CN106902864A - A kind of ammoxidation catalyst for diesel engine vent gas cleaning system and preparation method thereof - Google Patents
A kind of ammoxidation catalyst for diesel engine vent gas cleaning system and preparation method thereof Download PDFInfo
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- CN106902864A CN106902864A CN201710136964.2A CN201710136964A CN106902864A CN 106902864 A CN106902864 A CN 106902864A CN 201710136964 A CN201710136964 A CN 201710136964A CN 106902864 A CN106902864 A CN 106902864A
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- molecular sieve
- coating
- ammoxidation catalyst
- composite oxides
- slurries
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- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000004140 cleaning Methods 0.000 title claims description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 41
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 238000000576 coating method Methods 0.000 claims abstract description 37
- 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 34
- 239000011248 coating agent Substances 0.000 claims abstract description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000002002 slurry Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 8
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 8
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 239000010949 copper Substances 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 6
- 238000005342 ion exchange Methods 0.000 claims description 6
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 6
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical group [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 5
- 229910001431 copper ion Inorganic materials 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000000395 magnesium oxide Substances 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 229910001868 water Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 239000006255 coating slurry Substances 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- 238000002386 leaching Methods 0.000 claims description 2
- 239000010970 precious metal Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims 2
- 229960004643 cupric oxide Drugs 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 14
- 229910021529 ammonia Inorganic materials 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 5
- 239000007789 gas Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- -1 and volume is 1.236L Substances 0.000 description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 10
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229910002089 NOx Inorganic materials 0.000 description 7
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 4
- 239000004411 aluminium Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 3
- KMWBBMXGHHLDKL-UHFFFAOYSA-N [AlH3].[Si] Chemical compound [AlH3].[Si] KMWBBMXGHHLDKL-UHFFFAOYSA-N 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical group [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 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
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 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
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000000446 fuel 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
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 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
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 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
- 239000000376 reactant Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000003870 refractory metal Substances 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
- 229910000349 titanium oxysulfate Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000003643 water by type Substances 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
- B01J29/04—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
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
-
- 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
-
- 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
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Combustion & Propulsion (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)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of ammoxidation catalyst and preparation method thereof, belong to catalyst preparation technical field.It includes the coating coated on carrier, and the carrier；It is loaded with noble metal platinum in the coating, platinum load capacity is 0.01 1g/L, the coating includes composite oxides and molecular sieve, the composite oxides are 60% the 99% of coating quality；Molecular sieve is 1% the 40% of coating quality, and the coated weight of the coating is 80 150g/L.Preparation method of the present invention is simple, and step is easily operated, and the downstream that the catalyst for preparing is used for SCR methods uses, and can effectively reduce the escaping of ammonia.
Description
Technical field
The present invention relates to a kind of ammoxidation catalyst and preparation method thereof, belong to catalyst preparation technical field.
Background technology
Because Diesel engine has fuel economy higher and CO2The low advantage of discharge capacity, makes diesel vehicle most of
Developed country, particularly increasingly popularizes in Europe.Contain nitrogen oxides in the pollutant of emission of diesel engine（NOx）, particulate matter
（PM）And imperfect combustion carbon monoxide（CO）And hydro carbons（HC）.NOxMainly include nitric oxide（NO）And nitrogen dioxide
（NO2）.It is well known that NOxIt is one of the compound to form photochemical fog and acid rain, so as to trigger a series of health and environment
Problem.Accordingly, it would be desirable to by NOxIt is reduced to N2And other poisonous and harmful substances are not generated, in could eliminating motor-vehicle tail-gas
NOxTo the mankind and the adverse effect of environment.
SCR technology（SCR）It is that reducing agent is used under excess oxygen（Such as H2、HC、NH3/ urea）Will
NOxSelective reduction is N2And H2O, is NO in exhaust gas from diesel vehiclexThe one preferred technique of catalytic eliminating.NH3- SCR reactivities are higher,
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 energy
Enough meet the motor-vehicle tail-gas NO of Europe VIxDischarge standard.NOxWith NH3The key reaction of generation is in SCR catalyst：
4NH3 + 4NO + O2 → 4N2 + 6H2O
2NH3 + NO + NO2 → 2N2 + 3H2O
4NH3 + 3NO2 → 3.5N2 + 6H2O
4NH3 + 3O2 → 2N2 + 6H2O
In order to obtain the NO of maximumxConversion ratio, it is necessary to the NH added in atmosphere higher than stoichiometry3But, 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, damage gas extraction system in gas extraction system condensed downstream.Therefore, preferably in NH3By 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（ASC）.Preferable selectivity ammonia
Oxidation catalyst needs have sufficiently high NH in temperature range wider3Conversion ratio, and produce minimum nitrogen oxides.
As CN104812486A and CN105358250A discloses a kind of ammoxidation catalyst and preparation method thereof, the catalysis
Agent is divided into two-layer, and ground floor is noble metal catalyst layer, preferably by refractory metal oxide carried noble metal（Such as Pt, Pd and its
Combination）；The second layer is vanadium catalyst layer, with aluminum oxide, titanium dioxide, zirconium oxide, ceria, silica or theirs is mixed
Compound loads vanadium.But, these catalyst are inefficient when ammonia is converted, and NO under high temperaturexSelectivity is too high.
As CN103476495A discloses a kind of ammoxidation catalyst of excellent heat resistance, the catalyst lower floor is included in two
Loaded on the composite oxides of the composite oxides, aluminum oxide or aluminum oxide and silica of titanium oxide and silica expensive
Metallic element, upper strata includes the composite oxides formed by silica, tungsten oxide, ceria and zirconium dioxide.This is urged
Agent equally exists NO under high temperaturexSelectivity problem higher.
Therefore, the ammonia purifying property of ammoxidation catalyst still needs improvement, to realize ammoxidation efficiency high and N high2Choosing
The target of selecting property.
The content of the invention
The invention aims to solve the above problems, there is provided the ammoxidation for diesel engine vent gas cleaning system is urged
Agent and preparation method thereof.
The present invention is adopted the following technical scheme that：A kind of ammoxidation catalyst for diesel engine vent gas cleaning system, including
The coating coated on carrier, and the carrier；
Noble metal platinum is loaded with the coating, platinum load capacity is 0.01-1g/L, and the coating includes composite oxides and molecule
Sieve, the composite oxides are the 60%-99% of coating quality；Molecular sieve is the 1%-40% of coating quality, the coating of the coating
It is 80-150g/L to measure.
The composite oxides include aluminum oxide and ceria, and magnesia, silica, titanium dioxide, oxidation
One kind in copper, zirconium oxide；The mass fraction of aluminum oxide is 50%-90%, the quality point of ceria in the composite oxides
Number is 5%-20%.
The molecular sieve is Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13 molecules
Sieve.
The molecular sieve is Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13 molecular sieves
Processed by Copper Ion Exchange and be made.
The Copper Ion Exchange step is with 1 by the molecular sieve of not cupric and deionized water:1.5-4 adds there-necked flask
In, after putting into copper acetate for the 0.1%-8% of molecular sieve quality according to copper content, with vinegar acid for adjusting pH to 3-5,80 DEG C of waters bath with thermostatic control
Stirring exchanges 4-8h, deionized water suction filtration, being become colorless to the aqueous solution for leaching；Then 3-5h is calcined in 500-600 DEG C,
Obtain the molecular sieve after Copper Ion Exchange.
The described ammoxidation catalyst for diesel engine vent gas cleaning system, comprises the following steps：
（1）The preparation of composite oxides：Prepared using equi-volume impregnating and include magnesia, silica, titanium dioxide, oxidation
The composite oxides of one kind and aluminum oxide and ceria in copper, zirconium oxide；
（2）The preparation of slurries：It is the amount of 80-150g/L coatings according to needed for carrier size is calculated by the coated weight of coating, obtains
Required composite oxides and the amount of molecular sieve, will meet composite oxides and molecular sieve are added sequentially in deionized water, be combined
The gross mass of oxide and molecular sieve is 1-2 with the mass ratio of deionized water:3, stir, form slurries；
（3）Ball milling：To step（2）Gained slurries are processed with ball-milling technology, and granularity D90 is between 5-20 μm for control, is obtained and applies
Layer slurries；
（4）Coating：Load capacity according to noble metal is 0.01-1g/L, and the amount of noble metal, precious metal solution is added needed for calculating
To step（3）In gained coating slurry and stir, form noble coatings slurries, noble coatings slurries are quantitatively coated
Onto carrier；
（5）Ammoxidation catalyst：It is coated with being dried at the carrier of noble metal slurries is placed in 100-150 DEG C 6-10 hours, then
It is calcined 1-3 hours in 500-600 DEG C, that is, obtains the ammoxidation catalyst of purifying tail gas of diesel vehicles.
Beneficial effects of the present invention：Preparation method of the present invention is simple, and step is easily operated, and the catalyst for preparing is used for
The downstream of SCR methods uses, with ammoxidation efficiency high, and N at high temperature2Selectivity is high, can effectively reduce ammonia and escape
Ease.
Brief description of the drawings
Fig. 1 is inventive embodiments 1-4 in NH3NH under oxidation reaction condition3Conversion ratio.
Fig. 2 is embodiment of the present invention 1-4 in NH3N under oxidation reaction condition2Selectivity.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment 1
Catalyst is made up of carrier and coating, and noble metal platinum is loaded with coating, and coating coated weight is 120g/L, noble metal platinum
Load capacity is 0.15g/L, and catalyst carrier is carrier cordierite ceramic, and volume is 1.236L, and hole density is 400 mesh/square English
It is very little；Contain cerium-zirconium-aluminium composite oxide and beta-molecular sieve in coating.
For the ammoxidation catalyst of diesel engine vent gas cleaning system, comprise the following steps：
（1）The preparation of composite oxides cerium-zirconium-aluminium：It is 1 that cerium oxide is pressed first with the mass ratio of 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 is configured by the saturated extent of adsorption of cerium-aluminium composite oxide, then dipping stands 12h, dries at 120 DEG C
8h, 550 DEG C of roasting 2h.Zirconium oxide and the mass ratio of cerium-aluminium composite oxide are 1 wherein in cerium-zirconium-aluminium composite oxide:7；
（2）The preparation of slurries：By cerium-zirconium-aluminium composite oxide：Beta-molecular sieve：Deionized water quality ratio is 4:1:8 take material, stir
Mix and be formed uniformly slurries；
（3）Ball milling：Processed with ball-milling technology and obtain granularity D90 for 10 μm；
（4）Coating：Load capacity according to noble metal platinum is 0.15g/L in step（1）In slurries in add platinum nitrate solution；
（5）Ammoxidation catalyst：By step（4）Obtained noble coatings slurries are quantitatively coated on carrier by 120g/L,
Dried at 120 DEG C 8 hours, 550 DEG C are calcined 2 hours.
Embodiment 2
Specific preparation method and active testing are essentially identical with example 1, and difference is to replace zirconyl nitrate with titanyl sulfate
Obtained titanium-cerium-aluminium composite oxide.In titanium-cerium-aluminium composite oxide, the mass ratio of titanium oxide and cerium-aluminium composite oxide
It is 1:7.
Embodiment 3
Specific preparation method and active testing are essentially identical with example 1, and difference is composite oxides for cerium-silicon-aluminium is multiple
Close oxide.Cerium-silicon-the aluminium composite oxide impregnates silicon-aluminium composite oxide and prepares by cerous nitrate solution.Silicon-aluminium is multiple
Close in oxide, silica is 1 with the mass ratio of aluminum oxide:19.In cerium-silicon-aluminium composite oxide, cerium oxide is multiple with silicon-aluminium
The mass ratio for closing oxide is 1:9.
Embodiment 4
Specific preparation method and active testing are essentially identical with example 1, and difference is to replace beta-molecular sieve with Y type molecular sieve.
NH3Oxidation activity is evaluated
The NH of catalyst in evaluating embodiment in 150-500 DEG C of Temperature Programmed Processes3Oxidation activity, includes in evaluation atmosphere
300ppm NH3、10% O2、5% H2O、5% CO2, use N2As Balance Air.Volume space velocity is 100000 h-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 embodiment of the present invention 1-4 in NH3NH under oxidation reaction condition3Conversion ratio.At 200 DEG C, embodiment 2
There is 6% NH3Conversion ratio, the NH of other embodiment3Conversion ratio is 0；At 225 DEG C, 4 NH of embodiment3Conversion ratio is in 21-73%
Between, the wherein NH of embodiment 2 and 33Conversion ratio is higher, and about 70%；At 250 DEG C, the NH of embodiment 1-43Conversion ratio is in 96-
Between 99%；In 275-500 DEG C of temperature range, 4 NH of embodiment3Conversion ratio all reaches 100%.
Fig. 2 describes embodiment of the present invention 1-4 in NH3N under oxidation reaction condition2Selectivity.In 200-275 DEG C of temperature
In the range of, use the N of the embodiment 2 of titanium-cerium-aluminium composite oxide2Selectivity ratios other embodiment 1-7% high；In 300-500
In DEG C temperature range, cerium-zirconium is used -- the N of the embodiment 1 of aluminium composite oxide2Selectivity is more than 80%, in 325-475 DEG C of temperature
N in the range of degree2Selectivity is more than 90%, hence it is evident that higher than other embodiment.
Claims (6)
1. a kind of ammoxidation catalyst for diesel engine vent gas cleaning system, it is characterised in that：Including carrier, and the carrier
The coating of upper coating；
Noble metal platinum is loaded with the coating, platinum load capacity is 0.01-1g/L, and the coating includes composite oxides and molecule
Sieve, the composite oxides are the 60%-99% of coating quality；Molecular sieve is the 1%-40% of coating quality, the coating of the coating
It is 80-150g/L to measure.
2. the ammoxidation catalyst of diesel engine vent gas cleaning system is used for as claimed in claim 1, it is characterised in that：It is described multiple
Close oxide and include in aluminum oxide and ceria, and magnesia, silica, titanium dioxide, cupric oxide, zirconium oxide
Kind；The mass fraction of aluminum oxide is 50%-90% in the composite oxides, and the mass fraction of ceria is 5%-20%.
3. the ammoxidation catalyst of diesel engine vent gas cleaning system is used for as claimed in claim 1, it is characterised in that：Described point
Son sieve is Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13 molecular sieves.
4. the ammoxidation catalyst of diesel engine vent gas cleaning system is used for as claimed in claim 1, it is characterised in that：Described point
Son sieve is Y type molecular sieve, ZSM-5 molecular sieve, beta-molecular sieve, SAPO-34 molecular sieves or SSZ-13 molecular sieves by Copper Ion Exchange
Treatment is made.
5. the ammoxidation catalyst of diesel engine vent gas cleaning system is used for as claimed in claim 4, it is characterised in that：The copper
Ion-exchange step is with 1 by the molecular sieve of not cupric and deionized water:1.5-4 is added in there-necked flask, is according to copper content
After the 0.1%-8% input copper acetates of molecular sieve quality, with vinegar acid for adjusting pH to 3-5,80 DEG C of water bath with thermostatic control stirrings exchange 4-8h, go
Ionized water suction filtration, being become colorless to the aqueous solution for leaching；Then 3-5h is calcined in 500-600 DEG C, obtains Copper Ion Exchange
Molecular sieve afterwards.
6. the ammoxidation catalyst for diesel engine vent gas cleaning system described in claim 1, it is characterised in that including as follows
Step：
（1）The preparation of composite oxides：Prepared using equi-volume impregnating and include magnesia, silica, titanium dioxide, oxidation
The composite oxides of one kind and aluminum oxide and ceria in copper, zirconium oxide；
（2）The preparation of slurries：It is the amount of 80-150g/L coatings according to needed for carrier size is calculated by the coated weight of coating, obtains
Required composite oxides and the amount of molecular sieve, will meet composite oxides and molecular sieve are added sequentially in deionized water, be combined
The gross mass of oxide and molecular sieve is 1-2 with the mass ratio of deionized water:3, stir, form slurries；
（3）Ball milling：To step（2）Gained slurries are processed with ball-milling technology, and granularity D90 is between 5-20 μm for control, is obtained and applies
Layer slurries；
（4）Coating：Load capacity according to noble metal is 0.01-1g/L, and the amount of noble metal, precious metal solution is added needed for calculating
To step（3）In gained coating slurry and stir, form noble coatings slurries, noble coatings slurries are quantitatively coated
Onto carrier；
（5）Ammoxidation catalyst：It is coated with being dried at the carrier of noble metal slurries is placed in 100-150 DEG C 6-10 hours, then
It is calcined 1-3 hours in 500-600 DEG C, that is, obtains the ammoxidation catalyst of purifying tail gas of diesel vehicles.
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| CN108246360A (en) * | 2018-02-27 | 2018-07-06 | 南开大学 | A kind of Zn-Al-P-Si-oxide molecular sieve composite catalyst for ammoxidation |
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| CN113842921A (en) * | 2021-10-27 | 2021-12-28 | 合肥神舟催化净化器股份有限公司 | Ammonia oxidation catalyst for diesel engine based on ternary metal oxide, preparation method and application |
| CN113842921B (en) * | 2021-10-27 | 2023-11-24 | 合肥神舟催化净化器股份有限公司 | Ammonia oxidation catalyst for diesel engine based on ternary metal oxide, preparation method and application |
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