JP4833602B2 - Exhaust gas treatment method - Google Patents
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- JP4833602B2 JP4833602B2 JP2005205121A JP2005205121A JP4833602B2 JP 4833602 B2 JP4833602 B2 JP 4833602B2 JP 2005205121 A JP2005205121 A JP 2005205121A JP 2005205121 A JP2005205121 A JP 2005205121A JP 4833602 B2 JP4833602 B2 JP 4833602B2
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- arsine
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- 238000000034 method Methods 0.000 title claims description 20
- 239000007789 gas Substances 0.000 claims description 72
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 46
- 238000000746 purification Methods 0.000 claims description 46
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims description 23
- 150000001495 arsenic compounds Chemical class 0.000 claims description 20
- ZGNPLWZYVAFUNZ-UHFFFAOYSA-N tert-butylphosphane Chemical compound CC(C)(C)P ZGNPLWZYVAFUNZ-UHFFFAOYSA-N 0.000 claims description 20
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 claims description 19
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 19
- QTQRGDBFHFYIBH-UHFFFAOYSA-N tert-butylarsenic Chemical compound CC(C)(C)[As] QTQRGDBFHFYIBH-UHFFFAOYSA-N 0.000 claims description 15
- 238000000354 decomposition reaction Methods 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000012459 cleaning agent Substances 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims description 7
- 229910021536 Zeolite Inorganic materials 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 238000005108 dry cleaning Methods 0.000 claims description 7
- 239000000741 silica gel Substances 0.000 claims description 7
- 229910002027 silica gel Inorganic materials 0.000 claims description 7
- 239000010457 zeolite Substances 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000004927 clay Substances 0.000 claims description 4
- 239000005373 porous glass Substances 0.000 claims description 4
- HTDIUWINAKAPER-UHFFFAOYSA-N trimethylarsine Chemical compound C[As](C)C HTDIUWINAKAPER-UHFFFAOYSA-N 0.000 claims description 4
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- -1 isobutyl arsine Chemical compound 0.000 claims description 3
- TXBIZRLVIDXDGB-UHFFFAOYSA-N 2-methylpropylphosphane Chemical compound CC(C)CP TXBIZRLVIDXDGB-UHFFFAOYSA-N 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- WWVNWQJKWKSDQM-UHFFFAOYSA-N triethylarsane Chemical compound CC[As](CC)CC WWVNWQJKWKSDQM-UHFFFAOYSA-N 0.000 claims description 2
- RXJKFRMDXUJTEX-UHFFFAOYSA-N triethylphosphine Chemical compound CCP(CC)CC RXJKFRMDXUJTEX-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000000197 pyrolysis Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000012629 purifying agent Substances 0.000 description 6
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000020169 heat generation Effects 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000004480 active ingredient Substances 0.000 description 4
- 229910052785 arsenic Inorganic materials 0.000 description 4
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229940093920 gynecological arsenic compound Drugs 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- 239000005751 Copper oxide Substances 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- 238000009841 combustion method Methods 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- CAPAQZBRMPASPK-UHFFFAOYSA-N 2-methylpropylarsane Chemical compound CC(C)C[AsH2] CAPAQZBRMPASPK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- GCPXMJHSNVMWNM-UHFFFAOYSA-N arsenous acid Chemical compound O[As](O)O GCPXMJHSNVMWNM-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 231100001231 less toxic Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- Catalysts (AREA)
- Treating Waste Gases (AREA)
Description
本発明は排ガスの処理方法に関する。さらに詳細には半導体製造工程等から排出される有機燐化合物及び／または有機砒素化合物を含む排ガスを、効率よく安全に浄化することが可能な排ガスの処理方法に関する。 The present invention relates to an exhaust gas treatment method. More particularly, the present invention relates to an exhaust gas treatment method capable of efficiently and safely purifying exhaust gas containing an organic phosphorus compound and / or an organic arsenic compound discharged from a semiconductor manufacturing process or the like.
高電子移動度トランジスタ（ＨＥＭＴ）、ヘテロ接合ハイポーラトランジスタ（ＨＢＴ）等の高速デバイス、半導体レーザー、超高輝度ＬＥＤ、太陽電池等のオプトデバイスの製作においては、ホスフィンやアルシン等の有害原料が使用されている。また、近年、これらのガス原料に代わり、人体に対して比較的に毒性が低く、かつ取扱いが容易なターシャリーブチルホスフィン等の有機燐化合物、ターシャリーブチルアルシン等の有機砒素化合物が多く使用されるようになってきた。ターシャリーブチルホスフィン、ターシャリーブチルアルシンは、ホスフィン、アルシンと比較して毒性は低いが、これらを含む排ガスは浄化した後、大気に放出することが必要である。 Harmful raw materials such as phosphine and arsine are used in the production of high-speed devices such as high electron mobility transistors (HEMT) and heterojunction hyperpolar transistors (HBT), and opto-devices such as semiconductor lasers, ultra-bright LEDs, and solar cells. Has been. In recent years, organic gas compounds such as tertiary butylphosphine and organic arsenic compounds such as tertiary butylarsine, which are relatively low in toxicity to the human body and easy to handle, have been used in place of these gas raw materials. It has come to be. Tertiary butylphosphine and tertiary butylarsine are less toxic than phosphine and arsine, but exhaust gas containing these must be purified and then released to the atmosphere.
半導体製造工程から排出される排ガスの一般的な処理方法としては、排ガスを、水素、メタン、プロパン等を用いた焼却炉の火炎中に導入して燃焼させる燃焼法、薬液を溶解させた水溶液と接触させて浄化する湿式法、固体状の浄化剤が充填された浄化筒に導入し、浄化剤と接触させて浄化する乾式法等がある。しかし、燃焼法を適用した場合においては、ターシャリーブチルアルシンを燃焼すると有毒な亜砒酸等の粉末が生成し、後処理が困難になるという不都合があった。また、湿式法を適用した場合においては、ターシャリーブチルホスフィン、ターシャリーブチルアルシンは水にはほとんど溶けないため、これらを効率よく除去できず、湿式浄化装置の排出口から高い濃度で排出されてしまうという不都合があった。 As a general treatment method of exhaust gas discharged from the semiconductor manufacturing process, a combustion method in which exhaust gas is introduced into a flame of an incinerator using hydrogen, methane, propane, etc. and burned, an aqueous solution in which a chemical solution is dissolved, and There are a wet method for purifying by contact, a dry method for introducing into a purification cylinder filled with a solid purification agent, and purifying by contacting with the purification agent. However, when the combustion method is applied, burning tertiary butylarsine produces toxic powders such as arsenous acid, making post-treatment difficult. In addition, when the wet method is applied, tertiary butylphosphine and tertiary butylarsine are hardly soluble in water, so they cannot be removed efficiently, and are discharged at a high concentration from the outlet of the wet purification device. There was an inconvenience that the
従って、ターシャリーブチルホスフィン、ターシャリーブチルアルシン等を含む排ガスの浄化は、主に乾式法により行なわれてきた。また、従来から使用されてきた乾式浄化剤としては、例えば次の特許文献に示されるように、有効成分として酸化銅、水酸化銅を含む浄化剤、あるいはこれに酸化マンガン等の金属酸化物が加えられた浄化剤等が挙げられる。
しかしながら、前記のような金属酸化物を含む浄化剤を用いてターシャリーブチルホスフィン、ターシャリーブチルアルシン等を浄化した後の浄化剤は、酸素（空気）と接触すると激しく酸化反応して急激な発熱を起こし、これにより前記有害成分中の炭化水素基が燃焼して急激に多量の水蒸気及び二酸化炭素が発生し、危険な状態になるという問題点があった。そのため、これらのガスを浄化した後、浄化筒の後処理には、極めて慎重な操作が要求されるという不都合があった。また、金属酸化物を含む浄化剤を用いてターシャリーブチルホスフィン、ターシャリーブチルアルシンを浄化したときの浄化能力（浄化剤単位量当たりの有害成分の処理量）は、ホスフィン、アルシンを浄化したときの浄化能力と比較して著しく低かった。そのため浄化剤の詰め替え作業を頻繁に行なう必要があるとともに、多量の廃棄剤が発生した。 However, the purifier after purifying tertiary butylphosphine, tertiary butylarsine, etc. using a purifier containing a metal oxide as described above undergoes a violent oxidation reaction when it comes into contact with oxygen (air), resulting in rapid heat generation. As a result, the hydrocarbon group in the harmful component burns, and a large amount of water vapor and carbon dioxide are rapidly generated, resulting in a dangerous state. Therefore, after purifying these gases, the post-treatment of the purification cylinder has a disadvantage that an extremely careful operation is required. In addition, when purifying tertiary butylphosphine and tertiary butylarsine using a purifier containing metal oxide, the purification capacity (amount of harmful components per unit amount of purifier) is the same as when purifying phosphine and arsine. It was significantly lower than the purification capacity. Therefore, it was necessary to refill the cleaning agent frequently, and a large amount of waste agent was generated.
従って、本発明が解決しようとする課題は、有害成分として、ターシャリーブチルホスフィン等の有機燐化合物、あるいはターシャリーブチルアルシン等の有機砒素化合物を含む排ガスの浄化において、急激な発熱及びガス発生を起こす虞がなく、優れた浄化能力で効率よく安全にこれらの有害成分を含む排ガスを浄化することが可能な手段を提供することである。 Therefore, the problem to be solved by the present invention is that rapid heat generation and gas generation are caused in purification of exhaust gas containing organic phosphorus compounds such as tertiary butylphosphine or organic arsenic compounds such as tertiary butylarsine as harmful components. It is an object of the present invention to provide a means capable of purifying exhaust gas containing these harmful components efficiently and safely with no risk of occurrence.
本発明者らは、これらの課題を解決すべく鋭意検討した結果、ターシャリーブチルホスフィン等の有機燐化合物、ターシャリーブチルアルシン等の有機砒素化合物は、加熱下、水蒸気の存在下で、シリカゲル、ゼオライト等の珪素を含む無機多孔質体と接触させることにより、ホスフィン及び／またはアルシンと、炭化水素に容易に分解できること、分解後これらを含むガスをホスフィン及び／またはアルシンの乾式浄化剤と接触させて浄化することにより、急激な発熱及びガス発生を起こす虞がなく、優れた浄化能力で効率よく安全に浄化できること等を見出し、本発明の排ガスの処理方法に到達した。 The present inventors have made intensive studies to solve these problems, organic phosphorus compounds such as tertiary butyl phosphine, an organic arsenic compound such as tertiary butyl arsine, under heating, in the presence of water vapor, silica gel, By contacting with an inorganic porous material containing silicon such as zeolite, phosphine and / or arsine and hydrocarbon can be easily decomposed, and after decomposition, the gas containing these is contacted with a phosphine and / or arsine dry cleaning agent. As a result of the purification, the inventors have found that there is no risk of sudden heat generation and gas generation, and that the purification can be performed efficiently and safely with an excellent purification capability, and the exhaust gas treatment method of the present invention has been reached.
すなわち本発明は、有害成分として有機燐化合物及び／または有機砒素化合物を含む排ガスを、加熱下、水蒸気の存在下で、シリカゲル、ゼオライト、多孔質ガラス、及び粘土系多孔質から選ばれ、かつ珪素を含む無機多孔質体と接触させて、該有害成分を、ホスフィン及び／またはアルシンと、炭化水素に分解することを特徴とする排ガスの処理方法である。 That is, the present invention is an exhaust gas containing an organic phosphorus compound and / or an organic arsenic compound as a harmful component under heating and in the presence of water vapor, selected from silica gel, zeolite, porous glass, and clay-based porous material, and silicon. In which the harmful components are decomposed into phosphine and / or arsine and hydrocarbons in contact with an inorganic porous material containing .
本発明は、ターシャリーブチルホスフィン等の有機燐化合物、ターシャリーブチルアルシン等の有機砒素化合物を、直接的に乾式浄化剤と接触させて浄化する方式ではないので、浄化した後の浄化剤は、空気（酸素）と接触しても急激な発熱及びガス発生を起こすことがなく比較的に安全である。また、浄化剤は優れた浄化能力で、有機燐化合物及び／または有機砒素化合物が分解して生成したホスフィン及び／またはアルシンを除去できるので、有機燐化合物、有機砒素化合物を、直接的に浄化剤と接触させて浄化する従来の方法に比べて、浄化剤の詰め替え作業の頻度及び廃棄剤の発生量を大幅に少なくすることが可能である。 Since the present invention is not a method of purifying an organic phosphorus compound such as tertiary butylphosphine or an organic arsenic compound such as tertiary butylarsine by directly contacting with a dry cleaning agent, the purifying agent after purification is Even if it comes into contact with air (oxygen), it is relatively safe without causing sudden heat generation and gas generation. In addition, since the purifying agent can remove phosphine and / or arsine generated by decomposition of the organic phosphorus compound and / or the organic arsenic compound with an excellent purifying ability, the organic phosphorus compound and the organic arsenic compound can be directly removed. Compared with the conventional method of purifying by contacting with a cleaning agent, it is possible to greatly reduce the frequency of refilling operation of the cleaning agent and the amount of waste agent generated.
本発明の排ガスの処理方法は、主に半導体製造工程から排出される有機燐化合物及び／または有機砒素化合物を含む排ガスの浄化に適用される。
本発明の排ガスの処理方法において、処理の対象となる排ガスは、例えば、水素、窒素、アルゴン、ヘリウム等をベースガスとし、ターシャリーブチルホスフィン、イソブチルホスフィン、トリメチルホスフィン、トリエチルホスフィン等の有機燐化合物、ターシャリーブチルアルシン、イソブチルアルシン、トリメチルアルシン、トリエチルアルシン等の有機砒素化合物を有害成分として含む排ガスである。尚、本発明においては、分解処理により、有機燐化合物はホスフィンと炭化水素に、有機砒素化合物はアルシンと炭化水素に分解される。
The exhaust gas treatment method of the present invention is mainly applied to purification of exhaust gas containing an organic phosphorus compound and / or an organic arsenic compound discharged from a semiconductor manufacturing process.
In the exhaust gas treatment method of the present invention, the exhaust gas to be treated is based on, for example, hydrogen, nitrogen, argon, helium, etc., and an organic phosphorus compound such as tertiary butylphosphine, isobutylphosphine, trimethylphosphine, triethylphosphine, etc. The exhaust gas contains organic arsenic compounds such as tertiary butylarsine, isobutylarsine, trimethylarsine, and triethylarsine as harmful components. In the present invention, the organic phosphorus compound is decomposed into phosphine and hydrocarbon, and the organic arsenic compound is decomposed into arsine and hydrocarbon by the decomposition treatment.
本発明において使用される無機多孔質体としては、シリカゲル、ゼオライト、多孔質ガラス、粘土系多孔質体から選ばれ、かつ珪素を含む無機多孔質体である。これらの中でも後述するように粉末状の燐または砒素の発生を抑制できる点で珪素を多く含むシリカゲルを使用することが好ましい。本発明における無機多孔質体は、通常は比表面積が１０ｍ２／ｇ以上のもの、好ましくは比表面積が１００ｍ２／ｇ以上のものが使用される。 The inorganic porous material used in the present invention is an inorganic porous material selected from silica gel, zeolite, porous glass and clay-based porous material and containing silicon . Among these, as described later, it is preferable to use silica gel containing a large amount of silicon from the viewpoint that generation of powdered phosphorus or arsenic can be suppressed. The inorganic porous material in the present invention usually has a specific surface area of 10 m 2 / g or more, and preferably has a specific surface area of 100 m 2 / g or more.
本発明の排ガスの処理方法は、通常は前述の無機多孔質体が充填された加熱分解筒に、有機燐化合物及び／または有機砒素化合物を含む排ガスを導入することにより行なわれる。その際の無機多孔質体の充填長は、排ガスの流量、有害成分の濃度、無機多孔質体の種類等により一概に限定できないが、通常は５０〜１５００ｍｍ程度、好ましくは１００〜１０００ｍｍ程度である。充填長が５０ｍｍより短い場合は有害成分の一部が分解されずに下流側に流出する虞があり、充填長が１５００ｍｍより長い場合は圧力損失が大きくなりすぎる虞がある。無機多孔質体に導入する際の排ガスの空筒線速度（ＬＶ）は、通常は１００ｃｍ／ｓ以下、好ましくは１〜５０ｃｍ／ｓである。 The exhaust gas treatment method of the present invention is usually carried out by introducing exhaust gas containing an organic phosphorus compound and / or an organic arsenic compound into a pyrolysis cylinder filled with the above-mentioned inorganic porous material. The filling length of the inorganic porous body at that time cannot be generally limited by the exhaust gas flow rate, the concentration of harmful components, the type of inorganic porous body, etc., but is usually about 50 to 1500 mm, preferably about 100 to 1000 mm. . When the filling length is shorter than 50 mm, a part of harmful components may flow out downstream without being decomposed, and when the filling length is longer than 1500 mm, the pressure loss may become too large. The cylinder linear velocity (LV) of the exhaust gas when introduced into the inorganic porous body is usually 100 cm / s or less, preferably 1 to 50 cm / s.
また、有機燐化合物及び／または有機砒素化合物を、無機多孔質体に接触させて分解する際の温度条件は、通常は１５０〜１０００℃、好ましくは２００〜６００℃である。分解温度が１５０℃より低い場合は有害成分の一部が分解されずに下流側に流出する虞があり、１０００℃を超える場合は耐熱性の高い材料が要求される不都合がある。また、分解の際の排ガスの圧力条件は、通常は常圧または常圧近辺の圧力（５０〜２００ＫＰａ（絶対圧力））であるが、１０ＫＰａ（絶対圧力）のような減圧下、あるいは１０００ＫＰａ（絶対圧力）のような加圧下で操作することも可能である。 Moreover, the temperature conditions at the time of decomposing | disassembling an organic phosphorus compound and / or an organic arsenic compound in contact with an inorganic porous body are 150-1000 degreeC normally, Preferably it is 200-600 degreeC. When the decomposition temperature is lower than 150 ° C., there is a possibility that a part of harmful components may flow out downstream without being decomposed, and when it exceeds 1000 ° C., there is a disadvantage that a material having high heat resistance is required. The pressure condition of the exhaust gas at the time of decomposition is usually normal pressure or a pressure around normal pressure (50 to 200 KPa (absolute pressure)), but under reduced pressure such as 10 KPa (absolute pressure) or 1000 KPa (absolute It is also possible to operate under pressure such as pressure.
本発明の排ガスの処理方法により、有機燐化合物、有機砒素化合物を分解する際には、分解条件により燐、砒素の粉末が生成する。このことから、例えばターシャリーブチルホスフィンを、ホスフィンと炭化水素に分解する場合は、次の（式１）（式２）の反応が起こると推測される。他の有機燐化合物及び有機砒素化合物も（式１）（式２）と同様な反応が起こると考えられる。
従って、本発明の排ガスの処理方法においては、分解条件、加熱分解筒の構成条件によっては粉末状の燐または砒素が加熱分解筒に堆積し、圧力損失が徐々に大きくなる不都合が生じる。しかしながら、本発明においては、無機多孔質体として珪素を多く含む無機多孔質体を使用し、有害成分を水蒸気の存在下で分解することにより、（式２）の反応を抑制し（式１）の反応が起りやすく制御することができ、前記の条件を併せて分解処理を行なうことにより燐または砒素の発生を極めて微量まで抑制することが可能である。尚、水蒸気を供給する場合、通常はモル数換算で有機燐化合物及び有機砒素化合物の合計の０．１〜１０倍程度の水蒸気、好ましくは０．５〜２倍程度の水蒸気が供給される。但し、水蒸気量の上限は、ガス全体に対して２０ｖｏｌ％程度である。 Therefore, in the exhaust gas treatment method of the present invention, powdery phosphorus or arsenic deposits on the thermal decomposition cylinder depending on the decomposition conditions and the configuration conditions of the thermal decomposition cylinder, resulting in a disadvantage that the pressure loss gradually increases. However, in the present invention, the inorganic porous body containing a large amount of silicon is used as the inorganic porous body, and the harmful component is decomposed in the presence of water vapor to suppress the reaction of (Formula 2) (Formula 1). This reaction can easily be controlled, and the generation of phosphorus or arsenic can be suppressed to a very small amount by performing the decomposition treatment in combination with the above conditions. In addition, when supplying water vapor | steam, normally about 0.1-10 times water vapor | steam of the sum total of an organic phosphorus compound and an organic arsenic compound, Preferably about 0.5-2 times water vapor | steam is supplied in conversion of the number of moles. However, the upper limit of the water vapor amount is about 20 vol% with respect to the entire gas.
本発明においては、通常はさらに、ホスフィン及び／またはアルシンと炭化水素を含む分解処理後のガスが、乾式浄化剤と接触して浄化される。この際に使用される乾式浄化剤としては、ホスフィン及び／またはアルシンを、充分に低濃度になるまで除去することができるものであれば特に制限されることはないが、例えば、有効成分として酸化銅、塩基性炭酸銅、または水酸化銅を含む浄化剤、あるいはこれに酸化マンガン等の金属酸化物が加えられた浄化剤、さらに有効成分として活性炭、合成ゼオライト、または天然ゼオライトからなる浄化剤等を挙げることができる。 In the present invention, usually, the gas after the decomposition treatment containing phosphine and / or arsine and hydrocarbon is purified by contact with a dry cleaning agent. The dry cleaning agent used in this case is not particularly limited as long as it can remove phosphine and / or arsine to a sufficiently low concentration. Purifiers containing copper, basic copper carbonate, or copper hydroxide, or cleaners to which metal oxides such as manganese oxide are added, and cleaners made of activated carbon, synthetic zeolite, or natural zeolite as active ingredients Can be mentioned.
本発明において、ホスフィン及び／またはアルシンと炭化水素を含むガスを浄化するときは、これらを含むガスが前記の浄化剤が充填された浄化筒に導入されるが、その際に流量コントロールされた酸素含有ガス（空気）を浄化剤に供給することができる。酸素含有ガスを供給すると、ホスフィン及び／またはアルシンの酸化反応が起こり発熱するが、ターシャリーブチルホスフィン、ターシャリーブチルアルシンの場合と比べて極めて穏やかであり、危険な状態になるほどの発熱ではない。また、ガスの発生はほとんど起こらない。この操作により、浄化筒の後処理の際に、浄化剤が空気と接触してもより安全となる。尚、酸素含有ガスの供給は、間欠的に行なうこともできる。 In the present invention, when purifying a gas containing phosphine and / or arsine and hydrocarbon, the gas containing these is introduced into a purification cylinder filled with the above-mentioned purifying agent. The contained gas (air) can be supplied to the purifier. When an oxygen-containing gas is supplied, an oxidation reaction of phosphine and / or arsine occurs to generate heat, but it is extremely mild as compared with tertiary butyl phosphine and tertiary butyl arsine, and does not generate enough heat to be in a dangerous state. Moreover, almost no gas is generated. This operation makes it safer even if the purifier comes into contact with air during the post-treatment of the purification cylinder. The oxygen-containing gas can be supplied intermittently.
本発明の排ガスに使用される処理装置は、以上のような処理を行なうための装置であり、図１に示すように、無機多孔質体が充填された加熱分解筒２、及びその後段にホスフィン及び／またはアルシンの乾式浄化剤が充填された浄化筒３を備えてなる装置である。本発明においては、さらに水蒸気含有ガスを加熱分解筒に供給するための配管５が備えられ、酸素含有ガスを浄化筒に供給するための配管６及び気体流量制御器７を備えることもできる。また、加熱分解筒に導入されるガスと加熱分解筒から排出されるガスは、熱交換器を通過させて熱効率の向上を図ることもできる。
また、有機燐化合物及び／または有機砒素化合物を含む排ガスを連続して処理するために、これらを２ライン以上配置する構成とすることもできる。このような処理装置の配置により、ラインを順次切替えながら排ガスを浄化処理することが可能となる。
The processing apparatus used for the exhaust gas of the present invention is an apparatus for performing the above-described processing. As shown in FIG. 1, the
Moreover, in order to process continuously the exhaust gas containing an organic phosphorus compound and / or an organic arsenic compound, it can also be set as the structure which arrange | positions these two or more lines. Such an arrangement of the processing apparatuses makes it possible to purify the exhaust gas while sequentially switching the lines.
次に、本発明を実施例により具体的に説明するが、本発明がこれらにより限定されるものではない。 EXAMPLES Next, although an Example demonstrates this invention concretely, this invention is not limited by these.
（処理装置の製作）
無機多孔質体として市販のシリカゲル（１００〜２００ｍｅｓｈの球状粒子、比表面積４００ｍ２／ｇ）を、側面にヒーターを備えた内径１８ｍｍ、高さ４００ｍｍの加熱分解筒２に、充填長が２００ｍｍとなるように充填した。また、有効成分として酸化銅を９０ｗｔ％以上、他の金属酸化物及びバインダーを１０ｗｔ％以下の割合で含む浄化剤を、内径４０ｍｍ、高さ３００ｍｍの浄化筒３に、充填長が１００ｍｍとなるように充填した。次に、加熱分解筒が上流側、浄化筒が下流側となるように配置するとともに、排ガス導入管１、処理後ガス排出管４、水蒸気含有ガス供給管５、酸素含有ガス供給管６、冷却器８等を結合して、図１に示すような処理装置を製作した。
(Manufacture of processing equipment)
Commercially available silica gel (100-200 mesh spherical particles, specific surface area 400 m 2 / g) as an inorganic porous body, filling length 200 mm in
（浄化試験）
シリカゲルの温度が３５０℃となるように加熱分解筒を昇温した。次に、有害成分としてターシャリーブチルホスフィン１００００ｐｐｍを含む窒素ガスを、１２７ｍｌ／ｍｉｎ（２５℃）の流量で排ガス導入管から導入して、加熱分解筒でターシャリーブチルホスフィンをホスフィンと炭化水素に分解し、浄化筒でガス中のホスフィンを捕捉除去した。
(Purification test)
The pyrolysis cylinder was heated up so that the temperature of the silica gel was 350 ° C. Next, nitrogen gas containing 10,000 ppm of tertiary butylphosphine as a harmful component is introduced from the exhaust gas introduction pipe at a flow rate of 127 ml / min (25 ° C.), and the tertiary butylphosphine is decomposed into phosphine and hydrocarbons by a thermal decomposition cylinder. Then, phosphine in the gas was captured and removed by the purification cylinder.
ターシャリーブチルホスフィンを含む窒素ガスの処理中、１００００ｐｐｍの水蒸気を含む窒素ガスを、１２７ｍｌ／ｍｉｎ（２５℃）の流量で加熱分解筒に供給し、２００００ｐｐｍの酸素を含む窒素ガスを１２７ｍｌ／ｍｉｎ（２５℃）の流量で浄化筒に供給した。
尚、加熱分解筒から排出されたガスは、浄化筒に供給される前に５０℃以下となるように冷却器により冷却した。
During the treatment of nitrogen gas containing tertiary butylphosphine, nitrogen gas containing 10,000 ppm of water vapor is supplied to the pyrolysis cylinder at a flow rate of 127 ml / min (25 ° C.), and nitrogen gas containing 20000 ppm of oxygen is 127 ml / min ( (25 ° C.).
Note that the gas discharged from the pyrolysis cylinder was cooled by a cooler so that the temperature was 50 ° C. or less before being supplied to the purification cylinder.
この間、加熱分解筒と浄化筒の間から、ガスの一部を約５分間隔でサンプリングして、ターシャリーブチルホスフィン、ブテン、ブタンの濃度を測定し、ターシャリーブチルホスフィンの分解率を測定するとともに、ブテン、ブタンの含有比率から燐の生成状況を推測した。また、浄化筒の出口から、ガスの一部を約５分間隔でサンプリングして、ホスフィンが検出されるまでの時間を測定し、浄化剤の浄化能力（浄化剤単位量当たりの有害成分の処理量）を求めた。また、浄化剤の発熱温度（到達最高温度−浄化開始直前の温度）を測定した。これらの結果を表１に示す。 During this time, a part of the gas is sampled at intervals of about 5 minutes from between the thermal decomposition cylinder and the purification cylinder, and the concentrations of tertiary butylphosphine, butene and butane are measured, and the decomposition rate of tertiary butylphosphine is measured. At the same time, the production status of phosphorus was estimated from the content ratio of butene and butane. Also, from the outlet of the purification cylinder, a part of the gas is sampled at intervals of about 5 minutes, and the time until the phosphine is detected is measured, and the purification capacity of the purification agent (treatment of harmful components per unit amount of the purification agent) Amount). Further, the exothermic temperature of the purifier (the highest temperature reached—the temperature immediately before the start of purification) was measured. These results are shown in Table 1.
［実施例２］
実施例１の浄化試験における有害成分をターシャリーブチルアルシンに替えたほかは実施例１と同様にして浄化試験を行なった。その結果を表１に示す。
[Example 2]
A purification test was conducted in the same manner as in Example 1 except that the harmful component in the purification test of Example 1 was replaced with tertiary butylarsine. The results are shown in Table 1.
［実施例３〜５、参考例］
実施例１における無機多孔質体を、各々市販の合成ゼオライト（細孔径１０Å相当）、多孔質ガラス（１００〜２００ｍｅｓｈの粒状、平均細孔径４０Å、比表面積２００ｍ２／ｇ）、粘土系多孔質体（平均５０ｍｅｓｈの粒状珪藻土、比表面積３００ｍ２／ｇ）、活性炭（８〜３０ｍｅｓｈの粒状、比表面積１０００ｍ２／ｇ）に替えたほかは実施例１と同様にして浄化試験を行なった。その結果を表１に示す。
[Examples 3 to 5, Reference Example ]
Each of the inorganic porous bodies in Example 1 is a commercially available synthetic zeolite (corresponding to a pore diameter of 10 mm), porous glass (100-200 mesh granules, average pore diameter of 40 mm, specific surface area 200 m 2 / g), clay-based porous body. A purification test was carried out in the same manner as in Example 1 except that the average diatomaceous earth with 50 mesh, specific surface area of 300 m 2 / g, and activated carbon (8-30 mesh with specific surface area of 1000 m 2 / g) were used. The results are shown in Table 1.
［比較例１］
（処理装置の製作）
有効成分として酸化銅を９０ｗｔ％以上、他の金属酸化物及びバインダーを１０ｗｔ％以下の割合で含む実施例１で使用した浄化剤と同様の浄化剤を、内径４０ｍｍ、高さ３００ｍｍの浄化筒に、充填長が１００ｍｍとなるように充填した。次に、排ガス導入管、排出管、酸素含有ガス供給管等を結合して処理装置を製作した。
[Comparative Example 1]
(Manufacture of processing equipment)
A purifying agent similar to the purifying agent used in Example 1 containing 90 wt% or more of copper oxide as an active ingredient and 10 wt% or less of another metal oxide and a binder in a purifying cylinder having an inner diameter of 40 mm and a height of 300 mm. The filling length was 100 mm. Next, a treatment apparatus was manufactured by combining an exhaust gas introduction pipe, a discharge pipe, an oxygen-containing gas supply pipe, and the like.
（浄化試験）
続いて、有害成分としてターシャリーブチルホスフィン１００００ｐｐｍを含む窒素ガス、及び１００００ｐｐｍの酸素を含む窒素ガスを、各々１２７ｍｌ／ｍｉｎ（２５℃）の流量で浄化筒に導入して浄化を行なった。この間、浄化筒から排出されたガスの一部を約５分間隔でサンプリングし、ターシャリーブチルホスフィンが検出されるまでの時間を測定し、浄化剤の浄化能力（浄化剤単位量当たりの有害成分の処理量）を求めた。また、浄化剤の発熱温度（到達最高温度−浄化開始直前の温度）を測定した。これらの結果を表１に示す。
(Purification test)
Subsequently, nitrogen gas containing 10,000 ppm of tertiary butylphosphine as a harmful component and nitrogen gas containing 10,000 ppm of oxygen were introduced into the purification cylinder at a flow rate of 127 ml / min (25 ° C.) for purification. During this time, a part of the gas discharged from the purification cylinder is sampled at intervals of about 5 minutes, the time until tertiary butylphosphine is detected is measured, and the purification capacity of the purification agent (hazardous components per unit amount of the purification agent) The amount of processing was determined. Further, the exothermic temperature of the purifier (the highest temperature reached—the temperature immediately before the start of purification) was measured. These results are shown in Table 1.
［比較例２］
比較例１の浄化試験における有害成分をターシャリーブチルアルシンに替えたほかは比較例１と同様にして浄化試験を行なった。その結果を表１に示す。
[Comparative Example 2]
A purification test was conducted in the same manner as in Comparative Example 1 except that the harmful component in the purification test of Comparative Example 1 was replaced with tertiary butylarsine. The results are shown in Table 1.
以上のように、本発明の実施例は、急激な発熱を起こすことがなく比較的に安全である。また、浄化剤は優れた浄化能力で、有機燐化合物及び／または有機砒素化合物が分解して生成したホスフィン及び／またはアルシンを除去できることがわかる。 As described above, the embodiment of the present invention is relatively safe without causing sudden heat generation. Further, it can be seen that the purifying agent can remove phosphine and / or arsine generated by decomposition of the organic phosphorus compound and / or the organic arsenic compound with an excellent purifying ability.
１ 排ガス導入管
２ 加熱分解筒
３ 浄化筒
４ 処理後ガス排出管
５ 水蒸気含有ガス供給管
６ 酸素含有ガス供給管
７ 気体流量制御器
８ 冷却器
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