JPWO2010101073A1 - Reaction apparatus and reaction method - Google Patents

Reaction apparatus and reaction method Download PDF

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JPWO2010101073A1
JPWO2010101073A1 JP2011502732A JP2011502732A JPWO2010101073A1 JP WO2010101073 A1 JPWO2010101073 A1 JP WO2010101073A1 JP 2011502732 A JP2011502732 A JP 2011502732A JP 2011502732 A JP2011502732 A JP 2011502732A JP WO2010101073 A1 JPWO2010101073 A1 JP WO2010101073A1
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裕二 早坂
裕二 早坂
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Showa Denko KK
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
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    • B01D53/34—Chemical or biological purification of waste gases
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2255/20761—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D2255/20776—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2066—Fluorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract

内部にて反応を行う外筒１２と、外筒１２の一方の端部側に配され、被処理ガスと処理済ガスとの間で熱交換を行う熱交換器１６と、熱交換器１６に被処理ガスを供給する二重管１４の内管１４ａと、熱交換器１６から処理済ガスを取り出す二重管１４の外管１４ｂと、熱交換器１６に接続し外筒１２の内部に配され熱交換器１６が配される端部側から離間した外筒１２の他方の端部側に向けて被処理ガスを流通させる内筒１８と、を備えることを特徴とする反応装置１０により、小型化しやすく、また内部の温度分布をより均一化して反応ムラが生じにくい反応装置を提供する。An outer cylinder 12 that performs a reaction inside, a heat exchanger 16 that is disposed on one end side of the outer cylinder 12 and performs heat exchange between the gas to be processed and the processed gas, and a heat exchanger 16 An inner pipe 14a of the double pipe 14 for supplying the gas to be treated, an outer pipe 14b of the double pipe 14 for taking out the treated gas from the heat exchanger 16, and a heat exchanger 16 connected to the inside of the outer cylinder 12. An inner cylinder 18 for circulating the gas to be processed toward the other end side of the outer cylinder 12 spaced from the end side where the heat exchanger 16 is disposed. Provided is a reaction apparatus that is easy to miniaturize and that makes the internal temperature distribution more uniform and hardly causes uneven reaction.

Description

本発明は、例えば、フッ素化合物を分解するために用いられる反応装置等に関する。   The present invention relates to, for example, a reactor used for decomposing a fluorine compound.

現在の半導体デバイスの製造プロセスにおいては、微細パターンを形成するためエッチングやクリーニングを行うことがある。この際にフッ素化合物が使用される場合が多い。また、フッ素化合物は、一般に安定で、人体に対し無害なものが多いため、他にも例えば、エアコンの冷媒用などに使用されている。
しかしながら、これらのフッ素化合物の中には、大気中に放出されると、地球環境に対し大きな影響を与えるものが多い。即ち、成層圏のオゾン層を破壊し、オゾンホールを作り出す原因となる。また温暖化ガスとして地球温暖化の一因ともなり得る。そして、上述のようにフッ素化合物は一般に安定であり、その影響は長期間続く場合が多い。
そこで、地球環境に影響を与えないために、使用されたフッ素化合物を分解し、地球環境に対し無害な状態にして大気中に放出する必要がある。In the current semiconductor device manufacturing process, etching or cleaning may be performed to form a fine pattern. In this case, a fluorine compound is often used. In addition, since fluorine compounds are generally stable and often harmless to the human body, they are also used, for example, as refrigerants for air conditioners.
However, many of these fluorine compounds have a great influence on the global environment when released into the atmosphere. That is, it destroys the stratospheric ozone layer and creates ozone holes. It can also contribute to global warming as a warming gas. As described above, the fluorine compound is generally stable, and its influence often lasts for a long time.
Therefore, in order not to affect the global environment, it is necessary to decompose the used fluorine compound and make it harmless to the global environment and release it into the atmosphere.

ここで例えば、特許文献１には、Ａｌを含んでなる触媒を充填した反応器と、反応器で処理されるフッ素と炭素、硫黄、窒素の１つとの化合物を含むガス流に水蒸気を添加する水添加器と、反応器に充填された触媒及び反応器に導入されるフッ素化合物含有ガス流の少なくとも一方をフッ素化合物が加水分解しうる温度まで加熱するための加熱手段とを備えたフッ素含有化合物の分解処理装置が開示されている。   Here, for example, in Patent Document 1, water vapor is added to a gas stream containing a reactor filled with a catalyst containing Al and a compound of fluorine and one of carbon, sulfur, and nitrogen to be treated in the reactor. Fluorine-containing compound comprising a water addition device and a heating means for heating at least one of a catalyst charged in the reactor and a fluorine compound-containing gas stream introduced into the reactor to a temperature at which the fluorine compound can be hydrolyzed A decomposition processing apparatus is disclosed.

また、特許文献２には、外管と、内管と、内管の内部に設けられた触媒層と、外管に取り付けられたヒータとを有するフッ素含有化合物ガスの処理装置が開示されている。   Patent Document 2 discloses a fluorine-containing compound gas processing apparatus having an outer tube, an inner tube, a catalyst layer provided inside the inner tube, and a heater attached to the outer tube. .

特開２００１−２２４９２６号公報JP 2001-224926 A 特開２００８−１２６０９２号公報JP 2008-126092 A

しかしながら、Ａｌを含んでなる触媒を充填した反応器と、反応器で処理されるフッ素と炭素、硫黄、窒素の１つとの化合物を含むガス流に水蒸気を添加する水添加器と、反応器に充填された触媒及び反応器に導入されるフッ素化合物含有ガス流の少なくとも一方をフッ素化合物が加水分解しうる温度まで加熱するための加熱手段とを備えたフッ素含有化合物の分解処理装置は、フッ素化合物含有ガスを加熱する予熱器が必要である。そのためエネルギー効率が悪く、装置の容積が大きくなる。そして、予熱器の外壁近傍ではフッ素化合物含有ガスの温度が高いが外壁から離れるにつれて温度が低下するため、反応のムラが生じる問題がある。
更に、外管と、内管と、内管の内部に設けられた触媒層と、外管に取り付けられたヒータとを有するフッ素含有化合物ガスの処理装置については、フッ素含有化合物ガスの予熱が十分行われないため、同様に処理装置内部の温度分布が一様になりにくい。そのため反応のムラが生じる問題がある。However, a reactor filled with a catalyst comprising Al, a water adder that adds water vapor to a gas stream containing a compound of fluorine and one of carbon, sulfur, and nitrogen to be treated in the reactor, and a reactor The fluorine-containing compound decomposition treatment apparatus comprising: a packed catalyst and a heating unit for heating at least one of the fluorine compound-containing gas stream introduced into the reactor to a temperature at which the fluorine compound can be hydrolyzed. A preheater for heating the contained gas is required. Therefore, energy efficiency is bad and the volume of the apparatus becomes large. And although the temperature of a fluorine compound containing gas is high in the vicinity of the outer wall of a preheater, since temperature falls as it leaves | separates from an outer wall, there exists a problem which the nonuniformity of reaction arises.
Furthermore, for a fluorine-containing compound gas processing apparatus having an outer tube, an inner tube, a catalyst layer provided inside the inner tube, and a heater attached to the outer tube, the fluorine-containing compound gas is sufficiently preheated. Since it is not performed, the temperature distribution inside the processing apparatus is hardly uniform. Therefore, there is a problem that unevenness of reaction occurs.

上記課題に鑑み、本発明の目的は、小型化しやすく、また内部の温度分布をより均一化して反応ムラが生じにくい反応装置を提供することにある。
また、他の目的は、被処理ガスを高い効率で処理することができる反応方法を提供することにある。In view of the above problems, an object of the present invention is to provide a reaction apparatus that is easy to miniaturize and that makes the temperature distribution inside more uniform and hardly causes uneven reaction.
Another object is to provide a reaction method capable of treating a gas to be treated with high efficiency.

本発明の反応装置は、内部にて反応を行う外筒と、外筒の一方の端部側に配され、被処理ガスと処理済ガスとの間で熱交換を行う主熱交換部と、主熱交換部に被処理ガスを供給する管と、主熱交換部から処理済ガスを取り出す管と、主熱交換部に接続し、外筒の内部に配され、主熱交換部が配される端部側から離間した外筒の他方の端部側に向けて被処理ガスを流通させる内筒と、を備えることを特徴とする。   The reaction apparatus of the present invention includes an outer cylinder that performs a reaction inside, a main heat exchange unit that is disposed on one end side of the outer cylinder and performs heat exchange between the gas to be processed and the treated gas, A pipe for supplying the gas to be processed to the main heat exchange section, a pipe for taking out the treated gas from the main heat exchange section, and a main heat exchange section that are connected to the inside of the outer cylinder, and the main heat exchange section is arranged And an inner cylinder that circulates the gas to be processed toward the other end portion side of the outer cylinder that is separated from the end portion side.

ここで、被処理ガスは、フッ素化合物を含むことを特徴とすることが好ましく、反応は、フッ素化合物を銅（Ｃｕ）、錫（Ｓｎ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）からなる群から選ばれる金属の化合物の少なくとも一種、アルミナおよびアルカリ土類金属化合物を含有する反応剤により分解するものであることが好ましい。更に、反応は、外筒と内筒との間で行うことが好ましい。   Here, it is preferable that the gas to be treated contains a fluorine compound, and the reaction is performed by using copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W) as the fluorine compound. And at least one metal compound selected from the group consisting of vanadium (V), an alumina and an alkaline earth metal compound. Furthermore, the reaction is preferably performed between the outer cylinder and the inner cylinder.

更に本発明の反応装置は、内部の反応領域にて反応を行う外筒と、被処理ガスおよび処理済ガスを流通させ、被処理ガスと処理済ガスとの間で第１の熱交換を行う二重管と、二重管に接続し、被処理ガスと処理済ガスとの間で第２の熱交換を行う熱交換器と、熱交換器に接続し、外筒の内部に配され、被処理ガスと反応領域との間で第３の熱交換を行う内筒と、を備えることを特徴とする。   Furthermore, the reaction apparatus of the present invention causes the outer cylinder that performs the reaction in the internal reaction region, the gas to be processed and the processed gas to flow, and performs the first heat exchange between the gas to be processed and the processed gas. A double pipe, a heat exchanger connected to the double pipe and performing a second heat exchange between the gas to be treated and the treated gas, and connected to the heat exchanger, arranged inside the outer cylinder, And an inner cylinder that performs third heat exchange between the gas to be processed and the reaction region.

ここで、内筒の内部および外筒の外部に配される加熱器を更に備えることが好ましく、内筒の外側に取り付けられるフィンを更に備えることが更に好ましく、フィンは、反応領域の下側半分の位置に取り付けられることが更に好ましい。   Here, it is preferable to further include a heater disposed inside the inner cylinder and outside the outer cylinder, more preferably further including a fin attached to the outside of the inner cylinder, and the fin is a lower half of the reaction region. More preferably, it is attached to the position.

また本発明の反応方法は、二重管に被処理ガスおよび処理済ガスを流通させ、被処理ガスと処理済ガスとの間で第１の熱交換を行い、二重管に接続する熱交換器に被処理ガスおよび処理済ガスを流通させ、被処理ガスと処理済ガスとの間で第２の熱交換を行い、熱交換器に接続する内筒に被処理ガスを流通させ、被処理ガスと反応領域との間で第３の熱交換を行い、反応領域で被処理ガスを処理済ガスにする反応を行うことを特徴とする。   Moreover, the reaction method of this invention distribute | circulates to-be-processed gas and processed gas to a double pipe, performs 1st heat exchange between to-be-processed gas and processed gas, and heat exchange connected to a double pipe The gas to be treated and the treated gas are circulated through the heat exchanger, the second heat exchange is performed between the gas to be treated and the gas to be treated, and the gas to be treated is circulated through the inner cylinder connected to the heat exchanger. A third heat exchange is performed between the gas and the reaction region, and a reaction to convert the gas to be processed into a processed gas is performed in the reaction region.

ここで、被処理ガスは、フッ素化合物を含むガスであり、反応はフッ素化合物を分解するものであることが好ましい。   Here, the gas to be treated is a gas containing a fluorine compound, and the reaction is preferably one that decomposes the fluorine compound.

本発明によれば、小型化しやすく、また反応ムラが生じにくい反応装置等を提供できる。   ADVANTAGE OF THE INVENTION According to this invention, the reactor etc. which are easy to reduce in size and are hard to produce the reaction nonuniformity can be provided.

以下、添付図面を参照して、本発明の実施の形態について詳細に説明する。
図１は、本実施の形態が適用される反応装置の一例を説明した図である。
図１に示した反応装置１０は、内部にて反応を行う外筒１２と、被処理ガスおよび処理済ガスを流通させる二重管１４と、二重管１４に接続し外筒１２の一方の端部側に配され被処理ガスと処理済ガスとの間で熱交換を行う主熱交換部としての熱交換器１６と、主熱交換部としての熱交換器１６に接続し外筒１２内部に配され、熱交換器１６が配される端部側から離間した外筒１２の他方の端部側に向けて被処理ガスを流通させる内筒１８とを備える。
また、内筒１８の内部に配され被処理ガスを更に加熱すると共に外筒内部の反応領域に反応に必要な熱を供給するための加熱器としての内部ヒータ２０と、外筒１２の外部に配され同様に外筒内部の反応領域に反応に必要な熱を供給するための加熱器としての外部ヒータ２２と、内筒１８の外側に取り付けられ内部ヒータ２０からの熱を反応領域に均一に伝熱させるためのフィン２４と、温度を測定し図示しない制御装置により反応装置１０内部の温度制御を行うための熱電対等からなる温度センサ２６ａ，２６ｂ，２６ｃと、反応剤を充填するための反応剤投入口２８とを更に備える。Embodiments of the present invention will be described below in detail with reference to the accompanying drawings.
FIG. 1 is a diagram illustrating an example of a reaction apparatus to which the present embodiment is applied.
The reactor 10 shown in FIG. 1 includes an outer cylinder 12 that performs a reaction inside, a double pipe 14 that circulates a gas to be treated and a treated gas, and one of the outer cylinders 12 connected to the double pipe 14. A heat exchanger 16 serving as a main heat exchanging part arranged on the end side and exchanging heat between the gas to be treated and the treated gas, and connected to the heat exchanger 16 serving as the main heat exchanging part and connected to the inside of the outer cylinder 12 And an inner cylinder 18 that circulates the gas to be processed toward the other end side of the outer cylinder 12 that is spaced from the end side where the heat exchanger 16 is disposed.
In addition, an internal heater 20 serving as a heater for further heating the gas to be processed disposed inside the inner cylinder 18 and supplying a reaction region inside the outer cylinder to the reaction, and outside the outer cylinder 12 Similarly, an external heater 22 as a heater for supplying heat required for the reaction to the reaction area inside the outer cylinder, and heat from the internal heater 20 attached to the outside of the inner cylinder 18 are uniformly distributed to the reaction area. Fins 24 for conducting heat transfer, temperature sensors 26a, 26b, 26c comprising thermocouples for measuring the temperature and controlling the temperature inside the reactor 10 by a control device (not shown), and reaction for filling the reactants And an agent inlet 28.

外筒１２は、反応容器であり、内部で所定の反応を行わせることができる。本実施の形態では、被処理ガスとして、フッ素化合物を含むガスを外筒１２の内部に流通させる。そして、外筒１２と内筒１８との間に反応剤を充填し、この反応剤によりこのフッ素化合物を分解する反応を行う。
フッ素化合物としては、例えば、クロロフルオロカーボン類（以下、「ＣＦＣ」と略す。）、ハイドロクロロフルオロカーボン類（以下、「ＨＣＦＣ」と略す。）、パーフルオロカーボン類（以下、「ＰＦＣ」と略す。）、ハイドロフルオロカーボン類（以下、「ＨＦＣ」と略す。）、パーフルオロエーテル類（以下、「ＰＦＥ」と略す。）、ハイドロフルオロエーテル類（以下、「ＨＦＥ」と略す。）、フッ化硫黄等が該当する。The outer cylinder 12 is a reaction container, and a predetermined reaction can be performed inside. In the present embodiment, a gas containing a fluorine compound is circulated inside the outer cylinder 12 as the gas to be processed. And a reaction agent is filled between the outer cylinder 12 and the inner cylinder 18, and the reaction which decomposes | disassembles this fluorine compound with this reaction agent is performed.
Examples of the fluorine compound include chlorofluorocarbons (hereinafter abbreviated as “CFC”), hydrochlorofluorocarbons (hereinafter abbreviated as “HCFC”), perfluorocarbons (hereinafter abbreviated as “PFC”), and the like. Hydrofluorocarbons (hereinafter abbreviated as “HFC”), perfluoroethers (hereinafter abbreviated as “PFE”), hydrofluoroethers (hereinafter abbreviated as “HFE”), sulfur fluoride, etc. To do.

更に詳述すると、ＣＦＣとしては例えば、ＣＣｌＦ３、ＣＣｌ２Ｆ２、ＣＣｌ３Ｆ、Ｃ２Ｃｌ３Ｆ３、Ｃ２Ｃｌ２Ｆ４、Ｃ２ＣｌＦ５等の化合物、ＨＣＦＣとしては例えば、ＣＨＣｌＦ２、Ｃ２ＨＣｌ２Ｆ３等の化合物が挙げられる。またＰＦＣとしては例えば、ＣＦ４、Ｃ２Ｆ６、Ｃ３Ｆ８、Ｃ４Ｆ８（オクタフルオロシクロブタン）等の化合物、ＨＦＣとしては例えば、ＣＨ３Ｆ、ＣＨ２Ｆ２、ＣＨＦ３、Ｃ２Ｈ２Ｆ４等の化合物が挙げられる。またＰＦＥとしては例えば、ＣＦ３ＯＣＦ３、ＣＦ３ＯＣＦ２ＣＦ３等の化合物、ＨＦＥとしてはＣＨＦ２ＯＣＨＦ２、ＣＨＦ２ＯＣＨ２ＣＦ３、ＣＨ３ＯＣＦ２ＣＦ３等の化合物が挙げられる。またフッ化硫黄としては例えば、ＳＦ６、Ｓ２Ｆ１０等の化合物が挙げられる。More specifically, examples of the CFC include CClF 3 , CCl 2 F 2 , CCl 3 F, C 2 Cl 3 F 3 , C 2 Cl 2 F 4 , and C 2 ClF 5 , and examples of the HCFC include CHClF. 2 , compounds such as C 2 HCl 2 F 3 and the like. Examples of PFC include compounds such as CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 8 (octafluorocyclobutane), and examples of HFC include CH 3 F, CH 2 F 2 , CHF 3 , C A compound such as 2 H 2 F 4 may be mentioned. Examples of PFE include compounds such as CF 3 OCF 3 and CF 3 OCF 2 CF 3 , and examples of HFE include compounds such as CHF 2 OCHF 2 , CHF 2 OCH 2 CF 3 , and CH 3 OCF 2 CF 3 . Examples of sulfur fluoride include compounds such as SF 6 and S 2 F 10 .

これらのフッ素化合物は、単独でも２種以上の混合物であってもよい。また、フッ素化合物は、ヘリウム、アルゴン、窒素等の不活性ガス、あるいは空気をキャリアガスとして希釈されていることが好ましい。本実施の形態では、被処理ガス中のフッ素化合物の濃度は、０．０１ｖｏｌ％〜１０ｖｏｌ％であることが好ましい。   These fluorine compounds may be used alone or as a mixture of two or more. The fluorine compound is preferably diluted with an inert gas such as helium, argon or nitrogen, or air as a carrier gas. In this Embodiment, it is preferable that the density | concentration of the fluorine compound in to-be-processed gas is 0.01 vol%-10 vol%.

反応剤としては、例えば、銅（Ｃｕ）、錫（Ｓｎ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）からなる群から選ばれる金属の化合物の少なくとも一種、アルミナ、およびアルカリ土類金属化合物を含有するものを用いることができる。
このうち、アルミナは、代表的な酸性物質（固体酸）であり、それ単独であってもフッ素化合物を分解できる。しかし、分解されて生成したフッ素によってアルミナ表面がフッ素化され、ＡｌＦ３として被毒されて触媒活性が短時間で失活する。Examples of the reactant include at least one metal compound selected from the group consisting of copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W), and vanadium (V), and alumina. And those containing an alkaline earth metal compound can be used.
Of these, alumina is a typical acidic substance (solid acid), which can decompose a fluorine compound alone. However, the surface of the alumina is fluorinated by the fluorine generated by decomposition, poisoned as AlF 3 , and the catalytic activity is deactivated in a short time.

そこで、本実施の形態では、アルカリ土類金属化合物を含有させている。これにより従来より低い反応温度でフッ素化合物を分解でき、生成するフッ素もアルカリ土類金属フッ化物として固定化できる。以下、これについて更に詳細に説明を行う。
まず本実施の形態におけるフッ素化合物の分解反応は、例えば以下の式で表すことができる。Therefore, in the present embodiment, an alkaline earth metal compound is contained. As a result, the fluorine compound can be decomposed at a lower reaction temperature than before, and the generated fluorine can also be immobilized as an alkaline earth metal fluoride. This will be described in more detail below.
First, the decomposition reaction of the fluorine compound in the present embodiment can be expressed by the following formula, for example.

Figure 2010101073
Figure 2010101073

ここでの反応温度は、被処理ガス中に含まれるフッ素化合物の種類により異なる。例えばＰＦＣはフッ素化合物のうちで難分解性の化合物に分類され、中でもＣＦ4、Ｃ2Ｆ6等は最も難分解性であり、単なる熱分解だけで分解するには１２００℃〜１４００℃の高温を必要とするが、本実施の形態の方法によれば５５０℃以上であれば分解できる。また、ＨＣＦＣであるＣＨＣｌＦ2は、本実施の形態の方法によれば２００℃以上の温度であれば分解できる。このようにフッ素化合物の種類により、その分解温度はかなりの幅で開きがあり、その化合物の種類により反応器を最適温度に設定することが重要である。The reaction temperature here varies depending on the type of fluorine compound contained in the gas to be treated. For example, PFC is classified as a hardly decomposable compound among fluorine compounds. Among them, CF 4 , C 2 F 6 and the like are the most hardly decomposable, and high temperatures of 1200 ° C. to 1400 ° C. are necessary for decomposing only by thermal decomposition. However, according to the method of the present embodiment, it can be decomposed at 550 ° C. or higher. Further, CHClF 2 which is HCFC can be decomposed at a temperature of 200 ° C. or higher according to the method of the present embodiment. Thus, depending on the type of fluorine compound, the decomposition temperature varies widely, and it is important to set the reactor at the optimum temperature depending on the type of compound.

アルカリ土類金属化合物としては、アルカリ土類金属の炭酸塩、水酸化物または酸化物を用いることができる。このうちマグネシウム（Ｍｇ）、カルシウム（Ｃａ）、ストロンチウム（Ｓｒ）、バリウム（Ｂａ）の炭酸塩がより好ましく、カルシウムの炭酸塩である炭酸カルシウム（ＣａＣＯ３）が更に好ましい。反応剤に、炭酸カルシウムを用いた場合、アルミナと共存することにより、フッ素化合物が分解して生成するフッ素をフッ化カルシウム（ＣａＦ２）として固定することができる。このためアルミナのフッ素化を防止する役割を果たし、アルミナのフッ素化合物の分解機能（活性）を維持することができる。As the alkaline earth metal compound, an alkaline earth metal carbonate, hydroxide or oxide can be used. Of these, carbonates of magnesium (Mg), calcium (Ca), strontium (Sr), and barium (Ba) are more preferable, and calcium carbonate (CaCO 3 ), which is a carbonate of calcium, is more preferable. When calcium carbonate is used as the reactant, by coexisting with alumina, fluorine generated by decomposition of the fluorine compound can be fixed as calcium fluoride (CaF 2 ). For this reason, it plays the role which prevents the fluorination of an alumina, and can maintain the decomposition function (activity) of the fluorine compound of alumina.

また反応剤の成分の一つである、銅（Ｃｕ）、錫（Ｓｎ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）からなる群から選ばれる金属の化合物については、フッ素化合物を分解する助触媒としての働きがある。また、フッ素化合物の種類によっては、上記（２）式で例示したような反応で分解して生成する一酸化炭素を低酸素分圧下においても二酸化炭素まで酸化することができる。
上記化合物のうち、酸化銅（ＣｕＯ）、酸化錫（ＳｎＯ２）、酸化バナジウム（Ｖ２Ｏ５）などの酸化物を用いるのが好ましく、酸化銅、酸化錫を用いるのが更に好ましい。One of the components of the reactant is a metal compound selected from the group consisting of copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W), and vanadium (V). Acts as a co-catalyst for decomposing fluorine compounds. Depending on the type of the fluorine compound, carbon monoxide generated by decomposition by the reaction exemplified in the above formula (2) can be oxidized to carbon dioxide even under a low oxygen partial pressure.
Of the above compounds, oxides such as copper oxide (CuO), tin oxide (SnO 2 ), and vanadium oxide (V 2 O 5 ) are preferably used, and copper oxide and tin oxide are more preferably used.

本実施の形態では、アルミナとアルカリ土類金属化合物の含有量は、質量比で１：９〜１：１であることが好ましい。また、金属の化合物の含有量は、アルミナとアルカリ土類金属化合物合計質量との比で、１：９９〜５：９５であることが好ましい。   In the present embodiment, the content of alumina and the alkaline earth metal compound is preferably 1: 9 to 1: 1 by mass ratio. Moreover, it is preferable that content of a metal compound is 1: 99-5: 95 by the ratio of an alumina and an alkaline-earth metal compound total mass.

本実施の形態では、この反応剤を粒径が０．５ｍｍ〜１０ｍｍの粒状品とし、外筒１２の内側と内筒１８の外側の間に生じる空間に充填する。充填量としては、この空間全体に対し、８０％〜９０％の高さになるようにするのが好ましい。そして、この反応剤が充填された部分が、反応を行う反応領域となる。   In the present embodiment, the reactant is made into a granular product having a particle size of 0.5 mm to 10 mm, and is filled in a space generated between the inner side of the outer cylinder 12 and the outer side of the inner cylinder 18. The filling amount is preferably 80% to 90% of the entire space. And the part filled with this reactive agent becomes a reaction area | region which reacts.

外筒１２に用いられる材料としては、反応の際の反応温度や反応生成物に耐性があるものであれば、特に限定されることはないが、ステンレス等により作製することが好ましい。また外筒１２の形状としては、特に限定されることはないが、円柱形状であって、内径が１００ｍｍ〜２ｍであることが内部の温度の均一性の観点と強度の観点から好ましい。   The material used for the outer cylinder 12 is not particularly limited as long as it is resistant to the reaction temperature and reaction product during the reaction, but is preferably made of stainless steel or the like. The shape of the outer cylinder 12 is not particularly limited, but is preferably a columnar shape and has an inner diameter of 100 mm to 2 m from the viewpoint of uniformity of internal temperature and strength.

二重管１４は、内側の管である内管１４ａと外側の管である外管１４ｂとからなる。そして、内管１４ａまたは外管１４ｂのいずれかの管に被処理ガスを流通させ、もう一方の管で処理済ガスを流通させると共に、内側の管を通して、被処理ガスと処理済ガスとの間で第１の熱交換を行う。この場合、被処理ガスと処理済ガスは対向して流通するため二重管１４は、対向流式の二重管式熱交換器として捉えることもできる。被処理ガスは内管１４ａおよび外管１４ｂのどちらを通してもよいが、この熱交換の効率性の観点からは、内管１４ａを通した方が好ましい。即ち外管１４ｂに通すと、外管１４ｂは大気に接しているため、大気中に放熱を起こしてしまう。そのため被処理ガスは、放熱を生じにくい内管１４ｂを通した方がよい。また、処理済ガスは、できるだけ室温に近い温度にして放出することが好ましい。よって、その観点からも被処理ガスを内管１４ａに通し、処理済ガスを外管１４ｂに通した方が好ましい。つまり、処理済ガスの熱が外管１４ｂを通し放熱することができるため、処理済ガスの温度を低下させることができる。   The double tube 14 includes an inner tube 14a that is an inner tube and an outer tube 14b that is an outer tube. Then, the gas to be treated is circulated through either the inner pipe 14a or the outer pipe 14b, the treated gas is circulated through the other pipe, and between the gas to be treated and the treated gas through the inner pipe. The first heat exchange is performed. In this case, since the gas to be treated and the treated gas circulate opposite to each other, the double pipe 14 can also be regarded as a counter flow type double pipe heat exchanger. The gas to be treated may pass through either the inner pipe 14a or the outer pipe 14b, but it is preferable to pass through the inner pipe 14a from the viewpoint of the efficiency of this heat exchange. In other words, if the outer tube 14b is passed through, the outer tube 14b is in contact with the atmosphere, so that heat is radiated in the atmosphere. Therefore, it is better to pass the gas to be processed through the inner pipe 14b that is less likely to generate heat dissipation. The treated gas is preferably released at a temperature as close to room temperature as possible. Therefore, from this point of view, it is preferable to pass the gas to be processed through the inner pipe 14a and the processed gas through the outer pipe 14b. That is, since the heat of the processed gas can be radiated through the outer tube 14b, the temperature of the processed gas can be lowered.

主熱交換部としての熱交換器１６は、外筒１２の一方の端部側に配される。そして、二重管１４に接続し、例えば、内管１４ａにより熱交換器１６に被処理ガスを供給し、外管１４ｂにより熱交換器１６から処理済ガスを取り出す。また熱交換器１６において、被処理ガスと処理済ガスとの間で第２の熱交換を行う。
本実施の形態において、外筒１２と内筒１８に円柱形状のものを用いた場合、熱交換器１６は、ドーナツ形状のステンレスからなる板を重ね合わせて溶接し、被処理ガスと処理済ガスが別々の経路を通り、流通するようにしている。そして、被処理ガスと処理済ガスは、熱交換器１６内部をジグザグに対向する形で流通し、ドーナツ形状の板を通して熱交換を行うことができる。このように、流路をジグザグにすることで、小さい容積で多量の熱を交換することができる。本実施の形態では、被処理ガスおよび処理済ガスは、熱交換を行う部分においてこのジグザグの流路をそれぞれ２．５往復するように構成している。このジグザグの流路はそれぞれ１．５往復以上であることが好ましい。これより少ないと熱交換が不足し本装置出口の排ガス温度が高くなる傾向がある。
なお、処理済ガスは、反応領域の熱交換器１６側に複数開けられた小口径の孔３０を通して、熱交換器１６内部に侵入することができる。また熱交換器１６を通り抜けた被処理ガスは、内筒１８側面に開けられた複数の穴３２を通して、内筒１８内に侵入することができる。The heat exchanger 16 as the main heat exchange unit is disposed on one end side of the outer cylinder 12. And it connects to the double pipe 14, for example, to-be-processed gas is supplied to the heat exchanger 16 by the inner tube 14a, and processed gas is taken out from the heat exchanger 16 by the outer tube 14b. In the heat exchanger 16, the second heat exchange is performed between the gas to be processed and the processed gas.
In the present embodiment, when cylindrical ones are used for the outer cylinder 12 and the inner cylinder 18, the heat exchanger 16 superimposes and welds plates made of donut-shaped stainless steel, and the gas to be processed and the processed gas Circulate through different routes. And the to-be-processed gas and the processed gas can distribute | circulate through the inside of the heat exchanger 16 in the form which opposes a zigzag, and can perform heat exchange through a doughnut-shaped board. Thus, by making the flow path zigzag, a large amount of heat can be exchanged with a small volume. In the present embodiment, the gas to be processed and the processed gas are configured to reciprocate 2.5 times in the zigzag flow path at the portion where heat exchange is performed. Each zigzag flow path is preferably 1.5 reciprocations or more. If it is less than this, heat exchange is insufficient, and the exhaust gas temperature at the outlet of the apparatus tends to increase.
The treated gas can enter the heat exchanger 16 through a plurality of small-diameter holes 30 formed on the reaction region on the heat exchanger 16 side. Further, the gas to be processed that has passed through the heat exchanger 16 can enter the inner cylinder 18 through a plurality of holes 32 formed in the side surface of the inner cylinder 18.

なお熱交換器１６は、このような構造のものに限られるものではなく、スパイラル式熱交換器、プレート式熱交換器、多重円管式熱交換器等の種々の熱交換器を使用することができる。   The heat exchanger 16 is not limited to such a structure, and various heat exchangers such as a spiral heat exchanger, a plate heat exchanger, and a multi-tube heat exchanger may be used. Can do.

内筒１８は、外筒１２の内部に配される。そして、熱交換器１６に接続し、熱交換器１６が配される端部側から離間した外筒１２の他方の端部に向けて被処理ガスを流通させる。被処理ガスは、この内筒１８を通る際に、内筒１８を通して反応領域との間で第３の熱交換を行う。これにより被処理ガスを更に加熱することができる。内筒１８は、本実施の形態では１本で構成されるが、２本以上であってもよい。また内筒１８の位置については、本実施の形態のように１本で構成される場合は、外筒１２の中心部に設置することが好ましい。   The inner cylinder 18 is disposed inside the outer cylinder 12. And it connects to the heat exchanger 16, and it distribute | circulates to-be-processed gas toward the other edge part of the outer cylinder 12 spaced apart from the edge part side where the heat exchanger 16 is distribute | arranged. When the gas to be processed passes through the inner cylinder 18, the gas to be processed performs third heat exchange with the reaction region through the inner cylinder 18. Thereby, the gas to be treated can be further heated. The inner cylinder 18 is composed of one in the present embodiment, but may be two or more. Moreover, about the position of the inner cylinder 18, when comprised by 1 like this Embodiment, installing in the center part of the outer cylinder 12 is preferable.

また本実施の形態において、内筒１８は、内部に内部ヒータ２０を備える。この内部ヒータ２０は、被処理ガスを更に加熱すると共に外筒内部の反応領域に反応に必要な熱を供給する。また内筒１８の外側にはフィン２４が取り付けられている。内部ヒータ２０で発生した熱は、内筒１８およびこのフィン２４を通し反応領域まで伝熱する。またこのフィン２４を備えることにより、内部ヒータ２０で発生した熱を反応領域に、より均一に伝熱させることができる。ここで、本実施の形態の反応装置１０を熱交換器１６が配される側を下側として使用する場合、フィン２４は、反応領域の下側半分の位置に取り付けられ、上側半分には取り付けないことが好ましい。即ち、反応領域の上部は、対流により温度が上昇しやすく、この部分にもフィン２４を取付けると、下側より上側の温度が高くなりやすくなる。そのため、下側半分の位置に取り付けることで、反応領域の上部と下部の温度分布をより均一化することができる。   In the present embodiment, the inner cylinder 18 includes an internal heater 20 inside. The internal heater 20 further heats the gas to be processed and supplies heat necessary for the reaction to the reaction region inside the outer cylinder. A fin 24 is attached to the outside of the inner cylinder 18. Heat generated by the internal heater 20 is transferred to the reaction region through the inner cylinder 18 and the fins 24. Further, by providing the fins 24, heat generated by the internal heater 20 can be more uniformly transferred to the reaction region. Here, when the reaction apparatus 10 of the present embodiment is used with the side on which the heat exchanger 16 is disposed as the lower side, the fins 24 are attached to the lower half of the reaction region and attached to the upper half. Preferably not. That is, the temperature of the upper part of the reaction region is likely to rise due to convection, and if the fin 24 is attached to this part, the temperature on the upper side of the lower side tends to be higher. Therefore, the temperature distribution in the upper and lower portions of the reaction region can be made more uniform by attaching the lower half position.

またフィン２４は、複数枚取り付けることが好ましい。
図２は、図１に示した反応装置１０のII−II断面図である。
図２に示した反応装置１０では、フィン２４は、内筒１８の外側に１８枚取り付けられている。このように複数枚取り付けることにより反応領域の温度分布をより均一化することができる。ここでフィン２４の枚数や長さは、反応装置１０における反応条件によって適宜選択することができる。Moreover, it is preferable to attach a plurality of fins 24.
FIG. 2 is a II-II cross-sectional view of the reaction apparatus 10 shown in FIG.
In the reaction apparatus 10 shown in FIG. 2, 18 fins 24 are attached to the outside of the inner cylinder 18. By attaching a plurality of sheets in this way, the temperature distribution in the reaction region can be made more uniform. Here, the number and length of the fins 24 can be appropriately selected depending on the reaction conditions in the reaction apparatus 10.

内筒１８およびフィン２４に用いられる材料としては、反応の際に生じる反応熱や反応生成物に耐性があるものであれば、特に限定されることはないが、ステンレス等により作製することが好ましい。また内筒１８の形状としては、特に限定されることはないが、円柱形状であることが内部の温度の均一性の観点からは好ましい。
また、内部ヒータ２０には、例えば、インコネル（登録商標）ヒータを使用することができる。そして、このインコネル（登録商標）ヒータを例えば３本用い、デルタ結線を行って内筒１８の内部に収容することができる。The material used for the inner cylinder 18 and the fin 24 is not particularly limited as long as it is resistant to reaction heat and reaction products generated during the reaction, but is preferably made of stainless steel or the like. . The shape of the inner cylinder 18 is not particularly limited, but a cylindrical shape is preferable from the viewpoint of the uniformity of the internal temperature.
For example, an Inconel (registered trademark) heater can be used as the internal heater 20. Then, for example, three Inconel (registered trademark) heaters can be used and housed in the inner cylinder 18 by performing delta connection.

また本実施の形態では、外筒１２の外側に外部ヒータ２２を備える。この外部ヒータを備えることにより、反応領域の反応に必要な熱を外側からも供給することができる。外部ヒータ２２で発生した熱は、外筒１２を通し反応領域まで伝熱する。そして、外部ヒータ２２と内部ヒータ２０を双方備えることにより、反応領域の外側と内側の両方から加熱を行うことが可能となる。そのため、反応領域の温度分布を更に均一化することができる。
外部ヒータ２４には、例えば、インコロイ（登録商標）ヒータを使用することができる。そして均一に熱を供給する観点から、このインコロイ（登録商標）ヒータを外筒１２の周囲に設置することが好ましい。
また、メンテナンス等における本実施の形態の反応装置と制御装置との切り離しを容易にするため、ヒータおよび／または温度センサと制御装置とを、例えばメタルコンセントで接続することが好ましい。In the present embodiment, an external heater 22 is provided outside the outer cylinder 12. By providing this external heater, heat necessary for the reaction in the reaction region can be supplied also from the outside. The heat generated by the external heater 22 is transferred to the reaction region through the outer cylinder 12. And by providing both the external heater 22 and the internal heater 20, it becomes possible to heat from both the outer side and the inner side of the reaction region. Therefore, the temperature distribution in the reaction region can be made more uniform.
As the external heater 24, for example, an Incoloy (registered trademark) heater can be used. From the viewpoint of supplying heat uniformly, it is preferable to install this Incoloy (registered trademark) heater around the outer cylinder 12.
Further, in order to facilitate separation of the reaction device and the control device of the present embodiment in maintenance or the like, it is preferable to connect the heater and / or the temperature sensor and the control device with, for example, a metal outlet.

また更に、大気中への放熱を防止し、反応領域への加熱を更に効率よく行うために、外筒１２を保温材（図示せず）で覆うことが好ましい。保温剤としては、例えば、ガラスクロス、シリコンクロス等の材料で構成されたものを使用することができる。   Furthermore, it is preferable to cover the outer cylinder 12 with a heat insulating material (not shown) in order to prevent heat radiation to the atmosphere and to heat the reaction region more efficiently. As a heat retention agent, what was comprised with materials, such as a glass cloth and a silicon cloth, can be used, for example.

以上のような構成の反応装置１０では、被処理ガスであるフッ素化合物を含むガスは、まず二重管１４の内管１４ｂを流通する。この際に、被処理ガスと処理済ガスとの間で第１の熱交換を行う。次に二重管１４に接続する熱交換器１６内に入り、熱交換器１６の内部を流通し、再び処理済ガスとの間で第２の熱交換を行う。そして熱交換器１６に接続する内筒１８内に入る。被処理ガスは、内筒１８内を流通するときに反応領域との間で第３の熱交換を行うと共に内部ヒータ２０により加熱される。内筒１８を通り抜けた後は、反応領域に入り、処理剤により被処理ガスに含まれるフッ素化合物が分解される。この反応により被処理ガスは処理済ガスとなる。処理済ガスは、今度は熱交換器１６、二重管１４の外管１４ｂを流通しつつ被処理ガスとの間で上述の第２の熱交換、第１の熱交換を行う。そして、二重管１４を通り抜けた後は大気中に放出される。
このような反応は、二重管１４に被処理ガスおよび処理済ガスを流通させ、被処理ガスと処理済ガスとの間で第１の熱交換を行い、二重管１４に接続する熱交換器１６に被処理ガスおよび処理済ガスを流通させ、被処理ガスと処理済ガスとの間で第２の熱交換を行い、熱交換器１６に接続する内筒１８に被処理ガスを流通させ、被処理ガスと反応領域との間で第３の熱交換を行い、反応領域で被処理ガスを処理済ガスにする反応を行うことを特徴とする反応方法として捉えることもできる。In the reactor 10 configured as described above, a gas containing a fluorine compound, which is a gas to be treated, first circulates through the inner pipe 14b of the double pipe 14. At this time, the first heat exchange is performed between the gas to be processed and the processed gas. Next, the heat exchanger 16 enters the heat exchanger 16 connected to the double pipe 14, flows through the heat exchanger 16, and performs second heat exchange with the treated gas again. Then, it enters the inner cylinder 18 connected to the heat exchanger 16. The gas to be processed is heated by the internal heater 20 while performing third heat exchange with the reaction region when flowing in the inner cylinder 18. After passing through the inner cylinder 18, it enters the reaction region, and the fluorine compound contained in the gas to be processed is decomposed by the processing agent. By this reaction, the gas to be processed becomes a processed gas. The treated gas then performs the second heat exchange and the first heat exchange described above with the gas to be treated while flowing through the heat exchanger 16 and the outer pipe 14b of the double pipe 14. Then, after passing through the double pipe 14, it is released into the atmosphere.
In such a reaction, the gas to be treated and the treated gas are circulated through the double pipe 14, the first heat exchange is performed between the gas to be treated and the treated gas, and the heat exchange connected to the double pipe 14. The gas to be treated and the treated gas are circulated through the vessel 16, the second heat exchange is performed between the gas to be treated and the treated gas, and the gas to be treated is circulated through the inner cylinder 18 connected to the heat exchanger 16. Further, it can be understood as a reaction method characterized in that a third heat exchange is performed between the gas to be processed and the reaction region, and a reaction to convert the gas to be processed into a processed gas is performed in the reaction region.

本実施の形態の反応装置１０は、外筒１２と熱交換器１６とを一体化することができる。また、被処理ガスおよび処理済ガスを熱交換器１６に導入するための配管を二重管１４としている。これらの構造により反応装置１０の小型化を行いやすくなる。   In the reaction apparatus 10 of the present embodiment, the outer cylinder 12 and the heat exchanger 16 can be integrated. A pipe for introducing the gas to be treated and the treated gas into the heat exchanger 16 is a double pipe 14. These structures facilitate the downsizing of the reactor 10.

更に、二重管１４による第１の熱交換、熱交換器１６による第２の熱交換、内筒１８による第３の熱交換という３段階の熱交換を行うことにより、被処理ガスが十分に予熱され、反応領域に達するまでに十分な高温となる。そのため反応領域における温度分布が均一化しやすい。そのため反応ムラが生じにくくなる。また、反応領域における温度分布が均一でない場合、温度が高い部分での反応剤の消耗が激しくなる場合がある。そのためこの部分で反応剤の寿命がくると、全ての反応剤を交換する必要があり不経済である。本実施の形態の反応装置１０では、反応領域における温度分布が均一化しやすいので、反応ムラが生じにくくなるばかりでなく、反応剤の消耗が一様になりやすくなり反応剤の寿命を延ばすことができる。   Furthermore, the gas to be treated can be sufficiently obtained by performing the three-stage heat exchange of the first heat exchange by the double pipe 14, the second heat exchange by the heat exchanger 16, and the third heat exchange by the inner cylinder 18. Preheated and hot enough to reach the reaction zone. For this reason, the temperature distribution in the reaction region is easily uniformized. Therefore, reaction unevenness is less likely to occur. In addition, when the temperature distribution in the reaction region is not uniform, the consumption of the reactant in the portion where the temperature is high may become severe. For this reason, when the lifetime of the reactant is reached in this part, it is necessary to replace all the reactants, which is uneconomical. In the reaction apparatus 10 of the present embodiment, the temperature distribution in the reaction region is easily uniformed, so that not only reaction unevenness is likely to occur, but also the consumption of the reactants is likely to be uniform, thereby extending the lifetime of the reactants. it can.

また更に、内筒１８による第３の熱交換および内部ヒータ２０による加熱を行うことで、熱交換器１６の容積を小さくすることができる。このため、外筒１２と内筒１８との空間を大きく採ることができ、反応剤をより多く充填することができる。そのため、より高い効率で反応を起こすことができ、そして、より多くの被処理ガスを処理することができる。
外筒１２と内筒１８の間の空間容積つまり外筒内部の反応領域は、内部の温度の均一性の観点と強度の観点から２リットル〜３０００リットルであることが好ましい。また特に２リットル〜２００リットルであることが好ましい。この場合キャスター等を取り付けることが容易となり、反応装置１０の交換作業の際に有利となる。そして内部の温度の均一性および反応効率の観点から、４０リットル〜２００リットルであることが更に好ましい。
また上記の構造を有することで、反応温度が２００℃〜１０００℃の反応装置として使用でき、かつ、反応装置出口のガス温度を２００℃以下にすることができる。Furthermore, the volume of the heat exchanger 16 can be reduced by performing the third heat exchange by the inner cylinder 18 and the heating by the internal heater 20. For this reason, the space of the outer cylinder 12 and the inner cylinder 18 can be taken large, and more reactants can be filled. Therefore, the reaction can be caused with higher efficiency, and more gas to be processed can be processed.
The space volume between the outer cylinder 12 and the inner cylinder 18, that is, the reaction region inside the outer cylinder, is preferably 2 liters to 3000 liters from the viewpoint of the uniformity of the internal temperature and the strength. In particular, it is preferably 2 to 200 liters. In this case, it becomes easy to attach casters or the like, which is advantageous when the reactor 10 is replaced. And from a viewpoint of the uniformity of internal temperature and reaction efficiency, it is still more preferable that it is 40 liters-200 liters.
Moreover, by having said structure, it can be used as a reaction apparatus whose reaction temperature is 200 degreeC-1000 degreeC, and the gas temperature of the reactor exit can be 200 degrees C or less.

なお、本実施の形態においては、被処理ガスとしてフッ素化合物を含むガスを挙げ、このフッ素化合物を分解する反応について説明を行ったが、これに限られるものではない。被処理ガスとしてフッ素化合物以外のガスを使用し、反応剤をこのガスの反応に適したものに変更すれば、本実施の反応装置１０を適用することができる。
例えば、半導体製造装置におけるパージガスラインや手術室から排出される余剰麻酔ガス中に含まれる亜酸化窒素を分解除去するため、反応剤として固体触媒を使用する反応等に用いることができる。In the present embodiment, a gas containing a fluorine compound is exemplified as the gas to be treated, and the reaction for decomposing the fluorine compound has been described. However, the present invention is not limited to this. If a gas other than a fluorine compound is used as the gas to be treated and the reactant is changed to a gas suitable for the reaction of this gas, the reactor 10 of the present embodiment can be applied.
For example, in order to decompose and remove nitrous oxide contained in a surplus anesthetic gas discharged from a purge gas line or an operating room in a semiconductor manufacturing apparatus, it can be used for a reaction using a solid catalyst as a reactant.

反応装置として図１および図２に示した反応装置１０を用いた。反応剤としてアルミナと炭酸カルシウムを質量比で３：７とし、酸化錫をアルミナおよび炭酸カルシウムの合計重量に対し３質量％としたものを用いた。また、被処理ガスとして、フッ化物ガスであるＣＦ４を、６０００ｖｏｌｐｐｍの濃度で、２５０Ｌ／ｍｉｎの流量で反応装置１０内に流通させた。なおキャリアガスとしては窒素ガスを用いた。
その結果、処理済ガスのＣＦ４の濃度は０ｐｐｍとなり、ＣＦ４が分解できたことを確認した。また、この際に反応装置１０の外部と内部の温度分布の測定を行った。The reaction apparatus 10 shown in FIGS. 1 and 2 was used as the reaction apparatus. As the reactant, alumina and calcium carbonate were used in a mass ratio of 3: 7, and tin oxide was used in an amount of 3% by mass based on the total weight of alumina and calcium carbonate. Further, CF 4 which is a fluoride gas was circulated in the reactor 10 at a concentration of 6000 volppm and a flow rate of 250 L / min as a gas to be treated. Nitrogen gas was used as the carrier gas.
As a result, the concentration of CF 4 in the treated gas was 0 ppm, and it was confirmed that CF 4 could be decomposed. At this time, the temperature distribution inside and outside the reactor 10 was measured.

図３は、反応装置１０の温度分布を説明した図である。
図３において、横軸は温度を表し、縦軸は反応領域の高さ方向位置を表している。そして、それぞれの場所における外部温度と内部温度を示した。ここで外部温度は、温度センサ２６ｃ（図１参照）の高さ方向位置を順次変更することで測定された温度である。また内部温度は温度センサ２６ｂ（図１参照）の高さ方向位置を順次変更することで測定された温度である。
図３からわかる通り、内部温度および外部温度は反応領域の高さ方向位置に対し、５５０℃〜５８０℃の範囲内の概ね３０℃以内の温度差に収まっており、反応領域における均一な温度分布が実現できていることがわかる。FIG. 3 is a diagram illustrating the temperature distribution of the reaction apparatus 10.
In FIG. 3, the horizontal axis represents temperature, and the vertical axis represents the height direction position of the reaction region. And the external temperature and internal temperature in each place were shown. Here, the external temperature is a temperature measured by sequentially changing the height direction position of the temperature sensor 26c (see FIG. 1). The internal temperature is a temperature measured by sequentially changing the position in the height direction of the temperature sensor 26b (see FIG. 1).
As can be seen from FIG. 3, the internal temperature and the external temperature are within a temperature difference of approximately 30 ° C. within the range of 550 ° C. to 580 ° C. with respect to the height direction position of the reaction region, and uniform temperature distribution in the reaction region It can be seen that is realized.

本実施の形態が適用される反応装置の一例を説明した図である。It is a figure explaining an example of the reaction apparatus to which this Embodiment is applied. 図１に示した反応装置のII−II断面図である。It is II-II sectional drawing of the reactor shown in FIG. 反応装置の温度分布を説明した図である。It is a figure explaining the temperature distribution of the reactor.

１０…反応装置、１２…外筒、１４…二重管、１６…熱交換器、１８…内筒、２０…内部ヒータ、２２…外部ヒータ、２４…フィン DESCRIPTION OF SYMBOLS 10 ... Reaction apparatus, 12 ... Outer cylinder, 14 ... Double pipe, 16 ... Heat exchanger, 18 ... Inner cylinder, 20 ... Internal heater, 22 ... External heater, 24 ... Fin

Claims (10)

内部にて反応を行う外筒と、
前記外筒の一方の端部側に配され、被処理ガスと処理済ガスとの間で熱交換を行う主熱交換部と、
前記主熱交換部に前記被処理ガスを供給する管と、
前記主熱交換部から前記処理済ガスを取り出す管と、
前記主熱交換部に接続し、前記外筒の内部に配され、前記主熱交換部が配される端部側から離間した当該外筒の他方の端部側に向けて前記被処理ガスを流通させる内筒と、
を備えることを特徴とする反応装置。An outer cylinder that reacts internally;
A main heat exchanging part that is arranged on one end side of the outer cylinder and performs heat exchange between the gas to be treated and the treated gas;
A pipe for supplying the gas to be processed to the main heat exchange unit;
A pipe for taking out the treated gas from the main heat exchange section;
Connected to the main heat exchanging part, arranged inside the outer cylinder, the gas to be processed toward the other end part side of the outer cylinder separated from the end part side where the main heat exchanging part is arranged An inner cylinder to be distributed;
A reaction apparatus comprising: 前記被処理ガスは、フッ素化合物を含むことを特徴とする請求項１に記載の反応装置。   The reaction apparatus according to claim 1, wherein the gas to be treated contains a fluorine compound. 前記反応は、前記フッ素化合物を銅（Ｃｕ）、錫（Ｓｎ）、クロム（Ｃｒ）、モリブデン（Ｍｏ）、タングステン（Ｗ）、バナジウム（Ｖ）からなる群から選ばれる金属の化合物の少なくとも一種、アルミナおよびアルカリ土類金属化合物を含有する反応剤により分解するものであることを特徴とする請求項２に記載の反応装置。   In the reaction, the fluorine compound is at least one metal compound selected from the group consisting of copper (Cu), tin (Sn), chromium (Cr), molybdenum (Mo), tungsten (W), and vanadium (V), The reactor according to claim 2, wherein the reactor is decomposed by a reactant containing alumina and an alkaline earth metal compound. 前記反応は、前記外筒と前記内筒との間で行うことを特徴とする請求項１乃至３の何れか１項に記載の反応装置。   The reaction apparatus according to any one of claims 1 to 3, wherein the reaction is performed between the outer cylinder and the inner cylinder. 内部の反応領域にて反応を行う外筒と、
被処理ガスおよび処理済ガスを流通させ、当該被処理ガスと当該処理済ガスとの間で第１の熱交換を行う二重管と、
前記二重管に接続し、前記被処理ガスと前記処理済ガスとの間で第２の熱交換を行う熱交換器と、
前記熱交換器に接続し、前記外筒の内部に配され、被処理ガスと前記反応領域との間で第３の熱交換を行う内筒と、
を備えることを特徴とする反応装置。An outer cylinder that reacts in the internal reaction zone;
A double pipe that circulates the gas to be treated and the treated gas, and performs a first heat exchange between the gas to be treated and the treated gas;
A heat exchanger connected to the double pipe and performing a second heat exchange between the gas to be treated and the treated gas;
An inner cylinder connected to the heat exchanger, disposed inside the outer cylinder, and performing a third heat exchange between the gas to be processed and the reaction region;
A reaction apparatus comprising: 前記内筒の内部および前記外筒の外部に配される加熱器を更に備えることを特徴とする請求項５に記載の反応装置。   The reaction apparatus according to claim 5, further comprising a heater disposed inside the inner cylinder and outside the outer cylinder. 前記内筒の外側に取り付けられるフィンを更に備えることを特徴とする請求項５または６に記載の反応装置。   The reaction apparatus according to claim 5, further comprising a fin attached to the outside of the inner cylinder. 前記フィンは、前記反応領域の下側半分の位置に取り付けられることを特徴とする請求項７に記載の反応装置。   The reaction apparatus according to claim 7, wherein the fin is attached to a position of a lower half of the reaction region. 二重管に被処理ガスおよび処理済ガスを流通させ、当該被処理ガスと当該処理済ガスとの間で第１の熱交換を行い、
前記二重管に接続する熱交換器に被処理ガスおよび処理済ガスを流通させ、当該被処理ガスと当該処理済ガスとの間で第２の熱交換を行い、
前記熱交換器に接続する内筒に被処理ガスを流通させ、被処理ガスと反応領域との間で第３の熱交換を行い、
前記反応領域で被処理ガスを処理済ガスにする反応を行うことを特徴とする反応方法。The treated gas and the treated gas are circulated through the double pipe, and the first heat exchange is performed between the treated gas and the treated gas,
Distribute the treated gas and the treated gas to the heat exchanger connected to the double pipe, and perform a second heat exchange between the treated gas and the treated gas,
The gas to be processed is circulated through the inner cylinder connected to the heat exchanger, and a third heat exchange is performed between the gas to be processed and the reaction region,
A reaction method characterized by carrying out a reaction to convert a gas to be processed into a processed gas in the reaction region. 前記被処理ガスは、フッ素化合物を含むガスであり、前記反応は当該フッ素化合物を分解するものであることを特徴とする請求項９に記載の反応方法。   The reaction method according to claim 9, wherein the gas to be treated is a gas containing a fluorine compound, and the reaction decomposes the fluorine compound.
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