JP2002361041A - Method for pretreating for recovering pfc mixed waste gas - Google Patents
Method for pretreating for recovering pfc mixed waste gasInfo
- Publication number
- JP2002361041A JP2002361041A JP2001167216A JP2001167216A JP2002361041A JP 2002361041 A JP2002361041 A JP 2002361041A JP 2001167216 A JP2001167216 A JP 2001167216A JP 2001167216 A JP2001167216 A JP 2001167216A JP 2002361041 A JP2002361041 A JP 2002361041A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- pfc
- gas
- mixed exhaust
- perfluorocarbon
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007789 gas Substances 0.000 title claims abstract description 101
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000010812 mixed waste Substances 0.000 title abstract 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000001341 alkaline earth metal compounds Chemical class 0.000 claims abstract description 22
- VMTCKFAPVIWNOF-UHFFFAOYSA-N methane tetrahydrofluoride Chemical compound C.F.F.F.F VMTCKFAPVIWNOF-UHFFFAOYSA-N 0.000 claims abstract description 16
- GKZRDGURFXRWBA-UHFFFAOYSA-N CCC.F.F.F.F.F.F.F.F Chemical compound CCC.F.F.F.F.F.F.F.F GKZRDGURFXRWBA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000004065 semiconductor Substances 0.000 claims abstract description 12
- XTFWOFCBLZFHKM-UHFFFAOYSA-N CCCC.F.F.F.F.F.F.F.F Chemical compound CCCC.F.F.F.F.F.F.F.F XTFWOFCBLZFHKM-UHFFFAOYSA-N 0.000 claims abstract description 11
- HUAUNKAZQWMVFY-UHFFFAOYSA-M sodium;oxocalcium;hydroxide Chemical compound [OH-].[Na+].[Ca]=O HUAUNKAZQWMVFY-UHFFFAOYSA-M 0.000 claims description 18
- 238000002203 pretreatment Methods 0.000 claims description 17
- 239000011261 inert gas Substances 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 15
- CRWSWMKELFKJMC-UHFFFAOYSA-N CC.F.F.F.F.F.F Chemical compound CC.F.F.F.F.F.F CRWSWMKELFKJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000011084 recovery Methods 0.000 claims description 13
- 239000012159 carrier gas Substances 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 239000012528 membrane Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910018503 SF6 Inorganic materials 0.000 claims description 8
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 8
- 239000000292 calcium oxide Substances 0.000 claims description 7
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- QKCGXXHCELUCKW-UHFFFAOYSA-N n-[4-[4-(dinaphthalen-2-ylamino)phenyl]phenyl]-n-naphthalen-2-ylnaphthalen-2-amine Chemical compound C1=CC=CC2=CC(N(C=3C=CC(=CC=3)C=3C=CC(=CC=3)N(C=3C=C4C=CC=CC4=CC=3)C=3C=C4C=CC=CC4=CC=3)C3=CC4=CC=CC=C4C=C3)=CC=C21 QKCGXXHCELUCKW-UHFFFAOYSA-N 0.000 claims description 7
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 6
- UNRFQJSWBQGLDR-UHFFFAOYSA-N methane trihydrofluoride Chemical compound C.F.F.F UNRFQJSWBQGLDR-UHFFFAOYSA-N 0.000 claims description 6
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 6
- PYVHTIWHNXTVPF-UHFFFAOYSA-N F.F.F.F.C=C Chemical compound F.F.F.F.C=C PYVHTIWHNXTVPF-UHFFFAOYSA-N 0.000 claims description 5
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 5
- 239000000920 calcium hydroxide Substances 0.000 claims description 5
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 5
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 4
- -1 perfluoro compound Chemical class 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000002912 waste gas Substances 0.000 abstract 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 41
- 239000000376 reactant Substances 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 13
- 238000000354 decomposition reaction Methods 0.000 description 11
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- CIIGFMMENQROHZ-UHFFFAOYSA-N butane;hydrofluoride Chemical compound F.CCCC CIIGFMMENQROHZ-UHFFFAOYSA-N 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 102100024522 Bladder cancer-associated protein Human genes 0.000 description 1
- 101150110835 Blcap gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 102100033041 Carbonic anhydrase 13 Human genes 0.000 description 1
- 102100033029 Carbonic anhydrase-related protein 11 Human genes 0.000 description 1
- 101000867860 Homo sapiens Carbonic anhydrase 13 Proteins 0.000 description 1
- 101000867841 Homo sapiens Carbonic anhydrase-related protein 11 Proteins 0.000 description 1
- 101001075218 Homo sapiens Gastrokine-1 Proteins 0.000 description 1
- 101100493740 Oryza sativa subsp. japonica BC10 gene Proteins 0.000 description 1
- 239000004697 Polyetherimide Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- RPUCEXCNSJXOMV-UHFFFAOYSA-N ethane hydrofluoride Chemical compound F.CC RPUCEXCNSJXOMV-UHFFFAOYSA-N 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- INCUOXCPYWNZNZ-UHFFFAOYSA-N propane hydrofluoride Chemical compound F.CCC INCUOXCPYWNZNZ-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/30—Capture or disposal of greenhouse gases of perfluorocarbons [PFC], hydrofluorocarbons [HFC] or sulfur hexafluoride [SF6]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/151—Reduction of greenhouse gas [GHG] emissions, e.g. CO2
- Y02P20/155—Perfluorocarbons [PFC]; Hydrofluorocarbons [HFC]; Hydrochlorofluorocarbons [HCFC]; Chlorofluorocarbons [CFC]
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Treating Waste Gases (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、半導体製造プロセ
スなどから排出される種々のＰＦＣ（パ−フルオロコン
パウンド）を含有する排ガスより、四フッ化メタン（Ｃ
Ｆ4 ）、六フッ化エタン（Ｃ2 Ｆ6 ）、八フッ化プロパ
ン（Ｃ3 Ｆ8 ）及び八フッ化ブタン（Ｃ4Ｆ8 ）などの
有用成分を効率的に回収するための当該排ガスの前処理
方法（分離・濃縮方法）に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing methane tetrafluoride (C) from exhaust gases containing various PFCs (perfluoro compounds) discharged from a semiconductor manufacturing process or the like.
F 4 ), exhaust gas for efficiently recovering useful components such as ethane hexafluoride (C 2 F 6 ), propane octafluoride (C 3 F 8 ) and butane octafluoride (C 4 F 8 ) Pretreatment method (separation / concentration method).
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】半導体
製造プロセスなどで使用されている各種のＰＦＣ（パー
フルオロコンパウンド）は、温室効果ガスであり、その
排出抑制が重要となっている。このような半導体製造プ
ロセスなどから排出されるガスは、一般に窒素などの不
活性ガスをキャリヤーガスとして多量に含み、その他、
原料ガスからの未反応ガス、反応により生じる酸性ガス
（例えば、ＨＦ、ＳｉＦ4 、ＣＯＦ2 ）、酸化性ガス
（例えば、Ｏ3 、Ｆ2 ）及び副生物（例えば、窒素酸化
物、副生ＰＦＣ）を含む複雑な組成のガス混合物であ
る。2. Description of the Related Art Various PFCs (perfluorocompounds) used in semiconductor manufacturing processes and the like are greenhouse gases, and their emission control is important. Gases discharged from such semiconductor manufacturing processes and the like generally contain a large amount of an inert gas such as nitrogen as a carrier gas.
Unreacted gas from the raw material gas, acid gas generated by the reaction (eg, HF, SiF 4 , COF 2 ), oxidizing gas (eg, O 3 , F 2 ) and by-products (eg, nitrogen oxide, by-product PFC) ) Is a gas mixture of complex composition.
【０００３】従来、このような排ガスについては、酸性
ガスや酸化性ガスを所定の薬剤や装置により処理し、排
ガス中の有用な成分を回収することが行われてきた。例
えば、公表特許公報２０００−５０９６５３号には、ア
ルミニウム電解槽から出される排ガスからＣＦ4 及びＣ
2 Ｆ6 の少なくとも１つを回収する方法が、記載されて
いる。この方法では、無機フッ化物類並びにＣＦ4 及び
Ｃ2 Ｆ6 の少なくとも１つを含んでいる排ガスから無機
フッ化物類を除去する工程が含まれており、該無機フッ
化物類は具体的にはＦ2 、ＨＦ及びＮａＡｌＦ4 であ
り、これらを除去するためにソーダ石灰などのカセイス
クラバーを利用している。しかしながら、この方法で
は、無機フッ化物類をカセイスクラバーに吸収させるた
め、大量の廃液を抱えることになり、また装置構成が大
掛かりになるなどの問題がある。[0003] Conventionally, with respect to such exhaust gas, an acidic gas or an oxidizing gas has been treated with a predetermined chemical or device to recover useful components in the exhaust gas. For example, Japanese Patent Publication No. 2000-509653 discloses that CF 4 and C are contained in exhaust gas discharged from an aluminum electrolytic cell.
Process for recovering at least one of 2 F 6 is described. The method includes a step of removing inorganic fluorides from an exhaust gas containing at least one of inorganic fluorides and CF 4 and C 2 F 6 , wherein the inorganic fluorides are specifically F 2 , HF and NaAlF 4 , and a caustic scrubber such as soda lime is used to remove them. However, in this method, since the inorganic fluorides are absorbed by the case scrubber, there are problems that a large amount of waste liquid is held and that the apparatus configuration becomes large.
【０００４】また、公開特許公報２０００−５５６１号
には、半導体製造プロセスからの排ガス中に含まれてい
るパーフルオロカーボン、ハイドロフルオロカーボン、
三フッ化窒素、六フッ化硫黄などの化学的に安定なフッ
化物以外の不純物成分、即ち、四フッ化ケイ素、二フッ
化カルボニル、フッ化水素などの不安定で反応性の高い
フッ化物を、あらかじめ除去した後に、上記化学的に安
定なフッ化物の濃縮を行い、濃縮された該フッ化物を回
収するとともに、濃縮処理後のガス成分中に残留する微
量のフッ化物を分解処理するというフッ化物の処理方法
が記載されている。しかしながら、この方法では、目的
とする成分が広範であり、化学的に安定な成分であれば
多種多様に回収されてしまう。リサイクルの目的で、特
定の成分のみを回収するためには、さらに分離精製工程
が必要となる方法である。Further, Japanese Patent Laid-Open Publication No. 2000-5561 discloses perfluorocarbons, hydrofluorocarbons, and the like contained in exhaust gas from a semiconductor manufacturing process.
Impurity components other than chemically stable fluorides such as nitrogen trifluoride and sulfur hexafluoride, ie, unstable and highly reactive fluorides such as silicon tetrafluoride, carbonyl difluoride and hydrogen fluoride After removal in advance, the chemically stable fluoride is concentrated, the concentrated fluoride is recovered, and a small amount of fluoride remaining in the gas component after the concentration treatment is decomposed. A method of treating the compound is described. However, in this method, the target components are wide-ranging, and a wide variety of chemically stable components are collected. In order to recover only specific components for the purpose of recycling, this method requires an additional separation / purification step.
【０００５】従って、本発明の目的は、半導体製造プロ
セスなどから排出される種々のＰＦＣを含有する排ガス
より、有用なパ−フルオロカーボンを、簡単で効率良く
回収するための当該排ガスの前処理方法を提供すること
にある。Accordingly, an object of the present invention is to provide a method for pretreatment of exhaust gas containing various PFCs discharged from a semiconductor manufacturing process or the like for simply and efficiently recovering useful perfluorocarbon from the exhaust gas. To provide.
【０００６】[0006]
【課題を解決するための手段】本発明は、ＰＦＣ（パー
フルオロコンパウンド）混合排ガス中に含まれる四フッ
化メタン、六フッ化エタン、八フッ化プロパン及び八フ
ッ化ブタンより選ばれる少なくとも１種のパ−フルオロ
カーボンを回収するための当該排ガスの前処理方法であ
って、上記ＰＦＣ混合排ガスを、アルカリ土類金属化合
物と２００〜８００℃の条件下で接触させ、上記パ−フ
ルオロカーボンを上記ＰＦＣ混合排ガスから分離するこ
とを特徴とするＰＦＣ混合排ガスの回収前処理方法を提
供することにより、上記目的を達成したものである。SUMMARY OF THE INVENTION The present invention provides at least one of methane tetrafluoride, ethane hexafluoride, propane octafluoride and butane octafluoride contained in a PFC (perfluoro compound) mixed exhaust gas. A pretreatment method of said exhaust gas for recovering said perfluorocarbon, wherein said PFC mixed exhaust gas is brought into contact with an alkaline earth metal compound at a temperature of 200 to 800 ° C., and said perfluorocarbon is mixed with said PFC mixed gas. The above object has been achieved by providing a method for pre-recovery recovery of a PFC mixed exhaust gas, which is characterized in that the exhaust gas is separated from the exhaust gas.
【０００７】[0007]
【発明の実施の形態】以下、本発明のＰＦＣ混合排ガス
の回収前処理方法について詳述する。BEST MODE FOR CARRYING OUT THE INVENTION The pretreatment method for recovery of PFC mixed exhaust gas according to the present invention will be described below in detail.
【０００８】本発明の方法が適用されるＰＦＣ混合排ガ
スは、四フッ化メタン（ＣＦ4 ）、六フッ化エタン（Ｃ
2 Ｆ6 ）、八フッ化プロパン（Ｃ3 Ｆ8 ）及び八フッ化
ブタン（Ｃ4 Ｆ8 ）より選ばれる少なくとも１種のパ−
フルオロカーボンを含む排ガスであり、本発明の方法
は、特に半導体製造プロセスからの排ガスに好適に適用
される。この半導体製造プロセスからの排ガスには、上
記パ−フルオロカーボンの他に、一般に、窒素などの不
活性ガスがキャリヤーガスとして多量に含まれており、
その他、原料ガスからの未反応ガス、反応により生じる
酸性ガス、酸化性ガス及び副生物（具体的には、三フッ
化メタン、四フッ化エチレン、三フッ化窒素、六フッ化
硫黄、フッ化水素、四フッ化ケイ素、二フッ化カルボニ
ル、二酸化炭素など）が含まれている。The PFC mixed exhaust gas to which the method of the present invention is applied is methane tetrafluoride (CF 4 ), ethane hexafluoride (C
2 F 6), eight fluoride propane (C 3 F 8) and at least one path selected from eight fluoride butane (C 4 F 8) -
It is an exhaust gas containing a fluorocarbon, and the method of the present invention is suitably applied particularly to an exhaust gas from a semiconductor manufacturing process. Exhaust gas from this semiconductor manufacturing process generally contains a large amount of an inert gas such as nitrogen as a carrier gas, in addition to the above-mentioned perfluorocarbon,
In addition, unreacted gas from raw material gas, acid gas generated by the reaction, oxidizing gas, and by-products (specifically, methane trifluoride, ethylene tetrafluoride, nitrogen trifluoride, sulfur hexafluoride, fluoride Hydrogen, silicon tetrafluoride, carbonyl difluoride, carbon dioxide, etc.).
【０００９】また、本発明の方法で用いられるアルカリ
土類金属化合物としては、水酸化カルシウム、ソーダラ
イム及び酸化カルシウムなどがあげられ、これらを単独
又はは組み合わせて使用することができる。これらのア
ルカリ土類金属化合物としては、適度の大きさに破砕又
は成形されることが圧力損失が小さくなるので好まし
く、加熱条件下で接触反応させることでは、比表面積が
大きいことが望ましい。具体的には２．０〜１０．０mm
程度の粒度（比表面積約２．０〜２０ｍ2 ／ｇ）のもの
を使用するが、その形状、見掛け密度などは適宜選択す
れば良い。The alkaline earth metal compound used in the method of the present invention includes calcium hydroxide, soda lime and calcium oxide, and these can be used alone or in combination. These alkaline earth metal compounds are preferably crushed or formed into an appropriate size because pressure loss is reduced, and when subjected to contact reaction under heating conditions, it is desirable that the specific surface area be large. Specifically, 2.0-10.0mm
Particles having a specific particle size (specific surface area of about 2.0 to 20 m 2 / g) are used, and the shape, apparent density, and the like may be appropriately selected.
【００１０】而して、本発明は、上記ＰＦＣ混合排ガス
を、上記アルカリ土類金属化合物と２００〜８００℃の
条件下で接触させるものである。上記接触により、ＰＦ
Ｃ混合排ガス中に含まれる三フッ化メタン、四フッ化エ
チレン、三フッ化窒素、六フッ化硫黄、フッ化水素、四
フッ化ケイ素、二フッ化カルボニル、二酸化炭素などの
成分が分解されてアルカリ土類金属化合物に固定化さ
れ、ＰＦＣ混合排ガス中に含まれる有用成分（四フッ化
メタン、六フッ化エタン、八フッ化プロパン、八フッ化
ブタン）をキャリヤーガス若しくは不活性ガスとともに
ＰＦＣ混合排ガスから分離する（取り出す）ことができ
る。In the present invention, the PFC mixed exhaust gas is brought into contact with the alkaline earth metal compound at a temperature of 200 to 800 ° C. By the above contact, PF
Components such as methane trifluoride, ethylene tetrafluoride, nitrogen trifluoride, sulfur hexafluoride, hydrogen fluoride, silicon tetrafluoride, carbonyl difluoride, and carbon dioxide contained in the mixed exhaust gas are decomposed. PFC mixing useful components (methane tetrafluoride, ethane hexafluoride, propane octafluoride, butane octafluoride) immobilized on alkaline earth metal compounds and contained in PFC mixed exhaust gas together with carrier gas or inert gas It can be separated (extracted) from the exhaust gas.
【００１１】上記接触温度は、使用するアルカリ土類金
属化合物のＰＦＣ分解性能と、回収目的の有用成分の種
類、ＰＦＣ混合排ガス中に含まれるガス種などに応じ
て、上記温度範囲内で適宜決定される。また、使用する
アルカリ土類金属化合物も、そのＰＦＣ分解性能と、回
収目的の有用成分の種類、ＰＦＣ混合排ガス中に含まれ
るガス種などに応じて、１種以上が適宜選択される。The above-mentioned contact temperature is appropriately determined within the above-mentioned temperature range according to the PFC decomposition performance of the alkaline earth metal compound to be used, the kind of useful component for the purpose of recovery, the kind of gas contained in the PFC mixed exhaust gas, and the like. Is done. In addition, one or more alkaline earth metal compounds to be used are appropriately selected according to the PFC decomposition performance, the type of useful component for the purpose of recovery, the type of gas contained in the PFC mixed exhaust gas, and the like.
【００１２】例えば、ソーダライムのＰＦＣ分解性能
は、キャリヤーガスに窒素ガスを使用して、各ＰＦＣ濃
度１．０ｖｏｌ．％、混合ガス流速（空筒速度）１ｃｍ
／ｓｅｃの状態で、１０００ｍｍ高のソーダライムの層
に混合ガスを通過（内径約２００ｍｍ）させた場合、次
の通りである。まず、四フッ化エチレン（Ｃ2 Ｆ4 ）が
２００℃で１００％分解し、２５０℃で三フッ化メタン
（ＣＨＦ3 ）が実質上完全に分解する。さらに、４００
℃で三フッ化窒素（ＮＦ3 ）が、５００℃で六フッ化硫
黄（ＳＦ6 ）が、それぞれ実質上完全に分解する。しか
しながら、５００℃において八フッ化ブタン（Ｃ
4 Ｆ8 ）の分解率は５０％程度であり、四フッ化メタン
（ＣＦ4 ）、六フッ化エタン（Ｃ2 Ｆ6 ）及び八フッ化
プロパン（Ｃ3 Ｆ 8 ）に関しては６００℃でも分解され
ない。尚、公知のように、ソーダライムは５８０℃以上
で脱水され、酸化カルシウムとなる。For example, PFC decomposition performance of soda lime
Uses nitrogen gas as the carrier gas and concentrates each PFC.
1.0 vol. %, Mixed gas flow rate (cylinder speed) 1cm
/ Sec state, 1000mm high soda lime layer
When the mixed gas is passed through (the inner diameter is about 200 mm),
It is as follows. First, ethylene tetrafluoride (CTwoFFour)But
Decomposes 100% at 200 ° C and methane trifluoride at 250 ° C
(CHFThree) Decomposes substantially completely. In addition, 400
Nitrogen trifluoride (NFThree), At 500 ° C
Yellow (SF6) Each decompose substantially completely. Only
While heating at 500 ° C, butane octafluoride (C
FourF8) Is about 50% and methane tetrafluoride
(CFFour), Ethane hexafluoride (CTwoF6) And octafluoride
Propane (CThreeF 8Is decomposed even at 600 ° C
Absent. As is well known, soda lime is 580 ° C or higher.
Dehydrated into calcium oxide.
【００１３】また、酸化カルシウムのＰＦＣ分解性能
は、上記のソーダライムの場合と同一の条件下で次の通
りである。３００℃で三フッ化メタン（ＣＨＦ3 ）が１
００％分解し、５００℃で三フッ化窒素（ＮＦ3 ）及び
八フッ化ブタン（Ｃ4 Ｆ8 ）が実質上完全に分解する。
次いで、６００℃で六フッ化硫黄（ＳＦ6 ）が、さらに
７００℃で八フッ化プロパン（Ｃ3 Ｆ8 ）が、それぞれ
実質上完全に分解する。しかしながら、７００℃におい
て、六フッ化エタン（Ｃ2 Ｆ6 ）の分解率は７％にとど
まり、四フッ化メタン（ＣＦ4 ）の分解率はほぼ０％で
ある。The PFC decomposition performance of calcium oxide is as follows under the same conditions as in the case of the above-mentioned soda lime. Methane trifluoride (CHF 3 ) at 300 ° C
Decomposes by 00%, and at 500 ° C., nitrogen trifluoride (NF 3 ) and butane octafluoride (C 4 F 8 ) are substantially completely decomposed.
Then, sulfur hexafluoride (SF 6 ) at 600 ° C. and propane octafluoride (C 3 F 8 ) at 700 ° C. are substantially completely decomposed. However, at 700 ° C., the decomposition rate of ethane hexafluoride (C 2 F 6 ) is only 7%, and the decomposition rate of methane tetrafluoride (CF 4 ) is almost 0%.
【００１４】また、水酸化カルシウムのＰＦＣ分解性能
は、上記ソーダライムのＰＦＣ分解性能と略同等であ
る。これはソーダライムの主成分が水酸化カルシウムで
あることによると考えられる。The PFC decomposition performance of calcium hydroxide is substantially equal to the PFC decomposition performance of soda lime. This is considered to be because the main component of soda lime is calcium hydroxide.
【００１５】このようなアルカリ土類金属化合物のＰＦ
Ｃ分解性能に基づけば、アルカリ土類金属化合物として
ソーダライムを使用する場合は、上記接触温度を２００
〜６００℃、特に５００℃以上５８０℃未満に設定する
ことが好ましく、それにより四フッ化メタン（Ｃ
Ｆ4 ）、六フッ化エタン（Ｃ2 Ｆ6 ）、八フッ化プロパ
ン（Ｃ3 Ｆ8 ）及び八フッ化ブタン（Ｃ4 Ｆ8 ）を効率
良く分離することができる。また、アルカリ土類金属化
合物として酸化カルシウムを使用する場合は、上記接触
温度を２００〜７００℃、特に６００℃以上７００℃未
満に設定することが好ましく、それにより四フッ化メタ
ン（ＣＦ4 ）、六フッ化エタン（Ｃ2 Ｆ6 ）及び八フッ
化プロパン（Ｃ3 Ｆ8 ）を効率良く分離することができ
る。また、アルカリ土類金属化合物として水酸化カルシ
ウムを使用する場合は、ソーダライムの場合と同様、接
触温度を２００〜６００℃として実施することが好まし
く、それにより四フッ化メタン（ＣＦ4 ）、六フッ化エ
タン（Ｃ2 Ｆ6 ）、八フッ化プロパン（Ｃ3 Ｆ8 ）及び
八フッ化ブタン（Ｃ4 Ｆ8 ）を効率良く分離することが
できる。Such an alkaline earth metal compound PF
Based on the C decomposition performance, when soda lime is used as the alkaline earth metal compound, the contact temperature is set at 200.
To 600 ° C., especially 500 ° C. or higher and lower than 580 ° C., whereby methane tetrafluoride (C
F 4 ), ethane hexafluoride (C 2 F 6 ), propane octafluoride (C 3 F 8 ), and butane octafluoride (C 4 F 8 ) can be efficiently separated. When calcium oxide is used as the alkaline earth metal compound, the contact temperature is preferably set to 200 to 700 ° C., particularly 600 ° C. to less than 700 ° C., whereby methane tetrafluoride (CF 4 ) Ethane hexafluoride (C 2 F 6 ) and propane octafluoride (C 3 F 8 ) can be efficiently separated. When calcium hydroxide is used as the alkaline earth metal compound, the contact temperature is preferably set to 200 to 600 ° C. as in the case of soda lime, whereby methane tetrafluoride (CF 4 ) Ethane fluoride (C 2 F 6 ), propane octafluoride (C 3 F 8 ) and butane octafluoride (C 4 F 8 ) can be efficiently separated.
【００１６】また、上記のアルカリ土類金属化合物のＰ
ＦＣ分解性能に基づけば、温度が低い状態、例えば２０
０〜５００℃でも、ＰＦＣ混合排ガスをアルカリ土類金
属化合物と繰り返し接触させることにより、不用成分を
完全に分解することができる。In addition, P of the above alkaline earth metal compound
Based on FC decomposition performance, low temperature conditions, for example, 20
Even at 0 to 500 ° C., unnecessary components can be completely decomposed by repeatedly contacting the PFC mixed exhaust gas with the alkaline earth metal compound.
【００１７】上記のＰＦＣ混合排ガスとアルカリ土類金
属化合物との接触は、例えば、図１に示すような、反応
剤（３）としてアルカリ土類金属化合物がトレー（６）
上に充填されたカラムからなる反応筒（２）と、該反応
筒（２）を加熱する加熱装置（４）とからなるガス分解
装置により行うことが好ましい。該ガス分解装置におい
て、ＰＦＣ混合排ガスは、反応筒（２）の下部より導入
され、加熱装置（４）により所定温度に保持された反応
剤（３）（アルカリ土類金属化合物）と接触する。接触
後のガスは、反応筒（２）の上部より導出される。The contact between the PFC mixed exhaust gas and the alkaline earth metal compound is carried out, for example, by contacting the alkaline earth metal compound as a reactant (3) with a tray (6) as shown in FIG.
The reaction is preferably performed by a gas decomposer comprising a reaction tube (2) comprising a column filled above and a heating device (4) for heating the reaction tube (2). In the gas decomposition apparatus, the PFC mixed exhaust gas is introduced from the lower part of the reaction tube (2) and comes into contact with the reactant (3) (alkaline earth metal compound) maintained at a predetermined temperature by the heating device (4). The gas after the contact is led out from the upper part of the reaction tube (2).
【００１８】また、上記のＰＦＣ混合排ガスとアルカリ
土類金属化合物との接触によりＰＦＣ混合排ガスから分
離された、有用成分のパーフルオロカーボン（四フッ化
メタン、六フッ化エタン、八フッ化プロパン、八フッ化
ブタン）並びにキャリヤーガス若しくは不活性ガス（主
に窒素ガスなど）を含む混合ガスは、例えばガス分離膜
に通すことにより、当該パーフルオロカーボンとキャリ
ヤーガス若しくは不活性ガスとを分離することができ
る。分離されたパ−フルオロカーボンは回収容器に充填
される。上記ガス分離膜としては、一般的に使用されて
いるポリイミド、ポリスルホン又はポリエーテルイミド
などの高分子膜の他に、炭素膜やγ−アルミナ又はゼオ
ライトなどの無機膜を使用することにより、容易に分離
することができる。Also, useful components of perfluorocarbon (methane tetrafluoride, ethane hexafluoride, propane octafluoride, A mixed gas containing butane fluoride) and a carrier gas or an inert gas (mainly nitrogen gas or the like) can be separated from the perfluorocarbon and the carrier gas or the inert gas by passing through a gas separation membrane, for example. . The separated perfluorocarbon is filled in a collection container. As the gas separation membrane, commonly used polymer membranes such as polyimide, polysulfone or polyetherimide, as well as a carbon membrane or an inorganic membrane such as γ-alumina or zeolite, can be easily used. Can be separated.
【００１９】また、キャリヤーガス若しくは不活性ガス
と分離されたパ−フルオロカーボンが２成分以上のパ−
フルオロカーボンを含む場合には、各成分をそれぞれの
沸点差を利用することにより容易に単離することもでき
る。Further, the perfluorocarbon separated from the carrier gas or the inert gas contains two or more components.
When a fluorocarbon is contained, each component can be easily isolated by utilizing the respective boiling point differences.
【００２０】[0020]
【実施例】以下に実施例をあげて本発明をさらに説明す
るが、本発明は以下の実施例に制限されるものではな
い。EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to the following examples.
【００２１】実施例１ 〈装置及び工程〉図１に示す装置を用いて、次のように
して、半導体製造プロセスから排出されたＰＦＣ混合排
ガスから有用なパ−フルオロカーボンを分離、回収し
た。図１において、半導体製造装置における平行平板型
シリコン酸化膜エッチング装置（１）から排出されたＰ
ＦＣ混合排ガスを反応筒（２）の下部より反応筒（２）
内に導入する。反応筒（２）は、アルカリ土類金属化合
物（ソーダライム）からなる反応剤（３）が充填された
カラムであり、加熱装置（４）により、その反応筒
（２）内の反応剤（３）が５８０℃未満の所定温度に保
たれるようにしてある。加熱装置（４）は、反応筒
（２）内に設置された温度計（５）の温度をもとに温度
制御され、反応剤（３）が反応熱により高温になりすぎ
たときには、加熱装置（４）を適切に制御することによ
り反応剤（３）の温度を安定に保持できる構成となって
いる。加熱された反応筒（３）にあっては、加熱装置
（４）中央部に最高温度となる均熱ゾーンを有した温度
勾配が管軸方向に生じるため、導入ガスが５８０℃未満
の所定温度で反応剤（３）と接触できるように、反応筒
（３）内にトレー（６）を設けて均熱ゾーンに反応剤
（３）を充填できるようにしてある。この反応筒におい
てＰＦＣ混合排ガス中のＣＦ4 、Ｃ2 Ｆ6 は素通りする
が、特定成分（ＣＨＦ3 、Ｃ2 Ｆ4 、ＳｉＦ4 、ＨＦ）
はソーダライムに固定化され無害化される。Example 1 <Apparatus and Process> Using the apparatus shown in FIG. 1, useful perfluorocarbon was separated and recovered from the PFC mixed exhaust gas discharged from the semiconductor manufacturing process as follows. In FIG. 1, P discharged from a parallel plate type silicon oxide film etching apparatus (1) in a semiconductor manufacturing apparatus.
FC mixed exhaust gas from the lower part of the reaction tube (2) to the reaction tube (2)
Introduce within. The reaction tube (2) is a column packed with a reaction agent (3) composed of an alkaline earth metal compound (soda lime), and the reaction device (3) in the reaction tube (2) is heated by the heating device (4). ) Is maintained at a predetermined temperature of less than 580 ° C. The heating device (4) is temperature-controlled based on the temperature of a thermometer (5) installed in the reaction tube (2). When the temperature of the reactant (3) becomes too high due to the heat of the reaction, the heating device is heated. By appropriately controlling (4), the temperature of the reactant (3) can be stably maintained. In the heated reaction tube (3), a temperature gradient having a soaking zone having the highest temperature in the center of the heating device (4) is generated in the tube axis direction. A tray (6) is provided in the reaction tube (3) so that the reactant (3) can be filled in the soaking zone so that the reactant (3) can be brought into contact with the reactant (3). In this reaction column, CF 4 and C 2 F 6 in the PFC mixed exhaust gas pass through, but specific components (CHF 3 , C 2 F 4 , SiF 4 , HF)
Is fixed to soda lime and rendered harmless.
【００２２】反応筒（２）の下流にはＰＦＣ回収装置
（７）を設けてあり、該回収装置（７）内にはガス分離
膜用モジュール（図示せず）が装備されている。このガ
ス分離膜用モジュールにより、反応筒（２）からの導出
ガス中に含まれるＰＦＣ以外のガス（主にＮ2 ）を膜透
過させ、ＰＦＣを濃縮分離するものである。濃縮分離後
のＰＦＣは回収容器（図示せず）に充填される。A PFC recovery unit (7) is provided downstream of the reaction tube (2), and a module (not shown) for a gas separation membrane is provided in the recovery unit (7). With this gas separation membrane module, gases (mainly N 2 ) other than PFC contained in the gas derived from the reaction tube ( 2 ) are permeated through the membrane, and PFC is concentrated and separated. The PFC after the concentration separation is filled in a collection container (not shown).
【００２３】〈操作〉図１の装置において、反応筒
（２）である４０ＡのＳＵＳ製カラムのトレー（６）よ
り上の部分に、層高３００ｍｍになるようにソーダライ
ムからなる反応剤（３）を３００ｇ充填した（筒の内径
約４０ｍｍ）。加熱装置（４）により、反応筒（２）内
の反応剤（３）の温度を３００℃に加熱保持し、エッチ
ング装置（１）から排出されたＰＦＣ混合排ガス〔ＰＦ
Ｃ（Ｃ2 Ｆ4 、ＣＨＦ3 、Ｃ2 Ｆ6及びＣＦ4 ）、Ｎ2
ガス及びＨＦ、ＳｉＦ4 などの腐食性ガスを含む混合
物）を１リットル／ｍｉｎの流量で、反応筒（２）に導
入した。反応筒（２）の入口側及び出口側の配管には、
主排気ラインからサンプリングポートを設置し、サンプ
ルガスを採取した。サンプルの分析はフーリエ変換赤外
分光光度計（ＦＴＩＲ）によって行った。窒素（Ｎ2 ）
ガス以外の成分の割合を下記表１に示す。下記表１中、
「Ｎ．Ｄ．」とあるのは分析装置の検出下限（１０ｖｏ
ｌ．ｐｐｍ）以下であることを意味する。<Operation> In the apparatus shown in FIG. 1, a reactant (3) made of soda lime having a layer height of 300 mm was placed above the tray (6) of a 40A SUS column, which is a reaction tube (2). ) (300 mm inside diameter of the cylinder). The temperature of the reactant (3) in the reaction tube (2) is maintained at 300 ° C. by the heating device (4), and the PFC mixed exhaust gas [PF
C (C 2 F 4 , CHF 3 , C 2 F 6 and CF 4 ), N 2
A mixture containing a gas and a corrosive gas such as HF and SiF 4 ) was introduced into the reaction tube (2) at a flow rate of 1 liter / min. The piping on the inlet side and the outlet side of the reaction tube (2) includes:
A sampling port was installed from the main exhaust line to sample gas. Analysis of the samples was performed with a Fourier transform infrared spectrophotometer (FTIR). Nitrogen (N 2)
Table 1 below shows the proportions of components other than gas. In Table 1 below,
"ND" means the lower limit of detection (10 vol.) Of the analyzer.
l. ppm) or less.
【００２４】[0024]
【表１】 [Table 1]
【００２５】上記表１から、特定成分（ＣＨＦ3 、Ｃ2
Ｆ4 、ＳｉＦ4 、ＨＦ、ＣＯＦ2 及びＣＯ2 ）はもはや
検出されず、反応筒（２）に供給したＰＦＣ混合排ガス
は２種のＰＦＣ（ＣＦ4 及びＣ2 Ｆ6 ）に集約されたこ
とがわかる。From the above Table 1, the specific components (CHF 3 , C 2
F 4 , SiF 4 , HF, COF 2 and CO 2 ) were no longer detected, and the PFC mixed exhaust gas supplied to the reaction tube (2) was collected into two types of PFC (CF 4 and C 2 F 6 ). I understand.
【００２６】次に、反応筒（２）からの導出ガスをＰＦ
Ｃ回収装置（７）に供給してガス分離膜用モジュールに
よりＰＦＣを濃縮分離したところ、ＣＦ4 及びＣ2 Ｆ6
はそれぞれ９２％及び９８％の収率で回収でき、ＣＦ4
及びＣ2 Ｆ6 の回収濃度は、４０％及び５１％であっ
た。Next, the gas discharged from the reaction tube (2) is PF
When the PFC was supplied to the C recovery device (7) and concentrated and separated by the gas separation membrane module, CF 4 and C 2 F 6
Can be recovered in 92% and 98% yields, respectively, and CF 4
And the recovery concentrations of C 2 F 6 were 40% and 51%.
【００２７】参考例１〜８ ＰＦＣとしてのＮＦ3 、ＳＦ6 、ＣＨＦ3 、Ｃ2 Ｆ4 、
ＣＦ4 、Ｃ2 Ｆ6 、Ｃ 3 Ｆ8 及びＣ4 Ｆ8 のそれぞれを
窒素（Ｎ2 ）ガス中に濃度１ｖｏｌ．％となるように含
有させ、実施例１と同様にして、１リットル／ｍｉｎの
流量でソーダライムを充填した反応筒（２）に供給し、
該筒を通過させた。その反応温度と反応筒（２）の入口
側及び出口側の各種ＰＦＣガス濃度を測定した。このと
きの結果を下記表２に示す。Reference Examples 1 to 8 NF as PFCThree, SF6, CHFThree, CTwoFFour,
CFFour, CTwoF6, C ThreeF8And CFourF8Each of
Nitrogen (NTwo) Concentration of 1 vol. %
1 l / min in the same manner as in Example 1.
At a flow rate, it is supplied to a reaction tube (2) filled with soda lime,
The tube was passed. Reaction temperature and inlet of reaction tube (2)
The PFC gas concentrations at the outlet and outlet sides were measured. This and
The results are shown in Table 2 below.
【００２８】[0028]
【表２】 [Table 2]
【００２９】参考例９〜１５ 実施例１において、反応筒（２）に、層高が３００ｍｍ
になるようにＣａＯからなる反応剤（３）を充填した。
加熱装置（４）により、反応筒（２）内の反応剤（３）
の温度条件を変え、ＰＦＣとしてのＮＦ3 、ＳＦ6 、Ｃ
ＨＦ3 、ＣＦ4、Ｃ2 Ｆ6 、Ｃ3 Ｆ8 及びＣ4 Ｆ8 のそ
れぞれを窒素（Ｎ2 ）ガス中に濃度１ｖｏｌ．％となる
ように含有させ、流量が１リットル／ｍｉｎとなるよう
にマスフローコントローラーで制御して、反応筒（２）
に供給し、該筒を通過させた。その反応温度と反応筒
（２）の入口側及び出口側の各種ＰＦＣガス濃度を測定
した。このときの結果を下記表３に示す。Reference Examples 9 to 15 In Example 1, the reaction tube (2) was provided with a layer height of 300 mm.
Was filled with the reactant (3) composed of CaO.
Reactant (3) in reaction tube (2) by heating device (4)
NF 3 , SF 6 , C as PFC
Each of HF 3 , CF 4 , C 2 F 6 , C 3 F 8 and C 4 F 8 was dissolved in nitrogen (N 2 ) gas at a concentration of 1 vol. %, And controlled by a mass flow controller so that the flow rate becomes 1 liter / min.
And passed through the tube. The reaction temperature and the concentration of various PFC gases at the inlet and outlet of the reaction tube (2) were measured. The results at this time are shown in Table 3 below.
【００３０】[0030]
【表３】 [Table 3]
【００３１】参考例１６〜１９ 実施例１において、反応筒（２）に、層高が３００ｍｍ
になるようにソーダライムからなる反応剤（３）を充填
した。加熱装置（４）により、反応筒（２）内の反応剤
（３）の温度条件を変え、ＨＦ及びＳｉＦ4 のそれぞれ
を窒素（Ｎ2 ）ガス中に所定の濃度まで希釈させ、マス
フローコントローラーにて１リットル／ｍｉｎの流量に
制御して、反応筒（２）に供給し、該筒を通過させた。
このときの処理量について調べた結果を下記表４に示
す。尚、処理量は反応筒出口ガス中のＨＦ及びＳｉＦ4
の濃度が入口ガス中の濃度に対し５％濃度（５％以下）
に達するとき（反応の終点）までのＨＦ及びＳｉＦ 4 導
入量を処理量とした。Reference Examples 16 to 19 In Example 1, the reaction tube (2) had a layer height of 300 mm.
Fill the reactant (3) consisting of soda lime so that it becomes
did. The reactant in the reaction tube (2) by the heating device (4)
By changing the temperature condition of (3), HF and SiFFourEach of
To nitrogen (NTwo) Dilute to a predetermined concentration in gas
Flow rate of 1 liter / min with flow controller
Under control, it was supplied to the reaction tube (2) and passed through the tube.
Table 4 below shows the results of the examination of the processing amount at this time.
You. The amount of treatment was HF and SiF in the reaction tube outlet gas.Four
Concentration is 5% of the concentration in the inlet gas (less than 5%)
And SiF up to the point where the reaction reaches (the end of the reaction) FourGuidance
The input amount was defined as the processing amount.
【００３２】[0032]
【表４】 [Table 4]
【００３３】[0033]
【発明の効果】本発明の方法によれば、半導体製造プロ
セスなどから排出される種々のＰＦＣを含有する排ガス
より、有用なパ−フルオロカーボンを、簡単で効率良く
回収することができる。According to the method of the present invention, useful perfluorocarbon can be easily and efficiently recovered from various PFC-containing exhaust gases discharged from a semiconductor manufacturing process or the like.
【図１】本発明の方法を実施するための装置の一例を示
した説明図である。FIG. 1 is an explanatory diagram showing an example of an apparatus for performing a method of the present invention.
【符号の説明】 １ エッチング装置 ２ 反応筒 ３ 反応剤 ４ 加熱装置 ５ 温度計 ６ トレー ７ ＰＦＣ回収装置[Description of Signs] 1 Etching device 2 Reaction tube 3 Reactant 4 Heating device 5 Thermometer 6 Tray 7 PFC recovery device
───────────────────────────────────────────────────── フロントページの続き (72)発明者 安藤 秀樹 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 (72)発明者 八高 賢一 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 (72)発明者 真鍋 岳史 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 (72)発明者 枝澤 克人 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 (72)発明者 新田 昭彦 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 (72)発明者 後藤 正敏 東京都港区西新橋１丁目５番13号 第８東 洋海事ビル８Ｆ ＰＦＣ回収・再利用プロ ジェクト室内 Ｆターム(参考） 4D002 AA22 AC10 BA12 CA11 CA13 DA04 DA05 EA02 FA10 GA01 GB03 HA02 4D006 GA41 KA01 KA02 KB30 KD17 MB04 PA03 PB19 PC01 4H006 AA02 AD19 BB61 BC10 BC13 BE11 EA02 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Hideki Ando 1-5-13 Nishishinbashi, Minato-ku, Tokyo 8th Toyo Maritime Building 8F PFC Collection and Reuse Project Room (72) Inventor Kenichi Yadaka Tokyo 8th Toyo Kaiji Building, 8F Toyo Nautical Building, 1-5-13 Nishishinbashi, Minato-ku Building 8F PFC Collection / Reuse Project Room (72) Inventor Katsato Esawa 1-8-13 Nishishinbashi, Minato-ku, Tokyo 8th Toyo Maritime Building 8F PFC Collection / Reuse Project Room (72) Invention Akihiko Nitta 1-5-13 Nishi-Shimbashi, Minato-ku, Tokyo 8th Oriental Maritime Building 8F PFC collection and reuse project room (72) After the inventor Masatoshi 1-5-13 Nishi-Shimbashi, Minato-ku, Tokyo 8th Oriental Maritime Building 8F PFC collection and reuse project room F term (reference) 4D002 AA22 AC10 BA12 CA11 CA13 DA04 DA05 EA02 FA10 GA01 GB03 HA02 4D006 GA41 KA01 KA02 KB30 KD17 MB04 PA03 PB19 PC01 4H006 AA02 AD19 BB61 BC10 BC13 BE11 EA02
Claims (15)
合排ガス中に含まれる四フッ化メタン、六フッ化エタ
ン、八フッ化プロパン及び八フッ化ブタンより選ばれる
少なくとも１種のパ−フルオロカーボンを回収するため
の当該排ガスの前処理方法であって、上記ＰＦＣ混合排
ガスを、アルカリ土類金属化合物と２００〜８００℃の
条件下で接触させ、上記パ−フルオロカーボンを上記Ｐ
ＦＣ混合排ガスから分離することを特徴とするＰＦＣ混
合排ガスの回収前処理方法。1. A method for recovering at least one kind of perfluorocarbon selected from methane tetrafluoride, ethane hexafluoride, propane octafluoride and butane octafluoride contained in a PFC (perfluoro compound) mixed exhaust gas. Wherein the PFC mixed exhaust gas is brought into contact with an alkaline earth metal compound at a temperature of 200 to 800 ° C. to convert the perfluorocarbon to the P gas.
A pretreatment method for recovering a PFC mixed exhaust gas, which is separated from an FC mixed exhaust gas.
シウム、ソーダライム及び酸化カルシウムより選ばれる
少なくとも１種である請求項１記載の前処理方法。2. The pretreatment method according to claim 1, wherein the alkaline earth metal compound is at least one selected from calcium hydroxide, soda lime and calcium oxide.
であり、ＰＦＣ混合排ガスをソーダライムと２００〜６
００℃の条件下で接触させる請求項１記載の前処理方
法。3. The alkaline earth metal compound is soda lime, and PFC mixed exhaust gas is mixed with soda lime by 200 to 6%.
The pretreatment method according to claim 1, wherein the contact is performed under a condition of 00 ° C.
合物と２００〜５００℃の条件下で繰り返し接触させる
請求項１記載の前処理方法。4. The pretreatment method according to claim 1, wherein the PFC mixed exhaust gas is repeatedly contacted with the alkaline earth metal compound at a temperature of 200 to 500 ° C.
スから排出される、四フッ化メタン、六フッ化エタン、
八フッ化プロパン及び八フッ化ブタンより選ばれる少な
くとも１種のパ−フルオロカーボン並びにキャリヤーガ
スを含むＰＦＣ混合排ガスであり、上記パ−フルオロカ
ーボン並びに上記キャリヤーガスを上記ＰＦＣ混合排ガ
スから分離する請求項１〜４の何れかに記載の前処理方
法。5. A PFC mixed exhaust gas discharged from a semiconductor manufacturing process, comprising: methane tetrafluoride, ethane hexafluoride,
A PFC mixed exhaust gas containing at least one perfluorocarbon selected from propane octafluoride and butane octafluoride and a carrier gas, wherein the perfluorocarbon and the carrier gas are separated from the PFC mixed exhaust gas. 4. The pretreatment method according to any one of 4.
六フッ化エタン、八フッ化プロパン及び八フッ化ブタン
より選ばれる少なくとも１種のパ−フルオロカーボン並
びに不活性ガスを含むＰＦＣ混合排ガスであり、上記パ
−フルオロカーボン並びに上記不活性ガスを上記ＰＦＣ
混合排ガスから分離する請求項１〜４の何れかに記載の
前処理方法。6. The PFC mixed exhaust gas comprises methane tetrafluoride,
A PFC mixed exhaust gas containing at least one kind of perfluorocarbon selected from ethane hexafluoride, propane octafluoride and butane octafluoride and an inert gas, wherein the perfluorocarbon and the inert gas are mixed with the PFC.
The pretreatment method according to claim 1, wherein the pretreatment method is separated from the mixed exhaust gas.
タン、四フッ化エチレン、三フッ化窒素、六フッ化硫
黄、フッ化水素、四フッ化ケイ素、二フッ化カルボニル
及び二酸化炭素からなる群より選ばれる少なくとも１種
の化合物を含む請求項５又は６記載の前処理方法。7. The PFC mixed exhaust gas further comprises methane trifluoride, ethylene tetrafluoride, nitrogen trifluoride, sulfur hexafluoride, hydrogen fluoride, silicon tetrafluoride, carbonyl difluoride and carbon dioxide. The pretreatment method according to claim 5, comprising at least one compound selected from the group consisting of:
載の前処理方法。8. The pretreatment method according to claim 6, wherein the inert gas is nitrogen gas.
メタン、六フッ化エタン及び八フッ化プロパンより選ば
れる少なくとも１種のパ−フルオロカーボンを回収する
ための当該排ガスの前処理方法であって、上記ＰＦＣ混
合排ガスを、酸化カルシウムと２００〜７００℃未満の
条件下で接触させ、上記パ−フルオロカーボンを上記Ｐ
ＦＣ混合排ガスから分離することを特徴とするＰＦＣ混
合排ガスの回収前処理方法。9. A method for pretreating a PFC mixed exhaust gas to recover at least one kind of perfluorocarbon selected from methane tetrafluoride, ethane hexafluoride and propane octafluoride contained in the exhaust gas. And contacting the PFC mixed exhaust gas with calcium oxide under conditions of 200 to less than 700 ° C.
A pretreatment method for recovering a PFC mixed exhaust gas, which is separated from an FC mixed exhaust gas.
ン、六フッ化エタン及び八フッ化プロパンより選ばれる
少なくとも１種のパ−フルオロカーボン並びに不活性ガ
スを含むＰＦＣ混合排ガスであり、上記パ−フルオロカ
ーボン並びに上記不活性ガスを上記ＰＦＣ混合排ガスか
ら分離する請求項９記載の前処理方法。10. The PFC mixed exhaust gas containing at least one kind of perfluorocarbon selected from methane tetrafluoride, ethane hexafluoride and propane octafluoride and an inert gas, wherein the PFC mixed exhaust gas is The pretreatment method according to claim 9, wherein the inert gas is separated from the PFC mixed exhaust gas.
メタン、四フッ化エチレン、三フッ化窒素、六フッ化硫
黄、フッ化水素、四フッ化ケイ素、二フッ化カルボニル
及び二酸化炭素からなる群より選ばれる少なくとも１種
の化合物を含む請求項１０記載の前処理方法。11. The PFC mixed exhaust gas further comprises methane trifluoride, ethylene tetrafluoride, nitrogen trifluoride, sulfur hexafluoride, hydrogen fluoride, silicon tetrafluoride, carbonyl difluoride and carbon dioxide. The pretreatment method according to claim 10, comprising at least one compound selected from the group consisting of:
０記載の前処理方法。12. The method according to claim 1, wherein the inert gas is nitrogen gas.
0 pretreatment method.
の前処理方法により分離した、パ−フルオロカーボン並
びにキャリヤーガス若しくは不活性ガスを、ガス分離膜
に通し、当該パ−フルオロカーボンとキャリヤーガス若
しくは不活性ガスとを分離し、その後、当該パ−フルオ
ロカーボンを回収容器に充填することを特徴とする回収
方法。13. A perfluorocarbon and a carrier gas or an inert gas separated by the pretreatment method according to claim 5, passed through a gas separation membrane, and the perfluorocarbon and the carrier gas are separated. Alternatively, a recovery method characterized by separating an inert gas and then filling the perfluorocarbon in a recovery container.
分離されたパ−フルオロカーボンが２成分以上のパ−フ
ルオロカーボンを含む場合、各成分をそれぞれの沸点差
を利用して単離する請求項１３記載の回収方法。14. The recovery according to claim 13, wherein, when the perfluorocarbon separated from the carrier gas or the inert gas contains two or more perfluorocarbons, each component is isolated by utilizing a difference in boiling point. Method.
３記載の回収方法。15. The method according to claim 1, wherein the inert gas is nitrogen gas.
3. The collection method according to 3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008161863A (en) * | 2006-12-27 | 2008-07-17 | Ind Technol Res Inst | Exhaust gas reducing method and system of exhaust gas produced in manufacturing semiconductor |
| JP2010005542A (en) * | 2008-06-27 | 2010-01-14 | Tosoh Corp | Perfluorocarbon adsorbent and perfluorocarbon detoxifying process using the same |
| JP2011235216A (en) * | 2010-05-07 | 2011-11-24 | Kansai Univ | Method for decomposing and treating fluorine-based gas by means of zeolite |
| JP2013542052A (en) * | 2010-08-27 | 2013-11-21 | エンパイア テクノロジー ディベロップメント エルエルシー | Hydrofluorocarbon removal device |
-
2001
- 2001-06-01 JP JP2001167216A patent/JP3548135B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008161863A (en) * | 2006-12-27 | 2008-07-17 | Ind Technol Res Inst | Exhaust gas reducing method and system of exhaust gas produced in manufacturing semiconductor |
| JP2010005542A (en) * | 2008-06-27 | 2010-01-14 | Tosoh Corp | Perfluorocarbon adsorbent and perfluorocarbon detoxifying process using the same |
| JP2011235216A (en) * | 2010-05-07 | 2011-11-24 | Kansai Univ | Method for decomposing and treating fluorine-based gas by means of zeolite |
| JP2013542052A (en) * | 2010-08-27 | 2013-11-21 | エンパイア テクノロジー ディベロップメント エルエルシー | Hydrofluorocarbon removal device |
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