CN115518676A - Catalyst product for treating tail gas of lean-burn engine and application thereof - Google Patents
Catalyst product for treating tail gas of lean-burn engine and application thereof Download PDFInfo
- Publication number
- CN115518676A CN115518676A CN202211111489.0A CN202211111489A CN115518676A CN 115518676 A CN115518676 A CN 115518676A CN 202211111489 A CN202211111489 A CN 202211111489A CN 115518676 A CN115518676 A CN 115518676A
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- China
- Prior art keywords
- coating
- catalyst
- oxide
- catalyst composition
- burn engine
- 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.)
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- 238000000576 coating method Methods 0.000 claims abstract description 144
- 239000011248 coating agent Substances 0.000 claims abstract description 137
- 239000000203 mixture Substances 0.000 claims abstract description 54
- 239000007789 gas Substances 0.000 claims abstract description 38
- 239000000758 substrate Substances 0.000 claims abstract description 34
- 230000009467 reduction Effects 0.000 claims abstract description 30
- 239000011247 coating layer Substances 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000001179 sorption measurement Methods 0.000 claims abstract description 20
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 48
- 239000002808 molecular sieve Substances 0.000 claims description 29
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 29
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 28
- 238000011068 loading method Methods 0.000 claims description 26
- 229910052878 cordierite Inorganic materials 0.000 claims description 18
- 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 claims description 18
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 17
- 230000002829 reductive effect Effects 0.000 claims description 15
- 230000000274 adsorptive effect Effects 0.000 claims description 13
- 239000010949 copper Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 6
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000004480 active ingredient Substances 0.000 claims description 5
- 239000010953 base metal Substances 0.000 claims description 5
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 5
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
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- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 4
- 239000000292 calcium oxide Substances 0.000 claims description 4
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
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- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound 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 claims description 3
- 229910052676 chabazite Inorganic materials 0.000 claims description 3
- 229910000701 elgiloys (Co-Cr-Ni Alloy) Inorganic materials 0.000 claims description 3
- 229910052675 erionite Inorganic materials 0.000 claims description 3
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052677 heulandite Inorganic materials 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229910052680 mordenite Inorganic materials 0.000 claims description 3
- 229910052674 natrolite Inorganic materials 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052679 scolecite Inorganic materials 0.000 claims description 3
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052678 stilbite Inorganic materials 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 84
- 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 82
- 239000002002 slurry Substances 0.000 description 65
- 230000000052 comparative effect Effects 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 36
- 238000006722 reduction reaction Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 18
- 238000003756 stirring Methods 0.000 description 18
- 239000000725 suspension Substances 0.000 description 17
- 239000000853 adhesive Substances 0.000 description 12
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- 239000002245 particle Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 9
- 238000001354 calcination Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229910000510 noble metal Inorganic materials 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 5
- 239000003463 adsorbent Substances 0.000 description 5
- 239000011230 binding agent Substances 0.000 description 5
- 239000000084 colloidal system Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- 239000011593 sulfur Substances 0.000 description 5
- 229910002089 NOx Inorganic materials 0.000 description 4
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 239000000446 fuel Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 230000008929 regeneration Effects 0.000 description 3
- 238000011069 regeneration method Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 208000028659 discharge Diseases 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 235000013842 nitrous oxide Nutrition 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 244000304337 Cuminum cyminum Species 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical class ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229960001730 nitrous oxide Drugs 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
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- 239000010453 quartz Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
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- 238000007086 side reaction Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
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- 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
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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
- B01J35/19—Catalysts containing parts with different compositions
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
- B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/584—No clear coat specified at least some layers being let to dry, at least partially, before applying the next layer
-
- 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
- F01N3/10—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
- 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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- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
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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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/67—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2203/00—Other substrates
- B05D2203/30—Other inorganic substrates, e.g. ceramics, silicon
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Toxicology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention discloses a catalyst product for treating tail gas of a lean-burn engine and application thereof, wherein the catalyst product adopts a flow-through monolithic substrate, the hole wall of the substrate is provided with a layered catalyst covering the length of the whole substrate, and the layered catalyst comprises a first coating, a second coating and a third coating which are arranged from inside to outside; the first coating comprises a passive nitrogen oxide adsorption catalyst composition and the second coating comprises NO 2 Reducing the catalyst composition, the third coating comprising NO x Reducing the catalyst composition; the first coating absorbs NO in the tail gas at the temperature of below 150 DEG C x And release NO above 250 ℃ x (ii) a Second coating layer of NO x A certain proportion of NO 2 Conversion to NO 2 And NO concentration ratio of 0.8-1.2: 1; third coating NO x Conversion to N 2 . The catalyst product comprises PNA catalyst, NO 2 The reduction catalyst and the SCR catalyst are loaded in different areas of the same carrier to realize NO x Adsorption, release, NO 2 Reduction to NO, NO x Recycle of reduction, thereby increasing NO x The reduction processing rate of (2).
Description
Technical Field
The invention belongs to the field of catalysts for post-treatment of tail gas of fuel vehicles, and particularly relates to a catalyst product for treating tail gas of a lean burn engine and application thereof.
Background
The U.S. Environmental Protection Agency (EPA) regulates nitrogen dioxide (NO) based on the negative climate effects of nitrogen oxides 2 ) Nitrogen monoxide (NO) and dinitrogen monoxide (N) 2 O) is collectively referred to as NO x . The exhaust gas of diesel vehicles with high air-fuel ratio is NO x The main source of emissions. As a typical lean-burn engine, diesel vehicles typically employ a combination of selective reduction catalytic SCR technology and cooled exhaust gas recirculation technology to meet stringent emission regulations. However, the SCR catalyst can exert good NO only when the temperature of the exhaust gas reaches the light-off temperature (more than 200 ℃ C.) or higher x And (5) emission reduction effect. The temperature of tail gas in cold start stage of diesel vehicle is lower than 180 deg.C and lasts for about 3min, during which period NO x The emissions are hardly treated or emitted into the air. NO emitted in cold start x Contribute to the total NO x 80% of the emissions. In addition, in order to improve fuel economy, advanced combustion, engine miniaturization, turbocharging and other technologies are continuously updated and applied to the diesel engine, so that the exhaust temperature is lowered, and the duration and the strength of the cold start effect are more obvious.
For solving NO in tail gas in cold starting stage x Emission problem, passive NO x The adsorbent (PNA) is generated by the operation, and the PNA adsorbs NO when the SCR is low in activity x With the rising temperature of the tail gas, the PNA can convert NO into NO when the downstream SCR can be efficiently catalyzed x Rapidly releases and recovers NO x And (4) an adsorption function.
Cummins proposes a tissue architecture with PNA, i.e., DOC + PNA + SCRF (i.e., SCR catalysis)Agent coated on particulate trap (DPF) + CC-SCR. The system has excellent NO x Emission reduction effect, but relates to 5 post-processing units outside the machine, the system architecture is complex, the implementation cost is high, and huge pressure is brought to packaging and arrangement. Zhuang xinwanfeng disclosed a DOC and PNA coupling scheme called DCSC unit and multiple patented layouts were made for the different framework structure molecular sieve components of DCSC. The unit has the defects that because the DCSC contains a large amount of noble metal active components, the DCSC is unevenly distributed in the hierarchical pore canal of the carrier, the DCSC is easy to agglomerate at high temperature to form large particles, the charge density of the agglomerated particles is high, electrons are easy to be given, and NO in the original discharge is treated x The oxidation is much greater than the adsorption, resulting in passive NO exhibited by DCSC x Low adsorption capacity and NO due to DCSC treatment 2 Much higher than NO, not favorable for subsequent NH 3 SCR reacts rapidly, reducing the rate of selective catalytic reduction treatment.
Disclosure of Invention
In order to solve the problem of NO in tail gas in cold starting stage in the prior art x The invention provides the following technical scheme for solving the discharge problem:
in a first aspect, the present invention provides a catalyst article for treating the exhaust gas of a lean burn engine, the catalyst article being a flow-through monolith substrate having a layered catalyst disposed on the walls of the pores of the substrate over the entire length of the substrate, the layered catalyst comprising a first coating, a second coating and a third coating disposed from the inside to the outside; the first coating layer comprises a passive nox adsorber catalyst composition and the second coating layer comprises NO 2 Reducing the catalyst composition, the third coating comprising NO x Reducing the catalyst composition; the first coating absorbs NO in the tail gas at the temperature of less than 150 DEG C x And release NO above 250 ℃ x (ii) a Second coating layer of NO x A certain proportion of NO 2 Conversion to NO 2 And NO concentration ratio of 0.8-1.2: 1; third coating NO x Conversion to N 2 。
In some embodiments provided herein, the passive nox adsorber catalyst composition, NO 2 Reduction catalyst composition, NO x The ratio of the supported amount of the reduction catalyst composition is 30 to 50:10:95 to 120.
In some embodiments provided herein, the loading of the passive nitroxide adsorption catalyst composition in the first coating is from 30 to 50g/L; NO in the second coating 2 The loading of the reduced catalyst composition is 10 + -2 g/L; NO in the third coating x The loading of the reduction catalyst composition is 95-120 g/L.
In some embodiments provided by the present invention, the substrate is one of cordierite, silicon carbide, and metal.
In some embodiments of the present invention, the metal material is one of Fe-Cr-Ni alloy, co-Cr-Ni alloy, and Ni-Cr-Mo alloy.
In some embodiments provided herein, a passive nox adsorber catalyst composition includes a noble metal active component and a first adsorbent refractory support, the noble metal active component being at least one of Pd, ag, co, and the first adsorbent refractory support being a first molecular sieve or a metal oxide.
In some embodiments provided herein, the passive nox adsorber catalyst composition further comprises a base metal that is at least one of Mn, co, zr, ni, or a rare earth metal that is Ce or La.
In some embodiments provided herein, NO 2 The reductive catalyst composition comprises NO 2 Reducing the active ingredient and a second adsorptive refractory carrier, NO 2 The reduction active component is one or more of ferric oxide, cobalt oxide, copper oxide, barium oxide, calcium oxide, magnesium oxide, strontium oxide, tin oxide and germanium oxide, and the second adsorptive refractory carrier is silicon oxide or gamma-alumina.
In some embodiments provided herein, NO x The reducing catalyst composition comprises NO x Reducing the active ingredient and a third adsorptive refractory carrier, NO x The reducing active component is one or more of Cu, mn, V, fe, co, W, ni, zn, ti, cr, Y, zr, nb and Mo, and the third adsorptive refractory carrier includes analcime, chabazite, heulandite, stilbite, etc,One or symbiotic mixture of erionite, mordenite, scolecite and natrolite.
In a second aspect, the present invention provides a lean burn engine exhaust gas treatment device comprising a catalyst article for lean burn engine exhaust gas treatment.
Compared with the prior art, the PNA catalyst and NO are used in the invention 2 The reduction catalyst and the SCR catalyst are loaded on the same substrate, and the PNA catalyst solves the problem of low-temperature cold start NO x Emission problem, NO 2 The reduction catalyst improves the oxidation side reaction of the PNA catalyst, on one hand, NO and NO in tail gas are ensured 2 The balance of (a) is close to 1:1, promoting fast SCR reaction, on the other hand, avoiding low temperature NO x Excessive NO formation by adsorption 2 From the source, control N 2 And (4) O generation reaction.
Drawings
FIG. 1 coating scheme one of the invention used in examples 1-3.
FIG. 2 coating scheme two used in comparative examples 3-5 of the present invention.
FIG. 3 coating scheme three used in comparative examples 6 to 7 of the present invention.
Detailed Description
The invention is further described with reference to the following examples, which are intended to better illustrate the technical solution of the invention and not to limit the claims. The invention is not limited to the specific examples and embodiments described herein. It will be apparent to those skilled in the art that further modifications and improvements may be made without departing from the spirit and scope of the invention, and these are intended to be covered by the appended claims.
The existing tail gas treatment system of the lean-burn engine comprises an independent PNA unit and an independent SCR unit, wherein the PNA unit can oxidize 40% -90% of NO into NO 2 Resulting in NO and NO 2 The ratio is much less than 1. The invention loads PNA catalyst and SCR catalyst on the same monolith substrate to form NO with low temperature x Adsorption-functional SCR catalyst and addition of NO between PNA catalyst coating and SCR catalyst coating 2 Reduction ofCatalyst coating for oxidation of more than 90% of NO to NO 2 Re-reduction to NO, thereby regulating NO and NO 2 The ratio is close to 1.
The invention provides a catalyst product for treating lean-burn engine exhaust, which adopts a monolithic substrate, wherein the wall of the substrate hole is coated with a layered catalyst, the layered catalyst coats the whole length of the monolithic substrate and sequentially comprises a first coating, a second coating and a third coating from inside to outside; the first coating comprises a passive nitrogen oxide adsorption catalyst composition and the second coating comprises NO 2 Reducing the catalyst composition, the third coating comprising NO x Reducing the catalyst composition; the first coating absorbs NO in the tail gas at the temperature of below 150 DEG C x And release NO above 250 ℃ x (ii) a Second coating layer of NO x In a certain proportion of NO 2 Conversion to NO 2 And NO concentration ratio of 0.8-1.2: 1; third coating layer NO x Conversion to N 2 。
In some embodiments provided herein, the passive nox adsorber catalyst composition, NO 2 Reductive catalyst composition, NO x The ratio of the supported amount of the reducing catalyst composition is 30 to 50:10:95 to 120. In the proportion range, the second coating layer is ensured to partially remove NO 2 Reduction to NO enables the formation of NO and NO 2 The ratio of (a) to (b) is adjusted to approach 1.
In some embodiments provided herein, the first coating has an loading of the passive nitrogen oxide adsorbing catalyst composition of 30 to 50g/L; NO in the second coating 2 The loading of the reduced catalyst composition is 10 + -2 g/L; NO in the third coating x The loading of the reduced catalyst composition is 95 to 120g/L. The loading amount of the passive oxynitride adsorption catalyst composition in the first coating needs to balance the low-temperature adsorption performance and the system backpressure, so the loading amount is set to be 30-50 g/L, and when the loading amount is lower than 30g/L, NO is discharged from the tail of the cold start of an engine x Can not be sufficiently adsorbed, and NO can be further reduced by increasing the loading amount x Concentration, above 50g/L, of cold start NO x The conversion efficiency can not be further improved, and the system back pressure is increased due to the reverse falling, thereby the influenceEngine fuel economy. Second coating NO 2 The loading amount of the reduction catalyst composition is controlled to 10 + -2 g/L, and the main consideration is that the reduction catalyst composition is NO 2 The reduction efficiency of (a). With the second coating on the upper surface of the first coating, the desired reduction efficiency of the catalyst article can be met at this loading setting. The coating amount of the third coating is designed to be 95-120 g/L, the NOx reduction efficiency is mainly considered, different active components are selected, and different loading requirements exist, for example, when the active component is Cu, the coating amount can be reduced because the low-temperature performance is better than that of Fe.
In some embodiments of the present invention, the substrate is one of cordierite, silicon carbide, and metal.
In some embodiments of the present invention, the metal material is one of Fe-Cr-Ni alloy, co-Cr-Ni alloy, and Ni-Cr-Mo alloy.
In some embodiments provided herein, a passive nox adsorber catalyst composition includes a noble metal active component and a first adsorbent refractory support, the noble metal active component being at least one of Pd, ag, co, and the first adsorbent refractory support being a first molecular sieve or a metal oxide. The first molecular sieve is one of small pore molecular sieve with eight-membered ring structure, medium pore molecular sieve with ten-membered ring structure and large pore molecular sieve with twelve-membered ring structure, and the first molecular sieve can be one of BEA, FAU, MFI, CHA, LTA, AEI, FER and MCM, especially one of Beta, HEBA, SSZ-13, ZSM-5, SSZ-39 and HZSM-11. The grain size of the first molecular sieve is 0.01-10 mu m, and Si/Al = 1-30. Further, the grain size of the first molecular sieve is 100-1000 nm. The metal oxide refers to one of gamma-alumina, cerium oxide, praseodymium oxide, zirconium oxide and tungsten oxide and composite oxides thereof.
In some embodiments provided herein, the passive nox adsorber catalyst composition further comprises a base metal that is at least one of Mn, co, zr, ni, or a rare earth metal that is Ce or La.
Preferably, the noble metal content is 0.1wt% to 5wt% of the passive oxynitride adsorbing catalyst composition, and the base metal content is 0.1wt% to 1wt% of the passive oxynitride adsorbing catalyst composition.
In some embodiments provided herein, NO 2 The reductive catalyst composition comprises NO 2 Reducing the active ingredient and a second adsorptive refractory carrier, NO 2 The reduction active component is one or more of ferric oxide, cobalt oxide, copper oxide, barium oxide, calcium oxide, magnesium oxide, strontium oxide, tin oxide and germanium oxide, and the second adsorptive refractory carrier is silicon oxide or gamma-alumina. NO 2 The reductive catalyst composition is preferably a symbiotic mixture of at least one of iron oxide, cobalt oxide, copper oxide, barium oxide, calcium oxide, and magnesium oxide and one or both of silicon oxide and gamma-alumina.
In some embodiments provided herein, NO x The reducing catalyst composition comprises NO x Reducing the active ingredient and a third adsorptive refractory carrier, NO x The reducing active component is one or more of Cu, mn, V, fe, co, W, ni, zn, ti, cr, Y, zr, nb and Mo, and the third adsorptive refractory carrier includes one or symbiotic mixture of analcime, chabazite, heulandite, stilbite, erionite, mordenite, scolecite and natrolite. More preferably, the third adsorptive refractory carrier is one or a symbiotic mixture of BEA, FAU, MFI, CHA, LTA, AEI, MOR, KFI, ROH framework, NO x The reduction active component is one or a symbiotic mixture of Cu, fe, W, ti, zr and Mo.
In a second aspect, the present invention provides a lean burn engine exhaust gas treatment device comprising a catalyst article for lean burn engine exhaust gas treatment. With the composite catalyst provided by the application, a PNA unit does not need to be additionally arranged, and preferably, a lean burn engine tail gas treatment device comprising a catalyst product for the lean burn engine tail gas treatment is provided with a DOC unit, a DPF unit, a catalyst product unit for the lean burn engine tail gas treatment and an ASC unit according to the tail gas flowing direction.
The following table is a parameter table for each coating of the catalyst articles examples 1-3 and comparative examples 1-7 for lean burn engine exhaust treatment provided by the present invention.
TABLE 1
TABLE 1 (continue)
Example 1:
the present embodiment provides a method for preparing a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding palladium nitrate into FER microporous molecular sieve slurry with Si/Al =25, the grain size of 800nm and the molecular sieve D50 of 5-8 μm, stirring uniformly, adding 10% of alumina adhesive, adding water to adjust the solid content to 30%, and obtaining first slurry. The first slurry was uniformly coated on a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate by 40Hz negative pressure suction at the upper feed and outlet end, loaded with 35g/L dry weight, dried and calcined in 550 ℃ air to form a first coating layer having a noble metal content of 0.45wt%.
S2: adding water into gamma-alumina with the particle size of 1-3 mu m for mixing to prepare alumina suspension, adding nano barium oxide colloid suspension according to the mass ratio of the alumina to the barium oxide of 7. And uniformly coating the second slurry on the surface of the first coating in a mode of feeding at the upper gas outlet end and sucking at 40Hz negative pressure, loading the second coating with a dry weight of 10g/L, drying, and calcining in air at 550 ℃ to form the second coating.
S3: adding water into a commercially available SSZ-39 molecular sieve with the D50 of 5-8 mu m and the Cu content of 3.5%, stirring and dispersing for 30min, then adding 5% of alumina adhesive, and adding water to adjust the solid content to 30% to obtain third slurry. And uniformly coating the third slurry on the surface of the second coating in a mode of feeding and negative pressure suction at 40Hz at an air outlet end, loading the third coating with the dry weight of 95g/L, drying, and calcining in air at 550 ℃ to form a third coating, thus obtaining a catalyst product marked as catalyst No. 1.
Example 2:
the present embodiment provides a method for preparing a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding silver nitrate into gamma-alumina suspension with the average particle size of 100nm, uniformly stirring, adding 10% of alumina adhesive, and adding water to adjust the solid content to 28% to obtain first slurry. The first slurry was uniformly coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight through cordierite substrate with a dry weight of 50g/L by 40Hz negative pressure suction at the upper feed and outlet end. After drying, the coating was calcined in air at 550 ℃ to form a first coating.
S2: and adding water into the gamma-alumina with the particle size of 1-3 mu m for mixing to prepare alumina suspension, adding the nano barium oxide colloid suspension according to the mass ratio of the alumina to the barium oxide of 6. And uniformly coating the second slurry on the surface of the first coating in a mode of 40Hz negative pressure suction at the upper feeding end and the air outlet end, loading 10g/L of dry weight, drying, and calcining in air at 550 ℃ to form the second coating.
S3: adding water to the BEA molecular sieve containing 5.2wt% Fe, stirring and dispersing for 30min, adding 10% alumina binder, and adding water to adjust the solid content to 30% to obtain a third slurry. And uniformly coating the third slurry on the surface of the second coating in a mode of feeding and negative pressure suction at 40Hz of an air outlet end, loading the third slurry with a dry weight of 115g/L, drying, and calcining in air at 550 ℃ to form a third coating, thus obtaining the catalyst product.
Example 3:
the present embodiment provides a method for preparing a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding cobalt oxide into SSZ-13 microporous molecular sieve slurry with Si/Al =14 and the grain size of 200nm, uniformly stirring, and adding water to adjust the solid content of the slurry to 30% to obtain first slurry. The first slurry was uniformly coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight through cordierite substrate by 40Hz negative pressure suction at the upper feed and outlet end, loaded with 50g/L dry weight, dried and calcined in 550 deg.C air to form the first coating.
S2: adding water into gamma-alumina with the particle size of 1-3 mu m for mixing to prepare alumina suspension, adding nano barium oxide colloid suspension according to the mass ratio of alumina to barium oxide of 6. And uniformly coating the second slurry on the surface of the first coating in a mode of 40Hz negative pressure suction at the upper feeding end and the air outlet end, loading 10g/L of dry weight, drying, and calcining in air at 550 ℃ to form the second coating.
S3: adding water into an SSZ-39 molecular sieve containing 3.5% of Cu, stirring and dispersing for 30min, then adding 5% of alumina binder, and adding water to adjust the solid content to 30% to obtain third slurry. And uniformly coating the third slurry on the surface of the second coating in a mode of feeding at the upper part and sucking at the 40Hz negative pressure at the air outlet end, loading the third slurry with a dry weight of 95g/L, drying, and calcining in air at 550 ℃ to form a third coating, thus obtaining the catalyst product.
Comparative example 1:
this comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
adding water into an SSZ-39 molecular sieve with the D50 of 5-8 mu m and the Cu content of 3.2 wt%, stirring and dispersing for 30min, then adding 5% of alumina adhesive (hydrated alumina, TREO oxide content of 73.60%), adding water and adjusting to the solid content of 30% to obtain slurry. Coating the slurry on a straight-through cordierite ceramic carrier with the mesh number of 600, the wall thickness of 3.2mil, the length of 5 inches and the diameter of 12 inches in a mode of feeding at the upper feeding end and negative pressure suction at the air outlet end of 40Hz, drying, and calcining in air at 550 ℃ to obtain the catalyst product.
Comparative example 2:
this comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
adding water into a BEA molecular sieve containing 4.0% of Fe, stirring and dispersing for 30min, then adding 10% of alumina binder, and adding water to adjust the solid content to 32% to obtain slurry. The slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate by 40Hz negative pressure suction at the upper feed and outlet end. And calcining the dried product in air at 550 ℃ to obtain the catalyst product.
Comparative example 3:
this comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding palladium nitrate into FER microporous molecular sieve slurry with the grain size of 800nm and Si/Al =25, uniformly stirring, adding 10% of alumina adhesive, adding water to adjust the solid content of the slurry to 30%, and obtaining first slurry. The first slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter, straight-through cordierite substrate from the inlet end by the above feed, 40Hz negative pressure suction, dried at 30g/L dry weight and 1.5 inch coated length, and calcined in 550 deg.C air to form a first coating.
S2: and adding water into the gamma-alumina with the particle size of 1-3 mu m for mixing to prepare alumina suspension, adding the nano barium oxide colloid suspension according to the mass ratio of the alumina to the barium oxide of 6. The second slurry was applied to the other end of the straight through cordierite substrate from the outlet end in a top-fed, 40Hz negative pressure suction manner, over a length of 3.5 inches, with an upper loading dry weight of 10g/L, dried and calcined in air at 550 c to form a second coating, as shown in fig. 2, where the sum of the lengths of the first and second coatings was the total length of the substrate and the first coating had a greater thickness than the second coating.
S3: adding water into an SSZ-39 molecular sieve containing 3.5% of Cu, stirring and dispersing for 30min, then adding 5% of alumina binder, and adding water to adjust the solid content to 30% to obtain third slurry. Coating a third slurry on the surface of the second coating layer in a mode of feeding and negative pressure suction of 40Hz from the gas outlet end, wherein the coating length is 3.5 inches, the whole second coating layer is covered, the third slurry is loaded with 100g/L of dry weight, and the third slurry is calcined in air at 550 ℃ after being dried to form a third coating layer, namely the catalyst product is obtained and is marked as catalyst No. 2.
Comparative example 4:
the present comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding silver nitrate into SSZ-13 microporous molecular sieve slurry with the atomic ratio of Si/Al =14 and the grain size of 100nm, uniformly stirring, adding 10% of alumina adhesive, and adding water to adjust the solid content of the slurry to 30% to obtain first slurry. The first slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate from the inlet end by top feed, 40Hz negative pressure suction, dried and calcined at 550 ℃ in air to form a first coating, loading a dry weight of 40g/L, coating a length of 2 inches.
S2: and adding water into the gamma-alumina with the particle size of 1-3 mu m for mixing to prepare an alumina suspension, adding the nano iron oxide suspension according to the mass ratio of the alumina to the iron oxide of 3. The second slurry was applied to the other end of the straight through cordierite substrate from the outlet end in a top-fed, 40Hz negative pressure suction manner, over a 3 inch coating length with a dry top loading of 10g/L, dried and then calcined in air at 550 c to form a second coating, as shown in fig. 2, where the sum of the first and second coating lengths was the total length of the substrate and the first coating thickness was greater than the second coating.
S3: adding water into a BEA molecular sieve with the D50 of 5-8 mu m and the Fe content of 5.2%, stirring and dispersing for 30min, then adding 10% of alumina adhesive, and adding water to adjust the solid content to 30% to obtain third slurry. And coating a third slurry on the surface of the second coating layer in a mode of feeding and negative pressure suction of 40Hz from the gas outlet end, wherein the coating length is 3.5 inches, the whole second coating layer is covered, the third slurry is loaded with 120g/L of dry weight, and the third slurry is calcined in air at 550 ℃ after being dried to form a third coating layer, namely the catalyst product is obtained.
Comparative example 5:
this comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding palladium nitrate into FER microporous molecular sieve slurry with the grain size of 800nm and Si/Al =25, uniformly stirring, adding 10% of alumina adhesive, adding water to adjust the solid content of the slurry to 30%, and obtaining first slurry. From the inlet end, the slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate by top feed, 40Hz negative pressure suction, loaded with 35g/L dry weight, coated 2 inches long, dried and calcined in air at 550 ℃ to form a first coating.
S2: and adding water into the gamma-alumina with the particle size of 1-3 mu m for mixing to prepare an alumina suspension, adding the nano barium oxide colloid suspension according to the mass ratio of the alumina to the barium oxide of 6. The second slurry was applied to the other end of the straight-through cordierite substrate from the outlet end in a top-fed, 40Hz negative pressure suction manner, over a 2 inch coating length with a dry upper load of 10g/L, dried and then calcined in air at 550 c to form a second coating as shown in fig. 2, where the sum of the lengths of the first and second coatings was the total length of the substrate and the first coating thickness was greater than the second coating.
S3: adding water into an SSZ-39 molecular sieve containing 3.5 percent of Cu, stirring and dispersing for 30min, then adding 5 percent of alumina adhesive, and adding water to adjust the solid content to be 28 percent to obtain slurry. And coating a third slurry on the surface of the second coating layer in a mode of feeding and negative pressure suction of 40Hz from the gas outlet end, wherein the coating length is 3.5 inches, the whole second coating layer is covered, the dry weight of the third slurry is 95g/L, and the third slurry is calcined in air at 550 ℃ after being dried to form a third coating layer, namely the catalyst product is obtained.
Comparative example 6:
the present comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: adding silver nitrate into SSZ-13 microporous molecular sieve slurry with Si/Al =14 and the grain size of 200nm, stirring uniformly, adding 10% of alumina adhesive, and adding water to adjust the solid content of the slurry to 30%. From the inlet end, the slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate by top feed, 40Hz negative pressure suction, loaded with 45g/L dry weight, coated at 2.5 inches in length, dried and calcined in air at 550 ℃ to form a first coating.
S2: adding water into gamma-alumina with the particle size of 1-3 mu m for mixing to prepare an alumina suspension, adding the nano iron oxide suspension according to the mass ratio of the alumina to the iron oxide of 3. The second slurry was applied to the other end of the flow-through cordierite substrate from the outlet end in a top-feed, 40Hz negative pressure draw, 2.5 inches long, with an on-board dry weight of 10g/L, and dried and then calcined in air at 550 deg.C to form a second coating, as shown in FIG. 3, where the sum of the first and second coating lengths was the total length of the substrate and the thicknesses were the same.
S3: adding water into a BEA molecular sieve containing 5.2% of Fe, stirring and dispersing for 30min, then adding 10% of alumina adhesive, and adding water to adjust the solid content to 30% to obtain third slurry. And coating the third slurry on the surface of the first coating to the surface of the second coating from the air inlet end in a manner of feeding and 40Hz negative pressure suction, wherein the coating length is 5 inches, the dry weight of the upper carrier is 115g/L, and the third slurry is calcined in air at 550 ℃ after being dried to form a third coating, namely the catalyst product.
Comparative example 7:
the present comparative example provides a method of making a catalyst article for lean burn engine exhaust treatment, comprising the steps of:
s1: palladium nitrate is added into FER microporous molecular sieve slurry with the grain size of 800nm and the Si/Al =25, after uniform stirring, 10 percent of alumina adhesive is added, and water is added to adjust the solid content of the slurry to 30 percent. From the inlet end, the slurry was coated onto a 600 mesh, 3.2mil thick, 5 inch long, 12 inch diameter straight-through cordierite substrate by top feed, 40Hz negative pressure suction, loaded on a dry weight of 30/L, coated to a length of 3.5 inches, dried and calcined in air at 550 ℃ to form a first coating.
S2: and adding water into the gamma-alumina with the particle size of 1-3 mu m for mixing to prepare an alumina suspension, adding the nano iron oxide suspension according to the mass ratio of the alumina to the iron oxide of 3. The second slurry was applied to the other end of the flow-through cordierite substrate from the outlet end in a top-feed, 40Hz negative pressure suction manner to a 2 inch coat length with an on-board dry weight of 10g/L, and dried and then calcined in air at 550 ℃ to form a second coat, as shown in FIG. 3, where the sum of the first coat length and the second coat length was the total substrate length and the thicknesses were the same.
S3: adding water into an SSZ-39 molecular sieve containing 3.5% of Cu, stirring and dispersing for 30min, then adding 5% of alumina binder, and adding water to adjust the solid content to 28% to obtain third slurry. And (3) coating the third slurry on the surface of the first coating to the second coating from the air inlet end in a feeding and 40Hz negative pressure suction mode, wherein the coating length is 5 inches, the dry loading weight is 95g/L, and the third slurry is calcined in 550 ℃ air after being dried to form a third coating, namely the catalyst product, which is marked as catalyst No. 3.
After the hydrothermal aging test at 650 ℃ for 100 hours, the catalyst articles obtained in 3 examples and 7 comparative examples of the present invention were subjected to a steady-state performance test by drilling test samples having a diameter of 1 inch and a length of 5 inches, respectively. The experimental conditions are shown in Table 2. In the test process, the heating rate is set to be 6 ℃/min, the temperature is increased to 500 ℃, and the second data of the concentration of each gas-phase component at the inlet and the outlet are continuously recorded.
TABLE 2 atmosphere conditions for steady state performance testing
And subtracting the outlet NO concentration from the sum of 2 times of the inlet NO concentration, the outlet NO2 concentration and the outlet N2O concentration, wherein the ratio of the result to the inlet NO concentration is the NOx conversion rate. The following table shows the NOx conversion performance of the catalyst articles obtained in the examples and comparative examples. The cold start NOx adsorption efficiency is defined as the first 200 ℃ from the start to the inlet temperature.
TABLE 3 Steady State Performance test results
| 100℃ | 150℃ | 175℃ | 200℃ | 300℃ | |
| Example 1 | 66.20％ | 82.40％ | 92.70％ | 96.80％ | 98.90％ |
| Example 2 | 46.60％ | 70.70％ | 83.80％ | 92.50％ | 99.6 |
| Example 3 | 68.50％ | 83.20％ | 92.90％ | 97.20％ | 99.20％ |
| Comparative example 1 | 20.30％ | 70.10％ | 82.80％ | 90.20％ | 98.30％ |
| Comparative example 2 | 9.70％ | 44.30％ | 56.30％ | 70.30％ | 94.20％ |
| Comparative example 3 | 64.40％ | 80.60％ | 89.90％ | 94.40％ | 98.60％ |
| Comparative example 4 | 43.40％ | 68.70％ | 80.20％ | 92.40％ | 98.90％ |
| Comparative example 5 | 64.90％ | 81.50％ | 90.30％ | 95.50％ | 98.90％ |
| Comparative example 6 | 43.80％ | 68.60％ | 81.30％ | 92.10％ | 99.20％ |
| Comparative example 7 | 62.50％ | 81.30％ | 89.70％ | 94.80％ | 98.90％ |
As a result: comparative example 1 full length Cu-SSZ-39 catalyst comparative example 2 is a full length Fe-BEA catalyst and the advantages of comparative example 1 over comparative example 2 are mainly better low temperature zone efficiency but if under more stringent regulatory restrictions at cold start (below 200 ℃), some NO will still be present x And (4) the emission is easy to exceed the standard. Therefore, further improvement of the conversion efficiency in the low temperature region is required. The advantage of comparative example 2 is mainly that the efficiency in the high temperature region (not less than 300 ℃) is better than that of the copper-based catalyst, and the detailed explanation is not provided in the present invention.
The third coatings of example 1, example 3, comparative example 5 and comparative example 7 are all Cu-SSZ-39, and the main function of the third coatings is to convert NO released after adsorption of the first coating x And partially reduced NO from the second coating. The first and second coatings of examples 1 and 3 are full coating height, while the second and third coatings of comparative examples 3, 5, 7 are 30% -70% and 70% -30% respectively and different catalytic materials, since the second coatings of examples 1, 3 completely cover the first coating, ensuring NO desorbed from the first coating x Is fully adsorbed and catalytically reduced by the second coating layer, ensuring NO 2 And NO, thus the conversion efficiency of the embodiment 1 and the embodiment 3 is relatively improved. And the first coating and the second coating in the relation of flow-through in the comparison examples 3, 5 and 7, and the partially desorbed NO x NO adsorbed by the first coating without reduction by the second coating x During the release, the second coating is not completely reduced, but directly enters the third coating for NH 3 SCR catalyzed reactions, conversion efficiency is slightly lower.
In example 2, comparative example 4, and comparative example 6, the first coating and the second coating in the "flow-through" relationship of the partially desorbed NO were the same as in the above examples in comparative example 4 and comparative example 6 x NO adsorbed by the first coating without reduction by the second coating x During the release, the catalyst is not completely reduced by the second coating, but directly enters the third coating for NH 3 SCR catalytic reactions and therefore the conversion efficiency is slightly lower.
Both the sulfur poisoning test and the regeneration test of the samples were performed in a fixed bed quartz reactor. N at 600 deg.C 2 Pretreating for 30min under atmosphere, cooling the catalyst to 250 deg.C, and introducing 50ppm SO 2 、5％O 2 、10％H 2 O、N 2 As equilibrium gas, it was kept for 40min at a space velocity (GHSV) of 76000mL g cat -1 ·h -1 And finally obtaining the sulfated SCR catalyst. The catalyst regeneration desulfurization is carried out at 550 ℃ and 500ppmNH 3 、500ppmNO、10％O 2 、8％CO 2 、7％H 2 O and N 2 And (4) regenerating for 30min in the SCR atmosphere as the balance gas, wherein the space velocity is the same as the above. After the sulfur poisoning and regeneration tests were completed, steady state performance tests were performed using the simulated gas of table 2. The catalyst NO was calculated as above for the test procedure x The conversion efficiency. Table 4 shows the NO of the catalyst articles x Conversion performance. Cold Start NO x The adsorption efficiency is defined as the first 200 ℃ from the start to the inlet temperature.
Table 4 test results of catalyst articles provided by the present invention before and after sulfur poisoning
As shown in table 4, the first coating scheme (example 1, example 2, example 3) uses a layered design, and the first coating layer has a larger reactive interface with the second coating layer than the second coating scheme and the third coating scheme. And, since the second coating layer separates the first coating layer containing the noble metal having the oxidizing ability from the third coating layer, NO is generated from the first coating layer 2 Is effectively reduced to avoid NO 2 Escape directly with NH 3 Contact, reduce N 2 And (4) generating O. Thus, as can be seen from the steady state performance test results, the outlet maximum N of the catalyst involved in coating scheme one 2 The O concentration is much lower than coating scheme two (comparative example 3, comparative example 4, comparative example 5), coating scheme three (comparative example 6, comparative example 7).
Coating scheme two (comparative example 3, comparative example 4, comparative example 5) the first coating was placed on the inlet side and was in direct contact with the exhaust gas, and therefore had better low temperature adsorption. NO at test temperatures below 175 deg.C x The conversion efficiency is higher. The catalyst reduction layer interface limited by scheme 2 is smaller at temperatures above 200 deg.C, at which NO is present x The conversion efficiency was slightly lower.
Coating scheme three (comparative examples 6 and 7) the first coating was applied to the base coat to avoid SO 2 Is oxidized with NH 3 Or the active center in the catalyst forms stable sulfur species to cover the catalyst surface and reduce the catalytic reduction activity, so that the catalyst product has better sulfur resistance than the second coating scheme, and NO reaches the ignition temperature of the surface catalyst X The conversion efficiency is slightly higher.
While the foregoing is directed to the preferred embodiment of the present invention, other and further embodiments of the invention may be devised without departing from the basic scope thereof, and the scope thereof is determined by the claims that follow.
Claims (10)
1. A catalyst article for lean burn engine exhaust treatment employing a flow-through monolith substrate, characterized in that: the pore wall of the base material is provided with a layered catalyst covering the whole length of the base material, and the layered catalyst comprises a first coating, a second coating and a third coating which are arranged from inside to outside; the first coating layer comprises a passive nitrogen oxide adsorption catalyst composition and the second coating layer comprises NO 2 Reducing the catalyst composition, the third coating comprising NO x Reducing the catalyst composition; the first coating absorbs NO in the tail gas at the temperature of less than 150 DEG C x And release NO above 250 ℃ x (ii) a The second coating layer converts NO x In a certain proportion of NO 2 Conversion to NO 2 And NO concentration ratio of 0.8-1.2: 1; the third coating layer is free of NO x Conversion to N 2 。
2. The catalyst article for lean burn engine exhaust treatment according to claim 1, wherein: passive oxynitride adsorbing catalyst composition, NO 2 Reduction catalyst composition, NO x The ratio of the supported amount of the reduction catalyst composition is 30 to 50:10:95 to 120.
3. The catalyst article for lean burn engine exhaust gas treatment according to claim 1, wherein: the loading capacity of the passive oxynitride adsorption catalyst composition in the first coating is 30-50 g/L; NO in the second coating 2 The loading of the reduction catalyst composition is 10 +/-2 g/L; NO in the third coating x The loading of the reduction catalyst composition is 95-120 g/L.
4. The catalyst article for lean burn engine exhaust treatment according to claim 1, wherein: the substrate is made of one of cordierite, silicon carbide and metal materials.
5. The catalyst article for lean burn engine exhaust gas treatment according to claim 4, wherein: the metal material is one of Fe-Cr-Ni alloy, co-Cr-Ni alloy and Ni-Cr-Mo alloy.
6. The catalyst article for lean burn engine exhaust treatment according to claim 1, wherein: the passive oxynitride adsorption catalyst composition comprises a precious metal active component and a first adsorption refractory carrier, wherein the precious metal active component is at least one of Pd, ag and Co, and the first adsorption refractory carrier is a first molecular sieve or a metal oxide.
7. The catalyst article for lean burn engine exhaust treatment according to claim 6, wherein: the passive oxynitride adsorption catalyst composition further comprises base metal or rare earth metal, wherein the base metal is at least one of Mn, co, zr and Ni, and the rare earth metal is Ce or La.
8. The catalyst article for lean burn engine exhaust treatment according to claim 1, wherein: said NO 2 The reducing catalyst composition comprises NO 2 Reducing the active ingredient and a second adsorptive refractory carrier, said NO 2 The reduction active component is one or more of ferric oxide, cobalt oxide, copper oxide, barium oxide, calcium oxide, magnesium oxide, strontium oxide, tin oxide and germanium oxide, and the second adsorptive refractory carrier is silicon oxide or gamma-alumina.
9. The catalyst article for lean burn engine exhaust treatment according to claim 1, wherein: said NO x The reductive catalyst composition comprises NO x A reducing active component and a third adsorptive refractory carrier, said NO x The reducing active component is one or more of Cu, mn, V, fe, co, W, ni, zn, ti, cr, Y, zr, nb and Mo, and the third adsorptive refractory carrier comprises one or symbiotic mixture of analcime, chabazite, heulandite, stilbite, erionite, mordenite, scolecite and natrolite.
10. An exhaust gas treatment device for a lean burn engine, comprising the catalyst article for treating an exhaust gas of a lean burn engine according to any one of claims 1 to 9.
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