JP4350081B2 - Exhaust gas treatment method and apparatus - Google Patents

Exhaust gas treatment method and apparatus Download PDF

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JP4350081B2
JP4350081B2 JP2005275283A JP2005275283A JP4350081B2 JP 4350081 B2 JP4350081 B2 JP 4350081B2 JP 2005275283 A JP2005275283 A JP 2005275283A JP 2005275283 A JP2005275283 A JP 2005275283A JP 4350081 B2 JP4350081 B2 JP 4350081B2
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exhaust gas
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decomposition treatment
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豊司 篠原
洋一 森
康彦 鈴木
弘 青野
祐司 白尾
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Ebara Corp
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]

Description

本発明は排ガスの処理方法および装置に係り、特に半導体製造工程で半導体製造装置の内面等をドライクリーニングする工程や、酸化膜等の各種成膜をエッチングする工程などで排出されるフッ素含有化合物および一酸化炭素ガス（以下、COという）を含む排ガスを、効率よく無害化処理する方法および装置に関する。   The present invention relates to a method and apparatus for treating exhaust gas, and in particular, a fluorine-containing compound discharged in a step of dry cleaning an inner surface of a semiconductor manufacturing apparatus in a semiconductor manufacturing process, a step of etching various film formation such as an oxide film, and the like The present invention relates to a method and apparatus for efficiently detoxifying exhaust gas containing carbon monoxide gas (hereinafter referred to as CO).

半導体製造時のエッチング工程やＣＶＤ工程などにおいて、CHF3などのフッ化炭化水素や、CF4，C2F6，C3F8，C4F8，C5F8，C4F6，SF6，NF3などのパーフルオロ化合物（以下「PFC」という）などのフッ素含有化合物が使用されている。また、COやNH3やO2が半導体製造装置で使用されることもある。これらフッ素含有化合物やCOやNH3を使用した半導体製造装置から排出される排ガス中には、CO，NH3，SiF4，F2，COF2，C5F8，C4F6，NF3などの有害成分が含まれるとともに、有害ではないが地球温暖化効果のあるフッ素含有化合物が含まれている。そのため、フッ素含有化合物やCOを使用した半導体製造装置から排出される排ガスを環境中に排出する場合には、排ガス中に含まれる有害ガスの無害化および地球温暖化ガスの分解処理が必要となる。 Fluorohydrocarbons such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 8 , C 5 F 8 , C 4 F 6 , Fluorine-containing compounds such as perfluoro compounds (hereinafter referred to as “PFC”) such as SF 6 and NF 3 are used. Also, CO, NH 3 and O 2 may be used in semiconductor manufacturing equipment. In the exhaust gas discharged from semiconductor manufacturing equipment using these fluorine-containing compounds and CO or NH 3 , CO, NH 3 , SiF 4 , F 2 , COF 2 , C 5 F 8 , C 4 F 6 , NF 3 And fluorine-containing compounds that are not harmful but have a global warming effect. Therefore, when exhaust gas discharged from semiconductor manufacturing equipment using fluorine-containing compounds or CO is discharged into the environment, it is necessary to detoxify harmful gases contained in the exhaust gas and to decompose the greenhouse gases. .

排ガス中のSiF4，F2，COF2，C5F8，C4F6，NH3などの従来の有害ガス処理方法としては、合成ゼオライトなどの吸着剤を用いて有害成分を吸着処理する方法がある。しかしながら、COおよびPFCの除去はできないという問題がある。また、吸着剤の定期交換が必要となり、ランニングコストが高くなるという問題がある。
湿式排ガス処理装置(水洗処理)によるSiF4やF2，NH3などの水溶性ガスや加水分解性ガスの処理方法がある。しかしながら、COやPFCなどの水溶性以外のガスの除去はできないという問題がある。 Conventional harmful gas treatment methods such as SiF 4 , F 2 , COF 2 , C 5 F 8 , C 4 F 6 , NH 3 in exhaust gas are used to adsorb harmful components using an adsorbent such as synthetic zeolite. There is a way. However, there is a problem that CO and PFC cannot be removed. In addition, periodic replacement of the adsorbent is necessary, and there is a problem that running cost increases.
There are treatment methods for water-soluble gases and hydrolyzable gases such as SiF 4 , F 2 , and NH 3 using wet exhaust gas treatment equipment (water washing treatment). However, there is a problem that gases other than water-soluble such as CO and PFC cannot be removed.

また、排ガス中のCOの従来の処理方法として、酸化触媒とO2によりCOをCO2に酸化させる方法がある。しかし、PFCの分解除去はできないという問題がある。また、SiF4やF2などの酸性ガスやPFCが酸化触媒に接触すると、酸化触媒が被毒されCO酸化能力が低下し、酸化触媒の定期的な交換が必要となるという問題がある。 Further, as a conventional method for treating CO in exhaust gas, there is a method of oxidizing CO to CO 2 using an oxidation catalyst and O 2 . However, there is a problem that PFC cannot be decomposed and removed. In addition, when an acidic gas such as SiF 4 or F 2 or PFC comes into contact with the oxidation catalyst, there is a problem that the oxidation catalyst is poisoned, the CO oxidation ability is lowered, and the oxidation catalyst needs to be periodically replaced.

排ガス中の有害ガスとCOを同時処理する従来の方法としては、上記吸着処理、水洗処理および酸化処理の組合せにより可能である。ただし、処理剤の定期交換があるためランニングコストが高くなる。また、PFCの除去はできないという問題がある。   As a conventional method for simultaneously treating harmful gas and CO in exhaust gas, a combination of the above-described adsorption treatment, water washing treatment and oxidation treatment is possible. However, since there is a periodic replacement of the treatment agent, the running cost becomes high. There is also a problem that PFC cannot be removed.

各種PFC分解触媒を用いた除去方法が提案されている（特許文献１，２参照）。しかしながら、触媒の劣化が進んだ場合にCOやC5F8，C4F6といった有害成分がただちに流出する可能性がある。また、燃焼方式による処理方法が提案されているが、燃焼条件により副生成ガスとしてNOxやCOが発生する可能性がある。また、H2，都市ガス，プロパンガスなどの燃料が必要となり、燃料を供給するための設備が必要となり、運転管理も煩雑になるという問題がある。また、加熱酸化分解により分解する方法が提案されているが、CF4などの難分解性のPFCを分解するには1400℃以上の高温にする必要があり、材料やヒータなどに対する負荷が非常に大きいという問題がある。 Removal methods using various PFC decomposition catalysts have been proposed (see Patent Documents 1 and 2). However, when the catalyst is deteriorated, harmful components such as CO, C 5 F 8 , and C 4 F 6 may flow out immediately. Further, although a treatment method using a combustion method has been proposed, NOx and CO may be generated as a by-product gas depending on combustion conditions. Further, there is a problem that fuel such as H 2 , city gas, propane gas, etc. is required, equipment for supplying the fuel is required, and operation management becomes complicated. Further, a method of decomposing by heating oxidative decomposition is proposed, should be a high temperature of at least 1400 ° C. to decompose the hardly decomposable PFC such as CF 4, materials and the like load is very to the heater There is a problem of being big.

また、NH3もしくは低級飽和炭化水素ガスもしくは低級不飽和炭化水素ガスを添加して、遊離O2のない状態で加熱酸化分解する方法が提案されている（特許文献３，４，５参照）が、O2共存下での加熱酸化分解方法は提案されていない。また、水（H2O）存在下でプラズマによりPFCを分解する方法が提案されているが、PFCを分解する際にCOやHFといった有害ガスが発生し、また、サーマルNOxが発生する。そのためこれらを処理する排ガス処理装置が別途必要となる。 In addition, there has been proposed a method in which NH 3 or lower saturated hydrocarbon gas or lower unsaturated hydrocarbon gas is added to perform thermal oxidative decomposition without free O 2 (see Patent Documents 3, 4, and 5). However, no heat oxidative decomposition method in the presence of O 2 has been proposed. In addition, a method of decomposing PFC by plasma in the presence of water (H 2 O) has been proposed, but when decomposing PFC, harmful gases such as CO and HF are generated, and thermal NOx is generated. Therefore, an exhaust gas treatment apparatus for treating these is separately required.

特許第３２１７０３４号Japanese Patent No. 3217034 特許第３２３７６５１号Japanese Patent No. 3237651 特開平９−８５０４５号JP-A-9-85045 特開平１１−３３３２４７号JP-A-11-333247 特開２０００−３４２９３１号JP 2000-342931

本発明は上述した事情に鑑みて為されたもので、フッ素含有化合物およびCOを同時に且つ効率的に処理することができ、ランニングコストが廉価で、装置材料に対する負荷が低く装置コストを低減でき、且つ有害ガスの排出のない排ガスの処理方法および処理装置を提供することを目的とする。   The present invention has been made in view of the above-described circumstances, can treat fluorine-containing compounds and CO simultaneously and efficiently, has a low running cost, has a low load on apparatus materials, and can reduce apparatus costs. An object of the present invention is to provide an exhaust gas treatment method and a treatment apparatus that do not emit harmful gases.

本発明の排ガス処理は、フッ素含有化合物を含む排ガスに02および水(H20)を添加して700〜900℃の温度に加熱することにより加熱酸化分解処理を行い、該加熱酸化分解処理を行う間、前記排ガスを接触補助手段に接触させて該排ガスに乱流を起こさせ、ついで、触媒反応により前記加熱酸化分解処理で処理しきれなかったフッ素含有化合物の触媒反応分解処理を600〜900℃の温度で行い、ついで、前記触媒反応分解処理した排ガス中よりフッ素含有化合物を分解する際に生成する酸性ガスの除去を行い、前記加熱酸化分解処理は、炭素数４以上のフッ素含有化合物の分解処理を行い、前記触媒反応分解処理は、炭素数３以下のフッ素含有化合物の分解処理を行うことを特徴とする。ここで、前記加熱酸化分解処理の前に、前記フッ素含有化合物に含まれる粉体成分および水溶性成分および加水分解性成分の少なくとも１つを除去する処理を行うことが好ましい。 Exhaust gas treatment of the present invention performs a thermal oxidation decomposition treatment by heating with the addition of 0 2 and water to the exhaust gas containing fluorine-containing compounds (H 2 0) to a temperature of 700 to 900 ° C., heating oxidative decomposition During the process, the exhaust gas is brought into contact with the contact assisting means to cause turbulent flow in the exhaust gas, and then the catalytic reaction decomposition treatment of the fluorine-containing compound that could not be processed by the heating oxidative decomposition treatment by catalytic reaction is performed in 600 ~. carried out at a temperature of 900 ° C., then, have a row in the removal of acid gases generated during the decomposition of the fluorine-containing compound from the catalytic reaction decomposed treated flue gas, the heating oxidative decomposition treatment, the fluorine-containing 4 or more carbon atoms A decomposition treatment of the compound is performed, and the catalytic reaction decomposition treatment is performed by decomposing a fluorine-containing compound having 3 or less carbon atoms . Here, it is preferable to perform the process which removes at least 1 of the powder component contained in the said fluorine-containing compound, a water-soluble component, and a hydrolysable component before the said heat | fever oxidative decomposition process.

上記本発明によれば、吸着処理または気液接触処理でSiF4やF2といった有害性ガスを許容値（TLV-TWA値）以下の濃度まで除去することが可能である。また、好ましくは700〜900℃の加熱酸化処理により、CO酸化触媒を使わずにCOをCO2に酸化させ、許容値（TLV-TWA値）以下の濃度に処理可能である。また、C4F6やC5F8やNF3などの有害性PFCも加熱処理により許容値（TLV-TWA値）以下の濃度に完全に分解可能である。そして、フッ素含有化合物を加熱酸化分解処理によって分解する際に生じるHF等の酸性ガスは、その後の吸着処理または気液接触処理によって除去可能である。したがって、例えば1000℃以上の高温による加熱酸化分解処理を用いることなく、また触媒による処理を用いることなく、人体に有害とされる排ガス成分を無害化することができる。なお、700〜900℃の熱処理では、例えばCF4などの難分解性のPFCは分解が困難である。しかしながら、これらの成分は地球温暖化等の観点からすると問題があるが、人体に有害とされるものではなく、上記排ガスの処理方法によれば、人体に有害とされるガス成分は全て許容値以下に処理することができる。 According to the present invention, it is possible to remove harmful gases such as SiF 4 and F 2 to a concentration below an allowable value (TLV-TWA value) by adsorption treatment or gas-liquid contact treatment. Further, it is possible to oxidize CO to CO 2 without using a CO oxidation catalyst, preferably by heat oxidation treatment at 700 to 900 ° C., and to treat it at a concentration below an allowable value (TLV-TWA value). In addition, harmful PFCs such as C 4 F 6 , C 5 F 8 and NF 3 can be completely decomposed to a concentration below the allowable value (TLV-TWA value) by heat treatment. The acidic gas such as HF generated when the fluorine-containing compound is decomposed by the heat oxidative decomposition treatment can be removed by the subsequent adsorption treatment or gas-liquid contact treatment. Therefore, for example, exhaust gas components that are harmful to the human body can be rendered harmless without using a heat oxidative decomposition process at a high temperature of 1000 ° C. or higher and without using a catalyst. In addition, in the heat treatment at 700 to 900 ° C., for example, difficult-to-decompose PFC such as CF 4 is difficult to decompose. However, these components are problematic from the viewpoint of global warming and the like, but are not harmful to the human body, and according to the exhaust gas treatment method, all the gas components that are harmful to the human body are allowable values. The following can be processed.

なお、触媒反応により600〜900℃という比較的低温度でCF4などの難分解性PFCを完全に分解することも可能である。従って、例えば加熱酸化分解処理後に触媒反応を併用することで、これらの地球温暖化の観点から処理が必要とされるガス成分も完全に分解して除去することができる。 It is also possible to completely decompose hardly decomposable PFC such as CF 4 at a relatively low temperature of 600 to 900 ° C. by catalytic reaction. Therefore, for example, by using a catalytic reaction in combination after the heat oxidative decomposition treatment, these gas components that require treatment from the viewpoint of global warming can be completely decomposed and removed.

本発明によれば、半導体製造装置等から排出されるフッ素含有化合物及びCOを含む排ガスを効率よく経済的に無害化処理することができる。   ADVANTAGE OF THE INVENTION According to this invention, the waste gas containing the fluorine-containing compound and CO discharged | emitted from a semiconductor manufacturing apparatus etc. can be processed efficiently and economically harmless.

以下、本発明の実施形態について添付図面を参照しながら説明する。   Hereinafter, embodiments of the present invention will be described with reference to the accompanying drawings.

図１は、本発明の第１の実施形態の排ガス処理装置を示す。この排ガス処理装置は、フッ素含有化合物及びCOを含む排ガス中に含まれる粉体成分または水溶性成分または加水分解性成分を除去する前処理部１と、前処理後の排ガスの加熱酸化分解処理を行う加熱酸化分解処理部２と、上記加熱酸化分解処理によって生じたHF等の酸性ガスの後処理を行う後処理部４とを備えている。   FIG. 1 shows an exhaust gas treatment apparatus according to a first embodiment of the present invention. This exhaust gas treatment apparatus includes a pretreatment unit 1 that removes a powder component, a water-soluble component, or a hydrolyzable component contained in an exhaust gas containing a fluorine-containing compound and CO, and a heat oxidative decomposition treatment of the exhaust gas after the pretreatment. A heating oxidative decomposition treatment unit 2 to be performed and a post-processing unit 4 to perform a post-treatment of an acidic gas such as HF generated by the heat oxidative decomposition treatment are provided.

前処理部１として、気液接触用に例えば前処理用水スプレー塔が用いられている。このスプレー塔１には水道水もしくは工水が供給されており、水スプレーにより散水されている。フッ素含有化合物及びCOを含む排ガスは、水スプレー塔１の下部から上部に向かって流れ、水スプレーから散水された水と接触することで排ガス中の粉体成分、水溶性成分、加水分解性成分の除去を行う。なお、前処理部には水スプレー塔１以外にファンスクラバー、通気攪拌槽、ゼオライト・活性炭等の吸着剤を充填した吸着槽を設置しても同様の効果が得られる。   As the pretreatment unit 1, for example, a pretreatment water spray tower is used for gas-liquid contact. The spray tower 1 is supplied with tap water or industrial water, and is sprayed with water spray. Exhaust gas containing fluorine-containing compounds and CO flows from the lower part to the upper part of the water spray tower 1 and comes into contact with the water sprayed from the water spray so that the powder component, water-soluble component, and hydrolyzable component in the exhaust gas. Remove. In addition to the water spray tower 1, a similar effect can be obtained even if an adsorption tank filled with an adsorbent such as a zeolite / activated carbon is installed in the pretreatment section.

前処理部として使用する装置は、処理する排ガスの成分や粉体の混入状況、また、工場設備の状況により適切な装置を選定することができる。なお、吸着剤による吸着は、水を使用しないので排水処理設備がない場合に適している。また、As(砒素)やPb(鉛)などの特別管理物質が排ガス中に含まれる場合は、水洗処理は排水にこれらの成分が混入するため好ましくないので、吸着処理が適している。また、ファンスクラバーは、低水量で高い除去率が得られる。また、粉体捕集性能も非常に優れている。また、水スプレー塔は、構造が簡単であるので高い除去性能を得るためには水量を多くする必要があるが、装置が安価になる。また、通気攪拌槽は、攪拌槽内に中和液を投入しpH調整を行うことが可能で、水洗除去しにくい成分でも高い除去率を得られる。   As an apparatus used as the pretreatment unit, an appropriate apparatus can be selected depending on the components of exhaust gas to be treated, the state of mixing powder, and the state of factory equipment. Adsorption with an adsorbent is suitable when there is no wastewater treatment facility because water is not used. In addition, when specially controlled substances such as As (arsenic) and Pb (lead) are contained in the exhaust gas, the washing process is not preferable because these components are mixed in the waste water, and therefore, an adsorption process is suitable. Further, the fan scrubber can obtain a high removal rate with a low amount of water. In addition, the powder collection performance is also excellent. Further, since the water spray tower has a simple structure, it is necessary to increase the amount of water in order to obtain a high removal performance, but the apparatus becomes inexpensive. In addition, the aeration and stirring tank can adjust the pH by introducing a neutralizing solution into the stirring tank, and can obtain a high removal rate even for components that are difficult to wash and remove.

前処理部では、排ガス中に含まれる粉体成分、水溶性成分、または加水分解性成分を上述したように水又は吸着剤により除去する。例えば、SiF4，F2等の酸性ガスは前処理部で除去される。 In the pretreatment section, the powder component, water-soluble component, or hydrolyzable component contained in the exhaust gas is removed with water or an adsorbent as described above. For example, acid gases such as SiF 4 and F 2 are removed in the pretreatment section.

前処理部を通過した排ガスは加熱酸化分解処理槽２で分解処理される。分解処理は加熱酸化分解処理槽２で行われ、反応に必要なO2を供給するために空気配管５が接続されている。また、反応に必要な水配管６も接続されている。市水又は工水は加熱酸化分解処理槽２に導入される前に配管６に接続された水清浄器７により蒸留水相当に浄化される。そして、水気化器８により気化されて加熱酸化分解処理槽２に供給される。または、反応に必要な水は水気化器８により気化せず、そのままスプレーで加熱酸化分解処理槽に噴霧しても良い。そして、前記噴霧された水は加熱酸化分解処理槽にて加熱され、気化される。加熱酸化分解処理槽２には加熱手段としてセラミック製電気管状炉９が取り付けられて排ガスとO2と水（H2O）が混合した排ガス温度を700〜900℃に加熱する。これにより加熱酸化分解処理槽２内では以下の反応式によりCOの酸化処理および炭素数４以上のPFCおよびフッ化炭化水素およびNF3の分解処理が行われる。従って、排ガス中に含まれる人体に有害とされるガス成分は全て酸化または分解処理が可能である。 The exhaust gas that has passed through the pretreatment section is decomposed in the heat oxidation decomposition treatment tank 2. The decomposition treatment is performed in the heat oxidation decomposition treatment tank 2, and an air pipe 5 is connected to supply O 2 necessary for the reaction. A water pipe 6 necessary for the reaction is also connected. The city water or industrial water is purified to the equivalent of distilled water by the water purifier 7 connected to the pipe 6 before being introduced into the heating oxidative decomposition treatment tank 2. Then, it is vaporized by the water vaporizer 8 and supplied to the heating oxidative decomposition treatment tank 2. Alternatively, water necessary for the reaction may be sprayed as it is on the heat oxidation decomposition treatment tank without being vaporized by the water vaporizer 8. Then, the sprayed water is heated and vaporized in a heating oxidative decomposition treatment tank. A ceramic electric tubular furnace 9 is attached to the heating oxidative decomposition treatment tank 2 as a heating means, and the exhaust gas temperature in which exhaust gas, O 2 and water (H 2 O) are mixed is heated to 700 to 900 ° C. As a result, in the heat oxidative decomposition treatment tank 2, the oxidation treatment of CO and the decomposition treatment of PFC, fluorocarbon and NF 3 having 4 or more carbon atoms are performed by the following reaction formula. Therefore, all the gas components harmful to the human body contained in the exhaust gas can be oxidized or decomposed.

2CO ＋ O2 → 2CO2
CO ＋ H2O → CO2 ＋H2
2H2 ＋ O2 → 2H2O
C5F8 ＋ 4H2O ＋ 3O2 → 5CO2 ＋ 8HF
C4F8 ＋ 4H2O ＋ 2O2 → 4CO2 ＋ 8HF
2C4F6 ＋ 6H20 ＋ 5O2 → 8CO2 ＋ 12HF
2CHF3 ＋ 2H2O ＋ O2 → 3CO2 ＋ 8HF
2NF3 ＋ 3H2O → NO + NO2 + 6HF 2CO + O 2 → 2CO 2
CO + H 2 O → CO 2 + H 2
2H 2 + O 2 → 2H 2 O
C 5 F 8 + 4H 2 O + 3O 2 → 5CO 2 + 8HF
C 4 F 8 + 4H 2 O + 2O 2 → 4CO 2 + 8HF
2C 4 F 6 + 6H 2 0 + 5O 2 → 8CO 2 + 12HF
2CHF 3 + 2H 2 O + O 2 → 3CO 2 + 8HF
2NF 3 + 3H 2 O → NO + NO 2 + 6HF

酸化処理に際して、O2は、大気中の空気、O2富化空気、純O2等、いかなるO2源から供給しても良いし、過酸化物を用いても良い。なお、酸化および分解処理に700〜900℃の温度を用いるのは、この温度で上記ガス成分の酸化および分解処理が行えると共に、1000℃以上の高温域では、空気中のN2等より生じるサーマルNOXの生成量が増大するという問題があるからである。また、900℃以下とすることで、槽に必要な耐火材等に経済的なものを用いることができるからである。 In the oxidation treatment, O 2 may be supplied from any O 2 source such as air in the atmosphere, O 2 enriched air, pure O 2, or a peroxide. Note that the temperature of 700 to 900 ° C. is used for the oxidation and decomposition treatment, and the above gas components can be oxidized and decomposed at this temperature, and in the high temperature range of 1000 ° C. or more, the thermal generated from N 2 or the like in the air. This is because there is a problem that the amount of NO X produced increases. Moreover, it is because an economical thing can be used for a fireproof material etc. which are required for a tank by setting it as 900 degrees C or less.

後処理部４は、フッ素含有化合物を分解する際に生成するHF等の酸性ガスの後処理を行う。この実施形態においては、後処理用水スプレー塔４である。これには水道水もしくは工水が供給されており、水スプレーにより散水されている。排ガスは水スプレー塔４の下部から上部に向かって流れ、水スプレーから散水された水と接触することにより、加熱酸化分解処理槽２でPFCが分解する際に発生するHFの除去を行う。なお、後処理部には水スプレー塔４以外にファンスクラバー、通気攪拌槽、ゼオライト・活性炭等の吸着剤を充填した吸着槽を設置しても同様の効果が得られる。   The post-processing unit 4 performs post-processing of an acidic gas such as HF that is generated when the fluorine-containing compound is decomposed. In this embodiment, it is a post-treatment water spray tower 4. This is supplied with tap water or industrial water and is sprayed with water spray. The exhaust gas flows from the lower part to the upper part of the water spray tower 4 and comes into contact with the water sprayed from the water spray, thereby removing HF generated when the PFC is decomposed in the heated oxidative decomposition treatment tank 2. In addition to the water spray tower 4, a post scrubber, an aeration and stirring tank, and an adsorption tank filled with an adsorbent such as zeolite / activated carbon can be used to obtain the same effect.

図２は、本発明の第２の実施形態の排ガス処理装置を示す。この装置においては、加熱酸化分解処理が行われた排ガスは、引き続き触媒反応部である触媒反応槽３で触媒による分解処理が行われる。なお、触媒反応槽３を設けた以外の構成は、図１に示す排ガス処理装置の構成と同様である。   FIG. 2 shows an exhaust gas treatment apparatus according to a second embodiment of the present invention. In this apparatus, the exhaust gas that has been subjected to the thermal oxidative decomposition process is subsequently decomposed by a catalyst in the catalytic reaction tank 3 that is a catalytic reaction unit. The configuration other than the provision of the catalyst reaction tank 3 is the same as the configuration of the exhaust gas treatment apparatus shown in FIG.

触媒反応槽３にはPFC分解触媒が充填されていて排ガスは触媒層上層から下層に向かって流れる。また触媒反応槽３には加熱手段としてセラミック製電気管状炉１０が取り付けられており、触媒反応槽３の温度を600〜900℃になるように加熱している。これにより触媒反応部では炭素数３以下のPFCおよびSF6と触媒が接触することで以下の反応がおこり、PFCおよびSF6の分解処理が行われる。なお、分解反応に寄与するO2と水（H2O）は上流の加熱酸化分解処理槽２で導入されたものである。触媒としては、γアルミナ、アルミナジルコニウム複合酸化物にタングステン酸化物を担持した触媒等のフッ素含有化合物分解触媒が用いられる。これにより、加熱酸化分解処理槽２で処理しきれなかった難分解性のPFCおよびSF6の分解処理が行える。従って、この触媒反応による分解処理を付加することで、人体には直接影響がないとされるが、地球温暖化等に悪影響を及ぼすとされる排ガス成分を完全に除去することができる。 The catalyst reaction tank 3 is filled with a PFC decomposition catalyst, and the exhaust gas flows from the upper layer of the catalyst layer toward the lower layer. Further, a ceramic electric tubular furnace 10 is attached to the catalyst reaction tank 3 as a heating means, and the temperature of the catalyst reaction tank 3 is heated to 600 to 900 ° C. As a result, in the catalytic reaction section, the PFC and SF 6 having 3 or less carbon atoms come into contact with the catalyst to cause the following reaction, whereby the PFC and SF 6 are decomposed. Note that O 2 and water (H 2 O) that contribute to the decomposition reaction were introduced in the upstream heating oxidative decomposition treatment tank 2. As the catalyst, a fluorine-containing compound decomposition catalyst such as a catalyst in which tungsten oxide is supported on γ-alumina or alumina-zirconium composite oxide is used. Thereby, the decomposition process of the hardly decomposable PFC and SF 6 which could not be processed in the heat oxidation decomposition treatment tank 2 can be performed. Therefore, by adding the decomposition treatment by the catalytic reaction, it is considered that there is no direct influence on the human body, but exhaust gas components that are considered to have an adverse effect on global warming and the like can be completely removed.

CF4 ＋ 2H2O → CO2 ＋ 4HF
2C2F6 ＋ 6H2O ＋ O2 → 4CO2 ＋ 12HF
C3F8 ＋ 4H2O ＋ O2 → 3CO2 ＋ 8HF
2SF6 ＋ 3H2O ＋ O2 → SO2 ＋ SO3 + 6HF CF 4 + 2H 2 O → CO 2 + 4HF
2C 2 F 6 + 6H 2 O + O 2 → 4CO 2 + 12HF
C 3 F 8 + 4H 2 O + O 2 → 3CO 2 + 8HF
2SF 6 + 3H 2 O + O 2 → SO 2 + SO 3 + 6HF

図３は、本発明の第３の実施形態の排ガス処理装置を示す。この排ガス処理装置は、加熱酸化分解処理部と触媒反応部と後処理部を一体にしたガス処理槽１３を備えている。また、前処理部にファンスクラバー１４を設置している。ファンスクラバー１４には洗浄水が送水ポンプ１５から供給され、この洗浄水と排ガスがファンスクラバー１４内のファンの回転により接触し、排ガス中の粉体成分、水溶性成分、加水分解成分を除去する。   FIG. 3 shows an exhaust gas treatment apparatus according to a third embodiment of the present invention. This exhaust gas treatment apparatus includes a gas treatment tank 13 in which a heat oxidative decomposition treatment unit, a catalyst reaction unit, and a post-treatment unit are integrated. In addition, a fan scrubber 14 is installed in the pretreatment unit. The cleaning water is supplied to the fan scrubber 14 from the water pump 15, and the cleaning water and the exhaust gas come into contact with the rotation of the fan in the fan scrubber 14 to remove the powder component, water-soluble component, and hydrolysis component in the exhaust gas. .

加熱酸化分解処理部と触媒反応部と後処理部に相当するのがガス処理槽１３で、排ガスの通過する順に加熱酸化分解部１６と触媒反応部１７と後処理部１８が備えられている。加熱酸化分解部１６と触媒反応部１７と後処理部１８を一体構造とすることで、装置の小型化を計っている。また、一体とすることで加熱酸化分解部１６でセラミック電気管状炉１９により700〜900℃に加熱した排ガスを温度低下させることなく触媒反応部１７に導入することができる。従って、触媒反応部１７にはヒータなどの加熱手段を設ける必要が無く、保温材２０を触媒反応部１７の外周に設置するだけでよい。   A gas treatment tank 13 corresponds to a heat oxidative decomposition treatment section, a catalyst reaction section, and a post-treatment section, and is provided with a heat oxidative decomposition section 16, a catalyst reaction section 17, and a post-treatment section 18 in the order in which exhaust gas passes. By making the heating oxidative decomposition unit 16, the catalytic reaction unit 17, and the post-processing unit 18 into an integral structure, the apparatus is downsized. Moreover, by integrating, the exhaust gas heated to 700 to 900 ° C. by the ceramic electric tubular furnace 19 in the heating oxidative decomposition unit 16 can be introduced into the catalyst reaction unit 17 without lowering the temperature. Therefore, it is not necessary to provide heating means such as a heater in the catalyst reaction unit 17, and it is only necessary to install the heat insulating material 20 on the outer periphery of the catalyst reaction unit 17.

加熱酸化分解処理および触媒反応処理に必要なO2はガス処理槽１３の上部に接続された空気配管２１から供給される。また、水（H2O）は水清浄器２３により蒸留水相当に浄化され、その後にガス処理槽１３に導入される。その後、ガス処理槽１３内部のセラミック電気管状炉１９の外壁に設置された水気化配管２５を通過する際に、セラミック電気管状炉１９の排熱との熱交換により加熱され気化し、ガス処理槽１３の上部に備えられた加熱酸化分解処理部１６に導入される。ガス処理槽１３の下部には水スプレー１８を具備した後処理部が備えられており、水スプレー１８には送水ポンプ１５から洗浄水が供給される。 O 2 necessary for the heat oxidative decomposition treatment and the catalytic reaction treatment is supplied from an air pipe 21 connected to the upper portion of the gas treatment tank 13. Further, water (H 2 O) is purified to the equivalent of distilled water by the water purifier 23 and then introduced into the gas treatment tank 13. After that, when passing through the water vaporization pipe 25 installed on the outer wall of the ceramic electric tubular furnace 19 inside the gas treatment tank 13, the gas treatment tank is heated and vaporized by heat exchange with the exhaust heat of the ceramic electric tubular furnace 19. 13 is introduced into the heat oxidative decomposition processing unit 16 provided at the upper part of 13. A lower portion of the gas treatment tank 13 is provided with a post-treatment unit having a water spray 18, and cleaning water is supplied to the water spray 18 from a water supply pump 15.

処理対象の排ガスは、前処理用ファンスクラバ１４を通過した後、ミストセパレータ２６を通過し、ガス処理槽１３に導入される。また、後処理部１８でHFが除去された排ガスはミストセパレータ２７を通過した後、無害化された処理済みのガスとして排気される。   The exhaust gas to be treated passes through the pretreatment fan scrubber 14, then passes through the mist separator 26, and is introduced into the gas treatment tank 13. The exhaust gas from which HF has been removed by the post-processing section 18 passes through the mist separator 27 and is then exhausted as a detoxified treated gas.

COの酸化反応やPFCの分解に水（H2O）が必要であるが、この水（H2O）は気化して排ガス処理系に導入する。水の中にSiやCaなどが含まれていると水（H2O）を気化させる際にSiやCaが析出し(スケールが発生し)、装置内で閉塞が発生する恐れがある。また、Cｌなどは触媒の劣化の原因となる可能性がある。そのため供給される水（H2O）は純水や蒸留水などの清浄な水である必要がある。純水や蒸留水を装置に供給するためには独立した専用の配管を施工する必要があり、さらに、別途純水製造装置や蒸留水製造装置なども必要となるため設備に関する費用負担が大きくなる。水を清浄にする水清浄器を装置に備えることで、装置に供給する水は水道水や工業用水でよくなり、配管等の設備に関する費用が軽減される。 Water (H 2 O) is required for CO oxidation and PFC decomposition, but this water (H 2 O) is vaporized and introduced into the exhaust gas treatment system. If the water contains Si, Ca, etc., when vaporizing the water (H 2 O), Si or Ca may precipitate (scale will occur), which may cause clogging in the device. Further, Cl or the like may cause deterioration of the catalyst. Therefore, the supplied water (H 2 O) needs to be clean water such as pure water or distilled water. In order to supply pure water or distilled water to the equipment, it is necessary to construct an independent dedicated pipe. Furthermore, a separate pure water production equipment or distilled water production equipment is required, which increases the cost burden on the equipment. . By providing the apparatus with a water purifier that purifies water, the water supplied to the apparatus may be tap water or industrial water, and the costs related to equipment such as piping can be reduced.

次に、本発明の排ガス処理方法について説明する。
フッ素含有化合物およびCOを含む排ガス中に含まれる粉体成分または水溶性成分または加水分解性成分を前処理により除去する。排ガス中に含まれる粉体成分または水溶性成分または加水分解性成分の除去を行う前処理部として、吸着剤による吸着処理を行う吸着処理槽もしくはファンスクラバーもしくは水スプレー塔もしくは通気攪拌槽等のいずれかを用いる。 Next, the exhaust gas treatment method of the present invention will be described.
The powder component, water-soluble component, or hydrolyzable component contained in the exhaust gas containing the fluorine-containing compound and CO is removed by pretreatment. As a pretreatment part that removes the powder component, water-soluble component or hydrolyzable component contained in the exhaust gas, any of an adsorption treatment tank, a fan scrubber, a water spray tower, an aeration stirring tank, etc. that performs an adsorption treatment with an adsorbent Is used.

上記前処理により粉体成分または水溶性成分または加水分解性成分を除去した後のフッ素含有化合物およびCOを含む排ガスを、700〜900℃の温度でO2および水（H2O）と接触させてCOをCO2に酸化させるとともに炭素数４以上のフッ素含有化合物等の分解処理を行う。加熱酸化分解処理は、上記排ガスを通気可能とする中空内部、その中空内部のガス温度を700〜900℃に加熱可能な加熱手段、被処理ガスの導入口、O2導入口および水（H2O）導入口を備えた加熱酸化分解処理部にて行われる。
排ガスとO2，水（H2O）の接触効率を高め、且つ加熱効率を高めるための接触補助手段を備えることが好ましい。排ガスは接触補助手段により乱流が起こり、排ガスとO2，水（H2O）との接触効率を高めるとともに、接触補助手段自体がヒータから発せられる熱を輻射により受けて高温となり、排ガスへの伝熱面積が大きくなり、加熱効率を高めることができる。これにより加熱酸化分解処理部が小型化されヒータ容量を低く抑えることができる。 The exhaust gas containing the fluorine-containing compound and CO after removing the powder component, water-soluble component or hydrolyzable component by the above pretreatment is brought into contact with O 2 and water (H 2 O) at a temperature of 700 to 900 ° C. CO is oxidized to CO 2 and decomposes fluorine-containing compounds with 4 or more carbon atoms. The heat oxidative decomposition treatment includes a hollow interior in which the exhaust gas can be vented, a heating means capable of heating the gas temperature in the hollow to 700 to 900 ° C., a gas inlet, an O 2 inlet and water (H 2 O) It is carried out in a heating oxidative decomposition treatment unit equipped with an inlet.
It is preferable to provide a contact assisting means for increasing the contact efficiency between the exhaust gas, O 2 and water (H 2 O) and increasing the heating efficiency. The exhaust gas is turbulent by the contact assisting means, increasing the contact efficiency between the exhaust gas and O 2 , water (H 2 O), and the contact assisting means itself receives the heat generated by the heater by radiation and becomes high temperature. The heat transfer area becomes larger and the heating efficiency can be increased. As a result, the heat oxidative decomposition processing unit can be downsized and the heater capacity can be kept low.

最後に、加熱酸化分解処理部でフッ素含有化合物を分解処理する際に発生する酸性ガス（HF）を除去する。このHFの除去は、後処理部として吸着剤による吸着処理を行う吸着処理槽もしくはファンスクラバーもしくは水スプレーもしくは通気攪拌槽等を用いて行う。以上で、排ガス中の人体に有害とされるガス成分の処理が全て完了する。   Finally, the acidic gas (HF) generated when the fluorine-containing compound is decomposed in the heating oxidative decomposition processing section is removed. The removal of HF is performed using an adsorption treatment tank, a fan scrubber, a water spray, an aeration stirring tank, or the like that performs an adsorption treatment with an adsorbent as a post-processing section. This completes the processing of all gas components that are harmful to the human body in the exhaust gas.

さらに、地球温暖化の観点から問題となるガス成分を除去するためには、加熱酸化分解処理後に触媒による分解処理を行う。即ち、触媒反応部で600〜900℃の温度でフッ素含有化合物分解触媒とO2および水（H2O）を接触させることで炭素数３以下のフッ素含有化合物およびSF6の分解処理を行うことができる。触媒反応部では、フッ素含有化合物の分解触媒を充填することができ、触媒層温度を600〜900℃に加熱する加熱手段もしくは前段の加熱酸化分解処理部で700〜900℃に加熱したガスを600〜900℃の温度に保つ保温手段を備える。 Furthermore, in order to remove a gas component which is a problem from the viewpoint of global warming, a decomposition treatment with a catalyst is performed after the heat oxidative decomposition treatment. That is, the fluorine-containing compound decomposition catalyst, O 2 and water (H 2 O) are brought into contact with each other at a temperature of 600 to 900 ° C. in the catalytic reaction section to decompose the fluorine-containing compound having 3 or less carbon atoms and SF 6. Can do. The catalyst reaction section can be filled with a decomposition catalyst for the fluorine-containing compound, and the heating means for heating the catalyst layer temperature to 600 to 900 ° C. or the gas heated to 700 to 900 ° C. in the heating oxidation decomposition treatment section in the previous stage is 600. It is equipped with a heat retaining means for maintaining the temperature at ˜900 ° C.

なお、排ガス処理に使用する水（H2O）を清浄にするための純水発生装置もしくは蒸留装置もしくはフィルタ機構を備えてもよい。液体で供給される水（H2O）を加熱酸化分解処理部もしくは触媒反応部の排熱と熱交換することで気化させる機構を備えることが好ましい。これにより、排熱を利用するため水（H2O）を気化させるための特別な熱源を必要としない。 It is also provided with a pure water generator or distillation apparatus or filter arrangement for water used for the exhaust gas treatment (H 2 O) clean. It is preferable to provide a mechanism for vaporizing water (H 2 O) supplied as a liquid by exchanging heat with exhaust heat from the heat oxidation decomposition treatment unit or the catalytic reaction unit. This eliminates the need for a special heat source for vaporizing water (H 2 O) in order to use exhaust heat.

また、触媒層の下流側にセラミック製の充填物を備えることが好ましい。後処理部に水スプレーを採用して触媒反応部と後処理部を一体構造とした場合に、充填物を備えていると、水スプレーの水が触媒層へ到達するのを防ぎ、触媒の劣化を防止することができる。また、充填物の間隙に水が保持されることでPFC分解時に発生するHFと水との接触効率があがり、HF除去効率が高くなるとともに、排ガスの冷却効果も向上する。   Moreover, it is preferable to provide a ceramic filler on the downstream side of the catalyst layer. When a water spray is used for the post-processing unit and the catalyst reaction unit and the post-processing unit are integrated, the provision of a filler prevents water from the water spray from reaching the catalyst layer and causes catalyst deterioration. Can be prevented. In addition, since water is retained in the gap between the packings, the contact efficiency between HF and water generated during PFC decomposition is increased, the HF removal efficiency is increased, and the exhaust gas cooling effect is improved.

次に、図３に示す排ガス処理装置と同等の試験装置で行った排ガス処理の試験結果について説明する。各種の処理対象ガスを混合したN2ガスを試験装置に投入して、各部のガス成分濃度（ppm）を測定している。

Figure 0004350081
Next, the test result of the exhaust gas treatment performed by a test device equivalent to the exhaust gas treatment device shown in FIG. 3 will be described. N 2 gas mixed with various gases to be treated is put into the test equipment and the gas component concentration (ppm) of each part is measured.
Figure 0004350081

流入条件として、SiF4：60mL/min、CHF3：180mL/min、C4F8：60mL/min、C4F6：10mL/min、CO：1200mL/min、C5F8：10mL/min、NF3：120mL/min、SF6：120mL/min、CF4：450mL/min、の処理対象となるガスをN2ガス：120L/min中に混合して投入している。そして、酸化用O2源として空気３．０L/minを加熱酸化部に導入し、同様に酸化・分解用として純水５mL/minを加熱酸化部に導入している。入口、前処理部出口、加熱酸化部出口、後処理部出口におけるそれぞれのガス成分の濃度は表１に示すとおりである。 As the inflow conditions, SiF 4: 60mL / min, CHF 3: 180mL / min, C 4 F 8: 60mL / min, C 4 F 6: 10mL / min, CO: 1200mL / min, C 5 F 8: 10mL / min , NF 3 : 120 mL / min, SF 6 : 120 mL / min, CF 4 : 450 mL / min, the gas to be treated is mixed and introduced into N 2 gas: 120 L / min. Then, 3.0 L / min of air as an O 2 source for oxidation is introduced into the heating oxidation section, and similarly 5 mL / min of pure water is introduced into the heating oxidation section for oxidation and decomposition. Table 1 shows the concentration of each gas component at the inlet, the pretreatment section outlet, the heating oxidation section outlet, and the posttreatment section outlet.

上記表１に示す試験結果から、前処理部によりSiF4、HFが検出されず、前処理部で酸性ガスが良好に処理されていることが判る。そして、加熱酸化部でCO、C4F8、C5F8、C4F6、CHF3、NF3が検出されず、加熱酸化部でこれらのガス成分が良好に処理されていることが判る。さらに、加熱酸化部出口に存在していたCF4、SF6が後処理部出口で検出されず、触媒反応部および後処理部で良好に処理されていることが判る。また、後処理部出口においてHFが検出されず、触媒反応部でHFが発生しても後処理部で良好に処理されていることが判る。 From the test results shown in Table 1 above, it can be seen that SiF 4 and HF are not detected by the pretreatment part, and that the acid gas is well treated in the pretreatment part. And CO, C 4 F 8 , C 5 F 8 , C 4 F 6 , CHF 3 , NF 3 are not detected in the heating oxidation section, and these gas components are processed well in the heating oxidation section. I understand. Furthermore, it can be seen that CF 4 and SF 6 present at the outlet of the heated oxidation section are not detected at the outlet of the post-processing section and are well processed in the catalytic reaction section and the post-processing section. Further, HF is not detected at the outlet of the post-processing section, and it can be seen that even if HF is generated in the catalytic reaction section, the post-processing section performs well.

図４は本発明の排ガス処理装置の外観を示し、この装置は前処理部、加熱酸化分解処理部、触媒反応部、後処理部をすべて搭載することが可能で、PFC，ＣＯとともに酸性ガスやNH3などの水溶性成分、加水分解成分や粉体成分を低コストで高効率に除去することが可能である。従って、この装置は、半導体製造装置等から排出される反応性成分および有害成分の高い除去能力を備えている。また、この装置は、コンパクトな構造であり、据付面積が小さく、またメンテナンススペースも小さくできる。更に、例えばサーマルNOx等を排出することなく、基本的コンセプトとして万全の安全性を確立したものであり、機器として優れた安全性を有する。
なお、本実施例においては、前処理部前処理部、加熱酸化分解処理部、触媒反応部、後処理部をすべて搭載しているが、前処理部および後処理部は装置外に別途設置するようにしても良い。さらに、工場内にて複数の排ガス処理装置から出る排ガス中の酸性ガスを１ヶ所にて一括処理するような後処理部を含むシステムにしても良い。 FIG. 4 shows the external appearance of the exhaust gas treatment apparatus of the present invention. This apparatus can be equipped with a pretreatment part, a heat oxidation decomposition treatment part, a catalytic reaction part, and a post-treatment part. It is possible to remove water-soluble components such as NH 3 , hydrolysis components and powder components at low cost and high efficiency. Therefore, this apparatus has a high removal capability of reactive components and harmful components discharged from a semiconductor manufacturing apparatus or the like. In addition, this apparatus has a compact structure, requires a small installation area, and can reduce a maintenance space. Furthermore, for example, it has established a complete safety as a basic concept without discharging thermal NOx and the like, and has excellent safety as a device.
In this embodiment, the pre-processing unit pre-processing unit, the thermal oxidative decomposition processing unit, the catalytic reaction unit, and the post-processing unit are all mounted, but the pre-processing unit and the post-processing unit are separately installed outside the apparatus. You may do it. Furthermore, a system including a post-processing unit that collectively processes acidic gas in exhaust gas from a plurality of exhaust gas processing apparatuses in a factory may be used.

なお、本発明の排ガスの処理方法および装置は、上述の図示例にのみ限定されるものではなく、本発明の要旨を逸脱しない範囲において種々変更を加えうることは勿論である。   It should be noted that the exhaust gas treatment method and apparatus of the present invention are not limited to the illustrated examples described above, and it goes without saying that various changes can be made without departing from the scope of the present invention.

本発明の第１の実施形態の排ガス処理装置を示すブロック図である。1 is a block diagram illustrating an exhaust gas treatment apparatus according to a first embodiment of the present invention. 本発明の第２の実施形態の排ガス処理装置を示すブロック図である。It is a block diagram which shows the exhaust gas processing apparatus of the 2nd Embodiment of this invention. 本発明の第３の実施形態の排ガス処理装置を示すブロック図である。It is a block diagram which shows the exhaust gas processing apparatus of the 3rd Embodiment of this invention. 図１乃至図３の排ガス処理装置の外観図である。FIG. 4 is an external view of the exhaust gas treatment apparatus of FIGS. 1 to 3.

符号の説明Explanation of symbols

１ 前処理部（前処理用水スプレー塔）
２ 加熱酸化分解処理部（加熱酸化分解処理槽）
３ 触媒反応分解処理部（触媒反応槽）
４ 後処理部（後処理用水スプレー塔）
５，２１ 空気配管
６ 水配管
７，２３ 水清浄器
８ 水気化器
９，１０，１９ セラミック電気管状路
１３ ガス処理槽
１４ 前処理部（前処理用ファンスクラバ）
１５ 送水ポンプ
１５ａ 循環タンク
１６ 加熱酸化部
１７ 触媒反応部
１８ 後処理部
２０ 保温材
２５ 水気化配管
２６，２７ ミストセパレータ
1 Pretreatment section (Pretreatment water spray tower)
2 Heating oxidative decomposition treatment section (heated oxidative decomposition treatment tank)
3 Catalytic reaction decomposition treatment section (catalytic reaction tank)
4 Post-processing section (post-treatment water spray tower)
5, 21 Air piping 6 Water piping 7, 23 Water purifier 8 Water vaporizer 9, 10, 19 Ceramic electric tubular path 13 Gas treatment tank 14 Pre-processing section (pre-processing fan scrubber)
DESCRIPTION OF SYMBOLS 15 Water pump 15a Circulation tank 16 Heating oxidation part 17 Catalytic reaction part 18 Post-processing part 20 Thermal insulation material 25 Water vaporization piping 26, 27 Mist separator

Claims (3)

フッ素含有化合物を含む排ガスに02および水(H20)を添加して700〜900℃の温度に加熱することにより加熱酸化分解処理を行い、該加熱酸化分解処理を行う間、前記排ガスを接触補助手段に接触させて該排ガスに乱流を起こさせ、
ついで、触媒反応により前記加熱酸化分解処理で処理しきれなかったフッ素含有化合物の触媒反応分解処理を600〜900℃の温度で行い、
ついで、前記触媒反応分解処理した排ガス中よりフッ素含有化合物を分解する際に生成する酸性ガスの除去を行い、
前記加熱酸化分解処理は、炭素数４以上のフッ素含有化合物の分解処理を行い、
前記触媒反応分解処理は、炭素数３以下のフッ素含有化合物の分解処理を行うことを特徴とする排ガス処理方法。 Heat exhaust oxidative decomposition treatment is performed by adding 0 2 and water (H 2 0) to an exhaust gas containing a fluorine-containing compound and heating to a temperature of 700 to 900 ° C. During the heat oxidative decomposition treatment, Causing contact with the contact assist means to cause turbulence in the exhaust gas,
Next, a catalytic reaction decomposition treatment of the fluorine-containing compound that could not be processed by the heat oxidation decomposition treatment by a catalytic reaction is performed at a temperature of 600 to 900 ° C. ,
Then, you have rows in the removal of acid gases generated during the decomposition of the fluorine-containing compound from the catalytic reaction decomposed treated in the exhaust gas,
The thermal oxidative decomposition treatment is a decomposition treatment of a fluorine-containing compound having 4 or more carbon atoms,
The exhaust gas treatment method characterized in that the catalytic reaction decomposition treatment is a decomposition treatment of a fluorine-containing compound having 3 or less carbon atoms . 前記加熱酸化分解処理の前に、前記フッ素含有化合物に含まれる粉体成分および水溶性成分および加水分解性成分の少なくとも１つを除去する処理を行うことを特徴とする請求項１に記載の排ガス処理方法。 2. The exhaust gas according to claim 1 , wherein a treatment for removing at least one of a powder component, a water-soluble component, and a hydrolyzable component contained in the fluorine-containing compound is performed before the heat oxidative decomposition treatment. Processing method. 前記排ガスはフッ素含有化合物及びCOを含み、前記加熱酸化分解処理はCOの酸化処理も行うことを特徴とする請求項１に記載の排ガス処理方法。 The exhaust gas treatment method according to claim 1 , wherein the exhaust gas contains a fluorine-containing compound and CO, and the thermal oxidative decomposition treatment also performs CO oxidation treatment.
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