JP4195833B2

JP4195833B2 - Detecting agent storage container and toxic gas detection method using the same

Info

Publication number: JP4195833B2
Application number: JP2003166120A
Authority: JP
Inventors: 孝島田; 常勝米山
Original assignee: Japan Pionics Ltd
Current assignee: Japan Pionics Ltd
Priority date: 2003-06-11
Filing date: 2003-06-11
Publication date: 2008-12-17
Anticipated expiration: 2023-06-11
Also published as: JP2005003475A

Description

【０００１】
【発明の属する技術分野】
本発明は検知剤の収納容器及びそれを用いた有害ガスの検知方法に関する。さらに詳細には、半導体製造工程等から排出される有害ガスを、浄化筒に充填された浄化剤と接触させることにより浄化するとともに、浄化剤の充填部を通過するガスに含まれる有害ガス成分を検知するために用いられる検知剤の収納容器及びそれを用いた有害ガスの検知方法に関する。
【０００２】
【従来の技術】
半導体製造工業においては各種のガスが使用されており、水素化物ガスとしては、アルシン、ホスフィン、シラン、ジボラン、セレン化水素等が、酸性ガスとしては、フッ素、塩素、フッ化水素、塩化水素、三フッ化塩素、三フッ化ホウ素、三塩化ホウ素、四フッ化珪素、四塩化珪素、四塩化チタン、塩化アルミニウム、四フッ化ゲルマニウム、六フッ化タングステン等が、塩基性ガスとしては、アンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミン、ヒドラジン等が多量に使用されている。これらのガスは毒性を有するため、半導体製造工程等で使用された後、これらの有害ガス成分を含む排ガスは大気中に放出するに先立って浄化する必要がある。
【０００３】
従来より、前記の有害ガスの浄化方法としては、浄化剤を浄化筒に充填し、有害ガスを浄化筒に導入して、有害ガス成分を浄化剤と接触させて捕捉することにより浄化する乾式浄化方法が多く実施されてきた。乾式浄化方法において、各種の浄化剤は、各々有害ガス成分に対する固有の浄化能力（浄化剤単位量当りの有害ガス成分処理量）を有しており、ある程度の量の有害ガス成分を捕捉できるが、それを超えると捕捉できなくなり、有害ガス成分を下流側へ流してしまう虞があった。そのため、例えば浄化剤の充填部のうち比較的下流側の位置に浄化筒の外側から浄化筒内を観察することができる覗窓を設け、これに有害ガス成分と接触して変色する検知剤を充填して、浄化剤層が破過する直前で有害ガス成分を検知することが行なわれている。
【０００４】
【発明が解決しようとする課題】
乾式浄化方法においては、有害ガスが浄化剤と接触する際に、有害ガス成分と浄化剤が化学反応を起こすか、あるいは有害ガス成分が浄化剤に吸着されて、有害ガス成分が浄化剤に捕捉される。このような有害ガス成分の反応部または吸着部は、浄化剤層の上流側から徐々に下流側に進行する。しかしながら、浄化剤層の中心部と周辺部の位置の違い、有害ガスに含まれる粉化物の浄化剤層における堆積状態等により、有害ガス成分の反応部または吸着部は、通常は浄化剤層を均一に進行しない。特に浄化筒の径が大きい場合はこの傾向が顕著になり、覗窓の検知剤が変色していないにもかかわらず有害ガス成分が浄化筒の下流側へ流れる虞があった。
【０００５】
このため、有害ガス成分の反応部または吸着部の進行状態を正確に検知する方法として、例えば検知剤が充填された覗窓を複数個所に設置することが検討された。しかしながら、この方法では浄化剤の有害ガスとの反応、あるいは浄化剤による有害ガスの吸着が浄化筒の中心部で早く進行した場合は浄化筒の破過を見逃す虞があった。また、浄化剤の充填部を二分割し、浄化剤の充填部間に空間を設け、その空間部に検知剤が充填された覗窓を設けることも考えられたが、空間内における浄化筒半径方向のガスの拡散では、有害ガス成分の濃度が数ｐｐｍと低い場合は検知剤の変色が遅くなり、前記の方法と同様に有害ガス成分の捕捉部が浄化筒の中心部で早く進行した場合は浄化筒の破過を見逃す虞があった。
【０００６】
従って、本発明が解決しようとする課題は、半導体製造工程等から排出される有害ガスを、浄化筒に充填された浄化剤と接触させることにより浄化するとともに、浄化剤の充填部を通過するガスに含まれる有害ガス成分を検知剤によって検知する方法において、浄化剤の有害ガス成分との反応部、あるいは浄化剤による有害ガス成分の吸着部の進行状態を正確に検知することが可能な有害ガスの検知手段を提供することである。
【０００７】
【課題を解決するための手段】
本発明者らは、これらの課題を解決すべく鋭意検討した結果、前記のような有害ガス成分の検知において、浄化剤の充填部のうち、所望の位置からガスを取入れることができる形状及び大きさを有する容器を使用し、この容器の先端部に検知剤を充填して検知剤の充填部が覗窓に隣接するように浄化筒に装着し、前記取入部から流通するガスを検知剤と接触させて分析することにより、浄化剤の有害ガス成分との反応部、あるいは浄化剤による有害ガス成分の吸着部の進行状態を正確に検知できることを見い出し、本発明の検知剤の収納容器及びそれを用いた有害ガスの検知方法に到達した。
【０００８】
すなわち本発明は、検知剤を充填して浄化筒の覗窓部に装着する収納容器であって、検知剤の充填部、ガス導入部、及びガス排出部からなり、これらは互いに仕切により仕切られ、該検知剤の充填部と該ガス導入部の仕切、及び該検知剤の充填部と該ガス排出部の仕切はガス透過性材料であり、該ガス導入部と該ガス排出部の仕切はガス非透過性材料であり、該ガス導入部から取り入れられたガスが該検知剤の充填部を通過し、さらに該ガス排出部を通過して容器外へ排出される構成を有することを特徴とする検知剤の収納容器である。
また、本発明は、有害ガスを浄化筒に導入し、浄化筒に充填された浄化剤と接触させることにより有害ガスを浄化するとともに、浄化剤の充填部を通過する有害ガス成分を検知剤によって検知する方法であって、浄化筒の覗窓部に検知剤が充填された前記の収納容器を装着し、該収納容器に導入されたガスに含まれる有害ガス成分を検知剤により検知することを特徴とする有害ガスの検知方法でもある。
【０００９】
【発明の実施の形態】
本発明は、半導体製造工程等から排出される有害ガスを浄化筒に導入し、浄化筒に充填された浄化剤と接触させることにより有害ガスを浄化するとともに、浄化剤の充填部を通過するガスに含まれる有害ガス成分を検知するために用いられる検知剤の収納容器及びそれを用いた有害ガスの検知方法に適用される。
【００１０】
本発明の検知剤の収納容器は、検知剤の充填部、ガスを容器内に取入れ検知剤の充填部へ導入するガス導入部、及び検知剤の充填部を通過したガスを容器外へ排出するガス排出部からなる収納容器である。
また、本発明の有害ガスの検知方法は、浄化筒の覗窓部に検知剤が充填された前記の収納容器を装着し、収納容器に導入されたガスに含まれる有害ガス成分を検知剤により検知する方法である。
【００１１】
本発明における有害ガス成分は、半導体製造工程等から排出され、乾式浄化方法により浄化され得るものであれば特に制限されることがない。これらの有害ガス成分としては、例えば、アルシン、ホスフィン、シラン、ジボラン、セレン化水素等の水素化物ガス、フッ素、塩素、フッ化水素、塩化水素、三フッ化塩素、三フッ化ホウ素、三塩化ホウ素、四フッ化珪素、四塩化珪素、四塩化チタン、塩化アルミニウム、四フッ化ゲルマニウム、六フッ化タングステン等の酸性ガス、アンモニア、モノメチルアミン、ジメチルアミン、トリメチルアミン、ヒドラジン等の塩基性ガスを挙げることができる。これらは、通常は、窒素、水素、アルゴン、ヘリウム等のベースガスに含有された状態で排出される。
【００１２】
本発明における浄化剤は、前記有害ガス成分を含有する有害ガスを、乾式浄化方法により浄化できるものであれば特に制限されることがない。これらの浄化剤としては、例えば、二酸化マンガン及び酸化銅を主成分とする水素化物ガスの浄化剤、活性炭に蟻酸のアルカリ金属塩及び／または蟻酸のアルカリ土類金属塩を添着させたハロゲン系ガスの浄化剤、二酸化マンガン及び酸化銅を主成分とする組成物に銅塩を添着させた塩基性ガスの浄化剤等を挙げることができる。また、前記有害ガス成分との組み合せで、粉化物を生成するものであってもよい。
【００１３】
本発明における検知剤は、前記有害ガス成分を検知できるものであれば特に制限されることがない。これらの検知剤としては、例えば、無機質担体に変色成分としてモリブデン酸塩を担持させた水素化物ガスの検知剤、塩基性炭酸銅を変色成分とする水素化物ガスの検知剤、遷移金属の水酸化物とコンゴーレッドを変色成分とする酸性ガスの検知剤等を挙げることができる。
【００１４】
以下、本発明の検知剤の収納容器及びそれを用いた有害ガスの検知方法を、図１〜図６に基いて説明するが、本発明がこれらにより限定されるものではない。図１は、本発明の検知剤の収納容器の例を示す斜視図であり、図２は、図１の収納容器に検知剤を充填したときの鉛直方向の構成例を示す断面図である。図３、図４は、本発明の図１以外の検知剤の収納容器の例を示す斜視図である。図５は、検知剤が充填された本発明の収納容器を浄化筒の覗窓部に装着したときの鉛直方向の構成例を示す断面図であり、図６は、図５における収納容器近辺の構成を示す拡大図である。
【００１５】
本発明の検知剤の収納容器は、図１及び図２に示すように、検知剤の充填部１、ガスを容器内に取入れ検知剤の充填部へ導入するガス導入部２、及び検知剤の充填部を通過したガスを容器外へ排出するガス排出部３からなる収納容器である。本発明の検知剤の収納容器は、その形状、大きさに特に制限されることがない。形状については、円柱、角柱、立方体、直方体、球、楕球、円錐、円錐台、角錐、角錐台、これらに類似する形状、あるいはこれらを組合せた形状等とすることもできるが、円柱、角柱、またはこれらに類似する形状等、柱状の形状であることが好ましい。また、収納容器の柱方向の長さについては、通常は装着する浄化筒の内径の５〜７０％、好ましくは１０〜５０％となるように設定され、収納容器の柱方向と垂直方向の面の大きさについては、円形に換算した場合の径で、通常は浄化剤の充填長の１〜３０％、好ましくは５〜２０％となるように設定される。
【００１６】
本発明の検知剤の収納容器は、浄化筒に装着して使用した際に、図６に示すように、ガス導入部に取入れられたガスが検知剤の充填部を通過し、排出部から容器外へ排出されるような構成とされる。そのため、収納容器の構成は、通常は検知剤の充填部の形状を、円柱、角柱、またはこれらに類似する形状とし、ガス導入部及びガス排出部の形状を、前記形状を柱方向に二分割した形状として、図２及び図６に示すような配置に設定されるとともに、検知剤の充填部とガス導入部の仕切５、及び検知剤の充填部とガス排出部の仕切６としてガス透過性材料を用い、ガス導入部とガス排出部の仕切７としてガス非透過性材料を用いた構成とされる。（図２、図６に示す収納容器において、点線はガス透過性材料の面、実線はガス非透過性材料の面であることを示すものである。）
【００１７】
また、本発明の検知剤の収納容器においては、ガス導入部の外周面及びガス排出部の外周面は、図１に示すように全部がガス透過性材料８及び９で構成されるか、または、図３、図４に示すように各々の一部がガス透過性材料８あるいは９、各々の他の一部がガス非透過性材料８’及び９’で構成される。（図４のガス排出部の底面はガス透過性材料で構成されている。）尚、一部がガス透過性材料で構成される場合は、通常は側面以外の面がガス透過性材料とされる。検知剤の充填部の外周面１０、検知剤の充填部の覗窓部と隣接する側面１１、及びガス導入部とガス排出部の検知剤の充填部と反対方向の側面１２は、ガス透過性材料であってもよいし、ガス非透過性材料であってもよい。さらに、検知剤の充填部の覗窓部と隣接する側面１１は、外側から検知剤の変色を検知できるように透明な材料が用いられる。
【００１８】
本発明に使用されるガス透過性材料としては、有害ガス成分に対する耐腐食性を備え、浄化筒に装着し浄化剤を投入する際に、浄化剤の侵入を防止することができるものであれば特に制限されることがないが、例えば網状の炭素鋼、マンガン鋼、クロム鋼、モリブデン鋼、ステンレス鋼等を使用することができる。また、ガス非透過性材料としては、有害ガス成分に対する耐腐食性を備えたものであれば特に制限されることがないが、通常は板状の炭素鋼、マンガン鋼、クロム鋼、モリブデン鋼、ステンレス鋼等を使用することができる。
【００１９】
尚、図１に示す検知剤の収納容器は、容器全体の形状及び検知剤の充填部の形状が円柱であり、ガス導入部及びガス排出部の形状が、円柱を柱方向に二分割した形状である。また、この収納容器は、検知剤の充填部とガス導入部の仕切、検知剤の充填部とガス排出部の仕切、ガス導入部の外周面、及びガス排出部の外周面の構成材料として網状の金属を用い、検知剤の充填部の覗窓部と隣接する側面の構成材料として透明アクリル板を用い、その他の構成材料として金属板を用いたものである。
また、本発明においては、検知剤が充填された収納容器を浄化筒の覗窓部に装着するための手段が設けられるが、装着しやすくするために、検知剤の充填部の先端１３を、図６に示すように、浄化筒の覗窓部にワンタッチで嵌合される構造とすることが好ましい。
【００２０】
本発明の有害ガスの検知方法を実施する際には、以上のような収納容器が使用される。本発明の有害ガスの検知方法においては、収納容器に検知剤が充填された後、図３に示すように、検知剤の充填部が浄化筒の覗窓１７に隣接するように収納容器が設置され、さらに浄化筒に浄化剤が充填される。このように収納容器が浄化筒に設置される際には、通常は収納容器のガス導入部及びガス排出部には、浄化剤が入らないようにされる。
【００２１】
次に、有害ガスが浄化筒の有害ガスの導入口から導入され浄化される。有害ガス成分の反応部または吸着部は、浄化剤層の上流側から徐々に下流側に進行するが、浄化剤層の中心部と周辺部の位置の違い等により、これらは通常は浄化剤層を均一に進行しない。しかし、本発明においては、図５に示すように、浄化剤層の中心部を流れるガスから周辺部を流れるガスまで取入れて有害ガス成分を検知できるので、有害ガス成分が検知されない状態で浄化筒下流側へ流出することを防止できる。
【００２２】
【実施例】
次に、本発明を実施例により具体的に説明するが、本発明がこれらにより限定されるものではない。
【００２３】
実施例１
（検知剤の収納容器の製作）
検知剤の充填部の形状が、底面の径４０ｍｍ、高さ４０ｍｍの円柱であり、ガス導入部及びガス排出部の形状が、底面の径４０ｍｍ、高さ１００ｍｍの円柱を柱方向に二分割した形状である図１に示すような収納容器を製作した。尚、検知剤の充填部とガス導入部の仕切、及び検知剤の充填部とガス排出部の仕切を網状のステンレス鋼とするとともに、ガス導入部とガス排出部の仕切を板状のステンレス鋼とした。また、ガス導入部の外周面、及びガス排出部の外周面を網状のステンレス鋼、検知剤の充填部の外周面、及びガス導入部とガス排出部の検知剤の充填部と反対側の側面を板状のステンレス鋼とするとともに、検知剤の充填部の覗窓部と隣接する側面を透明のアクリル板とした。また、検知剤の充填部の先端部に長さ５ｍｍの嵌合部を設けた。
【００２４】
（浄化剤及び検知剤の調製）
次に、二酸化マンガン、酸化銅を主成分とする市販のホプカライト（日産ガードラー（株）製、直径１．５ｍｍ、長さ３〜１０ｍｍの押し出し成型品）１００重量部に対して、水酸化カリウムを３０重量部担持させて浄化剤を調製した。また、比表面積３００ｍ^２／ｇ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）３００ｇに、変色成分として燐モリブデン酸水和物３．０ｇ及び硫酸第二銅５水和物０．６ｇを水８１０ｍＬに溶解した溶液を含浸させた後、７５℃で乾燥させて検知剤を調製した。
【００２５】
（浄化筒の製作）
前述の検知剤の収納容器４個について、各々の検知剤の充填部に前記の検知剤を充填した。
次に、内径４００ｍｍのステンレス鋼製の浄化筒に、厚さ８０ｍｍとなるように前記の浄化剤を充填するとともに、浄化筒の周辺部４箇所に互いの距離が均等となるように設けられた覗窓部に前記の検知剤の収納容器を装着した。収納容器はその上面が浄化剤の上面と同一の高さになるように設定した。
さらに全体の充填長が４００ｍｍとなるように前記の浄化剤を追加充填した。
【００２６】
（検知試験）
乾燥窒素中にＳｉＨ_４を５０００ｐｐｍ含む有害ガスを、常圧、２５℃、流量２００Ｌ／ｍｉｎの条件下、ダウンフローで前述の浄化筒に導入し、浄化筒の周辺部４箇所に設置した検知剤が変色し始めるまでの時間を測定した。また、浄化筒の出口ガスの一部をサンプリングして、ＳｉＨ_４が検知されるまでの時間（浄化剤の破過時間）を測定した。これらの結果を表１に示す。また、浄化剤の充填長と検知剤の位置を考慮して、浄化剤の破過時間から計算した検知剤の変色開始時間を併せて示す。
【００２７】
実施例２
（検知剤の収納容器の製作）
検知剤の充填部の形状が、一辺４０ｍｍの立方体であり、ガス導入部及びガス排出部の形状が、縦４０ｍｍ、横４０ｍｍ、高さ１００ｍｍの直方体を柱方向に二分割した形状である図４に示すような収納容器を製作した。尚、検知剤の充填部とガス導入部の仕切、及び検知剤の充填部とガス排出部の仕切を網状のステンレス鋼とするとともに、ガス導入部とガス排出部の仕切を板状のステンレス鋼とした。また、ガス導入部の上面、及びガス排出部の下面を網状のステンレス鋼、ガス導入部の側面、ガス排出部の側面、及び検知剤の充填部の外周面を板状のステンレス鋼とするとともに、検知剤の充填部の覗窓部と隣接する側面を透明のアクリル板とした。また、検知剤の充填部の先端部に長さ５ｍｍの嵌合部を設けた。
【００２８】
（検知試験）
前記の収納容器を用いた以外は実施例１と同様にして浄化筒を設定した後、乾燥窒素中にＳｉＨ_４を５０００ｐｐｍ含む有害ガスを、常圧、２５℃、流量２００Ｌ／ｍｉｎの条件下、ダウンフローで前述の浄化筒に導入し、浄化筒の周辺部４箇所に設置した検知剤が変色し始めるまでの時間を測定した。また、浄化筒の出口ガスの一部をサンプリングして、ＳｉＨ_４が検知されるまでの時間（浄化剤の破過時間）を測定した。これらの結果を表１に示す。また、浄化剤の充填長と検知剤の位置を考慮して、浄化剤の破過時間から計算した検知剤の変色開始時間を併せて示す。
【００２９】
比較例１
（検知剤の収納容器の製作）
実施例１の検知剤の収納容器の製作において、ガス導入部及びガス排出部がなく、検知剤の充填部のみからなる収納容器を製作した。収納容器すなわち検知剤の充填部の形状は、底面の径４０ｍｍ、高さ４０ｍｍの円柱であり、検知剤の充填部の覗窓部と隣接する側面を透明のアクリル板とするとともに、その他の面は全て網状のステンレス鋼とした。また、検知剤の充填部の先端部に長さ５ｍｍの嵌合部を設けた。
【００３０】
（検知試験）
前記の収納容器を用いた以外は実施例１と同様にして浄化筒を設定した後、乾燥窒素中にＳｉＨ_４を５０００ｐｐｍ含む有害ガスを、常圧、２５℃、流量２００Ｌ／ｍｉｎの条件下、ダウンフローで前述の浄化筒に導入し、浄化筒の周辺部４箇所に設置した検知剤が変色し始めるまでの時間を測定した。また、浄化筒の出口ガスの一部をサンプリングして、ＳｉＨ_４が検知されるまでの時間（浄化剤の破過時間）を測定した。これらの結果を表１に示す。また、浄化剤の充填長と検知剤の位置を考慮して、浄化剤の破過時間から計算した検知剤の変色開始時間を併せて示す。
【００３１】
【表１】

【００３２】
【発明の効果】
本発明の検知剤の収納容器及びそれを用いた有害ガスの検知方法により、半導体製造工程等から排出される有害ガスを、浄化筒に充填された浄化剤と接触させて浄化する際に、浄化剤の有害ガス成分との反応部、あるいは浄化剤による有害ガス成分の吸着部の進行状態を正確に検知することが可能となった。
【図面の簡単な説明】
【図１】本発明の検知剤の収納容器の例を示す斜視図
【図２】図１の収納容器に検知剤を充填したときの鉛直方向の構成例を示す断面図
【図３】本発明の図１以外の検知剤の収納容器の例を示す斜視図
【図４】本発明の図１、図３以外の検知剤の収納容器の例を示す斜視図
【図５】検知剤が充填された本発明の収納容器を浄化筒の覗窓部に装着したときの鉛直方向の構成例を示す断面図
【図６】図５における収納容器近辺の構成を示す拡大図
【符号の説明】
１検知剤の充填部
２ガス導入部
３ガス排出部
４検知剤
５検知剤の充填部とガス導入部の仕切
６検知剤の充填部とガス排出部の仕切
７ガス導入部とガス排出部の仕切
８ガス導入部の外周面（ガス透過性材料）
８’ ガス導入部の外周面（ガス非透過性材料）
９ガス排出部の外周面（ガス透過性材料）
９’ ガス排出部の外周面（ガス非透過性材料）
１０検知剤の充填部の外周面
１１検知剤の充填部の覗窓部と隣接する側面
１２ガス導入部とガス排出部の検知剤の充填部と反対方向の側面
１３検知剤の充填部の先端
１４有害ガスの導入口
１５浄化剤
１６浄化されたガスの排出口
１７覗窓部
１８検知剤の収納容器
１９ガス流
２０覗窓部の構成材（透明アクリル材）[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a container for a detection agent and a method for detecting harmful gas using the same. More specifically, the harmful gas discharged from the semiconductor manufacturing process or the like is purified by bringing it into contact with the purification agent filled in the purification cylinder, and harmful gas components contained in the gas passing through the filling portion of the purification agent are removed. The present invention relates to a container for a detection agent used for detection and a method for detecting harmful gas using the same.
[0002]
[Prior art]
Various gases are used in the semiconductor manufacturing industry. As hydride gases, arsine, phosphine, silane, diborane, hydrogen selenide, etc. are used. As acid gases, fluorine, chlorine, hydrogen fluoride, hydrogen chloride, Chlorine trifluoride, boron trifluoride, boron trichloride, silicon tetrafluoride, silicon tetrachloride, titanium tetrachloride, aluminum chloride, germanium tetrafluoride, tungsten hexafluoride, etc. are basic gases such as ammonia, Monomethylamine, dimethylamine, trimethylamine, hydrazine and the like are used in large quantities. Since these gases are toxic, exhaust gases containing these harmful gas components must be purified before they are released into the atmosphere after being used in a semiconductor manufacturing process or the like.
[0003]
Conventionally, as a method for purifying the harmful gas, the dry purification is performed by filling the purifier with the purifier, introducing the harmful gas into the purifier, and capturing the harmful gas components in contact with the purifier. Many methods have been implemented. In the dry purification method, each of the various purification agents has a specific purification capacity for harmful gas components (hazardous gas component processing amount per unit amount of the purification agent), and can capture a certain amount of harmful gas components. If it exceeds that, it could not be captured, and harmful gas components could flow downstream. For this reason, for example, a viewing window that can observe the inside of the purification cylinder from the outside of the purification cylinder is provided at a relatively downstream position in the purification agent filling portion, and a detection agent that changes color in contact with harmful gas components is provided on this. Filling and detecting harmful gas components immediately before the purifier layer breaks through.
[0004]
[Problems to be solved by the invention]
In the dry purification method, when harmful gas comes into contact with the cleaning agent, the harmful gas component and the cleaning agent cause a chemical reaction, or the harmful gas component is adsorbed by the cleaning agent, and the harmful gas component is captured by the cleaning agent. Is done. Such a reaction part or adsorption part of the harmful gas component gradually proceeds downstream from the upstream side of the purifier layer. However, due to the difference in position between the central part and the peripheral part of the purifier layer, the accumulation state of the pulverized material contained in the harmful gas in the purifier layer, etc. It does not progress uniformly. In particular, when the diameter of the purification cylinder is large, this tendency becomes remarkable, and there is a possibility that harmful gas components may flow to the downstream side of the purification cylinder even though the detection agent of the observation window is not discolored.
[0005]
For this reason, as a method for accurately detecting the progressing state of the reaction part or the adsorption part of the harmful gas component, for example, it has been considered to install a plurality of observation windows filled with a detection agent. However, in this method, when the reaction of the purifying agent with the harmful gas or the adsorption of the harmful gas by the purifying agent proceeds quickly in the center of the purifying tube, there is a possibility that the breakthrough of the purifying tube may be missed. It was also considered that the purifying agent filling part was divided into two parts, a space was provided between the purifying agent filling parts, and a viewing window filled with the detection agent was provided in the space part. In the direction of gas diffusion, when the concentration of harmful gas components is as low as a few ppm, discoloration of the detection agent is delayed, and in the same way as in the above method, the trapping portion of the harmful gas components proceeds quickly at the center of the purification cylinder. Could overlook the spill tube.
[0006]
Accordingly, the problem to be solved by the present invention is to purify the harmful gas discharged from the semiconductor manufacturing process etc. by bringing it into contact with the purifying agent filled in the purifying cylinder and to pass through the purifier filling portion. Gas that can accurately detect the progress of the reaction part of the purification agent with the harmful gas component or the adsorption part of the harmful gas component by the purification agent in the method of detecting the harmful gas component contained in It is to provide a detection means.
[0007]
[Means for Solving the Problems]
As a result of intensive investigations to solve these problems, the present inventors have found a shape in which gas can be taken in from a desired position in the purifier filling portion in the detection of harmful gas components as described above, and Use a container having a size, fill the tip of the container with a detection agent, attach the detection agent to the purification cylinder so that the filling portion is adjacent to the viewing window, and detect the gas flowing from the intake portion. It is found that the advancing state of the reaction part with the harmful gas component of the purifying agent or the adsorption part of the harmful gas component by the purifying agent can be accurately detected by contacting with the analyzing agent, and the container for the detecting agent of the present invention and It reached the detection method of harmful gas using it.
[0008]
That is, the present invention is a storage container that is filled with a detection agent and is attached to a viewing window portion of a purification cylinder, and includes a filling portion of a detection agent, a gas introduction portion, and a gas discharge portion, which are partitioned by a partition. The partition between the detection agent filling portion and the gas introduction portion, and the partition between the detection agent filling portion and the gas discharge portion are gas permeable materials, and the partition between the gas introduction portion and the gas discharge portion is a gas. A non-permeable material, characterized in that the gas taken in from the gas introduction part passes through the filling part of the detection agent and further passes through the gas discharge part and is discharged out of the container. This is a container for a detection agent.
Further, the present invention purifies the harmful gas by introducing the harmful gas into the purification cylinder and bringing it into contact with the purification agent filled in the purification cylinder, and also detects the harmful gas component passing through the purifier filling portion with the detection agent. A method of detecting, wherein the storage container filled with the detection agent is attached to the viewing window portion of the purification cylinder, and the harmful gas component contained in the gas introduced into the storage container is detected by the detection agent. It is also a characteristic method for detecting harmful gases.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
The present invention purifies harmful gas by introducing harmful gas discharged from a semiconductor manufacturing process or the like into a purification cylinder and bringing it into contact with a purification agent filled in the purification cylinder, and gas that passes through a purifier filling portion. The present invention is applied to a detection agent storage container used for detecting harmful gas components contained in the gas and a method for detecting harmful gas using the same.
[0010]
The detection agent storage container of the present invention includes a detection agent filling portion, a gas introduction portion that introduces gas into the container and introduces the detection agent filling portion, and a gas that has passed through the detection agent filling portion is discharged out of the container. It is a storage container which consists of a gas discharge part.
Further, the harmful gas detection method of the present invention is configured such that the storage container filled with the detection agent is attached to the viewing window portion of the purification cylinder, and the harmful gas component contained in the gas introduced into the storage container is detected by the detection agent. It is a method of detection.
[0011]
The harmful gas component in the present invention is not particularly limited as long as it is discharged from a semiconductor manufacturing process or the like and can be purified by a dry purification method. Examples of these harmful gas components include hydride gases such as arsine, phosphine, silane, diborane, hydrogen selenide, fluorine, chlorine, hydrogen fluoride, hydrogen chloride, chlorine trifluoride, boron trifluoride, trichloride. Examples include acidic gases such as boron, silicon tetrafluoride, silicon tetrachloride, titanium tetrachloride, aluminum chloride, germanium tetrafluoride, tungsten hexafluoride, and basic gases such as ammonia, monomethylamine, dimethylamine, trimethylamine, and hydrazine. be able to. These are usually discharged in a state in which they are contained in a base gas such as nitrogen, hydrogen, argon, or helium.
[0012]
The purification agent in the present invention is not particularly limited as long as the harmful gas containing the harmful gas component can be purified by a dry purification method. Examples of these purifiers include hydride gas purifiers mainly composed of manganese dioxide and copper oxide, and halogen-based gases obtained by impregnating activated carbon with an alkali metal salt of formic acid and / or an alkaline earth metal salt of formic acid. And a purifying agent for basic gas in which a copper salt is impregnated with a composition mainly composed of manganese dioxide and copper oxide. Moreover, a powdered product may be generated in combination with the harmful gas component.
[0013]
The detection agent in the present invention is not particularly limited as long as it can detect the harmful gas component. These detection agents include, for example, hydride gas detection agents in which molybdate is supported as a discoloring component on an inorganic carrier, hydride gas detection agents having basic copper carbonate as a discoloration component, and transition metal hydroxides. Examples include acid gas detectors that use a product and Congo red as a color-changing component.
[0014]
Hereinafter, the container for the detection agent of the present invention and the method for detecting harmful gas using the same will be described with reference to FIGS. 1 to 6, but the present invention is not limited thereto. FIG. 1 is a perspective view showing an example of a detection agent storage container according to the present invention, and FIG. 2 is a cross-sectional view showing a vertical configuration example when the detection container is filled in the storage container of FIG. 3 and 4 are perspective views showing examples of the detection agent storage container other than FIG. 1 according to the present invention. FIG. 5 is a cross-sectional view showing a configuration example in the vertical direction when the storage container of the present invention filled with the detection agent is attached to the viewing window portion of the purification cylinder, and FIG. 6 is a view of the vicinity of the storage container in FIG. It is an enlarged view which shows a structure.
[0015]
As shown in FIGS. 1 and 2, the detection agent storage container of the present invention includes a detection agent filling unit 1, a gas introduction unit 2 for introducing gas into the detection agent and introducing the gas into the detection agent filling unit, and It is a storage container which consists of the gas discharge part 3 which discharges | emits the gas which passed the filling part out of a container. The detection agent storage container of the present invention is not particularly limited by its shape and size. The shape may be a cylinder, a prism, a cube, a rectangular parallelepiped, a sphere, an ellipse, a cone, a truncated cone, a pyramid, a truncated pyramid, a shape similar to these, or a combination of these. Or a columnar shape such as a shape similar to these. The length of the storage container in the column direction is normally set to be 5 to 70%, preferably 10 to 50% of the inner diameter of the purification cylinder to be mounted, and the surface in the direction perpendicular to the column direction of the storage container. The size of the diameter is a diameter when converted into a circle, and is usually set to be 1 to 30%, preferably 5 to 20% of the filling length of the purifier.
[0016]
When the detection agent storage container of the present invention is used by being attached to a purification cylinder, as shown in FIG. 6, the gas taken into the gas introduction part passes through the detection agent filling part, and is discharged from the discharge part to the container. It is set as the structure discharged | emitted outside. Therefore, the configuration of the storage container is usually that the shape of the filling portion of the detection agent is a cylinder, a prism, or a similar shape, and the shapes of the gas introduction portion and the gas discharge portion are divided into two in the column direction. 2 and 6, the gas permeability is set as a partition 5 for the detection agent filling portion and the gas introduction portion, and a partition 6 for the detection agent filling portion and the gas discharge portion. A material is used, and a gas non-permeable material is used as the partition 7 between the gas introduction part and the gas discharge part. (In the storage container shown in FIGS. 2 and 6, the dotted line indicates the surface of the gas-permeable material, and the solid line indicates the surface of the gas-impermeable material.)
[0017]
Further, in the detection agent storage container of the present invention, the outer peripheral surface of the gas introduction portion and the outer peripheral surface of the gas discharge portion are all composed of gas

permeable materials

8 and 9 as shown in FIG. 3 and 4, each part is composed of gas

permeable material

8 or 9, and each other part is composed of gas impermeable material 8 'and 9'. (The bottom surface of the gas discharge portion in FIG. 4 is made of a gas permeable material.) When a part is made of a gas permeable material, the surface other than the side is usually made of the gas permeable material. The The outer peripheral surface 10 of the detection agent filling portion, the side surface 11 adjacent to the viewing window portion of the detection agent filling portion, and the side surface 12 opposite to the detection agent filling portion of the gas introduction portion and the gas discharge portion are gas permeable. The material may be a gas impermeable material. Furthermore, a transparent material is used for the side surface 11 adjacent to the viewing window portion of the filling portion of the detection agent so that the discoloration of the detection agent can be detected from the outside.
[0018]
As the gas permeable material used in the present invention, any material having corrosion resistance against harmful gas components and capable of preventing the intrusion of the purifier when the purifier is installed in the purifier can be used. Although not particularly limited, for example, reticulated carbon steel, manganese steel, chromium steel, molybdenum steel, stainless steel, and the like can be used. In addition, the gas non-permeable material is not particularly limited as long as it has corrosion resistance against harmful gas components, but usually plate-like carbon steel, manganese steel, chromium steel, molybdenum steel, Stainless steel or the like can be used.
[0019]
The detection agent storage container shown in FIG. 1 has a cylindrical shape in the shape of the entire container and a filling portion of the detection agent, and the shapes of the gas introduction part and the gas discharge part are divided into two in the column direction. It is. In addition, this storage container has a mesh shape as a constituent material for the partition between the detection agent filling portion and the gas introduction portion, the partition between the detection agent filling portion and the gas discharge portion, the outer peripheral surface of the gas introduction portion, and the outer peripheral surface of the gas discharge portion. The transparent acrylic plate is used as the constituent material of the side surface adjacent to the observation window portion of the filling portion of the detection agent, and the metal plate is used as the other constituent material.
Further, in the present invention, means for mounting the storage container filled with the detection agent to the viewing window portion of the purification cylinder is provided, but for easy mounting, the tip 13 of the detection agent filling portion is As shown in FIG. 6, it is preferable to have a structure that can be fitted to the viewing window portion of the purification cylinder with one touch.
[0020]
When the harmful gas detection method of the present invention is carried out, the above storage container is used. In the hazardous gas detection method of the present invention, after the storage container is filled with the detection agent, the storage container is installed so that the detection agent filling portion is adjacent to the viewing window 17 of the purification cylinder, as shown in FIG. Further, the purification cylinder is filled with a purification agent. As described above, when the storage container is installed in the purification cylinder, the purification agent is normally prevented from entering the gas introduction part and the gas discharge part of the storage container.
[0021]
Next, the harmful gas is introduced and purified from the harmful gas inlet of the purification cylinder. The reaction part or adsorbing part of the harmful gas component gradually progresses from the upstream side of the purification agent layer to the downstream side. However, due to the difference in the position of the central part and the peripheral part of the purification agent layer, these are usually the purification agent layer. Does not proceed evenly. However, in the present invention, as shown in FIG. 5, since the harmful gas component can be detected by taking in the gas flowing in the central part of the purifier layer to the gas flowing in the peripheral part, the purification cylinder is in a state where no harmful gas component is detected. Outflow to the downstream side can be prevented.
[0022]
【Example】
EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
[0023]
Example 1
(Production of detection agent storage container)
The shape of the filling part of the detection agent is a cylinder with a bottom diameter of 40 mm and a height of 40 mm, and the shape of the gas introduction part and the gas discharge part is divided into a cylinder with a bottom diameter of 40 mm and a height of 100 mm in the column direction. A storage container having a shape as shown in FIG. 1 was produced. The partition between the detection agent filling portion and the gas introduction portion, and the separation between the detection agent filling portion and the gas discharge portion are made of mesh stainless steel, and the partition between the gas introduction portion and the gas discharge portion is made of plate-like stainless steel. It was. Further, the outer peripheral surface of the gas introduction unit and the outer peripheral surface of the gas discharge unit are made of stainless steel, the outer peripheral surface of the detection agent filling unit, and the side surface opposite to the detection agent filling unit of the gas introduction unit and the gas discharge unit. Is a plate-like stainless steel, and the side surface adjacent to the viewing window portion of the filling portion of the detection agent is a transparent acrylic plate. Further, a fitting portion having a length of 5 mm was provided at the tip of the filling portion of the detection agent.
[0024]
(Preparation of cleaning agent and detection agent)
Next, potassium hydroxide is added to 100 parts by weight of commercially available hopcalite (manufactured by Nissan Gardler Co., Ltd., extruded product with a diameter of 1.5 mm and a length of 3 to 10 mm) mainly composed of manganese dioxide and copper oxide. A cleaning agent was prepared by loading 30 parts by weight. Further, 300 g of granular silica gel (Fuji Silysia Chemical Co., Ltd., Caractect-10) having a specific surface area of 300 m ² / g, 3.0 g of phosphomolybdic acid hydrate and cupric sulfate pentahydrate 0 as discoloring components A detection agent was prepared by impregnating a solution of .6 g in 810 mL of water and then drying at 75 ° C.
[0025]
(Production of purification cylinder)
About the above-mentioned four detection agent storage containers, each detection agent filling portion was filled with the detection agent.
Next, a purification tube made of stainless steel having an inner diameter of 400 mm was filled with the aforementioned purification agent so as to have a thickness of 80 mm, and provided at the four peripheral portions of the purification tube so that the distance between them was uniform. The aforementioned detection agent storage container was attached to the viewing window. The storage container was set so that its upper surface was flush with the upper surface of the cleaning agent.
Further, the purification agent was additionally filled so that the entire filling length was 400 mm.
[0026]
(Detection test)
Detecting agent installed at four locations around the purification cylinder by introducing a noxious gas containing 5000 ppm SiH _{4 in} dry nitrogen into the above purification cylinder by downflow under the conditions of normal pressure, 25 ° C. and flow rate 200 L / min. The time until the color started to change was measured. Moreover, a part of the outlet gas of the purification cylinder was sampled, and the time until SiH ₄ was detected (purification agent breakthrough time) was measured. These results are shown in Table 1. In addition, taking into account the filling length of the cleaning agent and the position of the detection agent, the color change start time of the detection agent calculated from the breakthrough time of the purification agent is also shown.
[0027]
Example 2
(Production of detection agent storage container)
The shape of the filling part of the detection agent is a cube having a side of 40 mm, and the shape of the gas introduction part and the gas discharge part is a shape obtained by dividing a rectangular parallelepiped having a length of 40 mm, a width of 40 mm, and a height of 100 mm into two in the column direction. A storage container as shown in FIG. The partition between the detection agent filling portion and the gas introduction portion, and the separation between the detection agent filling portion and the gas discharge portion are made of mesh stainless steel, and the partition between the gas introduction portion and the gas discharge portion is made of plate-like stainless steel. It was. In addition, the upper surface of the gas introduction part and the lower surface of the gas discharge part are made of mesh-like stainless steel, the side face of the gas introduction part, the side face of the gas discharge part, and the outer peripheral surface of the filling part of the detection agent are made of plate-like stainless steel. The side surface adjacent to the viewing window portion of the filling portion of the detection agent was a transparent acrylic plate. Further, a fitting portion having a length of 5 mm was provided at the tip of the filling portion of the detection agent.
[0028]
(Detection test)
After setting the purification cylinder in the same manner as in Example 1 except that the above storage container was used, a harmful gas containing 5000 ppm of SiH _{4 in} dry nitrogen was subjected to conditions of normal pressure, 25 ° C., and a flow rate of 200 L / min. It introduced into the above-mentioned purification cylinder by a down flow, and the time until the detection agent installed in the peripheral part 4 places of a purification cylinder began to discolor was measured. Moreover, a part of the outlet gas of the purification cylinder was sampled, and the time until SiH ₄ was detected (purification agent breakthrough time) was measured. These results are shown in Table 1. In addition, taking into account the filling length of the cleaning agent and the position of the detection agent, the color change start time of the detection agent calculated from the breakthrough time of the purification agent is also shown.
[0029]
Comparative Example 1
(Production of detection agent storage container)
In the manufacture of the storage container for the detection agent of Example 1, a storage container having only the detection agent filling portion without the gas introduction part and the gas discharge part was manufactured. The shape of the storage container, that is, the detection agent filling portion is a cylinder with a bottom diameter of 40 mm and a height of 40 mm, and the side surface adjacent to the viewing window portion of the detection agent filling portion is a transparent acrylic plate, and other surfaces All were reticulated stainless steel. Further, a fitting portion having a length of 5 mm was provided at the tip of the filling portion of the detection agent.
[0030]
(Detection test)
After setting the purification cylinder in the same manner as in Example 1 except that the above storage container was used, a harmful gas containing 5000 ppm of SiH _{4 in} dry nitrogen was subjected to conditions of normal pressure, 25 ° C., and a flow rate of 200 L / min. It introduced into the above-mentioned purification cylinder by a down flow, and the time until the detection agent installed in the peripheral part 4 places of a purification cylinder began to discolor was measured. Moreover, a part of the outlet gas of the purification cylinder was sampled, and the time until SiH ₄ was detected (purification agent breakthrough time) was measured. These results are shown in Table 1. In addition, taking into account the filling length of the cleaning agent and the position of the detection agent, the color change start time of the detection agent calculated from the breakthrough time of the purification agent is also shown.
[0031]
[Table 1]

[0032]
【The invention's effect】
Purify the harmful gas discharged from the semiconductor manufacturing process, etc. by bringing it into contact with the purifier packed in the purification cylinder and purifying it by the detection agent storage container of the present invention and the harmful gas detection method using the same. It is possible to accurately detect the progress of the reaction part of the agent with the harmful gas component or the adsorption part of the harmful gas component by the purifier.
[Brief description of the drawings]
FIG. 1 is a perspective view showing an example of a detection agent storage container according to the present invention. FIG. 2 is a cross-sectional view showing a vertical configuration example when the detection container is filled with the detection container in FIG. FIG. 4 is a perspective view showing an example of a detection agent storage container other than that shown in FIG. 1. FIG. 4 is a perspective view showing an example of a detection agent storage container other than those shown in FIGS. Sectional drawing which shows the example of a structure of the perpendicular | vertical direction when the storage container of this invention was attached to the viewing-window part of the purification | cleaning cylinder [FIG. 6] The enlarged view which shows the structure of the storage container vicinity in FIG.
DESCRIPTION OF SYMBOLS 1 Detection agent filling part 2 Gas introduction part 3 Gas discharge part 4 Detection agent 5 Partition of detection agent filling part and gas introduction part 6 Partition of detection agent filling part and gas discharge part 7 Gas introduction part and gas discharge part Partition 8 Outer peripheral surface of gas inlet (gas permeable material)
8 'Outer peripheral surface of gas inlet (gas impermeable material)
9 Outer peripheral surface of gas discharge part (gas permeable material)
9 'Outer surface of gas discharge part (gas non-permeable material)
DESCRIPTION OF SYMBOLS 10 Outer peripheral surface of the detection agent filling part 11 Side surface 12 adjacent to the observation window part of a detection agent filling part Side surface 13 opposite to the detection agent filling part of a gas introduction part and a gas discharge part 13 Tip of a detection agent filling part 14 Hazardous gas inlet 15 Purifier 16 Purified gas outlet 17 Viewing window 18 Detecting agent storage container 19 Gas flow 20 Component of viewing window (transparent acrylic material)

Claims

A storage container that is filled with a detection agent and is attached to a viewing window portion of a purification cylinder, comprising a filling portion of a detection agent, a gas introduction portion, and a gas discharge portion, which are partitioned from each other by a partition, The partition between the filling part and the gas introduction part, and the partition between the filling part of the detection agent and the gas discharge part are gas permeable materials, and the partition between the gas introduction part and the gas discharge part is a gas non-permeable material. A detection agent storage container having a configuration in which the gas taken in from the gas introduction part passes through the filling part of the detection agent, passes through the gas discharge part, and is discharged to the outside of the container. .

The container for a detection agent according to claim 1, wherein the container has a cylindrical shape, a prismatic shape, or a shape similar thereto.

The shape of the filling portion of the detection agent is a cylinder, a prism, or a shape similar to these, and the shapes of the gas introduction portion and the gas discharge portion are shapes obtained by dividing the shape into two in the column direction. Container for detection agent.

The detection agent storage container according to claim 1 , wherein the gas permeable material is a net-like material.

The detection agent storage container according to claim 1, wherein the detection agent filling portion has a structure in which the tip of the detection agent filling portion is fitted to the observation window portion of the purification cylinder with one touch.

It is a method of introducing harmful gas into a purification cylinder and purifying the harmful gas by bringing it into contact with a purification agent filled in the purification cylinder, and detecting a harmful gas component passing through the purifier filling portion with a detection agent. The storage container according to claim 1, wherein the detection window is filled with a detection agent, and a harmful gas component contained in the gas introduced into the storage container is detected by the detection agent. How to detect harmful gases.