CN105492119A - 排气净化过滤器和排气净化装置 - Google Patents
排气净化过滤器和排气净化装置 Download PDFInfo
- Publication number
- CN105492119A CN105492119A CN201480047854.3A CN201480047854A CN105492119A CN 105492119 A CN105492119 A CN 105492119A CN 201480047854 A CN201480047854 A CN 201480047854A CN 105492119 A CN105492119 A CN 105492119A
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- Prior art keywords
- zeolite
- exhaust
- oxide
- gas purifying
- purifying filter
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
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- 238000000746 purification Methods 0.000 title abstract 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 83
- 239000010457 zeolite Substances 0.000 claims abstract description 79
- 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 76
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 74
- 239000007789 gas Substances 0.000 claims abstract description 49
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 17
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 10
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 11
- 229910052723 transition metal Inorganic materials 0.000 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 claims description 3
- 239000012013 faujasite Substances 0.000 claims description 3
- 238000009992 mercerising Methods 0.000 claims description 3
- 239000011236 particulate material Substances 0.000 claims description 3
- 239000013618 particulate matter Substances 0.000 abstract description 3
- 239000005022 packaging material Substances 0.000 description 31
- 239000011148 porous material Substances 0.000 description 18
- 238000010304 firing Methods 0.000 description 17
- 239000011734 sodium Substances 0.000 description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 239000004411 aluminium Substances 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000002002 slurry Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 5
- 230000009931 harmful effect Effects 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000004202 carbamide Substances 0.000 description 4
- QNEFNFIKZWUAEQ-UHFFFAOYSA-N carbonic acid;potassium Chemical compound [K].OC(O)=O QNEFNFIKZWUAEQ-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- -1 alkali metal salt Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910010100 LiAlSi Inorganic materials 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 210000002421 cell wall Anatomy 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 235000006481 Colocasia esculenta Nutrition 0.000 description 1
- 240000004270 Colocasia esculenta var. antiquorum Species 0.000 description 1
- TWDJIKFUVRYBJF-UHFFFAOYSA-N Cyanthoate Chemical compound CCOP(=O)(OCC)SCC(=O)NC(C)(C)C#N TWDJIKFUVRYBJF-UHFFFAOYSA-N 0.000 description 1
- 206010013786 Dry skin Diseases 0.000 description 1
- 208000035126 Facies Diseases 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- YOHSHTNSFRGVKA-UHFFFAOYSA-H O.[Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound O.[Al+3].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YOHSHTNSFRGVKA-UHFFFAOYSA-H 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000288 alkali metal carbonate Inorganic materials 0.000 description 1
- 150000008041 alkali metal carbonates Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 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
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 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 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052730 francium Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000892 gravimetry Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052680 mordenite Inorganic materials 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 210000002706 plastid Anatomy 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- ILEXKRKTVIXABY-UHFFFAOYSA-J zirconium(4+);dicarbonate;hydrate Chemical compound O.[Zr+4].[O-]C([O-])=O.[O-]C([O-])=O ILEXKRKTVIXABY-UHFFFAOYSA-J 0.000 description 1
- UXRMCZYAVOHQNB-UHFFFAOYSA-J zirconium(4+);disulfate;hydrate Chemical compound O.[Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UXRMCZYAVOHQNB-UHFFFAOYSA-J 0.000 description 1
Classifications
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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
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
-
- 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
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9459—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts
- B01D53/9463—Removing one or more of nitrogen oxides, carbon monoxide, or hydrocarbons by multiple successive catalytic functions; systems with more than one different function, e.g. zone coated catalysts with catalysts positioned on one brick
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
-
- 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
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/7049—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
- B01J29/7057—Zeolite Beta
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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
- 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
- B01J29/70—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
- B01J29/7615—Zeolite Beta
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
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Abstract
本发明在于提供一种排气净化过滤器和具备该过滤器的排气净化装置,其中,即使共存有使排气中所含的颗粒状物质(PM)燃烧的催化剂和将氮氧化物还原为氮的SCR催化剂,也不损害SCR催化剂的催化功能。该排气净化过滤器特征在于,具备:含有选自碱金属中的1种或2种以上的元素和选自Zr、Si、Al及Ti中的1种或2种以上的元素的氧化物、以及二氧化硅/氧化铝比为15以上的沸石。
Description
技术领域
本发明涉及具备使排气中所含的颗粒状物质(PM:particulatematter)燃烧的催化剂和将氮氧化物还原为氮的选择性还原(SCR:Selectivecatalyticreduction)催化剂的排气净化过滤器和排气净化装置。
背景技术
在从柴油机等内燃机排出的排气中,含有PM、氮氧化物(NOx)、烃、一氧化碳等有害成分,为了除去这些有害物质使用了各种方法。特别是从卡车、巴士等柴油车排出的NOx、PM成为城镇地区的大气污染的原因之一,因此越来越加强对这些有害物质的限制。
对于PM,在配置于排气的流路中的蜂窝过滤器捕集PM,在PM沉积了规定量时,通过加热过滤器使PM燃烧分解的方法等除去。但是,PM的燃烧温度高达550~650℃,因此,存在装置变得大型并且用于加热的能量成本高这样的问题。
为了以更低温使PM燃烧,使用载持有催化剂的蜂窝过滤器。作为这样的催化剂已知有铂系催化剂。铂系催化剂将一氧化氮氧化,利用所得到的二氧化氮的氧化能力使PM燃烧除去。但是,铂的生产量极少,存在需求供给平衡和价格大幅变动的风险。为此,在专利文献1中,提出了碱金属的硅酸盐、铝酸盐和锆酸盐作为由于碱金属高的催化活性能够使PM在低温燃烧的催化剂。
NOx通过使用SCR催化剂的方法等除去。例如,通过在配置于排气系统的蜂窝过滤器载持沸石系催化剂,向其注入由尿素等的氨前体物质得到的还原剂或氨自身,NOx如反应式(1)~(3)所示还原为氮。作为这样的方法,专利文献2中有提出。
4NH3+4NO+O2→4N2+6H2O(1)
2NH3+NO+NO2→2N2+3H2O(2)
8NH3+6NO2→7N2+12H2O(3)
为了除去PM和NOx,以在组合上述系统得到的装置、例如除去PM的装置的下游配置除去NOx的装置的方式,作为分别独立的装置配置于排气的流路中。但是,由于市场上小型化的需求,希望为使除去PM的装置和除去NOx的装置一体化的装置。
现有技术文献
专利文献
专利文献1:日本特开平10-118490号公报
专利文献2:日本特表2010-524677号公报
发明内容
发明所要解决的课题
如果使用于将PM燃烧除去的碱金属系催化剂和SCR催化剂共存,则碱金属系催化剂中所含的碱金属离子与SCR催化剂反应,存在损害作为SCR催化剂的功能的问题。
本发明的目的在于提供一种排气净化过滤器和具备该过滤器的排气净化装置,该排气净化过滤器中,即使共存有使排气中所含的PM燃烧的催化剂和将氮氧化物还原为氮的SCR催化剂,也不损害SCR催化剂的催化功能。
用于解决课题的方法
本发明提供以下的排气净化过滤器和排气净化装置。
项1一种排气净化过滤器,具备:含有选自碱金属中的1种或2种以上的元素和选自Zr、Si、Al及Ti中的1种或2种以上的元素的氧化物,以及二氧化硅/氧化铝比为15以上的沸石。
项2如项1所述的排气净化过滤器,其中,含有上述氧化物作为使排气中所含的颗粒状物质燃烧的催化剂,含有上述沸石作为将氮氧化物还原为氮的催化剂。
项3如项1或2所述的排气净化过滤器,其中,上述氧化物为A2XZrXSiYO3X+2Y、AXAlXSiYO2X+2Y、A2XTiXSiYO3X+2Y、A2XTiYOX+2Y、A2XZrYOX+2Y或AXAlYOX/2+3Y/2(各式中,A表示1种或2种以上的碱金属,X表示满足1≤X≤2的正实数,Y表示满足1≤Y≤6的正实数。)所示的化合物中的1种或2种以上。
项4如项1~3中任一项所述的排气净化过滤器,其中,上述沸石为选自丝光(mordenite)型沸石、八面(faujasite)型沸石、A型沸石、L型沸石、β沸石和ZSM-5型沸石中的1种或2种以上。
项5如项1~4中任一项所述的排气净化过滤器,其中,上述沸石含有过渡金属。
项6如项1~5中任一项所述的排气净化过滤器,其中,上述氧化物和上述沸石载持于载体。
项7如项6所述的排气净化过滤器,其中,上述载体为蜂窝过滤器。
项8一种排气净化装置,其具备项1~7中任一项所述的排气净化过滤器。
发明的效果
根据本发明,能够以低温使捕集的PM燃烧,并且能够将NOx还原除去。
具体实施方式
以下,对实施本发明的优选实施方式的一例进行说明。但是,下述的实施方式仅用于例示。本发明不受下述实施方式任何限定。
(氧化物)
本发明中所使用的氧化物特征在于,含有选自碱金属中的1种或2种以上的元素和选自Zr、Si、Al和Ti中的1种或2种以上的元素。可以认为,根据该构成,利用碱金属高的催化活性,能够使从内燃机等排出的PM以低温燃烧,并且抑制碱金属的溶出。
优选的实施方式的本发明中所使用的氧化物,更具体而言,能够以A2XZrXSiYO3X+2Y、AXAlXSiYO2X+2Y、A2XTiXSiYO3X+2Y、A2XTiYOX+2Y、A2XZrYOX+2Y、AXAlYOX/2+3Y/2等通式表示。式中,A表示碱金属,X表示满足1≤X≤2的正实数,Y满足1≤Y≤6的正实数。更优选Y为满足1≤Y≤4的正实数。作为碱金属,有Li、Na、K、Rb、Cs、Fr,其中,从经济上有利的观点考虑,优选Li、Na、K、Cs。
作为A2XZrXSiYO3X+2Y,例如,能够例示Li2ZrSiO5、Na2ZrSiO5、Na4Zr2Si3O12、Na2ZrSi2O7、Na2ZrSi3O9、K2ZrSiO5、K2ZrSi2O7、K2ZrSi3O9、Cs4Zr2Si3O12、Cs2ZrSi2O7、Cs2ZrSi3O9等。
作为AXAlXSiYO2X+2Y,例如,能够例示LiAlSiO4、LiAlSi2O6、LiAlSi3O8、NaAlSiO4、NaAlSi2O6、NaAlSi3O8、KAlSiO4、KAlSi2O6、KAlSi3O8等。
作为A2XTiXSiYO3X+2Y,例如,能够例示Li2TiSiO5、Li2TiSi2O7、Li2TiSi3O9、Na2TiSiO5、Na2TiSi2O7、Na2TiSi3O9、K2TiSiO5、K2TiSi2O7、K2TiSi3O9等。
作为A2XTiYOX+2Y,例如,能够例示Na2TiO3、Na2Ti2O5、Na2Ti4O9、Na2Ti6O13、Na2Ti8O17、K2TiO3、K2Ti2O5、K2Ti4O9、K2Ti6O13、K2Ti8O17等。
作为A2XZrYOX+2Y,例如,能够例示Na2ZrO3、K2ZrO3等。
作为AXAlYOX/2+3Y/2,例如,能够例示NaAlO2、NaAl5O8、KAlO2、KAl5O8等。
优选本发明中所使用的氧化物为A2XZrXSiYO3X+2Y、AXAlXSiYO2X+2Y、A2XTiXSiYO3X+2Y、A2XTiYOX+2Y。
本发明中所使用的氧化物能够在不损害其优异特性的范围内含有其它元素。例如,能够例示Fe、Cu、Nb、Ce、Ca、Mg、Sr、Ba、Y、Mn、P、La、Sm等。其它元素的含有比例优选为0.1~30.0摩尔%的范围。
本发明中所使用的氧化物的制造方法没有特别限定,例如,能够根据目标化合物的组成从碱金属盐、锆源、硅源、铝源、钛源中适当选择作为原料,通过将这些原料混合烧制来制造。烧制温度优选为700~1300℃的范围,更优选为800~1200℃的范围。
作为碱金属盐,有碱金属的碳酸盐、碳酸氢盐、氢氧化物、乙酸盐等有机酸盐、硫酸盐、硝酸盐等,优选碳酸盐。
作为锆源,只要是含有锆元素、不抑制通过烧制的氧化物的生成的原材料即可,没有特别限定,例如,有通过在空气中烧制得到氧化锆的化合物等。作为这样的化合物,例如,可以列举氧化锆、碳酸锆水合物、硫酸锆水合物等,优选氧化锆。
作为硅源,只要是含有硅元素、不抑制通过烧制的氧化物的生成的原材料即可,没有特别限定,例如,有通过在空气中烧制得到氧化硅的化合物等。作为这样的化合物,例如,可以列举氧化硅、硅等,优选氧化硅。
作为铝源,只要是含有铝元素、不抑制通过烧制的氧化物的生成的原材料即可,没有特别限定,例如,有通过在空气中烧制得到氧化铝的化合物等。作为这样的化合物,例如,可以列举氧化铝、碳酸铝水合物、硫酸铝水合物等,优选氧化铝。
作为钛源,只要是含有钛元素、不抑制通过烧制的氧化物的生成的原材料即可,没有特别限定,例如,有通过在空气中烧制得到氧化钛的化合物等。作为这样的化合物,例如,可以列举氧化钛、金红石矿石、氢氧化钛湿滤饼、水合二氧化钛等,优选氧化钛。
(沸石)
本发明中所使用的沸石的特征在于,二氧化硅/氧化铝比为15以上。二氧化硅/氧化铝比的下限值优选为20,更优选为25。二氧化硅/氧化铝比的上限值优选为100,更优选为50。可以认为,根据该构成,利用还原剂作为NOx的SCR催化剂作用,不受从氧化物溶出的碱金属离子的影响,能够将NOx还原除去。作为还原剂,例如,能够使用尿素、碳酸铵、肼、碳酸氢铵等的氨前体物质、或氨自身。
沸石是指为结晶性铝硅酸盐、且具有4个氧原子在硅元素和铝元素的周围规则地三维结合的晶体结构的多孔质体。作为本发明中所使用的沸石的晶体结构,有丝光型沸石、八面型沸石、A型沸石、L型沸石、β沸石、ZSM-5型沸石等,优选为β沸石、ZSM-5型沸石。另外,为了促进催化活性,能够通过离子交换在沸石中含有Cu、Fe、Pt、Ag、Ti、Mn、Ti、Ni、Co、Pd、Rh、V、Cr等过渡金属,过渡金属的合计量相对于沸石的总重量优选为1~15质量%。更优选为1~8质量%的范围。
本发明中所使用的沸石有天然产沸石和合成沸石,只要是上述构成即可,能够没有特别限制地使用。从具有更均一的二氧化硅/氧化铝比、结晶大小、结晶形态且杂质少的观点考虑,优选合成沸石。
(排气净化过滤器)
本发明的排气净化过滤器的特征在于具备氧化物和沸石,能够以低温使PM燃烧并且能够将NOx还原除去。另外,本发明的排气净化过滤器中在不损害其优异特性的范围内还能够具备氧化催化剂、三效催化剂(Three-WayCatalyst)、氧吸留催化剂等。
本发明的排气净化过滤器优选氧化物和沸石载持于载体。作为载体,只要有过滤功能即可,没有特别限定,能够使用现有公知的载体,例如,有蜂窝过滤器。具体而言,优选使用陶瓷制的壁流型蜂窝过滤器。作为材质的陶瓷,优选使用碳化硅、堇青石、莫来石、氧化铝、钛酸铝等,从耐热性、耐碱性的观点考虑,更优选钛酸铝。只要为壁流型即可,其小室(cell)数、壁厚没有特别限定,小室数优选为200~400个小室/平方英寸,壁厚优选为200~380μm。另外,小室壁面为多孔质即可,没有特别限制,优选具有长径为8~18μm左右的细孔,气孔率优选为45~65%。
作为使氧化物和沸石载持于载体的方法,可以列举浸渍法、喷雾法等。例如,利用浸渍法,将氧化物和/或沸石制备成含有粘合剂、分散剂等的浆料,在该制备的浆料中浸渍载体,提起并干燥后,将有机成分在300℃~800℃烧制除去,由此,能够使氧化物和沸石载持于载体。另外,也能够将作为载体原料的陶瓷与氧化物和/或沸石,与造孔剂等混合,将混合物成型为载体的形状之后,进行烧制,由此载持于载体。氧化物和沸石可以同时载持于载体,也可以分别载持。通过这样载持,能够将氧化物和沸石载持于载体的表面、小室壁面、细孔等来使用。
本发明中,氧化物和沸石能够根据目标性能选择适当载持量。氧化物例如相对于载体100质量份,能够以1~40质量份、优选以1~30质量份的范围使用。沸石例如相对于载体100质量份,能够以1~40质量份、优选以1~30质量份的范围使用。氧化物和沸石的比率优选为沸石相对于氧化物100质量份为5~200质量份的范围。
本发明中,作为处理对象的排气,能够列举从柴油机、汽油机等内燃机等排出的排气、各种燃烧设备等的排气。
本发明的排气净化过滤器通过配置于排气流路中,与排气接触来使用。这些排气中的PM的除去如下进行:使PM在过滤器沉积,将沉积了规定量PM的过滤器在氧的存在下加热至PM的燃烧温度。另外,这些排气中的NOx的除去在还原剂、例如尿素、碳酸铵、肼、碳酸氢铵等的氨前体物质、或氨自身的存在下进行。还原剂在排气流路中可以配置于本发明的排气净化过滤器的上游,供给适当需要量。
本发明的排气净化过滤器能够以一个过滤器使排气中的有害物质PM在低温燃烧,能够还原除去NOx。由于其优异功能,能够合适地用于柴油机用过滤器(DPF)、汽油机用过滤器等,能够对应市场上小型化的需求。
(排气净化装置)
本发明的排气净化装置具备上述本发明的排气净化过滤器。具体而言,除了上述本发明的排气净化过滤器以外,例如,还具备对排气净化过滤器供给还原剂等的设备、用于分解沉积的PM的将排气净化过滤器加热的设备等。
实施例
以下,对于本发明,基于实施例进行更详细的说明。本发明不受以下实施例任何限定,在不改变其要点的范围内能够适当变更实施。
[氧化物的合成]
(合成例1)
混合碳酸钠33.2质量份、氧化锆38.6质量份和氧化硅28.2质量份,在1200℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为Na4Zr2Si3O12的单相。
(合成例2)
混合碳酸钾36.2质量份、氧化锆32.3质量份和氧化硅31.5质量份,在1200℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为K2ZrSi2O7的单相。
(合成例3)
混合碳酸钠32.3质量份、氧化铝31.1质量份和氧化硅36.6质量份,在1200℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为NaAlSiO4的单相。
(合成例4)
混合碳酸钾38.4质量份、氧化铝28.3质量份和氧化硅33.3质量份,在1200℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为KAlSiO4的单相。
(合成例5)
混合碳酸钾49.7质量份、氧化钛28.7质量份和氧化硅21.6质量份,在1000℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为K2TiSiO5的单相。
(合成例6)
混合碳酸钾22.4质量份、氧化钛77.6质量份,在1000℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为K2Ti6O13的单相。
(合成例7)
混合碳酸钠28.5质量份、氧化铌71.5质量份,在950℃烧制4小时。通过X射线衍射确认了所得到的颗粒状固体为NaNbO3的单相。
(实施例1)
〔载体的制作和氧化物的载持〕
相对于氧化物(Na4Zr2Si3O12)10质量份,配合钛酸铝(MarusuGlaze公司制)90质量份、石墨10质量份、甲基纤维素10质量份和脂肪酸皂0.5质量份,再添加适当量水,进行混炼,得到能够挤出成型的坯料。
使用挤出成型机将所得到的坯料挤出成型为蜂窝结构体,得到成型体。模具的小室密度为300小室/平方英寸(46.5小室/cm2),隔壁厚度为300μm。
固体成分基本由上述的粒状钛酸铝颗粒和氧化物(Na4Zr2Si3O12)构成,添加粘度调整材料等添加物,制备浆料。此外,浆料中的固体成分的比率与上述同样。在作为蜂窝结构体的成型体中,以开口的小室和密封的小室相互成为方格花纹的方式,在蜂窝结构体的小室中注入该浆料,进行封口。
将所得到的成型体在600℃保持10小时,之后以25℃/小时升温至1000℃,在1000℃保持10小时进行烧制,由此,得到细孔径11μm、气孔率51%的蜂窝结构体。
[沸石的载持]
接着,以湿式混合ZSM‐5型沸石(HSZ‐840、东曹株式会社制)40重量份和乙酸铜2重量份,将其与硅溶胶20重量份和水40重量份混合,制备浆料。在制备的浆料中浸渍上述得到的蜂窝结构体。浸渍后在600℃~700℃烧制约4小时,制造排气净化过滤器。使用的沸石的二氧化硅/氧化铝比示于表1中。
蜂窝结构体中载持的沸石的量相对于钛酸铝90质量份为19质量份。
(实施例2)
将氧化物变更为K2ZrSi2O7,除此以外,以与实施例1相同的方法进行。细孔径为11μm,气孔率为53%。
(实施例3)
将氧化物变更为NaAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为51%。
(实施例4)
将氧化物变更为KAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为β沸石(HSZ‐940、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为53%。
(实施例5)
将氧化物变更为K2TiSiO5,将载体的制作中的成型体的烧制温度变更为850℃,并且将沸石变更为β沸石(HSZ‐930、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为11μm,气孔率为53%。
(实施例6)
将氧化物变更为K2Ti6O13,将载体的制作中的成型体烧制温度变更为850℃,并且将沸石变更为β沸石(HSZ‐930、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为9μm,气孔率为49%。
(实施例7)
将氧化物变更为NaAlSiO4将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为ZSM‐5型沸石(HSZ‐820、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为51%。
(实施例8)
将氧化物变更为NaAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为ZSM‐5型沸石(HSZ‐830、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为51%。
(实施例9)
将氧化物变更为KAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为ZSM‐5型沸石(HSZ‐820、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为53%。
(实施例10)
将氧化物变更为KAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为ZSM‐5型沸石(HSZ‐830、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为53%。
(实施例11)
将氧化物变更为KAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为53%。
(比较例1)
将沸石变更为Y型沸石(HSZ‐350:东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为11μm,气孔率为51%。
(比较例2)
将氧化物变更为NaAlSiO4,将载体的制作中的成型体的烧制温度变更为1100℃,并且将沸石变更为Y型沸石(HSZ‐350、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为51%。
(比较例3)
将氧化物变更为NaNbO3,将载体的制作中的成型体的烧制温度变更为850℃,除此以外,以与实施例1相同的方法进行。细孔径为9μm,气孔率为47%。
(比较例4)
不使用氧化物,将载体的制作中的成型体的烧制温度变更为1450℃,并且将沸石变更为β沸石(HSZ‐930、东曹株式会社制),除此以外,以与实施例1相同的方法进行。细孔径为13μm,气孔率为56%。
[NOx浓度评价]
预先将排气净化过滤器含浸于尿素水溶液中,在50℃干燥,将排气净化过滤器设置于模拟排气排气线路上。之后,使模拟排气(O2:10%、N2:90%、NO:50ppm、NO2:50ppm、CO:60ppm)上升至300℃,测定NOx浓度。将结果示于表1中。
[过滤器再生率]
预先测定排气净化过滤器的初始重量,在柴油机的排气线路依次设置氧化催化剂(DOC)和排气净化过滤器。接着,启动柴油机,以低温使PM沉积规定量(约8g/L)之后,暂时卸下排气净化过滤器,测定沉积的PM的重量。
接着,将排气净化过滤器设置于模拟排气排气线路之后,使模拟排气上升至540℃,开始再生试验。从到达540℃的时刻保持30分钟540℃±10℃的温度,经过30分钟之后,将模拟气体全部换为N2。
使温度降低至之后,再次取出排气净化过滤器,测定重量减少部分(=PM燃烧重量)。
由以下的计算式算出再生率。将结果示于表1中。
再生率(%)=100-[(PM沉积重量(g)-PM燃烧重量(g))/PM沉积重量(g)]×100
[表1]
由表1所示的结果可知,使用根据本发明的实施例1~11的排气净化过滤器时,NOx浓度降低,并且得到高的再生率。相对于此,使用与实施例1相同的氧化物、使用本发明的范围外的沸石的比较例1的排气净化过滤器中,NOx浓度变高,再生率降低。另外,使用与实施例3相同的氧化物、使用本发明的范围外的沸石的比较例2的排气净化过滤器中,也是NOx浓度变高,再生率降低。
比较例3中,使用与实施例1~3相同的沸石,使用本发明的范围外的氧化物,此时,也是NOx浓度变高,再生率降低。
由这些结果可知,通过组合使用本发明的范围的氧化物与本发明的范围的沸石,能够降低NOx浓度,并且得到高的再生率。
比较例4中,不使用氧化物,仅使用沸石。此时,能够降低NOx浓度。由此可知,使用本发明的范围外的氧化物时,氧化物中所含的碱金属对沸石的作用产生不良影响。因此,可以认为,通过使用本发明的范围的氧化物,能够抑制对沸石的作用产生不良影响的碱金属的溶出。
Claims (8)
1.一种排气净化过滤器,其特征在于,具备:
含有选自碱金属中的1种或2种以上的元素和选自Zr、Si、Al及Ti中的1种或2种以上的元素的氧化物,和
二氧化硅/氧化铝比为15以上的沸石。
2.如权利要求1所述的排气净化过滤器,其特征在于:
含有所述氧化物作为使排气中所含的颗粒状物质燃烧的催化剂,含有所述沸石作为将氮氧化物还原为氮的催化剂。
3.如权利要求1或2所述的排气净化过滤器,其特征在于:
所述氧化物为A2XZrXSiYO3X+2Y、AXAlXSiYO2X+2Y、A2XTiXSiYO3X+2Y、A2XTiYOX+2Y、A2XZrYOX+2Y或AXAlYOX/2+3Y/2所示的化合物中的1种或2种以上,各式中,A表示1种或2种以上的碱金属,X表示满足1≤X≤2的正实数,Y表示满足1≤Y≤6的正实数。
4.如权利要求1~3中任一项所述的排气净化过滤器,其特征在于:
所述沸石为选自丝光型沸石、八面型沸石、A型沸石、L型沸石、β沸石和ZSM-5型沸石中的1种或2种以上。
5.如权利要求1~4中任一项所述的排气净化过滤器,其特征在于:
所述沸石含有过渡金属。
6.如权利要求1~5中任一项所述的排气净化过滤器,其特征在于:
所述氧化物和所述沸石载持于载体。
7.如权利要求6所述的排气净化过滤器,其特征在于:
所述载体为蜂窝过滤器。
8.一种排气净化装置,其特征在于:
具备权利要求1~7中任一项所述的排气净化过滤器。
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FR3061037B1 (fr) | 2016-12-23 | 2021-07-02 | Ifp Energies Now | Solide porteur d'oxygene a base de tectosilicates, son procede de preparation et son utilisation pour un procede d'oxydo-reduction en boucle chimique |
WO2018181100A1 (ja) * | 2017-03-31 | 2018-10-04 | 大塚化学株式会社 | ハニカム構造体及び排ガス浄化装置 |
WO2018198999A1 (ja) * | 2017-04-26 | 2018-11-01 | 大塚化学株式会社 | ハニカム構造体及び排ガス浄化装置 |
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Also Published As
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JP6121542B2 (ja) | 2017-04-26 |
US20160199822A1 (en) | 2016-07-14 |
KR20160048082A (ko) | 2016-05-03 |
JPWO2015029853A1 (ja) | 2017-03-02 |
EP3040122A1 (en) | 2016-07-06 |
EP3040122A4 (en) | 2017-03-29 |
WO2015029853A1 (ja) | 2015-03-05 |
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