CN106944130A - A kind of SCR AOC combination catalysts of purification of diesel tail gas and preparation method thereof - Google Patents
A kind of SCR AOC combination catalysts of purification of diesel tail gas and preparation method thereof Download PDFInfo
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- CN106944130A CN106944130A CN201710136961.9A CN201710136961A CN106944130A CN 106944130 A CN106944130 A CN 106944130A CN 201710136961 A CN201710136961 A CN 201710136961A CN 106944130 A CN106944130 A CN 106944130A
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- aoc
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- molecular sieve
- purification
- tail gas
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000746 purification Methods 0.000 title claims abstract description 20
- 239000002808 molecular sieve Substances 0.000 claims abstract description 48
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 44
- 230000037452 priming Effects 0.000 claims abstract description 42
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 23
- 239000006255 coating slurry Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- -1 iron-chromium-aluminum Chemical compound 0.000 claims description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 229910052878 cordierite Inorganic materials 0.000 claims description 3
- 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 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004408 titanium dioxide Substances 0.000 claims description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229960004643 cupric oxide Drugs 0.000 claims description 2
- 239000000395 magnesium oxide Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 18
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 229910002089 NOx Inorganic materials 0.000 description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 4
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 229910001868 water Inorganic materials 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/80—Mixtures of different zeolites
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Crystallography & Structural Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to SCR AOC combination catalysts of a kind of purification of diesel tail gas and preparation method thereof, belong to catalyst preparation technical field.Including carrier, coating on AOC priming coats and SCR is coated with the carrier；The coated weight of the AOC priming coats is 50 150g/L, and the AOC priming coats include platinum-group noble metals, refractory oxide and the first molecular sieve；Wherein the coated weight of platinum-group noble metals is 0.01 1g/L, and the refractory oxide is 60% the 99% of AOC priming coat quality, and first molecular sieve is 1% the 40% of AOC priming coat quality；The coated weight of coating is 100 300g/L on the SCR, and the upper coatings of the SCR include the second molecular sieve of cupric, and wherein the mass fraction of copper is 0.1% 8%.Preparation method of the present invention is simple, and step is easily operated, and AOC priming coats and coating on the SCR that can be used in nitrous oxides selectivity catalysis reduction for ammoxidation function are respectively coated in catalyst carrier, and the using effect of catalyst is good.
Description
Technical field
The present invention relates to a kind of SCR-AOC combination catalysts of purification of diesel tail gas and preparation method thereof, belong to catalysis
Agent preparing technical field.
Background technology
Contain nitrogen oxides in the pollutant of diesel engine emissions（NOx）, particulate matter（PM）And it is imperfect combustion
Carbon monoxide（CO）And hydro carbons（HC）.NOx mainly includes nitric oxide（NO）And nitrogen dioxide（NO2）.It is well known that NOxIt is shape
A series of one of compound into photochemical fog and acid rain, so as to trigger health and environmental problem.Accordingly, it would be desirable to by NOxAlso
Originally it was N2And other poisonous and harmful substances are not generated, could eliminate NOx in motor-vehicle tail-gas to the unfavorable of the mankind and environment
Influence.
SCR technology（SCR）It is that reducing agent is used under excess oxygen（Such as H2、HC、NH3/ urea）Will
NOx selective reductions are N2And H2O, is the one preferred technique of NOx catalytic eliminatings in exhaust gas from diesel vehicle.NH3- SCR reactivities compared with
Height, and its active window is also of a relatively high.At present, NH3- SCR technology has been successfully applied in diesel car tail gas refining, and
It disclosure satisfy that the motor-vehicle tail-gas NO of Europe VIxDischarge standard.NOxWith NH3The key reaction occurred in SCR catalyst is：
4NH3 + 4NO + O2 → 4N2 + 6H2O
2NH3 + NO + NO2 → 2N2 + 3H2O
4NH3 + 3NO2 → 3.5N2 + 6H2O
4NH3 + 3O2 → 2N2 + 6H2O
In order to obtain the conversion rate of NOx of maximum, it is necessary to add the NH higher than stoichiometry into atmosphere3, but unreacted ammonia
Gas can cause secondary pollution, and this phenomenon is commonly referred to as " NH_3 leakage ".In addition, ammonia（Particularly its aqueous solution）With corrosion
Property, ammoniacal liquor can generate caustic mixture in gas extraction system condensed downstream, damage gas extraction system.Therefore, preferably in NH3Pass through row
Eliminated before tracheae, in order to by excessive NH3It is converted into N2, the purpose for reducing NH_3 leakage is reached, many business gas extraction system exist
SCR catalyst downstream is mounted with ammoxidation catalyst（AMOx）, also referred to as NH_3 leakage catalyst（AOC）.
Therefore, NOx can be eliminated by SCR by researching and developing a kind of catalyst article, while by excessive NH3Selective oxidation is
N2, selective ammonia oxidation catalyst need there is sufficiently high NH in wider temperature range3Conversion ratio, and produce at least
Nitrogen oxides is the research emphasis of this area.
The content of the invention
The invention aims to solve the above problems, there is provided a kind of SCR-AOC of purification of diesel tail gas combinations
Catalyst and preparation method thereof, the catalyst prepared can eliminate the NOx in diesel engine vent gas and reduce the escaping of ammonia.
The present invention is adopted the following technical scheme that：A kind of SCR-AOC combination catalysts of purification of diesel tail gas, including carry
Coating on AOC priming coats and SCR is coated with body, the carrier；
The coated weight of the AOC priming coats be 50-150g/L, the AOC priming coats include platinum-group noble metals, refractory oxide and
First molecular sieve；Wherein the coated weight of platinum-group noble metals is 0.01-1g/L, and the refractory oxide is AOC priming coat quality
60%-99%, first molecular sieve is the 1%-40% of AOC priming coat quality；
The coated weight of coating is that coating includes the second molecular sieve of cupric on 100-300g/L, the SCR on the SCR, wherein
The mass fraction of copper is 0.1%-8%.
The platinum-group noble metals are noble metal platinum and/or palladium, and the mass ratio of platinum palladium is 1:0-1.
The carrier is cordierite honeycomb ceramic or iron-chromium-aluminum metal honeycomb, the hole density of the carrier for 100-600 mesh/
Square inch.
The refractory oxide is aluminum oxide, magnesia, silica, titanium dioxide, cupric oxide, zirconium oxide, titanium dioxide
One or more of mixtures in cerium.
First molecular sieve of stating is Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13
One kind in molecular sieve.
Second molecular sieve is Cu/SAPO-34 molecular sieves or Cu/SSZ-13 molecular sieves.
The preparation method of the SCR-AOC combination catalysts of described purification of diesel tail gas, comprises the following steps：
（1）The preparation of AOC priming coat slurries：Refractory oxide and the first molecular sieve are added in deionized water, fire resisting oxidation
The mass ratio of the gross mass and deionized water of thing and molecular sieve is 1-2:3, stir, form slurries；It is milled to granularity D90
At 5-15 μm, slurries are made；
Noble metal mass fraction is added in slurries for 10%-20% noble metal nitrate solution, wherein the nitric acid of noble metal
Salting liquid is 1 with grind slurries quality ratio：10-1000, and stir, form AOC priming coat slurries；Then AOC priming coats are starched
Liquid is coated on carrier according to 50-150 g solidfied materials/L coated weight；
（2）The drying roasting of AOC priming coats：By step（1）Gained is coated with the carrier of AOC priming coats and done at 100-150 DEG C
It is dry 6-10 hours, it is calcined 1-3 hours at 500-600 DEG C, is cooled to room temperature stand-by；
（3）The preparation of the upper coating slurries of SCR：Second molecular sieve is added in deionized water, the matter of molecular sieve and deionized water
Amount is than being 1:1-3, stirs to form slurries；Granularity D90 is milled at 5-15 μm, coating slurry on SCR is made；
（4）The drying roasting of the upper coatings of SCR：By step（3）Prepare coating slurry on gained SCR solid for 100-300g by coated weight
Compound/L, which is coated to, to be loaded with the carrier of AOC priming coats, is dried 6-10 hours at 100-150 DEG C, at 500-600 DEG C
Roasting 1-3 hours, that is, obtain the SCR-AOC combination catalysts of purification diesel engine tail gas.
The Cu/SAPO-34 molecular sieves or Cu/SSZ-13 molecular sieves prepared according to patent CN103818927A
The preparation method of the SCR-AOC combination catalysts of purification of diesel tail gas, comprises the following steps：
（1）The preparation of AOC priming coat slurries：Refractory oxide and molecular sieve are added in deionized water, refractory oxide and
The gross mass of molecular sieve and the mass ratio of deionized water are 1:3-2:3, stir, form slurries；Granularity D90 is milled to exist
5-15 μm, coating slurry is made；
（2）Precious metal solution is added in coating slurry and stirred, AOC priming coat slurries is formed, AOC priming coats is starched
Liquid is quantitatively coated on carrier；
（3）The drying roasting of AOC priming coats：It is coated with the carrier of AOC priming coats to dry 8 hours at 120 DEG C, at 550 DEG C
Roasting 2 hours, is cooled to room temperature stand-by；
（4）The preparation of the upper coating slurries of SCR：Cu/SAPO-34 molecular sieves or Cu/SSZ-13 molecular sieves are added to deionized water
In, the mass ratio of molecular sieve and deionized water is 1:3-1:1, stir to form slurries；Granularity D90 is milled in 5-15 μ
M, is made coating slurry on SCR；
（5）The drying roasting of the upper coatings of SCR：Coating slurry on SCR is coated to by coated weight for 100-300g/L and has been loaded with
On the carrier of AOC priming coats, dried 8 hours at 120 DEG C, be calcined 2 hours at 550 DEG C, that is, obtain purification diesel engine tail gas
SCR-AOC combination catalysts.
Beneficial effects of the present invention：Preparation method of the present invention is simple, and step is easily operated, is respectively coated in catalyst carrier
There are the AOC priming coats and coating, catalyst on the SCR that can be used in nitrous oxides selectivity catalysis reduction for ammoxidation function
Using effect it is good.
Brief description of the drawings
Fig. 1 is the embodiment of the present invention 1 and 2 in NH3NH under oxidation reaction condition3Conversion ratio.
Fig. 2 is the embodiment of the present invention 1 and 2 in NH3N under oxidation reaction condition2Selectivity.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
A kind of SCR-AOC combination catalysts of purification of diesel tail gas, catalyst carrier is carrier cordierite ceramic, and volume is
1.236L, hole density is 400 mesh/square inch；Coating is included in coating on AOC priming coats and SCR, AOC priming coats on carrier
Containing cerium-zirconium-aluminium composite oxide, beta-molecular sieve and precious metals pt, the coated weight of AOC priming coats is 100g/L, precious metals pt
Load capacity is 0.15g/L.The upper coating compositions of SCR are Cu/SAPO-34 molecular sieves, and Cu mass fractions are 3.0%, Cu/SAPO-34 points
Son sieve is made according to patent CN103818927A, and the coated weight of the upper coatings of SCR is 120g/L.
Preparation method comprises the following steps：
（1）The preparation of AOC catalyst floors：98.7g ceriums-zirconium-aluminium composite oxide, 24.7g beta-molecular sieves are added to
In 197.5g deionized waters, stir, form slurries makes granularity D90 be 10 μm through ball milling；
The preparation method of cerium-zirconium-aluminium composite oxide：It is 1 first by the mass ratio of cerium oxide and aluminum oxide:9 prepare cerium-
In aluminium composite oxide, then cerium-zirconium-aluminum composite oxide is prepared by the method for incipient impregnation by by cerium-aluminium composite oxide
Thing；Zirconyl nitrate solution, dipping, at then standing 12 hours, 120 DEG C are configured by the saturated extent of adsorption of cerium-aluminium composite oxide
Drying is calcined 2 hours for 8 hours, 550 DEG C.The matter of zirconium oxide and cerium-aluminium composite oxide wherein in cerium-zirconium-aluminium composite oxide
Amount is than being 1:7；
1.26g platinum nitrate solutions are added in above-mentioned slurries（14.71 wt% Pt）, slurries are all coated to after stirring
On carrier, obtain being coated with the carrier of AOC priming coats；
（2）The drying roasting of AOC priming coats：By step（1）It is small that gained is coated with the drying 8 at 120 DEG C of the carrier of AOC priming coats
When, 550 DEG C are calcined 2 hours；
（3）The preparation of the upper coating slurries of SCR：148.3g Cu/SAPO-34 molecular sieves are added in 296.6g deionized waters, stirred
Mix uniform, form slurries；Make the granularity D90 of slurries be 10 μm through ball milling, coating slurry on SCR is made；
（4）The drying roasting of the upper coatings of SCR：Coating slurry is all coated on obtained AOC priming coats, done at 120 DEG C
Dry 8 hours, it is calcined 2 hours at 550 DEG C, that is, obtains the SCR-AOC combination catalysts of purification diesel engine tail gas.
Embodiment 2
Specific preparation method and active testing and example 1 are essentially identical, and difference is the Cu/SSZ-13 with copper content 3.0%
Molecular sieve replaces Cu/SAPO-34 molecular sieves.
The innovative point of the present invention is being applied in combination for SCR catalyst and AOC catalyst, here primarily to being presented two
Plant main flow NH3- SCR catalyst（Cu/SAPO-34 and Cu/SSZ-13）With the effect after AOC catalyst combination uses.
NH3 oxidation activities are evaluated
The NH3 oxidation activities of catalyst in embodiment are evaluated in 150-500 DEG C of Temperature Programmed Processes, evaluates and is included in atmosphere
300 ppm NH3、10% O2、5% H2O、5% CO2, use N2It is used as Balance Air.Volume space velocity is 100000h-1.Use Fourier
Leaf transformation infrared spectrum（FTIR）Analyzer detection outlet production concentration, thus calculates conversion ratio and the product selection of reactant
Property.
Fig. 1 describes the embodiment of the present invention 1 and 2 in NH3NH under oxidation reaction condition3Conversion ratio.In 200-230 DEG C of temperature
In the range of degree, the NH of 2 embodiments3Conversion ratio is almost identical；In 260-500 DEG C of temperature range, the NH of 2 embodiments3Conversion
Rate is both greater than 90%.
Fig. 2 describes the embodiment of the present invention 1 and 2 in NH3N under oxidation reaction condition2Selectivity.In 200-255 DEG C of temperature
In the range of, the N of 2 embodiments2Select similar temperament；In 255-500 DEG C of temperature range, Cu/SSZ-13 embodiment 2 is used
N2Selectivity is higher than the embodiment 1 using Cu/SAPO-34, in addition, the N in 310-490 DEG C of temperature range of embodiment 22Selectivity
More than 80%.
Claims (7)
1. a kind of SCR-AOC combination catalysts of purification of diesel tail gas, it is characterised in that：Including carrier, applied on the carrier
It is covered with coating on AOC priming coats and SCR；
The coated weight of the AOC priming coats be 50-150g/L, the AOC priming coats include platinum-group noble metals, refractory oxide and
First molecular sieve；Wherein the coated weight of platinum-group noble metals is 0.01-1g/L, and the refractory oxide is AOC priming coat quality
60%-99%, first molecular sieve is the 1%-40% of AOC priming coat quality；
The coated weight of coating is that coating includes the second molecular sieve of cupric on 100-300g/L, the SCR on the SCR, wherein
The mass fraction of copper is 0.1%-8%.
2. the SCR-AOC combination catalysts of purification of diesel tail gas as claimed in claim 1, it is characterised in that：The platinum family
Noble metal is noble metal platinum and/or palladium, and the mass ratio of platinum palladium is 1:0-1.
3. the SCR-AOC combination catalysts of purification of diesel tail gas as claimed in claim 1, it is characterised in that：The carrier
For cordierite honeycomb ceramic or iron-chromium-aluminum metal honeycomb, the hole density of the carrier is 100-600 mesh/square inch.
4. the SCR-AOC combination catalysts of purification of diesel tail gas as claimed in claim 1, it is characterised in that：The fire resisting
Oxide is the one or more in aluminum oxide, magnesia, silica, titanium dioxide, cupric oxide, zirconium oxide, ceria
Mixture.
5. the SCR-AOC combination catalysts of purification of diesel tail gas as claimed in claim 1, it is characterised in that：It is described to state
One molecular sieve is one kind in Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13 molecular sieves.
6. the SCR-AOC combination catalysts of purification of diesel tail gas as claimed in claim 1, it is characterised in that：Described second
Molecular sieve is Cu/SAPO-34 molecular sieves or Cu/SSZ-13 molecular sieves.
7. the preparation method of the SCR-AOC combination catalysts of the purification of diesel tail gas described in claim 1, it is characterised in that：
Comprise the following steps：
（1）The preparation of AOC priming coat slurries：Refractory oxide and the first molecular sieve are added in deionized water, fire resisting oxidation
The mass ratio of the gross mass and deionized water of thing and molecular sieve is 1-2:3, stir, form slurries；It is milled to granularity D90
At 5-15 μm, slurries are made；
Noble metal mass fraction is added in slurries for 10%-20% noble metal nitrate solution, wherein the nitric acid of noble metal
Salting liquid is 1 with grind slurries quality ratio：10-1000, and stir, form AOC priming coat slurries；Then AOC priming coats are starched
Liquid is coated on carrier according to 50-150 g solidfied materials/L coated weight；
（2）The drying roasting of AOC priming coats：By step（1）Gained is coated with the carrier of AOC priming coats and done at 100-150 DEG C
It is dry 6-10 hours, it is calcined 1-3 hours at 500-600 DEG C, is cooled to room temperature stand-by；
（3）The preparation of the upper coating slurries of SCR：Second molecular sieve is added in deionized water, the matter of molecular sieve and deionized water
Amount is than being 1:1-3, stirs to form slurries；Granularity D90 is milled at 5-15 μm, coating slurry on SCR is made；
（4）The drying roasting of the upper coatings of SCR：By step（3）Prepare coating slurry on gained SCR solid for 100-300g by coated weight
Compound/L, which is coated to, to be loaded with the carrier of AOC priming coats, is dried 6-10 hours at 100-150 DEG C, at 500-600 DEG C
Roasting 1-3 hours, that is, obtain the SCR-AOC combination catalysts of purification diesel engine tail gas.
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