CN107233912A - A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof - Google Patents
A kind of two-part catalyst handled for exhaust gas from diesel vehicle and preparation method thereof Download PDFInfo
- Publication number
- CN107233912A CN107233912A CN201710485488.5A CN201710485488A CN107233912A CN 107233912 A CN107233912 A CN 107233912A CN 201710485488 A CN201710485488 A CN 201710485488A CN 107233912 A CN107233912 A CN 107233912A
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- Prior art keywords
- catalyst
- ceo
- formula
- molecular sieve
- prepared
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- 239000003054 catalyst Substances 0.000 title claims abstract description 275
- 238000002360 preparation method Methods 0.000 title claims description 12
- 239000002808 molecular sieve Substances 0.000 claims abstract description 72
- 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 72
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 42
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000012545 processing Methods 0.000 claims abstract description 37
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 17
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 12
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 57
- 239000002105 nanoparticle Substances 0.000 claims description 54
- 239000002245 particle Substances 0.000 claims description 43
- 239000011258 core-shell material Substances 0.000 claims description 40
- 239000010948 rhodium Substances 0.000 claims description 35
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 13
- 229910052684 Cerium Inorganic materials 0.000 claims description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 238000000975 co-precipitation Methods 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 5
- 238000006555 catalytic reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 230000011218 segmentation Effects 0.000 claims description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 abstract description 80
- 239000007789 gas Substances 0.000 abstract description 68
- 239000013618 particulate matter Substances 0.000 abstract description 13
- 239000004071 soot Substances 0.000 abstract description 7
- 238000012360 testing method Methods 0.000 abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract 2
- 229910021529 ammonia Inorganic materials 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 58
- 238000003756 stirring Methods 0.000 description 41
- 239000000243 solution Substances 0.000 description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 29
- 239000000377 silicon dioxide Substances 0.000 description 27
- 241000264877 Hippospongia communis Species 0.000 description 24
- 238000012216 screening Methods 0.000 description 22
- 229910052681 coesite Inorganic materials 0.000 description 21
- 229910052593 corundum Inorganic materials 0.000 description 21
- 229910052906 cristobalite Inorganic materials 0.000 description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 21
- 229910052682 stishovite Inorganic materials 0.000 description 21
- 229910052905 tridymite Inorganic materials 0.000 description 21
- 238000010792 warming Methods 0.000 description 21
- 229910001845 yogo sapphire Inorganic materials 0.000 description 21
- 238000000576 coating method Methods 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 19
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 18
- 239000000919 ceramic Substances 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 15
- 238000000227 grinding Methods 0.000 description 14
- 239000003643 water by type Substances 0.000 description 14
- 235000019441 ethanol Nutrition 0.000 description 13
- 150000002823 nitrates Chemical class 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 229920003081 Povidone K 30 Polymers 0.000 description 9
- 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 9
- 125000005909 ethyl alcohol group Chemical group 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 6
- 229910052878 cordierite Inorganic materials 0.000 description 6
- 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 6
- 238000001035 drying Methods 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 235000019241 carbon black Nutrition 0.000 description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 3
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group metals or copper
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- 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
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
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- 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
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- B01J29/76—Iron group metals or copper
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- B01J29/76—Iron group metals or copper
- B01J29/7676—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—Zeolite Beta
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- 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
- B01D2258/012—Diesel engines and lean burn gasoline engines
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including:The catalyst A of the inlet end and catalyst B of outlet side;The catalyst A has formula:CeO2X/ molecular sieves;Wherein, X is selected from CuO, Fe2O3Or MnO2;The catalyst B has formula:M@CeO2/ molecular sieve;Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the two-part catalyst that the present invention is provided has high eradicating efficacy and selectivity in wide temperature range for exhaust gas from diesel vehicle processing to nitrogen oxides, and can eliminate particulate matter to a certain extent, while having escape ammonia to eliminate function.Wherein, catalyst B in outlet side also has DOC catalyst functions simultaneously.Test result indicates that, the two-part catalyst that the present invention is provided is in 150 550 DEG C, high-speed 240000h‑1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% and the N excellent in high temperature2Selectivity;And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
Description
Technical field
The present invention relates to have catalyst technical field, more particularly to a kind of two-part catalysis handled for exhaust gas from diesel vehicle
Agent and preparation method thereof.
Background technology
Nitrogen oxides (NOx) it is primarily referred to as NO and NO2, wherein NO accounts for 95%.Nitrogen oxides be main atmosphere pollution it
One, it is directly contacted with air and water can bring many harm, such as acid rain, photochemical fog, stratospheric ozone loss, the whole world
Climate change etc..Nitrogen oxides in air mostly come from moving source (motor vehicle) and stationary source (predominantly thermal power plant,
Industrial burning device) two aspects, wherein, the nitrogen oxides in the whole world 95% derives from vehicular emission (49%) and power plant emission
(46%).And increasing sharply for the growth and vehicles number with energy resource consumption, it is discharged into after a large amount of Fossil fuel consumptions big
The acidic materials such as the nitrogen oxides in gas are more and more, and atmosphere pollution is also increasingly serious.Therefore, as the whole world is to nitrogen oxides
Discharge limitation is more and more stricter, and how efficiently to eliminate nitrogen oxides becomes worldwide problem.
At present, the method for eliminating nitrogen oxides is a lot, wherein ammine selectivity catalytic reduction nitrous oxides (NH3- SCR), because
Its efficiency high, relative cost performance are high, have become one of maximally efficient method of elimination nitrogen oxides.And selective catalysis
One of key of nitrogen oxides reduction technology is exactly catalyst, traditional, the commercialized catalyst for being used for eliminating nitrogen oxides
Mainly V2O5-WO3/TiO2Catalyst, high NO can be shown at 300 DEG C~400 DEG CxRemoval efficiency.
But, use it for exhaust gas from diesel vehicle processing and there is also some problems, such as:Temperature window is narrow, high temperature N2Selectivity
Difference, there is N2O generation and NH3Oxidation, and TiO2Crystal structure change can occur at high temperature, catalytic activity is reduced, together
When vanadium exist to environment and poison and can to bear air speed low.The catalyst for vehicle maintenance service has Bath in the prior art
The SSZ-13 molecular sieve catalysts of husband, although temperature window is relatively wide, resistance to high-speed, but its, low temperature active is not high, it is impossible to eliminate
Particulate matter;And granular material discharged in exhaust gas from diesel vehicle has very big harm into air to people.Therefore, exploitation one kind can be
There is high eradicating efficacy and selectivity to nitrogen oxides in more wide temperature range, and particulate matter can be eliminated to a certain extent
Catalyst turns into those skilled in the art's technical problem urgently to be resolved hurrily.
The content of the invention
In view of this, it is an object of the invention to provide it is a kind of for exhaust gas from diesel vehicle handle two-part catalyst and its
Preparation method, the two-part catalyst that the present invention is provided is for exhaust gas from diesel vehicle processing, to nitrogen oxidation in wide temperature range
Thing has high eradicating efficacy and selectivity, and can eliminate particulate matter to a certain extent.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including:The catalyst A of inlet end
With the catalyst B of outlet side;
The catalyst A has formula shown in formula (I):
CeO2- X/ molecular sieve formula (I)s;
Wherein, X is selected from CuO, Fe2O3Or MnO2;
The catalyst B has formula shown in formula (II):
M@CeO2/ molecular sieve formula (II);
Wherein, M is selected from Rh, Pt or Pd.
It is preferred that, in the formula (I), CeO2Mol ratio with X is (3~19):1.
It is preferred that, in the formula (I), the molecular sieve is selected from ZSM-5, MCM-56 or BEA;
The CeO2- X and the mass ratio of molecular sieve are 1:(1~10).
It is preferred that, in the formula (II), M and CeO2 mol ratio are 1:(8~32).
It is preferred that, in the formula (II), the molecular sieve is selected from ZSM-5, MCM-56 or BEA;
The M@CeO2 and the mass ratio of molecular sieve are 1:(1~10).
It is preferred that, the mass ratio of the catalyst A and catalyst B are (0.5~3):1.
Present invention also offers a kind of preparation method of the two-part catalyst described in above-mentioned technical proposal, including following step
Suddenly:
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle;It is described
X ' sources are selected from copper source, source of iron or manganese source;
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Nuclear shell structure nano
Particle;M ' the sources are selected from rhodium source, platinum source or palladium source;
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is distinguished
Loaded with molecular sieve, respectively obtain catalyst A and catalyst B;
D) catalyst A is arranged on inlet end, catalyst B is arranged on outlet side, obtained for exhaust gas from diesel vehicle processing
Two-part catalyst;
The step a) and b) no order limitation.
It is preferred that, the temperature of hydro-thermal reaction described in step a) is 160 DEG C~200 DEG C, and the time is 20h~30h.
It is preferred that, temperature 50 C~70 DEG C of coprecipitation reaction described in step b), the time is 0.5h~1.5h.
It is preferred that, CeO described in step c)2The average grain diameter of-X nano particle is 3nm~5nm;The M@CeO2Nucleocapsid knot
The average grain diameter of structure nano-particle is 45nm~55nm.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, include the catalyst A of inlet end
With the catalyst B of outlet side;The catalyst A has formula:CeO2- X/ molecular sieves;Wherein, X is selected from CuO, Fe2O3Or MnO2;
The catalyst B has formula:M@CeO2/ molecular sieve;Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the present invention is carried
The two-part catalyst of confession for exhaust gas from diesel vehicle processing, have in wide temperature range to nitrogen oxides high eradicating efficacy and
Selectivity, and particulate matter can be eliminated to a certain extent.Test result indicates that, the two-part catalyst that the present invention is provided exists
150-550 DEG C, high-speed 240000h-1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% with
And in high temperature excellent N2Selectivity;And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
In addition, the two-part catalyst preparation process that provides of the present invention is simple, mild condition, cost are low, and not only to ring
Border is not polluted, and is also had urea concurrently and is decomposed and eliminate escape NH3Effect.
Brief description of the drawings
Fig. 1 is the CeO that embodiment 1 is prepared2-Fe2O3The TEM photos of nano-particle;
Fig. 2 is the Rh@CeO that embodiment 1 is prepared2The TEM photos of core-shell structure nanometer particle;
Fig. 3 is the CeO that embodiment 5 is prepared2-Fe2O3/ MCM-56 TEM photos;
Fig. 4 is the Rh@CeO that embodiment 5 is prepared2/ MCM-56 TEM photos;
Fig. 5 is embodiment 10, the activity contrast of the two-part catalyst nitrogen oxides reduction of the offer of comparative example 3~4
Figure.
Embodiment
The technical scheme in the embodiment of the present invention will be clearly and completely described below, it is clear that described implementation
Example only a part of embodiment of the invention, rather than whole embodiments.Based on the embodiment in the present invention, this area is common
The every other embodiment that technical staff is obtained under the premise of creative work is not made, belongs to the model that the present invention is protected
Enclose.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including:The catalyst A of inlet end
With the catalyst B of outlet side;
The catalyst A has formula shown in formula (I):
CeO2- X/ molecular sieve formula (I)s;
Wherein, X is selected from CuO, Fe2O3Or MnO2;
The catalyst B has formula shown in formula (II):
M@CeO2/ molecular sieve formula (II);
Wherein, M is selected from Rh, Pt or Pd.
In the present invention, the two-part catalyst is known for exhaust gas from diesel vehicle processing using those skilled in the art
Reactor such as tubular fixed-bed reactor.According to as well known to those skilled in the art, two sections for carrying out catalytic reaction
Formula catalyst has inlet end and outlet side according to gas flow direction in course of reaction, and the first haptoreaction gas of the inlet end goes out
Reaction gas is contacted behind gas end, it is not specifically limited to this by the present invention.
In the present invention, the two-part catalyst includes the catalyst A of inlet end and the catalyst B of outlet side.At this
In invention, the catalyst A has formula shown in formula (I):
CeO2- X/ molecular sieve formula (I)s;
Wherein, X is selected from CuO, Fe2O3Or MnO2, preferably CuO.In the present invention, the CeO2- X is catalyst A work
Property component, molecular sieve be catalyst A carrier.In the preferred embodiment of the invention, the X is CuO, and the catalyst A is
For CeO2- CuO/ molecular sieves;The X is Fe2O3, the catalyst A is CeO2-Fe2O3/ molecular sieve;The X is MnO2, institute
State catalyst A as CeO2-MnO2/ molecular sieve.In the present invention, in the formula (I), CeO2Mol ratio with X be preferably (3~
19):1, more preferably (4~17):1, yet more preferably (6~13):1, be most preferably (6.7~9.3):1.
In the present invention, in the formula (I), the molecular sieve is preferably selected from ZSM-5, MCM-56 or BEA, more preferably
MCM-56.The present invention is not particularly limited to the source of the molecular sieve, using above-mentioned ZSM- well known to those skilled in the art
5th, MCM-56 and BEA commercial goods or laboratory own product.In the preferred embodiment of the invention, the molecular sieve is
ZSM-5, the ZSM-5 silica alumina ratio are preferably (5~20):1, more preferably 12:1.In the preferred embodiment of the invention, institute
Molecular sieve is stated for MCM-56, the silica alumina ratio of the MCM-56 is preferably (15~30):1, more preferably 25:1.Of the invention preferred
Embodiment in, the molecular sieve be BEA, the silica alumina ratio of the BEA is preferably (15~25):1, more preferably 19:1.
In the present invention, in the formula (I), the CeO2- X and the mass ratio of molecular sieve are preferably 1:(1~10), it is more excellent
Elect 1 as:5.
In the present invention, the catalyst B has formula shown in formula (II):
M@CeO2/ molecular sieve formula (II);
Wherein, M is selected from Rh, Pt or Pd, preferably Pt.In the present invention, the M@CeO2For catalyst B activearm
Point, molecular sieve is catalyst A carrier.In the preferred embodiment of the invention, the M is Rh, and the catalyst B is Rh@
CeO2/ molecular sieve;The M is Pt, and the catalyst B is Pt@CeO2/ molecular sieve;The M is Pd, and the catalyst B is
Pd@CeO2/ molecular sieve.In the present invention, in the formula (II), M and CeO2Mol ratio be preferably 1:(8~32), more preferably
1:16.
In the present invention, in the formula (II), the molecular sieve is preferably selected from ZSM-5, MCM-56 or BEA, more preferably
MCM-56.The present invention is not particularly limited to the source of the molecular sieve, using above-mentioned ZSM- well known to those skilled in the art
5th, MCM-56 and BEA commercial goods or laboratory own product.In the preferred embodiment of the invention, the molecular sieve is
ZSM-5, the ZSM-5 silica alumina ratio are preferably (5~20):1, more preferably 12:1.In the preferred embodiment of the invention, institute
Molecular sieve is stated for MCM-56, the silica alumina ratio of the MCM-56 is preferably (15~30):1, more preferably 25:1.Of the invention preferred
Embodiment in, the molecular sieve be BEA, the silica alumina ratio of the BEA is preferably (15~25):1, more preferably 19:1.
In the present invention, in the formula (II), the M@CeO2Mass ratio with molecular sieve is 1:(1~10), more preferably
For 1:5.
In the present invention, the mass ratio of the catalyst A and catalyst B are preferably (0.5~3):1, more preferably 1:1.
Present invention also offers a kind of preparation method of the two-part catalyst described in above-mentioned technical proposal, including following step
Suddenly:
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle;It is described
X ' sources are selected from copper source, source of iron or manganese source;
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Nuclear shell structure nano
Particle;M ' the sources are selected from rhodium source, platinum source or palladium source;
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is distinguished
Loaded with molecular sieve, respectively obtain catalyst A and catalyst B;
D) catalyst A is arranged on inlet end, catalyst B is arranged on outlet side, obtained for exhaust gas from diesel vehicle processing
Two-part catalyst;
The step a) and b) no order limitation.
Cerium source, X ' sources and triethylamine are carried out hydro-thermal reaction by the present invention in the first solvent first, obtain CeO2- X nano
Particle.In the present invention, the cerium source is preferably cerous nitrate;X ' the sources are selected from copper source, source of iron or manganese source, wherein, the copper
Source is preferably copper nitrate, and the source of iron is preferably ferric nitrate, and the manganese source is preferably the manganese nitrate solution that mass fraction is 50%;
First solvent is preferably the ethanol solution of polyvinylpyrrolidone, and polyvinylpyrrolidone ethanol is molten in first solvent
Liquid preferred mass concentration is 10g/L~30g/L.The present invention does not have to the source of the cerium source, X ' sources, triethylamine and the first solvent
It is specifically limited, use above-mentioned cerous nitrate well known to those skilled in the art, copper nitrate, ferric nitrate, mass fraction for 50% nitre
The commercial goods of sour manganese solution, polyvinylpyrrolidone and ethanol.
The present invention is not particularly limited to the mode of the hydro-thermal reaction, using technical side well known to those skilled in the art
Case.In the present invention, the hydrothermal temperature is preferably 160 DEG C~200 DEG C, more preferably 180 DEG C;The hydro-thermal is anti-
The time answered is preferably 20h~30h, more preferably 24h.
In the present invention, the CeO obtained2The average grain diameter of-X nano particle is preferably 3nm~5nm.
Meanwhile, M ' sources, cerium source and ammoniacal liquor are carried out coprecipitation reaction by the present invention in the second solvent, obtain M@CeO2Nucleocapsid
Structure nano particle.In the present invention, the M ' sources are selected from rhodium source, platinum source or palladium source, wherein, rhodium source is preferably that rhodium nitrate is molten
Liquid, the platinum source is preferably platinum acid chloride solution, and the palladium source is preferably palladium nitrate solution;The cerium source is preferably that cerous nitrate is molten
Liquid;The ammoniacal liquor is preferably the ammoniacal liquor that mass concentration is 25%;Second solvent is preferably the aqueous solution or the iodate of KBr
The aqueous solution of potassium, the mass concentration of second solvent is preferably 0.3g/L~0.4g/L, more preferably 0.375g/L.The present invention
The source of the M ' sources, cerium source, ammoniacal liquor and the second solvent is not particularly limited, using well known to those skilled in the art above-mentioned
Rhodium nitrate solution, platinum acid chloride solution, palladium nitrate solution, cerous nitrate solution, mass concentration are 25% ammoniacal liquor, KBr and iodate
The commercial goods of potassium.
The present invention is not particularly limited to the mode of the coprecipitation reaction, using technology well known to those skilled in the art
Scheme.In the present invention, preferably 50 DEG C~70 DEG C of the temperature of the coprecipitation reaction, more preferably 60 DEG C;It is described coprecipitated
The time of shallow lake reaction is preferably 0.5h~1.5h, more preferably 1h.
In the present invention, the M@CeO obtained2The average grain diameter of core-shell structure nanometer particle is preferably 45nm~55nm, more
Preferably 50nm.
Obtain the CeO2- X nano particle and M@CeO2It is of the invention by obtained CeO after core-shell structure nanometer particle2-X
Nano-particle and obtained M@CeO2Core-shell structure nanometer particle is loaded with molecular sieve respectively, respectively obtain catalyst A and
Catalyst B.In the present invention, the molecular sieve is identical with described in above-mentioned technical proposal, will not be repeated here.The present invention is right
The mode of the load is not particularly limited, using the skill well known to those skilled in the art by nanometer particle load to molecular sieve
Art scheme, is particularly preferred as:
Nano-particle is dispersed in deionized water or ethanol, after being uniformly dispersed, adds after molecular sieve ultrasound 0.5h and stirs
4h makes it uniform, after being evaporated and being dried overnight, is calcined, obtains the molecular sieve of nanometer particle load.In the present invention, it is described
The temperature of calcining is preferably 400 DEG C~600 DEG C, more preferably 500 DEG C;The time of the calcining is preferably 1h~8h, more preferably
For 2h.
In the present invention, by CeO2- X nano particle and M@CeO2Core-shell structure nanometer particle is born with molecular sieve respectively
After load, the catalyst A and catalyst B respectively obtained is identical with described in above-mentioned technical proposal, will not be repeated here.
Respectively obtain after the catalyst A and catalyst B, catalyst A is set inlet end by the present invention, catalyst B is set
In outlet side, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.The present invention is to the catalyst A/ catalyst B two
Set-up mode in segmentation catalyst is not particularly limited, it is preferred to use by catalyst A/ catalyst B tablettings, grinding, screening takes
40-60 mesh granular sizes are directly used, or catalyst A/ catalyst B is coated on matrix obtained coated catalysts A/ coatings and urged
Agent B is reused.In the present invention, the coating matrix of the coated catalysts A/ coated catalysts B is preferably honeycomb pottery
Porcelain basal body or metal beehive carrier.
The two-part catalyst can be used for moving source or fixed combustion device includes various motor car engines and fire coal electricity
The purification of factory's tail gas nitrogen oxide.It is placed in when using in exhaust pipe, reducing agent and tail is sprayed into by two-part catalyst inlet end
Gas is mixed, wherein, NH3The ratio for counting consumption and NO is 0.8~1.2.
The invention provides a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including:The catalyst A of inlet end
With the catalyst B of outlet side;The catalyst A has formula:CeO2- X/ molecular sieves;Wherein, X is selected from CuO, Fe2O3Or MnO2;
The catalyst B has formula:M@CeO2/ molecular sieve;Wherein, M is selected from Rh, Pt or Pd.Compared with prior art, the present invention is carried
The two-part catalyst of confession for exhaust gas from diesel vehicle processing, have in wide temperature range to nitrogen oxides high eradicating efficacy and
Selectivity, and particulate matter can be eliminated to a certain extent.Test result indicates that, the two-part catalyst that the present invention is provided exists
150-550 DEG C, high-speed 240000h-1Under the conditions of, with active, the good stability of the conversion of nitrogen oxides higher than 80% with
And in high temperature excellent N2Selectivity;And the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
In addition, the two-part catalyst preparation process that provides of the present invention is simple, mild condition, cost are low, and not only to ring
Border is not polluted, and is also had urea concurrently and is decomposed and eliminate escape NH3Effect.
In addition, catalyst is easy to be coated in ceramic honey comb or metal beehive carrier in the two-part catalyst that the present invention is provided
Deng coated catalysts are obtained on matrix, it is expected to be directly used in diesel car tail gas refining, to meet the more strict discharge mark of state six
It is accurate.
In order to further illustrate the present invention, it is described in detail below by following examples.Following examples of the present invention
Raw materials used is commercial goods.
Embodiment 1
(1) CeO is prepared2-Fe2O3Nano-particle:
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.7422g cerous nitrates and 0.0218g ferric nitrates are added in liquid, stirring is added dropwise to 1.82g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
The CeO2-Fe2O3The TEM photos of nano-particle are as shown in figure 1, as shown in Figure 1, CeO2-Fe2O3Nano-particle
Average grain diameter is 3nm~5nm.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:
7.5mg KBrs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings
0.03M rhodium nitrate solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations
Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying
It is stand-by.
The Rh@CeO2The TEM photos of core-shell structure nanometer particle are as shown in Fig. 2 as shown in Figure 2, Rh@CeO2Nucleocapsid knot
The average grain diameter of structure nano-particle is 50nm or so.
(3) CeO is prepared2-Fe2O3/ZSM-5:
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 250mL, adds 1g molecular sieve ZSM-5 (n
(SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-Fe2O3/ ZSM-5, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/ZSM-5:
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ ZSM-5, i.e.,
Catalyst B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 2
(1) CeO is prepared2-Fe2O3Nano-particle:
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4661g cerous nitrates and 0.0186g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5:Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5:Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 3
(1) CeO is prepared2-Fe2O3Nano-particle:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4687g cerous nitrates and 0.0290g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5:Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5:Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 4
(1) CeO is prepared2-Fe2O3Nano-particle:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4166g cerous nitrates and 0.0580g ferric nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/ZSM-5:Be the same as Example 1.
(4) Rh@CeO are prepared2/ZSM-5:Be the same as Example 1.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 5
(1) CeO is prepared2-Fe2O3Nano-particle:Be the same as Example 4.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 1.
(3) CeO is prepared2-FeO/MCM-56:
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 130mL, adds 0.5g molecular sieves MCM-56
(n(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, empty
1 DEG C/min is warming up to 500 DEG C of holding 2h in gas, obtains CeO2-Fe2O3/ MCM-56, i.e. catalyst A;The CeO2-Fe2O3/
MCM-56 TEM photos are as shown in Figure 3;Finally by catalyst A tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/MCM-56:
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ MCM-56, i.e.,
Catalyst B;The Rh@CeO2/ MCM-56 TEM photos are as shown in Figure 4;Finally by catalyst B tablettings, grinding, screening takes 40-
60 mesh granular sizes are standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 6
(1) CeO is prepared2-Fe2O3Nano-particle:Be the same as Example 4.
(2) Rh@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 1.
(3) CeO is prepared2-Fe2O3/BEA:
Take the CeO of constant volume in step (1)2-Fe2O3Nanoparticle sol solution 130mL, adds 0.51g molecular sieve BEA (n
(SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-Fe2O3/ BEA, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Rh@CeO are prepared2/MCM-56:
Weigh the Rh@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated,
100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Rh@CeO2/ BEA, i.e. catalyst
B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 7
(1) CeO is prepared2- CuO nano-particles:
Weigh 5.4g polyvinylpyrrolidones (PVP-K30) and be dissolved in 360mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.7422g cerous nitrates and 0.0217g copper nitrates are added in liquid, stirring is added dropwise to 1.82g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings
0.03M platinum acid chloride solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations
Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying
It is stand-by.
(3) CeO is prepared2-CuO/ZSM-5:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 250mL, add 1g molecular sieve ZSM-5 (n
(SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/ZSM-5, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/ZSM-5:
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=24), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ ZSM-5, i.e.,
Catalyst B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 8
(1) CeO is prepared2- CuO nano-particles:Be the same as Example 7.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 250mL, add 1g molecular sieve MCM-56 (n
(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56:
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ MCM-56, i.e.,
Catalyst B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 9
(1) CeO is prepared2- CuO nano-particles:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4661g cerous nitrates and 0.0193g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 125.6mL, add 0.5g molecular sieves MCM-56
(n(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, empty
1 DEG C/min is warming up to 500 DEG C of holding 2h in gas, obtains CeO2- CuO/MCM-56, i.e. catalyst A;Finally by catalyst A tablettings,
Grinding, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 10
(1) CeO is prepared2- CuO nano-particles:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4687g cerous nitrates and 0.0290g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 123mL, add 0.5g molecular sieve MCM-56 (n
(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 11
(1) CeO is prepared2- CuO nano-particles:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
0.4166g cerous nitrates and 0.0580g copper nitrates are added in liquid, stirring is added dropwise to 1.22g triethylamines to after being completely dissolved, is stirred for
It is transferred to after 10min in reactor, 180 DEG C of hydro-thermal reaction 24h, it is stand-by to take out constant volume (0.0008g/mL) after having reacted.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-CuO/MCM-56:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 130mL, add 0.5g molecular sieve MCM-56 (n
(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/MCM-56, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 12
(1) CeO is prepared2- CuO nano-particles:Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings
0.03M platinum acid chloride solution 0.417mL, 0.1M cerous nitrate solution 4mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations
Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying
It is stand-by.
(3) CeO is prepared2-CuO/MCM-56:Be the same as Example 10.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 13
(1) CeO is prepared2- CuO nano-particles:Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:
7.5mg KIs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings
0.03M platinum acid chloride solution 0.8.34mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations
Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying
It is stand-by.
(3) CeO is prepared2-CuO/MCM-56:Be the same as Example 10.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 14
(1) CeO is prepared2- CuO nano-particles:Be the same as Example 10.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-CuO/BEA:
Take the CeO of constant volume in step (1)2- CuO nanoparticle sol solution 130mL, add 0.5g molecular sieve BEA (n
(SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2- CuO/BEA, i.e. catalyst A;Finally by catalyst A tablettings, grinding,
Screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/BEA:
Weigh the Pt@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated,
100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pt@CeO2/ BEA, i.e. catalyst
B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 15
(1) CeO is prepared2-Fe2O3Nano-particle:Be the same as Example 4.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle:
7.5mg KBrs are added in the beaker equipped with 20mL deionized waters, are sequentially added after 60 DEG C of stirring in water bath dissolvings
0.03M palladium nitrate solution 0.417mL, 0.1M cerous nitrate solution 2mL, are added dropwise to the water-reducible 0.05mL of 5mL deionizations
Mass concentration be 25% ammoniacal liquor, finally 60 DEG C stirring keep 1h, centrifugation precipitated, washing repeatedly after 100 DEG C drying
It is stand-by.
(3) CeO is prepared2-Fe2O3/ZSM-5:Be the same as Example 4.
(4) Pd@CeO are prepared2/ZSM-5:
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves ZSM-5 (n (SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ ZSM-5, i.e.,
Catalyst B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 16
(1) CeO is prepared2-Fe2O3Nano-particle:Be the same as Example 15.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 15.
(3) CeO is prepared2-Fe2O3/MCM-56:Be the same as Example 5.
(4) Pd@CeO are prepared2/MCM-56:
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves MCM-56 (n (SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are steamed
Dry, 100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ MCM-56, i.e.,
Catalyst B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 17
(1) CeO is prepared2-Fe2O3Nano-particle:Be the same as Example 15.
(2) Pd@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 15.
(3) CeO is prepared2-Fe2O3/BEA:Be the same as Example 6.
(4) Pd@CeO are prepared2/BEA:
Weigh the Pd@CeO in 0.2g steps (2)2Core-shell structure nanometer particle is scattered in 20mL deionized waters, plus
Enter 1g molecular sieves BEA (n (SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 80 DEG C of heating stirrings are evaporated,
100 DEG C of gained sample is dried overnight, and 1 DEG C/min is warming up to 500 DEG C of holding 2h in air, obtains Pd@CeO2/ BEA, i.e. catalyst
B;Finally by catalyst B tablettings, grinding, screening takes 40-60 mesh granular sizes standby.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 18
(1) CeO is prepared2-MnO2Nano-particle:
Weigh 3.6g polyvinylpyrrolidones (PVP-K30) and be dissolved in 240mL absolute ethyl alcohols;Treat that PVP is completely dissolved backward molten
It is 50% manganese nitrate solution that 0.4687g cerous nitrates and 0.04294g mass fractions are added in liquid, and stirring is dripped to after being completely dissolved
1.22g triethylamines are added, are stirred for being transferred in reactor after 10min, 180 DEG C of hydro-thermal reaction 24h, constant volume is taken out after having reacted
(0.0008g/mL) is stand-by.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-MnO2/ZSM-5:
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve ZSM-5 (n
(SiO2)/n(Al2O34h is stirred after)=12), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ ZSM-5, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/ZSM-5:Be the same as Example 7.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 19
(1) CeO is prepared2-MnO2Nano-particle:Be the same as Example 18.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-MnO2/MCM-56:
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve MCM-56 (n
(SiO2)/n(Al2O34h is stirred after)=25), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ MCM-56, i.e. catalyst A;Finally by catalyst A tablettings, grind
Mill, screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/MCM-56:Be the same as Example 8.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 20
(1) CeO is prepared2-MnO2Nano-particle:Be the same as Example 18.
(2) Pt@CeO are prepared2Core-shell structure nanometer particle:Be the same as Example 7.
(3) CeO is prepared2-MnO2/BEA:
Take the CeO of constant volume in step (1)2-MnO2Nanoparticle sol solution 130mL, adds 0.5g molecular sieve BEA (n
(SiO2)/n(Al2O34h is stirred after)=19), ultrasonic 0.5h makes it uniform, and 100 DEG C of stirrings are evaporated, and 100 DEG C are dried overnight, air
In 1 DEG C/min be warming up to 500 DEG C holding 2h, obtain CeO2-MnO2/ BEA, i.e. catalyst A;Finally by catalyst A tablettings, grinding,
Screening takes 40-60 mesh granular sizes standby.
(4) Pt@CeO are prepared2/BEA:Be the same as Example 14.
(5) 25mg catalyst A is arranged on to the inlet end of tubular fixed-bed reactor, 25mg catalyst B is arranged on tubular type
The outlet side of fixed bed reactors, obtains the two-part catalyst for exhaust gas from diesel vehicle processing.
Embodiment 21
(1) to mix to slurries uniform with 30% Ludox by the catalyst A for preparing embodiment 8;
(2) to mix to slurries uniform with 30% Ludox by the catalyst B for preparing embodiment 8;
(2) a diameter of 17mm is taken, calcining 2h goes the removal of impurity to length at 700 DEG C in atmosphere for 17mm cordierite, obtains
Cordierite honeycomb ceramic matrix;
(3) cordierite honeycomb ceramic matrix is immersed in the homogenate in step (1) and step (2) respectively, taken after 10min
Go out, dried in 100 DEG C of baking ovens and be calcined 2h at 10h, 500 DEG C of Muffle furnace, respectively obtain the ceramic honeycomb catalyst A and coating of coating
Ceramic honeycomb catalyst B;
(4) it is 0.5 that will take mass ratio:The ceramic honeycomb catalyst A of the 1 coating and ceramic honeycomb catalyst B of coating, its
In, the ceramic honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the ceramic honeycomb catalyst B of coating
The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
Embodiment 22
(1) to mix to slurries uniform with 25% Alumina gel by the catalyst A for preparing embodiment 8;
(2) to mix to slurries uniform with 25% Alumina gel by the catalyst B for preparing embodiment 8;
(2) a diameter of 17mm is taken, calcining 2h goes the removal of impurity to length at 700 DEG C in atmosphere for 17mm cordierite, obtains
Cordierite honeycomb ceramic matrix;
(3) cordierite honeycomb ceramic matrix is immersed in the homogenate in step (1) and step (2) respectively, taken after 10min
Go out, dried in 100 DEG C of baking ovens and be calcined 2h at 10h, 500 DEG C of Muffle furnace, respectively obtain the ceramic honeycomb catalyst A and coating of coating
Ceramic honeycomb catalyst B;
(4) it is 1 that will take mass ratio:The ceramic honeycomb catalyst A of the 1 coating and ceramic honeycomb catalyst B of coating, its
In, the ceramic honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the ceramic honeycomb catalyst B of coating
The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
Embodiment 23
(1) to mix to slurries uniform with 30% Ludox by the catalyst A for preparing embodiment 8;
(2) to mix to slurries uniform with 30% Ludox by the catalyst B for preparing embodiment 8;
(2) a diameter of 17mm is taken, length is that 17mm metal beehive carriers are cleaned in supersonic wave cleaning machine, in horse after drying
Not 900 DEG C of calcining 2h go the removal of impurity in stove, obtain metal beehive carrier;
(3) metal beehive carrier is immersed in respectively in the homogenate in step (1) and step (2), taken out after 10min, 100
Dried in DEG C baking oven at 10h, 500 DEG C of Muffle furnace and be calcined 2h, respectively obtain the metal honeycomb catalyst A of coating and the metal of coating
Honeycomb catalyst B;
(4) it is 2 that will take mass ratio:The metal honeycomb catalyst A of the 1 coating and metal honeycomb catalyst B of coating, its
In, the metal honeycomb catalyst A of coating is arranged on the inlet end of tubular fixed-bed reactor, the metal honeycomb catalyst B of coating
The outlet side of tubular fixed-bed reactor is arranged on, the two-part catalyst for exhaust gas from diesel vehicle processing is obtained.
The active of two-part catalyst nitrogen oxides reduction of the offer of the embodiment of the present invention 1~23 is detected,
Experiment condition is as follows:
Reacting gas is NO:500ppm, NH3:500ppm, O2:5%, Ar are Balance Air;
Total gas flow rate is 100mL/min, and reaction velocity (GHSV) is 240000mL/g/h;
Reaction temperature interval is from 150 DEG C to 550 DEG C;
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 1.
The activity for the two-part catalyst nitrogen oxides reduction that the embodiment of the present invention 1~23 of table 1 is provided
Data
As shown in Table 1, the two-part catalyst that the embodiment of the present invention 1~20 is provided is in 150-550 DEG C, high-speed
240000h-1Under the conditions of, it is excellent with active, the good stability of the conversion of nitrogen oxides higher than 80% and in high temperature
N2Selectivity.
Comparative example 1
The catalyst B that 25mg embodiments 8 are prepared is arranged on the inlet end of tubular fixed-bed reactor, and 25mg is implemented
The catalyst A that example 8 is prepared is arranged on the outlet side of tubular fixed-bed reactor, obtains two for exhaust gas from diesel vehicle processing
Segmentation catalyst.
Comparative example 2
The catalyst A mixing that catalyst B and the 25mg embodiment 8 that 25mg embodiments 8 are prepared is prepared, flat
Two parts of inlet ends for being separately positioned on tubular fixed-bed reactor and outlet side are divided into, is obtained for exhaust gas from diesel vehicle processing
Two-part catalyst.
The activity of the two-part catalyst nitrogen oxides reduction provided under the same conditions comparative example 1~2 is carried out
Detection, testing result is shown in Table 2.
The activity data for the two-part catalyst nitrogen oxides reduction that the comparative example 1~2 of table 2 is provided
As shown in Table 2, catalytic performance is drastically reduced after 300 DEG C of the two-part catalyst that comparative example 1~2 is provided.
Comparative example 3
The catalyst A that 50mg embodiments 10 are prepared is divided into two parts and is separately positioned on tubular fixed-bed reactor
Inlet end and outlet side, obtain for exhaust gas from diesel vehicle processing two-part catalyst.
Comparative example 4
The catalyst B that 50mg embodiments 10 are prepared is divided into two parts and is separately positioned on tubular fixed-bed reactor
Inlet end and outlet side, obtain for exhaust gas from diesel vehicle processing two-part catalyst.
The activity of the two-part catalyst nitrogen oxides reduction provided under the same conditions comparative example 3~4 is carried out
Detection, and contrasted with embodiment 10, as a result as shown in Figure 5.As shown in Figure 5, the two-part that the embodiment of the present invention 10 is provided
Catalyst compares comparative example 3~4, has high eradicating efficacy and selectivity to nitrogen oxides in wide temperature range.
The performance that the two-part catalyst that the embodiment of the present invention 9, comparative example 1~2 are provided removes soot particulate matter is examined
Survey, experiment condition is as follows:
0.0028g carbon blacks are mixed with the catalyst of tubular fixed-bed reactor inlet end;Reacting gas is NO:
500ppm, O2:5%, Ar are Balance Air;
Total gas flow rate is 40mL/min, and reaction velocity (GHSV) is 96000mL/g/h;
Reaction temperature interval is from 150 DEG C to 700 DEG C;
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 3.
The two-part catalyst that the embodiment 9 of table 3, comparative example 1~2 are provided removes the performance number of soot particulate matter
According to
Group | Ts(℃) | Tm(℃) | Te(℃) |
Embodiment 9 | 200 | 476 | 563 |
Comparative example 1 | 400 | 605 | 668 |
Comparative example 2 | 450 | 610 | 673 |
In table 3, Ts is that carbon black is converted into CO2Initial temperature, Tm be carbon black be converted into CO2Peak temperature, Te is carbon black
It is converted into CO2End temp.As shown in Table 3, the two-part catalyst that the embodiment of the present invention 9 is provided has compared to comparative example 1~2
There are the performance for preferably removing soot particulate matter, the soot particulate matter during tail gas can be eliminated at 450 DEG C or so.
NH is aoxidized to the two-part catalyst that the embodiment of the present invention 7 is provided3Performance detected that experiment condition is as follows:
Reacting gas is NH3:Concentration is respectively 1000ppm, 500ppm, 200ppm, 100ppm, O2:5%, Ar are balance
Gas, total gas flow rate is 40ml/min, and reaction velocity (GHSV) is 96000mL/g/h;
Reaction temperature interval is from 150 DEG C to 550 DEG C;
Gas uses Mass Spectrometer Method.
Testing result is shown in Table 4.
The two-part catalyst that the embodiment 7 of table 4 is provided is in different NH3NH is aoxidized under concentration3Performance data
As shown in Table 4, the two-part catalyst that the embodiment of the present invention 7 is provided, which has, eliminates escape NH3Effect.
The described above of the disclosed embodiments, enables professional and technical personnel in the field to realize or using the present invention.It is right
A variety of modifications of these embodiments will be apparent for those skilled in the art, and as defined herein one
As principle can realize in other embodiments without departing from the spirit or scope of the present invention.Therefore, the present invention will
It will not be intended to be limited to the embodiments shown herein, and be to fit to consistent with principles disclosed herein and features of novelty
Most wide scope.
Claims (10)
1. a kind of two-part catalyst handled for exhaust gas from diesel vehicle, including:The catalyst A of inlet end and the catalysis of outlet side
Agent B;
The catalyst A has formula shown in formula (I):
CeO2- X/ molecular sieve formula (I)s;
Wherein, X is selected from CuO, Fe2O3Or MnO2;
The catalyst B has formula shown in formula (II):
M@CeO2/ molecular sieve formula (II);
Wherein, M is selected from Rh, Pt or Pd.
2. two-part catalyst according to claim 1, it is characterised in that in the formula (I), CeO2Mol ratio with X is
(3~19):1.
3. two-part catalyst according to claim 1, it is characterised in that in the formula (I), the molecular sieve is selected from
ZSM-5, MCM-56 or BEA;
The CeO2- X and the mass ratio of molecular sieve are 1:(1~10).
4. two-part catalyst according to claim 1, it is characterised in that in the formula (II), M and CeO2Mol ratio
For 1:(8~32).
5. two-part catalyst according to claim 1, it is characterised in that in the formula (II), the molecular sieve is selected from
ZSM-5, MCM-56 or BEA;
The M@CeO2Mass ratio with molecular sieve is 1:(1~10).
6. two-part catalyst according to claim 1, it is characterised in that the mass ratio of the catalyst A and catalyst B
For (0.5~3):1.
7. a kind of preparation method of the two-part catalyst described in any one of claim 1~6, comprises the following steps:
A) cerium source, X ' sources and triethylamine are subjected to hydro-thermal reaction in the first solvent, obtain CeO2- X nano particle;X ' the sources
Selected from copper source, source of iron or manganese source;
B) M ' sources, cerium source and ammoniacal liquor are subjected to coprecipitation reaction in the second solvent, obtain M@CeO2Core-shell structure nanometer particle;
M ' the sources are selected from rhodium source, platinum source or palladium source;
C) CeO for obtaining step a)2The M@CeO that-X nano particle and step b) are obtained2Core-shell structure nanometer particle is respectively with dividing
Son sieve is loaded, and respectively obtains catalyst A and catalyst B;
D) catalyst A is arranged on inlet end, the outlet side that catalyst B is arranged on obtains two for exhaust gas from diesel vehicle processing
Segmentation catalyst;
The step a) and b) no order limitation.
8. preparation method according to claim 7, it is characterised in that the temperature of hydro-thermal reaction described in step a) is 160
DEG C~200 DEG C, the time is 20h~30h.
9. preparation method according to claim 7, it is characterised in that the temperature 50 C of coprecipitation reaction described in step b)
~70 DEG C, the time is 0.5h~1.5h.
10. preparation method according to claim 7, it is characterised in that CeO described in step c)2- X nano particle is averaged
Particle diameter is 3nm~5nm;The M@CeO2The average grain diameter of core-shell structure nanometer particle is 45nm~55nm.
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