JP3302137B2 - How to purify harmful gases - Google Patents
How to purify harmful gasesInfo
- Publication number
- JP3302137B2 JP3302137B2 JP28753593A JP28753593A JP3302137B2 JP 3302137 B2 JP3302137 B2 JP 3302137B2 JP 28753593 A JP28753593 A JP 28753593A JP 28753593 A JP28753593 A JP 28753593A JP 3302137 B2 JP3302137 B2 JP 3302137B2
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- zirconium
- gas
- purifying
- nitrogen
- 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.)
- Expired - Fee Related
Links
- 239000007789 gas Substances 0.000 title claims description 46
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 35
- 229910052726 zirconium Inorganic materials 0.000 claims description 35
- 238000000746 purification Methods 0.000 claims description 30
- 229910045601 alloy Inorganic materials 0.000 claims description 28
- 239000000956 alloy Substances 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 23
- GVGCUCJTUSOZKP-UHFFFAOYSA-N nitrogen trifluoride Chemical compound FN(F)F GVGCUCJTUSOZKP-UHFFFAOYSA-N 0.000 claims description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 19
- 239000011651 chromium Substances 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000012629 purifying agent Substances 0.000 claims description 16
- 239000010955 niobium Substances 0.000 claims description 14
- 239000011777 magnesium Substances 0.000 claims description 13
- 239000011575 calcium Substances 0.000 claims description 12
- 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 12
- 239000011701 zinc Substances 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 229910052791 calcium Inorganic materials 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 229910052749 magnesium Inorganic materials 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- 229910052720 vanadium Inorganic materials 0.000 claims description 7
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000004332 silver Substances 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- -1 Lium Chemical compound 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- DUQAODNTUBJRGF-ONEGZZNKSA-N dinitrogen difluoride Chemical compound F\N=N\F DUQAODNTUBJRGF-ONEGZZNKSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- GFADZIUESKAXAK-UHFFFAOYSA-N tetrafluorohydrazine Chemical compound FN(F)N(F)F GFADZIUESKAXAK-UHFFFAOYSA-N 0.000 claims description 3
- XNFDWBSCUUZWCI-UHFFFAOYSA-N [Zr].[Sn] Chemical compound [Zr].[Sn] XNFDWBSCUUZWCI-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000052 comparative effect Effects 0.000 description 61
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 52
- 238000000354 decomposition reaction Methods 0.000 description 15
- 239000002184 metal Substances 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229910052721 tungsten Inorganic materials 0.000 description 6
- 229910052684 Cerium Inorganic materials 0.000 description 5
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910052718 tin Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000012459 cleaning agent Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000011572 manganese Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- BYHQTRFJOGIQAO-GOSISDBHSA-N 3-(4-bromophenyl)-8-[(2R)-2-hydroxypropyl]-1-[(3-methoxyphenyl)methyl]-1,3,8-triazaspiro[4.5]decan-2-one Chemical compound C[C@H](CN1CCC2(CC1)CN(C(=O)N2CC3=CC(=CC=C3)OC)C4=CC=C(C=C4)Br)O BYHQTRFJOGIQAO-GOSISDBHSA-N 0.000 description 2
- WNEODWDFDXWOLU-QHCPKHFHSA-N 3-[3-(hydroxymethyl)-4-[1-methyl-5-[[5-[(2s)-2-methyl-4-(oxetan-3-yl)piperazin-1-yl]pyridin-2-yl]amino]-6-oxopyridin-3-yl]pyridin-2-yl]-7,7-dimethyl-1,2,6,8-tetrahydrocyclopenta[3,4]pyrrolo[3,5-b]pyrazin-4-one Chemical compound C([C@@H](N(CC1)C=2C=NC(NC=3C(N(C)C=C(C=3)C=3C(=C(N4C(C5=CC=6CC(C)(C)CC=6N5CC4)=O)N=CC=3)CO)=O)=CC=2)C)N1C1COC1 WNEODWDFDXWOLU-QHCPKHFHSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical group 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000011403 purification operation Methods 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- OMQSJNWFFJOIMO-UHFFFAOYSA-J zirconium tetrafluoride Chemical compound F[Zr](F)(F)F OMQSJNWFFJOIMO-UHFFFAOYSA-J 0.000 description 2
- CYJRNFFLTBEQSQ-UHFFFAOYSA-N 8-(3-methyl-1-benzothiophen-5-yl)-N-(4-methylsulfonylpyridin-3-yl)quinoxalin-6-amine Chemical compound CS(=O)(=O)C1=C(C=NC=C1)NC=1C=C2N=CC=NC2=C(C=1)C=1C=CC2=C(C(=CS2)C)C=1 CYJRNFFLTBEQSQ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000416536 Euproctis pseudoconspersa Species 0.000 description 1
- 229910017076 Fe Zr Inorganic materials 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000556720 Manga Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 241001676573 Minium Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000009982 effect on human Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- FZIONDGWZAKCEX-UHFFFAOYSA-N nitrogen triiodide Chemical compound IN(I)I FZIONDGWZAKCEX-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- OEBIHOVSAMBXIB-SJKOYZFVSA-N selitrectinib Chemical compound C[C@@H]1CCC2=NC=C(F)C=C2[C@H]2CCCN2C2=NC3=C(C=NN3C=C2)C(=O)N1 OEBIHOVSAMBXIB-SJKOYZFVSA-N 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Treating Waste Gases (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は有害ガスの浄化方法に関
し、さらに詳細には三弗化窒素など半導体製造工程で使
用され、また、使用中に生成する窒素弗化物の浄化方法
に関する。近年、三弗化窒素はシリコンやシリコン酸化
物などのドライエッチングに使用されたり、ＣＶＤ装置
のチャンバークリーニング用ガスとして使用されるなど
半導体工業の発展とともにその使用量が増加している。
このガスは水に対する溶解度は小さく、酸やアルカリと
もほとんど反応しないなど室温ではかなり安定である
が、許容濃度は１０ｐｐｍと報告されており、毒性が高
く、人体および環境に悪影響を与えるので、三弗化窒素
を含むガスは半導体製造工程などに使用後大気に放出す
るに先立って浄化する必要がある。また、三弗化窒素は
常温では安定であるが、エッチングやクリーニング工程
中に熱、放電などにより、四弗化二窒素、二弗化二窒
素、六弗化二窒素、弗素などを生成し、これらは三弗化
窒素よりも毒性が強いため、三弗化窒素と同様に除去し
なければならない。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for purifying harmful gases, and more particularly to a method for purifying nitrogen fluoride used in a semiconductor manufacturing process such as nitrogen trifluoride and generated during use. In recent years, the use amount of nitrogen trifluoride has been increasing with the development of the semiconductor industry, such as being used for dry etching of silicon or silicon oxide, or used as a gas for cleaning a chamber of a CVD apparatus.
This gas has a low solubility in water and is quite stable at room temperature, as it hardly reacts with acids or alkalis. However, its allowable concentration is reported as 10 ppm, it is highly toxic and has a bad effect on human bodies and the environment. It is necessary to purify a gas containing nitrogen iodide before releasing it to the atmosphere after use in a semiconductor manufacturing process or the like. Also, although nitrogen trifluoride is stable at room temperature, it generates dinitrogen tetrafluoride, dinitrogen difluoride, dinitrogen hexafluoride, fluorine, etc. by heat and discharge during the etching and cleaning steps, These are more toxic than nitrogen trifluoride and must be removed as well as nitrogen trifluoride.
【０００２】[0002]
【従来の技術】ガス中に含有される窒素弗化物を除去す
る方法として、従来より、１００℃以上の温度で金属
シリコンと接触させる方法（特開昭６３−１２３２
２）、２００℃以上の温度で金属チタンと接触させる
方法（特公昭６３−４８５７１）、Ｓｉ、Ｂ、Ｗ、Ｍ
ｏ、Ｖ、Ｓｅ、Ｔｅ、Ｇｅまたはこれらの非酸化物系化
合物と２００〜８００℃で接触させる方法（特公昭６３
−４８５７０）、三弗化窒素とハロゲン交換し得る金
属ハロゲン化物と接触させる方法（特公昭６３−４８５
６９）、Ｆｅ、Ｍｎ、Ｃｕなどの遷移金属の酸化物と
２５０℃以上の温度で接触させる方法（特開平３−１８
１３１６）、活性炭と３００〜６００℃で接触させる
方法（特開昭６２−２３７９２９）、Ｎｉ、Ｆｅ、Ｃ
ｏまたはＰｔ、Ｒｈ、Ｐｄなどの貴金属とアルミナおよ
びシリカの少なくとも１種を主成分とする物質を２００
℃以上の温度で接触させる方法（特開昭６２−２７３０
３９）などが提案されている。2. Description of the Related Art As a method of removing nitrogen fluoride contained in a gas, a method of contacting with metal silicon at a temperature of 100 ° C. or higher has conventionally been used (Japanese Patent Laid-Open No. 63-1232).
2), a method of contacting with metallic titanium at a temperature of 200 ° C. or more (JP-B-63-48571), Si, B, W, M
o, V, Se, Te, Ge or a non-oxide compound thereof at 200 to 800 ° C. (JP-B-63)
-48570), a method of contacting with a metal halide capable of halogen exchange with nitrogen trifluoride (JP-B-63-485).
69), a method of contacting with an oxide of a transition metal such as Fe, Mn, or Cu at a temperature of 250 ° C. or higher (JP-A-3-18
1316), a method of contacting with activated carbon at 300 to 600 ° C. (JP-A-62-237929), Ni, Fe, C
o or a noble metal such as Pt, Rh, Pd and a substance mainly composed of at least one of alumina and silica.
Contacting at a temperature of at least ℃ (JP-A-62-2730)
39) have been proposed.
【０００３】[0003]
【発明が解決しようとする課題】しかしながら、上記の
方法ではいずれも浄化能力が小さいばかりでなく、、
、の方法に関しては揮発性の弗化物が、の方法で
は塩素などハロゲンが、の方法では窒素酸化物がそれ
ぞれ発生し、それらの処理にコストがかかるという問題
や、、の方法では生成した弗化物が反応剤の表面を
覆って反応を阻害しないように３００℃以上に加熱する
必要がある。また、の方法は反応が激しく、また、高
温下で行われるため爆発の危険を伴うことや、比較的安
定で除去の難しい四弗化炭素が副生するという問題があ
る。さらに、の金属を用いる方法では有害ガスは副生
しないものの、十分な浄化能力を得るためには高温にし
なければならず、例えばニッケルの場合は２００℃程度
の温度では分解活性が低く、実用となるような能力を得
るためには４００℃程度以上に加熱する必要があり、さ
らに、反応の進行とともに反応剤の表面が弗化物に覆わ
れるため、十分な能力が得られない。However, all of the above methods not only have low purifying ability, but also
In the methods (1) and (2), volatile fluorides are generated, in the method (2) halogens such as chlorine are generated, and in the method (2), nitrogen oxides are generated. Must be heated to 300 ° C. or more so as not to cover the surface of the reactant and hinder the reaction. In addition, the method has a problem that the reaction is violent and that the reaction is performed at a high temperature, which may cause explosion, and that carbon tetrafluoride which is relatively stable and difficult to remove is produced as a by-product. Further, although no harmful gas is produced as a by-product in the method using metal, the temperature must be raised to obtain a sufficient purification ability. For example, nickel has low decomposition activity at a temperature of about 200 ° C. In order to obtain such a capability, it is necessary to heat to about 400 ° C. or higher, and further, the surface of the reactant is covered with fluoride as the reaction proceeds, so that sufficient capability cannot be obtained.
【０００４】[0004]
【課題を解決するための手段】本発明者らは、これら従
来技術の欠点を解決し、有害ガスや環境汚染の恐れのあ
るガスを生成することなく、窒素弗化物に対し、低温で
高い処理能力を得るための浄化方法を得るべく鋭意検討
を重ねた結果、４０重量％以上のジルコニウムを含むジ
ルコニウム系合金を浄化剤として用いることによって、
比較的低温で窒素弗化物を極めて効率良く除去し、か
つ、窒素弗化物を浄化した後のガス中には環境に悪影響
を及ぼすような物質が発生しないことを見い出し、本発
明を完成した。すなわち本発明は、 有害成分となる窒
素弗化物を含有するガスを、４０重量％以上のジルコニ
ウムと、その残部が、鉄、銅、銀、ニッケル、コバル
ト、マンガン、マグネシウム、カルシウム、亜鉛、アル
ミニウム、ランタン、セリウム、バナジウム、モリブデ
ン、チタン、クロム、タングステン、タンタル、ニオ
ブ、及び錫から選ばれる１種または２種以上の金属元素
で構成されるジルコニウム系合金からなる浄化剤と、加
熱下に接触させて、該有害成分を除去することを特徴と
する有害ガスの浄化方法である。本発明によれば空気、
窒素、アルゴンおよび水素中などに含有される三弗化窒
素を始め、四弗化二窒素、二弗化二窒素、六弗化二窒素
などその他の窒素弗化物をも効率良く除去することがで
きる。SUMMARY OF THE INVENTION The present inventors have solved the above-mentioned drawbacks of the prior art and have developed a method for treating nitrogen fluoride at a low temperature without producing harmful gas or gas which may cause environmental pollution. As a result of intensive studies to obtain a purification method for obtaining the ability, by using a zirconium-based alloy containing 40% by weight or more of zirconium as a purifying agent,
The present inventors have found that nitrogen fluoride is removed very efficiently at a relatively low temperature, and that no substance that adversely affects the environment is generated in the gas after purifying the nitrogen fluoride, thereby completing the present invention. That is, the present invention provides a gas containing nitrogen fluoride, which is a harmful component, containing at least 40% by weight of zirconia.
And the rest are iron, copper, silver, nickel,
G, manganese, magnesium, calcium, zinc, al
Minium, lanthanum, cerium, vanadium, molybdenum
, Titanium, chromium, tungsten, tantalum, nio
, And one or more metal elements selected from tin
A purifying agent composed of a zirconium-based alloy composed of
It is characterized by contacting under heat to remove the harmful components
This is a method for purifying harmful gases . Air according to the invention,
Efficient removal of other nitrogen fluorides such as nitrogen trifluoride, dinitrogen tetrafluoride, dinitrogen difluoride, dinitrogen hexafluoride, including nitrogen, argon and hydrogen. .
【０００５】本発明における浄化剤として、ジルコニウ
ム系合金が用いられる。[0005] As a purifying agent in the present invention, a zirconium-based alloy is used.
【０００６】本発明におけるジルコニウム系合金として
は、ジルコニウムと４０重量％以上のジルコニウムと、
その残部が、鉄、銅、銀、ニッケル、コバルト、マンガ
ン、マグネシウム、カルシウム、亜鉛、アルミニウム、
ランタン、セリウム、バナジウム、モリブデン、チタ
ン、クロム、タングステン、タンタル、ニオブ、及び錫
から選ばれる１種または２種以上の金属元素とからなる
合金である。これらのうちでも窒素弗化物との反応中に
揮発性の弗化物を生成しないこと、比較的安価で入手が
容易なことなどからジルコニウムと鉄、銅、ニッケル、
アルミニウム、マグネシウム、カルシウム、亜鉛、ラン
タン、セリウムからなる合金が好ましい。 The zirconium-based alloy according to the present invention includes zirconium, zirconium of 40% by weight or more,
The rest is iron, copper, silver, nickel, cobalt, manga
Magnesium, calcium, zinc, aluminum,
Lanthanum, cerium, vanadium, molybdenum, titanium
An alloy comprising one or more metal elements selected from the group consisting of chromium, chromium, tungsten, tantalum, niobium, and tin . Of these, zirconium and iron, copper, nickel, and the like do not generate volatile fluoride during the reaction with nitrogen fluoride, and are relatively inexpensive and easily available.
Alloys consisting of aluminum, magnesium, calcium, zinc, lanthanum and cerium are preferred.
【０００７】本発明において、窒素弗化物の除去作用は
主にジルコニウム成分によるものであり、このことは浄
化操作中に浄化剤と窒素弗化物との反応によって生成し
てくる粉状物を分析すると主として弗化ジルコニウムで
あることで裏付けられる。それ故、ジルコニウム含有量
が多くなる程単位重量当たりの浄化能力は大きくなる
が、ジルコニウム以外の金属成分は窒素弗化物の除去温
度を低下させる効果を有し、これらの金属を適度に含有
させることによって浄化反応温度を下げる点で優れた効
果が得られる。すなわち、ジルコニウム単体では実用と
なる浄化能力を得るためには３００℃程度の温度が必要
であるのに対し、合金の場合には同じ濃度、流量のガス
を処理する場合にこれよりも低い温度で処理することが
可能であり、例えば、ジルコニウム以外の金属の含有量
を４０重量％以下で選択することによって１７０〜２５
０℃のような低い温度でも実用的な浄化能力が得られ
る。In the present invention, the action of removing nitrogen fluoride is mainly due to the zirconium component. This is based on the analysis of powdery substances generated by the reaction between the cleaning agent and nitrogen fluoride during the cleaning operation. This is supported by the fact that it is mainly zirconium fluoride. Therefore, the purifying capacity per unit weight increases as the zirconium content increases, but metal components other than zirconium have the effect of lowering the removal temperature of nitrogen fluoride, and these metals should be contained appropriately. Thereby, an excellent effect in lowering the purification reaction temperature can be obtained. That is, a temperature of about 300 ° C. is required to obtain a purifying ability that can be practically used with zirconium alone, while a temperature lower than this is required when processing a gas having the same concentration and flow rate in the case of an alloy. For example, by selecting the content of a metal other than zirconium at 40% by weight or less, 170 to 25% can be used.
Practical purification ability can be obtained even at a low temperature such as 0 ° C.
【０００８】本発明において、浄化剤中のジルコニウム
の含有量は４０重量％以上であるが、好ましくは６０重
量％以上で残部が前記した金属元素である。ジルコニウ
ムが４０重量％よりも少ないと窒素弗化物の除去容量が
小さく、かつ、合金化による浄化温度の低下効果が小さ
くなるばかりでなく、条件によっては揮発性弗化物が副
生する恐れもある。[0008] In the present invention, the content of zirconium in the cleaning agent is 40 wt% or more, preferably metallic element the balance described above with 60% by weight or more. If the amount of zirconium is less than 40 % by weight, not only the capacity for removing nitrogen fluoride is small and the effect of lowering the purification temperature by alloying is reduced, but also volatile fluoride may be produced as a by-product depending on conditions. .
【０００９】ジルコニウム系合金を得るには、ジルコニ
ウムに前記のその他の金属の１種または２種以上を所定
の混合比率に混合した後、電子ビーム溶解、アルゴンア
ーク溶解、真空あるいは不活性ガス雰囲気での高周波加
熱溶解、抵抗加熱溶解などにより合金化することができ
る。得られた合金は、ボールミル、ジョークラッシャ
ー、ロールミルなどの機械的粉砕により６〜２０メッシ
ュ程度に粉砕して用いるか、あるいは１００メッシュ程
度の微細粒とした後に粒径１〜５ｍｍ程度の粒状、顆粒
状として、または微細粒としたものをペレット状などに
成型した形態で浄化剤として使用される。また、種々の
ジルコニウム系合金も市販されているので、これらをそ
のまま、あるいは適当な大きさに破砕するなどして用い
てもよい。In order to obtain a zirconium-based alloy, zirconium is mixed with one or more of the above-mentioned other metals at a predetermined mixing ratio, and then melted by electron beam, argon arc, vacuum or an inert gas atmosphere. Can be alloyed by high-frequency heating melting or resistance heating melting. The obtained alloy is used after being pulverized to about 6 to 20 mesh by mechanical pulverization using a ball mill, jaw crusher, roll mill, or the like, or after being made into fine particles of about 100 mesh, granules or granules having a particle size of about 1 to 5 mm. It is used as a purifying agent in the form of particles or in the form of fine particles molded into pellets or the like. Also, various zirconium-based alloys are commercially available, and may be used as they are or by crushing them to an appropriate size.
【００１０】本発明において、ジルコニウム系合金から
なる浄化剤は固定床として用いられる他、移動床、流動
床として用いることも可能である。通常は浄化剤は浄化
筒内に充填され、窒素弗化物を含有するガスはこの浄化
筒内に流され、浄化剤と接触させることにより、有害成
分である窒素弗化物が除去され、被処理ガスは浄化され
る。被処理ガスとの接触温度は、通常は１００〜８００
℃、好ましくは１５０〜５００℃、さらに好ましくは１
５０〜３００℃である。温度が１００℃よりも低いと窒
素弗化物の除去能力が低下し、また、温度が８００℃よ
りも高くなると浄化筒にステンレス鋼が使用できなくな
り、安全性が低下するばかりでなく、加熱エネルギーロ
スも大きくなる。なお、処理ガス中に大気成分が混入す
るような場合には、加熱温度が高くなると酸素と浄化剤
が反応して発熱を生ずる恐れがあるため、このような場
合には、浄化操作は２５０℃以下のような温度に保って
おこなうことが好ましい。浄化操作時の圧力は通常は常
圧であるが、減圧乃至１ｋｇ／ｃｍ2 Ｇのような加圧下
で操作することも可能である。In the present invention, the purifying agent composed of a zirconium-based alloy can be used not only as a fixed bed but also as a moving bed or a fluidized bed. Normally, a purifying agent is filled in a purifying column, and a gas containing nitrogen fluoride is flowed into the purifying column, and by contacting the purifying agent with the purifying agent, nitrogen fluoride as a harmful component is removed. Is purified. The contact temperature with the gas to be treated is usually 100 to 800.
° C, preferably 150 to 500 ° C, more preferably 1
50-300 ° C. If the temperature is lower than 100 ° C., the ability to remove nitrogen fluoride is reduced, and if the temperature is higher than 800 ° C., stainless steel cannot be used for the purifying column, and not only safety is reduced, but also heating energy loss occurs. Also increases. In the case where atmospheric components are mixed in the processing gas, if the heating temperature is increased, oxygen and the purifying agent may react to generate heat. In such a case, the purifying operation is performed at 250 ° C. It is preferable to carry out the treatment at the following temperature. The pressure during the purification operation is usually normal pressure, but it is also possible to operate under reduced pressure or a pressurized pressure such as 1 kg / cm 2 G.
【００１１】本発明の浄化方法が適用される被処理ガス
の流速には特に制限はないが、一般に被処理ガス中に含
有される窒素弗化物の濃度が高いほど流速を小さくする
ことが望ましい。浄化筒は有害ガスである窒素弗化物の
濃度、処理対象ガスの量などに応じて設計されるが、例
えば、窒素弗化物の濃度が１０００ｐｐｍ以下のように
低い場合には、空筒線速度（ＬＶ）は２０ｃｍ／ｓｅｃ
以下であり、それよりも高い濃度の場合は５ｃｍ／ｓｅ
ｃ以下の範囲で設計することが望ましい。浄化筒内の浄
化剤の充填長はガスの流量および有害ガスの濃度などに
よって異なり一概に特定はできないが、実用上通常は、
５０〜５００ｍｍ程度とされる。一般的にはこれらは充
填層の圧力損失、ガスの接触効率および有害ガスの濃度
などによって定められる。Although the flow rate of the gas to be treated to which the purification method of the present invention is applied is not particularly limited, it is generally desirable to reduce the flow rate as the concentration of nitrogen fluoride contained in the gas to be treated becomes higher. The purifying cylinder is designed in accordance with the concentration of the harmful gas nitrogen fluoride, the amount of the gas to be treated, and the like. For example, when the concentration of the nitrogen fluoride is as low as 1000 ppm or less, the linear velocity of the empty cylinder ( LV) is 20 cm / sec
Or less, and 5 cm / sec for a higher concentration
It is desirable to design within the range of c or less. The filling length of the purifying agent in the purifying column differs depending on the gas flow rate and the concentration of harmful gas, and cannot be specified unconditionally.
It is about 50 to 500 mm. Generally, these are determined by the pressure loss of the packed bed, the gas contact efficiency, the concentration of harmful gas, and the like.
【００１２】なお、本発明において、浄化操作中に反応
によって前記したように弗化ジルコニウムが生成し、こ
れらの粉末は処理ガスとともに外部に排出されるか、あ
るいは、筒の下部に落下するが、条件によってはその一
部が浄化剤充填部に残留して圧力損失が上昇することが
ある。このような場合には浄化筒にバイブレータなどを
取り付けて連続的または断続的に振動を与えることによ
って、粉末は筒の下部に落下し、圧力損失の上昇を防止
することができる。また、必要に応じ、排出ガス中の粉
末を捕捉するためのフィルターを浄化筒の下流側に設け
てもよい。In the present invention, zirconium fluoride is produced by the reaction during the purification operation as described above, and these powders are discharged to the outside together with the processing gas or fall to the lower part of the cylinder. Depending on the conditions, a part of the pressure may be left in the purifier-filled portion to increase the pressure loss. In such a case, by attaching a vibrator or the like to the purification cylinder and continuously or intermittently applying vibration, the powder falls to the lower part of the cylinder, and it is possible to prevent an increase in pressure loss. If necessary, a filter for capturing the powder in the exhaust gas may be provided on the downstream side of the purification column.
【００１３】実施例１ 市販のＺｒ−Ｆｅ合金（ジルコニウム８０重量％、残部
鉄）の破砕品を振るい分けて得た１０〜３２メッシュの
ものを用いた。このもの２８．３ｍｌを内径１９ｍｍ、
長さ４００ｍｍの石英製の浄化筒に充填した。この浄化
筒にＮＦ3 を１％含有するＨｅを、室温、常圧下で８５
ｍｌ／ｍｉｎ（空筒線速度ＬＶ＝０．５ｃｍ／ｓｅｃ）
の流量で流通させ、２０分後に浄化筒出口ガス中のＮＦ
3 濃度をガスクロマトグラフ法（検出下限１０ｐｐｍ）
によって分析した。その後、５０℃ずつ昇温し、それぞ
れの温度で１０分間保持した後、浄化筒出口ガス中のＮ
Ｆ3 濃度をガスクロマトグラフ法で測定することにより
各温度におけるＮＦ3 分解率を求めた。このようにして
得たデータの作図から三弗化窒素の分解率が９０％を超
る温度の下限を内挿により求めた。結果を表１に示す。Embodiment1 Commercially available Zr—Fe alloy (zirconium 80% by weight, balance
10) to 32 mesh obtained by crushing iron)
Was used. 28.3 ml of this was 19 mm in inner diameter,
It was filled in a 400 mm long quartz purifying cylinder. This purification
NF on tubeThree At room temperature under normal pressure is 85%.
ml / min (Vacuum linear velocity LV = 0.5 cm / sec)
20 minutes later, the NF in the gas at the outlet of the purification column
Three Gas chromatographic method (detection lower limit: 10 ppm)
Was analyzed by Then, raise the temperature by 50 ° C,
After holding at this temperature for 10 minutes, the N
FThree By measuring the concentration by gas chromatography
NF at each temperatureThree The decomposition rate was determined. Like this
From the plot of the obtained data, the decomposition rate of nitrogen trifluoride exceeds 90%
The lower limit of the temperature was determined by interpolation. Table 1 shows the results.
【００１４】また、この浄化剤８．５ｍｌを上記と同様
の浄化筒に充填して、Ｈｅを５００ｍｌ／ｍｉｎの流量
で流通させながら２００℃に昇温した後、ＮＦ3 を２％
含有するＨｅを、常圧下で５０９ｍｌ／ｍｉｎ（ＬＶ＝
３ｃｍ／ｓｅｃ）の流量で流通させ、出口ガスを市販の
ＮＦ3 検知器（ＴＧ−４１００ＴＡ、バイオニクス機器
（株）製）によりモニターし、出口ガス中のＮＦ3 濃度
が１０ｐｐｍに達した点を破過点として、破過までの時
間を測定した。その結果から計算により浄化能力〔合金
１Ｌ当たりに対する三弗化窒素の処理量（Ｌ）〕を求め
た。また、副生物発生の有無を見るために破過前に出口
ガス中の一酸化窒素（ＮＯ）、二酸化窒素（ＮＯ2 ）を
検知管（窒素酸化物分離定量用、検出下限 ＮＯ １ｐ
ｐｍ、ＮＯ2 ０．５ｐｐｍ（株）ガステック製）により
測定した。結果を表２に示す。Further, the cleaning agent 8.5ml and filled in the cleaning column similar to that described above, after the temperature of the He to 200 ° C. while flowing at a flow rate of 500 ml / min, NF 3 2%
The content of He was 509 ml / min under normal pressure (LV =
3 cm / sec), and the outlet gas was monitored by a commercially available NF 3 detector (TG-4100TA, manufactured by Bionics Instruments Co., Ltd.). The point at which the NF 3 concentration in the outlet gas reached 10 ppm was measured. The time to breakthrough was measured as a breakthrough point. From the results, the purifying ability [processing amount (L) of nitrogen trifluoride per liter of alloy] was calculated. In addition, in order to check for the generation of by-products, a detection tube (for nitrogen oxide separation and quantification, lower detection limit 1p) is used to detect nitrogen monoxide (NO) and nitrogen dioxide (NO 2 ) in the outlet gas before breakthrough.
pm, NO 2 0.5 ppm (manufactured by Gastech Co., Ltd.). Table 2 shows the results.
【００１５】実施例２〜４ 市販の、スポンジジルコニウムと還元鉄を用い、各種の
組成（ジルコニウム９０、５０および４０重量％、残部
鉄）になるようにジルコニウムと鉄を全量で約５００ｇ
となるように混合した後、電子ビーム溶解を２回繰り返
して得たＺｒ−Ｆｅ合金をボールミル中で粉砕し、１４
〜２０メッシュのものを振るい分けて組成割合の異なる
各種の合金を準備した。これら合金を用い、実施例１と
同様にして浄化実験をおこなった。結果を表１および表
２に示す。Embodiment2~4 Using commercially available sponge zirconium and reduced iron, various
Composition (90, 50 and 40% by weight of zirconium, balance
About 500g zirconium and iron in total so that it becomes iron)
And then repeat the electron beam melting twice
The Zr-Fe alloy obtained in the above was crushed in a ball mill,
~ 20 meshes are screened and the composition ratio is different
Various alloys were prepared. Example using these alloys1When
A purification experiment was performed in the same manner. Table 1 and Table
It is shown in FIG.
【００１６】比較例１ 市販の鉄線（直０．３ｍｍ）を長さ５〜１０ｍｍに切断
したものを用いた他は実施例１におけると同様にして実
験をおこなった。結果を表１、表２に示す。Comparative Example 1 An experiment was conducted in the same manner as in Example 1 except that a commercially available iron wire (straight 0.3 mm) cut into a length of 5 to 10 mm was used. The results are shown in Tables 1 and 2.
【００１７】[0017]
【表１】 表 １ 合金の組成比（ｗｔ％） ９０％以上 Ｆｅ Ｚｒ 分解下限温度 実施例１ ２０ ８０ １９５ 実施例２ １０ ９０ １９５ 実施例３ ５０ ５０ ２４５ 実施例４ ６０ ４０ ２５０ 比較例１ １００ ０ ３２５Table 1 Composition ratio (wt%) of alloy 90% or more Fe Zr decomposition lower limit temperature Example 1 20 80 195 Example 2 10 90 195 Example 3 50 50 245 Example 4 60 40 250 Comparative example 1 100 0 325
【００１８】[0018]
【表２】 表 ２ 浄化温度 浄化能力 窒素酸化物 （℃） （Ｌ／Ｌ） 実施例１ ２００ ５９４ ＮＤ 実施例２ ２００ ＞１００ ＮＤ 実施例３ ２５０ ＞１００ ＮＤ 実施例４ ２８０ ＞１００ ＮＤ 比較例１ ３００ ３ ＮＤ ４００ ７ ＮＤTable 2 Purification temperature Purification ability Nitrogen oxide (° C) (L / L) Example 1 200 594 ND Example 2 200> 100 ND Example 3 250> 100 ND Example 4 280> 100 ND Comparative example 1 300 3 ND 400 7 ND
【００１９】実施例５〜１３ 市販の、スポンジジルコニウムと銅および銀を用い、種
々の組成（ジルコニウム４０、５０、７５、９０重量
％、残部銅または銀）になるようにジルコニウムと各金
属を全量で約５００ｇとなるように混合した後、電子ビ
ーム溶解を２回繰り返して得た合金をボールミル中で粉
砕し、１４〜２０メッシュのものを振るい分けて浄化用
の合金をそれぞれ得た。このもの２８．３ｍｌを内径１
９ｍｍ、長さ４００ｍｍの石英製の浄化筒に充填した。Embodiment5~13 Using commercially available sponge zirconium and copper and silver, seed
Various compositions (zirconium 40, 50, 75, 90 weight
%, With the balance being copper or silver) zirconium and each gold
After mixing the genus to a total amount of about 500 g,
The alloy obtained by repeating the melting process twice is powdered in a ball mill.
Crushed and sifted 14 to 20 mesh to purify
Were obtained respectively. 28.3 ml of this product with an inner diameter of 1
It was filled into a 9 mm, 400 mm long quartz purifying cylinder.
【００２０】これにＮＦ3 を１％含有するＨｅを、室
温、常圧下で８５ｍｌ／ｍｉｎ（空筒線速度ＬＶ＝０．
５ｃｍ／ｓｅｃ）の流量で流通させ、２０分後に浄化筒
出口ガス中のＮＦ3 濃度をガスクロマトグラフ法（検出
下限１０ｐｐｍ）によって分析した。その後１００℃ず
つ昇温を行い、それぞれの温度で１０分間保持した後、
浄化筒出口ガス中のＮＦ3 濃度をガスクロマトグラフ法
により測定することにより各温度におけるＮＦ3 分解率
を求めた。このようにして得たデータから分解率９０％
を超える温度を作図による内挿によって求めた。結果を
表３に示す。He containing 1% of NF 3 was added thereto at room temperature and atmospheric pressure at a flow rate of 85 ml / min (vacuum linear velocity LV = 0.
The gas was circulated at a flow rate of 5 cm / sec), and after 20 minutes, the NF 3 concentration in the outlet gas of the purification column was analyzed by gas chromatography (lower detection limit: 10 ppm). After that, the temperature was increased by 100 ° C., and held at each temperature for 10 minutes.
The NF 3 decomposition rate at each temperature was determined by measuring the NF 3 concentration in the gas at the outlet of the purification column by gas chromatography. From the data thus obtained, a decomposition rate of 90%
Were determined by interpolation by plotting. Table 3 shows the results.
【００２１】次に、これらの浄化剤８．５ｍｌを同様な
浄化筒に充填してＨｅを５００ｍｌ／ｍｉｎの流量で流
通させながら表４に示す温度に各々の浄化筒を昇温させ
た後、ＮＦ3 を２％含有するＨｅを、常圧下で５０９ｍ
ｌ／ｍｉｎ（ＬＶ＝３ｃｍ／ｓｅｃ）の流量で流通さ
せ、出口ガスを市販のＮＦ3 検知器（ＴＧ−４１００Ｔ
Ａ、バイオニクス機器（株）製）によりモニターし、出
口ガス中のＮＦ3 濃度が１０ｐｐｍに達した時点を破過
点として浄化能力（合金１Ｌ当たりのＮＦ3 除去量
（Ｌ））を求めた。また、破過前に出口ガス中の一酸化
窒素（ＮＯ）、二酸化窒素（ＮＯ2 ）濃度を検知管（窒
素酸化物分離定量用、検出下限 ＮＯ；１ｐｐｍ、ＮＯ
2 ；０．５ｐｐｍ、ガステック社製）により測定した。
結果を表４に示す。Next, 8.5 ml of these purifying agents are filled in the same purifying cylinder, and each purifying cylinder is heated to a temperature shown in Table 4 while flowing He at a flow rate of 500 ml / min. 509 m of He containing 2% of NF 3 under normal pressure
1 / min (LV = 3 cm / sec), and the outlet gas is supplied to a commercially available NF 3 detector (TG-4100T).
A, manufactured by Bionics Instruments Co., Ltd.), and the purifying capacity (the amount of NF 3 removed (L) per liter of alloy (L)) was determined as the breakthrough point when the NF 3 concentration in the outlet gas reached 10 ppm. . Before the breakthrough, the concentration of nitric oxide (NO) and nitrogen dioxide (NO 2 ) in the outlet gas was measured using a detector tube (for nitrogen oxide separation and quantification, detection lower limit NO; 1 ppm, NO
2 ; 0.5 ppm, manufactured by Gastech Co., Ltd.).
Table 4 shows the results.
【００２２】比較例２、３ 市販の銅線（φ０．５ｍｍ）を５〜１０ｍｍに切断した
ものを集めたもの、市販の電解銀（３０〜４０メッシ
ュ）をそれぞれ用いて実施例５におけると同様にして実
験をおこなった。結果を表３および表４に示す。[0022] A collection of those cut Comparative Examples 2 and 3 commercially available copper wire (0.5 mm in diameter) to 5 to 10 mm, as in a commercial electroless silver (30-40 mesh) in Example 5 using the respective The experiment was performed. The results are shown in Tables 3 and 4.
【００２３】[0023]
【表３】 表 ３ 合金の組成比（重量％） ９０％以上 Ｚｒ Ｃｕ Ａｇ 分解下限温度（℃） 実施例５ ４０ ６０ ０ ２３５ 実施例６ ５０ ５０ ０ ２３５ 実施例７ ７５ ２５ ０ ２２０ 実施例８ ９０ １０ ０ ２２５ 実施例９ ４０ ０ ６０ ２６０ 実施例１０ ５０ ０ ５０ ２５５ 実施例１１ ７５ ０ ２５ ２３５ 実施例１２ ９０ ０ １０ ２５０ 実施例１３ ７５ １５ １０ ２２５ 比較例２ ０ １００ ０ ３３５ 比較例３ ０ ０ １００ ４３０Table 3 Composition ratio (% by weight) of alloy 90% or more ZrCuAg Decomposition lower limit temperature (° C.) Example 5 40 60 0 235 Example 6 50 50 0 235 Example 7 75 25 0 220 Example 8 90 10 0 225 Example 9 40 0 60 260 Example 10 50 0 50 255 Example 11 75 0 25 235 Example 12 90 0 10 250 Example 13 75 15 10 225 Comparative Example 2 0 100 0 335 Comparative Example 30 0 100 430
【００２４】[0024]
【表６】 表 ４ 浄化温度 浄化能力 窒素酸化物 （℃） （Ｌ／Ｌ） 実施例５ ２８０ ＞１００ ＮＤ 実施例６ ２５０ ＞１００ ＮＤ 実施例７ ２３０ ５６８ ＮＤ 実施例８ ２３０ ＞１００ ＮＤ 実施例９ ２８０ ＞１００ ＮＤ 実施例１０ ２８０ ＞１００ ＮＤ 実施例１１ ２５０ ＞１００ ＮＤ 実施例１２ ２６０ ＞１００ ＮＤ 実施例１３ ２５０ ＞１００ ＮＤ 比較例２ ３５０ １９ ＮＤ 比較例３ ５００ ８ ＮＤTable 4 Purification temperature Purification temperature Nitrogen oxide (° C) (L / L) Example 5 280> 100 ND Example 6 250> 100 ND Example 7 230 568 ND Example 8 230> 100 ND Example 9 280> 100 ND Example 10 280> 100 ND Example 11 250> 100 ND Example 12 260> 100 ND Example 13 250> 100 ND Comparative Example 2 350 19 ND Comparative Example 3 500 8 ND
【００２５】実施例１４〜２７ 市販の、スポンジジルコニウムとニッケル、コバルトま
たはマンガンを用い、種々の組成（ジルコニウム４０、
５０、７５、９０重量％、残部Ｎｉ、ＣｏまたはＭｎ）
になるようにジルコニウムとその他の金属を全量で約５
００ｇとなるように混合した後、電子ビーム溶解を２回
繰り返して得た合金をボールミル中で粉砕し、１４〜２
０メッシュのものを振るい分けて浄化用の合金をそれぞ
れ得た。このもの２８．３ｍｌを内径１９ｍｍ、長さ４
００ｍｍの石英製の浄化筒に充填した。Embodiment14~27 Commercially available sponge zirconium and nickel, cobalt
Or manganese, various compositions (zirconium 40,
50, 75, 90% by weight, balance Ni, Co or Mn)
Zirconium and other metals in a total amount of about 5
After mixing to give a volume of 00 g, melt the electron beam twice
The alloy obtained repeatedly was pulverized in a ball mill,
Separate 0 mesh mesh and purify the alloy for purification
I got it. 28.3 ml of this product was 19 mm in inner diameter and 4 in length.
It was filled into a 00 mm quartz purification column.
【００２６】それぞれの浄化剤について、実施例１にお
けると同様にして分解率９０％になる温度、浄化能力お
よび窒素酸化物の測定をおこなった。それぞれの結果を
表５および表６に示す。For each of the purifying agents, the temperature, the purifying ability and the nitrogen oxides at which the decomposition rate was 90% were measured in the same manner as in Example 1 . Tables 5 and 6 show the results.
【００２７】比較例４〜６ 市販の、ニッケル、コバルト、マンガンをそれぞれ振る
い分けて得た６〜３２メッシュのものを用いて実施例１
４と同様にして実験をおこなった。結果を表５および表
６に示す。Comparative Examples 4 to 6 Examples 1 to 6 were obtained using commercially available 6 to 32 mesh meshes obtained by sieving nickel, cobalt and manganese.
The experiment was performed in the same manner as in Example 4 . The results are shown in Tables 5 and 6.
【００２８】[0028]
【表５】 表 ５ 合金の組成比（重量％） ９０％以上 Ｚｒ Ｎｉ Ｃｏ Ｍｎ 分解下限温度（℃） 実施例１４ ４０ ６０ ０ ０ ２４０ 実施例１５ ５０ ５０ ０ ０ ２２０ 実施例１６ ７５ ２５ ０ ０ ２０５ 実施例１７ ９０ １０ ０ ０ ２０５ 実施例１８ ４０ ０ ６０ ０ ２６０ 実施例１９ ５０ ０ ５０ ０ ２４０ 実施例２０ ７５ ０ ２５ ０ ２２５ 実施例２１ ９０ ０ １０ ０ ２２５ 実施例２２ ４０ ０ ０ ６０ ２６５ 実施例２３ ５０ ０ ０ ５０ ２４５ 実施例２４ ７５ ０ ０ ２５ ２４５ 実施例２５ ９０ ０ ０ １０ ２４０ 実施例２６ ７５ １５ １０ ０ ２１０ 実施例２７ ９０ ５ ０ ５ ２１５ 比較例４ ０ １００ ０ ０ ２９０ 比較例５ ０ ０ １００ ０ ３１５ 比較例６ ０ ０ ０ １００ ３４０Table 5 Composition ratio of alloy (% by weight) 90% or more ZrNiCoMn Decomposition lower limit temperature (° C) Example 14 40 600 0 240 Example 15 50 50 00 220 Example 16 75 25 00 205 Example 17 90 10 00 205 Example 18 40 0 60 0 260 Example 19 50 0 50 0 240 Example 20 75 0 25 0 225 Example 21 90 0 10 0 225 Example 22 40 0 0 60 265 Example Example 23 50 00 50 245 Example 24 75 0 0 25 245 Example 25 90 0 0 10 240 Example 26 75 15 10 0 210 Example 27 90 5 0 5 215 Comparative Example 4 0 100 0 0 290 Comparative Example 5 0 0 100 0 315 Comparative Example 6 0 0 0 100 340
【００２９】[0029]
【表６】 表 ６ 浄化温度 浄化能力 窒素酸化物 （℃） （Ｌ／Ｌ） 実施例１４ ２８０ ＞１００ ＮＤ 実施例１５ ２５０ ＞１００ ＮＤ 実施例１６ ２１０ ５０４ ＮＤ 実施例１７ ２１０ ＞１００ ＮＤ 実施例１８ ２８０ ＞１００ ＮＤ 実施例１９ ２５０ ＞１００ ＮＤ 実施例２０ ２４０ ＞１００ ＮＤ 実施例２１ ２４０ ＞１００ ＮＤ 実施例２２ ２８０ ＞１００ ＮＤ 実施例２３ ２８０ ＞１００ ＮＤ 実施例２４ ２５０ ＞１００ ＮＤ 実施例２５ ２５０ ＞１００ ＮＤ 実施例２６ ２１０ ＞１００ ＮＤ 実施例２７ ２１５ ＞１００ ＮＤ 比較例４ ３００ １７ ＮＤ 比較例５ ３３０ １０ ＮＤ 比較例６ ３５０ １１ ＮＤTable 6 Purification temperature Purification capacity Nitrogen oxide (° C) (L / L) Example 14 280> 100 ND Example 15 250> 100 ND Example 16 210 504 ND Example 17 210> 100 ND Example 18 280> 100 ND Example 19 250> 100 ND Example 20 240> 100 ND Example 21 240> 100 ND Example 22 280> 100 ND Example 23 280> 100 ND Example 24 250> 100 ND Example 25 250> 100 ND Example 26 210> 100 ND Example 27 215> 100 ND Comparative Example 4 300 17 ND Comparative Example 5 330 10 ND Comparative Example 6 350 11 ND
【００３０】実施例２８〜４９ 市販の、スポンジジルコニウムとマグネシウム、カルシ
ウム、亜鉛、アルミニウム、ランタンまたはセリウムを
用い、種々の組成（ジルコニウム４０、５０、７５、９
０重量％、残部Ｍｇ、Ｃａ、Ｚｎ、Ａｌ、ＬａまたはＣ
ｅ）になるようにジルコニウムと各金属を全量で約５０
０ｇとなるように混合した後、電子ビーム溶解を２回繰
り返して得た合金をボールミル中で粉砕し、１４〜２０
メッシュのものを振るい分けて浄化用の合金を得た。Example28~49 Commercially available sponge zirconium and magnesium, calcium
, Zinc, aluminum, lanthanum or cerium
Used, various compositions (zirconium 40, 50, 75, 9
0% by weight, balance Mg, Ca, Zn, Al, La or C
e) zirconium and each metal in a total amount of about 50
After mixing to 0 g, the electron beam melting was repeated twice.
The obtained alloy is pulverized in a ball mill, and
The mesh was sifted to obtain an alloy for purification.
【００３１】それぞれの浄化剤について、実施例１にお
けると同様にして分解率９０％になる温度、浄化能力お
よび窒素酸化物の測定をおこなった。それぞれの結果を
表７および表８に示す。For each of the purifying agents, the temperature, the purifying ability, and the nitrogen oxides at which the decomposition rate was 90% were measured in the same manner as in Example 1 . Tables 7 and 8 show the results.
【００３２】比較例７〜１１ 市販の、砂状マグネシウム、粒状カルシウム、粒状亜鉛
（粒径１〜２ｍｍ）、粒状アルミニウム（粒径２〜３ｍ
ｍ）、粒状セリウム（粒径１〜２ｍｍ）を用いて実施例
２８と同様にして実験をおこなった。結果を表７、表８
に示す。Comparative Examples 7-11 Commercially available sandy magnesium, granular calcium, granular zinc (particle size 1-2 mm), and granular aluminum (particle size 2-3 m)
m), Examples using granular cerium (particle diameter 1-2 mm)
An experiment was performed in the same manner as in Example 28 . Tables 7 and 8 show the results.
Shown in
【００３３】[0033]
【表７】 表 ７ 合金の組成比（重量％） ９０％以上 Ｚｒ 他の金属 分解下限温度（℃） 実施例２８ ４０ Ｍｇ ６０ ２２５ 実施例２９ ５０ Ｍｇ ５０ ２２５ 実施例３０ ７５ Ｍｇ ２５ １９０ 実施例３１ ９０ Ｍｇ １０ １９５ 実施例３２ ４０ Ｃａ ６０ ２３０ 実施例３３ ５０ Ｃａ ５０ ２３０ 実施例３４ ７５ Ｃａ ２５ ２００ 実施例３５ ９０ Ｃａ １０ ２１０ 実施例３６ ４０ Ｚｎ ６０ ２４５ 実施例３７ ５０ Ｚｎ ５０ ２１５ 実施例３８ ７５ Ｚｎ ２５ ２０５ 実施例３９ ９０ Ｚｎ １０ ２００ 実施例４０ ４０ Ａｌ ６０ ２４０ 実施例４１ ５０ Ａｌ ５０ ２４０ 実施例４２ ７５ Ａｌ ２５ ２１５ 実施例４３ ９０ Ａｌ １０ ２１０ 実施例４４ ４０ Ｌａ ６０ ２４５ 実施例４５ ５０ Ｌａ ５０ ２４０ 実施例４６ ７５ Ｌａ ２５ ２３０ 実施例４７ ９０ Ｌａ １０ ２４０ 実施例４８ ４０ Ｃｅ ６０ ２３５ 実施例４９ ５０ Ｃｅ ５０ ２４５ 実施例５０ ７５ Ｃｅ ２５ ２１５ 実施例５１ ９０ Ｃｅ １０ ２２５ 実施例５２ ７５ Ｍｇ１５ Ａｌ１０ １９５ 実施例５３ ９０ Ｍｇ ５ Ｚｎ ５ １９５ 比較例７ ０ Ｍｇ １００ ２７０ 比較例８ ０ Ｃａ １００ ２８０ 比較例９ ０ Ｚｎ １００ ３４０ 比較例１０ ０ Ａｌ １００ ４６５ 比較例１１ ０ Ｌａ １００ ３２０ 比較例１２ ０ Ｃｅ １００ ３１０Table 7 Table 7 Composition ratio (% by weight) of alloy 90% or more Zr and other metals Decomposition lower limit temperature (° C) Example 28 40 Mg 60 225 Example 29 50 Mg 50 225 Example 30 75 Mg 25 190 Example 31 90 Mg 10 195 Example 32 40 Ca 60 230 Example 33 50 Ca 50 230 Example 34 75 Ca 25 200 Example 35 90 Ca 10 210 Example 36 40 Zn 60 245 Example 37 50 Zn 50 215 Example 38 75 Zn 25 205 Example 39 90 Zn 10 200 Example 40 40 Al 60 240 Example 41 50 Al 50 240 Example 42 75 Al 25 215 Example 43 90 Al 10 210 Example 44 40 La 60 245 Example 45 50 La 50 240 example 46 75 La 2 230 Example 47 90 La 10 240 Example 48 40 Ce 60 235 Example 49 50 Ce 50 245 Example 50 75 Ce 25 215 Example 51 90 Ce 10 225 Example 52 75 Mg15 Al10 195 Example 53 90 Mg 5 Zn 5 195 Comparative Example 70 Mg 100 270 Comparative Example 80 Ca 100 280 Comparative Example 90 Zn 100 340 Comparative Example 100 Al 100 465 Comparative Example 110 La 100 320 Comparative Example 120 Ce 100 310
【００３４】[0034]
【表８】 表 ８ 温 度 浄化能力 窒素酸化物 ℃ （Ｌ／Ｌ） 実施例２８ ２５０ ＞１００ ＮＤ 実施例２９ ２５０ ＞１００ ＮＤ 実施例３０ ２００ ４０４ ＮＤ 実施例３１ ２００ ＞１００ ＮＤ 実施例３２ ２５０ ＞１００ ＮＤ 実施例３３ ２１０ ＞１００ ＮＤ 実施例３４ ２２０ ３８９ ＮＤ 実施例３５ ２８０ ＞１００ ＮＤ 実施例３６ ２８０ ＞１００ ＮＤ 実施例３７ ２５０ ＞１００ ＮＤ 実施例３８ ２３０ ３８１ ＮＤ 実施例３９ ２３０ ＞１００ ＮＤ 実施例４０ ２８０ ＞１００ ＮＤ 実施例４１ ２５０ ＞１００ ＮＤ 実施例４２ ２３０ ４９５ ＮＤ 実施例４３ ２３０ ＞１００ ＮＤ 実施例４４ ２６０ ＞１００ ＮＤ 実施例４５ ２６０ ＞１００ ＮＤ 実施例４６ ２５０ ４０６ ＮＤ 実施例４７ ２６０ ＞１００ ＮＤ 実施例４８ ２５０ ＞１００ ＮＤ 実施例４９ ２５０ ＞１００ ＮＤ 実施例５０ ２３０ ＞１００ ＮＤ 実施例５１ ２３０ ＞１００ ＮＤ 実施例５２ ２１０ ＞１００ ＮＤ 実施例５３ ２１０ ＞１００ ＮＤ 比較例７ ３００ １６ ＮＤ 比較例８ ３００ １１ ＮＤ 比較例９ ４００ ２５ ＮＤ 比較例１０ ５００ ９ ＮＤ 比較例１１ ３５０ １２ ＮＤ 比較例１２ ３５０ １９ ＮＤTable 8 Temperature Purification capacity Nitrogen oxide ° C (L / L) Example 28 250> 100 ND Example 29 250> 100 ND Example 30 200 404 ND Example 31 200> 100 ND Example 32 250 > 100 ND Example 33 210> 100 ND Example 34 220 389 ND Example 35 280> 100 ND Example 36 280> 100 ND Example 37 250> 100 ND Example 38 230 381 ND Example 39 230> 100 ND Example 40 280> 100 ND Example 41 250> 100 ND Example 42 230 495 ND Example 43 230> 100 ND Example 44 260> 100 ND Example 45 260> 100 ND Example 46 250 406 ND Example 47 260> 100 ND example 48 50> 100 ND Example 49 250> 100 ND Example 50 230> 100 ND Example 51 230> 100 ND Example 52 210> 100 ND Example 53 210> 100 ND Comparative Example 7 300 16 ND Comparative Example 8 300 11 ND Comparative Example 9 400 25 ND Comparative Example 10 500 9 ND Comparative Example 11 350 12 ND Comparative Example 12 350 19 ND
【００３５】実施例５４〜８６ 市販のスポンジジルコニウムとバナジウム、モリブデ
ン、チタン、クロム、タングステン、タンタル、ニオブ
または錫を用い、種々の組成（Ｚｒ４０、５０、７０、
９０重量％、残部Ｖ、Ｍｏ、Ｔｉ、Ｃｒ、Ｗ、Ｔａまた
はＮｂ。ＳｎについてはＺｒ５０、７０、９０重量％残
部Ｓｎ）になるようにジルコニウムと各金属を全量で約
５００ｇとなるように混合した後、電子ビーム溶解を２
回繰り返して得た合金をボールミル中で粉砕し、１４〜
２０メッシュのものを振るい分けてそれぞれ浄化用の合
金とした。Embodiment 54~ 86 Commercially available sponge zirconium and vanadium, molybdenum
, Titanium, chromium, tungsten, tantalum, niobium
Or, using tin, various compositions (Zr40, 50, 70,
90% by weight, balance V, Mo, Ti, Cr, W, Ta or
Is Nb. About Sn, Zr50, 70, 90% by weight remaining
Zirconium and each metal in a total amount of about
After mixing to 500 g, the electron beam melting was performed for 2 hours.
Pulverized in a ball mill the alloy obtained by repeating
Separate the 20 mesh mesh and clean
Gold.
【００３６】それぞれの浄化剤について、実施例１にお
けると同様にして分解率９０％になる温度、浄化能力お
よび窒素酸化物の測定をおこなった。それぞれの結果を
表９および表１０に示す。For each of the purifying agents, the temperature, the purifying ability and the nitrogen oxides at which the decomposition rate was 90% were measured in the same manner as in Example 1 . Tables 9 and 10 show the results.
【００３７】比較例１３〜２０ 市販の、粒状バナジウム、モリブデン、チタン、クロ
ム、タングステン、タンタル、ニオブ、錫（各々粒径１
〜２ｍｍ）のそれぞれについて実施例５４と同様にして
実験をおこなった。結果を表９、１０に示す。なお、錫
について分解率が９０％に到達しないため、浄化能力は
測定しなかった。Comparative Examples 13 to 20 Commercially available granular vanadium, molybdenum, titanium, chromium, tungsten, tantalum, niobium, tin (each having a particle size of 1
〜2 mm) in the same manner as in Example 54 . The results are shown in Tables 9 and 10. Since the decomposition rate of tin did not reach 90%, the purifying ability was not measured.
【００３８】[0038]
【表９】 表 ９ 合金組成 ９０％ 実験Ｎｏ． （重量％） 分解温度 Ｚｒ 他金属 （℃） 実施例５４ ４０ Ｖ ６０ ２３５ 実施例５５ ５０ Ｖ ５０ ２０５ 実施例５６ ７０ Ｖ ３０ １７０ 実施例５７ ９０ Ｖ １０ １７５ 実施例５８ ４０ Ｍｏ ６０ ２５０ 実施例５９ ５０ Ｍｏ ５０ １９０ 実施例６０ ７０ Ｍｏ ３０ １８０ 実施例６１ ９０ Ｍｏ １０ １８０ 実施例６２ ４０ Ｔｉ ６０ ２０５ 実施例６３ ５０ Ｔｉ ５０ １９５ 実施例６４ ７０ Ｔｉ ３０ １６５ 実施例６５ ９０ Ｔｉ １０ １７０ 実施例６６ ４０ Ｃｒ ６０ ２３０ 実施例６７ ５０ Ｃｒ ５０ ２３５ 実施例６８ ７０ Ｃｒ ３０ ２００ 実施例６９ ９０ Ｃｒ １０ ２０５ 実施例７０ ４０ Ｗ ６０ １９５ 実施例７１ ５０ Ｗ ５０ １８５ 実施例７２ ７０ Ｗ ３０ １８０ 実施例７３ ９０ Ｗ １０ １８５ 実施例７４ ４０ Ｔａ ６０ １８５ 実施例７５ ５０ Ｔａ ５０ １８０ 実施例７６ ７０ Ｔａ ３０ １７５ 実施例７７ ９０ Ｔａ １０ １９０ 実施例７８ ４０ Ｎｂ ６０ ２２５ 実施例７９ ５０ Ｎｂ ５０ １９５ 実施例８０ ７０ Ｎｂ ３０ １７５ 実施例８１ ９０ Ｎｂ １０ １８５ 実施例８２ ５０ Ｓｎ ５０ ２００ 実施例８３ ７０ Ｓｎ ３０ １９５ 実施例８４ ９０ Ｓｎ １０ ２００ 実施例８５ ７０ Ｖ１５ Ｔｉ１５ １６０ 実施例８６ ９０ Ｖ ５ Ｍｏ ５ １７５ 比較例１３ ０ Ｖ １００ ４１５ 比較例１４ ０ Ｍｏ １００ ３９５ 比較例１５ ０ Ｔｉ １００ ２８５ 比較例１６ ０ Ｃｒ １００ ４３５ 比較例１７ ０ Ｗ １００ ４５０ 比較例１８ ０ Ｔａ １００ ４２５ 比較例１９ ０ Ｎｂ １００ ４３０ 比較例２０ ０ Ｓｎ １００ −Table 9 Table 9 Alloy composition 90% (% By weight) Decomposition temperature Zr Other metal (° C.) Example 54 40 V 60 235 Example 55 50 V 50 205 Example 56 70 V 30 170 Example 57 90 V 10 175 Example 58 40 Mo 60 250 Example 59 50 Mo 50 190 Example 60 70 Mo 30 180 Example 61 90 Mo 10 180 Example 62 40 Ti 60 205 Example 63 50 Ti 50 195 Example 64 70 Ti 30 165 Example 65 90 Ti 10 170 Example 66 40 Cr 60 230 Example 67 50 Cr 50 235 Example 68 70 Cr 30 200 Example 69 90 Cr 10 205 Example 70 40 W 60 195 Example 71 50 W 50 185 Example 72 70 W 30 180 Example 73 90 W 10 185 example 74 40 T 60 185 Example 75 50 Ta 50 180 Example 76 70 Ta 30 175 Example 77 90 Ta 10 190 Example 78 40 Nb 60 225 Example 79 50 Nb 50 195 Example 80 70 Nb 30 175 Example 81 90 Nb 10 185 Example 82 50 Sn 50 200 Example 83 70 Sn 30 195 Example 84 90 Sn 10 200 Example 85 70 V15 Ti15 160 Example 86 90 V5 Mo5 175 Comparative Example 130 0 V 100 415 Comparative Example 140 Mo 100 395 Comparative Example 150 Ti 100 285 Comparative Example 160 Cr 100 435 Comparative Example 170 W 100 450 Comparative Example 180 Ta 100 425 Comparative Example 190 Nb 100 430 Comparative Example 200 Sn 100 −
【００３９】[0039]
【表１０】 表 １０ 浄化温度 浄化能力 窒素酸化物 Ｎｏ． （℃） （Ｌ／Ｌ） 実施例５４ ２５０ ＞１００ ＮＤ 実施例５５ ２２０ ＞１００ ＮＤ 実施例５６ １８０ ＞１００ ＮＤ 実施例５７ １８０ ＞１００ ＮＤ 実施例５８ ２８０ ＞１００ ＮＤ 実施例５９ ２００ ＞１００ ＮＤ 実施例６０ １９０ ＞１００ ＮＤ 実施例６１ １９０ ＞１００ ＮＤ 実施例６２ ２２０ ＞１００ ＮＤ 実施例６３ ２００ ＞１００ ＮＤ 実施例６４ １８０ ＞１００ ＮＤ 実施例６５ １８０ ＞１００ ＮＤ 実施例６６ ２５０ ＞１００ ＮＤ 実施例６７ ２５０ ＞１００ ＮＤ 実施例６８ ２３０ ＞１００ ＮＤ 実施例６９ ２３０ ＞１００ ＮＤ 実施例７０ ２２０ ＞１００ ＮＤ 実施例７１ ２００ ＞１００ ＮＤ 実施例７２ １９０ ＞１００ ＮＤ 実施例７３ １９０ ＞１００ ＮＤ 実施例７４ ２１０ ＞１００ ＮＤ 実施例７５ ２００ ＞１００ ＮＤ 実施例７６ ２００ ＞１００ ＮＤ 実施例７７ ２００ ＞１００ ＮＤ 実施例７８ ２５０ ＞１００ ＮＤ 実施例７９ ２１０ ＞１００ ＮＤ 実施例８０ １９０ ＞１００ ＮＤ 実施例８１ １９０ ＞１００ ＮＤ 実施例８２ ２２０ ＞１００ ＮＤ 実施例８３ ２２０ ＞１００ ＮＤ 実施例８４ ２２０ ＞１００ ＮＤ 実施例８５ １８０ ＞１００ ＮＤ 実施例８６ １９０ ＞１００ ＮＤ 比較例１３ ４５０ ２３ ＮＤ 比較例１４ ４５０ ２８ ＮＤ 比較例１５ ３００ ４１ ＮＤ 比較例１６ ４５０ １０ ＮＤ 比較例１７ ４７０ ２１ ＮＤ 比較例１８ ４５０ ２２ ＮＤ 比較例１９ ４５０ ３４ ＮＤ 比較例２０ − − ＮＤ[Table 10] Purification temperature Purification capacity Nitrogen oxide No. (° C) (L / L) Example 54 250> 100 ND Example 55 220> 100 ND Example 56 180> 100 ND Example 57 180> 100 ND Example 58 280> 100 ND Example 59 200> 100 ND Example 60 190> 100 ND Example 61 190> 100 ND Example 62 220> 100 ND Example 63 200> 100 ND Example 64 180> 100 ND Example 65 180> 100 ND Example 66 250> 100 ND Implementation Example 67 250> 100 ND Example 68 230> 100 ND Example 69 230> 100 ND Example 70 220> 100 ND Example 71 200> 100 ND Example 72 190> 100 ND Example 73 190> 100 ND Example 74 210> 100 ND implementation 75 200> 100 ND Example 76 200> 100 ND Example 77 200> 100 ND Example 78 250> 100 ND Example 79 210> 100 ND Example 80 190> 100 ND Example 81 190> 100 ND Example 82 220> 100 ND Example 83 220> 100 ND Example 84 220> 100 ND Example 85 180> 100 ND Example 86 190> 100 ND Comparative Example 13 450 23 ND Comparative Example 14 450 28 ND Comparative Example 15 300 41 ND Comparative Example 16 450 10 ND Comparative Example 17 470 21 ND Comparative Example 18 450 22 ND Comparative Example 19 450 34 ND Comparative Example 20--ND
【００４０】[0040]
【発明の効果】本発明のガスの浄化方法によれば、ガス
中に含有される三弗化窒素などの窒素弗化物を比較的低
温で効率よく除去することができる。しかも、窒素酸化
物など有害な副生物を生ずることがなく、半導体製造工
程などの排出ガスの浄化に優れた効果が得られる。According to the gas purification method of the present invention, nitrogen fluoride such as nitrogen trifluoride contained in the gas can be efficiently removed at a relatively low temperature. Moreover, no harmful by-products such as nitrogen oxides are generated, and an excellent effect of purifying exhaust gas in a semiconductor manufacturing process or the like can be obtained.
【００４１】[0041]
【表９】 表 ９ 合金組成 ９０％ 実験Ｎｏ． （重量％） 分解温度 Ｚｒ 他金属 （℃） 実施例５６ ４０ Ｖ ６０ ２３５ 実施例５７ ５０ Ｖ ５０ ２０５ 実施例５８ ７０ Ｖ ３０ １７０ 実施例５９ ９０ Ｖ １０ １７５ 実施例６０ ４０ Ｍｏ ６０ ２５０ 実施例６１ ５０ Ｍｏ ５０ １９０ 実施例６２ ７０ Ｍｏ ３０ １８０ 実施例６３ ９０ Ｍｏ １０ １８０ 実施例６４ ４０ Ｔｉ ６０ ２０５ 実施例６５ ５０ Ｔｉ ５０ １９５ 実施例６６ ７０ Ｔｉ ３０ １６５ 実施例６７ ９０ Ｔｉ １０ １７０ 実施例６８ ４０ Ｃｒ ６０ ２３０ 実施例６９ ５０ Ｃｒ ５０ ２３５ 実施例７０ ７０ Ｃｒ ３０ ２００ 実施例７１ ９０ Ｃｒ １０ ２０５ 実施例７２ ４０ Ｗ ６０ １９５ 実施例７３ ５０ Ｗ ５０ １８５ 実施例７４ ７０ Ｗ ３０ １８０ 実施例７５ ９０ Ｗ １０ １８５ 実施例７６ ４０ Ｔａ ６０ １８５ 実施例７７ ５０ Ｔａ ５０ １８０ 実施例７８ ７０ Ｔａ ３０ １７５ 実施例７９ ９０ Ｔａ １０ １９０ 実施例８０ ４０ Ｎｂ ６０ ２２５ 実施例８１ ５０ Ｎｂ ５０ １９５ 実施例８２ ７０ Ｎｂ ３０ １７５ 実施例８３ ９０ Ｎｂ １０ １８５ 実施例８４ ５０ Ｓｎ ５０ ２００ 実施例８５ ７０ Ｓｎ ３０ １９５ 実施例８６ ９０ Ｓｎ １０ ２００ 実施例８７ ７０ Ｖ１５ Ｔｉ１５ １６０ 実施例８８ ９０ Ｖ ５ Ｍｏ ５ １７５ 比較例１３ ０ Ｖ １００ ４１５ 比較例１４ ０ Ｍｏ １００ ３９５ 比較例１５ ０ Ｔｉ １００ ２８５ 比較例１６ ０ Ｃｒ １００ ４３５ 比較例１７ ０ Ｗ １００ ４５０ 比較例１８ ０ Ｔａ １００ ４２５ 比較例１９ ０ Ｎｂ １００ ４３０ 比較例２０ ０ Ｓｎ １００ −Table 9 Table 9 Alloy composition 90% (% By weight) Decomposition temperature Zr Other metal (° C.) Example 56 40 V 60 235 Example 57 50 V 50 205 Example 58 70 V 30 170 Example 59 90 V 10 175 Example 60 40 Mo 60 250 Example 61 50 Mo 50 190 Example 62 70 Mo 30 180 Example 63 90 Mo 10 180 Example 64 40 Ti 60 205 Example 65 50 Ti 50 195 Example 66 70 Ti 30 165 Example 67 90 Ti 10 170 Example 68 40 Cr 60 230 Example 69 50 Cr 50 235 Example 70 70 Cr 30 200 Example 71 90 Cr 10 205 Example 72 40 W 60 195 Example 73 50 W 50 185 Example 74 70 W 30 180 Example 75 90 W 10 185 Example 76 40 T 60 185 Example 77 50 Ta 50 180 Example 78 70 Ta 30 175 Example 79 90 Ta 10 190 Example 80 40 Nb 60 225 Example 81 50 Nb 50 195 Example 82 70 Nb 30 175 Example 83 90 Nb10 185 Example 84 50 Sn 50 200 Example 85 70 Sn 30 195 Example 86 90 Sn 10 200 Example 87 70 V15 Ti15 160 Example 88 90 V 5 Mo 5 175 Comparative Example 130 0 V 100 415 Comparative Example 140 Mo 100 395 Comparative Example 150 Ti 100 285 Comparative Example 160 Cr 100 435 Comparative Example 170 W 100 450 Comparative Example 180 Ta 100 425 Comparative Example 190 Nb 100 430 Comparative Example 200 Sn 100 −
【００４２】[0042]
【表１０】 表 １０ 浄化温度 浄化能力 窒素酸化物 Ｎｏ． （℃） （Ｌ／Ｌ） 実施例５６ ２５０ ＞１００ ＮＤ 実施例５７ ２２０ ＞１００ ＮＤ 実施例５８ １８０ ＞１００ ＮＤ 実施例５９ １８０ ＞１００ ＮＤ 実施例６０ ２８０ ＞１００ ＮＤ 実施例６１ ２００ ＞１００ ＮＤ 実施例６２ １９０ ＞１００ ＮＤ 実施例６３ １９０ ＞１００ ＮＤ 実施例６４ ２２０ ＞１００ ＮＤ 実施例６５ ２００ ＞１００ ＮＤ 実施例６６ １８０ ＞１００ ＮＤ 実施例６７ １８０ ＞１００ ＮＤ 実施例６８ ２５０ ＞１００ ＮＤ 実施例６９ ２５０ ＞１００ ＮＤ 実施例７０ ２３０ ＞１００ ＮＤ 実施例７１ ２３０ ＞１００ ＮＤ 実施例７２ ２２０ ＞１００ ＮＤ 実施例７３ ２００ ＞１００ ＮＤ 実施例７４ １９０ ＞１００ ＮＤ 実施例７５ １９０ ＞１００ ＮＤ 実施例７６ ２１０ ＞１００ ＮＤ 実施例７７ ２００ ＞１００ ＮＤ 実施例７８ ２００ ＞１００ ＮＤ 実施例７９ ２００ ＞１００ ＮＤ 実施例８０ ２５０ ＞１００ ＮＤ 実施例８１ ２１０ ＞１００ ＮＤ 実施例８２ １９０ ＞１００ ＮＤ 実施例８３ １９０ ＞１００ ＮＤ 実施例８４ ２２０ ＞１００ ＮＤ 実施例８５ ２２０ ＞１００ ＮＤ 実施例８６ ２２０ ＞１００ ＮＤ 実施例８７ １８０ ＞１００ ＮＤ 実施例８８ １９０ ＞１００ ＮＤ 比較例１３ ４５０ ２３ ＮＤ 比較例１４ ４５０ ２８ ＮＤ 比較例１５ ３００ ４１ ＮＤ 比較例１６ ４５０ １０ ＮＤ 比較例１７ ４７０ ２１ ＮＤ 比較例１８ ４５０ ２２ ＮＤ 比較例１９ ４５０ ３４ ＮＤ 比較例２０ − − ＮＤ[Table 10] Purification temperature Purification capacity Nitrogen oxide No. (° C) (L / L) Example 56 250> 100 ND Example 57 220> 100 ND Example 58 180> 100 ND Example 59 180> 100 ND Example 60 280> 100 ND Example 61 200> 100 ND Example 62 190> 100 ND Example 63 190> 100 ND Example 64 220> 100 ND Example 65 200> 100 ND Example 66 180> 100 ND Example 67 180> 100 ND Example 68 250> 100 ND Implementation Example 69 250> 100 ND Example 70 230> 100 ND Example 71 230> 100 ND Example 72 220> 100 ND Example 73 200> 100 ND Example 74 190> 100 ND Example 75 190> 100 ND Example 76 210> 100 ND Implementation 77 200> 100 ND Example 78 200> 100 ND Example 79 200> 100 ND Example 80 250> 100 ND Example 81 210> 100 ND Example 82 190> 100 ND Example 83 190> 100 ND Example 84 220> 100 ND Example 85 220> 100 ND Example 86 220> 100 ND Example 87 180> 100 ND Example 88 190> 100 ND Comparative Example 13 450 23 ND Comparative Example 14 450 28 ND Comparative Example 15 300 41 ND Comparative Example 16 450 10 ND Comparative Example 17 470 21 ND Comparative Example 18 450 22 ND Comparative Example 19 450 34 ND Comparative Example 20 --- ND
【００４３】[0043]
【発明の効果】本発明のガスの浄化方法によれば、ガス
中に含有される三弗化窒素などの窒素弗化物を比較的低
温で効率よく除去することができる。しかも、窒素酸化
物など有害な副生物を生ずることがなく、半導体製造工
程などの排出ガスの浄化に優れた効果が得られる。According to the gas purification method of the present invention, nitrogen fluoride such as nitrogen trifluoride contained in the gas can be efficiently removed at a relatively low temperature. Moreover, no harmful by-products such as nitrogen oxides are generated, and an excellent effect of purifying exhaust gas in a semiconductor manufacturing process or the like can be obtained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｂ０１Ｊ 21/10 ＺＡＢ Ｂ０１Ｊ 23/14 ＺＡＢＡ 23/02 ＺＡＢ 23/20 ＺＡＢＡ 23/06 ＺＡＢ 23/24 ＺＡＢＡ 23/14 ＺＡＢ 23/30 ＺＡＢＡ 23/20 ＺＡＢ 23/34 ＺＡＢＡ 23/24 ＺＡＢ 23/74 ＺＡＢＡ 23/30 ＺＡＢ 23/84 ＺＡＢ 23/34 ＺＡＢ 23/89 ＺＡＢＡ 23/74 ＺＡＢ Ｂ０１Ｄ 53/34 １３４Ｃ 23/84 ＺＡＢ ＺＡＢ 23/889 １２８ 23/89 ＺＡＢ Ｂ０１Ｊ 23/84 ３１１Ａ (31)優先権主張番号 特願平4−332949 (32)優先日 平成４年12月14日(1992．12．14) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平4−355408 (32)優先日 平成４年12月21日(1992．12．21) (33)優先権主張国 日本（ＪＰ） (31)優先権主張番号 特願平4−355409 (32)優先日 平成４年12月21日(1992．12．21) (33)優先権主張国 日本（ＪＰ） (56)参考文献 特開 平２−201984（ＪＰ，Ａ) 特開 平２−172814（ＪＰ，Ａ) 特開 昭61−287424（ＪＰ，Ａ) 渡辺 信淳 編，別冊化学工業 第28 巻 第８号 フッ素化学と工業，日本, 株式会社 化学工業社，1984年 ４月15 日，209−211, (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 53/34 - 53/96 B01J 20/00 - 20/34 ＣＡＰＬＵＳ（ＳＴＮ) ＪＩＣＳＴファイル（ＪＯＩＳ)──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification code FI B01J 21/10 ZAB B01J 23/14 ZABA 23/02 ZAB 23/20 ZABA 23/06 ZAB 23/24 ZABA 23/14 ZAB 23 / 30 ZABA 23/20 ZAB 23/34 ZABA 23/24 ZAB 23/74 ZABA 23/30 ZAB 23/84 ZAB 23/34 ZAB 23/89 ZABA 23/74 ZAB B01D 53/34 134C 23/84 ZAB ZAB 23 / 889 128 23/89 ZAB B01J 23/84 311A (31) Priority claim number Japanese Patent Application No. 4-332949 (32) Priority date December 14, 1992 (1992.1.12.14) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-355408 (32) Priority date December 21, 1992 (1992.1.21) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 4-355409 (32) The other day December 21, 1992 (Dec. 21, 1992) (33) Priority country Japan (JP) (56) References JP-A-2-201984 (JP, A) JP-A-2-172814 (JP) , A) JP-A-61-287424 (JP, A) Watanabe Shinjun, eds., Separate Volume Chemical Industry, Vol. 28, No. 8, Fluorochemistry and Industry, Japan, Chemical Industry Co., Ltd., April 15, 1984, 209-211 , (58) Fields surveyed (Int. Cl. 7 , DB name) B01D 53/34-53/96 B01J 20/00-20/34 CAPLUS (STN) JICST file (JOIS)
Claims (3)
スを、４０重量％以上のジルコニウムと、その残部が、
鉄、銅、銀、ニッケル、コバルト、マンガン、マグネシ
ウム、カルシウム、亜鉛、アルミニウム、ランタン、セ
リウム、バナジウム、モリブデン、チタン、クロム、タ
ングステン、タンタル、ニオブ、及び錫から選ばれる１
種または２種以上の金属元素で構成されるジルコニウム
系合金からなる浄化剤と、加熱下に接触させて、該有害
成分を除去することを特徴とする有害ガスの浄化方法。1. A gas containing nitrogen fluoride, which is a harmful component, comprises at least 40% by weight of zirconium and the balance
Iron, copper, silver, nickel, cobalt, manganese, magnesium
, Calcium, zinc, aluminum, lanthanum,
Lium, vanadium, molybdenum, titanium, chromium, copper
1 selected from Ngsten, Tantalum, Niobium and Tin
Zirconium composed of one or more metal elements
A method for purifying harmful gases, comprising removing a harmful component by contacting a purifying agent comprising a system alloy with heating under heating.
素、二弗化二窒素及び六弗化二窒素から選ばれる少なく
とも１種である請求項１に記載の浄化方法。2. The method according to claim 1, wherein the nitrogen fluoride is at least one selected from nitrogen trifluoride, dinitrogen tetrafluoride, dinitrogen difluoride and dinitrogen hexafluoride.
０〜８００℃である請求項１に記載の浄化方法。3. The temperature at which the purifying agent and the gas are brought into contact with each other is 10
The purification method according to claim 1, wherein the temperature is 0 to 800C.
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| Application Number | Priority Date | Filing Date | Title |
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| JP28753593A JP3302137B2 (en) | 1992-11-09 | 1993-10-22 | How to purify harmful gases |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29880692 | 1992-11-09 | ||
| JP32557292 | 1992-12-04 | ||
| JP33294992 | 1992-12-14 | ||
| JP33294892 | 1992-12-14 | ||
| JP4-355408 | 1992-12-21 | ||
| JP4-298806 | 1992-12-21 | ||
| JP35540992 | 1992-12-21 | ||
| JP35540892 | 1992-12-21 | ||
| JP4-325572 | 1992-12-21 | ||
| JP4-332949 | 1992-12-21 | ||
| JP4-332948 | 1992-12-21 | ||
| JP4-355409 | 1992-12-21 | ||
| JP28753593A JP3302137B2 (en) | 1992-11-09 | 1993-10-22 | How to purify harmful gases |
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| Publication Number | Publication Date |
|---|---|
| JPH06238128A JPH06238128A (en) | 1994-08-30 |
| JP3302137B2 true JP3302137B2 (en) | 2002-07-15 |
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| JP2003053137A (en) * | 2001-08-17 | 2003-02-25 | Japan Pionics Co Ltd | Cleaning method of harmful gas |
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Non-Patent Citations (1)
| Title |
|---|
| 渡辺 信淳 編，別冊化学工業 第２８巻 第８号 フッ素化学と工業，日本，株式会社 化学工業社，１９８４年 ４月１５日，２０９−２１１， |
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