JPH10192653A - Treatment of gas containing fluorine compound - Google Patents
Treatment of gas containing fluorine compoundInfo
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- JPH10192653A JPH10192653A JP9004349A JP434997A JPH10192653A JP H10192653 A JPH10192653 A JP H10192653A JP 9004349 A JP9004349 A JP 9004349A JP 434997 A JP434997 A JP 434997A JP H10192653 A JPH10192653 A JP H10192653A
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Ｃ2Ｆ6などのフッ
素化合物含有ガスを低温で効率良く分解する分解処理方
法及び触媒材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decomposition treatment method and a catalyst material for efficiently decomposing a fluorine compound-containing gas such as C 2 F 6 at a low temperature.
【０００２】[0002]
【従来の技術】Ｃ2Ｆ6などのフッ素化合物ガスは、半導
体エッチング材料，半導体洗浄用などに大量に使用され
ている。しかし、これらの物質は大気中に放出される
と、地球の温暖化を引き起こす温暖化物質であることが
わかってきた。今後、これらの化合物の使用後の処理に
対して、厳しい規制が行われると予想される。2. Description of the Related Art Fluorine compound gases such as C 2 F 6 are used in large quantities for semiconductor etching materials, semiconductor cleaning, and the like. However, these substances have been found to be warming substances that, when released into the atmosphere, cause global warming. It is expected that strict regulations will be imposed on the treatment of these compounds after use.
【０００３】ところで、Ｃ2Ｆ6などのガスは、分子構成
成分としてフッ素（Ｆ）を多く含有している。フッ素は
すべての元素の中で最も電気陰性度が大きく、化学的に
非常に安定な物質を形成する。特にＣ2Ｆ6などは分子内
力が強く、反応性に乏しい物質である。この性質から、
分解するには高温が必要であり、大量のエネルギを消費
する。また、高温での分解反応は生成するフッ化水素な
どのガスによる装置材料の腐食速度が大きく、適切な分
解処理方法がないのが現状である。Incidentally, gases such as C 2 F 6 contain a large amount of fluorine (F) as a molecular constituent. Fluorine has the highest electronegativity of all elements and forms a very chemically stable substance. In particular, C 2 F 6 and the like are substances having strong intramolecular forces and poor reactivity. From this property,
Decomposition requires high temperatures and consumes large amounts of energy. Further, in the decomposition reaction at a high temperature, the rate of corrosion of the device material by the generated gas such as hydrogen fluoride is high, and at present, there is no appropriate decomposition treatment method.
【０００４】分解処理方法として、現在、提案されつつ
あるのは、高温での燃焼技術である。しかしながらこの
方法では、大量の燃料を使用するためエネルギー効率が
低く、また、燃焼に伴って生成する１０００℃以上のハ
ロゲン化合物による炉壁の損傷の問題もある。従って、
より低温で分解できる技術が必要である。[0004] As a decomposition treatment method, a combustion technique at a high temperature is currently being proposed. However, in this method, a large amount of fuel is used, so that the energy efficiency is low, and there is also a problem of damage to the furnace wall due to a halogen compound of 1000 ° C. or higher generated during combustion. Therefore,
Technology that can decompose at lower temperatures is needed.
【０００５】触媒については、これまでに、ＴｉＯ2−
ＷＯ3触媒が有機ハロゲン化合物の分解用触媒として、
特公平6−59388号公報に報告されている。この触媒はＴ
ｉＯ2の０.１〜２０ｗｔ％ のＷを含む触媒（原子比に
すると、Ｔｉが９２％以上９９.９６％以下、Ｗが８％
以下０.０４％以上）であり、ppmオーダーのＣＣｌ４を
処理するのに３７５℃で分解率９９％を１５００時間保
持していた。有機ハロゲン化合物中で触媒毒としての影
響はＣｌだけでなく、むしろＦの方が大きい。該公報で
は、炭素数１の有機ハロゲン化合物、すなわちＣ
Ｆ４ ，Ｃｌ2Ｆ2等が分解できるとしているが、フッ素
化合物に関する分解結果の実施例はない。また、炭素数
１の有機ハロゲン化合物の分解に比べ、一般に炭素数２
の有機ハロゲン化合物は分解しにくい。別の例として
は、Ａｌ2Ｏ3−ＺｒＯ2−ＷＯ3触媒がフッ素化合物ガス
の分解触媒として、特開平7−80303号公報に報告されて
いる。この触媒は、フロン類を燃焼分解する触媒であ
り、フロン−１１５（Ｃ2ＣｌＦ5）を処理するのに６０
０℃で燃焼分解反応を行い、分解率９８％を１０時間保
持していた。この方法は燃焼助剤として、ｎ−ブタン等
の炭化水素を添加するため、処理コストが大きくなる。
また、Ｃ2Ｆ6等の炭素とフッ素のみの化合物の分解は、
フロン−１１５に比べ、さらに難しいが、これらの物質
に関する分解結果の実施例はない。[0005] As for the catalyst, TiO 2-
WO 3 catalyst is used as a catalyst for decomposing organic halogen compounds.
It is reported in Japanese Patent Publication No. 6-59388. This catalyst is T
Catalyst containing 0.1 to 20 wt% W of iO 2 (in terms of atomic ratio, Ti is 92% or more and 99.96% or less, and W is 8%
(Hereinafter 0.04% or more), and a decomposition rate of 99% was maintained at 375 ° C. for 1500 hours for treating CCl 4 on the order of ppm. In organic halogen compounds, the effect as a catalyst poison is not only Cl but also F. In this publication, an organic halogen compound having 1 carbon atom, that is, C
It is stated that F 4 , Cl 2 F 2 and the like can be decomposed, but there is no example of the decomposition result relating to the fluorine compound. In addition, as compared to decomposition of an organic halogen compound having 1 carbon atom, generally,
Is difficult to decompose. As another example, Al 2 O 3 -ZrO 2 -WO 3 catalyst as a catalyst for decomposing the fluorine compound gas is reported in JP-A-7-80303. This catalyst is burned to decompose the catalyst fluorocarbons, to process CFC -115 a (C 2 ClF 5) 60
The combustion decomposition reaction was performed at 0 ° C., and the decomposition rate was maintained at 98% for 10 hours. In this method, since a hydrocarbon such as n-butane is added as a combustion aid, the processing cost increases.
In addition, the decomposition of compounds containing only carbon and fluorine, such as C 2 F 6 ,
Although more difficult than CFC-115, there are no examples of decomposition results for these substances.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、炭素
を２つ以上含み、フッ素原子を含む化合物、もしくは窒
素原子とフッ素原子を含む化合物の少なくとも一方を含
むガスを低温で効率よく分解処理する方法及び触媒を提
供するものである。An object of the present invention is to efficiently decompose a gas containing two or more carbon atoms and containing a fluorine atom or a gas containing at least one of a nitrogen atom and a fluorine atom at a low temperature. And a catalyst.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、フッ素化
合物含有ガスを低温でかつ高効率で分解が可能で、しか
も分解生成物として遊離されるフッ化水素による装置の
腐食が生じにくい分解処理方法の検討を詳細に進めた結
果、本発明に至った。Means for Solving the Problems The present inventors have found that a fluorine-containing gas can be decomposed at a low temperature and with high efficiency, and the decomposition of hydrogen fluoride which is liberated as a decomposition product does not easily occur in the apparatus. As a result of studying the treatment method in detail, the present invention has been achieved.
【０００８】即ち、炭素を２つ以上含み、かつフッ素原
子を含む化合物、もしくは窒素原子とフッ素原子を含む
化合物の少なくとも一方を含むガス流を、特定のフッ素
化合物分解触媒と、約４００〜約８００℃の温度で、有
効量の水蒸気の存在下で接触させることにより、ガス流
中のフッ素をＨＦに転化できることを見い出した。分解
触媒としては、アルミナ，チタニア，シリカ，ジルコニ
アの少なくとも一種を含む触媒を用いることができる。That is, a gas stream containing at least one of a compound containing two or more carbon atoms and containing a fluorine atom or a compound containing a nitrogen atom and a fluorine atom is mixed with a specific fluorine compound decomposition catalyst by about 400 to about 800 It has been found that by contacting at a temperature of ° C. in the presence of an effective amount of water vapor, fluorine in the gas stream can be converted to HF. As the decomposition catalyst, a catalyst containing at least one of alumina, titania, silica, and zirconia can be used.
【０００９】フッ素化合物としては、Ｃ2Ｆ6などのよう
に炭素数が２以上のＣとＦとの化合物、ＮＦ3 などのＮ
とＦとの化合物などがある。Examples of the fluorine compound include compounds of C and F having 2 or more carbon atoms, such as C 2 F 6, and N, such as NF 3.
And F and the like.
【００１０】さらに、触媒にＳｉ，Ｍｇ，Ｚｒ，Ｗ，Ｓ
ｎ，Ｃｅ，Ｍｎ，Ｂｉ，Ｎｉのうちの少なくとも一成分
を添加すると、フッ素化合物含有ガスをより高い活性で
分解できることを見い出した。これらの触媒はアルミ
ナ，チタニア，シリカ，ジルコニア、そしてＳｉ，Ｍ
ｇ，Ｚｒ，Ｗ，Ｓｎ，Ｃｅ，Ｍｎ，Ｂｉ，Ｎｉ，Ｐ，Ｂ
のうちの少なくとも一成分の酸化物を混合物、あるいは
複合酸化物の形態で含有している。特にアルミナとチタ
ニアを含む触媒では、アルミナが７５ｗｔ％以上９８ｗ
ｔ％以下、チタニアが２５％以下２ｗｔ％以上である場
合に効果が大きい。また、Ｓｉ，Ｍｇ，Ｚｒ，Ｗ，Ｓ
ｎ，Ｃｅ，Ｍｎ，Ｂｉ，Ｎｉ，Ｐ，Ｂの酸化物を触媒主
量に対して０.１〜１０ｗｔ％ で含む場合に効果が大き
い。Further, Si, Mg, Zr, W, S
It has been found that when at least one of n, Ce, Mn, Bi and Ni is added, the fluorine compound-containing gas can be decomposed with higher activity. These catalysts include alumina, titania, silica, zirconia, and Si, M
g, Zr, W, Sn, Ce, Mn, Bi, Ni, P, B
Of at least one of the components in the form of a mixture or a composite oxide. In particular, in a catalyst containing alumina and titania, alumina is 75 wt% or more and 98 w
The effect is large when the content of titania is 2% by weight or less and the content of titania is 2% by weight or less. Also, Si, Mg, Zr, W, S
The effect is significant when the oxides of n, Ce, Mn, Bi, Ni, P, and B are contained in an amount of 0.1 to 10 wt% with respect to the main amount of the catalyst.
【００１１】フッ素化合物含有ガスの分解触媒の開発の
ため種々検討した結果、触媒の性質として、フッ素と適
度な強さの結合を形成する金属成分を含有する必要があ
ることを見い出した。特に、炭素とフッ素とからなる化
合物の場合、分子自体が安定であるため、フッ化物生成
エンタルピーが大きい金属成分を含有する触媒が高分解
活性を示すことを見い出した。あまり安定な結合を形成
してしまうと触媒上からフッ素化合物が離れないため、
活性が徐々に低下する。一方で結合力が弱すぎると十分
な分解率が得られない。本発明の対象ガスであるＣ2Ｆ6
などは、分子内力が強く、反応性の乏しい物質である。
これらのガスを燃焼させる場合、1500〜２０００℃の温
度が必要と言われている。我枚は、本対象ガスは、アル
ミナ，チタニア，シリカ，ジルコニアを単独で触媒とし
て用いても分解できることを見い出したが、より高い分
解率を得る触媒としては、アルミナとチタニアを含んで
なる触媒が好ましいことを見い出した。アルミナはフッ
素化合物を触媒上に引き付ける働きをし、チタニアは触
媒上のフッ素化合物を引き離す働きをすると思われる。As a result of various studies for the development of a catalyst for decomposing a fluorine compound-containing gas, it has been found that the catalyst must contain a metal component which forms a bond having an appropriate strength with fluorine. In particular, in the case of a compound comprising carbon and fluorine, it has been found that a catalyst containing a metal component having a large enthalpy of fluoride formation exhibits high decomposition activity because the molecule itself is stable. If a stable bond is formed, the fluorine compound will not separate from the catalyst,
Activity gradually decreases. On the other hand, if the bonding strength is too weak, a sufficient decomposition rate cannot be obtained. C 2 F 6 which is the target gas of the present invention
Are substances having strong intramolecular force and poor reactivity.
When burning these gases, it is said that a temperature of 1500 to 2000 ° C. is required. We found that the target gas could be decomposed by using alumina, titania, silica, and zirconia alone as a catalyst. I found something favorable. Alumina appears to work to attract fluorine compounds onto the catalyst, and titania appears to work to release fluorine compounds on the catalyst.
【００１２】Ｓｉ，Ｍｇ，Ｚｒ，Ｗ，Ｓｎ，Ｃｅ，Ｍ
ｎ，Ｂｉ，Ｎｉの酸化物は、アルミナ，チタニア，シリ
カ，ジルコニアとの協奏効果を発現させると思われる。
また、触媒中のチタニアの安定化に寄与していると考え
られる。Si, Mg, Zr, W, Sn, Ce, M
It is considered that the oxides of n, Bi, and Ni exhibit a concerted effect with alumina, titania, silica, and zirconia.
Further, it is considered that this contributes to stabilization of titania in the catalyst.
【００１３】本発明のフッ素化合物含有ガスの分解処理
方法では、Ｃ2Ｆ6などのフッ素化合物を、不活性ガスで
希釈してもよいことを見い出した。フッ素化合物の濃度
を希釈することで、触媒に対する負荷が小さくなり、分
解活性を長時間維持することができる。希釈ガスとして
は、Ａｒ，Ｎ2 ，Ｈｅなどの不活性ガスを用いることが
できる。In the method for decomposing a fluorine compound-containing gas of the present invention, it has been found that a fluorine compound such as C 2 F 6 may be diluted with an inert gas. By diluting the concentration of the fluorine compound, the load on the catalyst is reduced, and the decomposition activity can be maintained for a long time. As a diluting gas, an inert gas such as Ar, N 2 , and He can be used.
【００１４】本発明の対象とするフッ素含有化合物はＣ
2Ｆ6,ＮＦ3などのＰＦＣ(perfluorocompound）あるいは
ＦＦＣ（fully fluorocompound）と呼ばれるもので、代
表的な反応としては次のようなものがある。The fluorine-containing compound which is the object of the present invention is C
What is called a 2 F 6, NF 3 etc. PFC (perfluorocompound) or FFC (fully fluorocompound), there are the following as a typical reaction.
【００１５】Ｃ2Ｆ6＋３Ｈ2Ｏ→ＣＯ＋ＣＯ2＋６ＨＦ Ｃ2Ｆ6＋２Ｈ2Ｏ＋１／２Ｏ2→２ＣＯ2＋６ＨＦ ＮＦ3＋３Ｈ2Ｏ→ＮＯ2＋１／２Ｏ2＋６ＨＦ これらのフッ素化合物は、処理するガス中に水素原子を
フッ素化合物中のＦ数と少なくとも同等になるよう添加
することが望ましい。このことにより、化合物中のＦは
ＨＦになり、分解生成物中のＦは後処理しやすいハロゲ
ン化水素の形態となる。このときの水素源としては、水
蒸気のほかに、水素，炭化水素などを用いることができ
るが、炭化水素を用いた場合、炭化水素が触媒上で燃焼
し、供給する熱エネルギを小さくすることができる。C 2 F 6 + 3H 2 O → CO + CO 2 + 6HF C 2 F 6 + 2H 2 O + 1 / 2O 2 → 2CO 2 + 6HF NF 3 + 3H 2 O → NO 2 + 1 / 2O 2 + 6HF These fluorine compounds are gases to be treated. It is desirable to add a hydrogen atom therein so as to be at least equivalent to the F number in the fluorine compound. As a result, F in the compound becomes HF, and F in the decomposition product becomes a form of hydrogen halide which can be easily post-treated. As the hydrogen source at this time, in addition to steam, hydrogen, hydrocarbons, and the like can be used. When hydrocarbons are used, the hydrocarbons burn on the catalyst, and the supplied thermal energy can be reduced. it can.
【００１６】また、反応ガス中に酸素などの酸化ガスを
含有させることで、ＣＯの酸化反応も同時に起こらせる
ことができる。ＣＯの酸化反応が不完全な場合は、分解
生成ガス中のＨＦを除去した後、ＣＯ酸化触媒に接触さ
せてＣＯをＣＯ2 に転換させることもできる。Also, by including an oxidizing gas such as oxygen in the reaction gas, an oxidation reaction of CO can be simultaneously caused. When the oxidation reaction of CO is incomplete, after removing HF in the decomposition product gas, it is possible to convert CO into CO 2 by contacting with a CO oxidation catalyst.
【００１７】本発明の触媒を用いれば、Ｃ2Ｃｌ3Ｆ3，
Ｃ2Ｃｌ2Ｆ4，Ｃ2ＣｌＦ5などのフロン類，ＨＦＣ１３
４ａなどの代替フロン類、また、ＳＦ6 等の化合物も分
解できる。また、ＣＣｌ3Ｆ ，ＣＣｌ2Ｆ2などの物質も
十分分解できる。なお、塩素化合物を処理した場合の化
合物中のＣｌは、ＨＣｌに転化される。When the catalyst of the present invention is used, C 2 Cl 3 F 3 ,
CFCs such as C 2 Cl 2 F 4 and C 2 ClF 5 , HFC13
Alternative fluorocarbons such as 4a and compounds such as SF 6 can also be decomposed. In addition, substances such as CCl 3 F and CCl 2 F 2 can be sufficiently decomposed. Note that Cl in the compound when the chlorine compound is treated is converted to HCl.
【００１８】本発明で用いられる反応温度は、約４００
〜約８００℃が好ましい。これ以上の高温で使用する
と、高分解率は得られるが、触媒の劣化が速い。また、
装置材料の腐食速度が急激に大きくなる。逆に、これ以
下の温度では、分解率が低い。また、生成したＨＦを中
和除去する工程としては、アルカリ溶液をスプレーして
洗浄するものが効率が高く、結晶析出などによる配管の
閉塞が起こりにくいので好ましい。アルカリ溶液中に分
解生成ガスをバブリングする方法あるいは充填塔を用い
て洗浄する方法でもよい。The reaction temperature used in the present invention is about 400
~ 800 ° C is preferred. When used at higher temperatures, a high decomposition rate can be obtained, but the catalyst deteriorates quickly. Also,
The corrosion rate of the equipment material increases rapidly. Conversely, at temperatures below this, the decomposition rate is low. As the step of neutralizing and removing the generated HF, a step of washing by spraying an alkali solution is preferred because it is highly efficient and the pipe is hardly clogged due to crystal precipitation or the like. A method of bubbling a decomposition product gas in an alkaline solution or a method of washing using a packed tower may be used.
【００１９】本発明の触媒を調製するためのＡｌ原料と
しては、γ−アルミナ，γ−アルミナとδ−アルミナの
混合物などを使用することができる。特にベーマイトな
どをＡｌ原料として用い、最終的な焼成により酸化物を
形成するのも好ましい方法である。As the Al raw material for preparing the catalyst of the present invention, γ-alumina, a mixture of γ-alumina and δ-alumina, and the like can be used. In particular, it is also preferable to use boehmite or the like as an Al raw material and form an oxide by final firing.
【００２０】本発明の触媒を調製するためのＴｉ原料と
しては、硫酸チタン，チタニアゾル，チタンスラリ、な
どを使用することができる。As the Ti raw material for preparing the catalyst of the present invention, titanium sulfate, titania sol, titanium slurry and the like can be used.
【００２１】さらに、Ｓｉ，Ｍｇ，Ｚｒなどの第三金属
成分の原料としては、各種、硝酸塩，アンモニウム塩，
塩化物などを用いることができる。Further, as a raw material of the third metal component such as Si, Mg, Zr, etc., various kinds of nitrates, ammonium salts,
Chloride or the like can be used.
【００２２】本発明の触媒の製造法は通常触媒の製造に
用いられる沈殿法，含浸法，混練法などいずれも使用で
きる。As the method for producing the catalyst of the present invention, any of a precipitation method, an impregnation method, a kneading method and the like usually used for producing a catalyst can be used.
【００２３】また、本発明における触媒は、そのまま粒
状，ハニカム状などに成形して使用することができる。
成形法としては、押し出し成形法，打錠成形法，転動造
粒法などを目的に応じ任意の方法を採用できる。また、
セラミックスや金属製のハニカムや板にコーティングし
て使用することもできる。The catalyst according to the present invention can be used as it is in the form of granules, honeycombs or the like.
As the molding method, an arbitrary method such as an extrusion molding method, a tablet molding method, a tumbling granulation method and the like can be adopted according to the purpose. Also,
It can also be used by coating on ceramics or metal honeycombs or plates.
【００２４】本発明のフッ素化合物含有ガス処理方法
は、他の処理方法に比べて低温でフッ素化合物を分解す
ることができる。The method of treating a fluorine compound-containing gas of the present invention can decompose a fluorine compound at a lower temperature than other treatment methods.
【００２５】フッ素化合物含有ガスを処理する場合、分
解して生成するＨＦなどの酸成分による装置材料の腐食
が問題となるが、本発明によれば、使用する温度が比較
的低温であるため、腐食速度が遅く、装置のメンテナン
スなどが不要となる。When a fluorine compound-containing gas is treated, corrosion of equipment materials due to acid components such as HF generated by decomposition is a problem. However, according to the present invention, since the temperature used is relatively low, The corrosion rate is low, and maintenance of the equipment is not required.
【００２６】本発明のフッ素化合物含有ガス処理方法を
実施する装置は、フッ素化合物を分解する触媒反応槽と
分解生成ガス中の酸成分を中和除去する設備を備えるだ
けでよく、装置を小型化できる。The apparatus for carrying out the method for treating a gas containing a fluorine compound of the present invention need only be equipped with a catalyst reaction tank for decomposing a fluorine compound and a facility for neutralizing and removing an acid component in a decomposition product gas. it can.
【００２７】[0027]
【発明の実施の形態】以下、実施例にて本発明をさらに
詳細に説明する。本発明は、これら実施例にのみ限定さ
れるものではない。DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to examples. The present invention is not limited to only these examples.
【００２８】図１は、本発明の分解処理方法を半導体生
産プロセスのプラズマＣＶＤ装置のクリーニング工程で
用いる場合の実施例を示す。FIG. 1 shows an embodiment in which the decomposition treatment method of the present invention is used in a cleaning step of a plasma CVD apparatus in a semiconductor production process.
【００２９】プラズマＣＶＤ装置は、半導体ウェハー表
面にＳｉＯ2 膜を蒸着法で形成させる装置である。しか
し、ＳｉＯ2 膜は装置内全体に付着してしまうので、不
必要な箇所に付いたＳｉＯ2 を除去する必要がある。こ
のＳｉＯ2 をクリーニングするためにＣ2Ｆ6が用いられ
る。Ｃ2Ｆ6を含むクリーニングガスは、ＣＶＤチャンバ
へ送られ、プラズマで励起してＳｉＯ2を除去する。そ
の後、チャンバ内をＮ2で置換し、Ｃ2Ｆ6濃度を約３〜
５％に希釈して約１５ｌ／min でチャンバから排出して
いる。The plasma CVD apparatus is an apparatus for forming an SiO 2 film on the surface of a semiconductor wafer by a vapor deposition method. However, since the SiO 2 film adheres to the entire inside of the apparatus, it is necessary to remove the SiO 2 attached to unnecessary portions. C 2 F 6 is used to clean this SiO 2 . The cleaning gas containing C 2 F 6 is sent to a CVD chamber and excited by plasma to remove SiO 2 . Thereafter, the inside of the chamber is replaced with N 2 , and the C 2 F 6 concentration is reduced to about 3 to
It is diluted to 5% and discharged from the chamber at about 15 l / min.
【００３０】この排出ガスに空気３を添加しＣ2Ｆ6を希
釈した。この希釈ガスに、さらに水蒸気４を添加した反
応ガス５を分解工程に送る。反応ガス中のＣ2Ｆ6濃度は
約０.５％ である。分解工程では、反応ガス５を、空間
速度３０００毎時（空間速度（ｈ~1）＝反応ガス流量
（ｍｌ／ｈ）／触媒量（ｍｌ））の条件でＡｌ2Ｏ3系触
媒と７００℃で接触させる。この場合、反応ガスを加熱
してもよく、電気炉などにより触媒を加熱してもよい。
分解ガス６は、排ガス洗浄工程に送られる。排ガス洗浄
工程では、分解ガス６にアルカリ水溶液がスプレーさ
れ、分解ガス中の酸成分が除去された排ガス７が系外に
放出される。Ｃ2Ｆ6の分解率は、反応ガス５と排ガス７
をＦＩＤ（Flame Ionization Detector の略称）ガスク
ロマトグラフ，ＴＣＤ（Thermal Conductivity Detecto
r の略称）ガスクロマトグラフを用いて分析し、入り口
及び出口の物質収支により求める。Air 3 was added to the exhaust gas to dilute C 2 F 6 . The reaction gas 5 obtained by further adding steam 4 to the dilution gas is sent to a decomposition step. The concentration of C 2 F 6 in the reaction gas is about 0.5%. In the decomposition step, the reaction gas 5 is mixed with the Al 2 O 3 -based catalyst at 700 ° C. under the condition of a space velocity of 3000 per hour (space velocity (h 1 ) = reaction gas flow rate (ml / h) / catalyst amount (ml)). Make contact. In this case, the reaction gas may be heated, or the catalyst may be heated by an electric furnace or the like.
The decomposition gas 6 is sent to an exhaust gas cleaning step. In the exhaust gas cleaning step, an alkaline aqueous solution is sprayed on the decomposition gas 6, and the exhaust gas 7 from which the acid component in the decomposition gas has been removed is discharged out of the system. The decomposition rate of C 2 F 6 is determined by the reaction gas 5 and exhaust gas 7
FID (Flame Ionization Detector) gas chromatograph, TCD (Thermal Conductivity Detector)
Analyze using a gas chromatograph, and determine from the material balance at the entrance and exit.
【００３１】以下、各種フッ素化合物分解触媒の活性を
調べた結果について説明する。Hereinafter, the results of examining the activities of various fluorine compound decomposition catalysts will be described.
【００３２】［実施例１］純度９９％以上のＣ2Ｆ6ガス
に空気を添加して希釈した。この希釈ガスに、さらに水
蒸気を添加した。水蒸気は純水を０.１１ｍｌ／minで反
応管上部へマイクロチューブポンプを用いて供給しガス
化させた。反応ガス中のＣ2Ｆ6濃度は約０.５％ であっ
た。この反応ガスを、電気炉により反応管外部から７０
０℃に加温した触媒と空間速度３０００毎時で接触させ
た。Example 1 C 2 F 6 gas having a purity of 99% or more was diluted by adding air. Steam was further added to this dilution gas. Steam was supplied as pure water at a rate of 0.11 ml / min to the upper portion of the reaction tube by using a micro tube pump to be gasified. The C 2 F 6 concentration in the reaction gas was about 0.5%. This reaction gas is supplied from the outside of the reaction tube to 70 by an electric furnace.
The catalyst was brought into contact with the catalyst heated to 0 ° C. at a space velocity of 3000 per hour.
【００３３】反応管は内径１９mmのインコネル製の反応
管で、触媒層を反応管中央に有しており、内部に外径３
mmのインコネル製の熱電対保護管を有している。触媒層
を通過した分解生成ガスは水酸化ナトリウム溶液中にバ
ブリングさせ、系外に放出した。Ｃ2Ｆ6の分解率は、Ｆ
ＩＤガスクロマトグラフ，ＴＣＤガスクロマトグラフに
より、次式で求めた。The reaction tube is a reaction tube made of Inconel having an inner diameter of 19 mm, having a catalyst layer at the center of the reaction tube, and having an outer diameter of 3 mm inside.
It has a thermocouple protection tube made of Inconel. The decomposition product gas that passed through the catalyst layer was bubbled into a sodium hydroxide solution and released outside the system. The decomposition rate of C 2 F 6 is F
It was determined by the following equation using an ID gas chromatograph and a TCD gas chromatograph.
【００３４】[0034]
【数１】 (Equation 1)
【００３５】以下に上記条件における試験に供した各触
媒の調製法を示す。The preparation method of each catalyst used in the test under the above conditions is shown below.
【００３６】触媒１；Ａｌ2Ｏ3 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を粉砕し、
０.５−１mm 粒径に篩い分けし、１２０℃で２時間乾燥
し、７００℃で２時間焼成したものを試験に供した。Catalyst 1; Granulated alumina (NKHD-24) manufactured by Al 2 O 3 Sumitomo Chemical Co., Ltd.
The mixture was sieved to a particle size of 0.5-1 mm, dried at 120 ° C. for 2 hours, and calcined at 700 ° C. for 2 hours and subjected to a test.
【００３７】触媒２；ＴｉＯ2 堺化学製粒状チタニア（ＣＳ−２００−２４）を粉砕
し、０.５−１mm 粒径に篩い分けし、１２０℃で２時間
乾燥し、７００℃で２時間焼成したものを試験に供し
た。Catalyst 2: TiO 2 Granular titania (CS-200-24) manufactured by Sakai Chemical Co., Ltd. was pulverized, sieved to a particle size of 0.5-1 mm, dried at 120 ° C. for 2 hours, and calcined at 700 ° C. for 2 hours. Those that were subjected to the test.
【００３８】触媒３；ＺｒＯ2 硝酸ジルコニル２００ｇを１２０℃で２時間乾燥し、７
００℃で２時間焼成した。得られた粉末を金型に入れ、
５００kgｆ／cm2 の圧力で圧縮成型した。成型品を粉
砕，篩い分けして０.５−１mm 粒径のジルコニアに造粒
し、試験に供した。Catalyst 3: 200 g of ZrO 2 zirconyl nitrate was dried at 120 ° C. for 2 hours,
Baking was performed at 00 ° C. for 2 hours. Put the obtained powder in a mold,
Compression molding was performed at a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved, granulated into zirconia having a particle size of 0.5-1 mm, and subjected to a test.
【００３９】触媒４；ＳｉＯ2 Fuji Silysia製粒状シリカ（ＣＡＲＩＡＣＴ−１０）を
粉砕し、０.５−１mm粒径に篩い分けし、１２０℃で２
時間乾燥し、７００℃で２時間焼成したものを試験に供
した。Catalyst 4: Granulated silica (CARIACT-10) manufactured by SiO 2 Fuji Silysia was crushed, sieved to a 0.5-1 mm particle size,
After drying for 700 hours and calcining at 700 ° C. for 2 hours, it was subjected to the test.
【００４０】触媒５；ＴｉＯ2−ＺｒＯ2 堺化学製粒状チタニア（ＣＳ−２００−２４）を０.５m
m 以下に粉砕した。この粉末１００ｇに対し硝酸ジルコ
ニル７８.３ｇ を加え、純水を添加しながら混練した。
混練後、１２０℃で２時間乾燥し、７００℃で２時間焼
成した。得られた粉末を金型に入れ、５００kgｆ／cm2
の圧力で圧縮成型した。成型品を粉砕，篩い分けして
０.５−１mm 粒径に造粒し、試験に供した。Catalyst 5: TiO 2 -ZrO 2 0.5 m granular titania (CS-200-24) manufactured by Sakai Chemical Co., Ltd.
m or less. 78.3 g of zirconyl nitrate was added to 100 g of this powder, and kneaded while adding pure water.
After kneading, the mixture was dried at 120 ° C. for 2 hours and calcined at 700 ° C. for 2 hours. The obtained powder is placed in a mold, and 500 kgf / cm 2
Compression molding. The molded product was pulverized and sieved, granulated to a particle size of 0.5-1 mm, and subjected to a test.
【００４１】触媒６；Ａｌ2Ｏ3−ＭｇＯ 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を０.５mm
以下の粒径に粉砕した。この粉末１００ｇに対し、硝酸
マグネシウム５６.４ｇ を加え、純水を添加しながら混
練した。混練後、１２０℃で２時間乾燥し、７００℃で
２時間焼成した。得られた粉末を金型に入れ、５００kg
ｆ／cm2 の圧力で圧縮成型した。成型品を粉砕，篩い分
けして０.５−１mm 粒径として試験に供した。Catalyst 6: Al 2 O 3 —MgO 0.5 mm granular alumina (NKHD-24) manufactured by Sumitomo Chemical Co., Ltd.
It was pulverized to the following particle size. 56.4 g of magnesium nitrate was added to 100 g of this powder, and kneaded while adding pure water. After kneading, the mixture was dried at 120 ° C. for 2 hours and calcined at 700 ° C. for 2 hours. Put the obtained powder in a mold, 500kg
Compression molding was performed at a pressure of f / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００４２】触媒７；Ａｌ2Ｏ3−ＴｉＯ2 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を０.５mm
以下の粒径に粉砕した。この粉末１００ｇに対し、メタ
チタン酸スラリの乾燥粉末５６.４ｇ を加え、純水を添
加しながら混練した。混練後、１２０℃で２時間乾燥
し、７００℃で２時間焼成した。得られた粉末を金型に
入れ、５００kgｆ／cm2 の圧力で圧縮成型した。成型品
を粉砕，篩い分けして０.５−１mm 粒径として試験に供
した。Catalyst 7: Al 2 O 3 —TiO 2 Granular alumina (NKHD-24) manufactured by Sumitomo Chemical Co., Ltd.
It was pulverized to the following particle size. To 100 g of this powder, 56.4 g of a dry powder of metatitanate slurry was added and kneaded while adding pure water. After kneading, the mixture was dried at 120 ° C. for 2 hours and calcined at 700 ° C. for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００４３】触媒８；Ａｌ2Ｏ3−ＳｉＯ2 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を０.５mm
以下の粒径に粉砕した。この粉末１００ｇに対し、Ｓｉ
Ｏ2 ゾルの乾燥粉末１３.２ｇ を加え、純水を添加しな
がら混練した。混練後、１２０℃で２時間乾燥し、７０
０℃で２時間焼成した。得られた粉末を金型に入れ、５
００kgｆ／cm2 の圧力で圧縮成型した。成型品を粉砕，
篩い分けして０.５−１mm 粒径として試験に供した。Catalyst 8: Al 2 O 3 —SiO 2 Granular alumina (NKHD-24) manufactured by Sumitomo Chemical Co., Ltd.
It was pulverized to the following particle size. For 100 g of this powder, Si
13.2 g of a dry powder of O 2 sol was added and kneaded while adding pure water. After kneading, drying at 120 ° C. for 2 hours, 70
It was baked at 0 ° C. for 2 hours. Put the obtained powder in a mold,
It was compression molded at a pressure of 00 kgf / cm 2 . Crush the molded product,
The mixture was sieved and subjected to a test with a particle size of 0.5-1 mm.
【００４４】上記触媒１〜８の試験結果を図２に示す。FIG. 2 shows the test results of the catalysts 1 to 8.
【００４５】［実施例２］本実施例は、実施例１と同様
の条件で、第三成分添加の効果を調べたものである。各
触媒は以下のように調製した。Example 2 In this example, the effect of the addition of the third component was examined under the same conditions as in Example 1. Each catalyst was prepared as follows.
【００４６】触媒９；Ａｌ2Ｏ3−ＴｉＯ2 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を粉砕し、
０.５−１mm 粒径に篩い分けし、１２０℃で２時間乾燥
した。これに、３０％硫酸チタン溶液１７６ｇを含浸し
た。含浸後、２５０〜３００℃で約５時間乾燥し、７０
０℃で２時間焼成した。これを試験に供した。Catalyst 9; Al 2 O 3 —TiO 2 Granulated alumina (NKHD-24) manufactured by Sumitomo Chemical Co., Ltd.
It was sieved to a particle size of 0.5-1 mm and dried at 120 ° C. for 2 hours. This was impregnated with 176 g of a 30% titanium sulfate solution. After impregnation, dry at 250-300 ° C for about 5 hours,
It was baked at 0 ° C. for 2 hours. This was subjected to a test.
【００４７】触媒１０；Ａｌ2Ｏ3−ＴｉＯ2−ＺｒＯ2 住友化学製粒状アルミナ（ＮＫＨＤ−２４）を粉砕し、
０.５−１mm 粒径に篩い分けし、１２０℃で２時間乾燥
した。これに、３０％硫酸チタン溶液１７６ｇを含浸し
た。含浸後、２５０〜３００℃で約５時間乾燥し、７０
０℃で２時間焼成し、触媒Ａを作製した。続いて、触媒
Ａ５０ｇに、硝酸ジルコニル２水和物６.７ｇを９０ｇ
のＨ2Ｏに溶かした水溶液を含浸した。含浸後、１２０
℃で２時間乾燥し、７００℃で２時間焼成した。これを
試験に供した。Catalyst 10: Al 2 O 3 —TiO 2 —ZrO 2 Granulated alumina (NKHD-24) manufactured by Sumitomo Chemical Co., Ltd.
It was sieved to a particle size of 0.5-1 mm and dried at 120 ° C. for 2 hours. This was impregnated with 176 g of a 30% titanium sulfate solution. After impregnation, dry at 250-300 ° C for about 5 hours,
It was calcined at 0 ° C. for 2 hours to prepare Catalyst A. Subsequently, 6.7 g of zirconyl nitrate dihydrate was added to 90 g of catalyst A in 50 g.
With an aqueous solution dissolved in H 2 O. After impregnation, 120
C. for 2 hours and calcined at 700.degree. C. for 2 hours. This was subjected to a test.
【００４８】触媒１１；Ａｌ2Ｏ3−ＴｉＯ2−ＷＯ3 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、パラタングステン酸アンモニウム６.５
ｇをＨ2Ｏに溶かした９０ｇの水溶液を含浸した。含浸
後、１２０℃で２時間乾燥し、７００℃で２時間焼成し
た。これを試験に供した。Catalyst 11: Al 2 O 3 —TiO 2 —WO 3 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 6.5 g of ammonium paratungstate was added to 50 g of Catalyst A.
g in H 2 O was impregnated with 90 g of an aqueous solution. After impregnation, it was dried at 120 ° C. for 2 hours and fired at 700 ° C. for 2 hours. This was subjected to a test.
【００４９】触媒１２；Ａｌ2Ｏ3−ＴｉＯ2−ＳｉＯ2 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、２０ｗｔ％シリカゾル７.５ｇをＨ2Ｏに
溶かした９０ｇの水溶液を含浸した。含浸後、１２０℃
で２時間乾燥し、７００℃で２時間焼成した。これを試
験に供した。 触媒１３；Ａｌ2Ｏ3−ＴｉＯ2−ＳｎＯ2 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、塩化すず２水和物５.６ｇをＨ2Ｏに溶か
した９０ｇの水溶液を含浸した。含浸後、120℃で２時
間乾燥し、７００℃で２時間焼成した。これを試験に供
した。Catalyst 12: Al 2 O 3 —TiO 2 —SiO 2 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 50 g of the catalyst A was impregnated with 90 g of an aqueous solution in which 7.5 g of 20 wt% silica sol was dissolved in H 2 O. 120 ° C after impregnation
For 2 hours and calcined at 700 ° C. for 2 hours. This was subjected to a test. Catalyst 13: Al 2 O 3 —TiO 2 —SnO 2 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 50 g of Catalyst A was impregnated with 90 g of an aqueous solution in which 5.6 g of tin chloride dihydrate was dissolved in H 2 O. After impregnation, it was dried at 120 ° C. for 2 hours and fired at 700 ° C. for 2 hours. This was subjected to a test.
【００５０】触媒１４；Ａｌ2Ｏ3−ＴｉＯ2−ＣｅＯ2 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、硝酸セリウム６水和物１０.９ｇをＨ2Ｏ
に溶かした９０ｇの水溶液を含浸した。含浸後、１２０
℃で２時間乾燥し、７００℃で２時間焼成した。これを
試験に供した。 触媒１５；Ａｌ2Ｏ3−ＴｉＯ2−ＭｎＯ2 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、硝酸マンガン６水和物７.２ｇをＨ2Ｏに
溶かした９０ｇの水溶液を含浸した。含浸後、１２０℃
で２時間乾燥し、７００℃で２時間焼成した。これを試
験に供した。Catalyst 14: Al 2 O 3 —TiO 2 —CeO 2 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 10.9 g of cerium nitrate hexahydrate was added to 50 g of catalyst A in H 2 O.
Was impregnated with 90 g of an aqueous solution. After impregnation, 120
C. for 2 hours and calcined at 700.degree. C. for 2 hours. This was subjected to a test. Catalyst 15: Al 2 O 3 —TiO 2 —MnO 2 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 50 g of the catalyst A was impregnated with 90 g of an aqueous solution in which 7.2 g of manganese nitrate hexahydrate was dissolved in H 2 O. 120 ° C after impregnation
For 2 hours and calcined at 700 ° C. for 2 hours. This was subjected to a test.
【００５１】触媒１６；Ａｌ2Ｏ3−ＴｉＯ2−Ｂｉ2Ｏ3 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、硝酸ビスマス６水和物７.４ｇをＨ2Ｏに
溶かした９０ｇの水溶液を含浸した。含浸後、１２０℃
で２時間乾燥し、７００℃で２時間焼成した。これを試
験に供した。Catalyst 16: Al 2 O 3 —TiO 2 —Bi 2 O 3 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 50 g of Catalyst A was impregnated with 90 g of an aqueous solution of 7.4 g of bismuth nitrate hexahydrate dissolved in H 2 O. 120 ° C after impregnation
For 2 hours and calcined at 700 ° C. for 2 hours. This was subjected to a test.
【００５２】触媒１７；Ａｌ2Ｏ3−ＴｉＯ2−ＮｉＯ 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、硝酸ニッケル６水和物７.３ｇをＨ2Ｏに
溶かした９０ｇの水溶液を含浸した。含浸後、１２０℃
で２時間乾燥し、７００℃で２時間焼成した。これを試
験に供した。Catalyst 17: Al 2 O 3 —TiO 2 —NiO Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 50 g of the catalyst A was impregnated with 90 g of an aqueous solution in which 7.3 g of nickel nitrate hexahydrate was dissolved in H 2 O. 120 ° C after impregnation
For 2 hours and calcined at 700 ° C. for 2 hours. This was subjected to a test.
【００５３】触媒１８；Ａｌ2Ｏ3−ＴｉＯ2−ＢＯ4 触媒１０と同様の方法で触媒Ａを作製した。続いて、触
媒Ａ５０ｇに、ほう酸アンモニウム８水和物１２.０ｇ
をＨ2Ｏに溶かした９０ｇの水溶液を含浸した。含浸
後、１２０℃で２時間乾燥し、７００℃で２時間焼成し
た。これを試験に供した。Catalyst 18: Al 2 O 3 —TiO 2 —BO 4 Catalyst A was prepared in the same manner as the catalyst 10. Subsequently, 12.0 g of ammonium borate octahydrate was added to 50 g of Catalyst A.
Was dissolved in H 2 O and impregnated with 90 g of an aqueous solution. After impregnation, it was dried at 120 ° C. for 2 hours and fired at 700 ° C. for 2 hours. This was subjected to a test.
【００５４】上記触媒９〜１８と、実施例１中の触媒１
の活性を図３に示す。The above catalysts 9 to 18 and catalyst 1 in Example 1
Is shown in FIG.
【００５５】［実施例３］本実施例は、アルミナ原料及
びチタニア原料を変化させて各種触媒を調製し、実施例
１と同様の方法で活性を調べた例である。Example 3 In this example, various catalysts were prepared by changing the alumina raw material and titania raw material, and the activity was examined in the same manner as in Example 1.
【００５６】触媒１９；Ａｌ2Ｏ3 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で２時間乾燥した。この乾燥粉末２００ｇを３
００℃で０.５ 時間焼成し、さらに焼成温度を７００℃
にあげ２時間焼成した。得られた粉末を金型に入れ、５
００kgｆ／cm2の圧力で圧縮成型した。成型品を粉砕，
篩い分けして０.５−１mm 粒径として試験に供した。Catalyst 19: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 CONDEA was dried at 120 ° C. for 2 hours. 200 g of this dry powder
Firing at 00 ° C for 0.5 hours, and then firing at 700 ° C
Raised for 2 hours. Put the obtained powder in a mold,
It was compression molded at a pressure of 00 kgf / cm 2 . Crush the molded product,
The mixture was sieved and subjected to a test with a particle size of 0.5-1 mm.
【００５７】触媒２０；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末２００ｇと３
０％硫酸チタン溶液２４８.４ｇ を純水約２００ｇを添
加しながら混練した。混練後、２５０〜３００℃で約５
時間乾燥し、７００℃で２時間焼成した。得られた粉末
を金型に入れ、５００kgｆ／cm2 の圧力で圧縮成型し
た。成型品を粉砕，篩い分けして０.５−１mm 粒径とし
て試験に供した。Catalyst 20: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 —TiO 2 CONDEA was dried at 120 ° C. for 1 hour. 200 g of this dry powder and 3
248.4 g of a 0% titanium sulfate solution was kneaded while adding about 200 g of pure water. After kneading, at 250-300 ° C, about 5
It was dried for 700 hours and baked at 700 ° C. for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００５８】触媒２１；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末２００ｇと、
３０％チタニアゾル７８.６ｇ に純水を加えた約１００
ｇの水溶液を混練した。混練後、１２０℃で約２時間乾
燥し、７００℃で２時間焼成した。得られた粉末を金型
に入れ、５００kgｆ／cm2 の圧力で圧縮成型した。成型
品を粉砕，篩い分けして０.５−１mm 粒径として試験に
供した。上記の触媒１９〜２１の活性を実施例１と同様
の方法で調べた結果を図４に示す。And Al 2 O 3 -TiO 2 CONDEA Ltd. boehmite powder (PURAL SB) was dried 1 hour at 120 ° C.; [0058] Catalyst 21. 200 g of this dry powder,
About 100% of pure water added to 78.6 g of 30% titania sol
g of the aqueous solution was kneaded. After kneading, the mixture was dried at 120 ° C. for about 2 hours and calcined at 700 ° C. for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm. FIG. 4 shows the results of examining the activities of the catalysts 19 to 21 in the same manner as in Example 1.
【００５９】［実施例４］本実施例は、実施例３の触媒
２０中のＡｌとＴｉの組成を変化させた触媒を調製し、
活性を調べた結果である。Example 4 In this example, a catalyst was prepared by changing the composition of Al and Ti in the catalyst 20 of Example 3,
This is the result of examining the activity.
【００６０】触媒２２；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末１００ｇと３
０％硫酸チタン溶液４８.８ｇ を純水約１５０ｇを添加
しながら混練した。混練後、２５０〜３００℃で約５時
間乾燥し、700℃で２時間焼成した。得られた粉末を金
型に入れ、５００kgｆ／cm2 の圧力で圧縮成型した。成
型品を粉砕，篩い分けして０.５−１mm 粒径として試験
に供した。Catalyst 22: AlTwoOThree-TiOTwo CONDEA boehmite powder (PURAL SB)
Dried at 120 ° C. for 1 hour. 100 g of this dry powder and 3
48.8 g of 0% titanium sulfate solution and about 150 g of pure water
While kneading. After kneading, about 5 o'clock at 250-300 ° C
After drying, the mixture was fired at 700 ° C. for 2 hours. Gold powder obtained
500kgf / cmTwoCompression molding. Success
Pulverize and sieve the mold and test as 0.5-1mm particle size
Was served.
【００６１】触媒２３；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末１００ｇと３
０％硫酸チタン溶液８２.４ｇ を純水約１２０ｇを添加
しながら混練した。混練後、２５０〜３００℃で約５時
間乾燥し、700℃で２時間焼成した。得られた粉末を金
型に入れ、５００kgｆ／cm2 の圧力で圧縮成型した。成
型品を粉砕，篩い分けして０.５−１mm 粒径として試験
に供した。Catalyst 23: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 —TiO 2 CONDEA was dried at 120 ° C. for 1 hour. 100 g of this dry powder and 3
82.4 g of a 0% titanium sulfate solution was kneaded while adding about 120 g of pure water. After kneading, the mixture was dried at 250 to 300 ° C for about 5 hours and calcined at 700 ° C for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００６２】触媒２４；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末１００ｇと３
０％硫酸チタン溶液１７４.４ｇ を純水約７０ｇを添加
しながら混練した。混練後、２５０〜３００℃で約５時
間乾燥し、700℃で２時間焼成した。得られた粉末を金
型に入れ、５００kgｆ／cm2 の圧力で圧縮成型した。成
型品を粉砕，篩い分けして０.５−１mm 粒径として試験
に供した。Catalyst 24: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 —TiO 2 CONDEA was dried at 120 ° C. for 1 hour. 100 g of this dry powder and 3
174.4 g of a 0% titanium sulfate solution was kneaded while adding about 70 g of pure water. After kneading, the mixture was dried at 250 to 300 ° C for about 5 hours and calcined at 700 ° C for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００６３】触媒２５；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末１００ｇと３
０％硫酸チタン溶液３９２ｇを添加しながら混練した。
混練後、２５０〜３００℃で約５時間乾燥し、７００℃
で２時間焼成した。得られた粉末を金型に入れ、５００
kgｆ／cm2 の圧力で圧縮成型した。成型品を粉砕，篩い
分けして０.５−１mm 粒径として試験に供した。Catalyst 25: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 —TiO 2 CONDEA was dried at 120 ° C. for 1 hour. 100 g of this dry powder and 3
The mixture was kneaded while adding 392 g of a 0% titanium sulfate solution.
After kneading, drying at 250-300 ° C for about 5 hours, 700 ° C
For 2 hours. The obtained powder is put in a mold, and 500
Compression molding was performed at a pressure of kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm.
【００６４】上記の触媒２２〜２５の活性を実施例１と
同様の方法で調べた結果を図５に示す。FIG. 5 shows the results of examining the activities of the catalysts 22 to 25 in the same manner as in Example 1.
【００６５】［実施例５］本実施例は、触媒調製時に硫
酸を添加した場合の例である。Example 5 This example is an example in which sulfuric acid was added during catalyst preparation.
【００６６】触媒２６；Ａｌ2Ｏ3−ＴｉＯ2 ＣＯＮＤＥＡ製ベーマイト粉末（ＰＵＲＡＬ ＳＢ）を
１２０℃で１時間乾燥した。この乾燥粉末１５０ｇに、
石原産業製ＣＳ−Ｎ３０％チタニアゾル溶液５８.８ｇ
と、９７％硫酸溶液４４.８ｇ を純水２５０ｍｌで希釈
した水溶液を添加し混練した。混練後、２５０〜３００
℃で約５時間乾燥し、７００℃で２時間焼成した。得ら
れた粉末を金型に入れ、５００kgｆ／cm2 の圧力で圧縮
成型した。成型品を粉砕，篩い分けして０.５−１mm 粒
径として試験に供した。試験条件は、空間速度を１００
０毎時とした以外は実施例１と同様である。試験の結
果、反応温度６５０℃でＣ2Ｆ6の分解率８０％が得られ
た。Catalyst 26: Boehmite powder (PURAL SB) manufactured by Al 2 O 3 —TiO 2 CONDEA was dried at 120 ° C. for 1 hour. To 150 g of this dry powder,
Ishihara Sangyo CS-N 30% titania sol solution 58.8 g
And an aqueous solution obtained by diluting 44.8 g of a 97% sulfuric acid solution with 250 ml of pure water was added and kneaded. 250-300 after kneading
C. for about 5 hours and calcined at 700.degree. C. for 2 hours. The obtained powder was put in a mold and compression-molded under a pressure of 500 kgf / cm 2 . The molded product was pulverized and sieved to give a test having a particle size of 0.5-1 mm. The test condition is that the space velocity is 100
It is the same as Example 1 except that the time is set to 0 every hour. As a result of the test, a decomposition rate of C 2 F 6 of 80% was obtained at a reaction temperature of 650 ° C.
【００６７】[0067]
【発明の効果】本発明によれば、Ｃ2Ｆ6，ＮＦ3 などの
フッ素含有ガスを効率良く分解処理することができる。According to the present invention, fluorine-containing gases such as C 2 F 6 and NF 3 can be efficiently decomposed.
【図１】本発明の一実施例による処理プロセスを示す工
程図である。FIG. 1 is a process chart showing a processing process according to an embodiment of the present invention.
【図２】各種フッ素化合物分解触媒の性能を示すグラフ
である。FIG. 2 is a graph showing the performance of various fluorine compound decomposition catalysts.
【図３】各種フッ素化合物分解触媒の性能を示すグラフ
である。FIG. 3 is a graph showing the performance of various fluorine compound decomposition catalysts.
【図４】各種フッ素化合物分解触媒の性能を示すグラフ
である。FIG. 4 is a graph showing the performance of various fluorine compound decomposition catalysts.
【図５】各種フッ素化合物分解触媒の性能を示すグラフ
である。FIG. 5 is a graph showing the performance of various fluorine compound decomposition catalysts.
【符号の説明】 １…Ｃ2Ｆ6、２…Ｎ2 、３…空気、４…水蒸気、５…反
応ガス、６…分解ガス、７…排ガス。[Description of Signs] 1 ... C 2 F 6 , 2 ... N 2 , 3 ... Air, 4 ... Steam, 5 ... Reaction gas, 6 ... Decomposition gas, 7 ... Exhaust gas.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安田 健 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 山下 寿生 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 小豆畑 茂 茨城県日立市大みか町七丁目１番１号 株 式会社日立製作所日立研究所内 (72)発明者 玉田 慎 茨城県日立市幸町三丁目１番１号 株式会 社日立製作所日立工場内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Ken Yasuda 7-1-1, Omikacho, Hitachi City, Ibaraki Prefecture Inside Hitachi, Ltd. Hitachi Research Laboratory, Ltd. (72) Inventor Hisao Yamashita 7-1 Omikacho, Hitachi City, Ibaraki Prefecture # 1 Inside Hitachi, Ltd.Hitachi Research Laboratory (72) Inventor Shigeru Azuhata 7-1-1, Omika-cho, Hitachi City, Ibaraki Prefecture Inside Hitachi, Ltd.Hitachi Research Laboratory (72) Inventor Shin Tamada, Hitachi City, Ibaraki Prefecture 3-1-1, Machi-cho Hitachi, Ltd. Hitachi Plant
Claims (6)
む化合物、もしくは窒素原子とフッ素原子を含む化合物
の少なくとも一方を含むガス流を、アルミナ，チタニ
ア，シリカ，ジルコニアの少なくとも一種を含む触媒と
約４００〜８００℃の温度で、有効量の水蒸気の存在下
で接触させて、前記ガス流中のＦをＨＦに転化する工程
を含んでなることを特徴とするフッ素化合物含有ガスの
処理方法。1. A catalyst comprising at least one of alumina, titania, silica and zirconia, wherein a gas stream containing two or more carbon atoms and containing a fluorine atom or a compound containing at least one of a nitrogen atom and a fluorine atom is used. And converting the F in the gas stream to HF by contacting the gas at a temperature of about 400 to 800 ° C. in the presence of an effective amount of steam. .
化合物含有ガスが、炭素を２つ以上含むＣとＦとの化合
物、もしくはＮとＦとの化合物であることを特徴とする
フッ素化合物含有ガスの処理方法。2. The method according to claim 1, wherein the fluorine compound-containing gas is a compound of C and F or a compound of N and F containing two or more carbon atoms. Gas treatment method.
が、さらにＳｉ，Ｍｇ，Ｚｒ，Ｗ，Ｓｎ，Ｃｅ，Ｍｎ，
Ｂｉ，Ｎｉのうちの少なくとも一成分を含むことを特徴
とするフッ素化合物含有ガスの処理方法。3. The method of claim 1, wherein said catalyst further comprises Si, Mg, Zr, W, Sn, Ce, Mn,
A method for treating a fluorine compound-containing gas, comprising at least one component of Bi and Ni.
しくはＮとＦとの化合物を少なくとも一方を含むガス流
を処理する触媒であって、アルミナとチタニアを含み、
アルミナが７５ｗｔ％以上９８ｗｔ％以下、チタニアが
２５ｗｔ％以下２ｗｔ％以上であることを特徴とするフ
ッ素化合物分解触媒。4. A catalyst for treating a gas stream containing at least one of a compound of C and F or a compound of N and F containing two or more carbons, comprising alumina and titania.
A fluorine compound decomposition catalyst comprising 75 wt% to 98 wt% of alumina and 25 wt% to 2 wt% of titania.
ｉ，Ｍｇ，Ｚｒ，Ｗ，Ｓｎ，Ｃｅ，Ｍｎ，Ｂｉ，Ｎｉ，
Ｐ，Ｂのうちの少なくとも一成分を含むことを特徴とす
るフッ素化合物分解触媒。5. The catalyst according to claim 4, further comprising S
i, Mg, Zr, W, Sn, Ce, Mn, Bi, Ni,
A fluorine compound decomposition catalyst comprising at least one of P and B.
ｇ，Ｚｒ，Ｗ，Ｓｎ，Ｃｅ，Ｍｎ，Ｂｉ,Ｎｉ，Ｐ，Ｂ
の酸化物を、アルミナーチタニア触媒主量に対し、０.
１wt％〜１０ｗｔ％で含むことを特徴とするフッ素化合
物分解触媒。6. The catalyst according to claim 5, wherein Si, M
g, Zr, W, Sn, Ce, Mn, Bi, Ni, P, B
Of the oxide with respect to the main amount of the alumina-titania catalyst.
A fluorine compound decomposition catalyst, which is contained at 1 wt% to 10 wt%.
Priority Applications (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP00434997A JP3977887B2 (en) | 1997-01-14 | 1997-01-14 | Treatment method for fluorine compound-containing gas |
| US09/005,006 US20010001652A1 (en) | 1997-01-14 | 1998-01-09 | Process for treating flourine compound-containing gas |
| US10/215,045 US6942841B2 (en) | 1997-01-14 | 2002-08-09 | Process for treating fluorine compound-containing gas |
| US10/676,013 US20040067185A1 (en) | 1997-01-14 | 2003-10-02 | Process for treating fluorine compound-containing gas |
| US10/677,961 US6855305B2 (en) | 1997-01-14 | 2003-10-03 | Process for treating fluorine compound-containing gas |
| US10/679,297 US7347980B2 (en) | 1997-01-14 | 2003-10-07 | Process for treating fluorine compound-containing gas |
| US11/294,376 US20060093547A1 (en) | 1997-01-14 | 2005-12-06 | Process for treating fluorine compound-containing gas |
| US11/334,345 US20060120938A1 (en) | 1997-01-14 | 2006-01-19 | Process for treating fluorine compound-containing gas |
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Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10323537A (en) * | 1997-03-24 | 1998-12-08 | Showa Denko Kk | Catalytic cracking method of prefluoro compound |
| WO2000009258A1 (en) * | 1998-08-17 | 2000-02-24 | Ebara Corporation | Method and apparatus for treating waste gas containing fluorochemical |
| WO2001021304A1 (en) * | 1999-09-17 | 2001-03-29 | Guild Associates | Alumina-based catalyst composition and method of destruction of pfc and hfc |
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1997
- 1997-01-14 JP JP00434997A patent/JP3977887B2/en not_active Expired - Fee Related
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