CN104379256B - 具有co/hc点火和hc储存功能的pt‑pd柴油氧化催化剂 - Google Patents
具有co/hc点火和hc储存功能的pt‑pd柴油氧化催化剂 Download PDFInfo
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- CN104379256B CN104379256B CN201280072223.8A CN201280072223A CN104379256B CN 104379256 B CN104379256 B CN 104379256B CN 201280072223 A CN201280072223 A CN 201280072223A CN 104379256 B CN104379256 B CN 104379256B
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- washcoat
- catalyst
- surface area
- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 103
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 53
- 230000003647 oxidation Effects 0.000 title claims abstract description 52
- 230000006386 memory function Effects 0.000 title description 3
- 239000010457 zeolite Substances 0.000 claims abstract description 68
- 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 67
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 64
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 51
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 51
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 50
- 239000002912 waste gas Substances 0.000 claims abstract description 39
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229910002091 carbon monoxide Inorganic materials 0.000 claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 23
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 16
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 238000012545 processing Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 53
- 229910044991 metal oxide Inorganic materials 0.000 claims description 35
- 150000004706 metal oxides Chemical class 0.000 claims description 35
- 239000003870 refractory metal Substances 0.000 claims description 30
- 239000004071 soot Substances 0.000 claims description 28
- 239000013618 particulate matter Substances 0.000 claims description 20
- 238000006555 catalytic reaction Methods 0.000 claims description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- 239000012530 fluid Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 5
- 238000004891 communication Methods 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 5
- 238000002407 reforming Methods 0.000 claims description 5
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- CSSYLTMKCUORDA-UHFFFAOYSA-N barium(2+);oxygen(2-) Chemical compound [O-2].[Ba+2] CSSYLTMKCUORDA-UHFFFAOYSA-N 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000006069 physical mixture Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- 150000008064 anhydrides Chemical class 0.000 claims description 2
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- 241000790917 Dioxys <bee> Species 0.000 claims 1
- 229910003978 SiClx Inorganic materials 0.000 claims 1
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 40
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 30
- 239000000203 mixture Substances 0.000 abstract description 25
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000377 silicon dioxide Substances 0.000 abstract description 15
- 230000003993 interaction Effects 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract description 4
- 239000007789 gas Substances 0.000 description 20
- 239000000463 material Substances 0.000 description 18
- 238000011144 upstream manufacturing Methods 0.000 description 16
- 229910002089 NOx Inorganic materials 0.000 description 8
- 230000008859 change Effects 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 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 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 235000019580 granularity Nutrition 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000011232 storage material Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- -1 accelerator Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000000712 assembly Effects 0.000 description 2
- 238000000429 assembly Methods 0.000 description 2
- 230000004323 axial length Effects 0.000 description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910001593 boehmite Inorganic materials 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000002594 sorbent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 229910052649 zeolite group Inorganic materials 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HVXCTUSYKCFNMG-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O-2].[Zr+4].[Al+3] HVXCTUSYKCFNMG-UHFFFAOYSA-N 0.000 description 1
- VCRLKNZXFXIDSC-UHFFFAOYSA-N aluminum oxygen(2-) zirconium(4+) Chemical compound [O--].[O--].[Al+3].[Zr+4] VCRLKNZXFXIDSC-UHFFFAOYSA-N 0.000 description 1
- JYIBXUUINYLWLR-UHFFFAOYSA-N aluminum;calcium;potassium;silicon;sodium;trihydrate Chemical compound O.O.O.[Na].[Al].[Si].[K].[Ca] JYIBXUUINYLWLR-UHFFFAOYSA-N 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 229910001603 clinoptilolite Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
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- B01D53/34—Chemical or biological purification of waste gases
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- B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
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- 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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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- 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
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Abstract
描述了用于废气排放的处理,例如未燃烧烃(HC)和一氧化碳(CO)的氧化和氮氧化物(NOx)的还原的柴油氧化催化剂。更特别地,本发明涉及洗涂层组合物,所述组合物包含高二氧化硅:氧化铝沸石以及铂和钯使得沸石将这些铂族金属与沸石的负相互作用最小化。
Description
技术领域
本发明涉及具有一氧化碳/烃(CO/HC)点火和烃(HC)储存功能的Pt/Pd柴油氧化催化剂。更具体而言,本发明涉及包含沸石和铂族金属(PGM)如铂和钯使得沸石使这些铂族金属与沸石的负相互作用最小化的催化剂组合物。
发明背景
贫燃发动机,例如柴油发动机和贫燃汽油发动机的操作提供给使用者优异的燃料经济性,且由于它们在贫燃料条件下以高空气/燃料比操作,具有非常低的气相烃和一氧化碳排放。特别地,柴油发动机还提供与汽油发动机相比在其燃料经济性、耐久性和它们在低速下产生高扭矩的能力方面的显著优点。
然而,从排放观点看,柴油发动机显示出比其火花点火对应物相比更严重的问题。排放问题涉及颗粒物质(PM)、氮氧化物(NOx)、未燃烧烃(HC)和一氧化碳(CO)。NOx是用于描述氮氧化物的各种化学物种,尤其包括一氧化氮(NO)和二氧化氮(NO2)的术语。
颗粒物质的两种主要组分是挥发性有机部分(VOF)和烟炱部分(烟炱)。VOF以层冷凝在烟炱上,并衍生自柴油燃料和油。取决于废气的温度,VOF可作为蒸气或者作为气溶胶(液体冷凝物的细滴)存在于柴油废气中。烟炱主要由碳颗粒组成。来自柴油废气的颗粒物质由于其细粒度是非常可吸入的,这在较高暴露含量下引起健康风险。此外,VOF包含多环芳烃,其中一些被怀疑是致癌物。
烟炱可通过壁流式过滤器收集,所述过滤器可包含具有在阻塞的蜂巢结构上游和下游侧上的交替通道末端的多通道蜂巢结构。这产生在每一端上的棋盘型图案。在上游或入口端阻塞的通道在下游或出口端是开放的。这容许气体进入开放上游通道,流过多孔壁并通过具有开放下游端的通道离开。待处理气体通过通道的开放的上游端进入催化结构中并被阻止通过相同通道的阻塞下游端离开。气压迫使气体通过多孔结构壁进入在上游端封闭且在下游端开放的通道。这类结构主要已知用于从废气流中过滤出颗粒。通常该类结构具有在基底上的催化剂,所述催化剂增强颗粒的氧化。公开这类催化结构的典型专利包括美国专利Nos.3,904,551;4,329,162;4,340,403;4,364,760;4,403,008;4,519,820;4,559,193;和4,563,414。
已知包含分散于耐熔金属氧化物载体上的铂族金属的氧化催化剂用于处理柴油发动机的废气以通过催化这些污染物的氧化而将烃和一氧化碳气体污染物转化成二氧化碳和水。这类催化剂通常包含在置于柴油动力发动机的废气流通道中的称为柴油氧化催化剂(DOC)的装置或更简单地催化转化器中以在废气排到大气中以前将其处理。通常,柴油氧化催化剂在陶瓷或金属基底承载体(例如流通式单块承载体,如下文所述)上形成,一种或多种催化剂涂料组合物沉积于所述载体上。除气体HC、CO和颗粒物质的SOF部分的转化外,包含铂族金属(其通常分散于耐熔氧化物载体上)的氧化催化剂促进一氧化氮(NO)氧化成NO2。
用于处理内燃发动机的废气的催化剂在相对低温操作阶段,例如发动机操作的初始冷启动阶段期间不太有效,因为发动机废气不是在对有效地催化转化废气中的有害组分而言足够高的温度下。为此,吸附剂材料在初始冷启动阶段期间可作为催化处理系统的一部分提供以吸附气体污染物,通常是烃,并保持它们,所述吸附剂材料可以为沸石。当废气温度提高时,将吸附的烃从吸附剂中驱出并在较高温度下经受催化处理。
如上所述,已知包含分散在耐熔金属氧化物载体上的铂族金属的氧化催化剂用于处理来自柴油发动机的废气排放。在贫条件下以及在燃料硫的存在下的高温老化以后,铂(Pt)仍为对将DOC中的CO和HC氧化而言最有效的铂族金属。然而,包含Pd的催化剂提供在较高温度老化(>700℃)下稳定Pt和降低催化剂成本方面的优点。然而,Pd基DOC对于CO和HC氧化通常显示出较高的点火温度,当与HC储存材料一起使用时尤其如此,可能导致HC和或CO点火的延迟。含Pd的DOC可能毒害Pt将链烷烃转化和/或将NO氧化的活性,并且还可使催化剂更易受硫毒害。这些特征通常防止Pd作为氧化催化剂用于贫燃操作中,尤其是其中对于答多数驱动条件,发动机温度保持在250℃以下的轻型柴油应用。
理想的是提供解决上述缺点中的一个或多个的催化剂制品。
发明内容
提供用于废气排放的处理,例如未燃烧烃(HC)和一氧化碳(CO)的氧化以及氮氧化物(NOx)的还原的柴油氧化催化剂。本发明实施方案涉及包含沸石的新型洗涂层(washcoat)组合物,所述沸石使沸石与铂族金属之间的负相互作用最小化。
第一方面,提供用于处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,所述制品包含柴油氧化催化剂和基底。柴油氧化催化剂包含涂覆于所述基底上的第一洗涂层(washcoat layer),所述第一洗涂层包含高表面积耐熔金属氧化物载体、负载于高表面积耐熔金属氧化物载体上的含有铂(Pt)和钯(Pd)的铂族金属组分,和二氧化硅与氧化铝之比大于1000的第一沸石组分。
详细方面提供处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,所述制品包含柴油氧化催化剂和基底,其中柴油氧化催化剂包含涂覆于所述基底上的第一洗涂层和涂覆于第一洗涂层上的第二洗涂层,其中第一和第二洗涂层之一包含高表面积耐熔金属氧化物载体,且第一和第二洗涂层中的另一个包含高表面积耐熔金属氧化物载体、负载于高表面积耐熔金属氧化物载体上的含有铂(Pt)和钯(Pd)的铂族金属组分和二氧化硅与氧化铝之比大于1000的第一沸石组分。
另一方面是用于处理包含烃、一氧化碳和其它废气组分的柴油发动机废气流的系统,所述排放处理系统包含:借助排气歧管与发动机流体连通的废气导管;提供在其中的催化剂制品,其中基底为流通式基底或壁流式基底;以及与复合物流体连通的以下中的一种或多种:烟炱过滤器、选择性催化还原(SCR)催化剂制品以及NOx储存和还原(NSR)催化剂制品。
其它方面包括处理包含烃、一氧化碳和颗粒物质的柴油废气流的方法,所述方法包括:(a)提供:提供在其中的催化剂制品;(b)使所述柴油废气流与用于处理废气排放的所述催化剂制品接触使得氧化催化剂将废气中的烃和一氧化碳氧化成二氧化碳和水;和(c)将离开柴油氧化催化剂的废气输送至下游烟炱过滤器和NOx转化催化剂。
附图简要说明
图1为可包含根据一个实施方案的柴油氧化催化剂(DOC)洗涂层组合物的蜂巢型耐熔承载体元件的透视图;
图2为相对于图1放大且沿着平行于图1载体的端面的平面取得的部分横截面视图,其显示图1所示气体流动通道之一的放大图;和
图3为根据一个实施方案的发动机排放处理系统的示意图。
具体实施方式
在描述本发明的几个典型实施方案以前,应当理解本发明不限于以下说明书中所述构造或工艺步骤的细节。本发明能够赋予其它实施方案并且以各种方法实践和进行。
本发明涉及包含沸石的柴油氧化催化剂(DOC)组合物,所述沸石使沸石与铂族金属之间的负相互作用最小化。这类沸石的特征是高二氧化硅与氧化铝之比(SAR)。SAR可以为250:1;500:1;750:1;1000:1;1200:1;10,000:1。在一个或多个实施方案中,沸石基本不含氧化铝,其测定可通过X射线衍射或感应耦合等离子体分析进行。“基本不含氧化铝”意指所述氧化铝不有意地提供于沸石中。然而,认识到氧化铝一定程度地迁移或扩散至沸石中,认为该次要量被认为是非实质的(即材料的<4重量%、3%、2%或者甚至1%)。因此,本文所述的“基本不含氧化铝的沸石”为包含不多于5000ppm或0.5重量%氧化铝的沸石。
本发明还涉及处理包含未燃烧烃(HC)和一氧化碳(CO)的柴油发动机废气流排放的方法。可将来自柴油发动机的废气流在包含本发明实施方案的洗涂层组合物的废气处理装置中处理。根据本发明,废气流首先与含沸石的层接触,随后与其下的任何层接触。
本发明实施方案的氧化催化剂洗涂层组合物可通过本领域中任何已知的方法施涂于基底表面上。例如,催化剂洗涂层可通过喷涂、粉末涂覆或刷涂或者将表面浸入催化剂组合物中而施涂。基底可以为流通式设计或壁流式设计。
第一方面,提供用于处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,所述制品包含柴油氧化催化剂和基底。柴油氧化催化剂包含涂覆在所述基底上的第一洗涂层,所述第一洗涂层包含高表面积耐熔金属氧化物载体、负载于高表面积耐熔金属氧化物载体上的包含铂(Pt)和钯(Pd)的铂族金属组分和二氧化硅与氧化铝之比大于1000的第一沸石组分。
在一个实施方案中,第一沸石组分可具有大于1200的二氧化硅与氧化铝之比。在另一实施方案中,第一沸石组分不含氧化铝。另一实施方案中,第一洗涂层包含第二沸石组分。第一沸石组分可选自具有β、ZSM-5(其为根据International Zeolite Association(IZA)命名法的MFI类型)、和MCM-22(其为根据International Zeolite Association(IZA)命名法的MWW类型)骨架类型的沸石。高表面积耐熔金属氧化物载体包含氧化铝、二氧化硅、二氧化钛、二氧化铈和氧化锆、其物理混合物、其化学组合及其原子掺杂组合中的一种。在详细实施方案中,高表面积耐熔金属氧化物载体包含氧化铝。第一洗涂层可进一步包含促进剂,所述促进剂为选自氧化钡(BaO)、氧化镁(MgO)、氧化镧(La2O3)及其混合物的一种或多种碱性氧化物。
其它实施方案包括存在于第一洗涂层上的第二洗涂层,所述第二洗涂层包含高表面积耐熔金属氧化物载体。第二洗涂层可进一步包含负载于高表面积耐熔金属氧化物载体上的铂族金属组分。
又另外的实施方案可包括存在于第二洗涂层上的第三洗涂层,所述第三洗涂层包含高表面积耐熔金属氧化物载体。
在一个或多个实施方案中,第二洗涂层、第三洗涂层或者二者进一步包含沸石组分。用于第二和第三洗涂层的沸石可独立地选自具有β、MFI和MWW骨架类型的沸石。这些沸石也可具有大于1000(或1100,或者甚至1200等)的二氧化硅与氧化铝之比。
详细方面提供用于处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,所述制品包含柴油氧化催化剂和基底,其中柴油氧化催化剂包含涂覆于所述基底上的第一洗涂层和涂覆于第一洗涂层上的第二洗涂层,其中第一和第二洗涂层之一包含高表面积耐熔金属氧化物载体,且第一和第二洗涂层中的另一个包含高表面积耐熔金属氧化物载体、负载于高表面积耐熔金属氧化物载体上的包含铂(Pt)和钯(Pd)的铂族金属组分,和二氧化硅与氧化铝之比大于1000的第一沸石组分。在双层催化剂制品的一个实施方案中,第一洗涂层包含高表面积耐熔金属氧化物载体。在可选实施方案中,第二洗涂层包含高表面积耐熔金属氧化物载体。另一实施方案提供存在于第二洗涂层上的第三洗涂层,所述第三洗涂层包含高表面积耐熔金属氧化物载体和任选包含沸石。
另一方面是用于处理包含烃、一氧化碳和其它废气组分的柴油发动机废气流的系统,所述排放处理系统包含:借助排气歧管与柴油发动机流体连通的废气导管;在其中提供的催化剂制品,其中基底为流通式基底或壁流式基底;与复合物流体连通的以下中的一种或多种:烟炱过滤器、选择性催化还原(SCR)催化剂制品以及NOx储存和还原(NSR)催化剂制品。
其它方面包括用于处理包含烃、一氧化碳和颗粒物质的柴油废气流的方法,所述方法包括:(a)提供:提供在其中的催化剂制品;(b)使所述柴油废气流与用于处理废气排放的所述催化剂制品接触使得氧化催化剂将废气中的烃和一氧化碳氧化成二氧化碳和水;和(c)将离开柴油氧化催化剂的废气输送至下游烟炱过滤器和NOx转化催化剂。NOx转化催化剂可包含位于催化的烟炱过滤器(CSF)下游的选择性催化还原(SCR)组件。
在催化剂洗涂层中“载体”的是指通过结合、分散、浸渍或其它合适方法接收铂族金属、稳定剂、促进剂、粘合剂等的材料。有用的高表面积载体包括一种或多种耐熔氧化物。高表面积耐熔金属氧化物载体指具有超过20m2/g,在一些具体实施方案中,超过50m2/g的表面积的金属氧化物载体。在一个或多个实施方案中,表面积可以为60-350m2/g,通常90-250m2/g。合适的高表面积耐熔金属氧化物的实例包括但不限于氧化铝、二氧化硅、二氧化钛、二氧化铈和氧化锆以及其物理混合物、化学组合和/或原子掺杂组合。在具体实施方案中,耐熔金属氧化物可包含混合氧化物,例如二氧化硅-氧化铝、无定形或结晶铝硅酸盐、氧化铝-氧化锆、氧化铝-氧化镧、氧化铝-氧化铬、氧化铝-氧化钡、氧化铝-二氧化铈等。在一个实施方案中,载体具体地由如下组分组成:氧化铝,具体地包括γ、δ、θ或过渡型氧化铝元件,例如γ和eta氧化铝,以及如果存在的话,次要量的其它耐熔氧化物,例如约至多20重量%。典型的耐熔金属氧化物包含具有约50至约300m2/g的比表面积的高表面积γ氧化铝,例如也称为“γ氧化铝”或“活性氧化铝”的氧化铝载体材料通常显示出超过60平方米每g(“m2/g”),通常至多约200m2/g或更高的BET表面积。“BET表面积”指通过N2吸附测定表面积的Brunauer,Emmett,Teller方法。理想地,活性氧化铝具有60-350m2/g,通常90-250m2/g的比表面积。耐熔氧化物载体上的载荷具体地为约0.5至约6g/in3,更具体地约2至约5g/in3,最具体地约2.5至约3.5g/in3。
含沸石层的高表面积载体材料具体地为选自氧化铝、氧化铝-二氧化铈、氧化锆及其混合物的耐熔氧化物材料。
本发明实施方案的含沸石层可包含一种或多种烃(HC)储存组分以吸附烃(HC)。通常,可使用任何烃储存材料,例如微孔材料,例如使铂族金属与材料的相互作用最小化的沸石或沸石状材料。具体而言,烃储存材料为沸石。沸石可以为天然或合成沸石,例如八面沸石、菱沸石、斜发沸石、丝光沸石、硅沸石(silicalite)、沸石X、沸石Y、超稳沸石Y、ZSM-5沸石、offretite或β沸石。沸石吸附剂材料的具体实例具有高二氧化硅与氧化铝之比。沸石可具有至少约250/1、500/1、750/1、1000/1,具体而言至少约1200/1的二氧化硅/氧化铝摩尔比,还例示了约1000/1-1200/1,以及约至10,000/1的有用范围。具体的沸石包括ZSM、Y和β沸石。特别具体的吸附剂可包含具有大于>1000的高二氧化硅与氧化铝之比的β沸石。沸石载荷可以为0.1g/in3或更大以确保足够的HC储存能力并防止在低温储存以后的温度跃升期间储存的链烷烃的过早释放。具体而言,沸石含量为0.4-0.7g/in3。高于1.0g/in3的较高沸石载荷可导致储存的甲苯(如果存在于进料中的话)过早释放。芳烃和链烷烃从沸石中的过早释放可导致CO和HC点火的延迟。
在一个实施方案中,一种或多种沸石可通过与稀土金属离子交换而稳定化。在另一实施方案中,本发明实施方案的洗涂层可包含一种或多种稀土氧化物(例如二氧化铈)以促进重质HC的氧化。
在一个实施方案中,本发明实施方案的洗涂层组合物包含涂覆于单一基底或承载体元件上的两层不同的洗涂层,其中一层(例如第一或顶洗涂层)在另一个(例如第二或底洗涂层)上。在该实施方案中,将第二或底洗涂层涂覆于基底(例如流通式单块)的整个轴长上并将第一或顶洗涂层涂覆于第二或底洗涂层的整个轴长上。
该实施方案的洗涂层组合物可通过参考图1和2而更容易地理解。图1和2显示根据本发明一个实施方案的耐熔承载体元件2。参考图1,耐熔承载体元件2为具有圆柱形外表面4、上游端面6和与端面6相同的下游端面8的圆柱形形状。承载体元件2具有在其中形成的多个细平行气体流动通道10。如图2所见,流动通道10由壁12形成并从上游端面6至下游端面8延伸通过承载体2,其中通道10为无阻碍的以容许流体如气流经由其气体流动通道10纵向通过承载体2。如在图2中更容易看出的,壁12的尺寸和构造使得气体流动通道10具有基本有规则多边形形状,在所示实施方案中基本正方形,但根据J.C.Dettling等人的1982年6月15日公告的美国专利No.4,335,023具有圆角。离散的底层14,其在本领域中以及在下文中有时称为“洗涂层”,粘附或涂覆于承载体元件的壁12上。如图2所示,第二离散顶洗涂层16涂覆于底洗涂层14上。
如图2中所示,承载体元件包含由气体流动通道10提供的空隙空间,且这些通道10的横截面积和限定通道的壁12的厚度会从一类承载体元件至另一类变化。类似地,施涂于这类承载体上的洗涂层的重量可根据情况变化。因此,在描述洗涂层或者组合物的催化金属组分或其它组分的量时,方便地使用每单位体积催化剂承载体的组分重量单位。因此,单位克/立方英寸(“g/in3”)和克/立方英尺(“g/ft3”)在本文中用于意指组分的重量/体积承载体元件,包括承载体元件的空隙空间的体积。
在操作期间,来自贫燃发动机的包含烃、一氧化碳、氮氧化物和硫氧化物的废气排放首先遭遇顶洗涂层16,其后遭遇底洗涂层14。
在另一实施方案中,本发明实施方案的不同洗涂层可分区涂覆使得一个洗涂层在基底的上游端,其它洗涂层在下游端上。例如,上游洗涂层可涂覆于基底的上游区域的一部分上,下游洗涂层可涂覆于基底的下游部分上。在该实施方案中,本发明实施方案的顶洗涂层涂覆于基底的上游部分上(即上游洗涂层)且底洗涂层涂覆于基底的下游部分上(即下游洗涂层)。
根据一个或多个实施方案,氧化催化剂洗涂层组合物置于基底上。基底可以为常用于制备催化剂的那些材料中的任一种,具体地包含陶瓷或金属蜂巢结构。可使用任何合适的基底,例如具有从基底的入口或出口面延伸通过其中的细平行气体流动通道使得通道对流过其中的流体开放的类型的单块基底(在本文中称为流通式基底)。从其流体入口至其流体出口基本为直路径的通道由催化材料作为洗涂层涂覆于其上的壁限定使得流过通道的气体接触催化材料。单块基底的流动通道为薄壁通道,其可具有任何合适的横截面形状和尺寸,例如梯形、矩形、正方形、正弦形、六边形、椭圆形、圆形等。
这类单块承载体每平方英寸横截面可包含至多约700或更多的流动通道(或“室”),但可使用少得多的流动通道。例如,承载体可具有约7-600,更通常地约100-400室每平方英寸(“cpsi”)。室可具有为矩形、正方形、圆形、椭圆形、三角形、六边形或者具有其它多边形形状的横截面。用于本发明实施方案的催化剂的基底可以为陶瓷或金属的。
基底也可以为蜂巢型壁流式过滤器、绕制或填充纤维过滤器、开孔泡沫、烧结金属过滤器等,优选壁流式过滤器。用于负载CSF组合物的壁流式基底具有沿着基底的纵轴延伸的多个细、基本平行的气体流动通道。通常,各通道在基底体的一端被堵塞,同时交替通道在相对端面上被堵塞。
本发明实施方案的柴油氧化催化剂(DOC)可用于包含一个或多个用于柴油废气排放处理的额外组件的联合排放处理系统中。例如,排放处理系统可进一步包含烟炱过滤器组件和/或选择性催化还原(SCR)组件。柴油氧化催化剂可位于烟炱过滤器和/或选择性催化还原组件的上游或下游。
除借助使用氧化催化剂处理废气排放外,本发明可使用烟炱过滤器除去颗粒物质。烟炱过滤器可位于DOC的上游或下游,但特别地位于柴油氧化催化剂下游。在具体实施方案中,烟炱过滤器为催化的烟炱过滤器(CSF)。本发明实施方案的CSF包含涂有包含一种或多种催化剂的洗涂层的基底,所述催化剂用于以烧掉捕获的烟炱和或将废气流排放氧化。一般而言,烟炱燃烧催化剂可以为用于烟炱燃烧的任何已知催化剂。例如,CSF可涂有一种或多种高表面积耐熔氧化物(例如氧化铝、二氧化硅、二氧化硅氧化铝、氧化锆和氧化锆氧化铝)和/或氧化催化剂(例如二氧化铈-氧化锆)以燃烧未燃烧的烃以及燃烧一些程度的颗粒物质。然而,具体而言,烟炱燃烧催化剂为包含一种或多种铂族金属(PM)催化剂(铂、钯和/或铑)的氧化催化剂。
一般而言,可使用任何已知的过滤器基底,包括例如蜂巢型壁流式过滤器、绕制或填充纤维过滤器、开孔泡沫、烧结金属过滤器等,尤其是壁流式过滤器。用于负载CSF组合物的壁流式基底具有沿着基底的纵轴延伸的多个细、基本平行的气体流动通道。通常,各通道在基底体的一端被堵塞,而交替通道在相对端面上被堵塞。这类单块承载体每平方英寸横截面可包含至多约700或更多的流动通道(或“室”),但可使用少得多的流动通道。例如,承载体可具有约7-600,更通常地约100-400室每平方英寸(“cpsi”)。室可具有为矩形、正方形、圆形、椭圆形、三角形、六边形或者具有其它多边形形状的横截面。
任选将用于本发明实施方案中的多孔壁流式过滤器催化,即所述元件的壁具有在其上或包含在其中的一种或多种催化材料,上文描述了这类CSF催化剂组合物。催化材料可存在于元件的仅入口侧、仅出口侧、入口和出口侧,或者壁本身可完全或部分地由催化材料组成。在另一实施方案中,本发明可包括在元件的入口和/或出口壁上使用一层或多层催化材料洗涂层和一层或多层催化材料洗涂层的组合。
本发明实施方案的废气处理系统可进一步包含选择性催化还原(SCR)组件。SCR可位于DOC和/或烟炱过滤器上游或下游。特别地,SCR组件位于烟炱过滤器组件下游。用于排放处理系统中的合适SCR催化剂组分能够在600℃以下的温度有效地催化NOx组分还原,因此即使在通常与较低废气温度相关的低载荷条件下也可处理足够水平的NOx。具体而言,取决于加入系统中的还原剂的量,催化剂颗粒能够将至少50%的NOx组分转化成N2。组合物的另一理想属性是它具有催化O2与任何过量NH3反应形成N2和H2O的能力,使得NH3不排放到大气中。用于排放处理系统中的有用SCR催化剂组合物还应对大于650℃的温度具有耐热性。这类高温可在上游催化的烟炱过滤器的再生期间遇到。
合适的SCR催化剂组合物描述于例如美国专利No.4,961,917('917专利)和美国专利No.5,516,497中,通过引用将其二者全部并入本文中。'917专利中公开的组合物包含存在于沸石中的铁和铜促进剂中的一种或两种,以促进剂加沸石的总重量约0.1-30重量%,特别是约1-5重量%的量包含。除它们催化用NH3将NOx还原成N2的能力外,公开的组合物还可促进过量NH3与O2的氧化,对于具有更高促进剂浓度的那些组合物尤其如此。
在一个实施方案中,本发明涉及包含一种或多种用于柴油发动机废气排放处理的其它组件的排放处理系统。典型排放处理系统可通过参考图3更容易地理解,所述图3描述了根据本发明实施方案的这一实施方案的排放处理系统32的图示。参考图3,包含气体污染物(例如未燃烧烃、一氧化碳和NOx)和颗粒物质的废气流经由管线36从发动机34输送至涂有本发明实施方案的新型洗涂层组合物的柴油氧化催化剂(DOC)38中。在DOC 38中,未燃烧的气体和非挥发性烃(即VOF)和一氧化碳很大程度地燃烧以形成二氧化碳和水。另外,NOx组分的一部分NO可在DOC中氧化成NO2。废气流接着经由管线40输送至催化的烟炱过滤器(CSF)42,所述催化的烟炱过滤器捕集存在于废气流内的颗粒物质。任选催化CSF 42用于被动再生。在经由CSF 42除去颗粒物质以后,废气流经由管线44输送至下游选择性催化还原(SCR)组件16中以处理和/或转化NOx。
实施例
实施例1
通过将多种洗涂层涂覆于基底上而制备柴油氧化催化剂复合物。洗涂层包含具有不同性能的沸石。对于洗涂层,将1.0g/in3高多孔γ氧化铝用硝酸钯水溶液浸渍以得到1.3重量%的铂族金属浓度。加入两倍量的氢氧化钡并将所得粉末分散于水中以获得固体含量为28重量%的分散体。加入胺稳定的hydroxo Pt IV配合物以得到2:1重量比的Pt和Pd干含量。通过酸将pH值调整至4.0的值。将分散体研磨至15μm的d90粒度。加入0.5g/in3的量的如表1所示沸石和0.05g/in3勃姆石并分散。随后将分散体涂覆于单块上,在空气中在110℃下干燥并在空气中在590℃下煅烧。
表1
实施例 | 沸石 | 离子形式 | Si与Al之比 |
1A | 高Si/Alβ | 质子交换的 | 1000 |
1B | β | 质子交换的 | 无Al |
1C | MWW | 质子交换的 | 无Al |
1D | 高Si/Al MFI | 质子交换的 | 1200 |
实施例2
对比
通过将多种洗涂层涂覆在基底上而制备柴油氧化催化剂复合物。洗涂层包含具有各种性能的沸石。对于洗涂层,将1.0g/in3高多孔γ氧化铝用硝酸钯水溶液浸渍以得到1.3重量%的铂族金属浓度。加入两倍量的氢氧化钡并将所得粉末分散于水中以获得固体含量为28重量%的分散体。加入胺稳定的hydroxo Pt IV配合物以得到2:1重量比的Pt和Pd干含量。通过酸将pH值调整至4.0的值。将分散体研磨至15μm的d90粒度。加入0.5g/in3的量的如表1所示沸石和0.05g/in3勃姆石并分散。随后将分散体涂覆于单块上,在空气中在110℃下干燥并在空气中在590℃下煅烧。
表2
实施例 | 沸石 | 离子形式 | Si与Al之比 |
2A | Beta | 质子交换的 | 150 |
2B | ZSM-5 | 质子交换的 | 90 |
实施例3
试验
将实施例1和2的组合物在具有2.7L发动机排量的4缸轻型柴油发动机上在750℃的恒温下老化20小时。然后评估催化剂在2.0L 4缸柴油发动机上在新欧洲驾驶周期(NEDC)期间的活性。催化剂活性通过测量驾驶周期期间入口和出口浓度而评估。评估周期的总CO转化率作为入口与出口浓度之间的差与入口浓度之比计算。CO转化率(以%表示,y轴)的结果作为对各配制剂的3次相继试验操作的平均值显示于表3中。
表3
实施例 | CO转化率(%) |
1A | 56.9 |
1B | 57.4 |
1C | 55.8 |
1D | 56.8 |
2A对比 | 52.8 |
2B对比 | 53.8 |
在整个该说明书关于“一个实施方案”、“某些实施方案”、“一个或多个实施方案”或“实施方案”的提及意指关于该实施方案描述的特定特征、结构、材料或特性包括在本发明的至少一个实施方案中。因此,在整个该说明书中的各个位置处表述如“在一个或多个实施方案中”、“在某些实施方案中”、“在一个实施方案中”或“在实施方案中”的出现未必指同一本发明实施方案。此外,特定特征、结构、材料或特性可在一个或多个实施方案中以任何合适的方式组合。以上方法的描述顺序不应认为是限定性的,且方法可使用无序或者具有省略或添加的所述操作。
应当理解以上描述意欲为说明性的且不是限制性的。许多其它实施方案会是本领域技术人员经回顾以上描述而了解的。因此,本发明的范围参考所附权利要求书以及该权利要求书授权的等价物的全部范围一起决定。
Claims (16)
1.用于处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,其包含柴油氧化催化剂和基底:
柴油氧化催化剂包含涂覆于所述基底上的第一洗涂层,第一洗涂层包含高表面积耐熔金属氧化物载体、负载于具有超过20m2/g的表面积的高表面积耐熔金属氧化物载体上的包含铂(Pt)和钯(Pd)的铂族金属组分,和不含氧化铝的第一沸石组分。
2.根据权利要求1的催化剂制品,其中第一洗涂层包含第二沸石组分。
3.根据权利要求1的催化剂制品,其中第一沸石组分选自具有β、MFI和MWW骨架类型的沸石。
4.根据权利要求1的催化剂制品,其中高表面积耐熔金属氧化物载体包含氧化铝、二氧化硅、二氧化钛、二氧化铈和氧化锆、它们的物理混合物、它们的化学组合中的一种。
5.根据权利要求4的催化剂制品,其中高表面积耐熔金属氧化物载体包含氧化铝。
6.根据权利要求1的催化剂制品,其中第一洗涂层上存在第二洗涂层,第二洗涂层包含高表面积耐熔金属氧化物载体。
7.根据权利要求6的催化剂制品,其中第二洗涂层进一步包含负载于高表面积耐熔金属氧化物载体上的铂族金属组分。
8.根据权利要求6的催化剂制品,其中第二洗涂层上存在第三洗涂层,第三洗涂层包含高表面积耐熔金属氧化物载体。
9.根据权利要求8的催化剂制品,其中第二洗涂层、第三洗涂层或二者进一步包含沸石组分。
10.根据权利要求1的催化剂制品,其中第一洗涂层进一步包含促进剂,所述促进剂为选自氧化钡(BaO)、氧化镁(MgO)、氧化镧(La2O3)中的一种或多种碱性氧化物。
11.根据权利要求1的催化剂制品,其中基底为流通式基底或壁流式基底。
12.用于处理来自柴油发动机的包含烃、一氧化碳和颗粒物质的废气排放的催化剂制品,其包含柴油氧化催化剂和基底:
柴油氧化催化剂包含涂覆于所述基底上的第一洗涂层和涂覆于第一洗涂层上的第二洗涂层,其中第二洗涂层包含高表面积耐熔金属氧化物载体,且第一洗涂层包含高表面积耐熔金属氧化物载体、负载于高表面积耐熔金属氧化物载体上的包含铂(Pt)和钯(Pd)的铂族金属组分,和不含氧化铝的第一沸石组分。
13.根据权利要求12的催化剂制品,其中第二洗涂层上存在第三洗涂层,第三洗涂层包含高表面积耐熔金属氧化物载体和任选包含沸石。
14.用于处理包含烃、一氧化碳和其它废气组分的柴油发动机废气流的系统,所述排放处理系统包含:
借助排气歧管与柴油发动机流体连通的废气导管;
根据权利要求1-13任一项的催化剂制品,其中基底为流通式基底或壁流式基底;和
与复合物流体连通的以下中的一种或多种:烟炱过滤器、选择性催化还原(SCR)催化剂制品和NOx储存和还原(NSR)催化剂制品。
15.处理包含烃、一氧化碳和颗粒物质的柴油废气流的方法,所述方法包括:(a)提供权利要求1-13任一项的催化剂制品;(b)使所述柴油废气流与用于处理废气排放的所述催化剂制品接触使得氧化催化剂将废气中的烃和一氧化碳氧化成二氧化碳和水;和(c)将离开柴油氧化催化剂的废气输送至下游烟炱过滤器和NOx转化催化剂。
16.根据权利要求15的方法,其中NOx转化催化剂包含位于催化的烟炱过滤器(CSF)下游的选择性催化还原(SCR)组件。
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- 2012-04-05 EP EP12715513.3A patent/EP2834002B1/en active Active
- 2012-04-05 WO PCT/US2012/032319 patent/WO2013151549A1/en active Application Filing
- 2012-04-05 CA CA2869666A patent/CA2869666A1/en not_active Abandoned
- 2012-04-05 CN CN201280072223.8A patent/CN104379256B/zh active Active
- 2012-04-05 BR BR112014024246A patent/BR112014024246A2/pt not_active IP Right Cessation
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- 2012-04-05 JP JP2015504536A patent/JP6138911B2/ja active Active
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US9533295B2 (en) | 2017-01-03 |
EP2834002B1 (en) | 2019-03-20 |
WO2013151549A1 (en) | 2013-10-10 |
US20150174564A1 (en) | 2015-06-25 |
EP2834002A1 (en) | 2015-02-11 |
MX2014012010A (es) | 2015-09-04 |
ZA201408007B (en) | 2016-08-31 |
JP6138911B2 (ja) | 2017-05-31 |
BR112014024246A2 (pt) | 2017-07-04 |
IN2014DN08697A (zh) | 2015-05-22 |
KR101962504B1 (ko) | 2019-03-26 |
RU2014144091A (ru) | 2016-05-27 |
KR20140146643A (ko) | 2014-12-26 |
JP2015514010A (ja) | 2015-05-18 |
CN104379256A (zh) | 2015-02-25 |
RU2599985C2 (ru) | 2016-10-20 |
CA2869666A1 (en) | 2013-10-10 |
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