WO2015099024A1 - アンモニア分解触媒 - Google Patents
アンモニア分解触媒 Download PDFInfo
- Publication number
- WO2015099024A1 WO2015099024A1 PCT/JP2014/084277 JP2014084277W WO2015099024A1 WO 2015099024 A1 WO2015099024 A1 WO 2015099024A1 JP 2014084277 W JP2014084277 W JP 2014084277W WO 2015099024 A1 WO2015099024 A1 WO 2015099024A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- ammonia
- zeolite
- exhaust gas
- type zeolite
- Prior art date
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 236
- 239000003054 catalyst Substances 0.000 title claims abstract description 234
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 117
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 70
- 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 101
- 239000010457 zeolite Substances 0.000 claims abstract description 100
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 99
- 239000007789 gas Substances 0.000 claims abstract description 88
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 46
- 239000011574 phosphorus Substances 0.000 claims abstract description 46
- 238000005342 ion exchange Methods 0.000 claims abstract description 39
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 34
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 42
- 239000010949 copper Substances 0.000 claims description 34
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 25
- 239000005751 Copper oxide Substances 0.000 claims description 21
- 229910000431 copper oxide Inorganic materials 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 19
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 9
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- 229910052680 mordenite Inorganic materials 0.000 claims description 5
- 239000010970 precious metal Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 description 38
- 239000002002 slurry Substances 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 30
- 229910010413 TiO 2 Inorganic materials 0.000 description 24
- 230000000694 effects Effects 0.000 description 23
- 239000002245 particle Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 10
- 230000007423 decrease Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000002351 wastewater Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 239000006227 byproduct Substances 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 241000264877 Hippospongia communis Species 0.000 description 6
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000010865 sewage Substances 0.000 description 5
- 150000003464 sulfur compounds Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- -1 and W Inorganic materials 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052720 vanadium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001879 copper Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 1
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- 229940116349 dibasic ammonium phosphate Drugs 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229910052675 erionite Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910001657 ferrierite group Inorganic materials 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 238000004868 gas analysis Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000009533 lab test Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 235000019837 monoammonium phosphate Nutrition 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002897 organic nitrogen compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
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- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
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- Y02C20/00—Capture or disposal of greenhouse gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Definitions
- the present invention relates to an ammonia decomposition catalyst and a method for treating exhaust gas containing ammonia (ammonia exhaust gas). More particularly, the present invention relates to an ammonia decomposition catalyst for use in ammonia exhaust gas having a high water content.
- NH 3 gas and aqueous ammonia is widely as industrial applications, are used in large quantities, and NH 3 nitrogen in sewage treatment, waste water containing NH 3 used in the particle removing process in semiconductor manufacturing and the like.
- NH 3 gas is a substance with an irritating odor, and its emission amount is regulated by the Water Pollution Prevention Law because it is a bad odor prevention law when released into the atmosphere and as a BOD increasing substance as wastewater (waste water).
- a stripping method is known in which alkali is added to NH 3 nitrogen and steam or air is sent in a state where the temperature is raised.
- NH 3 in waste water is separated into a gas phase by a diffusion tower.
- the released NH 3 is oxidized and decomposed into harmless N 2 and water by an NH 3 oxidation catalyst and released to the atmosphere (see Patent Document 1).
- ammonia oxidation catalyst here, at least one metal element selected from Fe, Ni, Co, Pt, Pd, Ru, V, Cu, Cr, W, and Mo is used, titania, zirconia, alumina, silica, Activated carbon and those supported or contained in at least one carrier of these complexes are used.
- a method of treating NH 3 -containing exhaust gas with a two-stage catalyst layer has been proposed.
- NH 3 is treated with an ammonia oxidation catalyst containing Ti and Ag and one or more of Fe, Mn, Zn, Mo, V, and W, and nitrogen oxides of by-products generated by the treatment of NH 3 are treated.
- reduction treatment is performed with a known catalyst layer comprising Ti, Mo and V in the latter stage (see Patent Document 2).
- Patent Document 2 since the method of treating with the two-stage catalyst layer uses a part of the NH 3 gas before the treatment for the reduction treatment of the nitrogen oxide in the latter stage, a part of the NH 3 gas before the treatment is extracted and the catalyst in the latter stage is treated. It is necessary to control the means for sending to the bed and its gas flow, which complicates the apparatus and reaction control.
- the concentration of NO x also changes, making it difficult to desire stable operation.
- an NH 3 oxidation catalyst for treating excess NH 3 in a denitration catalyst is effective (see Patent Document 3). .
- N 2 O decomposition catalyst As possible in front of the step by suppressing the generation of the NO X decomposing NH 3 in NH 3 decomposition catalyst, contacting nitrous oxide generated processing gas a (N 2 O) in the N 2 O decomposition catalyst in a subsequent step A processing method has been proposed.
- the N 2 O decomposition catalyst that can be used in the latter stage include a catalyst in which Cu is supported on a zeolite composed of silicon and oxygen represented by the formula (SiO 2 ) 55 , Fe ion exchange ⁇ zeolite, and the like (Patent Document 4). reference).
- a catalyst comprising a catalyst component 1 for reducing nitrogen oxides and a second component having an activity of oxidizing NH 3 to generate NO X has been proposed.
- a catalyst containing titanium oxide and W, V or Mo oxide and silica, zeolite or alumina supporting noble metal was used, and the catalyst was measured by measuring the outlet N 2 O concentration and oxygen in the process.
- a purification method for adjusting the gas flow rate of the layer and the oxygen concentration in the process has been proposed (see Patent Document 5 and Patent Document 6).
- the catalyst in the above prior art examples contains V, and there are cases where V is scattered when the operating temperature range exceeds 410 ° C., and there is a need for an NH 3 decomposition catalyst that does not contain V. Yes.
- the present inventors have reported an invention of a catalyst for purifying exhaust gas containing organic nitrogen compounds formed by mixing copper oxide particles and zeolite particles, which can be converted to be harmless by converting organic compounds to N 2 (patent) Reference 7).
- a catalyst for purifying exhaust gas containing organic nitrogen compounds formed by mixing copper oxide particles and zeolite particles which can be converted to be harmless by converting organic compounds to N 2 (patent) Reference 7.
- ammonia exhaust gas having a water vapor concentration of less than 2 to 10% by volume for example, when decomposing ammonia in exhaust gas containing high concentration of water vapor having a water vapor concentration of 10% by volume or more, the same catalyst may be used.
- the ammonia decomposition rate is not sufficient, and the activity may decrease when used for a long time.
- copper oxide component 1: zeolite (component 2): noble metal (as a catalyst having high durability in the presence of high moisture, high sulfur and long life for stripping exhaust gas in sewage treatment.
- An ammonia decomposition catalyst was reported in which 40 parts by weight and (d) phosphorus content was 0.01 to 5% by weight as P based on the total weight of copper oxide and zeolite (see Patent Document 8). .
- Non-Patent Document 1 a catalyst having a two-layer structure having an SCR layer on a Pt / Al 2 O 3 layer has been reported (see Non-Patent Document 1). Laboratory experiments describe that providing an SCR layer reduces NO formation and improves N 2 selectivity, but also reduces overall NH 3 conversion.
- Non-Patent Document 2 a two-layer ammonia slip catalyst composed of an SCR layer and a PGM layer is reported (see Non-Patent Document 2).
- the objects of the present invention are: (1) A catalyst that decomposes ammonia to make NO x by-product ratio 0.6% or less, suppresses by-product formation of N 2 O as little as possible, converts ammonia into N 2, and renders it harmless Providing, (2) To provide a catalyst capable of decomposing ammonia in ammonia exhaust gas having a water concentration of 10 to 60% by volume, and further having a water concentration of 10 to 50% by volume into nitrogen with high efficiency, (3) It is to provide a catalyst having durability even when treating exhaust gas containing a sulfur compound as well as initial activity.
- the ammonia decomposition catalyst and ammonia exhaust gas treatment method of the present invention are as follows. That is, the present invention is a catalyst for treating ammonia exhaust gas containing moisture, A lower layer having a noble metal, an inorganic oxide, phosphorus, a first proton-type zeolite or a first ion-exchanged zeolite ion-exchanged with Cu, Co or Fe ions, and provided on the lower layer, An upper layer having a second proton type zeolite or a second ion exchange type zeolite ion-exchanged with Cu, Co or Fe ions, In the ammonia decomposition catalyst.
- Yet another aspect of the present invention is a method for treating an ammonia exhaust gas containing moisture, comprising:
- the method for treating exhaust gas includes the step of bringing the ammonia decomposition catalyst into contact with ammonia exhaust gas to decompose ammonia into nitrogen and water.
- the ammonia decomposition catalyst of the present invention exhibits a high NH 3 decomposition rate even in an ammonia exhaust gas with a high water content, and can suppress high NO X suppression and N 2 O byproduct.
- ammonia decomposition catalyst of the present invention has high durability even when treating exhaust gas containing sulfur compounds as well as initial activity.
- FIG. 1 is a drawing showing a comparison of performance evaluation between the comparative catalyst (B-3) and the catalysts of the present invention (A-1) and (D-1).
- FIG. 2 is a drawing showing the results of a durability test of the catalyst (A-1) of the present invention at an inlet temperature of 340 ° C.
- FIG. 3 is a drawing showing the results of a durability test of the catalyst (D-1) of the present invention at inlet temperatures of 250 ° C. and 340 ° C.
- FIG. 4 is a drawing showing a comparison of durability tests between the conventional catalyst (C-4) and the catalyst of the present invention (A-1).
- FIG. 5 is a drawing showing the results of a durability test of a conventional catalyst (C-4).
- Ammonia exhaust gas containing water An ammonia exhaust gas having a water concentration of 10% by volume or more.
- Decomposition rate Represents the ratio (%) of ammonia concentration in the exhaust gas before and after contacting the catalyst.
- NO X production rate and N 2 O production rate The ratio (%) of the NO x concentration or N 2 O produced in the exhaust gas after contact to the ammonia concentration in the exhaust gas before contact with the catalyst.
- Nitrogen oxide Refers to both NO X and N 2 O, and may be expressed as NO X or the like.
- N 2 selectivity A numerical value obtained by subtracting the generation rate of NO X and the like in exhaust gas after contacting the catalyst from the decomposition rate. That is, it is the ratio of ammonia converted to N 2 before contacting the catalyst.
- New catalyst A catalyst that has just been prepared or has just been used for exhaust gas treatment. The activity of the new catalyst is called initial activity.
- Catalyst used A catalyst after exhaust gas has been treated for a long time. For the evaluation of catalyst durability, the activity of the catalyst used is measured.
- the present invention is a catalyst for treating ammonia exhaust gas containing moisture, A lower layer having a noble metal, an inorganic oxide, phosphorus, a first proton-type zeolite or a first ion-exchanged zeolite ion-exchanged with Cu, Co or Fe ions, and provided on the lower layer, An upper layer having a second proton type zeolite or a second ion exchange type zeolite ion-exchanged with Cu, Co or Fe ions, In the ammonia decomposition catalyst. That is, it is particularly characterized in that an upper layer containing a denitration component is further provided on a lower layer containing an ammonia oxidation catalyst component and a denitration component.
- noble metal used in the present invention examples include Pt, Pd, Ir, Rh, or a composite thereof.
- Pt is particularly preferable because it has a large effect of improving decomposition activity and N 2 selectivity.
- the content of the noble metal is preferably 0.05% by weight or more and 5% by weight or less, and preferably 0.2% by weight or more and 2% by weight with respect to the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer.
- the amount of noble metal supported is preferably 0.05 g / L or more and 5 g / L or less, more preferably 0.1 g / L or more and 3 g / L or less, more preferably 0.2 g / L or more, based on the catalyst volume. 1 g / L or less is more preferable. Within the above range, better results can be obtained with respect to the ammonia decomposition rate, NO x production rate and N 2 O production rate.
- inorganic oxide examples include titania (TiO 2 ), zirconia (ZrO 2 ), silica (SiO 2 ), alumina and ceria / zirconia composite oxide or solid solution (CeO 2 .ZrO 2) . And a molar ratio of CeO 2 : ZrO 2 is 1: 3 to 3: 1).
- the inclusion of the above-described inorganic oxide is particularly effective for improving the action of the noble metal, that is, the decomposition activity, particularly the durability of the decomposition activity during long-term use.
- the content of the inorganic oxide in the catalyst is preferably 5% by weight or more and 50% by weight or less, preferably 10% by weight or more and 35% by weight based on the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer. More preferably, it is less than wt%.
- the amount of the inorganic oxide supported is preferably 1 g / L or more and 50 g / L or less, more preferably 5 g / L or more and 20 g / L or less with respect to the catalyst volume. Within the above range, better results can be obtained with respect to the ammonia decomposition rate, NO x production rate and N 2 O production rate.
- the inorganic oxide is contained in the catalyst in a state where a noble metal is supported.
- the TiO 2 0.1 wt relative to particles advance in the TiO 2% ⁇ 5 wt% on the TiO 2 particles (this is expressed as Pt / TiO 2.) Pt, other said particles By mixing with these components, a catalyst composition containing a noble metal and an inorganic oxide can be prepared.
- the particle size of the inorganic oxide used in the present invention is preferably a particle having an average particle size of 0.1 ⁇ m or more and 100 ⁇ m or less in order to more effectively exhibit the function of the noble metal component in the catalyst composition.
- the particle size is the size of the secondary particles, and is the length of the major axis when observed by SEM.
- An average particle diameter is an average value when a long diameter is measured using SEM about at least 10 particle
- TiO 2 that can be used in the present invention preferably has a BET specific surface area of 5 to 200 m 2 / g, more preferably 10 to 150 m 2 / g.
- ZrO 2 that can be used in the present invention is a ZrO 2 powder that is generally commercially available, regardless of whether it is monoclinic, tetragonal, or cubic, and is particularly porous with a specific surface area of 10 m 2 / g or more. Those are preferred. Also, composite ZrO 2 , such as ZrO 2 .nCeO 2 , ZrO 2 .nSiO 2 , ZrO 2 .nTiO 2 (where n is generally 0.25 to 0.75), etc. can be used.
- SiO 2 that can be used in the present invention includes high silica zeolite having a zeolite structure, such as mordenite.
- the lower layer of the ammonia decomposition catalyst of the present invention contains phosphorus together with noble metals, inorganic oxides, proton type or ion exchange type zeolites.
- the content of phosphorus is preferably 0.1% by weight or more and 10% by weight or less, preferably 1% by weight or more and 5% by weight or less, based on the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer. More preferred.
- the amount of phosphorus supported is preferably 0.1 g / L or more and 10 g / L or less, more preferably 0.5 g / L or more and 5 g / L or less with respect to the catalyst volume.
- the phosphorus content may be determined in consideration of the composition of the exhaust gas, that is, the ammonia concentration, the moisture concentration, and the processing conditions, that is, the processing temperature, the catalyst usage time, and the like. If the content or supported amount is too lower than the above range, the durability improvement effect is insufficient, whereas if the phosphorus content or supported amount is too higher than the above range, the initial activity may be reduced. is there.
- a conventional ammonia decomposition catalyst tends to cause a decrease in activity due to deterioration when used for a long time at a reaction temperature in ammonia exhaust gas containing a large amount of moisture.
- the ammonia decomposition catalyst of the present invention since phosphorus is contained, the activity is hardly lowered, and long-term decomposition activity performance is maintained, and high N 2 selectivity is maintained. .
- the inclusion of phosphorus also effectively prevents a decrease in activity when an ammonia exhaust gas containing a sulfur compound such as hydrogen sulfide, thiophene or sulfide is treated.
- Ammonia decomposition catalyst of the present invention further contains a phosphorus, the new catalyst and the catalyst used both with a high ammonia decomposition rate, of reducing by-product such as NO X, the effect is observed.
- the phosphorus may be ubiquitous on the upper layer side in the lower layer. That is, it may be configured such that the phosphorus content decreases sequentially or stepwise from the top of the lower layer.
- the proton type zeolite that can be used in the present invention may be a natural product or a synthetic product. Examples thereof include mordenite, erionite, ferrierite, chapasite, X-type zeolite, ⁇ -type zeolite, MFI-type zeolite, Y-type zeolite, and SAPO.
- Zeolite used in the present invention is proton type (H type), ammonium ion; alkali metal ion such as Na and K; alkaline earth metal ion such as Mg and Ca; group 8 metal ion such as Fe; An ion-exchanged zeolite ion-exchanged with any of Group 9 metal ions such as Co; Group 10 metal ions such as Ni; Group 11 metal ions such as Cu can be used. One or a mixture of two or more of these may be used.
- the first proton type zeolite or the first ion exchange type zeolite used in the lower layer may be the same as or different from the second proton type zeolite or the second ion exchange type zeolite in the upper layer. Both are preferably Cu ion exchange type zeolite.
- the content of the proton type zeolite or ion exchange type zeolite contained in the lower layer is preferably 40% by weight or more and 95% by weight or less based on the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer, More preferably, it is more than 90% by weight.
- the supported amount of proton type zeolite or ion exchange type zeolite contained in the lower layer is preferably 5 g / L or more and 95 g / L or less, more preferably 10 g / L or more and 90 g / L or less with respect to the catalyst volume. Within the above range, better results can be obtained with respect to the ammonia decomposition rate, NO x production rate and N 2 O production rate.
- the supported amount of proton type zeolite or ion exchange type zeolite contained in the upper layer is preferably 20 g / L or more and 150 g / L or less, more preferably 30 g / L or more and 130 g / L or less with respect to the catalyst volume. Within the above range, better results can be obtained with respect to the ammonia decomposition rate, NO x production rate and N 2 O production rate.
- the content of the proton type zeolite or ion exchange type zeolite contained in the upper layer is preferably 20% by weight or more and 400% by weight or less with respect to the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer. 40% by weight or more and 300% by weight or less is more preferable. Within the above range, better results can be obtained with respect to the ammonia decomposition rate, NO x production rate and N 2 O production rate.
- Copper oxide can be further contained in the lower layer of the ammonia decomposition catalyst of the present invention.
- Copper oxide refers to an oxide containing copper and includes a copper-containing composite oxide.
- the copper oxide include a copper oxide represented by a composition formula of a general formula CuO X (0.45 ⁇ X ⁇ 1.1). Typically, it is CuO and Cu 2 O, and includes a copper oxide present in a copper-containing composite oxide such as hopcalite.
- the copper oxide in the catalyst of the present invention has a function of maintaining high decomposition activity and N 2 selectivity.
- the content is preferably 1% by weight or more and 30% by weight or less, and more preferably 5% by weight or more and 10% by weight or less based on the total weight of the noble metal, inorganic oxide, phosphorus and zeolite contained in the lower layer.
- the copper oxide ratio is less than 1% by weight, the production of NO x and the like increases, and as a result, the N 2 selectivity may decrease.
- the copper oxide ratio exceeds 30% by weight, In particular, the proportion of zeolite decreases and the decomposition rate decreases.
- the supported amount of copper oxide is preferably 0.5 g / L or more and 20 g / L or less, more preferably 5 g / L or more and 10 g / L or less with respect to the catalyst volume. Within the above range, better results can be obtained with respect to the NO x production rate, N 2 selectivity and ammonia decomposition rate.
- Copper oxide is uniformly mixed in the catalyst together with zeolite and inorganic oxide.
- the average particle size is preferably 0.1 ⁇ m or more and 100 ⁇ m or less from the viewpoint of uniform dispersion with other components.
- the definitions of the particle diameter and the average particle diameter are as described above.
- the solid particles of the copper oxide As a means for containing the copper oxide in the catalyst, it is particularly preferable to use the solid particles of the copper oxide as a starting material.
- an aqueous solution containing a copper-containing compound for example, a copper salt such as copper sulfate or copper acetate, is mixed with other catalyst components, impregnated in the catalyst, and 300 to 600 in an air atmosphere.
- a method of converting a copper salt into a copper oxide by firing at ° C is mentioned.
- the ammonia decomposition catalyst of the present invention has a two-layer structure.
- the lower layer has a noble metal, an inorganic oxide, phosphorus, a first proton type zeolite or a first ion exchange type zeolite, and the upper layer has a second proton type zeolite or a second ion exchange type zeolite.
- Ammonia decomposition catalyst of the present invention by which the two-layer structure as described above, high moisture using the content of ammonia gas showed high NH 3 decomposition rate, and suppression of high NO x, sub of N 2 O Life can be suppressed.
- the thickness of the lower layer is preferably 10 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
- the thickness of the upper layer is preferably 10 to 200 ⁇ m, more preferably 30 to 100 ⁇ m.
- a support may be further provided on the surface of the lower layer opposite to the upper layer.
- circulation and a large contact area with gas is preferable.
- Preferred shapes include honeycombs, sheets, meshes, fibers, pipes and filters.
- an inorganic binder or an organic binder can be appropriately mixed and used.
- the inorganic binder include colloidal silica, silica sol, alumina sol, silicic acid sol, titania sol, boehmite, clay, kaolin, and sepiolite.
- a noble metal-containing aqueous solution is placed in a container, and an inorganic oxide is added thereto.
- the inorganic oxide is sufficiently impregnated with an aqueous solution containing a noble metal, and then heated with stirring to evaporate moisture and dry. Thereafter, the powder is further heated in a dryer, and the obtained powder is fired in the air to obtain inorganic oxide particles carrying a predetermined amount of noble metal (as a metal component).
- a predetermined amount of silica sol and the first proton type zeolite or the first ion exchange type zeolite are mixed together to prepare a slurry composition for the lower layer.
- This slurry is applied to a support and the surplus is blown off by air blow. Then, it heats and dries, and also calcinates in a high-temperature furnace under air circulation to obtain a lower layer catalyst.
- the method for incorporating phosphorus into the lower layer is as follows. That is, first, a phosphorus solution is prepared by mixing a solution of a phosphorus-containing compound and deionized water. Next, this solution is applied to the catalyst for the lower layer containing the precious metal, the inorganic oxide and the first proton type zeolite or the first ion exchange type zeolite prepared in advance, and the excess liquid is blown off by air blow. Thereafter, drying and baking are performed.
- the ammonia exhaust gas treatment catalyst of the present invention can further contain a copper oxide in the lower layer.
- a slurry for the upper layer is prepared by mixing deionized water with a predetermined amount of silica sol (for example, Snowtex C manufactured by Nissan Chemical Industries) and the second proton type zeolite or the second ion exchange type zeolite. This slurry is applied on the lower layer produced above, and the surplus is blown off by air blow. Thereafter, drying and baking are performed in the same manner as described above. Thereby, the ammonia decomposition catalyst which consists of two layers of this invention is obtained.
- silica sol for example, Snowtex C manufactured by Nissan Chemical Industries
- the phosphorus is ubiquitous on the upper layer side in the lower layer. That is, the phosphorus content is configured to decrease sequentially or stepwise from the top of the lower layer.
- the present invention also relates to a method for treating an ammonia exhaust gas containing moisture.
- This treatment method includes a step of decomposing ammonia into nitrogen and water by bringing the two-layered ammonia decomposition catalyst obtained above and ammonia exhaust gas into contact with each other.
- ammonia exhaust gas in which the ammonia decomposition catalyst of the present invention is used is not particularly limited as long as ammonia is contained in the exhaust gas.
- Examples include exhaust gas containing ammonia from various factories such as semiconductor factories, coke oven exhaust gas, leaked ammonia-containing gas from flue gas denitrification process, and exhaust gas generated by stripping ammonia-containing wastewater from sewage treatment plants, sludge treatment facilities, etc. It is done.
- ammonia exhaust gas is, for example, ammonia exhaust gas having a water concentration of 10% by volume or more, particularly ammonia exhaust gas having a water concentration of 20 to 50% by volume.
- the ammonia concentration of the ammonia exhaust gas to which the present invention can be applied is, for example, 10 vol ppm to 5 vol%.
- Ammonia exhaust gas and air are brought into contact with the catalyst of the present invention to convert ammonia into harmless nitrogen gas and water for oxidative decomposition.
- This oxidative decomposition temperature is appropriately determined depending on the properties in the exhaust gas (water vapor concentration or ammonia concentration), the reaction conditions (temperature, space velocity), the degree of catalyst deterioration, etc., but is usually 200 to 500 ° C., preferably 250 to 450 ° C. It is appropriate to select from these temperature ranges.
- the space velocity (SV) of the exhaust gas to be treated with respect to the catalyst may be appropriately selected from the range of 100 to 100,000 hr ⁇ 1 in consideration of the gas properties (ammonia concentration and moisture concentration), the target value of the ammonia decomposition rate, and the like.
- the concentration of ammonia in the gas supplied to the catalyst reactor is preferably adjusted to 3% by volume or less, preferably 2% by volume or less.
- concentration of ammonia exceeds 3% by volume, the temperature of the catalyst layer rises too much due to heat generated by the reaction, and the catalyst tends to deteriorate.
- an oxygen amount / theoretical required oxygen amount ratio of 1.03 to 10.0 at the inlet of the catalyst reactor preferably 1.1 to Air or oxygen-containing gas may be mixed from the outside so as to be 5.0.
- the theoretical required oxygen amount is the stoichiometric oxygen amount obtained from the equation (1).
- the ammonia concentration at the inlet of the reactor is 1.0% by volume
- the oxygen concentration is 0.77 to 7.5. % By volume, preferably 0.83 to 3.8% by volume.
- ⁇ Sludge from the sewage treatment plant is dehydrated with a dehydrator and the generated waste water is distilled with a distillation facility.
- a separation device is provided for further promoting evaporation of moisture and ammonia by blowing steam or steam and nitrogen gas from the outside. Water vapor containing ammonia separated by distillation is separated into water and ammonia in a separation tank, and exhaust heat is recovered. After that, steam (ammonia exhaust gas) containing high-concentration moisture and ammonia is introduced into the catalytic reactor, a necessary amount of air is introduced from outside, and the ammonia is decomposed into nitrogen and water vapor by contacting the catalyst and harmless. Process. An outline of the process is introduced in, for example, Japanese Patent Application Laid-Open No. 2002-28637.
- the catalyst of the present invention is preferably applied to the treatment of exhaust gas from activated sludge treatment.
- the exhaust gas has a severe composition for the catalyst such that the water concentration is 20 to 70% by volume, the sulfur compound is 10 to 200 ppm by weight with respect to S, the ammonia is 100 volume ppm to 3% by volume, and the balance is nitrogen. That is, the exhaust gas in which the catalyst of the present invention exhibits a particularly effective action is a gas mainly composed of water vapor and nitrogen, except for ammonia. Furthermore, the catalyst of the present invention is particularly preferably used for ammonia treatment in exhaust gas containing sulfur compounds.
- the exhaust gas discharged from the activated sludge treatment is an example, and it goes without saying that the exhaust gas is not limited to this, and it goes without saying that it is also used for ordinary ammonia exhaust gas treatment mainly composed of air. Yes.
- This powder was mixed with 64.4 g of deionized water to form a slurry.
- the slurry, 249 g of silica sol (Snowtex C, manufactured by Nissan Chemical Industries, Ltd.) and 142.3 g of Cu ion exchange ⁇ zeolite (manufactured by Clariant Catalyst, hereinafter sometimes referred to as “Cu ⁇ ”) are mixed and used for the lower layer.
- a slurry was prepared.
- This lower layer slurry was applied to a support of cordierite honeycomb 200 cells (number of cells: 200 cells / square inch, vertical 50 mm ⁇ width 50 mm ⁇ height 50 mm, volume: 0.125 liter), and the excess was blown by air blow Blowed away. Then, it dried for 4 hours with a 150 degreeC dryer, and also baked at 500 degreeC for 4 hours in the high temperature furnace under air circulation, and obtained the catalyst for lower layers.
- the amount of Pt at this time was 0.5 g per liter of catalyst, and the amount of Cu ion-exchanged ⁇ zeolite was 70 g.
- Catalyst A-2 The amount of Pt was changed from Pt (5.0) / TiO 2 to Pt (2.0) / TiO 2 , and other than that was prepared in the same manner as Catalyst A-1, and Catalyst A-2 was obtained.
- the catalyst A-2 was prepared in the same manner as the catalyst A-2 except that the TiO 2 of the catalyst A-2 was changed to ZrO 2 (manufactured by the first rare element), and a catalyst A-3 was obtained.
- the catalyst A-2 was prepared in the same manner as the catalyst A-2 except that the TiO 2 of the catalyst A-2 was changed to CeZrO 2 (manufactured by the first rare element), and a catalyst A-4 was obtained.
- the catalyst A-1 was prepared in the same manner as the catalyst A-1 by reducing the content of the Cu ion-exchanged ⁇ zeolite in the lower layer slurry of the catalyst A-1 so that the supported amount per unit volume was 20 g / liter and 40 g / liter, respectively. , A-6 was obtained.
- Catalysts A-7 and A-8> The loading amount of the upper layer slurry (Cu ⁇ slurry) of the catalyst A-1 was adjusted so that the loading amounts per unit volume were 40 g / liter and 120 g / liter, respectively, to obtain catalyst A-7 and catalyst A-8.
- ⁇ Catalyst D-1> In; (4.5 wt% Pt concentration), TiO 2 powder aqueous solution of dinitro-diamine platinum in the evaporation dish; a (manufactured by Ishihara Sangyo Kaisha, Ltd., average particle size 1 [mu] m, BET specific surface area of 60 m 2 / g) was added, TiO 2 The powder was sufficiently impregnated with an aqueous solution. Thereafter, the water was evaporated with stirring at a temperature of 80 to 90 ° C. and dried. Thereafter, it was further heated to 150 ° C. in a dryer. The obtained powder was baked in air at a temperature of 500 ° C.
- This lower layer slurry was applied to a support of cordierite honeycomb 200 cells (number of cells: 200 cells / square inch, vertical 50 mm ⁇ width 50 mm ⁇ height 50 mm, volume: 0.125 liter), and the excess was blown by air blow Blowed away. Then, it dried for 4 hours with a 150 degreeC dryer, and also baked at 500 degreeC for 4 hours in the high temperature furnace under air circulation, and obtained the catalyst for lower layers.
- the amount of Pt at this time was 0.5 g per liter of catalyst, and the amount of Cu ion exchange SAPO-34 zeolite was 70 g.
- ⁇ Comparative catalyst B-1> A slurry was prepared by mixing Pt (5.0) / TiO 2 powder, deionized water, and silica sol. This slurry was applied to a support of cordierite honeycomb 200 cells, and the excess was blown off by air blow. Thereafter, it was dried in a dryer at 150 ° C. for 4 hours, and further calcined at 500 ° C. for 4 hours in a high-temperature furnace under air flow to obtain a comparative catalyst B-1.
- ⁇ Comparative catalyst B-4> A slurry was prepared by mixing 64.4 g of deionized water, 249 g of silica sol (Snowtex C manufactured by Nissan Chemical Industries) and 142.3 g of Cu ion exchange ⁇ zeolite (manufactured by Clariant Catalyst). This slurry was applied onto the comparative catalyst B-2, and the excess was blown off by air blow. Thereafter, drying and calcination were carried out in the same manner as described above to obtain a comparative catalyst B-4.
- ⁇ Comparative catalyst B-5> An upper layer slurry (Cu ⁇ slurry) was applied on the comparative catalyst B-1, and dried and fired in the same manner as the comparative catalyst B-4, to obtain a comparative catalyst B-5. At this time, the coating amount was adjusted so that the amount of Cu ion-exchanged ⁇ zeolite supported on the upper layer was 70 g per liter of catalyst volume.
- Comparative catalyst B-1 is a catalyst containing Pt and titanium oxide.
- Comparative catalyst B-2 is a catalyst obtained by adding Cu ion-exchanged ⁇ zeolite to the components of comparative catalyst B-1.
- Comparative catalyst B-3 is a catalyst obtained by further adding phosphorus to comparative catalyst B-2, and is a catalyst containing a component corresponding to Patent Document 8.
- the comparative catalyst B-4 has a catalyst containing the catalyst component of the comparative catalyst B-2 as a lower layer, and the upper layer contains the same components as the upper layer of the present invention.
- Comparative catalyst B-5 has a catalyst containing the catalyst component of comparative catalyst B-1 as a lower layer, and the upper layer contains the same components as the upper layer of the present invention.
- Table 1 shows the composition of each catalyst (excluding the support).
- NH 3 decomposition rate 100- ⁇ (outlet NH 3 concentration) / (inlet NH 3 concentration) ⁇ 100 ⁇ NO x production rate (%): (Outlet NO x concentration) / (Inlet NH 3 concentration) ⁇ 100 N 2 O production rate (%): ⁇ (outlet N 2 O concentration) / (inlet NH 3 concentration) ⁇ x 100 N 2 selectivity (%): 100- ⁇ (100-NH 3 decomposition rate) + NO x production rate + N 2 O production rate ⁇ 2 ⁇
- the catalyst (A-1 to A-8) of the present invention having the component of the comparative catalyst B-3 as the lower layer and the upper layer containing the denitration component has high moisture (30%).
- the NO X production rate is 0.6% or less
- the N 2 O production rate is suppressed
- the N 2 selectivity is also significantly high.
- the catalyst (D-1) of the present invention containing CuSAPO as the upper and lower zeolite components similarly shows not only a high NH 3 decomposition rate against ammonia exhaust gas containing high moisture (30%), but also NO. It can be seen that the X production rate is 0.6% or less, the N 2 O production rate is suppressed, and the N 2 selectivity is also significantly high.
- the comparative catalyst B-3 corresponding to only the lower layer of the present invention has a very high NO x production rate of 1.80% and a low N 2 selectivity (see FIG. 1).
- the catalyst containing the denitration component Cu ion exchange ⁇ zeolite
- the NO x production rate becomes 0.6% or less
- the N 2 O production rate is suppressed
- the N 2 selectivity is also reduced. It can be seen that there was an unexpected effect that was significantly higher.
- the results of the comparative catalysts B-4 to B-5 have a low NO x production rate, but a relatively high N 2 O production rate and a relatively low N 2 selectivity.
- Durability tests were performed using catalysts A-1 and D-1.
- the catalyst when the inlet temperature is 340 ° C., the catalyst is not deteriorated even after 1000 hours, not only shows a high NH 3 decomposition rate, but also shows a NO x production rate of 0.6% or less, N 2 O The production rate was suppressed and the N 2 selectivity was also kept significantly high.
- the comparative catalyst started to decrease in NH 3 decomposition rate after 800 hours, and then rapidly decreased and decreased to 95% after 1200 hours. That is, the comparative catalyst was significantly deteriorated in a short time as compared with the present invention A-1.
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Abstract
Description
(1)アンモニアを分解して、NOXの副生率が0.6%以下であり、N2Oの副生成もできるだけ少なく抑制して、アンモニアをN2に転化して、無害化する触媒を提供すること、
(2)水分濃度が10~60容量%、更には水分濃度が10~50容量%のアンモニア排ガス中のアンモニアを高い効率で窒素に分解する触媒を提供すること、
(3)初期活性はもとより、硫黄化合物を含む排ガスを処理しても、耐久性を有する触媒を提供することにある。
貴金属と、無機酸化物と、リンと、第1のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第1のイオン交換型ゼオライトと、を有する下層、及び
前記下層上に設けられ、第2のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第2のイオン交換型ゼオライト、を有する上層、
を含む、アンモニア分解触媒にある。
前記のアンモニア分解触媒とアンモニア排ガスとを接触させて、アンモニアを窒素と水に分解する工程;を含む、排ガス処理方法にある。
本明細書で用いる用語の意味は、特に断らない限り以下のとおりである;
水分を含むアンモニア排ガス:水分濃度が10容量%以上のアンモニア排ガスをいう。
分解率: 触媒に接触する前と接触した後の排ガス中のアンモニア濃度の比率(%)を表す。
NOX生成率およびN2O生成率: 触媒に接触する前の排ガス中のアンモニア濃度に対する、接触後の排ガス中に生成したNOx濃度あるいはN2Oの比率(%)を表す。
窒素酸化物: NOXとN2Oの両方を指し、NOX等と表現することがある。
N2選択率: 分解率から、触媒に接触後の排ガス中NOX等の生成率を差し引いた数値を表す。すなわち触媒に接触する前のアンモニアのうち、N2に転化した割合である。
新触媒: 調製直後あるいは排ガス処理に使用して間もない段階の触媒をいう。新触媒の活性を初期活性という。
使用触媒: 長期間排ガスを処理した後の触媒をいう。触媒耐久性の評価には、使用触媒の活性等を測定する。
貴金属と、無機酸化物と、リンと、第1のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第1のイオン交換型ゼオライトと、を有する下層、及び
前記下層上に設けられ、第2のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第2のイオン交換型ゼオライト、を有する上層、
を含む、アンモニア分解触媒にある。すなわち、アンモニア酸化触媒成分と脱硝成分を含有する下層上にさらに脱硝成分を含有する上層を設けたことを特に特徴とする。
本発明で使用される貴金属には、Pt、Pd、Ir、Rhまたはその複合物等が挙げられる。これら貴金属の中でも、Ptは分解活性およびN2選択率の向上効果が大きいため、特に好ましい。
本発明で使用される無機酸化物としては、例えば、チタニア(TiO2)、ジルコニア(ZrO2)、シリカ(SiO2)、アルミナおよびセリア・ジルコニアの複合酸化物または固溶体(CeO2・ZrO2で表され、CeO2:ZrO2モル比は1:3~3:1である)から選ばれる少なくとも1種が挙げられる。上記した無機酸化物を含有させることは、貴金属の作用、すなわち分解活性の向上、とりわけ長期間使用中における分解活性の持続性向上に特に有効である。これらのなかでも、特にTiO2およびZrO2、セリア・ジルコニアは長期間使用における分解活性の持続効果が優れている。該無機酸化物の触媒中における含有量は、下層に含まれる貴金属、無機酸化物、リン及びゼオライトの重量の合計に対して5重量%以上、50重量%以下が好ましく、10重量%以上、35重量%以下がより好ましい。また、無機酸化物の担持量は、触媒容積に対して1g/L以上、50g/L以下が好ましく、5g/L以上、20g/L以下がより好ましい。上記の範囲内であると、アンモニア分解率、NOX生成率及びN2O生成率に関してより良好な結果が得られる。
本発明において、アンモニア分解触媒の下層にリンを含有させるのに使用できるリン含有化合物としては、リン酸(H3PO4)、メタリン酸、リン酸二水素アンモニウム(NH4H2PO4)、第二リン酸アンモニウム((NH4)2HPO4)等の水溶性のリン酸、これらのNa塩、K塩、アンモニウム塩等の無機塩又は有機酸エステルが例示される。
下層にリンを含有させるには、まず、リン含有化合物の溶液と脱イオン水を混ぜ合わせ、リン溶液を調製する。そして、この溶液を予め作成した貴金属、無機酸化物及び第1のプロトン型ゼオライトまたは第1のイオン交換型ゼオライトを含有する層に塗布し、余剰液をエアブローにて吹き飛ばす。その後、乾燥、焼成を実施する。
本発明で用いることができるプロトン型ゼオライトは天然品であっても合成品であってもよい。例えば、モルデナイト、エリオナイト、フェリエライト、シャパサイト、X型ゼオライト、β型ゼオライト、MFI型ゼオライト、Y型ゼオライト、及びSAPO等が挙げられる。本発明で用いられるゼオライトはプロトン型(H型)のほか、アンモニウムイオン;Na、K等のアルカリ金属のイオン;Mg、Ca等のアルカリ土類金属のイオン;Fe等の8族金属のイオン;Co等の9族金属のイオン;Ni等の10族金属のイオン;Cu等の11族金属イオンのいずれかとイオン交換したイオン交換型ゼオライトを用いることができる。これらの1種または2種以上の混合物を使用してもよい。
本発明のアンモニア分解触媒の下層に銅酸化物をさらに含有させることができる。銅酸化物は、銅を含む酸化物を指し、銅含有複合酸化物を含む。銅酸化物としては、一般式CuOX(0.45≦X≦1.1)の組成式で表される銅酸化物が挙げられる。典型的にはCuO及びCu2Oであり、ホプカライト等の銅含有複合酸化物で存在する銅酸化物を含む。
本発明のアンモニア分解触媒は、二層構造からなる。下層には、貴金属、無機酸化物、リン、第1のプロトン型ゼオライトまたは第1のイオン交換型ゼオライトを有し、上層には第2のプロトン型ゼオライトまたは第2のイオン交換型ゼオライトを有する。本発明のアンモニア分解触媒は、前記のような二層構造にしたことにより、高水分含有アンモニア排ガスに使用しても高いNH3分解率を示し、高いNOxの抑制と、N2Oの副生が抑制できる。
本発明の二層構造触媒は、前記下層における前記上層とは反対側の面に支持体をさらに設けることができる。使用する支持体の形状に特に制限はなく、ガス流通時に発生する差圧が小さく、ガスとの接触面積が大きい形状が好ましい。好ましい形状には、ハニカム、シート、メッシュ、繊維、パイプ、フィルターが含まれる。支持体の材質に特に制限はなく、コージェライト、アルミナ等公知の触媒担体、炭素繊維、金属繊維、ガラス繊維、セラミック繊維、チタン、アルミニウム、ステンレス等の金属が挙げられる。
以下、本発明のアンモニア分解触媒の製造方法について、一実施形態を説明する。ただし、製造方法については以下の方法に限定されるものではない。
まず、容器の中に貴金属含有水溶液を入れ、これに無機酸化物を加える。無機酸化物中に貴金属含有水溶液を十分含浸させた後、攪拌しながら加熱して水分を蒸発させ、乾燥させる。その後、更に乾燥機中で加熱し、得られた粉末を空気中で焼成して、貴金属(金属分として)が所定量担持された無機酸化物粒子を得る。
脱イオン水と所定量のシリカゾル(例えば、日産化学工業製スノーテックスC)及び第2のプロトン型ゼオライトまたは第2のイオン交換型ゼオライトを混ぜ合わせて、上層用スラリーを調製する。このスラリーを上記で作製した下層上に塗布し、余剰をエアブローにて吹き飛ばす。その後、上記と同様に乾燥、焼成を実施する。これにより、本発明の二層からなるアンモニア分解触媒を得る。
4NH3 +3O2 →6H2O+2N2・・・(1)
<触媒A-1>
蒸発皿の中でジニトロジアミン白金の水溶液(Pt濃度;4.5重量%)に、TiO2粉末(石原産業社製、平均粒径1μm、BET比表面積;60m2/g)を加え、TiO2粉末中に水溶液を十分含浸させた。その後、温度80~90℃で、攪拌しながら水分を蒸発させ、乾燥させた。その後、更に乾燥機中で150℃に加熱した。得られた粉末を空気中、500℃の温度で1時間焼成して、Pt(金属分として)が5.0重量%担持したTiO2粒子(これをPt(5.0)/TiO2と表示する。)を得た。この粉末と脱イオン水64.4gとを混ぜ合わせてスラリー状物とした。このスラリー状物とシリカゾル(日産化学工業製スノーテックスC)249gとCuイオン交換βゼオライト(クラリアント触媒製、以下「Cuβ」と表記することもある。)142.3gとを混ぜ合わせて、下層用スラリーを調製した。この下層用スラリーをコージライトハニカム200セル(セル数;200セル/平方インチ、たて50mm×横50mm×高さ50mm、容積;0.125リットル)の支持体に塗布し、余剰をエアブローにて吹き飛ばした。その後、150℃の乾燥機にて4時間乾燥し、更に空気流通下の高温炉にて500℃にて4時間焼成し下層用触媒を得た。このときのPt量は触媒1リットル当り0.5g、Cuイオン交換βゼオライトの量は70gであった。
Pt量をPt(5.0)/TiO2からPt(2.0)/TiO2に変更し、それ以外は触媒A-1と同様に調製し、触媒A-2を得た。
上記触媒A-2のTiO2をZrO2(第一希元素製)に変更し、それ以外は触媒A-2と同様に調製し、触媒A-3を得た。
上記触媒A-2のTiO2をCeZrO2(第一希元素製)に変更し、それ以外は触媒A-2と同様に調製し、触媒A-4を得た。
上記触媒A-1の下層用スラリー中のCuイオン交換βゼオライトの含有量を減らし単位容積あたりの担持量を20g/リットル、40g/リットルとして触媒A-1と同様に調製しそれぞれ触媒A-5、A-6を得た。
上記触媒A-1の上層用スラリー(Cuβスラリー)の担持量を調整し、単位容積あたりの担持量を40g/リットル、120g/リットルとしてそれぞれ触媒A-7、触媒A-8を得た。
蒸発皿の中でジニトロジアミン白金の水溶液(Pt濃度;4.5重量%)に、TiO2粉末(石原産業社製、平均粒径1μm、BET比表面積;60m2/g)を加え、TiO2粉末中に水溶液を十分含浸させた。その後、温度80~90℃で、攪拌しながら水分を蒸発させ、乾燥させた。その後、更に乾燥機中で150℃に加熱した。得られた粉末を空気中、500℃の温度で1時間焼成して、Pt(金属分として)が5.0重量%担持したTiO2粒子(これをPt(5.0)/TiO2と表示する。)を得た。この粉末と脱イオン水64.4gとを混ぜ合わせてスラリー状物とした。このスラリー状物とシリカゾル(日産化学工業製スノーテックスC)249gとCuイオン交換SAPO-34ゼオライト(UOP社製、以下「CuSAPO」と表記することもある。)142.3gとを混ぜ合わせて、下層用スラリーを調製した。この下層用スラリーをコージライトハニカム200セル(セル数;200セル/平方インチ、たて50mm×横50mm×高さ50mm、容積;0.125リットル)の支持体に塗布し、余剰をエアブローにて吹き飛ばした。その後、150℃の乾燥機にて4時間乾燥し、更に空気流通下の高温炉にて500℃にて4時間焼成し下層用触媒を得た。このときのPt量は触媒1リットル当り0.5g、Cuイオン交換SAPO-34ゼオライトの量は70gであった。
Pt(5.0)/TiO2粉末と脱イオン水とシリカゾルとを混ぜあわせスラリーを調製した。このスラリーをコージライトハニカム200セルの支持体に塗布し、余剰をエアブローにて吹き飛ばした。その後、150℃の乾燥機にて4時間乾燥し、更に空気流通下の高温炉にて500℃にて4時間焼成し比較触媒B-1を得た。
Pt(5.0)/TiO2粉末と脱イオン水とシリカゾルとCuイオン交換βゼオライトとを混ぜ合わせスラリーとした。このスラリーを、比較触媒B-1と同様にしてコージライト支持体に塗布し、乾燥焼成を行い比較触媒B-2を得た。
Pt(5.0)/TiO2粉末と脱イオン水とシリカゾルとCuイオン交換βゼオライトとを混ぜ合わせスラリーとした。このスラリーを、比較触媒B-1と同様にコージライト支持体に塗布し乾燥焼成を行い、第1層触媒を得た。
脱イオン水64.4gとシリカゾル(日産化学工業製スノーテックスC)249gとCuイオン交換βゼオライト(クラリアント触媒社製)142.3gとを混ぜ合わせて、スラリーを調製した。このスラリーを比較触媒B-2上に塗布し、余剰をエアブローにて吹き飛ばした。その後、上記と同様に乾燥、焼成を実施し、比較触媒B-4を得た。
前記比較触媒B-1上に上層用スラリー(Cuβスラリー)を塗布し、比較触媒B-4と同様に乾燥焼成を行い比較触媒B-5を得た。このとき、上層のCuイオン交換βゼオライトの担持量が触媒容積1リットル当り70gとなるように塗布量を調整した。
従来触媒C-4は、WO2006/006702号公報に記載の従来技術触媒(Pt=0.03;10-TiO2;CuO=10;H-モルデナイトを含む触媒(触媒組成110g/リットル)である。
前記で得られたハニカム型触媒から円柱状(直径21mm、長さ50mm)のハニカム型触媒を採取し、これを流通式反応装置に充填した。マスフローコントローラーにより流量を制御して所定のガス量を流通した。電気炉にて触媒を加熱することで触媒入口の温度(入口温度)を所定の温度として、アンモニア分解活性を評価した。
ガス条件:
SV=10,000h-1、NH3=1%、H20=30%、Airバランス
アンモニア: ガスクロマトグラフィー(TCD検出器)またはガス検知管
NOx: ケミルミネッセンス(化学発光式)分析装置
N2O: ガスクロマトグラフィー(TCD検出器)
NH3分解率(%):100-{(出口 NH3濃度)/ (入口NH3濃度) × 100}
NOx生成率(%):(出口NOx濃度)/(入口NH3濃度)× 100
N2O生成率(%):{(出口N2O濃度) / (入口NH3濃度)}x 100
N2選択率(%):100-{(100-NH3分解率)+NOx生成率+N2O生成率×2}
触媒A-1およびD-1を使用して耐久性試験を行った。評価試験は上記の活性評価試験と同様にして行った。入口温度をA-1においては340℃として、D-1においては250℃および340℃として試験を行った。ガス条件は、A-1においてはSV=5,000h-1、D-1においては10000h-1、NH3=1%(10000ppm)、H20=30%、Airバランスである。試験期間は、13,000時間である。
従来技術触媒(C-4:Pt=0.03;10-TiO2;CuO=10;H-モルデナイトを含む触媒(触媒組成g/リットル))の耐久試験を行い、本発明の触媒(A-1)と比較した。評価試験は上記の活性評価試験と同様にして行った。入口温度340℃で試験を行った。ガス条件は、SV=5,000h-1)、NH3=1%、H20=30%、Airバランスである。
Claims (13)
- 水分を含むアンモニア排ガスを処理するための触媒であって、
貴金属と、無機酸化物と、リンと、第1のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第1のイオン交換型ゼオライトと、を有する下層、及び
前記下層上に設けられ、第2のプロトン型ゼオライトまたはCu、CoもしくはFeイオンとイオン交換された第2のイオン交換型ゼオライト、を有する上層、
を含む、アンモニア分解触媒。 - 前記リンは、前記下層内において、前記上層側に偏在している、請求項1に記載のアンモニア分解触媒。
- 前記下層内に、さらに銅酸化物を含む、請求項1又は2に記載のアンモニア分解触媒。
- 前記貴金属がPt、Pd、Ir、Rhまたはその複合物であり、前記無機酸化物がチタニア、ジルコニア、セリアジルコニア、アルミナ、シリカまたはその混合物である、請求項1~3のいずれか1項に記載のアンモニア分解触媒。
- 前記プロトン型ゼオライト及び/又は前記イオン交換型ゼオライトが、β型、MFI型、Y型、モルデナイト型、SAPOからなる群から選択される請求項1~4のいずれか1項に記載のアンモニア分解触媒。
- 前記第1及び/又は第2のイオン交換型ゼオライトがCuイオン交換βゼオライトである、請求項5に記載のアンモニア分解触媒。
- 前記第1及び/又は第2のイオン交換型ゼオライトがCuイオン交換SAPOゼオライトである、請求項5に記載のアンモニア分解触媒。
- 前記下層における前記上層とは反対側の面に設けられた支持体をさらに有する、請求項1~7のいずれか1項に記載のアンモニア分解触媒。
- 前記下層における貴金属、無機酸化物、リン、プロトン型ゼオライト又はイオン交換型ゼオライトの相対割合(重量比)は、貴金属:無機酸化物:リン:プロトン型ゼオライト又はイオン交換型ゼオライト=0.05~5:5~50:0.1~10:40~95であり、上層のゼオライトの含有量は、下層に含まれる貴金属、無機酸化物、リン及びゼオライトの重量の合計に対して20重量%以上、400重量%以下である、請求項1~8のいずれか1項に記載のアンモニア分解触媒。
- 前記下層の厚さが10μm~200μmあり、前記上層の厚さが10μm~200μmである、請求項1~9のいずれか1項に記載のアンモニア分解触媒。
- 水分を含むアンモニア排ガスを処理するための方法であって、
請求項1~10のいずれか1項に記載のアンモニア分解触媒とアンモニア排ガスとを接触させて、アンモニアを窒素と水に分解する工程;を含む、排ガス処理方法。 - アンモニア排ガスは、水分濃度が10容量%以上である、請求項11に記載の排ガス処理方法。
- アンモニア排ガスは、水分濃度が20~50容量%である、請求項12に記載の排ガス処理方法。
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