CN117299194A - Synchronous NH removal 3 And N 2 Double-effect catalyst of O and preparation method and application thereof - Google Patents
Synchronous NH removal 3 And N 2 Double-effect catalyst of O and preparation method and application thereof Download PDFInfo
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- CN117299194A CN117299194A CN202311131950.3A CN202311131950A CN117299194A CN 117299194 A CN117299194 A CN 117299194A CN 202311131950 A CN202311131950 A CN 202311131950A CN 117299194 A CN117299194 A CN 117299194A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 230000001360 synchronised effect Effects 0.000 title claims description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 103
- 238000000576 coating method Methods 0.000 claims abstract description 103
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims abstract description 16
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 15
- 239000011230 binding agent Substances 0.000 claims abstract description 14
- 229910052788 barium Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000002002 slurry Substances 0.000 claims description 59
- 238000001354 calcination Methods 0.000 claims description 34
- 238000011068 loading method Methods 0.000 claims description 32
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 24
- 239000000843 powder Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 22
- 229910044991 metal oxide Inorganic materials 0.000 claims description 19
- 150000004706 metal oxides Chemical class 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical group O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 17
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 claims description 15
- 150000003839 salts Chemical class 0.000 claims description 14
- 239000006255 coating slurry Substances 0.000 claims description 13
- 230000001105 regulatory effect Effects 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 229910052697 platinum Inorganic materials 0.000 claims description 12
- 229910020599 Co 3 O 4 Inorganic materials 0.000 claims description 8
- 229910052878 cordierite Inorganic materials 0.000 claims description 8
- 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 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 8
- 229910017052 cobalt Inorganic materials 0.000 claims description 7
- 239000010941 cobalt Substances 0.000 claims description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 7
- 230000001276 controlling effect Effects 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000004408 titanium dioxide Substances 0.000 claims description 7
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 claims description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 6
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 6
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical group [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical class [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 229910052719 titanium Chemical class 0.000 claims description 5
- 239000010936 titanium Chemical class 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims 1
- 239000011247 coating layer Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 14
- 239000002131 composite material Substances 0.000 abstract description 5
- 231100000572 poisoning Toxicity 0.000 abstract description 4
- 230000000607 poisoning effect Effects 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- -1 barium modified cobalt oxide Chemical class 0.000 abstract description 2
- 239000012018 catalyst precursor Substances 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 description 19
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 239000007789 gas Substances 0.000 description 7
- 235000010215 titanium dioxide Nutrition 0.000 description 7
- 230000008569 process Effects 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 102220043159 rs587780996 Human genes 0.000 description 5
- 239000003513 alkali Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002089 NOx Inorganic materials 0.000 description 2
- 229910001422 barium ion Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000003546 flue gas Substances 0.000 description 2
- 238000000691 measurement method Methods 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical class [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003517 fume Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- WWHFPJVBJUJTEA-UHFFFAOYSA-N n'-[3-chloro-4,5-bis(prop-2-ynoxy)phenyl]-n-methoxymethanimidamide Chemical compound CONC=NC1=CC(Cl)=C(OCC#C)C(OCC#C)=C1 WWHFPJVBJUJTEA-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000002195 synergetic effect 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
- B01J29/04—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
-
- 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
- B01D53/9427—Processes characterised by a specific catalyst for removing nitrous oxide
-
- 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
- B01D53/9436—Ammonia
Abstract
The invention provides a method for synchronously removing NH 3 And N 2 The double-effect catalyst of O comprises a carrier and a coating layer coated on the surface of the carrier, wherein the coating layer comprises an inner coating layer and an outer coating layer; the inner coating is tightly attached to the surface of the carrier, and the outer coating coats the surface of the inner coating; the inner coating comprises the following components: pt, co 3 O 4 、BaO、Al 2 O 3 And TiO 2 The outer coating comprises Cu-SSZ-13 and a binder; the invention adopts barium modified cobalt oxide to obtain high-activity N 2 O removes material while using Al 2 O 3 And TiO 2 Composite coating layer integrating TiO 2 Is resistant to poisoning and Al 2 O 3 And reduces the N of the traditional ASC catalyst 2 O production amount, two catalysts are combined and coated on the same carrier, thus obtaining the catalyst capable of synchronously removing NH 3 And N 2 A double-effect catalyst of O; the invention also provides a method for synchronously removing NH 3 And N 2 The preparation method of the double-effect catalyst of O obtains the double-effect catalyst with high activity by researching the selection of the catalyst precursor, the component proportion and the post-treatment mode.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a method for synchronously removing NH 3 And N 2 A double-effect catalyst of O and its preparing process and application are disclosed.
Background
According to emission standards of light automobile pollutant emission limit and measurement method (Chinese sixth stage) and heavy diesel automobile pollutant emission limit and measurement method (Chinese sixth stage), the current national six-emission technical route commonly adopted in China is mainly in the form of 'EGR+DOC+DPF+SCR+ASC', or in the form of DDPF (DOC and DPF integrated), SDPF (SCR and DPF integrated), and CDPF (DPF loaded with a small amount of noble metal to promote active regeneration). Wherein, an EGR (exhaust gas recirculation) system, that is, a technology of separating a part of exhaust gas after combustion of an internal combustion engine and leading the separated exhaust gas into an air inlet side for re-combustion, can achieve the effects of inhibiting the generation of nitrogen oxides and improving the fuel economy; DOC (DieselOxidation Catalyst) diesel oxidation catalyst, typically the first stage in a three-stage exhaust pipe, typically uses noble metals or ceramics as catalyst supports; its main function is to oxidize carbon monoxide and hydrocarbons in the exhaust gas,the nitrogen oxide is converted into carbon dioxide and water, and can absorb soluble organic components and part of carbon particles, reduce the emission of part of PM (particulate matters) and oxidize nitrogen monoxide into nitrogen dioxide; DPF (DieselParticulateFilter) the diesel particulate trap, which is also the second stage in the three-stage exhaust pipe, has the main function of trapping PM particles, the PM reduction capacity is about 90%, and after the DPF device captures enough particulate matters, the trapped particulate matters are digested in order to avoid clogging, and this process is called DPF regeneration; SCR (SelectiveCatalyticReduction) selective catalytic reduction technology, which is also the last stage in the exhaust pipe, uses urea as a reducing agent, and converts nitrogen oxides into nitrogen and water by using a catalyst to chemically react with the nitrogen oxides; ASC (Ammoniaslipcatalyst) ammonia escape catalyst, namely in order to prevent ammonia from escaping, because the vehicle may have urea leakage, low reaction efficiency and other conditions, ammonia generated by urea decomposition may not participate in the reaction and directly exhaust the atmosphere, and ASC reduces the ammonia leaked from the exhaust gas at the rear end of SCR through catalytic oxidation. The main function of ASC is to make excess NH 3 Oxidation to N 2 、N 2 O, NOx simultaneous recatalysis of NOx and NH 3 The reaction is N 2 。
However, the emission standard of the engine is increasingly strict, the European seven standard is out of the table, and NH is increased 3 And N 2 The emission limit requirements of O, the upcoming national seven standards will also have corresponding emission limits, which presents a great challenge to existing aftertreatment technologies. The prior engine aftertreatment technology is specially aimed at NH 3 ASC catalyst (ammonia slip catalyst) but not for N 2 O, if a processing device is additionally arranged, the space requirement is larger; if NH can be realized on original ASC 3 And N 2 O is synchronously removed, so that the existing post-treatment process can be utilized to the greatest extent, a post-treatment system of national seventh standard in the future is simplified, and the cost is reduced.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, an object of the present invention is to provide a synchronous NH removal 3 And N 2 Double-effect catalyst of O and preparation method and application thereofApplication to obtain a new treatment technique capable of simultaneously removing NH 3 And N 2 O。
To achieve the above and other related objects, the present invention provides a method for simultaneously removing NH 3 And N 2 The double-effect catalyst of O comprises a carrier and a coating layer coated on the surface of the carrier, wherein the coating layer comprises an inner coating layer and an outer coating layer; the inner coating is tightly attached to the surface of the carrier, and the outer coating coats the surface of the inner coating; the inner coating comprises the following components in percentage by mass in terms of dry weight: pt0.05-0.08%; co (Co) 3 O 4 16-19％；BaO 1-4％；Al 2 O 3 15 to 16 percent of TiO 2 : 63-64%; the outer coating comprises the following components in percentage by mass in terms of dry weight: cu-SSZ-13: 96-99%; and (2) a binder: 1 to 4 percent.
Preferably, the support is selected from the group consisting of honeycomb cordierite.
Preferably, the binder is selected from one or more of pseudo-boehmite, liquid silica gel and aluminum hydroxide sol.
Preferably, the BaO is Co 3 O 4 And the mass percentage of the total BaO is as follows: 5% -20%.
Preferably, the loading of the inner coating is 80-120 g/L.
Preferably, the coating is loaded with 80-120 g/L.
The invention also provides for the synchronous NH removal as described above 3 And N 2 The preparation method of the double-effect catalyst of O comprises the following steps:
a. preparation of the inner coating slurry: dipping a metal oxide or salt solution of barium on the metal oxide or salt of cobalt, and calcining to prepare active powder; dissolving metal oxides or salts of platinum, aluminum and titanium in a solvent, adding active powder, mixing, and regulating the solid content and the pH value to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: grinding Cu-SSZ-13, adding a binder, mixing, and adjusting the solid content and the pH value to obtain slurry of the outer coating;
c. and (3) coating: coating the slurry of the inner coating on a carrier, controlling the dry loading capacity of the slurry of the inner coating, drying and calcining the slurry of the outer coating, controlling the dry loading capacity of the slurry of the outer coating, and drying and calcining again to obtain the double-effect catalyst.
The invention also provides a method for synchronously removing NH 3 And N 2 The application of the double-effect catalyst of O in the field of engine tail gas treatment.
As described above, the present invention has the following advantageous effects:
1) The invention synchronously removes NH 3 And N 2 The double-effect catalyst of O adopts barium modified cobalt oxide to obtain high-activity N 2 O removes material while using Al 2 O 3 And TiO 2 Composite coating layer integrating TiO 2 Is resistant to poisoning and Al 2 O 3 And reduces the N of the traditional ASC catalyst 2 O production amount; NH Using Pt 3 Oxidation and combination of Cu molecular sieve coating to form NH 3 And the generated NO reacts again to generate N 2 And H 2 O; the two catalysts are combined and coated on the same carrier in a mode of inner coating and outer coating and a proper proportion, so that NH can be synchronously removed 3 And N 2 Double effect catalyst of O.
2) The invention synchronously removes NH 3 And N 2 The preparation method of the double-effect catalyst of O obtains the double-effect catalyst with high activity through the selection of the catalyst precursor, the component proportion and the research of the post-treatment mode.
3) The invention synchronously removes NH 3 And N 2 The double-effect catalyst of O can directly treat N relative to the existing EGR- & gt DOC- & gt DPF- & gt SCR- & gt ASC aftertreatment system when in use 2 O is removed and integrated in ASC, a device is not required to be added separately, space occupation is avoided, extra cost of carriers and packaging is saved, and pollutant control is realized under the condition that the system is unchanged, so that the system is simplified, and meanwhile, the cost is reduced.
Drawings
FIG. 1 shows the synchronous NH removal of the present invention 3 And N 2 Double effect catalyst of O as a function of temperatureChemical pair N 2 O removal rate.
FIG. 2 shows the synchronous NH removal of the present invention 3 And N 2 Double-effect catalyst of O for NH along with temperature change 3 Is not limited, and the removal rate of the catalyst is improved.
Detailed Description
Other advantages and effects of the present invention will become apparent to those skilled in the art from the following disclosure, which describes the embodiments of the present invention with reference to specific examples. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Please refer to the accompanying drawings. It should be noted that, the illustrations provided in the present embodiment merely illustrate the basic concept of the present invention by way of illustration, and only the components related to the present invention are shown in the drawings and are not drawn according to the number, shape and size of the components in actual implementation, and the form, number and proportion of the components in actual implementation may be arbitrarily changed, and the layout of the components may be more complex.
The first aspect of the invention provides a method for synchronously removing NH 3 And N 2 The double-effect catalyst of O comprises a carrier and a coating layer coated on the surface of the carrier, wherein the coating layer comprises an inner coating layer and an outer coating layer; the inner coating is tightly attached to the surface of the carrier, and the outer coating coats the surface of the inner coating; the inner coating comprises the following components in percentage by mass in terms of dry weight: pt 0.05-0.08%; co (Co) 3 O 4 16-19％；BaO 1-4％；Al 2 O 3 15 to 16 percent of TiO 2 : 63-64%; the outer coating comprises the following components in percentage by mass in terms of dry weight: cu-SSZ-13: 96-99%; and (2) a binder: 1 to 4 percent.
Wherein, the mass percent of Pt in the inner coating layer can be 0.05-0.06%, 0.06-0.07% or 0.07-0.08%. In a preferred embodiment of the invention, the mass percentage of Pt is 0.07%.
Co in inner coating 3 O 4 The mass percentage of (2) can be 16-17%, 17-18%Or 18 to 19 percent.
The mass percentage of BaO in the inner coating layer can be 1-2%, 2-3% or 3-4%.
Al in the inner coating 2 O 3 The mass percentage of (C) can be 15-15.1%, 15.1-15.2%, 15.2-15.3%, 15.3-15.4%, 15.4-15.5%, 15.5-15.6%, 15.6-15.7%, 15.7-15.8%, 15.8-15.9% or 15.9-16%. In a preferred embodiment of the invention, al 2 O 3 The mass percentage of (2) is 15.99%.
TiO in the inner coating 2 The mass percentage of (3) may be 63-63.1%, 63.1-63.2%, 63.2-63.3%, 63.3-63.4%, 63.4-63.5%, 63.5-63.6%, 63.6-63.7%, 63.7-63.8%, 63.8-63.9% or 63.9-64%. In a preferred embodiment of the invention, tiO 2 Is 63.94% by mass.
In a preferred embodiment of the present invention, the Al 2 O 3 And TiO 2 The mass percentage ratio of (2) is 1:4.
In a preferred embodiment of the invention, the Co 3 O 4 And BaO is 20% by mass.
In a preferred embodiment of the invention, the BaO is Co 3 O 4 And the mass percentage of the total BaO is as follows: 5% -20%. For example, 5 to 6%, 6 to 7%, 7 to 8%, 8 to 9%, 9 to 10%, 10 to 11%, 11 to 12%, 12 to 13%, 13 to 14%, 14 to 15%, 15 to 16%, 16 to 17%, 17 to 18%, 18 to 19% or 19 to 20%.
The mass percentage of the Cu-SSZ-13 in the outer coating can be 96-97%, 97-98% or 98-99%. In a preferred embodiment of the invention, the Cu-SSZ-13 is 98% by mass. The Cu-SSZ-13 is a Cu-SSZ-13 molecular sieve.
The mass percentage of the binder in the outer coating layer can be 1-2%, 2-3% or 3-4%. In a preferred embodiment of the invention, the mass percentage of the binder is 2%.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, the carrier is selected from honeycomb cordierite.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, the binder is one or more selected from pseudo-boehmite, liquid silica gel and aluminum hydroxide sol.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, the loading capacity of the inner coating is 80-120 g/L. For example 80 to 85g/L, 85 to 90g/L, 90 to 95g/L, 95 to 100g/L, 100 to 105g/L, 105 to 110g/L, 110 to 115g/L or 115 to 120g/L. In a preferred embodiment of the invention, the washcoat loading is 100g/L.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, the loading capacity of the outer coating is 80-120 g/L. For example 80 to 85g/L, 85 to 90g/L, 90 to 95g/L, 95 to 100g/L, 100 to 105g/L, 105 to 110g/L, 110 to 115g/L or 115 to 120g/L. In a preferred embodiment of the invention, the topcoat loading is 100g/L.
Wherein the loading is the mass of catalyst attached to the unit volume of carrier.
In a second aspect, the present invention provides a method for simultaneous NH removal as described above 3 And N 2 The preparation method of the double-effect catalyst of O comprises the following steps:
a. preparation of the inner coating slurry: dipping a metal oxide or salt solution of barium on the metal oxide or salt of cobalt, and calcining to prepare active powder; dissolving metal oxides or salts of platinum, aluminum and titanium in a solvent, adding active powder, mixing, and regulating the solid content and the pH value to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: grinding Cu-SSZ-13, adding a binder, mixing, and adjusting the solid content and the pH value to obtain slurry of the outer coating;
c. and (3) coating: coating the slurry of the inner coating on a carrier, controlling the dry loading capacity of the slurry of the inner coating, drying and calcining the slurry of the outer coating, controlling the dry loading capacity of the slurry of the outer coating, and drying and calcining again to obtain the double-effect catalyst.
The invention synchronously removes NH 3 And N 2 In the preparation method of the double-effect catalyst of O, in the step a, the metal oxide or salt solution of the barium is selected from one or more of barium acetate solution or barium hydroxide solution.
In step a, the metal oxide or salt of cobalt is selected from cobalt carbonate.
In step a, the metal oxide or salt of platinum is selected from platinum nitrate.
In step a, the metal oxide or salt of aluminum is selected from pseudo-boehmite.
In the step a, the metal oxide or salt of titanium is selected from titanium dioxide.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, in the step a, the calcining temperature is 450-500 ℃. For example, 450 to 455 ℃, 455 to 460 ℃, 460 to 465 ℃, 465 to 470 ℃, 470 to 475 ℃, 475 to 480 ℃, 480 to 485 ℃, 485 to 490 ℃, 490 to 495 ℃ or 495 to 500 ℃.
In the step a, the calcination time is 1-3 h. For example 1 to 2 hours or 2 to 3 hours.
In the step a, the solvent is deionized water.
In the step a, the solid content is 30-40%. For example, 30 to 31%, 31 to 32%, 32 to 33%, 33 to 34%, 34 to 35%, 35 to 36%, 36 to 37%, 37 to 38%, 38 to 39% or 39 to 40%. In a preferred embodiment of the invention, in step a, the solids content is 33 to 35%.
In the step a, the pH is 6 to 7.
The invention synchronously removes NH 3 And N 2 In the preparation method of the double-effect catalyst of O, the specific process for preparing the slurry of the inner coating comprises the following steps: dipping barium acetate solution on cobalt carbonate, and calcining at 450 ℃ for 2 hours to obtain active powder; adding a platinum nitrate solution into a proper amount of deionized water, uniformly stirring, adding titanium white and pseudo-boehmite, mixing, adding active powder, stirring, regulating the solid content of the slurry to be 30-40% and the pH value to be 6-7, and obtaining the slurry of the inner coating.
The invention is identical withStep removal of NH 3 And N 2 In the double-effect catalyst of O, in the step b, the grinding is carried out until the D50 is less than or equal to 3 mu m. For example, D50 is 0.5 μm or less, D50 is 0.5 to 1.0 μm, D50 is 1.0 to 1.5 μm, D50 is 1.5 to 2.0 μm, D50 is 2.0 to 2.5 μm or D50 is 2.5 to 3.0 μm.
In the step b, the solid content is 25-35%. For example, 25 to 26%, 26 to 27%, 27 to 28%, 28 to 29%, 29 to 30%, 30 to 31%, 31 to 32%, 32 to 33%, 33 to 34% or 34 to 35%. In a preferred embodiment of the invention, in step b, the solids content is 29% to 31%.
In the step b, the pH is 5-6.
The invention synchronously removes NH 3 And N 2 In the preparation method of the double-effect catalyst of O, the concrete process for preparing the slurry of the outer coating comprises the following steps: adding Cu-SSZ-13 into a proper amount of water, uniformly stirring, grinding until the D50 is less than or equal to 3 mu m, adding a binder, stirring, and regulating the solid content of the slurry to 25-35% and the pH value to 5-6 to obtain the slurry of the outer coating.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, in the step a and the step b, the regulator adopted for regulating the pH is one or more selected from tartaric acid or tetramethyl amine hydroxide.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, in the step c, the dry loading of the slurry of the inner coating is 80-120 g/L. For example 80 to 85g/L, 85 to 90g/L, 90 to 95g/L, 95 to 100g/L, 100 to 105g/L, 105 to 110g/L, 110 to 115g/L or 115 to 120g/L. In a preferred embodiment of the invention, the dry loading of the slurry of the inner coating is 100g/L.
In the step c, the dry loading of the slurry of the outer coating is 80-120 g/L. For example 80 to 85g/L, 85 to 90g/L, 90 to 95g/L, 95 to 100g/L, 100 to 105g/L, 105 to 110g/L, 110 to 115g/L or 115 to 120g/L. In a preferred embodiment of the invention, the dry loading of the slurry of the topcoat is 100g/L.
Wherein, the dry loading in the step c refers to the loading calculated by mass after sizing and drying calcination.
In the step c, the drying and calcining are carried out by heating to 180-220 ℃ from 30min at room temperature, for example, 180-185 ℃, 185-190 ℃, 190-195 ℃, 195-200 ℃, 200-205 ℃, 205-210 ℃, 210-215 ℃ or 215-220 ℃, preserving heat for 1h, heating to 530-580 ℃ within 60min, for example, 530-535 ℃, 535-540 ℃, 540-545 ℃, 545-550 ℃, 550-555 ℃, 555-560 ℃, 560-565 ℃, 565-570 ℃, 570-575 ℃ or 575-580 ℃, preserving heat for 2h, and naturally cooling. In a preferred embodiment of the invention, the drying and calcining are carried out by heating from room temperature for 30min to 200 ℃, preserving heat for 1h, heating to 550 ℃ within 60min, preserving heat for 2h, and then naturally cooling.
In step c, the drying and calcining are carried out in a muffle furnace.
In the step c, the coating adopts a mode of feeding downwards and vacuumizing. The lower feeding in the invention means that the slurry passes through the carrier from bottom to top.
The invention synchronously removes NH 3 And N 2 In the double-effect catalyst of O, pt and Co in the inner coating of the double-effect catalyst 3 O 4 、BaO、Al 2 O 3 And TiO 2 The mass percentage ratio of (2) is as follows: (0.05-0.08): (16-19): (1-4): (15-16): (63-64).
The invention synchronously removes NH 3 And N 2 In the preparation method of the double-effect catalyst of O, a cobalt precursor is used and modified by barium, and CoCO 3 Hedvall effect in the decomposition process promotes the alkali towards Co 3 O 4 The migration of the crystal lattice, and thus the alkali ions, after calcination, are distributed not only on the surface of the catalyst but also in the bulk of the catalyst. The alkali on the surface is inactive and the alkali component migrating into the bulk affects Co 3 O 4 Thereby promoting Co 3 O 4 For N 2 Catalytic activity of direct O decomposition. Using TiO 2 Partially replace traditional Al 2 O 3 NH is reduced 3 Oxidation process N 2 O formation while controlling TiO 2 And Al 2 O 3 Ratio of (2) and Al 2 O 3 Can solve the problem of TiO by adding 2 Sintering at high temperatures.
A third aspect of the invention provides a synchronous NH removal as described above 3 And N 2 The application of the double-effect catalyst of O in the field of engine tail gas treatment.
Example 1
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
a. preparation of the inner coating slurry: 5g of barium acetate is dissolved in 10g of deionized water, immersed on 40.0g of cobalt carbonate, and calcined for 2 hours at 450 ℃ to obtain active powder; adding 0.85g of platinum nitrate solution (platinum content is 12.5%) into 280g of deionized water, uniformly stirring, adding 110.9g of titanium dioxide and 30.0g of pseudo-boehmite, stirring for 10min, adding active powder, continuously stirring for 30min, and regulating the solid content of the slurry to 33% -35%, and ph6-7 to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: 150g of Cu-SSZ13 are added into 280g of deionized water, uniformly stirred and ground until D50=2.76 mu m, 3g of pseudo-boehmite is added and stirred for 30min; adjusting the solid content to 29% -31%, and ph5-6 to obtain slurry of the outer coating;
c. and (3) coating: the inner coating slurry is coated on the honeycomb cordierite, and the carrier size isThe dry loading is 100g/L; the slurry of the outer coating is continuously coated after drying and calcining, the loading capacity is 100g/L, and the NH can be synchronously removed after drying and calcining 3 And N 2 Double effect catalyst of O.
Comparative example 1
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
a. preparation of the inner coating slurry: calcining 44.4g of cobalt carbonate at 450 ℃ for 2 hours to obtain active powder, wherein the obtained active powder does not contain BaO; adding 0.85g of platinum nitrate solution (platinum content is 12.5%) into 280g of deionized water, uniformly stirring, adding 110.9g of titanium dioxide and 30.0g of pseudo-boehmite, stirring for 10min, adding active powder, continuously stirring for 30min, and regulating the solid content of the slurry to 33% -35%, wherein ph6-7 is the slurry of the inner coating;
b. preparing slurry of the outer coating: 150g of Cu-SSZ13 are added into 280g of deionized water, uniformly stirred and ground until D50=2.76 mu m, 3g of pseudo-boehmite is added and stirred for 30min; adjusting the solid content to 29% -31%, and ph5-6 to obtain slurry of the outer coating;
c. and (3) coating: the inner coating slurry is coated on the honeycomb cordierite, and the carrier size isThe dry loading is 100g/L; the slurry of the outer coating is continuously coated after drying and calcining, the loading capacity is 100g/L, and the NH can be synchronously removed after drying and calcining 3 And N 2 Double effect catalyst of O.
Comparative example 2
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
a. preparation of the inner coating slurry: dissolving 12.5g of barium acetate in 10g of deionized water, dipping the solution onto 33.3g of cobalt carbonate, and calcining the solution at 450 ℃ for 2 hours to obtain active powder, wherein the BaO ratio of the obtained active powder is 25%; adding 0.85g of platinum nitrate solution (platinum content is 12.5%) into 280g of deionized water, uniformly stirring, adding 110.9g of titanium dioxide and 30.0g of pseudo-boehmite, stirring for 10min, adding active powder, continuously stirring for 30min, and regulating the solid content of the slurry to 33% -35%, wherein ph6-7 is the slurry of the inner coating;
b. preparing slurry of the outer coating: 150g of Cu-SSZ13 are added into 280g of deionized water, uniformly stirred and ground until D50=2.76 mu m, 3g of pseudo-boehmite is added and stirred for 30min; adjusting the solid content to 29% -31%, and ph5-6 to obtain slurry of the outer coating;
c. and (3) coating: the inner coating slurry is coated on the honeycomb cordierite, and the carrier size isThe dry loading is 100g/L; the slurry of the outer coating is continuously coated after drying and calcining, the loading capacity is 100g/L, and the NH can be synchronously removed after drying and calcining 3 And N 2 Double effect catalyst of O.
Comparative example 3
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
a. preparation of the inner coating slurry: 5g of barium acetate is dissolved in 10g of deionized water, immersed on 27g of cobaltosic oxide, and calcined for 2 hours at 450 ℃ to obtain active powder; adding 0.85g of platinum nitrate solution (platinum content is 12.5%) into 280g of deionized water, uniformly stirring, adding 110.9g of titanium dioxide and 30.0g of pseudo-boehmite, stirring for 10min, adding active powder, continuously stirring for 30min, and regulating the solid content of the slurry to 33% -35%, and ph6-7 to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: 150g of Cu-SSZ13 are added into 280g of deionized water, uniformly stirred and ground until D50=2.76 mu m, 3g of pseudo-boehmite is added and stirred for 30min; adjusting the solid content to 29% -31%, and ph5-6 to obtain slurry of the outer coating;
c. and (3) coating: the inner coating slurry is coated on the honeycomb cordierite, and the carrier size isThe dry loading is 100g/L; the slurry of the outer coating is continuously coated after drying and calcining, the loading capacity is 100g/L, and the NH can be synchronously removed after drying and calcining 3 And N 2 Double effect catalyst of O.
Comparative example 4
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
the proportion of each component is adjusted to lead Co in the prepared double-effect catalyst to be 3 O 4 And BaO is 15% by mass.
Comparative example 5
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
the proportion of each component is adjusted to lead Co in the prepared double-effect catalyst to be 3 O 4 And the sum of the mass percentages of BaO is 25%.
Comparative example 6
Synchronous NH removal 3 And N 2 Preparation of double-effect catalyst of O:
a. preparation of the inner coating slurry: adding 0.85g of platinum nitrate solution (platinum content is 12.5%) into 280g of deionized water, uniformly stirring, adding 110.9g of titanium dioxide and 30.0g of pseudo-boehmite, stirring for 10min, adding active powder, continuously stirring for 30min, and regulating the solid content of the slurry to 33% -35%, and ph6-7 to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: 150g of Cu-SSZ13 are added into 280g of deionized water, uniformly stirred and ground until D50=2.76 μm, 3g of binder is added and stirred for 30min; adjusting the solid content to 29% -31%, and ph5-6 to obtain slurry of the outer coating;
c. and (3) coating: the inner coating slurry is coated on the honeycomb cordierite, and the carrier size isThe dry loading is 100g/L; the slurry of the outer coating is continuously coated after drying and calcining, the loading capacity is 100g/L, and the NH can be synchronously removed after drying and calcining 3 And N 2 Double effect catalyst of O.
NH was removed simultaneously with the preparation of example 1 and comparative examples 1 to 6 3 And N 2 After the double-effect catalyst of O is subjected to hydrothermal aging at 800 ℃ for 16 hours, the catalyst is subjected to space velocity 60000 hours -1 ，150-400℃，H 2 O：7％，O 2 ：10％，N 2 O：500ppm，NH 3 : the denitration performance test is carried out under the environment of 500ppm, the heating rate is 10 ℃/min and the initial stable temperature is 120 ℃.
The testing method comprises the following steps: using blank carrier, regulating each flowmeter parameter according to the above-mentioned fume condition and making it reach required value, after stabilizing at 120 deg.C recording reactor outlet NH 3 And N 2 O concentration as the sample inlet NH 3 And N 2 O concentration calculation; and replacing the blank carrier with a test sample, setting the heating rate after the blank carrier is stabilized at 120 ℃, using a Fourier infrared flue gas analyzer to monitor the outlet flue gas parameter on line, calculating the efficiency according to the two values, and obtaining a temperature and efficiency relation curve.
Test results are shown in FIG. 1 and FIG. 2, and in comparative example 1, N of the catalyst prepared without Ba-modified Co is as compared with example 1 2 The O removal performance is low; comparative example 2 where too much Ba was added, the catalyst prepared resulted in N 2 Loss of O removal performance; comparative example 3 direct Co use 3 O 4 The performance of the prepared sample is low by replacing cobalt precursor; comparative examples 4 and 5 mainly adjust the mass ratio of active powder to the overall coating, it can be found that when active powder 1 is low, the N of the dual effect catalyst product 2 The O removal performance is low, when the active powder is too high in proportion, the N of the product 2 O removal performance is not improved but NH 3 The removal performance is lost; comparative example 6 without active powder 1, the product obtained had only NH 3 Removal capacity, N 2 O is instead generated.
Synchronous NH removal of example 1 of the present invention 3 And N 2 The double-effect catalyst of O has higher NH 3 And N 2 The O synergic removal performance is mainly due to the following: coCO 3 Hedvall effect in the decomposition process promotes migration of Ba to Co 3 O 4 In the crystal lattice, therefore, ba ions are distributed not only on the surface of the catalyst but also on Co after calcination 3 O 4 In the bulk of (a), this portion of the Ba ions promotes N 2 Carrying out direct decomposition reaction of O; the titanium oxide and aluminum oxide composite carrier is used, so that the performance of the active component is improved to the maximum extent, and meanwhile, the titanium oxide and aluminum oxide composite carrier has good high temperature resistance and poisoning resistance.
In summary, the present invention removes NH simultaneously 3 And N 2 The double-effect catalyst of O uses Ba modified cobalt oxide to obtain high-activity N 2 O removing material using Al 2 O 3 And TiO 2 Composite coating layer integrating TiO 2 Is resistant to poisoning and Al 2 O 3 And reduces the N of the traditional ASC catalyst 2 O production amount, two catalysts are combined and coated on the same carrier, thus obtaining the catalyst capable of synchronously removing NH 3 And N 2 Double effect catalyst of O. Therefore, the invention effectively overcomes various defects in the prior art and has high industrial utilization value.
The above embodiments are merely illustrative of the principles of the present invention and its effectiveness, and are not intended to limit the invention. Modifications and variations may be made to the above-described embodiments by those skilled in the art without departing from the spirit and scope of the invention. Accordingly, it is intended that all equivalent modifications and variations of the invention be covered by the claims, which are within the ordinary skill of the art, be within the spirit and scope of the present disclosure.
Claims (10)
1. Synchronous NH removal 3 And N 2 The double-effect catalyst of O is characterized by comprising a carrier and a coating coated on the surface of the carrier, wherein the coating comprises an inner coating and an outer coating; the inner coating is tightly attached to the surface of the carrier, and the outer coating coats the surface of the inner coating; the inner coating comprises the following components in percentage by mass in terms of dry weight: pt 0.05-0.08%; co (Co) 3 O 4 16～19％；BaO 1～4％；Al 2 O 3 15 to 16 percent of TiO 2 : 63-64%; the outer coating comprises the following components in percentage by mass in terms of dry weight: cu-SSZ-13: 96-99%; and (2) a binder: 1 to 4 percent.
2. The synchronous NH removal of claim 1 3 And N 2 A dual-effect catalyst for O, wherein the support is selected from the group consisting of honeycomb cordierite;
and/or the binder is selected from one or more of pseudo-boehmite, liquid silica gel and aluminum hydroxide sol;
and/or the BaO occupies Co 3 O 4 And the mass percentage of the total BaO is as follows: 5% -20%;
and/or, the loading capacity of the inner coating is 80-120 g/L;
and/or, the loading capacity of the outer coating is 80-120 g/L.
3. Synchronous NH removal according to any of claims 1-2 3 And N 2 A process for preparing the double-effect catalyst of O, which comprises the following stepsThe steps are as follows:
a. preparation of the inner coating slurry: dipping a metal oxide or salt solution of barium on the metal oxide or salt of cobalt, and calcining to prepare active powder; dissolving metal oxides or salts of platinum, aluminum and titanium in a solvent, adding active powder, mixing, and regulating the solid content and the pH value to obtain slurry of the inner coating;
b. preparing slurry of the outer coating: grinding Cu-SSZ-13, adding a binder, mixing, and adjusting the solid content and the pH value to obtain slurry of the outer coating;
c. and (3) coating: coating the slurry of the inner coating on a carrier, controlling the dry loading capacity of the slurry of the inner coating, drying and calcining the slurry of the outer coating, controlling the dry loading capacity of the slurry of the outer coating, and drying and calcining again to obtain the double-effect catalyst.
4. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that in the step a, the metal oxide or salt solution of barium is selected from one or more of barium acetate solution or barium hydroxide solution;
and/or in step a, the metal oxide or salt of cobalt is selected from cobalt carbonate;
and/or, in step a, the metal oxide or salt of platinum is selected from platinum nitrate;
and/or, in step a, the metal oxide or salt of aluminum is selected from pseudo-boehmite;
and/or in the step a, the metal oxide or salt of titanium is selected from titanium dioxide.
5. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that in the step a, the calcining temperature is 450-500 ℃;
and/or in the step a, the calcination time is 1-3 h;
and/or, in the step a, the solvent is deionized water;
and/or, in the step a, the solid content is 30-40%;
and/or, in the step a, the pH is 6-7.
6. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that in the step b, the grinding is carried out until the D50 is less than or equal to 3 mu m;
and/or, in the step b, the solid content is 25-35%;
and/or in the step b, the pH is 5-6.
7. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that in the step a and the step b, the regulator adopted for regulating the pH is one or more selected from tartaric acid or tetramethyl amine hydroxide.
8. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that in the step c, the loading capacity of the slurry of the inner coating is 80-120 g/L;
and/or, in the step c, the loading capacity of the slurry of the outer coating is 80-120 g/L;
and/or in the step c, the drying and calcining are carried out by heating to 180-220 ℃ from room temperature for 30min, preserving heat for 1h, heating to 530-580 ℃ within 60min, preserving heat for 2h, and then naturally cooling;
and/or, in step c, the drying and calcining are carried out in a muffle furnace;
and/or, in the step c, the coating adopts a mode of vacuum pumping by feeding down.
9. The synchronous NH removal of claim 3 3 And N 2 The preparation method of the double-effect catalyst of O is characterized in that Pt and Co in an inner coating of the double-effect catalyst 3 O 4 、BaO、Al 2 O 3 And TiO 2 The mass percentage ratio of (2) is as follows: 0.05 to 0.08 (16 to 19), 1 to 4, 15 to 16 and 63 to 64.
10. Synchronous NH removal according to any of claims 1-2 3 And N 2 The application of the double-effect catalyst of O in the field of engine tail gas treatment.
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