JP5297208B2 - Fluorine-containing compound treating agent and exhaust gas treating method - Google Patents
Fluorine-containing compound treating agent and exhaust gas treating method Download PDFInfo
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 55
- 239000011737 fluorine Substances 0.000 title claims abstract description 55
- 150000001875 compounds Chemical class 0.000 title claims abstract description 51
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 23
- 238000012856 packing Methods 0.000 claims abstract description 12
- 238000004898 kneading Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 6
- 238000000465 moulding Methods 0.000 claims abstract description 4
- 239000002245 particle Substances 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 13
- 238000010304 firing Methods 0.000 claims description 9
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 8
- -1 perfluoro compound Chemical class 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 5
- 230000006835 compression Effects 0.000 claims 1
- 238000007906 compression Methods 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 3
- 229910018626 Al(OH) Inorganic materials 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 35
- 239000011575 calcium Substances 0.000 description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000018044 dehydration Effects 0.000 description 5
- 238000011049 filling Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminum fluoride Inorganic materials F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 229910001634 calcium fluoride Inorganic materials 0.000 description 2
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 2
- 239000000920 calcium hydroxide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005108 dry cleaning Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000005755 formation reaction Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910003691 SiBr Inorganic materials 0.000 description 1
- 229910003902 SiCl 4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 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
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 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
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010436 fluorite Substances 0.000 description 1
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000010079 rubber tapping Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 1
- 229960000909 sulfur hexafluoride Drugs 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 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]
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
本発明は、フッ素含有化合物を含むガスの処理に関し、特に、半導体工業において半導体製造装置の内面等をドライクリーニングする工程や、酸化膜等の各種成膜をエッチングする工程から排出されるフッ素含有化合物、特にパーフルオロ化合物（ＰＦＣ）を含む排ガスを処理する際に用いるフッ素含有化合物処理剤及び排ガス処理方法に関する。 The present invention relates to treatment of a gas containing a fluorine-containing compound, and in particular, a fluorine-containing compound discharged from a step of dry-cleaning an inner surface of a semiconductor manufacturing apparatus or a step of etching various film formation such as an oxide film in the semiconductor industry. In particular, the present invention relates to a fluorine-containing compound treating agent and an exhaust gas treating method used when treating an exhaust gas containing a perfluoro compound (PFC).
半導体や液晶の製造工程中に多種類の有害ガスが使用されており、環境中への排気による環境汚染や、地球温暖化ガスの排出による温暖化促進が懸念される。特に、半導体工業における半導体製造装置内面のクリーニング工程や、エッチング工程或いはＣＶＤ工程などにおいては、ＣＨＦ３などのフッ化炭化水素や、ＣＦ４、Ｃ２Ｆ６、Ｃ３Ｆ８、Ｃ４Ｆ６、Ｃ４Ｆ８、Ｃ５Ｆ８、ＳＦ６、ＮＦ３などのパーフルオロ化合物（ＰＦＣ）などのフッ素含有化合物が用いられており、これらのプロセスからの排ガス中に含まれるフッ素含有化合物は、地球温暖化ガスとしてその除去システムの確立が急務とされている。 Many kinds of harmful gases are used during the manufacturing process of semiconductors and liquid crystals, and there is concern about environmental pollution due to exhaust into the environment and promotion of global warming due to the discharge of global warming gas. In particular, in a cleaning process of an inner surface of a semiconductor manufacturing apparatus in the semiconductor industry, an etching process, a CVD process, or the like, a fluorinated hydrocarbon such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , C 4 F 6. , C 4 F 8 , C 5 F 8 , SF 6 , and fluorine-containing compounds such as perfluoro compounds (PFC) such as NF 3 are used. The fluorine-containing compounds contained in the exhaust gas from these processes are: As a global warming gas, it is urgently required to establish a removal system.
フッ素含有化合物を含む排ガスの処理方法としては、例えば、酸化アルミニウム及びアルカリ土類金属の酸化物を含む処理剤を用いて排ガス中のフルオロカーボンを分解処理する方法（特許文献１）；酸化アルミニウム及びアルカリ土類金属の酸化物を含む処理剤を用いて排ガス中のフッ化硫黄を分解処理する方法（特許文献２）；アルミナ及びアルカリ土類金属化合物、及び場合によっては銅、錫、バナジウム等の金属の酸化物を含む処理剤を用いて排ガス中のフッ素化合物を分解処理する方法（特許文献３）；水酸化アルミニウムと水酸化カルシウムとを含む処理剤を用いて排ガス中のＰＦＣを分解処理する方法（特許文献４）；などが提案されている。 As a method for treating exhaust gas containing a fluorine-containing compound, for example, a method of decomposing fluorocarbon in exhaust gas using a treatment agent containing aluminum oxide and an oxide of an alkaline earth metal (Patent Document 1); aluminum oxide and alkali A method of decomposing sulfur fluoride in exhaust gas using a treating agent containing an earth metal oxide (Patent Document 2); alumina and alkaline earth metal compounds, and in some cases metals such as copper, tin, vanadium, etc. Method for Decomposing Fluorine Compound in Exhaust Gas Using Treatment Agent Containing Oxide (Patent Document 3); Method for Decomposing PFC in Exhaust Gas Using Treatment Agent Containing Aluminum Hydroxide and Calcium Hydroxide (Patent Document 4); and the like have been proposed.
しかしながら、上記のような従来の処理方法は、特にＣＦ４などの難分解性ガスを処理する場合、処理温度が８００〜１０００℃と高いため、処理装置の熱による劣化が速く、装置のエネルギー消費量も大きいという問題があった。また、従来の処理剤は、使用寿命が短くて交換頻度が高いという問題を包含していた。例えば、特許文献１〜３に開示されている方法では、ＰＦＣを酸化アルミニウム（アルミナ）と反応させてフッ化アルミニウムを生成させることによってＰＦＣガスを分解している。しかしながら、酸化アルミニウムの反応活性が低いので、この反応を効率よく進行させるためには、高温の反応条件が必要である。更に、生成したフッ化アルミニウムが酸化アルミニウムの表面に層を形成し、これによって酸化アルミニウムが被毒されて短時間で触媒活性を失うおそれがあり、その様な場合は、処理剤の交換頻度が高くなってしまうという問題がある。 However, the conventional processing method as described above, particularly when processing a hardly decomposable gas such as CF 4 , has a high processing temperature of 800 to 1000 ° C., so that the processing apparatus is rapidly deteriorated by heat, and the energy consumption of the apparatus is high. There was a problem that the amount was large. Moreover, the conventional processing agent included the problem that service life is short and replacement frequency is high. For example, in the methods disclosed in Patent Documents 1 to 3, PFC gas is decomposed by reacting PFC with aluminum oxide (alumina) to produce aluminum fluoride. However, since the reaction activity of aluminum oxide is low, high-temperature reaction conditions are required to allow this reaction to proceed efficiently. Further, the generated aluminum fluoride forms a layer on the surface of the aluminum oxide, which may poison the aluminum oxide and lose the catalytic activity in a short time. There is a problem of becoming high.
ＰＦＣガスを水酸化アルミニウムと反応させて、水酸化アルミニウムの水酸基の水素によってフッ素をフッ化水素とし、次に生成したフッ化水素を水酸化カルシウムと反応させてフッ化カルシウムを生成させることによって、ＰＦＣガスなどのフッ素含有化合物を従来法よりも低い温度で効率よく分解処理することができる方法が提案されている（特許文献４）。しかし、かかる方法は、小型の装置では効果があるものの、実機規模にスケールアップすると、アルミニウムの活性が阻害され、十分な除去効果を示さない場合があることが確認された。
本発明は、かかる従来技術の問題点を解決し、スケールアップした実機でも失活せずにＰＦＣガスを効率よく分解することができ、耐久性に優れた排ガス処理剤及び排ガスの処理方法を提供することを課題とする。 The present invention solves such problems of the prior art, and provides an exhaust gas treatment agent and an exhaust gas treatment method that are capable of efficiently decomposing PFC gas without being deactivated even with a scaled-up actual machine, and having excellent durability. The task is to do.
上記課題を解決するために、本発明では、平均粒子径（メディアン径）５５μｍ以上１
６０μｍ以下のＡｌ（ＯＨ）３とＣａ（ＯＨ）２とのモル比が３：７〜５：５である混合物を、かさ密度が９５０ｇ／Ｌ以上に混練成形後、乾燥した成形物を４３０℃よりも高く８９０℃以下の温度範囲で焼成して非晶質Ａｌ ２ Ｏ ３ とＣａＯとの複合酸化物を形成したことを特徴とする排ガス中のフッ素含有化合物処理剤としたものである。
また、本発明では、前記焼成して得られた非晶質Ａｌ ２ Ｏ ３ とＣａＯとの複合酸化物を、１Ｌ容積当たり０．６８ｋｇ以上の充填密度で充填することとしたものである。
In order to solve the above problems, in the present invention, the average particle diameter (median diameter) is 55 μm or more and 1
A mixture in which the molar ratio of Al (OH) 3 and Ca (OH) 2 of 60 μm or less is from 3: 7 to 5: 5 is kneaded and molded to a bulk density of 950 g / L or more, and then the dried molded product is 430 ° C. Higher than 890 ° C. and a composite oxide of amorphous Al 2 O 3 and CaO is formed to form a fluorine-containing compound treating agent in exhaust gas .
In the present invention, a composite oxide of amorphous Al 2 O 3 and CaO obtained by the firing is obtained by a filling in the packing density of more than 0.68kg per 1L volume.
また、本発明では、前記フッ素含有化合物処理剤と、フッ素含有化合物を含む排ガスとを５５０℃〜８５０℃の温度で接触させることを特徴とする排ガス処理方法としたものである。
前記フッ素含有化合物処理剤において、混練成形は、押し出し成形機を用い、加圧圧縮させながら押し出し成形するのがよく、また、前記において、フッ素含有化合物としては、ＰＦＣを有効に処理することができる。
Moreover, in this invention, it is set as the waste gas processing method characterized by making the said fluorine-containing compound processing agent and the waste gas containing a fluorine-containing compound contact at the temperature of 550 degreeC-850 degreeC.
In the fluorine-containing compound treating agent, the kneading and molding is preferably carried out by using an extrusion molding machine while pressing and compressing, and in the above, PFC can be effectively treated as the fluorine-containing compound. .
本発明によれば、平均粒子径（メディアン径）５５μｍ以上１６０μｍ以下のＡｌ（ＯＨ）３と、Ｃａ（ＯＨ）２とのモル比が３：７〜５：５である混合物を、かさ密度が９５０ｇ／Ｌ以上に混練成形するか、又は、混練成形後に乾燥して焼成した成形物を、０．６８ｋｇ／Ｌ以上の充填密度で充填することによって、かさ密度又は充填密度が、それらより以下の成形物に比べ、フッ素含有化合物の処理性能が上昇し、また、耐久性に優れた処理剤とすることができた。 According to the present invention, a mixture having an average particle diameter (median diameter) of 55 μm or more and 160 μm or less of Al (OH) 3 and Ca (OH) 2 having a molar ratio of 3: 7 to 5: 5 is obtained. By filling a molded product kneaded and molded to 950 g / L or more, or dried and baked after kneading and molding at a filling density of 0.68 kg / L or more, the bulk density or the packing density is less than them. Compared to the molded product, the treatment performance of the fluorine-containing compound was improved, and a treatment agent excellent in durability could be obtained.
以下に、本発明を詳細に説明する。
本発明のフッ素含有化合物処理剤の原材料であるＡｌ（ＯＨ）３は、その平均粒子径が５５μｍ以上、好ましくは、６０μｍ以上１６０μｍ以下、より好ましくは９０μｍ以上１２０μｍ以下である。ここで、平均粒子径とは、メディアン径を意味し、粒子径ごとに頻度（含有量）を積算し、含有量の累積が最小粒子径からはじめて５０％になる点での粒子径である。
平均粒子径が上記範囲外であると、フッ素含有化合物処理剤としての所望の処理性能が得られず、短時間でＣＦ４除去率が９５％以下に劣化してしまい、実用に耐えない。
The present invention is described in detail below.
Al (OH) 3 which is a raw material of the fluorine-containing compound treating agent of the present invention has an average particle size of 55 μm or more, preferably 60 μm or more and 160 μm or less, more preferably 90 μm or more and 120 μm or less. Here, the average particle diameter means the median diameter, and is the particle diameter at which the frequency (content) is integrated for each particle diameter, and the accumulation of the content reaches 50% from the minimum particle diameter.
If the average particle size is out of the above range, desired treatment performance as a fluorine-containing compound treating agent cannot be obtained, and the CF 4 removal rate deteriorates to 95% or less in a short time, which is not practical.
本発明のフッ素含有化合物処理剤の原材料であるＣａ（ＯＨ）２の平均粒子径はＡ１（ＯＨ）３の平均粒径によって変動するが、Ａ１（ＯＨ）３よりもＣａ（ＯＨ）２の平均粒子径（メディアン径）は小さい方が好ましい。Ｃａ（ＯＨ）２の平均粒子径（メディアン径）としては、好ましくは１μｍ以上１０μｍ以下、より好ましくは３μｍ以上８μｍ以下、最も好ましくは４μｍ以上６μｍ以下である。 The average particle diameter of Ca (OH) 2 that is a raw material of the fluorine-containing compound treating agent of the present invention varies depending on the average particle diameter of A1 (OH) 3 , but the average of Ca (OH) 2 is higher than that of A1 (OH) 3. A smaller particle diameter (median diameter) is preferred. The average particle diameter (median diameter) of Ca (OH) 2 is preferably 1 μm to 10 μm, more preferably 3 μm to 8 μm, and most preferably 4 μm to 6 μm.
Ａ１（ＯＨ）３とＣａ（ＯＨ）２とは、平均粒子径の大きいＡ１（ＯＨ）３を核にして、その表層にＣａ（ＯＨ）２が効率よく配置されることで活性が維持されると考えられる。よって、Ｃａ（ＯＨ）２の粒径がＡ１（ＯＨ）３の平均粒径に比べて小さすぎるとＡ１（ＯＨ）３の表面全体を隙間なく覆い、ＰＦＣとの接触を阻止して結果的にＰＦＣの分解を阻害し、逆にＣａ（ＯＨ）２の粒径がＡ１（ＯＨ）３の平均粒径に比べて大きすぎるとＰＦＣ分解時のＦとの接触効率が低下し結果的に分解が不充分となり、何れの場合もＰＦＣの分解効率を下げると考えられる。 The activity of A1 (OH) 3 and Ca (OH) 2 is maintained by efficiently arranging Ca (OH) 2 on the surface layer of A1 (OH) 3 having a large average particle diameter as a nucleus. it is conceivable that. Thus, Ca (OH) covers without gaps an entire surface of the excessively when A1 (OH) 3 smaller than the average particle diameter of the particle size of 2 A1 (OH) 3, resulting in by preventing contact between the PFC Inhibiting the decomposition of PFC, conversely, if the Ca (OH) 2 particle size is too large compared to the average particle size of A1 (OH) 3 , the contact efficiency with F during PFC decomposition is reduced, resulting in decomposition. In any case, it is considered that the PFC decomposition efficiency is lowered.
上記混合物におけるＡ１（ＯＨ）３とＣａ（ＯＨ）２とのモル比は、３：７〜５：５、好ましくは３：７〜４：６である。Ａ１（ＯＨ）３とＣａ（ＯＨ）２とのモル比が上記範囲外であると、ＰＦＣ分解処理剤としての所望の処理性能が得られず、短時間でＣＦ４除去率が処理目標の９５％以下に劣化してしまい、実用に耐えない。
本発明のフッ素含有化合物処理剤は、上記混合物を混練機で混練して、押し出し成形して得たかさ密度が９５０ｇ／Ｌ以上の成形物を乾燥し、４３０℃よりも高く８９０℃以下の温度範囲、好ましくは５８０℃〜８５０℃、より好ましくは５９０℃〜６３０℃の温度範囲で、窒素流又は空気流中で焼成することにより得られる。
The molar ratio of A1 (OH) 3 and Ca (OH) 2 in the above mixture is 3: 7 to 5: 5, preferably 3: 7 to 4: 6. If the molar ratio of A1 (OH) 3 and Ca (OH) 2 is outside the above range, the desired processing performance as a PFC decomposition treatment agent cannot be obtained, and the CF 4 removal rate is a processing target of 95 in a short time. %, It will not be practical.
The fluorine-containing compound treating agent of the present invention is obtained by drying a molded product having a bulk density of 950 g / L or more obtained by kneading the above mixture with a kneader and extrusion molding, and having a temperature higher than 430 ° C. and lower than 890 ° C. It is obtained by calcining in a nitrogen stream or an air stream in the temperature range, preferably 580 ° C to 850 ° C, more preferably 590 ° C to 630 ° C.
Ａ１（ＯＨ）３とＣａ（ＯＨ）２との成形物の焼成温度は、脱水可能な温度であって且つ失活しない温度範囲であることが必要になる。Ａ１（ＯＨ）３の脱水温度は約２７０℃であり、Ｃａ（ＯＨ）２の脱水温度は約４３０℃であるから、少なくとも４３０℃を超えることが好ましい。温度範囲が８９０℃を超えると、ＣＦ４除去率が低下する。焼成温度は、排ガスの処理温度より低い温度で焼成することが望ましい。
高熱処理により酸化アルミニウムが結晶化してしまい、活性が劣化することによると考えられる。
The firing temperature of the molded product of A1 (OH) 3 and Ca (OH) 2 needs to be a temperature that allows dehydration and does not deactivate. Since the dehydration temperature of A1 (OH) 3 is about 270 ° C. and the dehydration temperature of Ca (OH) 2 is about 430 ° C., it is preferable to exceed at least 430 ° C. When the temperature range exceeds 890 ° C., the CF 4 removal rate decreases. The firing temperature is desirably lower than the exhaust gas treatment temperature.
It is considered that aluminum oxide is crystallized by high heat treatment and the activity deteriorates.
Ａ１（ＯＨ）３とＣａ（ＯＨ）２との成形物は、窒素流又は空気流中で焼成する。窒素流又は空気流は、成形物を固定配置して焼成する場合は一定時間で流入方向を逆転させ、もしくは成形物を移動させつつ、窒素又は空気流中で焼成させることが好ましい。焼成により進行する脱水反応の結果、発生する水分を混合物周囲に滞留させず、速やかに蒸発・除去させるためである。高熱高湿雰囲気でＡ１（ＯＨ）３とＣａ（ＯＨ）２との成形物を焼成し続けると、水分の存在により酸化アルミニウムが結晶化（活性点における微細構造レベルでの結晶化を意味する）してしまい、活性が劣化すると考えられる。よって、Ａ１（ＯＨ）３や焼成により得られる酸化アルミニウムなどの周囲に不活性ガスを流すことによって、発生する水分を速やかに除去することが必要である。窒素流又は空気流の向流気流は、例えば、Ａ１（ＯＨ）３とＣａ（ＯＨ）２との成形物をカラムに充填して、カラムの上下から窒素流又は空気流を送るなどして与えることができる。 A molded product of A1 (OH) 3 and Ca (OH) 2 is fired in a nitrogen stream or an air stream. When the molded product is fixedly disposed and fired, the nitrogen flow or the air flow is preferably fired in a nitrogen or air stream while reversing the inflow direction for a certain time or moving the molded product. This is because moisture generated as a result of the dehydration reaction that proceeds by firing is not allowed to stay around the mixture, but is quickly evaporated and removed. When a molded product of A1 (OH) 3 and Ca (OH) 2 is continuously fired in a high-heat and high-humidity atmosphere, aluminum oxide is crystallized due to the presence of moisture (meaning crystallization at the fine structure level at the active site). Therefore, the activity is considered to deteriorate. Therefore, it is necessary to quickly remove the generated water by flowing an inert gas around A1 (OH) 3 or aluminum oxide obtained by baking. The countercurrent airflow of nitrogen flow or air flow is given by, for example, filling a column with a molded product of A1 (OH) 3 and Ca (OH) 2 and sending nitrogen flow or air flow from the top and bottom of the column. be able to.
焼成時間は特に限定されず、使用するＡ１（ＯＨ）３とＣａ（ＯＨ）２との量によっても変動するが、一般的に６〜１２時間とするのが脱水効果やエネルギー消費効率の点で好ましく、８〜１０時間とするのがさらに好ましい。技術的にはＣａ（ＯＨ）２が脱水する温度（約４３０℃）まで昇温した後、さらに１〜２時間焼成することで充分であると考えられる。焼成温度に達するまでの昇温速度が速すぎると脱水が不充分な場合が生じ、遅すぎると経済的理由（エネルギーや時間を消費する）から好ましくない。通常は、１００℃／ｈｒの昇温速度が最適である。
本発明の調製方法により得られる成形物は、反応槽内で０．６８ｋｇ／Ｌ以上の充填密度で充填してフッ素含有化合物処理剤として用いられる。
The firing time is not particularly limited and varies depending on the amounts of A1 (OH) 3 and Ca (OH) 2 used, but generally 6 to 12 hours is the point of dehydration effect and energy consumption efficiency. Preferably, the time is 8 to 10 hours. Technically, it is considered sufficient that the temperature is raised to a temperature at which Ca (OH) 2 dehydrates (about 430 ° C.) and then baked for an additional 1-2 hours. If the rate of temperature rise until reaching the firing temperature is too fast, dehydration may be insufficient, and if it is too slow, it is not preferred for economic reasons (consuming energy and time). Usually, a temperature increase rate of 100 ° C./hr is optimum.
The molded product obtained by the preparation method of the present invention is filled as a fluorine-containing compound treating agent by filling with a packing density of 0.68 kg / L or more in a reaction vessel.
６５０℃で７〜９時間焼成して得られたフッ素含有化合物処理剤のＸＲＤ分析チャートを図１に示す。上段のピークデータは、得られたフッ素含有化合物処理剤の生データからの解析ピークであり、下段のカードピークは、ライブラリーデータからのＣａＯの特性ピークである。得られたフッ素含有化合物処理剤のピークは、ＣａＯのライブラリーデータピークと完全に一致する。参考として、図２に結晶性アルミナの標準Ｘ線回析スペクトルを示すが、得られたフッ素含有化合物処理剤にはＡｌ２Ｏ３の特性ピークが見られない。Ｃａ（ＯＨ）２は、全量が焼成によりＣａＯに変化しているといえる。これらのことから、本発明のフッ素含有化合物処理剤には、焼成により発生する水分がすべて除かれ、水熱反応が進まないため、結晶性Ａｌ２Ｏ３が生じていないと考えられる。 An XRD analysis chart of the fluorine-containing compound treating agent obtained by baking at 650 ° C. for 7 to 9 hours is shown in FIG. The upper peak data is an analysis peak from raw data of the obtained fluorine-containing compound treating agent, and the lower card peak is a characteristic peak of CaO from library data. The peak of the obtained fluorine-containing compound treating agent completely coincides with the library data peak of CaO. For reference, FIG. 2 shows a standard X-ray diffraction spectrum of crystalline alumina, but no characteristic peak of Al 2 O 3 is observed in the obtained fluorine-containing compound treating agent. It can be said that the total amount of Ca (OH) 2 is changed to CaO by firing. From these facts, it is considered that the fluorine-containing compound treating agent of the present invention does not generate crystalline Al 2 O 3 because all the water generated by firing is removed and the hydrothermal reaction does not proceed.
本発明のフッ素含有化合物処理剤は、 非晶質Ａｌ２Ｏ３ とＣａＯとの複合酸化物であり、以下のように酸素を介して緩やかに結合していると考えられる。 The fluorine-containing compound treating agent of the present invention is a composite oxide of amorphous Al 2 O 3 and CaO, and is considered to be loosely bonded through oxygen as follows.
本発明のフッ素含有化合物処理剤をフッ素化合物と接触させると、（Ａｌ＿Ｏ）部分の触媒作用により
ＣＦ４→Ｃ＋４Ｆ
の分解反応が進み、（Ｏ＿Ｃａ）部分からの酸素（Ｏ）とカルシウム（Ｃａ）とにより
Ｃ＋２Ｏ→ＣＯ２
４Ｆ＋２Ｃａ→２ＣａＦ２
の酸化還元反応が進むと考えられる。
When the fluorine-containing compound treating agent of the present invention is brought into contact with a fluorine compound, CF 4 → C + 4F is caused by the catalytic action of the (Al_O) moiety.
As the decomposition reaction proceeds, oxygen (O) and calcium (Ca) from the (O_Ca) portion cause C + 2O → CO 2
4F + 2Ca → 2CaF 2
It is thought that the redox reaction proceeds.
このように、本発明のフッ素含有化合物処理剤を用いてフッ素含有化合物を含む排ガスを処理すると、ＰＦＣが分解して、フッ化カルシウム（ＣａＦ２）が生成する。フッ化カルシウムは、フッ素製造の原料として知られる蛍石の主成分であり、酸で処理することによってフッ素ガスを発生させることができる。したがって、本発明のフッ素含有化合物処理剤は、極めて効率的にフッ素含有化合物を含むガスからフッ素を再利用可能な形態で回収することができる。
なお、本フッ素含有化合物処理剤には、酸化力向上助剤として、Ｐｄ、Ｐｔ、Ｒｈ、Ｒｕ等、及び／又は耐熱向上剤として、ＺｒＯ２、Ｌａ等、その他の物質を添加してもよい。
Thus, when the exhaust gas containing a fluorine-containing compound is treated using the fluorine-containing compound treating agent of the present invention, PFC is decomposed and calcium fluoride (CaF 2 ) is generated. Calcium fluoride is a main component of fluorite known as a raw material for producing fluorine, and fluorine gas can be generated by treatment with acid. Therefore, the fluorine-containing compound treating agent of the present invention can very efficiently recover fluorine in a reusable form from the gas containing the fluorine-containing compound.
The fluorine-containing compound treating agent may contain other substances such as Pd, Pt, Rh, Ru, etc. as an oxidizing power improvement aid and / or ZrO 2 , La, etc. as a heat resistance improver. .
本発明のフッ素含有化合物処理剤により処理することのできるフッ素含有化合物としては、ＣＨＦ３等のフッ化炭化水素、ＣＦ４、Ｃ２Ｆ６、Ｃ３Ｆ８、ＳＦ６、ＮＦ３などのパーフルオロ化合物（ＰＦＣ）等を挙げることができる。このようなフッ素含有化合物を含むガスとしては、半導体工業で半導体製造装置の内面等をドライクリーニングする工程や、各種成膜をエッチングする工程で排出される排ガスなどを挙げることができる。 Examples of the fluorine-containing compound that can be treated with the fluorine-containing compound treating agent of the present invention include fluorinated hydrocarbons such as CHF 3 , CF 4 , C 2 F 6 , C 3 F 8 , SF 6 , NF 3 and the like. A fluoro compound (PFC) etc. can be mentioned. Examples of such a gas containing a fluorine-containing compound include exhaust gas discharged in a process of dry cleaning the inner surface of a semiconductor manufacturing apparatus in the semiconductor industry and a process of etching various film formations.
また、本発明のフッ素含有化合物処理剤は、ＰＦＣなどに加えて、酸化性ガス、酸性ガスなども分解処理することができる。半導体製造工程から排出される排ガス中には、ＰＦＣばかりでなく、他にＦ２、Ｃｌ２、Ｂｒ２等の酸化性ガス、ＨＦ、ＳｉＦ４、ＣＯＦ２、ＨＣｌ、ＨＢｒ、ＳｉＣｌ４、ＳｉＢｒ４等の酸性ガスなどが含まれる場合がある。本発明の排ガス処理剤によれば、これらの酸化性ガスや酸性ガスも、ＰＦＣ等のフッ素含有化合物と共に分解処理することができる。 Further, the fluorine-containing compound treating agent of the present invention can decompose oxidizing gas, acidic gas, etc. in addition to PFC. In the exhaust gas discharged from the semiconductor manufacturing process, not only PFC but also oxidizing gases such as F 2 , Cl 2 , Br 2 , HF, SiF 4 , COF 2 , HCl, HBr, SiCl 4 , SiBr 4 are used. And so on. According to the exhaust gas treating agent of the present invention, these oxidizing gas and acidic gas can also be decomposed together with a fluorine-containing compound such as PFC.
以下、実施例により、本発明を更に具体的に説明する。
（１） フッ素含有化合物処理剤の調製
（ａ） 原料
Ａ１（ＯＨ）３ ：５５μｍ（メディアン径）、純度９９．８％以上
Ｃａ（ＯＨ）２ ：１．９μｍ（メディアン径）（原料のＣａＯの純度
は、７４．５ｗｔ％）
Hereinafter, the present invention will be described more specifically with reference to examples.
(1) Preparation of fluorine-containing compound treating agent (a) Raw material A1 (OH) 3 : 55 μm (median diameter), purity 99.8% or more Ca (OH) 2 : 1.9 μm (median diameter) (of raw material CaO purity
Is 74.5wt%)
（ｂ） 製造方法に関して
Ａ１（ＯＨ）３ Ｃａ（ＯＨ）２を水を添加しながら混練機で混練する。
混練機兼押し出し成形機として、例えばスクリュープレスが用いられ、Ａ１（ＯＨ）３と Ｃａ（ＯＨ）２をスクリュー部に供給し、水を添加しながら加圧圧縮させつつ前進させる。この際に発熱が激しい場合は、混練部外周を冷却させながら混練してもよい。その際、混練強度を変化させてかさ密度を制御する。混練強度を強くするとかさ密度は大きくなる。スクリュー先端に取り付けた金網の孔から材料を連続的に押し出し押出し成形する。金網の孔径は直径２ｍｍである。
次に、吐出成型された造粒品を、乾燥させ、中の水分を除去する。
乾燥は、輻射熱によることが好ましい。１００℃以上、１５０℃未満の雰囲気（空気又は窒素雰囲気）中で、造粒品を移動させながら乾燥させることが好ましい。これらの製造工程により、かさ密度が１〜０．８７ｋｇ／Ｌの成形物を得る。
この成形物を６１０℃±２０℃で焼成（ロータリーキルンが好ましい。）して、性能試験に用いた。
(B) Production method A1 (OH) 3 Ca (OH) 2 is kneaded with a kneader while adding water.
For example, a screw press is used as a kneading machine / extrusion molding machine, and A1 (OH) 3 and Ca (OH) 2 are supplied to the screw part and advanced while being pressurized and compressed while adding water. If the heat generation is intense at this time, the kneading part may be kneaded while cooling the outer periphery. At that time, the bulk density is controlled by changing the kneading strength. Increasing the kneading strength increases the bulk density. The material is continuously extruded and extruded through holes in a wire mesh attached to the screw tip. The hole diameter of the wire net is 2 mm.
Next, the discharged granulated product is dried to remove moisture therein.
Drying is preferably by radiant heat. It is preferable to dry the granulated product while moving it in an atmosphere (air or nitrogen atmosphere) of 100 ° C. or higher and lower than 150 ° C. By these manufacturing steps, a molded product having a bulk density of 1 to 0.87 kg / L is obtained.
This molded product was fired at 610 ° C. ± 20 ° C. (preferably a rotary kiln) and used for a performance test.
（ｃ） かさ密度の測定方法
１Ｌ用のメスシリンダーに混合体を１Ｌ近く入れ、メスシリンダーごとタッピング（メスシリンダーの底を台の上でこきざみにたたいて、剤を沈みこませる）し、剤が沈み込んだ分を追加し、さらにタッピングを行い、最終的に沈みこまなくなった状態での容積（１Ｌ）と重さからかさ密度（単位：ｇ／Ｌ）を求めている。
（ｄ） 充填密度の調整
容積４９ｍｌのミニカラムにフッ素含有化合物を充填し、その重さと容積から充填密度を求めた。
実際の反応槽への充填密度の調整には、電直バイブレーターを用いることができる。電直バイブレーターとは、モーター直結の振動を振動棒／振動板に伝達するもので、振動棒／板を処理剤中で振動させることで、反応槽内の処理剤の充填密度を高めることができる。
(C) Bulk density measurement method Put the mixture in a measuring cylinder for 1L, and tap the entire measuring cylinder (tap the bottom of the measuring cylinder on the table to sink the agent). The part in which the agent is submerged is added, tapping is further performed, and the bulk density (unit: g / L) is obtained from the volume (1 L) and the weight in the state where the agent has finally stopped sinking.
(D) Adjustment of packing density A mini-column with a volume of 49 ml was packed with a fluorine-containing compound, and the packing density was determined from its weight and volume.
An electric direct vibrator can be used to adjust the packing density in the actual reaction vessel. Electro-direct vibrator transmits vibration directly connected to a motor to a vibrating bar / vibrating plate. By vibrating the vibrating bar / plate in the processing agent, the packing density of the processing agent in the reaction vessel can be increased. .
（２） 性能試験
前記のように調整したフッ素含有化合物処理剤を各４９ｍｌミニカラムに充填し、ＣＦ４流入濃度：１．０％、ガス流量：４１０ｍｌ／ｍｉｎ、処理温度：７５０℃で５時間通ガスした後、初期ＣＦ４除去率を求めた。
また、続いてＣＦ４ガス出しを続け、除去率が９５％を下回るまでの時間として「処理時間」を求め、除去率が９５％になった時点でのＣＦ４処理量として「初期活性ＣＦ４処理量」を求めた。かさ密度、充填密度とそれらの結果を表１に示す。
(2) Performance test Each 49 ml mini-column is filled with the fluorine-containing compound treating agent prepared as described above, CF 4 inflow concentration: 1.0%, gas flow rate: 410 ml / min, treatment temperature: 750 ° C. for 5 hours. After gassing, the initial CF 4 removal rate was determined.
Subsequently, the CF 4 gas is continuously discharged, “processing time” is obtained as the time until the removal rate falls below 95%, and “initial activation CF 4 ” is obtained as the CF 4 treatment amount when the removal rate reaches 95%. The throughput was determined. Table 1 shows the bulk density and packing density.
ここでの処理時間は８時間以上、又は、初期ＣＦ４除去率の少なくともいずれか一方が９９％以上であることが実用できる処理剤性能として望ましい。
これらの結果から、かさ密度は０．９５ｋｇ／Ｌ以上、充填密度は０．６８以上でＣＦ４除去率、処理時間ともの良好な性能が得られることがわかった。
The treatment time here is preferably 8 hours or more, or at least one of the initial CF 4 removal rates is 99% or more as a practical treatment agent performance.
From these results, it was found that the bulk density was 0.95 kg / L or more, the packing density was 0.68 or more, and good performance in terms of CF 4 removal rate and processing time was obtained.
Claims (6)
．６８ｋｇ以上の充填密度で充填したことを特徴とする請求項1記載の排ガス中のフッ素含有化合物処理剤。 A composite oxide of amorphous Al 2 O 3 and CaO obtained by the firing was reduced to 0 per liter volume.
. 2. The fluorine-containing compound treating agent in exhaust gas according to claim 1 , which is filled at a packing density of 68 kg or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2009002192A JP5297208B2 (en) | 2009-01-08 | 2009-01-08 | Fluorine-containing compound treating agent and exhaust gas treating method |
Applications Claiming Priority (1)
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| KR20200021083A (en) | 2017-06-16 | 2020-02-27 | 쿠라리안토 쇼쿠바이 가부시키가이샤 | Decomposition remover of fluorine-containing gas, method for producing same, method for removing fluorine-containing gas using same, and method for recovering fluorine resources |
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| JPH10314576A (en) * | 1997-05-16 | 1998-12-02 | Kotegawa Sangyo Kk | Acid gas removing material |
| JP3789277B2 (en) * | 1999-04-28 | 2006-06-21 | 昭和電工株式会社 | Reagent for decomposing fluorine compounds, decomposing method and use thereof |
| JP4255114B2 (en) * | 2003-05-07 | 2009-04-15 | 電気化学工業株式会社 | CFC decomposition method |
| JP5048208B2 (en) * | 2004-03-19 | 2012-10-17 | 株式会社荏原製作所 | Method and apparatus for treating gas containing fluorine-containing compound |
| JP4786143B2 (en) * | 2004-05-25 | 2011-10-05 | 学校法人東海大学 | Method for producing double oxide ceramics |
| JP4394555B2 (en) * | 2004-09-30 | 2010-01-06 | 株式会社日立製作所 | Method and apparatus for treating fluorine compound-containing gas |
| JP4708857B2 (en) * | 2005-05-16 | 2011-06-22 | 電気化学工業株式会社 | Molded body, method for producing the same, and method for promoting oxidation reaction using the same |
| JP5020136B2 (en) * | 2007-07-10 | 2012-09-05 | 株式会社荏原製作所 | Fluorine fixing agent, PFC decomposition treatment agent, and preparation method thereof |
| JP5284873B2 (en) * | 2008-10-29 | 2013-09-11 | 株式会社荏原製作所 | Gas processing apparatus and semiconductor manufacturing apparatus |
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