CN106238037A - One possesses high storage NH3sCR catalyst of ability and preparation method thereof - Google Patents
One possesses high storage NH3sCR catalyst of ability and preparation method thereof Download PDFInfo
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- CN106238037A CN106238037A CN201610619400.XA CN201610619400A CN106238037A CN 106238037 A CN106238037 A CN 106238037A CN 201610619400 A CN201610619400 A CN 201610619400A CN 106238037 A CN106238037 A CN 106238037A
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- undercoating
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 238000002360 preparation method Methods 0.000 title claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 114
- 239000011248 coating agent Substances 0.000 claims abstract description 112
- 239000002131 composite material Substances 0.000 claims abstract description 78
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 41
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000919 ceramic Substances 0.000 claims abstract description 35
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 24
- 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 abstract description 24
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical group [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 claims abstract description 23
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical group [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 13
- 239000000725 suspension Substances 0.000 claims description 36
- 239000000843 powder Substances 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 20
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 17
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 16
- 229920000053 polysorbate 80 Polymers 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- 238000002390 rotary evaporation Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 12
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 claims description 12
- 229910052720 vanadium Inorganic materials 0.000 claims description 11
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims description 10
- 239000004408 titanium dioxide Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910001868 water Inorganic materials 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 150000002927 oxygen compounds Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000006255 coating slurry Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 36
- 238000012360 testing method Methods 0.000 description 26
- 239000004202 carbamide Substances 0.000 description 18
- 235000013877 carbamide Nutrition 0.000 description 18
- 239000000306 component Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 7
- 239000007921 spray Substances 0.000 description 6
- 239000003292 glue Substances 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000001186 cumulative effect Effects 0.000 description 4
- 238000002347 injection Methods 0.000 description 4
- 239000007924 injection Substances 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 101100203596 Caenorhabditis elegans sol-1 gene Proteins 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 239000001913 cellulose Substances 0.000 description 2
- 238000005538 encapsulation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 210000001367 artery Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
- 210000003462 vein Anatomy 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0205—Impregnation in several steps
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0211—Impregnation using a colloidal suspension
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to one and possess high storage NH3SCR catalyst of ability and preparation method thereof, catalyst uses cordierite honeycomb ceramic to be carrier, is coated with undercoating and external coating on the duct inwall of carrier, and undercoating component is silicon-titanium composite oxide or sial composite oxides；External coating component is barium oxide and the composite oxide supported material of titanium tungsten, and undercoating, external coating are all with Ludox as binding agent, and according in interior rear outer sequential applications to cordierite honeycomb ceramic carrier, coated weight is respectively 80 ~ 100 g/L and 120 ~ 150 g/L.Preparation method of the present invention is simple, it is easy to operation, and the undercoating using silicon-titanium composite oxide or sial composite oxides to make catalyst has higher NH3Storage performance, it is possible to realize low NH in exhaust environment3Reducing agent NH needed for external coating reaction under supply condition3Sufficient input, and then improve the SCR catalyst NOx conversion efficiency in WHTC cold-start phase, also be able to reduce the NOx emission under low row's temperature environment in real vehicle application simultaneously.
Description
Technical field
The present invention relates to one and possess high storage NH3SCR catalyst of ability and preparation method thereof, belongs to catalyst and prepares skill
Art field.
Background technology
Carbamide-SCR (Urea-SCR, selective catalytic reduction) is to have at present most
One of diesel engine vent gas NOx treatment technology of effect.This technology uses the aqueous solution of urea of 32.5% to be reducing agent, at tail gas high temperature
The lower urea liquid hydrolysis of effect generates NH3, NH under the effect of catalyst3Redox reaction is there is with the NOx in tail gas,
Become harmless N throughout one's life2And H2O discharges, it is achieved effective purification of NOx.
Due to carbamide it is generally required to complete hydrolysis NH3 could be generated 200 DEG C of temperatures above, therefore, urinate in SCR system
The spray temperature that rises of cellulose solution is also normally placed in more than 200 DEG C.But in the state V stage, " city vehicle diesel engine exhaust pollutes
Thing emission limit and measuring method (WHTC operating condition method) " regulation implement the low temperature NOx conversion efficiency of SCR system is proposed more
High requirement.In WHTC cold start-up test loop, the testing time electromotor row's temperature that there are about 40% is less than 200 DEG C, i.e. less than urine
Temperature is sprayed in rising of cellulose solution, and carbamide does not sprays；And have testing time electromotor row's temperature of about 75% to be less than 300 DEG C, it is unfavorable for
The hydrolysis of carbamide.Above-mentioned factor can cause reducing agent NH required in SCR reaction3Total amount reduces, and then have impact on SCR system
The system transformation efficiency to NOx.
For the problem that WHTC cold start-up electromotor row's temperature is too low, the most conventional solution has following two: (1) drops
Low SCR system carbamide plays spray temperature.For reply cold start-up NOx process, it will usually urea liquid is risen spray temperature and falls to approximately 180
DEG C, increase carbamide injecting time in WHTC test loop as far as possible.But cryogenic spray carbamide can cause urea crystals problem, and
Urea hydrolyzation is the highest, NOx conversion efficiency is promoted effect limited；
(2) gas exhaust piping and the Insulation of encapsulation casing.SCR catalyst encapsulation casing uses double-layer barrel evacuation to set
Meter, to promote heat insulation effect, but can cause being substantially increased of packaging cost；Gas exhaust piping parcel heat-preservation cotton is damaged to reduce temperature
Lose, but effect is limited.
SCR catalyst is as the core component of SCR system, and it is responsible for catalysis NOx and NH3The function of reaction, due to SCR
Course of reaction is NH3First adsorb on surface, catalyst activity position, with NOx, redox reaction occurs the most again.Therefore, catalysis
Agent itself also has certain NH3Storage capacity.
Research shows at state IV/V stage wide variety of business vanadia-based SCR catalysts, and it is at the NH of 200 DEG C3Amount of storage
Up to about 0.4g/L；And at Europe VI stage wide variety of copper zeolite catalyst, it is at the NH of 200 DEG C3Amount of storage is up to about
2.0g/L.But molecular sieve catalyst price is high, and Sulfur tolerance is poor, is not suitable for the application in state V stage；And current catalytic component based on vanadium
NH3 amount of storage is the most on the low side, for without reducing agent NH3It is limited that conversion rate of NOx in the case of addition promotes effect.Therefore, if
Promote the NH of catalytic component based on vanadium3Storage capacity, then can make catalyst in the case of not having carbamide injection, utilize and itself store
A large amount of NH3React with the NOx in motor exhaust, reach to significantly reduce the effect of WHTC cold start-up test NOx emission value
Really.Meanwhile, in real vehicle is applied, high NH3The catalyst of storage capacity also can be greatly reduced electromotor startup stage and carbamide
Spraying system, less than tail gas NOx emission during normal working temperature state, reduces atmospheric pollution.
Summary of the invention
The invention aims to solve existing vanadia-based SCR catalysts in WHTC test cold-start phase due to NH3Deposit
Reserves are on the low side and cause NOxThe problem that transformation efficiency is on the low side, it is provided that what preparation method was the most easily operated possesses high storage NH3Energy
SCR catalyst of power and preparation method thereof.
The present invention adopts the following technical scheme that a kind of SCR catalyst possessing high storage NH3 ability, makes pottery with cordierite honeycomb
Porcelain is carrier, is coated with catalyst coatings on the duct inwall of carrier, and described catalyst coat includes being close to carrier duct inwall
Undercoating, the external coating on undercoating upper strata, described internally coated coated weight is 80～100g/L, and described undercoating component is silicon
Titanium composite oxide or sial composite oxides；The coated weight of described external coating is 120～150g/L, and external coating component is vanadium oxygen
Compound and the composite oxide supported material of titanium tungsten, described undercoating and external coating use binding agent to be attached on carrier.
Further, in described internally coated component silicon-titanium composite oxide, silicon dioxide and the mass ratio of titanium dioxide
It is 0.67～1.5:1.
Further, in described internally coated component sial composite oxides, silicon dioxide and the quality of aluminium sesquioxide
Ratio is 0.67～1.5:1.
Further, in described external coating the mass ratio of barium oxide and the composite oxide supported material of titanium tungsten be 0.03～
0.06:1。
Further, in described external coating in the composite oxide supported material of titanium tungsten, Tungstic anhydride. and the matter of titanium dioxide
Amount ratio is 0.05～0.15:1.
Further, described binding agent is silicon oxide, and described binding agent and undercoating, the mass ratio of external coating are 0.1
～0.15:1.
Possess the preparation method of the SCR catalyst of high storage NH3 ability, comprise the steps:
(1) preparation of undercoating silicon-titanium composite oxide: by butyl titanate, triethanolamine and Ludox in mass ratio 1:
1:0.52～1.17 mixing, adds said mixture ethanol water and forms mixed solution, be subsequently adding Tween 80, will mixing
Liquid carries out rotary evaporation, and evaporating water obtains pressed powder, finally pressed powder roasting is obtained silicon-titanium composite oxide；
(2) preparation of undercoating sial composite oxides: Ludox and Alumina gel in mass ratio 0.45～1:1 are mixed,
The mass fraction of Alumina gel is 20-25%, said mixture adds ethanol water and forms mixed solution, be subsequently adding tween
80, mixed liquor is carried out rotary evaporation evaporating water and obtains pressed powder, finally pressed powder roasting is obtained sial composite oxygen
Compound；
(3) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate
1:1:0.014 in mass ratio～0.043 mixing, adds said mixture ethanol water and forms mixed solution, be subsequently adding
Tween 80, carries out rotary evaporation evaporating water by mixed liquor and obtains pressed powder, pressed powder roasting finally obtains titanium tungsten multiple
Close oxide carried material；
(4) preparation of undercoating serosity: sial prepared by silicon-titanium composite oxide step (1) prepared or step (2)
Composite oxides mix with Ludox in mass ratio 2～3:1, and add deionized water, form suspension, and regulation deionized water adds
Entering amount, making solid matter mass mark in suspension is 30～40%, to suspension ball milling, controls granularity D90 and is less than 5um,
Obtain undercoating serosity；
(5) preparation of external coating serosity: the composite oxide supported material of titanium tungsten, vanadium source and the silicon step (3) prepared are molten
Glue 1:0.038～0.077:0.11 in mass ratio mixes, and adds deionized water, forms suspension, and regulation deionized water adds
Amount, making the mass fraction of solid matter in suspension is 30～40%, to suspension ball milling, controls granularity D90 and is less than 5um,
Obtain external coating serosity；
(6) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (4)
In, stopping 5～20s, extract out with the speed of 50～100mm/s subsequently, the pressure-air with 0.4～0.6MPa is many by carrier surface
Remaining serosity blows away, and coated honeycomb ceramic carrier is placed at 100～120 DEG C drying 1～3h, then at 400～500 DEG C
Roasting 2～4h, repeated several times reaches 80～100g/L to the undercoating amount being coated on honeycomb substrate；
(7) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (6), be soaked in
In serosity prepared by step (5), stop 5～20s, extract out, with the height of 0.4～0.6MPa with the speed of 50～100mm/s subsequently
Pressure air serosity unnecessary for carrier surface is blown away, coated honeycomb ceramic carrier is placed at 100～120 DEG C drying 1～
3h, then in 400～500 DEG C of roastings 2～4h, repeated several times to the external coating amount being coated on honeycomb substrate reach 120～
150g/L, completes the preparation of catalyst.
Further, adding mass fraction in the mixture in described step (1), step (2) and step (3) is 50%
Ethanol water forms mixed liquor, and the addition of ethanol water and the mass ratio of mixture are 1:1, are subsequently adding mixed liquor total
Quality 1～the Tween 80 of 2%, stir mixed liquor 6～10h under rpm/mim rotating speed, and rotated at 60～80 DEG C by mixed liquor
Evaporation 4～8h, is evaporated moisture and obtains pressed powder, gained pressed powder is dried at 100～120 DEG C 2～3h, finally exists
Roasting 3～6h at 400～500 DEG C.
Further, the vanadium source in described step (5) is ammonium metavanadate.
Further, in described step (1), step (2), step (4) and step (5), the mass fraction of Ludox is
25-35%.
Preparation method of the present invention is simple, it is easy to operation, uses silicon-titanium composite oxide or sial composite oxides to make and urge
The undercoating of agent has higher NH3Storage performance, it is possible to realize low NH in exhaust environment3To external coating under supply condition
The required reducing agent NH of reaction3Sufficient input, and then improve the SCR catalyst NOx conversion efficiency in WHTC cold-start phase, with
Time also be able to reduce the NOx emission under low row's temperature environment in real vehicle application.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is further illustrated.
Embodiment one:
Catalyst with the cordierite honeycomb ceramic of 300 mesh as carrier, a size of diameter 190.5mm* height 101.6mm cylinder
Body 2 pieces (each 1 piece of forward and backward level), cumulative volume is 5.8L.Cordierite honeycomb ceramic carrier duct inwall is coated with catalyst be coated with
Layer.Catalyst coat comprises undercoating and external coating: undercoating is for being close to carrier duct inner wall section, and component is silicon titanium composite oxygen
Compound, undercoating coated weight is 80g/L；External coating is for being coated in the upper part of undercoating, and it comprises barium oxide active component
And the composite oxide supported material of titanium tungsten, the coated weight of external coating is 120g/L.Undercoating, external coating are all with silicon oxide for bonding
Agent strengthens the adhesive force between coating and carrier.
In silicon-titanium composite oxide in undercoating, silicon dioxide is 0.67:1 with the mass ratio of titanium dioxide；External coating
In component, barium oxide is 0.03:1 with the mass ratio of the composite oxide supported material of titanium tungsten；Titanium tungsten composite oxygen in external coating
In compound support materials, Tungstic anhydride. is 0.05:1 with the mass ratio of titanium dioxide；In inside and outside coating, binding agent is siliceous
Amount is 0.1:1 with coating quality ratio.
Catalyst preparation step is as follows:
(1) preparation of undercoating silicon-titanium composite oxide: by butyl titanate, triethanolamine and the silicon of 30% mass fraction
Colloidal sol 1:1:0.52 in mass ratio mixes, by said mixture and ethanol water 1:1 in mass ratio that mass fraction is 50%
It is mixed to form mixed liquor, adds the Tween 80 of the most above-mentioned mixed liquor gross mass 1%, then above-mentioned mixed with the stirring of 300rpm rotating speed
Close liquid 6h, then by mixed liquor rotary evaporation 4h at 60 DEG C, moisture is evaporated and obtains pressed powder, gained pressed powder is existed
Drying 2h at 100 DEG C, finally roasting 3h at 400 DEG C, obtains silicon-titanium composite oxide；
(2) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate
1:1:0.014 in mass ratio mixes, and said mixture and the ethanol water 1:1 in mass ratio that mass fraction is 50% is mixed
Form mixed liquor, add the Tween 80 of the most above-mentioned mixed liquor gross mass 1%, then above-mentioned mixed with the stirring of 300rpm/mim rotating speed
Close liquid 6h, then by mixed liquor rotary evaporation 4h at 60 DEG C, moisture is evaporated and obtains pressed powder, gained pressed powder is existed
Dry 2h, finally roasting 3h at 400 DEG C at 100 DEG C, obtain the composite oxide supported material of titanium tungsten；
(3) preparation of undercoating serosity: silicon-titanium composite oxide step (1) prepared and the silicon of 30% mass fraction are molten
Glue 3:1 in mass ratio mixes, and adds deionized water, forms suspension, regulates deionized water addition, makes solid in suspension
Material mass mark is 30%, to suspension ball milling, controls granularity D90 and is less than 5um, obtain undercoating coating serosity；
(4) preparation of external coating serosity: the composite oxide supported material of external coating titanium tungsten prepared by step (2), inclined vanadium
The Ludox 1:0.038:0.11 in mass ratio mixing of acid ammonium and 30% mass fraction, and add deionized water, form suspension,
Regulation deionized water addition, making solid matter mass mark in suspension is 30%, to suspension ball milling, controls granularity
D90 is less than 5um, obtains external coating coating serosity；
(5) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (3)
In, stop 5s, extract out with the speed of 50mm/s subsequently, with the pressure-air of 0.4MPa, serosity unnecessary for carrier surface is blown away,
Coated honeycomb ceramic carrier is placed at 100 DEG C drying 1h, and then at 400 DEG C of roasting 2h, repeated several times is to being coated to
Undercoating amount on honeycomb substrate reaches 80g/L；
(6) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (5), be soaked in
In serosity prepared by step (4), stop 5s, extract out, with the pressure-air of 0.4MPa by carrier table with the speed of 50mm/s subsequently
The unnecessary serosity in face blows away, and coated honeycomb ceramic carrier is placed at 100 DEG C drying 1h, then at 400 DEG C of roasting 2h, weight
Reach 120g/L to the external coating coated weight being coated on honeycomb substrate several times again, complete catalyst and prepare.
Embodiment two:
Catalyst with the cordierite honeycomb ceramic of 300 mesh as carrier, a size of diameter 190.5mm* height 101.6mm cylinder
Body 2 pieces (each 1 piece of forward and backward level), cumulative volume is 5.8L.Cordierite honeycomb ceramic carrier duct inwall is coated with catalyst be coated with
Layer.Catalyst coat comprises undercoating and external coating: undercoating is for being close to carrier duct inner wall section, and component is silicon titanium composite oxygen
Compound, internally coated coated weight is 100g/L；External coating is for being coated in the upper part of undercoating, and it comprises barium oxide and titanium tungsten
Composite oxide supported material, the coated weight of external coating is 150g/L.Inside and outside coating all strengthens coating with silicon oxide for binding agent
And the adhesive force between carrier.
In silicon-titanium composite oxide in undercoating, silicon dioxide is 1.5:1 with the mass ratio of titanium dioxide；External coating group
In Fen, barium oxide is 0.06:1 with the mass ratio of the composite oxide supported material of titanium tungsten；Titanium tungsten combined oxidation in external coating
In thing support materials, Tungstic anhydride. is 0.15:1 with the mass ratio of titanium dioxide；In inside and outside coating, binding agent silicon dioxide quality
It is 0.1:1 with coating quality ratio.
Catalyst preparation step is as follows:
(1) preparation of undercoating silicon-titanium composite oxide: by butyl titanate, triethanolamine and the silicon of 30% mass fraction
Colloidal sol 1:1:1.17 in mass ratio mixes, by said mixture and ethanol water 1:1 in mass ratio that mass fraction is 50%
It is mixed to form mixed liquor, adds the Tween 80 of the most above-mentioned mixed liquor gross mass 2%, then above-mentioned mixed with the stirring of 500rpm rotating speed
Close liquid 10h, then by mixed liquor rotary evaporation 8h at 80 DEG C, moisture is evaporated and obtains pressed powder, by gained pressed powder
Drying 3h at 120 DEG C, finally roasting 6h at 500 DEG C, obtains silicon-titanium composite oxide；
(2) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate
1:1:0.043 in mass ratio mixes, and said mixture and the ethanol water 1:1 in mass ratio that mass fraction is 50% is mixed
Form mixed liquor, add the Tween 80 of the most above-mentioned mixed liquor gross mass 2%, then above-mentioned mixed with the stirring of 500rpm/mim rotating speed
Close liquid 10h, then by mixed liquor rotary evaporation 8h at 80 DEG C, moisture is evaporated and obtains pressed powder, by gained pressed powder
At 120 DEG C, dry 3h, finally roasting 6h at 500 DEG C, obtain the composite oxide supported material of titanium tungsten；
(3) preparation of undercoating serosity: silicon-titanium composite oxide step (1) prepared and the silicon of 30% mass fraction are molten
Glue 3:1 in mass ratio mixes, and adds deionized water, forms suspension, regulates deionized water addition, makes solid in suspension
Material mass mark is 40%, to suspension ball milling, controls granularity D90 and is less than 5um, obtain undercoating coating serosity；
(4) preparation of external coating serosity: the composite oxide supported material of external coating titanium tungsten prepared by step (2), inclined vanadium
The Ludox 1:0.077:0.11 in mass ratio mixing of acid ammonium and 30% mass fraction, and add deionized water, form suspension,
Regulation deionized water addition, making solid matter mass mark in suspension is 40%, to suspension ball milling, controls granularity
D90 is less than 5um, obtains external coating coating serosity；
(5) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (3)
In, stop 20s, extract out with the speed of 100mm/s subsequently, with the pressure-air of 0.6MPa, serosity unnecessary for carrier surface is blown
Walking, coated honeycomb ceramic carrier is placed at 120 DEG C drying 3h, then at 500 DEG C of roasting 4h, repeated several times is to coating
Undercoating amount on honeycomb substrate reaches 100g/L；
(6) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (5), be soaked in
In serosity prepared by step (4), stop 20s, extract out, with the pressure-air of 0.6MPa by carrier with the speed of 100mm/s subsequently
The serosity of excess surface blows away, and coated honeycomb ceramic carrier is placed at 120 DEG C drying 3h, then at 500 DEG C of roasting 4h,
Repeated several times reaches 150g/L to the external coating amount being coated on honeycomb substrate, completes catalyst and prepares.
Embodiment three:
Catalyst with the cordierite honeycomb ceramic of 300 mesh as carrier, a size of diameter 190.5mm* height 101.6mm cylinder
Body 2 pieces (each 1 piece of forward and backward level), cumulative volume is 5.8L.Cordierite honeycomb ceramic carrier duct inwall is coated with catalyst
Coating.Catalyst coat comprises undercoating and external coating: undercoating is for being close to carrier duct inner wall section, and its component is that sial is multiple
Closing oxide, internally coated coated weight is 82g/L；External coating is for being coated in the upper part of undercoating, and it comprises barium oxide and lives
Property component and the composite oxide supported material of titanium tungsten, the coated weight of external coating is 125g/L.Inside and outside coating is all viscous with silicon oxide
Knot agent strengthens the adhesive force between coating and carrier.
In sial composite oxides in undercoating, silicon dioxide is 0.67:1 with the mass ratio of aluminium sesquioxide；Outer painting
In layer component, barium oxide is 0.03:1 with the mass ratio of the composite oxide supported material of titanium tungsten；Titanium tungsten in external coating is combined
In oxide carried material, Tungstic anhydride. is 0.05:1 with the mass ratio of titanium dioxide；In inside and outside coating, binding agent silicon dioxide
Quality is 0.1:1 with coating quality ratio.
Catalyst preparation step is as follows:
(1) preparation of undercoating sial composite oxides: by the Ludox of 30% mass fraction and 20% mass fraction
Alumina gel 0.45:1 in mass ratio mixes, by said mixture and ethanol water 1:1 in mass ratio that mass fraction is 50%
It is mixed to form mixed liquor, adds the Tween 80 of the most above-mentioned mixed liquor gross mass 1%, then with in the stirring of 300rpm/mim rotating speed
State mixed liquor 6h, then by mixed liquor rotary evaporation 4h at 60 DEG C, moisture is evaporated and obtains pressed powder, by gained solid powder
2h is dried at end at 100 DEG C, and finally roasting 3h at 400 DEG C, obtains sial composite oxides；
(2) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate
1:1:0.014 in mass ratio mixes, and said mixture and the ethanol water 1:1 in mass ratio that mass fraction is 50% is mixed
Form mixed liquor, add the Tween 80 of the most above-mentioned mixed liquor gross mass 1%, then stir above-mentioned mixed liquor with 300rpm rotating speed
6h, then by mixed liquor rotary evaporation 4h at 60 DEG C, is evaporated moisture and obtains pressed powder, by gained pressed powder 100
Dry 2h, finally roasting 3h at 400 DEG C at DEG C, obtain the composite oxide supported material of titanium tungsten；
(3) preparation of undercoating serosity: sial composite oxides step (1) prepared and the silicon of 30% mass fraction are molten
Glue 3:1 in mass ratio mixes, and adds deionized water, forms suspension, regulates deionized water addition, makes solid in suspension
Material mass mark is 30%, to suspension ball milling, controls granularity D90 and is less than 5um, obtain undercoating coating serosity；
(4) preparation of external coating serosity: the composite oxide supported material of external coating titanium tungsten prepared by step (2), inclined vanadium
The Ludox 1:0.038:0.11 in mass ratio mixing of acid ammonium and 30% mass fraction, and add deionized water, form suspension,
Regulation deionized water addition, making solid matter mass mark in suspension is 30%, to suspension ball milling, controls granularity
D90 is less than 5um, obtains external coating coating serosity；
(5) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (3)
In, stop 5s, extract out with the speed of 50mm/s subsequently, with the pressure-air of 0.4MPa, serosity unnecessary for carrier surface is blown away,
Coated honeycomb ceramic carrier is placed at 100 DEG C drying 1h, and then at 400 DEG C of roasting 2h, repeated several times is to being coated to
Undercoating amount on honeycomb substrate reaches 82g/L；
(6) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (5), be soaked in
In serosity prepared by step (4), stop 5s, extract out, with the pressure-air of 0.4MPa by carrier table with the speed of 50mm/s subsequently
The unnecessary serosity in face blows away, and coated honeycomb ceramic carrier is placed at 100 DEG C drying 1h, then at 400 DEG C of roasting 2h, weight
Reach 125g/L to the external coating amount being coated on honeycomb substrate several times again, complete catalyst and prepare.
Embodiment four:
Catalyst with the cordierite honeycomb ceramic of 300 mesh as carrier, a size of diameter 190.5mm* height 101.6mm cylinder
Body 2 pieces (each 1 piece of forward and backward level), cumulative volume is 5.8L.Cordierite honeycomb ceramic carrier duct inwall is coated with catalyst be coated with
Layer.Catalyst coat comprises undercoating and external coating: undercoating is for being close to carrier duct inner wall section, and component is sial composite oxygen
Compound, internally coated coated weight is 98g/L；External coating, for being coated in the upper part of undercoating, comprises barium oxide and titanium tungsten is multiple
Closing oxide carried material, the coated weight of external coating is 149g/L.Inside and outside coating all with silicon oxide for binding agent strengthen coating with
Adhesive force between carrier.
In sial composite oxides in undercoating, silicon dioxide is 1.5:1 with the mass ratio of aluminium sesquioxide；External coating
In component, barium oxide is 0.06:1 with the mass ratio of the composite oxide supported material of titanium tungsten；Titanium tungsten composite oxygen in external coating
In compound support materials, Tungstic anhydride. is 0.15:1 with the mass ratio of titanium dioxide；In inside and outside coating, binding agent is siliceous
Amount is 0.1:1 with coating quality ratio.
Catalyst preparation step is as follows:
(1) preparation of undercoating sial composite oxides: by the Ludox of 30% mass fraction and 20% mass fraction
Alumina gel 1:1 in mass ratio mixes, and said mixture and the ethanol water 1:1 in mass ratio that mass fraction is 50% is mixed
Form mixed liquor, add the Tween 80 of the most above-mentioned mixed liquor gross mass 2%, then above-mentioned mixed with the stirring of 500rpm/mim rotating speed
Close liquid 10h, then by mixed liquor rotary evaporation 8h at 80 DEG C, moisture is evaporated and obtains pressed powder, by gained pressed powder
Drying 3h at 120 DEG C, finally roasting 6h at 500 DEG C, obtains sial composite oxides；
(2) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate
1:1:0.043 in mass ratio mixes, and said mixture and the ethanol water 1:1 in mass ratio that mass fraction is 50% is mixed
Form mixed liquor, add the Tween 80 of the most above-mentioned mixed liquor gross mass 2%, then stir above-mentioned mixed liquor with 500rpm rotating speed
10h, then by mixed liquor rotary evaporation 8h at 80 DEG C, is evaporated moisture and obtains pressed powder, by gained pressed powder 120
Dry 3h, finally roasting 6h at 500 DEG C at DEG C, obtain the composite oxide supported material of titanium tungsten；
(3) preparation of undercoating serosity: sial composite oxides step (1) prepared and the silicon of 30% mass fraction are molten
Glue 3:1 in mass ratio mixes, and adds deionized water, forms suspension, regulates deionized water addition, makes solid in suspension
Material mass mark is 40%, to suspension ball milling, controls granularity D90 and is less than 5um, obtain undercoating coating serosity；
(4) preparation of external coating serosity: the composite oxide supported material of external coating titanium tungsten prepared by step (2), inclined vanadium
The Ludox 1:0.077:0.11 in mass ratio mixing of acid ammonium and 30% mass fraction, and add deionized water, form suspension,
Regulation deionized water addition, making solid matter mass mark in suspension is 40%, to suspension ball milling, controls granularity
D90 is less than 5um, obtains external coating coating serosity；
(5) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (3)
In, stop 20s, extract out with the speed of 100mm/s subsequently, with the pressure-air of 0.6MPa, serosity unnecessary for carrier surface is blown
Walking, coated honeycomb ceramic carrier is placed at 120 DEG C drying 3h, then at 500 DEG C of roasting 4h, repeated several times is to coating
Undercoating amount on honeycomb substrate reaches 98g/L；
(6) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (5), be soaked in
In serosity prepared by step (4), stop 20s, extract out, with the pressure-air of 0.6MPa by carrier with the speed of 100mm/s subsequently
The serosity of excess surface blows away, and coated honeycomb ceramic carrier is placed at 120 DEG C drying 3h, then at 500 DEG C of roasting 4h,
Repeated several times reaches 149g/L to the external coating amount being coated on honeycomb substrate, completes catalyst and prepares.
Catalyst storage NH3Aptitude tests:
NH according to engine pedestal dynamic response test catalyst3Amount of storage.Test engine discharge capacity is about 3.0L, for
State's V electromotor.It is connected in the exhaust pipe of engine after catalyst sealing is installed, and urea injection system is installed, with 32.% mass
Mark aqueous solution of urea is reducing agent.All test samples all carry out pretreatment before testing, and i.e. control engine operating condition,
Making catalyst in inlet temperature (400 ± 10) DEG C, air speed is 40000h-1Under conditions of run 2h, period do not sprays carbamide.NH3
Storage test process reference literature: " the engine test research of vanadia-based SCR catalysts dynamic response characteristic, " internal combustion engine
Report ", 2009,27 (5): 417-422 " report method carries out.Measurement condition is set to catalyst inlet temperature for (200 ± 5) DEG C；Empty
Speed is (40000 ± 1000) h-1.Take NH3Leakage is equal to the NH of 10ppm3Storage value is as test value.
For increasing the comparative of result, store up NH3Aptitude tests simultaneously using diesel vehicle SCR system business catalytic component based on vanadium as
Comparative example.
Test result is as shown in table 1.
Table 1NH3Storage test value
| Test sample | NH3Amount of storage (g/L) |
| Embodiment one | 0.88 |
| Embodiment two | 1.12 |
| Embodiment three | 0.85 |
| Embodiment four | 1.03 |
| Comparative example | 0.42 |
As shown in Table 1, its NH of catalyst that prepared by the present invention3Amount of storage will relatively business catalytic component based on vanadium exceed about 1.02～
1.67 again.High NH3In the inside and outside pair of coated composite structure that amount of storage catalyst of the present invention to be had benefited from uses, undercoating is combined
The high NH of oxide3Storage performance.Meanwhile, high storage NH3Ability is also beneficial to promote catalyst NO under low row's temperature environmentxTurn
Change performance.
WHTC cold start emission is tested:
According to HJ689-2014 " city vehicle diesel engine exhaust pollutant emission limit and measuring method (WHTC
Operating condition method) " regulation, use cold start-up WHTC test loop to evaluate the activity of catalyst.Test engine, catalyst sample,
Aerofluxus and post processing pipeline arrange equivalent storage NH3Aptitude tests.Each exemplar is the most all at catalyst inlet temperature (200
± 5) DEG C, air speed is (40000 ± 1000) h-1Operating mode under run 0.5h, period presses NH3: the equivalent proportion of NO=1.2 is urinated
Element injection.During WHTC loop test, the carbamide injection arteries and veins spectrogram of all exemplars is the most identical, i.e. urea injecting quantity is the most equal.
Test result is as shown in table 2.
Table 2WHTC cold start-up NOxEmission test result
As shown in Table 2, the catalyst that prepared by the present invention its at the NO of WHTC cold start-upxDischarge value is low compared with comparative example about
25.55～33.09%, have benefited from the present invention and prepare inside and outside pair of coating compound action of catalyst: undercoating composite oxides
High NH3Storage performance makes it can lay in substantial amounts of NH before WHTC tests3React for SCR；Make external coating in test process
Undercoating storage NH can be obtained3Sufficient input, and then ensure that SCR reactivity, reduce NOxDischarge.
Claims (10)
1. one kind possesses high storage NH3The SCR catalyst of ability, it is characterised in that: with cordierite honeycomb ceramic as carrier, at carrier
Duct inwall on be coated with catalyst coatings, described catalyst coat includes being close to the undercoating of carrier duct inwall, undercoating
The external coating on upper strata, described internally coated coated weight is 80 ~ 100 g/L, described undercoating component be silicon-titanium composite oxide or
Sial composite oxides；The coated weight of described external coating is 120 ~ 150 g/L, and external coating component is that barium oxide and titanium tungsten are combined
Oxide carried material, described undercoating and external coating use binding agent to be attached on carrier.
Possesses high storage NH the most as claimed in claim 13The SCR catalyst of ability, it is characterised in that: described internally coated component
In silicon-titanium composite oxide, silicon dioxide is 0.67 ~ 1.5:1 with the mass ratio of titanium dioxide.
Possesses high storage NH the most as claimed in claim 13The SCR catalyst of ability, it is characterised in that: described internally coated component
In sial composite oxides, silicon dioxide is 0.67 ~ 1.5:1 with the mass ratio of aluminium sesquioxide.
Possesses high storage NH the most as claimed in claim 13The SCR catalyst of ability, it is characterised in that: vanadium oxygen in described external coating
Compound is 0.03 ~ 0.06:1 with the mass ratio of the composite oxide supported material of titanium tungsten.
Possesses high storage NH the most as claimed in claim 13The SCR catalyst of ability, it is characterised in that: titanium tungsten in described external coating
In composite oxide supported material, Tungstic anhydride. is 0.05 ~ 0.15:1 with the mass ratio of titanium dioxide.
Possesses high storage NH the most as claimed in claim 13The SCR catalyst of ability, it is characterised in that: described binding agent is oxidation
Silicon, described binding agent and undercoating, the mass ratio of external coating are 0.1 ~ 0.15:1.
7. the height that possesses described in claim 1 stores up NH3The preparation method of the SCR catalyst of ability, it is characterised in that: include as follows
Step:
(1) preparation of undercoating silicon-titanium composite oxide: by butyl titanate, triethanolamine and Ludox 1:1 in mass ratio:
0.52 ~ 1.17 mixing, adds said mixture ethanol water and forms mixed solution, be subsequently adding Tween 80, by mixed liquor
Carrying out rotary evaporation, evaporating water obtains pressed powder, finally pressed powder roasting is obtained silicon-titanium composite oxide；
(2) preparation of undercoating sial composite oxides: Ludox and Alumina gel 0.45 ~ 1:1 in mass ratio are mixed, Alumina gel
Mass fraction be 20-25%, said mixture is added ethanol water and forms mixed solution, be subsequently adding Tween 80, will be mixed
Conjunction liquid carries out rotary evaporation evaporating water and obtains pressed powder, finally pressed powder roasting is obtained sial composite oxides；
(3) preparation of the composite oxide supported material of external coating titanium tungsten: by butyl titanate, triethanolamine and ammonium paratungstate by matter
Measure and mix than 1:1:0.014 ~ 0.043, said mixture is added ethanol water and forms mixed solution, be subsequently adding tween
80, mixed liquor is carried out rotary evaporation evaporating water and obtains pressed powder, finally pressed powder roasting is obtained titanium tungsten composite oxygen
Compound support materials；
(4) preparation of undercoating serosity: sial prepared by silicon-titanium composite oxide step (1) prepared or step (2) is combined
Oxide mixes with Ludox 2 ~ 3:1 in mass ratio, and adds deionized water, forms suspension, regulates deionized water addition,
Making solid matter mass mark in suspension is 30 ~ 40%, to suspension ball milling, controls granularity D90 and is less than 5 um, in obtaining
Coating slurry；
(5) preparation of external coating serosity: the composite oxide supported material of titanium tungsten, vanadium source and Ludox prepared by step (3) by
Mass ratio 1:0.038 ~ 0.077:0.11 mixing, and add deionized water, form suspension, regulate deionized water addition, make
In suspension, the mass fraction of solid matter is 30 ~ 40%, to suspension ball milling, controls granularity D90 and is less than 5 um, outside obtaining
Coating slurry；
(6) the coating roasting of undercoating serosity: take cordierite honeycomb ceramic carrier, is soaked in serosity prepared by step (4), stops
Stay 5 ~ 20 s, extract out with the speed of 50 ~ 100 mm/s subsequently, with the pressure-air of 0.4 ~ 0.6 MPa, carrier surface is unnecessary
Serosity blows away, and coated honeycomb ceramic carrier is placed at 100 ~ 120 DEG C drying 1 ~ 3 h, then 400 ~ 500 DEG C of roastings
2 ~ 4 h, repeated several times reaches 80 ~ 100 g/L to the undercoating amount being coated on honeycomb substrate；
(7) the coating roasting of external coating serosity: take cordierite honeycomb ceramic carrier prepared by step (6), be soaked in step
(5), in the serosity prepared, stop 5 ~ 20 s, extract out with the speed of 50 ~ 100 mm/s subsequently, empty with the high pressure of 0.4 ~ 0.6 MPa
Serosity unnecessary for carrier surface is blown away by gas, coated honeycomb ceramic carrier is placed at 100 ~ 120 DEG C drying 1 ~ 3 h, so
After reach 120 ~ 150 g/ at 400 ~ 500 DEG C of roasting 2 ~ 4 h, repeated several times to the external coating amount being coated on honeycomb substrate
L, completes the preparation of catalyst.
Possesses high storage NH the most as claimed in claim 73The preparation method of the SCR catalyst of ability, it is characterised in that: described step
(1), step (2) and step (3) add ethanol water that mass fraction is 50% suddenly in the mixture and forms mixed liquor, second
The addition of alcohol-water solution and the mass ratio of mixture are 1:1, are subsequently adding the Tween 80 of mixed liquor gross mass 1 ~ 2%, 300 ~
Mixed liquor 6 ~ 10 h is stirred under 500 rpm/mim rotating speeds, and by mixed liquor rotary evaporation 4 ~ 8 h at 60 ~ 80 DEG C, by moisture
It is evaporated and obtains pressed powder, gained pressed powder is dried at 100 ~ 120 DEG C 2 ~ 3 h, finally roasting at 400 ~ 500 DEG C
3~6 h。
Possesses high storage NH the most as claimed in claim 73The preparation method of the SCR catalyst of ability, it is characterised in that: described step
Suddenly the vanadium source in (5) is ammonium metavanadate.
Possess the preparation method of the SCR catalyst of high storage NH3 ability the most as claimed in claim 7, it is characterised in that: described
In step (1), step (2), step (4) and step (5), the mass fraction of Ludox is 25-35%.
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| WO2005046869A1 (en) * | 2003-11-15 | 2005-05-26 | Robert Bosch Gmbh | Exhaust system for a combustion engine |
| CN101380543A (en) * | 2008-09-11 | 2009-03-11 | 南京工业大学 | Fume denitration composite catalyst using titanium-base ceramics as carrier and preparation method thereof |
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| CN102921405A (en) * | 2012-09-29 | 2013-02-13 | 重庆大学 | SiO2-containing denitration catalyst and preparation method thereof |
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