JP4292052B2 - Method and apparatus for processing gas containing CO and H2 - Google Patents
Method and apparatus for processing gas containing CO and H2 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 25
- 238000012545 processing Methods 0.000 title description 14
- 239000003054 catalyst Substances 0.000 claims description 111
- 239000007789 gas Substances 0.000 claims description 108
- 238000007254 oxidation reaction Methods 0.000 claims description 61
- 230000003647 oxidation Effects 0.000 claims description 51
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 26
- 229910044991 metal oxide Inorganic materials 0.000 claims description 23
- 150000004706 metal oxides Chemical class 0.000 claims description 23
- 229910000510 noble metal Inorganic materials 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 5
- 238000007599 discharging Methods 0.000 claims description 4
- 239000010970 precious metal Substances 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 28
- 238000000354 decomposition reaction Methods 0.000 description 10
- 239000000919 ceramic Substances 0.000 description 7
- 231100000572 poisoning Toxicity 0.000 description 6
- 230000000607 poisoning effect Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000011278 co-treatment Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
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Description
本発明はＣＯ及びＨ2を含むガスの処理方法に関し、特に、主として半導体製造工程のエッチング装置などから排出されるＣＯ及びＨ2を含む排ガスの処理方法及び装置に関する。 The present invention relates to a method for treating a gas containing CO and H 2 , and particularly relates to a method and an apparatus for treating an exhaust gas containing CO and H 2 discharged mainly from an etching apparatus or the like in a semiconductor manufacturing process.
近年、半導体工業の発展と共に、半導体製造工程において種々のガスが使用されるようになり、これらの工程からはＣＯやＨ2といった可燃性ガスが排出されることが多い。ＣＯは、可燃性ガスである上に、毒性が強く人体に有害であるため、これを含むガスを大気中に放出する前に処理が必要である。また、Ｈ2は各種の製造工程で使用されると共に、Ｌｏｗ−ｋ膜（層間絶縁膜）のエッチング工程において膜の特性を保つためにＮＨ3をプロセスガスとして使用すると、副生成ガスとしてＨ2が発生する。Ｈ2は有害ガスではないが、ＣＯと同じく可燃性ガスである。また、有害ガスであるＣＯの処理装置の性能把握のために、ガス検知器（ガルバニル電池法）で処理ガスをモニターすると、ＣＯの他にも同時に検知してしまう（干渉性：ＣＯ２５ppmとＨ2１７０ppmとが同感度）。このため、ＣＯの処理装置をガス検知器で適切に管理するためには、Ｈ2も同時に処理する必要がある。 In recent years, with the development of the semiconductor industry, various gases have been used in semiconductor manufacturing processes, and combustible gases such as CO and H 2 are often discharged from these processes. Since CO is a flammable gas and is highly toxic and harmful to the human body, it needs to be treated before releasing the gas containing it into the atmosphere. Also, the H 2 is used in various manufacturing processes, Low-k film by using the NH 3 to keep the properties of the film in an etching step (interlayer insulating film) as a process gas, H 2 as a by-product gas Occurs. H 2 is not a harmful gas, but it is a flammable gas like CO. In addition, if the processing gas is monitored with a gas detector (galvanyl battery method) in order to grasp the performance of the processing apparatus for CO, which is a harmful gas, it is detected at the same time in addition to CO (coherence: CO25 ppm and H 2). 170ppm is the same sensitivity). For this reason, in order to appropriately manage the CO treatment apparatus with the gas detector, it is necessary to treat H 2 at the same time.
従来技術において、ＣＯ及びＨ2を含むガスを処理する方法としては、ＣＯ及びＨ2を分解するための触媒として、(1)ＰｄやＰｔをγ−アルミナなどの担体に担持させた貴金属触媒を用いる方法や、(2)酸化銅、酸化マンガンなどの金属酸化物系触媒を用いる方法などが提案されている。これらの提案された方法は、上記の触媒を用いて被処理ガスを処理することで、ガス中のＣＯ及びＨ2を同時に酸化分解処理するというものである。 In the prior art, as a method of treating a gas containing CO and H 2 as a catalyst for decomposing the CO and H 2, a (1) a noble metal catalyst supported with Pd or Pt on a support such as γ- alumina There have been proposed a method of using, and (2) a method of using a metal oxide catalyst such as copper oxide and manganese oxide. These proposed methods treat the gas to be treated using the above-mentioned catalyst, thereby simultaneously oxidizing and decomposing CO and H 2 in the gas.
しかしながら、貴金属触媒を用いる場合、Ｈ2は室温で分解処理することが可能であるが、ＣＯについては処理温度を１２０℃以上にする必要がある。また、金属酸化物系触媒を用いる場合には、ＣＯは室温で分解処理することが可能であるが、Ｈ2については２００℃以上にする必要がある。よって、提案された方法によってＣＯ及びＨ2を同時に処理しようとすると、貴金属触媒については１２０℃以上、金属酸化物系触媒については２００℃以上の処理温度が必要であった。しかし、半導体各種製造工程から排出される実際の排ガス中には、ＣＯやＨ2に加えてＣ2Ｆ4（テトラフルオロエチレン）が含まれている。この物質は、１００℃以上の温度で貴金属触媒や金属酸化物触媒と激しく反応してフッ化物を生成し、この生成物が触媒の表面上を覆うことで、触媒を被毒してＣＯやＨ2の酸化反応効率を著しく低下させることが分かった。 However, when a noble metal catalyst is used, H 2 can be decomposed at room temperature, but for CO, the treatment temperature needs to be 120 ° C. or higher. When a metal oxide catalyst is used, CO can be decomposed at room temperature, but H 2 needs to be 200 ° C. or higher. Therefore, when CO and H 2 are to be treated simultaneously by the proposed method, a treatment temperature of 120 ° C. or higher is required for the noble metal catalyst and 200 ° C. or higher is required for the metal oxide catalyst. However, actual exhaust gas discharged from various semiconductor manufacturing processes contains C 2 F 4 (tetrafluoroethylene) in addition to CO and H 2 . This substance reacts violently with a precious metal catalyst or metal oxide catalyst at a temperature of 100 ° C. or more to produce fluoride, and this product covers the surface of the catalyst, poisoning the catalyst, and CO or H It was found that the oxidation reaction efficiency of 2 was significantly reduced.
Ｃ2Ｆ4は、毒性はなく、可燃性ガスでもないので処理しなくても良いガスであり、ＣＯのガス検知器に対しても応答せず、干渉もしない。したがって、Ｃ2Ｆ4の分解反応による触媒の被毒を極力抑えて、ＣＯとＨ2とを同時に分解処理することができで、且つ長時間処理が可能なガスの処理方法及び装置の開発が望まれていた。 C 2 F 4 is not toxic and is not a flammable gas, so it does not need to be treated. It does not respond to or interfere with the CO gas detector. Therefore, development of a gas processing method and apparatus capable of simultaneously decomposing CO and H 2 while suppressing the poisoning of the catalyst due to the decomposition reaction of C 2 F 4 as much as possible and capable of long-time processing. It was desired.
Ｃ2Ｆ4は、毒性はなく、可燃性ガスでもないので処理しなくても良いガスであり、ＣＯのガス検知器に対しても応答せず、干渉もしない。したがって、Ｃ2Ｆ4の分解反応による触媒の被毒を極力抑えて、ＣＯとＨ2とを同時に分解処理することができで、且つ長時間処理が可能なガスの処理方法及び装置の開発が望まれていた。 C 2 F 4 is not toxic and is not a flammable gas, so it does not need to be treated. It does not respond to or interfere with the CO gas detector. Therefore, development of a gas processing method and apparatus capable of simultaneously decomposing CO and H 2 while suppressing the poisoning of the catalyst due to the decomposition reaction of C 2 F 4 as much as possible and capable of long-time processing. It was desired.
本発明者らは、上記の課題を解決すべく鋭意研究を重ねた結果、ＣＯとＨ2とを含むガスの処理において、被処理ガスをまずＣＯ酸化触媒、次にＨ2酸化触媒に順次接触させることで、各分解対象物質の分解反応の温度を低く抑え、これによってＣ2Ｆ4の分解反応を抑制することができることを見出し、本発明を完成するに到った。本発明によれば、ＣＯの酸化分解、Ｈ2の酸化分解のいずれの反応も、室温〜１００℃の温度で進行させることができる。 As a result of intensive studies to solve the above-mentioned problems, the present inventors contacted the gas to be treated first with the CO oxidation catalyst and then with the H 2 oxidation catalyst in the treatment of the gas containing CO and H 2. As a result, it was found that the temperature of the decomposition reaction of each decomposition target substance can be kept low, thereby suppressing the decomposition reaction of C 2 F 4 , and the present invention has been completed. According to the present invention, both the oxidative decomposition of CO and the oxidative decomposition of H 2 can proceed at a temperature of room temperature to 100 ° C.
即ち、本発明の一態様は、ＣＯ及びＨ2を含む被処理ガスを処理する方法であって、当該被処理ガスを、酸素の共存下で、まずＣＯ酸化触媒と接触させ、次にＨ2酸化触媒と接触させることを特徴とする方法に関する。 That is, one embodiment of the present invention is a method for treating a gas to be treated containing CO and H 2. The gas to be treated is first contacted with a CO oxidation catalyst in the presence of oxygen, and then H 2. The present invention relates to a method characterized by contacting with an oxidation catalyst.
本発明にしたがって、ＣＯ及びＨ2を含む被処理ガスを、酸素の共存下で、まずＣＯ酸化触媒と接触させ、次にＨ2酸化触媒と接触させると、被処理ガス中のＣＯ及びＨ2は次式の反応によって酸化される。 According to the present invention, when a gas to be treated containing CO and H 2 is first brought into contact with a CO oxidation catalyst in the presence of oxygen and then brought into contact with an H 2 oxidation catalyst, CO and H 2 in the gas to be treated are brought into contact. Is oxidized by the reaction:
本発明方法において、ＣＯ酸化触媒としては、酸化銅（ＩＩ）及び酸化マンガン（ＩＩ）を主成分とする組成物により構成される金属酸化物系触媒を用いることができる。組成物中の酸化銅（ＩＩ）と酸化マンガン（ＩＩ）との割合としては、酸化銅（ＩＩ）１重量部に対して酸化マンガン（ＩＩ）２．０〜２．５重量部が好ましい。金属酸化物系触媒の形状としては、破砕品、押出成形品、打錠成形品などを用いることができる。後述するように、触媒を加熱して反応を行わせる場合には、通気抵抗の上昇などを考慮すれば、円柱状の打錠成形品で直径４〜５mm、特に好ましくは４．７mm、高さ４〜５mm、特に好ましくは４．７mmのものを好ましく用いることができる。本発明においてＣＯ酸化触媒として用いることのできる金属酸化物の具体例としては、例えば、ズードケミー社製のＮ−１４０（組成：ＣｕＯ＝２２ｗｔ％，ＭｎＯ＝５０ｗｔ％）、重松製作所製のホプカリット触媒などを挙げることができる。 In the method of the present invention, as the CO oxidation catalyst, a metal oxide catalyst composed of a composition mainly composed of copper (II) oxide and manganese (II) oxide can be used. As a ratio of copper (II) oxide and manganese (II) oxide in the composition, 2.0 to 2.5 parts by weight of manganese (II) oxide is preferable with respect to 1 part by weight of copper (II) oxide. As the shape of the metal oxide catalyst, a crushed product, an extruded product, a tableted product, or the like can be used. As will be described later, when the reaction is carried out by heating the catalyst, in consideration of an increase in ventilation resistance, etc., it is a cylindrical tableting molded product having a diameter of 4 to 5 mm, particularly preferably 4.7 mm, and a height. Those having a thickness of 4 to 5 mm, particularly preferably 4.7 mm can be preferably used. Specific examples of the metal oxide that can be used as the CO oxidation catalyst in the present invention include, for example, N-140 (composition: CuO = 22 wt%, MnO = 50 wt%) manufactured by Zude Chemie, Hopkarit catalyst manufactured by Shigematsu Seisakusho, etc. Can be mentioned.
一方、本発明方法において、Ｈ2酸化触媒としては、Ｐｄ又はＰｔのいずれかをγ−アルミナに担持させた成形物により構成される貴金属触媒を用いることができる。γ−アルミナへの貴金属の担持量は、それぞれ、成形物１００重量部に対して貴金属０．１〜５重量部が好ましく、０．５重量部が特に好ましい。貴金属の担持量が０．１重量部よりも小さいとＨ2の酸化力が弱くなり、一方５重量部よりも大きいと触媒が高価になる。貴金属を担持させる担体として用いられるγ−アルミナは、比表面積が１３０m2/g以上のものが好ましく、形状は球状で大きさ４〜６mmのものが好ましい。本発明においてＨ酸化触媒として用いることのできる貴金属触媒の具体例としては、例えば、ズードケミー社製のＥＴ−０５０（０．５％のＰｄをγ−アルミナに担持）、日揮ユニバーサル社製のＲＩＳＣ−８８−０６−ＥＢ、ヘレウス社製のＫ−０２４７などを挙げることができる。 On the other hand, in the method of the present invention, as the H 2 oxidation catalyst, a noble metal catalyst composed of a molded product in which either Pd or Pt is supported on γ-alumina can be used. The amount of noble metal supported on γ-alumina is preferably 0.1 to 5 parts by weight, particularly preferably 0.5 parts by weight, based on 100 parts by weight of the molded product. If the amount of noble metal supported is less than 0.1 parts by weight, the oxidizing power of H 2 becomes weak, whereas if it exceeds 5 parts by weight, the catalyst becomes expensive. The γ-alumina used as a carrier for supporting the noble metal preferably has a specific surface area of 130 m 2 / g or more, and preferably has a spherical shape and a size of 4 to 6 mm. Specific examples of the noble metal catalyst that can be used as the H oxidation catalyst in the present invention include, for example, ET-050 (0.5% Pd supported on γ-alumina) manufactured by Zude Chemie, RISC- manufactured by JGC Universal 88-06-EB, K-0247 manufactured by Heraeus, and the like.
本発明方法において、上述の触媒によるＣＯ及びＨ2の酸化は、酸素の共存下で行う。酸素の添加量としては、被処理ガス中に含まれるＣＯ及びＨ2を酸化するために必要なＯ2量と等量であればよく、好ましくは等量の２倍量程度の酸素を被処理ガスに添加することが好ましい。酸素添加の手段としては、空気を被処理ガス中に混合することによって行うことができる。 In the method of the present invention, the oxidation of CO and H 2 by the above catalyst is performed in the presence of oxygen. The amount of oxygen added may be equal to the amount of O 2 required to oxidize CO and H 2 contained in the gas to be processed, and preferably about twice as much oxygen as the amount to be processed. It is preferable to add to gas. The oxygen can be added by mixing air into the gas to be treated.
本発明方法においては、被処理ガスと各触媒との接触温度は室温〜１００℃程度が好ましい。各触媒によるＣＯ及びＨ2の酸化は室温で進行させることができるが、ＣＯが酸化されて生成したＣＯ2が触媒の活性点に吸着して触媒の能力を低下させる場合があるので、このＣＯ2を脱離させるために若干の加熱を行うことが好ましい。この観点からは、被処理ガスと触媒との接触を６０℃程度の温度で行うことが特に好ましい。 In the method of the present invention, the contact temperature between the gas to be treated and each catalyst is preferably about room temperature to 100 ° C. Although the oxidation of CO and H 2 by each catalyst can proceed at room temperature, CO 2 produced by oxidation of CO may be adsorbed on the active sites of the catalyst and reduce the ability of the catalyst. In order to desorb 2 , it is preferable to carry out a slight heating. From this point of view, it is particularly preferable to perform contact between the gas to be treated and the catalyst at a temperature of about 60 ° C.
本発明を図面を参照して図面を参照して以下により具体的に説明する。図１は、本発明方法を実施するためのガス処理装置の一具体例の概念図である。図１に示す装置は、反応槽３と、反応槽に被処理ガスを導入する被処理ガス導入ライン１と、反応槽から処理済みのガスを排出するガス排出ライン７とを具備する。反応槽３は複数の層に分割されている。図１に示す形態では、３層に分割されていて、一番下の層には、ＣＯ酸化触媒として金属酸化物系触媒４が、中央の層には、Ｈ2酸化触媒として貴金属系触媒５がそれぞれ充填されている。また、好ましくは貴金属触媒層５の上部に更に金属酸化物触媒が充填されている予備槽６を設けることが好ましい。反応槽３の内部には、温度を測定するための熱電対８が挿入されている。また、反応槽の外側には、セラミックヒーターなどの加熱装置７が配置されている。
The present invention will be described more specifically below with reference to the drawings. FIG. 1 is a conceptual diagram of a specific example of a gas processing apparatus for carrying out the method of the present invention. The apparatus shown in FIG. 1 includes a
反応槽３の内部を熱電対８で温度測定しながら、加熱装置７によって所定の温度に加熱保持する。被処理ガスを、被処理ガス導入ライン１から導入する。この際、被処理ガス導入ライン１の途中に酸素源として空気２を供給することで、反応系に酸素を添加する。酸素の添加は、図１に示すように被処理ガス導入ラインに対して行ってもよいし、或いは反応槽３に直接供給してもよい。酸素を添加された被処理ガスは、反応槽３内のＣＯ酸化触媒層４を通過し、この間に、被処理ガス中のＣＯがＣＯ2に酸化される。次に、被処理ガスは反応槽３内のＨ2酸化触媒層５を通過し、この間に、被処理ガス中のＨ2がＨ2Ｏに酸化される。Ｈ2酸化触媒層５の出口には、ガス検知器１０と接続されたガス検知器ライン９を配置して、出口ガス中のＣＯ濃度をモニターすることが好ましい。金属酸化物触媒の被毒或いは能力低下などの原因で出口ガス中にＣＯが検出されたら、被処理ガスの導入を停止して、触媒を交換若しくは再生処理にかける。しかしながら、ウエハーの処理中などの理由により被処理ガスの導入を直ちに停止できない場合には、反応槽の最上部に予備層６を配置して、この中にＣＯ酸化触媒として金属酸化物系触媒５’を充填することが好ましい。このような層６を配置することにより、出口ガス中に少量リークしたＣＯを酸化処理することが可能である。処理が完了したガスは、排出ライン７を通して排出される。
While the temperature of the inside of the
本発明にかかる装置においては、反応槽内における金属酸化物系触媒と貴金属触媒との充填比率は、容積比で金属酸化物系触媒１に対して、貴金属触媒を０．１〜１とすることが好ましく、貴金属触媒を０．２５とすることが特に好ましい。 In the apparatus according to the present invention, the filling ratio of the metal oxide catalyst to the noble metal catalyst in the reaction tank is 0.1 to 1 for the metal oxide catalyst 1 with respect to the volume ratio of the metal oxide catalyst. It is particularly preferable that the noble metal catalyst is 0.25.
本発明は、上記に説明したガス処理装置にも関する。即ち、本発明の他の態様は以下の通りである。
ＣＯ酸化触媒が充填された層とＨ2酸化触媒が充填された層とを有する反応槽と、反応槽のＣＯ酸化触媒層に被処理ガスを導入するための被処理ガス導入ラインと、被処理ガス導入ライン中若しくは反応槽中に酸素を添加するための手段と、反応槽のＨ2酸化触媒層から処理済のガスを排出するガス排出ラインと、を具備することを特徴とする、ＣＯ及びＨ2を含む被処理ガスを処理するための装置；
ＣＯ酸化触媒層に、酸化銅（ＩＩ）及び酸化マンガン（ＩＩ）を主成分とする金属酸化物系触媒が充填されており、Ｈ2酸化触媒層に、パラジウム又は白金をγ−アルミナに担持させた貴金属触媒が充填されている上記に記載の装置；
反応槽に加熱手段が取り付けられている上記のいずれかに記載の装置。
The present invention also relates to the gas processing apparatus described above. That is, another aspect of the present invention is as follows.
A reaction vessel having a layer filled with a CO oxidation catalyst and a layer filled with an H 2 oxidation catalyst, a gas introduction line for introducing a gas to be treated into the CO oxidation catalyst layer of the reaction vessel, and a treatment CO, characterized by comprising: means for adding oxygen in the gas introduction line or in the reaction tank; and a gas discharge line for discharging the treated gas from the H 2 oxidation catalyst layer of the reaction tank. An apparatus for treating a gas to be treated containing H 2 ;
The CO oxidation catalyst layer is filled with a metal oxide catalyst mainly composed of copper (II) oxide and manganese oxide (II), and palladium or platinum is supported on γ-alumina on the H 2 oxidation catalyst layer. An apparatus as described above, which is filled with a precious metal catalyst;
The apparatus according to any one of the above, wherein heating means is attached to the reaction vessel.
また、図１では、単一の反応槽内にＣＯ酸化触媒層及びＨ2酸化触媒層を配置した形態を示したが、これらの各層を別々の反応槽として配置し、これらの槽間を接続することによって反応装置を形成することもできる。即ち、本発明の他の態様は、ＣＯ酸化触媒が充填されたＣＯ酸化反応槽と、Ｈ2酸化触媒が充填されたＨ2酸化反応槽と、上記両槽を接続する接続ラインと、ＣＯ酸化反応槽に被処理ガスを導入するための被処理ガス導入ラインと、被処理ガス導入ライン中若しくはＣＯ酸化反応槽中に酸素を添加するための手段と、Ｈ2酸化反応槽から処理済のガスを排出するガス排出ラインと、を具備することを特徴とする、ＣＯ及びＨ2を含む被処理ガスを処理するための装置に関する。 Further, in FIG. 1, there is shown an embodiment in which to place the CO oxidation catalyst layer and H 2 oxidation catalyst layer in a single reaction vessel, it placed these layers as separate reaction vessel, connected between these tanks By doing so, a reactor can also be formed. That is, another aspect of the present invention includes a CO oxidation reaction tank filled with a CO oxidation catalyst, an H 2 oxidation reaction tank filled with an H 2 oxidation catalyst, a connection line connecting the two tanks, and a CO oxidation Process gas introduction line for introducing process gas into the reaction tank, means for adding oxygen in the process gas introduction line or CO oxidation reaction tank, and gas treated from the H 2 oxidation reaction tank And an apparatus for processing a gas to be processed containing CO and H 2 .
以下の実施例により、本発明をより具体的に説明する。
参考例１
図１に示す構成の装置によって通ガス試験を行った。セラミックヒーターカラム（内径１５０ｍｍ）に、１層目として市販の金属酸化物系触媒（ズードケミー社製、Ｎ−１４０、組成：ＣｕＯ＝２２ｗｔ％，ＭｎＯ＝５０ｗｔ％、径４．７ｍｍ×長さ４．７ｍｍのタブレット形状）を１２リットル充填し、次に２層目として市販の貴金属触媒（ズードケミー社製、ＥＴ−０５０、０．５％のＰｄをγ−アルミナに担持したもの、径４〜６ｍｍの球状）を３リットル充填して、主処理層を形成した。この上に、更に上記と同じ金属酸化物系触媒を１リットル充填して予備処理層を形成した。
The following examples illustrate the invention more specifically.
Reference example 1
A gas passing test was performed using an apparatus having the configuration shown in FIG. In a ceramic heater column (inner diameter 150 mm), as a first layer, a commercially available metal oxide catalyst (Z-Chem, N-140, composition: CuO = 22 wt%, MnO = 50 wt%, diameter 4.7 mm ×
カラムの内部温度が６０℃になるようにセラミックヒーターで加熱し、カラムの底部からＣＯ，Ｈ2，Ｏ2（空気），Ｎ2の混合ガスを通ガスした。ガス流量は、ＣＯ＝９００mL/min、Ｈ2＝３７０mL/min、空気＝２０L/min、Ｎ2＝４０L/minで、流入濃度をＣＯ＝１．５％、Ｈ2＝０．６０％、Ｏ2＝６．９％とした。 The column was heated with a ceramic heater so that the internal temperature of the column reached 60 ° C., and a mixed gas of CO, H 2 , O 2 (air), and N 2 was passed through the bottom of the column. The gas flow rate is CO = 900 mL / min, H 2 = 370 mL / min, air = 20 L / min, N 2 = 40 L / min, the inflow concentration is CO = 1.5%, H 2 = 0.60%, O 2 = 6.9%.
主処理層の出口に配置したガス検知器ラインの取出し口から主処理層の処理ガスを適宜サンプリングし、ＣＯ及びＨ2をガスクロマトグラフ質量分析装置（アネルバ製、ＡＧＳ−７０００Ｕ）を用いて分析した。 The processing gas of the main processing layer was appropriately sampled from the outlet of the gas detector line arranged at the outlet of the main processing layer, and CO and H 2 were analyzed using a gas chromatograph mass spectrometer (AGS-7000U, manufactured by Anelva). .
１時間通ガスを継続したが、その間、主処理層出口ガス中にＣＯ及びＨ2はいずれも常時検出限界以下（ＣＯ＜２ppm、Ｈ2＜２ppm）であった。 The gas was continued for 1 hour, but during that time, both CO and H 2 were always below the detection limit (CO <2 ppm, H 2 <2 ppm) in the main treatment layer outlet gas.
比較例１
参考例１で用いたものと同じセラミックヒーターカラム内に、参考例１と同じ金属酸化物系触媒のみを１５リットル充填し、参考例１と同様の条件で通ガスした。通ガスを開始して５分後に触媒層の出口ガスをサンプリングして分析したところ、Ｈ２ガスが入口濃度とほぼ同じ０．６０％検出された。ＣＯは、この時点では不検出であった。
Comparative Example 1
The same ceramic heater column as that used in Reference Example 1, only the same metal oxide-based catalyst as in Reference Example 1 was charged 15 liters, was passed through the gas under the same conditions as in Reference Example 1. When the outlet gas of the catalyst layer was sampled and analyzed 5 minutes after the start of gas flow, H 2 gas was detected as 0.60%, which was almost the same as the inlet concentration. CO was not detected at this point.
比較例２
参考例１で用いたものと同じセラミックヒーターカラム内に、参考例１と同じ貴金属触媒のみを１５リットル充填し、参考例１と同様の条件で通ガスした。通ガスを開始して１０分後に触媒層の出口ガスをサンプリングして分析したところ、ＣＯが４５ｐｐｍと許容濃度（ＡＣＧＩＨのＴＬＶ−ＴＷＡ値＝２５ｐｐｍ）を超えて検出された。Ｈ２は、この時点では不検出であった。
Comparative Example 2
The same ceramic heater column as that used in Reference Example 1, only the same noble metal catalyst as in Reference Example 1 was charged 15 liters, was passed through the gas under the same conditions as in Reference Example 1. 10 minutes after starting the gas flow, the outlet gas of the catalyst layer was sampled and analyzed. As a result, CO was detected to exceed 45 ppm and the allowable concentration (ACGIH TLV-TWA value = 25 ppm). H 2 was not detected at this point.
比較例１及び２の結果から、金属酸化物系触媒及び貴金属触媒を単独で用いてＣＯ及びＨ2の酸化処理を行おうとすると、６０℃程度の加熱温度では十分に処理ができないことが分かる。 From the results of Comparative Examples 1 and 2, it can be seen that if a metal oxide catalyst and a noble metal catalyst are used alone to carry out the oxidation treatment of CO and H 2 , the treatment cannot be sufficiently performed at a heating temperature of about 60 ° C.
参考例３
金属酸化物系触媒と貴金属触媒のＣ２Ｆ４による被毒の影響を検討するために、処理温度とＣ２Ｆ４の分解率との関係を調べた。
Reference example 3
In order to examine the influence of poisoning of the metal oxide catalyst and the noble metal catalyst by C 2 F 4 , the relationship between the treatment temperature and the decomposition rate of C 2 F 4 was examined.
セラミック製ミニカラム（径４２ｍｍ×長さ１３６ｍｍ）内に、参考例１と同じ金属酸化物系触媒並びに貴金属触媒を、それぞれ単独で１８８ｍＬ充填した。それぞれのカラムをセラミック電気管状炉に装着し、カラムの中心温度を段階的に変化させて被処理ガスの通ガスを行った。カラム温度は、５０℃、７５℃、１００℃、１２５℃、１５０℃とした。ガス流量は、Ｃ２Ｆ４＝１．３ｍＬ／ｍｉｎ、Ｏ２＝４０ｍＬ／ｍｉｎ、Ｎ２＝４００ｍＬ／ｍｉｎで、流入濃度はＣ２Ｆ４＝２９５０ｐｐｍ、Ｏ２＝９．１％とした。
In a ceramic mini column (diameter 42 mm × length 136 mm), 188 mL each of the same metal oxide catalyst and noble metal catalyst as in Reference Example 1 was packed. Each column was attached to a ceramic electric tube furnace, and the gas to be treated was passed through the column at a stepwise change in the center temperature. Column temperature was 50 degreeC, 75 degreeC, 100 degreeC, 125 degreeC, and 150 degreeC. The gas flow rates were C 2 F 4 = 1.3 mL / min, O 2 = 40 mL / min, N 2 = 400 mL / min, and the inflow concentration was C 2 F 4 = 2950 ppm and O 2 = 9.1%.
カラム出口ガスをサンプリングしてＣ2Ｆ4に関してガスクロマトグラフ質量分析装置（アネルバ製、ＡＧＳ−７０００Ｕ）を用いて分析した。Ｃ2Ｆ4の出口濃度がほぼ一定となった９０分後の濃度を基に、次式によって分解率を求めた。結果を表１に示す。 The column outlet gas was sampled and analyzed for C 2 F 4 using a gas chromatograph mass spectrometer (manufactured by Anerva, AGS-7000U). Based on the concentration after 90 minutes when the outlet concentration of C 2 F 4 became almost constant, the decomposition rate was determined by the following equation. The results are shown in Table 1.
表１より、処理温度（被処理ガスと触媒との接触温度）が１００℃を超えるとＣ２Ｆ４の分解率が急激に上昇することが分かる。この結果から、Ｃ２Ｆ４の分解により金属（又は貴金属）のフッ化物が生成してこれが触媒の表面を覆うことによって触媒が被毒されるという現象を抑制するためには、被処理ガスと触媒との接触温度を１００℃以下に抑えることが好ましいことが理解できる。 From Table 1, it can be seen that when the treatment temperature (contact temperature between the gas to be treated and the catalyst) exceeds 100 ° C., the decomposition rate of C 2 F 4 rapidly increases. From this result, in order to suppress the phenomenon that a metal (or noble metal) fluoride is generated by decomposition of C 2 F 4 and this covers the surface of the catalyst, the catalyst is poisoned. It can be understood that the contact temperature with the catalyst is preferably suppressed to 100 ° C. or lower.
本発明によれば、Ｈ2及びＣＯを含むガスを処理するにあたって、従来法よりも低い温度でＨ2及びＣＯの酸化処理が可能である。したがって、従来法における被処理ガスを高温で触媒と接触させることによるＣ2Ｆ4の分解に起因する触媒の被毒を抑制することができ、半導体製造工程からのＣＯ及びＨ2を含む排ガスの処理を極めて好適に行うことが可能になる。 According to the present invention, when treating a gas containing H 2 and CO, can be oxidized in H 2 and CO at low temperature than the conventional method. Therefore, the poisoning of the catalyst due to the decomposition of C 2 F 4 by contacting the gas to be treated with the catalyst at a high temperature in the conventional method can be suppressed, and the exhaust gas containing CO and H 2 from the semiconductor manufacturing process can be suppressed. It becomes possible to perform processing very suitably.
Claims (8)
Ｈ２酸化触媒は、触媒全量１００重量部に対してパラジウム又は白金を０．１〜５重量部含む、請求項２に記載の方法。 The CO oxidation catalyst contains 2.0 to 2.5 parts by weight of manganese (II) oxide per 1 part by weight of copper (II) oxide,
The method according to claim 2, wherein the H 2 oxidation catalyst contains 0.1 to 5 parts by weight of palladium or platinum with respect to 100 parts by weight of the total amount of the catalyst.
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| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
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| EXPY | Cancellation because of completion of term |