WO2010109671A1 - 揮発性無機水素化物含有排ガス除害剤及び揮発性無機水素化物含有排ガス除害方法 - Google Patents
揮発性無機水素化物含有排ガス除害剤及び揮発性無機水素化物含有排ガス除害方法 Download PDFInfo
- Publication number
- WO2010109671A1 WO2010109671A1 PCT/JP2009/056401 JP2009056401W WO2010109671A1 WO 2010109671 A1 WO2010109671 A1 WO 2010109671A1 JP 2009056401 W JP2009056401 W JP 2009056401W WO 2010109671 A1 WO2010109671 A1 WO 2010109671A1
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- WO
- WIPO (PCT)
- Prior art keywords
- metal
- solid metal
- zeolite
- detoxifying
- carbonate
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910010276 inorganic hydride Inorganic materials 0.000 title abstract 4
- 239000010457 zeolite Substances 0.000 claims abstract description 77
- 239000007787 solid Substances 0.000 claims abstract description 71
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 56
- 229910052751 metal Inorganic materials 0.000 claims abstract description 48
- 239000002184 metal Substances 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 45
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 26
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 239000000203 mixture Substances 0.000 claims abstract description 23
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 22
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 22
- 229910052987 metal hydride Inorganic materials 0.000 claims description 44
- 150000004681 metal hydrides Chemical class 0.000 claims description 44
- 229910044991 metal oxide Inorganic materials 0.000 claims description 17
- 150000004706 metal oxides Chemical class 0.000 claims description 17
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 14
- 238000006386 neutralization reaction Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 239000003513 alkali Chemical class 0.000 claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-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
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 14
- 238000011282 treatment Methods 0.000 abstract description 11
- -1 basic metal carbonate Chemical class 0.000 abstract description 10
- 229910052728 basic metal Inorganic materials 0.000 abstract description 8
- 239000004065 semiconductor Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 56
- 238000001784 detoxification Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
- 150000002736 metal compounds Chemical class 0.000 description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 11
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 229910000077 silane Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 229940116318 copper carbonate Drugs 0.000 description 7
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000004480 active ingredient Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 5
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 150000007514 bases Chemical class 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910000078 germane Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 235000001968 nicotinic acid Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
Classifications
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- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
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- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0218—Compounds of Cr, Mo, W
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- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
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- B01J20/0233—Compounds of Cu, Ag, Au
- B01J20/0237—Compounds of Cu
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- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- B01J20/16—Alumino-silicates
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J20/30—Processes for preparing, regenerating, or reactivating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
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- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/42—Materials comprising a mixture of inorganic materials
Definitions
- the present invention relates to a detoxifying agent and detoxification method for metal hydride-containing exhaust gas, and more particularly to a detoxifying agent and detoxification method for metal hydride-containing exhaust gas generated in a semiconductor manufacturing plant, a liquid crystal manufacturing plant, or the like.
- Exhaust gas treatment includes a wet method and a dry method, and the former is a method of cleaning exhaust gas with a chemical solution. Since the wet method uses a large amount of water and chemicals, a large amount of waste water must be treated after treatment, and the facilities are large and take up space. On the other hand, in the latter, exhaust gas is circulated through a packed column of a particulate solid processing agent, and the hazardous and harmful gases are separated by chemical action of the gas to be removed and the processing agent, that is, adsorption and / or chemical reaction. It is a detoxifying method and is often performed in the treatment of exhaust gas containing metal hydride or exhaust gas containing halide gas.
- Patent Document 1 a detoxifying agent comprising a metal oxide
- Patent Documents 2, 3, 4 a detoxifying agent comprising a metal hydroxide, a metal carbonate or a basic metal carbonate
- Patent Documents 5 and 6 a detoxifying agent obtained by modifying a metal hydroxide, metal carbonate or basic metal carbonate with a basic compound such as an alkali metal
- Patent Documents 5 and 6 monosilane using zeolite A detoxifying agent
- Patent Document 7 that removes a trace amount of phosphine (PH 3 ) in (SiH 4 ) is disclosed.
- the detoxifying agent composed of metal hydroxide, metal carbonate or basic metal carbonate has excellent detoxifying ability, but it has higher detoxifying ability as the amount of special gas used increases with recent technological progress. Therefore, the amount of exhaust gas treated per volume of the detoxifying agent as described above is no longer sufficient.
- the amount of exhaust gas treated per volume of the detoxifying agent is not sufficient for the detoxifying agent obtained by modifying a metal hydroxide, metal carbonate or basic metal carbonate with a basic compound such as an alkali metal.
- a metal hydroxide, metal carbonate or basic metal carbonate with a basic compound such as an alkali metal there is a step of mixing and molding powders and alkali components as detoxifying components, and when producing in large quantities on an industrial scale, there is a safety problem due to the use of strong alkali .
- various capital investments, such as a closed system are required, resulting in various problems such as high production costs.
- JP 05-269339 A Japanese Patent Laid-Open No. 06-319945 Japanese Patent Application Laid-Open No. 08-192020 Japanese Patent No. 26049991 Japanese Patent Laid-Open No. 08-155259 JP 2002-136634 A Japanese Patent Laid-Open No. 62-212217
- An object of the present invention is to provide a detoxifying agent and a detoxifying method exhibiting high detoxifying ability in the detoxification treatment of exhaust gas containing metal hydride generated in a semiconductor manufacturing process.
- zeolites are added to solid metal hydroxide, solid metal carbonate, solid metal basic carbonate, or a mixture of these compounds.
- the present invention was completed by finding that it has excellent detoxifying performance for exhaust gas containing metal hydride.
- a metal hydride-containing exhaust gas detoxifier characterized by adding zeolites to solid metal basic carbonate, solid metal oxide, solid metal hydroxide, solid metal carbonate or a mixture of these compounds is there.
- the metal component of the solid metal basic carbonate, solid metal oxide, solid metal hydroxide, solid metal carbonate or a mixture of these compounds is selected from copper, iron, cobalt, nickel, manganese, zinc, and chromium.
- a metal hydride-containing exhaust gas abatement agent characterized by (3) A metal hydride-containing exhaust gas abatement agent characterized in that the zeolite content is 10 to 90% by weight based on the total weight of the abatement agent.
- a metal hydride-containing exhaust gas abatement agent characterized by (5) A method for detoxifying a metal hydride-containing exhaust gas, wherein the metal hydride-containing exhaust gas is brought into contact with the detoxifying agent described in (1) to (4) above.
- the detoxifying agent of the present invention is applied to the detoxification of various metal hydride-containing exhaust gases such as silane, phosphine, and arsine generated in a semiconductor manufacturing factory or a liquid crystal manufacturing factory, and can efficiently absorb metal hydride gas. Since the absorption capacity is large, the utility value in operation is high.
- metal hydride-containing exhaust gases such as silane, phosphine, and arsine generated in a semiconductor manufacturing factory or a liquid crystal manufacturing factory
- metal hydride gas Since the absorption capacity is large, the utility value in operation is high.
- zeolites with solid metal oxides, solid metal hydroxides, solid metal carbonates, solid metal basic carbonates or mixtures of these compounds, the physical properties of the zeolites can be exploited using the pores and high surface area. By combining adsorption and chemical reaction, even higher concentrations of metal hydrides can have high detoxifying ability, and the absorption capacity can be increased.
- the present invention relates to a detoxifying agent obtained by adding a zeolite to a solid metal oxide, solid metal hydroxide, solid metal carbonate, solid metal basic carbonate or a mixture of these compounds.
- the metal compounds that form the main component of the detoxifying agent are solid metal oxides, solid metal hydroxides, solid metal carbonates, solid basic metal carbonates, or a mixture thereof, which can exist stably. Any metal can be used, but copper, iron, cobalt, nickel, manganese, zinc and chromium, which are usually easily available and inexpensive, are advantageously used.
- the solid metal compounds oxides, hydroxides, carbonates, or basic carbonates can be used.
- an aqueous solution of an alkaline compound is used. It can also manufacture by neutralization reaction.
- alkali compounds it is preferable to use sodium, potassium hydroxide, carbonate, aqueous ammonia, urea or the like. The precipitate obtained by the neutralization reaction is washed with water, filtered and dried.
- both solid metal compounds by the precipitation method may be used not only as a single compound but also as a mixture.
- a compound obtained by precipitating the compound alone may be mixed, but it is preferable to obtain a precipitate containing a plurality of components by the coprecipitation method.
- Zeolite is an aluminosilicate containing SiO 2 and Al 2 O 3 as constituents, and having a chemical composition containing alkali metals, alkaline earth metals or other metals.
- the structure of zeolite is a structure in which tetrahedral structures of SiO 4 or AlO 4 centering on Si or Al are regularly arranged in three dimensions. Since the tetrahedral structure of AlO 4 is negatively charged, cations such as alkali metals are held in the pores and cavities. A cation can be easily exchanged for another cation such as a proton.
- zeolite classified by crystal structure There are many types of zeolite classified by crystal structure, and the type of zeolite added to the solid metal compounds used in the present invention is not particularly limited.
- FAU Y-type zeolite
- a type zeolite, X type zeolite, L type zeolite may be used.
- SiO 2 / Al 2 O 3 ratio of the zeolite but it is desirably 3 to 150, and particularly preferably 3 to 50.
- the specific surface area of the zeolite is preferably 100 m 2 / g or more, more preferably 400 m 2 / g or more.
- the content of zeolite is 10% to 90% by weight, preferably 10 to 50% by weight, expressed as the amount of metal with respect to the total weight of the treating agent.
- the hydride detoxifying ability is not sufficiently improved, and if the amount is 90% by weight or more, the effect of improving the treatment performance due to the reduction of the active metal is not recognized.
- zeolites can be produced by known methods, such as silica sources such as silica, silica sol and sodium silicate, alumina sources such as alumina gel, alumina sol and sodium aluminate, sodium hydroxide and sodium silicate.
- silica sources such as silica, silica sol and sodium silicate
- alumina sources such as alumina gel, alumina sol and sodium aluminate
- sodium hydroxide and sodium silicate sodium silica sources
- silica sources such as silica, silica sol and sodium silicate
- alumina sources such as alumina gel, alumina sol and sodium aluminate
- sodium hydroxide and sodium silicate sodium silicate.
- a raw material mixture containing an alkali source, water, and, if necessary, an organic base such as an amine is hydrothermally synthesized, and after separation of the product, it is washed with water, dried, and ion exchanged to obtain a proton type zeolite.
- the alkali metal zeolite prepared by the above hydrothermal synthesis is treated with an ammonium chloride or ammonium nitrate aqueous solution to obtain an ammonium zeolite, and then calcined at a temperature range of about 400 to 700 ° C. to produce a proton type zeolite. It can be.
- powdered products, molded products thereof, or granulated powders after molding are used, and in the case of solid metal compounds produced by the precipitation method, powders, After the completion of kneading with the metal compound precursor, the molded product formed into a molded product by extrusion or tableting, or a crushed product after molding is used.
- zeolites are added during the neutralization reaction between an aqueous solution of metal salts, which are precursors of metal compounds, and alkali compounds. After final precipitation, filtration, drying, or by adding zeolites to metal compounds, physically kneading, further forming a molded product by extrusion or tableting, and then further drying or baking to finally remove the detoxifying agent Manufacturing.
- the temperature for drying or firing is not particularly limited, but is preferably 80 ° C. to 200 ° C.
- the shape of the manufactured detoxifying agent there is no particular limitation on the shape of the manufactured detoxifying agent, and silica, alumina, magnesia, or other inorganic binders that are effective for improving the strength as necessary in order to ensure mechanical strength that can be used. Can be added.
- the disinfectant obtained by adding zeolite to solid metal hydroxide, solid metal carbonate, solid metal basic carbonate or a mixture of these compounds is packed in a flow-type packed tower in actual use.
- the metal hydride gas is then detoxified by contact with an exhaust gas containing the metal hydride.
- the inventors of the present invention filled the detoxifying agent obtained by a series of operations into a stainless steel flow reactor, and circulated a reducing gas containing silane, phosphine, and germane as a metal hydride gas to the reactor.
- a reducing gas containing silane, phosphine, and germane as a metal hydride gas to the reactor.
- the metal hydride containing gas leakage amount in the exit gas was measured and monitored by a break monitor (manufactured by Bionics), thereby performing a detoxification performance measurement test of the metal hydride-containing gas at room temperature.
- the combination of pores and high surface area in the zeolites of the present invention with solid metal oxide, solid metal hydroxide, solid metal carbonate, solid metal basic carbonate or a mixture of these compounds is effective in physics.
- By causing the chemical adsorption and chemical reaction it is possible to exhibit a much higher detoxifying ability than before. Even with a high concentration of metal hydride gas in the order of%, a very good detoxifying ability was exhibited.
- the performance evaluation of the present pesticide was performed by measuring the detoxification performance of the metal hydride gas contained in the nitrogen gas.
- the measurement is performed by a normal pressure flow type reaction apparatus, and the apparatus, conditions, and operation method are as follows.
- Detoxification performance measuring device Normal pressure flow reactor Reaction tube size: Inner diameter 28mm, Length 700mm Measurement conditions Amount of used pesticide: 60 cc (filling height 100 mm) GHSV: 300 hr -1 Pressure: Normal pressure Reaction temperature: Normal temperature Reaction gas composition: SiH4 (silane) 1% N2 balance
- the detoxifying agent (Metallic hydride gas abatement performance measurement operation method and abatement performance calculation method) 60 cc of the detoxifying agent is packed in the reaction tube so that the filling height is 100 mm and is installed in the measuring device, and then the metal hydride gas diluted with nitrogen is circulated through the packed bed of the detoxifying agent. After starting the gas flow, the metal hydride gas leakage into the reaction tube outlet gas was measured and monitored with a break monitor (manufactured by Nippon Bionics), and the cumulative amount of silane that flowed in until the outlet concentration reached 5 ppm was determined. The amount is converted per kg of processing agent. Specifically, the detoxification performance of the metal hydride gas is calculated from the measurement result by the following formula.
- Example 1 50% by weight Y-type zeolite based on the oxide of the product obtained by neutralization reaction is added to an aqueous solution of copper sulfate to form a copper sulfate / zeolite aqueous solution, and by neutralization reaction with sodium carbonate prepared accordingly. A precipitate of basic copper carbonate was obtained. Subsequently, the impurities were sufficiently removed by washing with water, followed by filtration and drying at 110 ° C. to obtain a salted copper carbonate / zeolite.
- Example 2 Commercially available basic copper carbonate is used as a metal compound, and after adding 100 g of pure water to 160 g of basic copper carbonate and 40 g of Y-type zeolite in a kneader and mixing well, it is extruded to a size of 3 mm in diameter and dried at 110 ° C. did. The obtained molded body was filled in a reaction tube. Table 1 shows the silane abatement performance results of the abatement agent thus prepared.
- Example 3 The same procedure as in Example 2 was conducted except that the amount of Y-type zeolite added was 50% by weight. The results are shown in Table 1.
- Example 4 The procedure was the same as in Example 2 except that the amount of Y-type zeolite added was 80% by weight. The results are shown in Table 1.
- Example 5 The procedure was the same as in Example 2 except that the zeolite type added was BEA25, and the results are shown in Table 1.
- Example 6 The procedure was the same as in Example 2 except that the zeolite type added was BEA 150, and the results are shown in Table 1.
- Example 7 The procedure was the same as in Example 2 except that the type of zeolite added was MOR 20, and the results are shown in Table 1.
- Example 8 The procedure was the same as in Example 2 except that the added zeolite was MFI27 (proton type). The results are shown in Table 1.
- Example 9 The procedure was the same as in Example 2 except that the added zeolite was MFI27 (ammonium type). The results are shown in Table 1.
- Example 10 A composite compound of copper and zinc by a neutralization reaction between an aqueous solution in which 280 g of copper sulfate and 160 g of zinc sulfate are dissolved in 0.8 L of pure water and an alkaline aqueous solution in which 240 g of sodium carbonate prepared according to this is dissolved in 3 L of pure water. A precipitate was obtained. Subsequently, the impurities were sufficiently removed by washing with water, followed by filtration, drying at 120 ° C., and baking at 300 ° C. to obtain copper oxide and zinc oxide. The same operation as in Example 3 was performed except that the obtained composite oxide of copper oxide and zinc oxide was used. The results are shown in Table 1.
- Example 11 A composite compound of iron and manganese by a neutralization reaction between an aqueous solution in which 480 g of iron sulfate and 160 g of manganese sulfate are dissolved in 2 L of pure water and an alkaline aqueous solution in which 350 g of sodium carbonate prepared in accordance with this is dissolved in 1.7 L of pure water. A precipitate was obtained. Subsequently, the impurities were sufficiently removed by washing with water, followed by filtration, drying at 120 ° C., and baking at 500 ° C. to obtain iron oxide and manganese oxide. The same operation as in Example 3 was performed except that the obtained composite oxide of iron oxide and manganese oxide was used. The results are shown in Table 1.
- Example 1 Comparative Example 1 In Example 1, an experiment was performed in the same manner as in Example 1 except that zeolite was not added. The results are shown in Table 1.
- Example 3 (Comparative Example 3) In Example 10, an experiment was performed in the same manner as in Example 10 except that zeolite was not added. The results are shown in Table 1.
- Example 4 (Comparative Example 4) In Example 11, the experiment was performed in the same manner as in Example 11 except that zeolite was not added. The results are shown in Table 1.
- Examples 10 and 11 metal hydride gas abatement compared to Comparative Examples 3 and 4 where no zeolites were added to the same active component metal oxide mixture
- the performance was remarkably high.
- Examples 10 and 11 are slightly inferior compared with Examples 1 to 9 and Comparative Example 1 using different active ingredient basic copper carbonates. Although it is difficult to do, it has been shown that when the zeolite is added in the same active ingredient, the detoxification performance is remarkably improved.
- the detoxifying agent of the present invention can be applied to the detoxification of exhaust gases containing various metal hydrides such as silane, phosphine, and arsine generated in semiconductor manufacturing plants or liquid crystal manufacturing plants. Focusing on the combination of zeolites with materials, solid metal hydroxides, solid metal carbonates, solid metal basic carbonates or mixtures of these compounds, and using the pores and high surface area of zeolites to achieve physical adsorption and Combined with chemical reaction, even high concentration metal hydride can have high detoxification ability, can absorb metal hydride gas more efficiently than before, and has high absorption capacity, so it has high operational utility value .
- various metal hydrides such as silane, phosphine, and arsine generated in semiconductor manufacturing plants or liquid crystal manufacturing plants. Focusing on the combination of zeolites with materials, solid metal hydroxides, solid metal carbonates, solid metal basic carbonates or mixtures of these compounds, and using the pores and high surface area of zeolites to achieve physical adsorption and Combined with chemical reaction, even high
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Abstract
Description
(1)固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物にゼオライト類を添加することを特徴とする金属水素化物含有排ガス除害剤である。
(2)固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物の金属成分が、銅、鉄、コバルト、ニッケル、マンガン、亜鉛、クロムから選択されることを特徴とする金属水素化物含有排ガス除害剤である。
(3)ゼオライトの含有量が、除害剤全重量に対して10~90重量%であることを特徴とする金属水素化物含有排ガス除害剤である。
(4)固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物の前駆体である金属塩類とアルカリ化合物類との中和反応による沈殿中にゼオライト類を添加する又は固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物からなる金属粉体にゼオライト類を添加し混練後成型されることを特徴とする金属水素化物含有排ガス除害剤である。
(5)金属水素化物含有排ガスを、上記(1)~(4)に記載される除害剤に接触させることを特徴とする金属水素化物含有排ガスの除害方法である。
除害性能測定装置:常圧流通式反応装置
反応管のサイズ :内径28mm、長さ700mm
測定条件
使用除害剤量:60cc(充填高さ100mm)
GHSV :300hr-1
圧力 :常圧
反応温度 :常温
反応ガス組成:SiH4(シラン)1%
N2 バランス
除害剤60ccを充填高が100mmになるように反応管内に詰めて測定装置に設置し、次いで窒素で希釈した金属水素化物ガスを除害剤充填層に流通する。ガス流通開始後、反応管出口ガス中への金属水素化物ガス漏洩をブレークモニター(日本バイオニクス製)で測定、監視し、その出口濃度が5ppmに達するまでに流入したシランの積算量を求め、その量を処理剤1kg当りに換算する。具体的には測定結果から次の式によって金属水素化物ガスの除害性能は計算される。
除害性能(L/kg)=A×(B/100)×(C/E)
ここで、A:測定ガス流量(L/min.)
B:金属水素化物ガス濃度(容積%)
C:金属水素化物ガスの出口濃度が所定の濃度に達するまでの累積ガス流通時間(min.)
E:処理剤充填量(kg)
硫酸銅の水溶液に中和反応で得られる生成物の酸化物ベースで50重量%のY型ゼオライトを添加し硫酸銅/ゼオライト水溶液となし、これに合わせて準備した炭酸ナトリウムとの中和反応により塩基性炭酸銅の沈殿物を得た。次いで水洗することによって不純物類を充分除去した後濾過、110℃で乾燥し、塩性炭酸銅/ゼオライトを得た。得られた塩性炭酸銅/ゼオライトを用い、ニーダー中で塩基性炭酸銅/ゼオライト200gに対して純水120gを加えて充分混合した後、直径3mmのサイズに押出し成型し、110℃で乾燥した。得られた成型体を反応管に充填させた。このように調製した除害剤のシラン除害性能結果を表1に示した。
金属化合物として市販の塩基性炭酸銅を用い、ニーダー中で塩基性炭酸銅160gとY型ゼオライト40gに純水100gを加えて充分混合した後、直径3mmのサイズに押出し成型し、110℃で乾燥した。得られた成型体を反応管に充填させた。このように調製した除害剤のシラン除害性能結果を表1に示した。
Y型ゼオライトの添加量が50重量%以外は実施例2と同様に行い、その結果を表1に示した。
Y型ゼオライトの添加量が80重量%以外は実施例2と同様に行い、その結果を表1に示した。
添加したゼオライト種類がBEA25以外は実施例2と同様に行い、その結果を表1に示した。
添加したゼオライト種類がBEA150以外は実施例2と同様に行い、その結果を表1に示した。
添加したゼオライト種類がMOR20以外は実施例2と同様に行い、その結果を表1に示した。
添加したゼオライト種類がMFI27(プロトン型)以外は実施例2と同様に行い、その結果を表1に示した。
添加したゼオライト種類がMFI27(アンモニウム型)以外は実施例2と同様に行い、その結果を表1に示した。
硫酸銅280gと硫酸亜鉛160gを純水0.8Lに溶解した水溶液と、これに合わせて準備した炭酸ナトリウム240gを純水3Lに溶解したアルカリ水溶液との中和反応により、銅と亜鉛の複合化合物の沈殿物を得た。次いで水洗することによって不純物類を十分除去した後濾過、120℃で乾燥し、300℃で焼成し、酸化銅と酸化亜鉛を得た。得られた酸化銅と酸化亜鉛の複合酸化物を用いた以外は、実施例3と同様に行った。この結果を表1に示した。
硫酸鉄480gと硫酸マンガン160gを純水2Lに溶解した水溶液と、これに合わせて準備した炭酸ナトリウム350gを純水1.7Lに溶解したアルカリ水溶液との中和反応により、鉄とマンガンの複合化合物の沈殿物を得た。次いで水洗することによって不純物類を十分除去した後濾過、120℃で乾燥し、500℃で焼成し、酸化鉄と酸化マンガンを得た。得られた酸化鉄と酸化マンガンの複合酸化物を用いた以外は、実施例3と同様に行った。この結果を表1に示した。
実施例1において、ゼオライトを加えないこと以外は、実施例1と全く同様にして、実験を行った。この結果を表1に示した。
市販のべマイトにY形ゼオライトを加えニーダー中でベマイト/ゼオライト200gに対して酢酸2gと純水160gを加えて充分混合した後、直径3mmのサイズに押出し成型し、110℃で乾燥した。得られた成型体を反応管に充填させた。このように調製した除害剤の性能結果を表1に示した。
実施例10において、ゼオライトを加えないこと以外は、実施例10と全く同様にして、実験を行った。この結果を表1に示した。
実施例11において、ゼオライトを加えないこと以外は、実施例11と全く同様にして、実験を行った。この結果を表1に示した。
Claims (5)
- 固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物にゼオライト類を添加することを特徴とする金属水素化物含有排ガス除害剤。
- 固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物の金属成分が、銅、鉄、コバルト、ニッケル、マンガン、亜鉛、クロムから選択されることを特徴とする請求項1に記載の金属水素化物含有排ガス除害剤。
- ゼオライト類の含有量が、除害剤全重量に対して10~90重量%であることを特徴とする請求項1または2に記載の金属水素化物含有排ガス除害剤。
- 固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物の前駆体である金属塩類とアルカリ化合物類との中和反応による沈殿中にゼオライト類を添加する又は固体金属塩基性炭酸塩、固体金属酸化物、固体金属水酸化物、固体金属炭酸塩又はこれら化合物の混合物からなる金属粉体にゼオライト類を添加し混練後成型されることを特徴とする請求項1乃至3のいずれか一項に記載の金属水素化物含有排ガス除害剤。
- 金属水素化物含有排ガスを、請求項記載1乃至4のいずれか一項に記載の除害剤に接触させることを特徴とする金属水素化物含有排ガスの除害方法。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020117024985A KR101623228B1 (ko) | 2009-03-27 | 2009-03-27 | 휘발성 무기 수소화물 함유 배기가스 제해제 및 휘발성 무기 수소화물 함유 배기가스 제해 방법 |
DE112009004601.0T DE112009004601T5 (de) | 2009-03-27 | 2009-03-27 | Mittel zur Entgiftung von Abgas, enthaltend flüchtige anorganische Hydride und Verfahren zur Entgiftung von Abgas, enthaltend flüchtige anorganische Hydride |
US13/260,512 US8568672B2 (en) | 2009-03-27 | 2009-03-27 | Agent for detoxifying discharge gas containing volatile inorganic hydride and method of detoxifying discharge gas containing volatile inorganic hydride |
JP2011505790A JP6006492B2 (ja) | 2009-03-27 | 2009-03-27 | 揮発性無機水素化物含有排ガス除害剤及び揮発性無機水素化物含有排ガス除害方法 |
PCT/JP2009/056401 WO2010109671A1 (ja) | 2009-03-27 | 2009-03-27 | 揮発性無機水素化物含有排ガス除害剤及び揮発性無機水素化物含有排ガス除害方法 |
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US (1) | US8568672B2 (ja) |
JP (1) | JP6006492B2 (ja) |
KR (1) | KR101623228B1 (ja) |
DE (1) | DE112009004601T5 (ja) |
WO (1) | WO2010109671A1 (ja) |
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FR3117886A1 (fr) * | 2020-12-21 | 2022-06-24 | IFP Energies Nouvelles | Procede de captation de silicium en absence d’hydrogene |
FR3117887A1 (fr) * | 2020-12-21 | 2022-06-24 | IFP Energies Nouvelles | Procede de captation de silicium a faible vitesse spatiale horaire |
Citations (5)
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JPH08192024A (ja) * | 1995-01-20 | 1996-07-30 | Mitsui Toatsu Chem Inc | 排ガスの処理剤及び処理方法 |
JPH08318131A (ja) * | 1995-05-26 | 1996-12-03 | Mitsui Toatsu Chem Inc | 排ガスの処理剤及び処理方法 |
JP2003126647A (ja) * | 2001-10-22 | 2003-05-07 | Nippon Sanso Corp | 特殊ガスの除害方法及び装置 |
JP2007021318A (ja) * | 2005-07-14 | 2007-02-01 | Japan Pionics Co Ltd | 排ガスの処理方法及び処理装置 |
JP2007098194A (ja) * | 2005-09-30 | 2007-04-19 | Sharp Corp | 除害装置 |
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JPH0645447B2 (ja) | 1986-03-12 | 1994-06-15 | 三井東圧化学株式会社 | 水素化ケイ素の精製方法 |
JPH0729049B2 (ja) * | 1987-04-30 | 1995-04-05 | 三菱重工業株式会社 | 燃焼排ガス中の砒素化合物除去方法 |
JPH02139033A (ja) * | 1988-11-18 | 1990-05-29 | Chiyoda Corp | 有毒ガス吸着剤、その製造方法及びそれを用いる排ガスの浄化方法 |
JPH0724738B2 (ja) | 1993-02-05 | 1995-03-22 | 三井東圧化学株式会社 | 排ガスの高度処理剤 |
JP2561616B2 (ja) | 1993-03-17 | 1996-12-11 | 日本酸素株式会社 | 有害成分の固体除去剤 |
JP3557539B2 (ja) | 1994-12-07 | 2004-08-25 | 日本酸素株式会社 | 有害ガスの除害方法及び除害剤 |
JP2604991B2 (ja) * | 1994-12-22 | 1997-04-30 | 古河機械金属株式会社 | 排ガスの処理剤 |
US5916836A (en) * | 1996-12-27 | 1999-06-29 | Tricat Management Gmbh | Method of manufacture of molecular sieves |
JP4488616B2 (ja) | 2000-11-02 | 2010-06-23 | 三井化学株式会社 | 排ガスの処理剤及び処理方法 |
AU2003211667A1 (en) * | 2002-03-13 | 2003-09-22 | China Petroleum And Chemical Corporation | The transalkylation method of benzene and c9+ aromatic hydrocarbons |
JP2003326128A (ja) * | 2002-05-09 | 2003-11-18 | Ebara Corp | ヒ素又はヒ素化合物を含む排ガスの処理方法及び装置 |
-
2009
- 2009-03-27 US US13/260,512 patent/US8568672B2/en not_active Expired - Fee Related
- 2009-03-27 JP JP2011505790A patent/JP6006492B2/ja not_active Expired - Fee Related
- 2009-03-27 DE DE112009004601.0T patent/DE112009004601T5/de not_active Withdrawn
- 2009-03-27 KR KR1020117024985A patent/KR101623228B1/ko active IP Right Grant
- 2009-03-27 WO PCT/JP2009/056401 patent/WO2010109671A1/ja active Application Filing
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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JPH08192024A (ja) * | 1995-01-20 | 1996-07-30 | Mitsui Toatsu Chem Inc | 排ガスの処理剤及び処理方法 |
JPH08318131A (ja) * | 1995-05-26 | 1996-12-03 | Mitsui Toatsu Chem Inc | 排ガスの処理剤及び処理方法 |
JP2003126647A (ja) * | 2001-10-22 | 2003-05-07 | Nippon Sanso Corp | 特殊ガスの除害方法及び装置 |
JP2007021318A (ja) * | 2005-07-14 | 2007-02-01 | Japan Pionics Co Ltd | 排ガスの処理方法及び処理装置 |
JP2007098194A (ja) * | 2005-09-30 | 2007-04-19 | Sharp Corp | 除害装置 |
Also Published As
Publication number | Publication date |
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JP6006492B2 (ja) | 2016-10-12 |
US8568672B2 (en) | 2013-10-29 |
KR20120020101A (ko) | 2012-03-07 |
DE112009004601T5 (de) | 2014-01-09 |
JPWO2010109671A1 (ja) | 2012-09-27 |
KR101623228B1 (ko) | 2016-05-31 |
US20120107201A1 (en) | 2012-05-03 |
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