CN106574534B - 排气净化装置 - Google Patents
排气净化装置 Download PDFInfo
- Publication number
- CN106574534B CN106574534B CN201580042490.4A CN201580042490A CN106574534B CN 106574534 B CN106574534 B CN 106574534B CN 201580042490 A CN201580042490 A CN 201580042490A CN 106574534 B CN106574534 B CN 106574534B
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- Prior art keywords
- catalyst
- exhaust
- layer
- emission
- control equipment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000003054 catalyst Substances 0.000 claims abstract description 155
- 238000001179 sorption measurement Methods 0.000 claims abstract description 54
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 48
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 43
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000011973 solid acid Substances 0.000 claims abstract description 28
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000001301 oxygen Substances 0.000 claims abstract description 16
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 16
- 230000009467 reduction Effects 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 57
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 40
- 239000004215 Carbon black (E152) Substances 0.000 claims description 37
- 229930195733 hydrocarbon Natural products 0.000 claims description 36
- 150000002430 hydrocarbons Chemical class 0.000 claims description 35
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 30
- 229910021536 Zeolite Inorganic materials 0.000 claims description 29
- 239000010457 zeolite Substances 0.000 claims description 29
- 238000006722 reduction reaction Methods 0.000 claims description 26
- 239000002245 particle Substances 0.000 claims description 21
- 239000000377 silicon dioxide Substances 0.000 claims description 20
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 13
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003921 oil Substances 0.000 claims description 12
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 11
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- 230000009257 reactivity Effects 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 235000012239 silicon dioxide Nutrition 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 2
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 claims 1
- 239000010410 layer Substances 0.000 description 110
- 239000000446 fuel Substances 0.000 description 38
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 30
- 239000000203 mixture Substances 0.000 description 23
- 241000269350 Anura Species 0.000 description 17
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 17
- 239000007787 solid Substances 0.000 description 14
- 238000002347 injection Methods 0.000 description 13
- 239000007924 injection Substances 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 230000006870 function Effects 0.000 description 11
- 239000004411 aluminium Substances 0.000 description 10
- 229910052782 aluminium Inorganic materials 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 10
- 239000002828 fuel tank Substances 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 210000002421 cell wall Anatomy 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 239000000428 dust Substances 0.000 description 5
- 230000006698 induction Effects 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- -1 sulphur compound Chemical class 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical group O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- BKAJSVLIASNUEV-UHFFFAOYSA-N S=O.S(=O)=O Chemical compound S=O.S(=O)=O BKAJSVLIASNUEV-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 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
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910009112 xH2O Inorganic materials 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
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- 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
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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- 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
- B01J29/068—Noble metals
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- 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
- B01J29/7015—CHA-type, e.g. Chabazite, LZ-218
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
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- B01J37/0246—Coatings comprising a zeolite
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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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/0807—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents
- F01N3/0814—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by using absorbents or adsorbents combined with catalytic converters, e.g. NOx absorption/storage reduction catalysts
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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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/18—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
- F01N3/20—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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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
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
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- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2251/00—Reactants
- B01D2251/20—Reductants
- B01D2251/208—Hydrocarbons
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- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/104—Silver
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/2092—Aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2255/90—Physical characteristics of catalysts
- B01D2255/902—Multilayered catalyst
- B01D2255/9022—Two layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/911—NH3-storage component incorporated in the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- 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
- B01D53/9477—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 separate bricks, e.g. exhaust systems
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Abstract
一种排气净化装置,具备使排气所含的氮氧化物还原的还原催化剂。还原催化剂具备催化剂层和覆盖催化剂层的吸附层。催化剂层包含承载银的催化剂载体。吸附层包含具有酸性的固体酸金属氧化物,吸附层的氧量大于催化剂层的氧量。吸附层具有吸附在催化剂层中生成的氨并使排气所含的硫氧化物和已吸附的氨接触的特性。
Description
技术领域
本公开的技术涉及用于使排气所含的氮氧化物的量减少的排气净化装置。
背景技术
在车辆的排气通路中搭载有用于使排气所含的氮氧化物的量减少的排气净化装置。例如,如专利文献1记载的那样,排气净化装置具备含银的还原催化剂,还原催化剂促进烃和氮氧化物的反应,据此,排气净化装置使排气所含的氮氧化物的量减少。
现有技术文献
专利文献
专利文献1:特表2009-516125号公报
但是,流向还原催化剂的排气通常除了氮氧化物之外还包含硫氧化物。排气所含的硫氧化物与还原催化剂所含的银反应,在还原催化剂中生成含银和硫的化合物。结果是,还原催化剂促进烃和氮氧化物的反应的功能被破坏,排气所含的氮氧化物的量不易减少。
发明内容
本公开的技术的目的是提供一种抑制排气所含的氮氧化物的量不易减少的排气净化装置。
在一方式中提供排气净化装置。排气净化装置具备还原催化剂,所述还原催化剂位于排气通路的中途,使排气所含的氮氧化物还原。所述还原催化剂具备催化剂层和吸附层,所述吸附层覆盖所述催化剂层并形成与所述排气接触的所述还原催化剂的表面。所述催化剂层包含承载银的催化剂载体。所述催化剂载体是氧化铝和沸石中的任一种,促进所述氮氧化物与烃反应生成氨的还原反应。所述吸附层包含具有酸性的固体酸金属氧化物,所述吸附层的氧量大于所述催化剂层的氧量。所述吸附层具有吸附在所述催化剂层中生成的氨并使所述排气所含的硫氧化物和所述吸附的氨接触的特性。
附图说明
图1是将排气净化装置的一实施方式与排气净化装置所搭载的发动机的概略构成一起示出的概略构成图。
图2是示出还原催化剂的截面结构的剖视图。
图3是示出图2的3-3线的还原催化剂的截面结构的一部分的剖视图。
图4是用于说明排气净化装置的作用的图。
图5是用于说明排气净化装置的作用的图。
图6是用于说明排气净化装置的作用的图。
图7是用于说明排气净化装置的作用的图。
具体实施方式
参照图1至图7说明排气净化装置的一实施方式。以下按排气净化装置所搭载的发动机的概略构成、排气净化装置具备的还原催化剂的构成、排气净化装置的作用的顺序进行说明。
[发动机的概略构成]
参照图1说明发动机的概略构成。
如图1所示,发动机10的缸体11具有排成一列的6个汽缸11a。在缸体11的附近配置有在汽缸11a的排列方向延伸的共轨12。作为燃料的轻油被升高压力并贮存于共轨12中。共轨12与6个燃料喷射阀13连接,各燃料喷射阀13朝向相互不同的汽缸11a喷射轻油。
缸体11与对汽缸11a供给吸入空气的吸气歧管14的第1端部连接,吸气歧管14中的与缸体11相反侧的第2端部与吸入空气流动的吸气管15的第1端部连接。在吸气管15上从吸气管15中的缸体11附近、即吸入空气流中的下游开始依次配置有中间冷却器16和构成涡轮增压器17的压缩机17a。此外,吸气歧管14、吸气管15、中间冷却器16以及压缩机17a构成吸气通路,吸入空气从吸气管15中的与吸气歧管14相反侧的第2端部朝向缸体11流动。
缸体11在缸体11中的与吸气歧管14相对的位置与排气歧管18的第1端部连接。排气歧管18中的与缸体11相反侧的第2端部与从缸体11排出的排气流动的排气管19的第1端部连接。排气歧管18和排气管19各自通过与构成涡轮增压器17的涡轮17b连接而相互连接。
在发动机10上搭载有通过减少排气所含的氮氧化物(以下为NOx)而对排气进行净化的排气净化装置20。排气净化装置20具备过滤器21、还原催化剂22、过滤器添加阀23、催化剂添加阀24、燃料箱25以及燃料添加泵26。
在排气净化装置20中,过滤器21和还原催化剂22配置于排气管19,过滤器21配置于作为排气流动的方向的流通方向中的比还原催化剂22靠上游。过滤器21和还原催化剂22分别配置于形成为筒状的壳体内。此外,排气歧管18、排气管19、过滤器21的壳体以及还原催化剂22的壳体构成排气通路,排气从排气歧管18朝向排气管19中的与排气歧管18相反侧的第2端部流动。
过滤器21通过捕获作为排气所含的微粒的一例的灰尘、烃、SOF(Solvle OrganicFraction:可溶有机成分)等而对排气进行净化,还原催化剂22通过使排气所含的NOx还原而减少排气所含的NOx。
过滤器21包含氧化催化剂,氧化催化剂使排气中所含的燃料燃烧。在过滤器21的再生处理、即使被过滤器21捕获的灰尘燃烧的处理中,过滤器添加阀23朝向排气喷射燃料,氧化催化剂促进该喷射的燃料的燃烧。由此,通过过滤器21的温度升高至例如600℃,从而被过滤器21捕获的灰尘燃烧。此时,流经过滤器21的排气的温度也升高,因此对还原催化剂22也供应温度已升高的排气。过滤器21是加热部的一例。因为过滤器21捕获排气所含的微粒,所以微粒不易附着于还原催化剂22。其结果是,不易发生还原催化剂22的功能由于微粒的附着而被破坏的情况。另外,过滤器21含有的氧化催化剂也具有使排气中所含的NOx还原的功能。
过滤器添加阀23配置于流通方向中的比过滤器21靠上游,朝向流经排气管19的排气喷射轻油。催化剂添加阀24配置于流通方向上的过滤器21与还原催化剂22之间,朝向流经排气管19的排气喷射轻油。
燃料箱25贮存从过滤器添加阀23和催化剂添加阀24喷射的轻油。燃料箱25可以是与共轨12连接的燃料箱,也可以是与和共轨12连接的燃料箱不同的燃料箱。燃料箱25与燃料供给管25a连接,燃料供给管25a在从燃料箱25朝向各添加阀延伸的中途分支为与过滤器添加阀23连接的过滤器管25a1和与催化剂添加阀24连接的催化剂管25a2。
燃料供给管25a在比分支为2个管的位置更靠燃料箱25的位置与燃料添加泵26连接。燃料添加泵26将燃料箱25内的轻油以规定的排出压朝向过滤器添加阀23和催化剂添加阀24排出。燃料添加泵26例如是电动式的泵。
在过滤器管25a1上装配有过滤器阀25b,过滤器阀25b使由过滤器管25a1形成的第1燃料通路开放和断开,在催化剂管25a2上装配有催化剂阀25c,催化剂阀25c使由催化剂管25a2形成的第2燃料通路开放和断开。
在过滤器阀25b打开的期间第1燃料通路开放,另一方面,在过滤器阀25b关闭的期间第1燃料通路断开。在催化剂阀25c打开的期间第2燃料通路开放,另一方面,在催化剂阀25c关闭的期间第2燃料通路断开。
排气净化装置20例如当过滤器21捕获的灰尘的量为规定量以上时,使过滤器21再生。当使过滤器21再生时,排气净化装置20将过滤器阀25b打开,且驱动燃料添加泵26,从过滤器添加阀23朝向排气喷射规定量的燃料。结果是,由于排气的温度升高,从而被过滤器21捕获的灰尘燃烧。另外,在过滤器21的再生处理中,与氧化催化剂促进过滤器添加阀23朝向排气喷射的燃料燃烧的同时,过滤器21能促进NOx的还原。
排气净化装置20例如当还原催化剂的温度包含于规定的范围内时,利用还原催化剂22将NOx还原。在还原NOx时,排气净化装置20将催化剂阀25c打开,且驱动燃料添加泵26,从催化剂添加阀24朝向排气喷射规定量的燃料。结果是,还原催化剂22促进使用排气所含的烃的NOx的还原反应。此外,排气净化装置20可以分别地进行过滤器21的再生和NOx的还原,也可以同时进行。
[还原催化剂的构成]
参照图2和图3说明还原催化剂22的构成。此外,图2中示出沿着与流通方向正交的面的还原催化剂22的截面结构。另外,图3中为了图示便利,示出沿图2的3-3线的还原催化剂22的截面结构中、单元壁和与单元壁中的沿着流通方向延伸的1个面层叠的多层催化剂52的截面结构。
如图2所示,还原催化剂22具备整体式载体51,整体式载体51具有圆筒形状。整体式载体51具有由沿着流通方向延伸的多个壁部构成的单元壁51a,单元壁51a中的与流通方向正交的方向的截面形状为格子状。整体式载体51具有通过单元壁51a分隔的多个单元51h。各单元51h是沿着流通方向延伸的孔,且各单元51h中的与流通方向正交的方向的截面形状为大致矩形。
整体式载体51的形成材料使用陶瓷或者金属。在整体式载体51的形成材料是陶瓷时,形成材料使用例如堇青石、二氧化硅、碳化硅、氮化硅、莫来石、锆石、氧化铝以及钛酸铝等。在整体式载体51的形成材料是金属时,形成材料使用例如铁、钛、不锈钢、以及以铁为主成分的其他合金等。
单元壁51a在构成各单元51h的内周面的壁部具有多层催化剂52。多层催化剂52与在单元51h内流动的排气接触。
如图3所示,多层催化剂52具有覆盖整体式载体51的单元壁51a的催化剂层61和覆盖催化剂层61的吸附层62。吸附层62通过覆盖催化剂层61,从而形成与还原催化剂22中的排气Ex接触的表面22s。
催化剂层61是促进利用烃将NOx还原的反应的催化剂。催化剂层61包含银和承载银的催化剂载体,作为催化剂载体,包含晶格中至少含铝的金属氧化物。催化剂载体是氧化铝和沸石中的任一种。优选催化剂层61包含银氧化铝或者银沸石。在催化剂层61包含银氧化铝时,催化剂层61通过例如将承载银的γ-氧化铝的粒子和承载银的θ-氧化铝的粒子中的至少一方涂敷于整体式载体51上而构成。
在催化剂层61包含银沸石时,催化剂层61例如包含沸石所含的阳离子被银离子置换的沸石的粒子。
在催化剂层61中作为NOx的还原剂使用的轻油中的烃除了包含排气中所含的烃之外,还包含由过滤器添加阀23和催化剂添加阀24中的至少一方添加到排气中的烃。烃主要包含碳原子数为10至20的烷烃(饱和烃),包含直链状的烷烃和支链状的烷烃。
催化剂层61促进基于NOx、烃以及氧的NOx的还原反应。由此,催化剂层61通过使排气所含的NOx还原为氮和氨(以下为NH3),从而减少排气所含的NOx。即,从还原催化剂22出去的排气所含的NOx的量比进入到还原催化剂22中的排气所含的NOx的量少。
吸附层62吸附在催化剂层61中生成的NH3。吸附层62具有如下特性:促进使用已吸附的NH3的NOx的还原反应,另一方面,使排气所含的硫氧化物和已吸附的氨接触。吸附层62包含作为具有酸性的金属氧化物的固体酸金属氧化物。吸附层62通过将固体酸金属氧化物的粒子涂敷于催化剂层61和整体式载体51上而构成。
固体酸金属氧化物具有作为提供质子(以下为H+)的酸位点的布朗斯台德酸位点、和作为接受电子对的酸位点的路易斯酸位点中的至少一方。
构成吸附层62的固体酸金属氧化物与构成催化剂层61的粒子的形成材料相比,作为酸位点的量的氧量大。由此,在催化剂层61生成的NH3吸附于吸附层62的酸位点的概率变高。因此,在催化剂层61生成的NH3容易吸附于吸附层62的酸位点。
吸附层62的固体酸金属氧化物包含金属氧化物、复合金属氧化物、沸石以及硅铝磷酸盐(以下为SAPO)中的至少一种。作为金属氧化物,例如优选氧化铝。作为复合金属氧化物,例如优选二氧化硅氧化铝、二氧化硅二氧化钛以及二氧化硅氧化镁中的任一种。即,固体金属氧化物优选是选自由氧化铝、二氧化硅氧化铝、二氧化硅二氧化钛、二氧化硅氧化镁、沸石以及SAPO构成的组的至少一种。
沸石是通过以下通式A示出的结晶性硅铝酸盐硅铝酸盐。
(M1,M2 1/2)m(AlmSinO2(m+n))·xH2O…(A)
此外,M1是例如Li+、Na+以及K+等,M2是例如Ca2+、Mg2+以及Ba2+等。沸石优选具有例如菱沸石结构,进一步优选菱沸石。
SAPO是磷酸铝(AlPO4)所含的铝和磷酸的一部分用硅置换的结晶性物质。SAPO可以具有沸石型的晶体结构,也可以具有沸石不存在的晶体结构。
二氧化硅氧化铝、沸石以及SAPO是在晶格中包含硅和铝的金属氧化物。那些金属氧化物中的二氧化硅氧化铝比与作为结晶特性的耐热性和NH3的吸附性有关。二氧化硅氧化铝比是硅相对于晶格中所含的铝的比、即Si/Al。包含硅和铝的金属氧化物表现出二氧化硅氧化铝比越高则越高的耐热性,另一方面,表现出二氧化硅氧化铝比越低则越高的吸附性。因此,二氧化硅氧化铝比优选设定为,赋予金属氧化物稳定保持在排气中的耐热性的值、且使NH3的吸附性最高的值。
氧化铝优选是比表面积高的γ-氧化铝。在氧化铝中,为了中和晶格中的铝具有的负电荷,形成晶格的氧原子的一部分形成氢氧基。另外,氧化铝中由于键合不连续而包含具有正电荷的原子或具有负电荷的原子。由于氧化铝的氢氧基或具有电荷的原子作为酸位点执行功能,从而NH3被吸附层62吸附。
在金属氧化物中,与氧化铝同样,氢氧基或具有电荷的原子作为酸位点执行功能,因此NH3被吸附层62吸附。
在沸石和SAPO中,与氧化铝同样,氢氧基或具有电荷的原子作为酸位点执行功能,因此NH3被吸附层62吸附。
固体金属氧化物是多孔质材料,优选作为固体金属氧化物具有的孔的直径的孔径大于NH3的分子尺寸,且小于轻油中所含的烃的分子尺寸。此外,所谓固体金属氧化物的孔径大于NH3的分子尺寸是指,NH3的分子能进入固体金属氧化物具有的孔的状态。另外,所谓固体金属氧化物的孔径小于烃的分子尺寸是指,烃的分子不能进入固体金属氧化物具有的孔的状态。
由此,NH3进入到固体金属氧化物的孔中,另一方面,烃不进入到固体金属氧化物的孔中。因此,NH3被固体金属氧化物吸附,另一方面,烃通过在多个固体金属氧化物的粒子之间所形成的间隙到达催化剂层61。因此,NH3被吸附层62吸附,且烃通过在吸附层62所形成的间隙到达催化剂层61,由此可抑制吸附层62不易吸附NH3。除此之外,因为烃到达催化剂层61,所以不易发生使用烃的NOx的还原反应。
固体金属氧化物的孔径优选为以上以下,更优选为以上以下。因此,固体金属氧化物优选是具有菱沸石结构的SAPO-34和具有与菱沸石相似的结构的SAPO-47。
[排气净化装置的作用]
参照图4至图7说明排气净化装置20的作用。此外,在图4至图7中,在其上形成有多层催化剂52的整体式载体51的图示省略。
如图4所示,例如,在催化剂添加阀24朝向排气喷射轻油时,排气所含的烃(HC)、NOx以及氧(O2)通过吸附层62到达催化剂层61。即,通过构成吸附层62的固体酸金属氧化物的粒子的间隙、或者固体酸金属氧化物的粒子具有的孔的间隙,烃、NOx以及氧到达催化剂层61。特别是,烃通过固体酸金属氧化物的粒子之间的间隙到达催化剂层61。由此,在催化剂层61中NOx被还原,由此生成N2和NH3。
如图5所示,在催化剂层61中所生成的NH3由于吸附层62具有的酸位点而被催化剂层61吸附。例如,在NH3由于催化剂层61具有的布朗斯台德酸位点而被吸附时,发生通过以下反应式1表示的反应。
NH3+H+→NH4 +…(1)
如图6所示,当排气所含的硫氧化物(SOx)、例如三氧化硫(SO3)到达吸附层62时,在吸附层62中发生被吸附层62吸附的NH3和三氧化硫的反应、即用以下反应式2表示的反应。
2NH3+SO3+H2O→(NH4)2SO4…(2)
这样,因为还原催化剂22的表面22s由吸附NH3的吸附层62形成,所以对还原催化剂22供给的排气所含的硫氧化物首先与吸附层62接触。接着,硫氧化物、例如三氧化硫与NH3反应而生成作为反应生成物的硫酸铵,由此硫氧化物被吸附层62捕获。因此,可抑制对还原催化剂22供应的硫氧化物通过吸附层62到达催化剂层61,并可抑制催化剂层61所含的银与硫氧化物反应。
并且,因为排气所含的硫氧化物是比NOx强的强酸,所以吸附层62促进使用NH3还原NOx的反应,另一方面,吸附层62已吸附的NH3与排气所含的硫氧化物反应。因此,与吸附层62促进使用NH3还原NOx的反应的构成相比,催化剂层61不易与排气所含的硫氧化物接触。此外,硫氧化物不仅包含上述的三氧化硫,也包含四氧化硫(SO4)。
如图7所示,在过滤器添加阀23朝向排气喷射轻油时,过滤器21的温度升高,由此对还原催化剂22供应的排气的温度升高到硫酸铵的分解温度以上的规定温度、例如400℃以上的温度。由此,被吸附层62捕获的硫酸铵热分解,从而生成NH3、二氧化硫、氮以及水。
由于硫酸铵分解,从而吸附层62能重新吸附NH3。此外,生成作为硫酸铵分解而生成的硫氧化物的二氧化硫。但是,二氧化硫相对于银的反应性比上述的三氧化硫等相对于银的反应性低,因此不易生成二氧化硫和银的化合物。即,排气所含的硫氧化物相对于银的反应性比由于硫酸铵分解而生成的二氧化硫相对于银的反应性高,所以即使由于硫酸铵热分解而生成二氧化硫,也不易生成含银和硫的化合物。
如上所述,根据一实施方式的排气净化装置,能得到以下列举的优点。
(1)因为覆盖催化剂层61的吸附层62形成还原催化剂22的表面22s,所以排气所含的硫氧化物与吸附层62已吸附的氨反应。由此,因为硫氧化物被吸附层62吸附,所以可抑制硫氧化物与催化剂层61接触。结果是,不易破坏催化剂层61的功能,因此可抑制排气所含的NOx的量不易减少。
(2)在直径小于烃的分子尺寸的孔中,由于氨进入到孔内而吸附于固体酸金属氧化物,所以氨的吸附不会被烃妨碍。因此,在构成吸附层62的固体酸金属氧化物中,吸附NH3的概率变高。
(3)烃的大部分通过在吸附层62所含的多个粒子之间所形成的间隙而到达催化剂层61。因此,吸附层62吸附NH3的概率升高,且用于NOx的还原的烃可靠地供给到催化剂层61。
(4)因为固体酸金属氧化物是选自由氧化铝、二氧化硅氧化铝、二氧化硅二氧化钛、二氧化硅氧化镁、沸石以及硅铝磷酸盐构成的组中的至少一种,所以NH3被固体酸金属氧化物具有的酸位点吸附。此外,固体酸金属氧化物优选是沸石中的菱沸石。
(5)通过吸附层62已生成的反应生成物热分解,从而生成相对于银的反应性比排气的硫氧化物低的硫氧化物,并从吸附层62释放。因此,成为可抑制催化剂层61和银的反应并且吸附层62能再次吸附排气中的硫氧化物的状态。
此外,上述的实施方式能按如下适当变更后实施。
·在排气的流通方向上的还原催化剂22的上游,作为加热部的一例配置有过滤器21。不限于此,加热部例如也可以是燃烧器,而且也可以是与过滤器21不同的排气净化装置20搭载的氧化催化剂。总之,加热部只有在流通方向上的还原催化剂22的上游能升高排气的温度即可,通过这样的构成,也能得到与上述(5)相同的优点。
·过滤器21也可以省略,即使是这样的构成,通过由排气升高还原催化剂22的温度,从而还原催化剂22的硫化铵很多发生热分解。
·吸附层62所含的固体酸金属氧化物可以是氧化铝、二氧化硅氧化铝、二氧化硅二氧化钛、二氧化硅氧化镁、沸石以及SAPO以外的固体酸金属氧化物。总之,只要是具有布朗斯台德酸位点和路易斯酸位点中的至少一个、且氧量比催化剂层61大的材料即可。
·在吸附层62所含的固体酸金属氧化物具有的多个孔中,不必所有的孔的孔径大于NH3的分子尺寸且不小于烃的分子尺寸。例如,多个孔的至少一部分的孔径可以大于NH3的分子尺寸且大于烃的分子尺寸。即使是这样的构成,在构成吸附层62的固体金属氧化物的至少一部分中,也能得到与上述(3)相同的优点。
·固体酸金属氧化物具有的多个孔的孔径可以为NH3的分子尺寸以下。即使是这样的构成,因为至少在固体酸金属氧化物的粒子的表面所形成的酸位点吸附有NH3,所以能得到与上述(1)同样的优点。
·固体酸金属氧化物具有的多个孔的孔径可以为烃的分子尺寸以上。即使是这样的构成,既然固体酸金属氧化物具有酸位点,就能得到与上述(1)相同的优点。
·构成催化剂层61的金属氧化物的孔的孔径可以为构成吸附层62的固体酸金属氧化物的孔的孔径以下。即使是这样的构成,因为至少存在于催化剂层61的表面的银离子促进烃还原氮氧化物的反应,所以在催化剂层61中氮氧化物很多被还原。
·沸石和SAPO可以包含碱金属、例如Na+被H+置换的质子置换型的沸石和SAPO。即使是这样的构成,质子置换型的沸石和SAPO也通过H+吸附NH3。沸石和SAPO可以包含碱金属被多价的阳离子置换的阳离子置换型沸石和SAPO。在该情况下,阳离子优选是不赋予吸附层62促进使用NH3的NOx的还原反应的功能的多价离子。在阳离子置换型的沸石和SAPO中,有时因为将多价的阳离子中的正电荷中和而结合有氢氧基。即使是这样的构成,氢氧基作为对NH3提供H+的酸位点执行功能,因此NH3被吸附层62吸附。
·沸石和SAPO可以包含质子型的沸石和SAPO。在该情况下,质子型的沸石和SAPO在孔内的一价的阳离子、例如Na+被氢氧基NH4 +置换后,通过烧成而生成。即使是这样的构成,质子型的沸石和SAPO也具有在形成晶格的氧的一部分结合有氢的氢氧基,氢氧基作为给予H+的酸位点执行功能。
·还原催化剂22具备的整体式载体51不限于圆筒形状,例如也可以是长方体形状等多角筒状。另外,单元51h的截面形状不限于矩形,也可以是例如梯形、正方形、正弦曲线状、六边形、椭圆状以及圆形等。
·还原催化剂22也可以不是具备整体式载体51的构成,而是作为载体具有丸状的载体或者板状的载体的构成。即使是这样的构成,只要是还原催化剂22具备的吸附层62覆盖催化剂层61且形成与排气接触表面的构成,就能得到与上述(1)相同的优点。
·排气净化装置20也可以不具备过滤器添加阀23。即使是这样的构成,例如,只要是在从燃料喷射阀13喷射的燃料流到排气管19的条件下,燃料从燃料喷射阀13朝向汽缸11a喷射即可。由此,过滤器21的再生处理通过从燃料喷射阀13喷射的燃料进行。
·排气净化装置20也可以不具备过滤器添加阀23和催化剂添加阀24两者。在这样的构成中,只要在从燃料喷射阀13喷射的燃料流到排气管19的条件下,燃料从燃料喷射阀13朝向汽缸11a喷射即可。由此,过滤器21的再生处理和利用还原催化剂22的NOx的还原通过从燃料喷射阀13喷射的燃料进行。
·排气净化装置20在使过滤器21再生时,从过滤器添加阀23向排气喷射燃料,升高过滤器21的温度。不限于此,排气净化装置20例如根据发动机10的运转状态推定排气所含的硫氧化物的量,在所推定的硫氧化物的量大于规定量时,为了升高对还原催化剂22供给的排气的温度,也可以从过滤器添加阀23向排气喷射燃料。根据这样的构成,被吸附层62吸附的硫酸铵分解,吸附层62能吸附新的硫氧化物,因此可抑制银与硫氧化物反应。此外,在硫氧化物的量大于规定量时,为了生成与硫氧化物反应的NH3,优选从催化剂添加阀24也同时喷射燃料。
对从上述的实施方式掌握的技术思想追加记载。
(附记1)
根据权利要求2所述的排气净化装置,
所述多个孔各自的直径大于所述氨的分子尺寸且小于所述烃的分子尺寸。
根据这样的构成,烃的大部分通过在吸附层所含的多个粒子之间所形成的间隙而到达催化剂层。因此,吸附层容易吸附氨,且用于氮氧化物的还原的烃可靠地供给到催化剂层。
(附记2)
根据权利要求2所述的排气净化装置,
所述加热部是捕获所述排气中的微粒的过滤器。
根据这样的构成,还原催化剂例如与通过过滤器除去了微粒的至少一部分的排气接触。由此,微粒不易附着于还原催化剂,因此不易引起还原催化剂的功能由于微粒的附着而被破坏。因此,可抑制排气所含的氮氧化物的量不易减少。
Claims (6)
1.一种排气净化装置,其被搭载于柴油发动机,
具备:
还原催化剂,所述还原催化剂位于排气通路的中途,使排气所含的氮氧化物还原;
加热部,所述加热部在所述排气流动的方向上位于比所述还原催化剂靠上游的位置,所述加热部对所述排气加热;
催化剂添加阀,所述催化剂添加阀在所述排气流动的方向上位于所述加热部与所述还原催化剂之间,朝向所述排气喷射轻油;
所述还原催化剂具备催化剂层和吸附层,所述吸附层覆盖所述催化剂层并形成与所述排气接触的所述还原催化剂的表面,
所述催化剂层包含承载银的催化剂载体,所述催化剂载体是氧化铝和沸石中的任一种,促进所述氮氧化物与烃反应生成氨的还原反应,
所述吸附层包含具有酸性的固体酸金属氧化物,所述吸附层的氧量大于所述催化剂层的氧量,所述吸附层具有吸附在所述催化剂层中生成的氨并使所述排气所含的硫氧化物和所述吸附的氨接触的特性,由此,使已吸附的所述氨与所述排气所含的三氧化硫或者四氧化硫反应生成硫酸铵,
在推定出的所述排气所含的所述硫氧化物的量大于预定量时,所述加热部将温度升高至所述硫酸铵热分解的温度以上的规定温度,生成与所述三氧化硫或者所述四氧化硫相比相对于所述银的反应性低的二氧化硫,
与所述加热部提高所述排气的温度的同时,所述催化剂添加阀对所述排气喷射轻油。
2.根据权利要求1所述的排气净化装置,
所述固体酸金属氧化物是具有多个孔的多孔质材料,
所述吸附层包含由所述固体酸金属氧化物形成的多个粒子,
所述多个孔中的至少一部分的直径小于所述烃的分子尺寸。
3.根据权利要求2所述的排气净化装置,
所述多个孔各自的直径大于所述氨的分子尺寸且小于所述烃的分子尺寸。
4.根据权利要求1所述的排气净化装置,
所述固体酸金属氧化物是选自由氧化铝、二氧化硅氧化铝、二氧化硅二氧化钛、二氧化硅氧化镁、沸石以及硅铝磷酸盐构成的组中的至少一种。
5.根据权利要求4所述的排气净化装置,
所述固体酸金属氧化物是菱沸石。
6.根据权利要求1~5中的任一项所述的排气净化装置,
所述加热部是捕获所述排气中的微粒的过滤器。
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CN1838989A (zh) * | 2003-09-27 | 2006-09-27 | 韩国电力技术株式会社 | 用于低温脱除氮氧化物的钒/氧化钛基催化剂以及使用该催化剂脱除氮氧化物的方法 |
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