (II) nitrate solution to an aqueous potassium hydroxide solution. Since cobalt (II) hydroxide is relatively easily oxidized in air and changes its color from green to dark green, it is preferable to handle it in an inert gas.
[0011]
Manganese (II) hydroxide is a white crystal and can be prepared by adding a manganese (II) nitrate solution to an aqueous potassium hydroxide solution. Manganese (II) hydroxide is relatively easily oxidized in the air and turns brown, so it is preferable to handle it in an inert gas.
Congo Red, one of the discoloring components of the present invention, is widely used as a pH indicator and is commercially available, so it is convenient to use it.
[0012]
In the present invention, a mixture of a transition metal hydroxide and Congo Red, which is a discoloring component, may be used as a detecting agent in the form of powder, or may be molded into a pellet or the like, or may be supported on an inorganic carrier or the like. It can also be.
Mixing ratio of the mixture of the transition metal hydroxide and Congo Red as a powder, or in the form of a pellet or the like and used as a detecting agent, the discoloration sensitivity is not obtained when the ratio of Congolet is small. If it is too large, the discoloration becomes unclear, so that the weight ratio (hydroxide: Congo red) is usually 1: 0.01 to 0.00001, preferably 1: 0.005 to 0.0001. . These mixtures can be used after being formed into pellets or granules by a usual dry or wet molding method. In molding, a small amount of a lubricant or a molding agent which is inactive to a hydroxide of a transition metal and Congo Red can be used to facilitate molding.
[0013]
A mixture of a transition metal hydroxide, which is a discoloring component, and Congo Red can be used by being supported on a carrier. In particular, since cobalt hydroxide is difficult to handle stably, it is preferable to use it by supporting it on a carrier.
The carrier when the mixture of the transition metal hydroxide and Congo Red is carried on the inorganic carrier can be selected from a wide range.For example, silica gel, silica alumina, alumina, zirconia, a catalyst carrier such as titania, among others A white or colorless one is preferably used, and among them, silica gel is particularly preferred. As silica gel, those which are generally commercially available for desiccants have a specific surface area of about 450 to 800 m 2 / g, and these may be used, but in order to achieve the object of the present invention more highly. preferably those in the range of a specific surface area of 50 to 400 m 2 / g obtained by hydrothermal synthesis method. If the specific surface area is too small, the discoloration speed may be reduced.
[0014]
As a method of supporting the color-changing component when using a carrier, for example, the carrier may be immersed in a solution in which the color-changing component is dissolved or suspended in water or various organic solvents, or a solution of the color-changing component while stirring the carrier. Alternatively, the suspension may be spread on the carrier surface and carried.
[0015]
The loading amount of the transition metal hydroxide and Congo Red on the inorganic carrier is usually 1: 0.15 to 0.0001: 0.1 to 0.00001 in weight ratio (inorganic carrier: hydroxide: Congo Red), Preferably it is 1: 0.05-0.005: 0.01-0.0001.
If the amount of the transition metal hydroxide supported on the inorganic carrier is less than the above range, no sensitivity can be obtained, and if the amount is too large, the change in color before and after discoloration is determined depending on the type of the transition metal (in the case of cobalt). It becomes difficult.
If the amount of Congo Red carried on the inorganic carrier is less than the above range, no sensitivity can be obtained, and if the amount is too large, it is difficult to determine the change in color before and after discoloration.
In order to prevent the oxidation of the transition metal hydroxide during the preparation of the detecting agent, the supporting operation and the drying are preferably performed in a nitrogen atmosphere. Further, it is preferable that the obtained detection agent is stored while avoiding contact with oxygen.
[0016]
The speed of the gas brought into contact with the detecting agent is not particularly limited. However, in a semiconductor manufacturing process apparatus or an exhaust gas treatment apparatus, the standard linear velocity of the cylinder is usually about 0.01 to 100 cm / sec. However, when these devices are purged, the linear velocity may exceed 100 cm / sec. Usually, when the cylinder reference linear velocity is lower than the above range, the discoloration becomes slow, and when it is high, the pressure loss may increase.
The temperature of the gas at the time of contact is usually -20 to 100 ° C, and the pressure is about 0.001 to 20 kg / cm 2 abs.
[0017]
The detection agent of the present invention is a solid, and is usually used by filling it in a transparent inspection window portion provided in a glass detection tube, a transparent container made of transparent plastic or the like, or a gas purification cylinder, etc. The presence of halogen and acid gas contained in the detection agent can be known from the color change of the detection agent. Further, when the detecting agent of the present invention is used together with a purifying agent or the like, the detecting agent is filled downstream of the purifying agent layer in the purifying cylinder or between a plurality of purifying agent layers, or the detecting tube filled with the detecting agent is purified. It is used in the form connected to the back of a cylinder.
[0018]
As described above, by using the detection agent of the present invention, the detection agent is sharply discolored from persimmon to red to black by contact with a halogen gas and some acidic gases such as chlorine fluoride and chlorine trifluoride, and is detected. When the agent comes into contact with another acid gas other than chlorine fluoride and chlorine trifluoride, it can be easily detected by sharply changing the color from persimmon to red to blue to dark blue.
[0019]
【Example】
Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
Examples 1 to 9
(Preparation 1 of detection agent)
100 g of granular silica gel (Carrieract-10, manufactured by Fuji Silysia Chemical Ltd.) having a particle size of 5 to 10 mesh, a specific surface area of 325 m 2 / g, a pore volume of 0.99 ml / g, and a packing density of 0.420 g / ml. Was impregnated with a solution prepared by dissolving 5.0 g of cobalt nitrate hexahydrate in 153 ml of water, 50 ml of a 1N aqueous sodium hydroxide solution was added thereto, and the mixture was stirred and dried under reduced pressure at a temperature of 50 ° C. with a rotary evaporator. . A solution prepared by dissolving 0.1 g of Congo Red in 100 ml of water was added thereto, and the mixture was stirred, and completely dried under reduced pressure again using a rotary evaporator to prepare a detection agent.
[0020]
(Measurement of detection ability 1)
A large number of glass tubes each having an inner diameter of 19 mm filled with 2.0 g of this detecting agent were prepared, and 10 ppm and 1 ppm of chlorine, 50 ppm and 5 ppm of hydrogen chloride, 10 ppm of bromine, 10 ppm of fluorine, and 50 ppm of boron trichloride were prepared. , 50 ppm of tungsten hexafluoride, and nitrogen gas containing 10 ppm of chlorine trifluoride were respectively contacted at an empty cylinder reference linear velocity of 5.9 cm / sec, and the time until discoloration was started was measured.
Table 1 shows the results.
[0021]
[Table 1]
Examples 10 and 11
(Preparation 2 of detection agent)
A solution of 20.0 g of nickel sulfate hexahydrate dissolved in 153 ml of water was impregnated into 100 g of the same granular silica gel as in Example 1, and then 250 ml of a 1N aqueous sodium hydroxide solution was added and mixed. Next, the mixture was left standing for 12 hours while stirring with occasional stirring, and the supernatant was discarded, followed by drying under reduced pressure at a temperature of 50 ° C. using a rotary evaporator. A solution prepared by dissolving 0.02 g of Congo Red in 100 ml of water was added thereto, and completely dried again with a rotary evaporator to prepare a detection agent.
[0023]
(Measurement of detection ability 2)
A glass tube was filled with 2.0 g of the detection agent in the same manner as in Example 1, and nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was brought into contact with each other at a standard linear velocity of the cylinder of 5.9 cm / sec. The time until discoloration started was measured.
Table 2 shows the results.
[0024]
[Table 2]
Examples 12 and 13
(Preparation 3 of detection agent)
100 g of the same granular silica gel as in Example 1 was impregnated with a solution of 20.0 g of manganese sulfate 4 to 5 hydrate dissolved in 153 ml of water, and 250 ml of a 1N aqueous sodium hydroxide solution was added and stirred. Next, the mixture was left standing for 12 hours while stirring with occasional stirring, and the supernatant was discarded and dried under reduced pressure at a temperature of 50 ° C. using a rotary evaporator. A solution prepared by dissolving 0.02 g of Congo Red in 100 ml of water was added thereto, and completely dried again with a rotary evaporator to prepare a detection agent.
[0026]
(Measurement of detection ability 3)
A glass tube was filled with 2.0 g of this detecting agent in the same manner as in Example 1, and nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was passed through the tube at a standard linear velocity of 5.9 cm / sec, and contacted. Then, the time until discoloration started was measured.
Table 3 shows the results.
[0027]
[Table 3]
Examples 14 and 15
(Preparation 4 of detection agent)
Activated alumina having a particle size of 8 to 16 mesh, a specific surface area of 210 m 2 / g, a pore volume of 0.99 g, an average pore diameter of 100 °, and a packing density of 0.68 g / ml (manufactured by Mizusawa Chemical Industry Co., Ltd., Neobeads GB8 to 16) Impregnated with a solution in which 150 g of cobalt nitrate hexahydrate 5.0 g was dissolved in 153 ml of water, 50 ml of a 1N aqueous sodium hydroxide solution was added thereto, followed by stirring. Next, the mixture was left standing for 12 hours while stirring with occasional stirring, and the supernatant was discarded and dried under reduced pressure at a temperature of 50 ° C. using a rotary evaporator. A solution prepared by dissolving 0.1 g of Congo Red in 100 ml of water was added thereto, and dried completely again by a rotary evaporator to prepare a detection agent.
[0029]
(Measurement of detection ability 4)
A glass tube was filled with 2.0 g of this detecting agent in the same manner as in Example 1, and nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was passed through the tube at a standard linear velocity of 5.9 cm / sec, and contacted. Then, the time until discoloration started was measured.
Table 4 shows the results.
[0030]
[Table 4]
Examples 16 and 17
(Preparation 5 of detection agent)
A solution prepared by dissolving 0.04 g of Congo Red in 22 g of water was added to 100 g of nickel hydroxide 1.5 hydrate, 2 ml of a 1N aqueous solution of sodium hydroxide was further added, and the paste was placed in a mold. After drying at ℃, it was crushed to 6 to 10 mesh to prepare a detecting agent.
[0032]
(Measurement of detection ability 5)
A glass tube was filled with 2.0 g of this detecting agent in the same manner as in Example 1, and nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was passed through the tube at a standard linear velocity of 5.9 cm / sec, and contacted. Then, the time until discoloration started was measured.
Table 4 shows the results.
[0033]
[Table 5]
Example 18
(Confirmation of the effect of nitrogen gas)
Next, 2.0 g of the detecting agent used in Example 1 was filled into a glass tube having an inner diameter of 19 mm, and 100% nitrogen gas was passed through the glass tube at a reference linear velocity of 6.4 cm / sec to make contact with the glass tube. The presence or absence was observed. As a result, no discoloration was observed even after 7200 minutes had passed.
[0035]
Examples 19 and 20
(Measurement of detection ability 6)
Nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was brought into contact with the detecting agent used in Example 18 at a linear velocity of 5.9 cm / sec, and the time until discoloration was started was measured.
Table 6 shows the results.
[0036]
[Table 6]
Examples 21 to 24
(Measurement of detection agent capacity 7)
A glass tube having an inner diameter of 19 mm was filled with 2.0 g of the same type of detecting agent as used in Examples 1 to 9, and contained 50 ppm of hydrogen fluoride, silicon tetrafluoride, boron trifluoride, and silicon tetrachloride. Nitrogen gas was passed through at a linear velocity of 5.9 cm / sec to contact each other, and the time until discoloration started was measured.
Table 7 shows the results.
[0038]
[Table 7]
Examples 25 and 26
(Preparation of detection agent 6)
As the carrier, 150 g of activated alumina (Neobeads GB8 to 16 of Mizusawa Chemical Co., Ltd.) having 8 to 16 mesh, specific surface area of 210 m 2 / g, pore volume of 0.99 ml / g, and packing density of 0.68 g / ml was used. A solution obtained by dissolving 5.0 g of cobalt nitrate hexahydrate in 153 ml of water was impregnated. Next, 50 ml of 1N sodium hydroxide was added thereto, followed by stirring. Then, the mixture was allowed to react for 12 hours while stirring occasionally, and the supernatant was discarded, and excess water was dried under reduced pressure at a temperature of 50 ° C. using a rotary evaporator. Further, a solution prepared by dissolving 0.1 g of congolet in 100 ml of water was added, and the solution was completely dried again with a rotary evaporator to prepare a detecting agent.
[0040]
(Measurement of detecting agent ability 8)
A glass tube was filled with 2.0 g of this detecting agent in the same manner as in Example 1, and a nitrogen gas containing 10 ppm of chlorine and 50 ppm of hydrogen chloride was passed through the tube to measure the time until discoloration started.
Table 8 shows the results.
[0041]
Examples 27 and 28
(Preparation 7 of detection agent)
Example 25 was repeated except that 150 g of titania (manufactured by Nissan Gardler Co., Ltd., CS-300-46) having a spherical shape with a diameter of 5 mm, a specific surface area of 39 m 2 / g, and a pore volume of 0.33 ml / g was used as the carrier. , 26 were prepared in the same manner as described above.
(Measurement of detection agent ability 9)
The time until the discoloration of the nitrogen gas containing chlorine and hydrogen chloride was started was measured in the same manner as in Examples 25 and 26 for this detector.
Table 8 shows the results.
[0042]
Examples 29 and 30
(Preparation 8 of detection agent)
Example 25 was repeated except that 150 g of zirconia (manufactured by Norton, XZ-16052) having a diameter of 2 to 3 mm, a length of about 5 mm, a specific surface area of 90 m 2 / g and a pore volume of 0.31 ml / g was used as the carrier. , 26 were prepared in the same manner as described above.
(Measurement of detecting agent ability 10)
In the same manner as in Examples 25 and 26, the time until the discoloration of the nitrogen gas containing chlorine and hydrogen chloride started was measured.
Table 8 shows the results.
[0043]
Examples 31 and 32
(Preparation 9 of detection agent)
A detection agent was prepared in the same manner as in Examples 25 and 26 except that 150 g of silica alumina (manufactured by Norton, SA377) having a diameter of 5 mm and a specific surface area of 80 m 2 / g was used as a carrier.
(Measurement of detecting agent ability 11)
In the same manner as in Examples 25 and 26, the time until the discoloration of the nitrogen gas containing chlorine and hydrogen chloride was started was measured for this detector.
Table 8 shows the results.
[0044]
[Table 8]
Comparative Example 1
(Preparation 10 of detection agent)
A solution prepared by dissolving 0.1 g of Congo Red in 200 ml of water was added to 100 g of the same granular silica gel used in Example 1, and excess water was dried under reduced pressure at a temperature of 50 ° C. using a rotary evaporator to prepare a detection agent. did.
(Measurement of detecting agent ability 12)
A glass tube was filled with 2.0 g of this detecting agent in the same manner as in Example 1, and nitrogen gas containing 10 ppm of chlorine was brought into contact with the gas at a linear velocity of 5.9 cm / sec to contact the glass tube, and the time until discoloration started. Was measured.
The results are shown in Table 9, and the detection agent decolorized within 1 minute after ventilation.
[0046]
[Table 9]
【The invention's effect】
The detection agent of the present invention has the following excellent features.
{Circle around (1)} Since moisture is not required for detection of halogen gas and acid gas, detection can always be performed with high sensitivity irrespective of the amounts of moisture in the gas to be measured and the detection agent.
{Circle around (2)} When the detection agent comes into contact with a halogen gas or an acid gas, the color changes from a bright color to a dark color.
Claims (5)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP09173997A JP3567058B2 (en) | 1996-08-23 | 1997-03-26 | Detecting agent |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24134996 | 1996-08-23 | ||
| JP8-241349 | 1996-08-23 | ||
| JP09173997A JP3567058B2 (en) | 1996-08-23 | 1997-03-26 | Detecting agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH10115608A JPH10115608A (en) | 1998-05-06 |
| JP3567058B2 true JP3567058B2 (en) | 2004-09-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP09173997A Expired - Fee Related JP3567058B2 (en) | 1996-08-23 | 1997-03-26 | Detecting agent |
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| Country | Link |
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| JP (1) | JP3567058B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2020018953A (en) * | 2018-07-30 | 2020-02-06 | クラリアント触媒株式会社 | Halogen gas remover and manufacturing method therefor, and method for monitoring consumption state of remover |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012002239A1 (en) * | 2010-06-29 | 2012-01-05 | 独立行政法人産業技術総合研究所 | Agent for detecting halide, method for detecting halide, and detection sensor |
| JP6184071B2 (en) * | 2012-09-28 | 2017-08-23 | ユニ・チャーム株式会社 | Disposable diaper with indicator housing |
| JP6123548B2 (en) * | 2013-07-29 | 2017-05-10 | 宇部興産株式会社 | Method for measuring concentration of halogen molecule in halogen compound and apparatus for measuring concentration of halogen molecule in halide |
| JP5920948B2 (en) * | 2014-10-14 | 2016-05-18 | 国立研究開発法人産業技術総合研究所 | Detection method and detection sensor |
| JP7007552B2 (en) * | 2017-07-11 | 2022-02-10 | セントラル硝子株式会社 | Chlorine gas detector and exhaust gas dry abatement device. |
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1997
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2020018953A (en) * | 2018-07-30 | 2020-02-06 | クラリアント触媒株式会社 | Halogen gas remover and manufacturing method therefor, and method for monitoring consumption state of remover |
| JP7253132B2 (en) | 2018-07-30 | 2023-04-06 | クラリアント触媒株式会社 | Halogen gas remover, method for producing same, and method for monitoring consumption of remover |
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| Publication number | Publication date |
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| JPH10115608A (en) | 1998-05-06 |
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