CN106902865A - Diesel vehicle particle oxidative catalyst and preparation method thereof - Google Patents
Diesel vehicle particle oxidative catalyst and preparation method thereof Download PDFInfo
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- CN106902865A CN106902865A CN201710075106.1A CN201710075106A CN106902865A CN 106902865 A CN106902865 A CN 106902865A CN 201710075106 A CN201710075106 A CN 201710075106A CN 106902865 A CN106902865 A CN 106902865A
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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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/74—Noble metals
- B01J29/7415—Zeolite Beta
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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
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
-
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- 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
Abstract
The present invention relates to a kind of diesel vehicle particle oxidative catalyst and preparation method thereof, including carrier, the coated weight of coating is 10 ~ 40g/L on carrier, and coating includes sial composite oxides, Rare-Earth Ce O2, beta-molecular sieve and zirconium glue caking agent, the mass ratio of precious metals pt and precious metals pd is 1 in coating:5~3:1, the coated weight of precious metals pt and precious metals pd is 5 ~ 90g/ft3.Preparation method of the present invention is simple, and step is easily operated, and silicon aluminum oxide is mixed in coating slurry as dispersant, the main material that rare earth material is aoxidized as particle, molecular sieve is that low temperature HC stores material, improves HC absorption under low temperature, add zirconium glue caking agent, carried noble metal Pt and Pd.The catalyst for preparing possesses lower CO initiation temperatures, the T of CO50Reduction can effectively facilitate HC and NO NO2Catalysis oxidation, reduces the discharge of HC;Due to NO2There is oxidability higher, NO higher to particle during low temperature2Accounting can promote the catalysis oxidation to particle and with endurance quality higher.
Description
Technical field
The present invention relates to a kind of diesel vehicle particle oxidative catalyst and preparation method thereof, belong to catalyst preparation technology neck
Domain.
Background technology
Compression-ignited diesel vehicle (high air-fuel ratio) can run under lean burn conditions, therefore diesel vehicle has good fuel-economy
Property, Just because of this, diesel vehicle has relatively low pollutant emission (HC classes, CO), however, diesel vehicle can produce NOx higher and
Grain discharge, particulate matter is mainly made up of carbon soot particles (Soot), soluble organic mixture (SOF) and sulfate.Diesel vehicle
Particle is mainly made up of carbon soot particles and SOF, and SOF is mainly derived from fuel oil and lubricating oil, with liquid or volatilization state form
In the presence of this depends on delivery temperature;Soot is mainly made up of (dehydrogenation carbonization) carbon particle.These tiny particulate emissions are to air
In certain risk is caused to human health.
Diesel vehicle granule capturing catalyst can coat one layer of diesel vehicle oxidation catalyst coating, diesel vehicle oxidizing catalytic
The active component of agent is mainly made up of precious metals pt and Pd, HC, CO that one side catalyst can be in catalysis oxidation gas phase, while
The particulate catalytic of part can also be oxidized to CO2And H2O, on the other hand, diesel vehicle oxidation catalyst can promote NO to NO2
Oxidation.
Diesel vehicle granule capturing catalyst is wall-flow particulate trap catalyst, and it is multi-cellular honeycomb structures, with
Lower feature:First, have under basic condition inlet end and outlet side point, two, air inlet end opening, outlet side closing, outlet end opening,
Inlet end is closed, and air-flow passes through from the wall of loose structure, and the particle in tail gas can be accumulated on (Soot, SOF) trapping wall,
With the increase of particulate accumulation quality, the back pressure of granule capturing catalyst can be improved, and back pressure is directly proportional pass to accumulation granular mass
System, when the quality of accumulation reaches a threshold value, oil consumption of diesel engine can increase, and power can decline, and this when, system can be adopted
Take initiative regeneration mode to regenerate the particle on beaded catalyst, burnt, back pressure and treatment are reduced so as to reach
The purpose of grain.
The soot particulate matter of diesel vehicle is mainly made up of carbon black pellet and SOF, and the phosphorus content of SOF is more than 9, one under normal circumstances
As C11-C50 composition, not exclusively produced by fuel oil or lubricating oil, SOF mainly to evaporate state or liquid, or both shape coexists
State, its existence form depends on delivery temperature.In order to reduce the discharge of total particle, SOF parts can by with CSF coating layer touch,
Reaction, so as to generate CO2And H2O, and vapor phase contaminants HC, CO, NOX, also by catalytic treatment, gas phase HC (C2-C6) can be oxidized
It is CO2And H2O。
The catalyst coat of current diesel vehicle has that CO initiation temperatures are higher, and this may result in HC species and NO-NOXOxygen
Change can be deteriorated, because during low temperature, the adsorption capacity of CO and noble metal is stronger, and active sites are occupied by CO, only when CO desorption reactions
After the completion of, HC species and NO-NO2Reaction just start, CO T higher50HC species and NO-NO can be suppressed2Reaction, from without
Beneficial to the catalysis oxidation of partial particulate (SOF).
The content of the invention
The invention aims to solve the above problems, there is provided a kind of diesel vehicle particle oxidative catalyst and its system
Preparation Method, the catalyst for preparing has more preferable CO and HC low temperature light-off performance, NO-NO higher2Conversion ratio, and it is durable
Property is more preferable.
The present invention is adopted the following technical scheme that:A kind of diesel vehicle particle oxidative catalyst, including carrier, on the carrier
Coating is coated with, the coated weight of the coating is 10~40g/L, and the coating includes sial composite oxides, Rare-Earth Ce O2、β-
Molecular sieve and zirconium glue caking agent, contain precious metals pt and precious metals pd, the coating of precious metals pt and precious metals pd in the coating
It is 5~90g/ft3 to measure, and the mass ratio of precious metals pt and precious metals pd is 1:5~3:1.
Further, sial composite oxides, Rare-Earth Ce O in the coating2, the mass ratio between β-molecular sieve be
0.525~0.84:0.1~0.15:0.05~0.3.
Further, the carrier is carborundum honeycomb substrate, and its structure is wall-flow type structure, and the mesh number of the carrier is
200~300 mesh.
Further, the mass percent of silicon is 1.5~8% in the sial composite oxides, and remaining is Al2O3。
The preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
(1) material is weighed:By weight 0.525~0.84:0.1~0.15:0.05~0.3 weighs sial respectively is combined
Oxide, β-molecular sieve, CeO2, and sial composite oxides and β-molecular sieve are mixed;
(2) noble metal is weighed:The coated weight of coating is 10~40g/L, and the coated weight of precious metals pt and precious metals pd is 5
~90g/ft3, the wherein mass ratio of precious metals pt and precious metals pd is 1:5~3:1, needed for the size according to carrier calculates coating
Amount and precious metals pt and precious metals pd aequum;
(3) load of noble metal:By Pd (NO3)2Solution presses CeO2The 90% of water absorption rate be diluted with water rear incipient wetness impregnation in
CeO2On, by [Pt (NH3)4](OH)2Solution is diluted with water rear incipient wetness impregnation in silicon by the 90% of sial composite oxides water absorption rate
On aluminium composite oxide and β-molecular sieve mixture material, 12h is aged respectively;
(4) treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial for being loaded with precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined;
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing are equal
It is even, it is eventually adding zirconium glue caking agent and is made slurries, the solidfied material dry weight of zirconium glue caking agent accounts for total material solidfied material in slurries
0.01~0.025%, slurries add dust technology to adjust the pH to less than 4.5 of slurries after ball milling;
(6) slurry coating coating:The coating of coating is carried out with quantitative coating special plane, carrier is positioned over the painting of coating special plane
Cover at chamber, be that the slurries that 10~40g/L will be calculated are added in slurry disk according to the coated weight of coating, carry out quantitative coating,
Slurries are coated to the hole wall inner side of carrier by coating special plane;
(7) slurries drying and roasting:The catalyst for having coated by 100~150 DEG C of flash bakings, drying time is 3~
6h falls the water evaporation in coating;Drying rear catalyst is put into Muffle furnace, 450~550 DEG C of 1~4h of roasting are prepared
Diesel vehicle platinum base oxidative catalyst.
Further, CeO in the step (3)2Water absorption rate be 80g water/100g CeO2, the sial composite oxides
Water absorption rate be 110g water/100g sial composite oxides.
Further, drying temperature is 100~150 DEG C in the step (4), and drying time 3-8h, sintering temperature is 450
~550 DEG C, 1~5h of roasting time.
Further, in the step (5) ball milling rear slurry granularity to D90 be 3~6um.
The invention has the advantages that:(1) precious metals pt and precious metals pd are loaded based on different matrix, precious metals pd load
In CeO2On, precious metals pt is carried on the mixed material of sial composite oxides and β-molecular sieve, and precious metals pd is carried on CeO2
Light-off performance of the coating to CO can be improved, CO initiation temperatures are reduced, so as to promote HC species and NO-NO2Reaction;(2)
Precious metals pt and precious metals pd use incipient wetness impregnation technology in loading process so that two kinds of noble metals are easier to enter carrier
On the inwall of duct;(3) precious metals pt, the synergy of precious metals pd are conducive to the generation of alloy in catalyst, it is possible to increase urge
The anti-caking power of agent, strengthens the endurance quality of catalyst, improves the activity of catalyst;(4) by noble-metal-supported mode
Optimization and rare earth material use, preferable ignition effect is obtained in the case where noble metal addition is less, reduce and urge
The production cost of agent, improves the competitiveness of particle oxidative catalyst.
Brief description of the drawings
The overall pressure difference that Fig. 1 is measured in being tested by the back pressure done to embodiment three in the present invention is illustrated with the change of flow
Figure.
Specific embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated.
A diameter of 143.8mm is used in three below example, the cylindrical silicon carbide honeycomb of a height of 176mm is carrier,
Volume is 2.85L, and vehicle weight is 2260g, and the concentration of precious metals pd is the Pd (NO of 0.14613g (noble metal)/g (liquid)3)2
Solution, the concentration of precious metals pt is the [Pt (NH of 0.1191g (noble metal)/g (liquid)3)4](OH)2Solution.
Embodiment one:
A kind of preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
(1) material is weighed:By weight 0.68:0.1:0.2 weigh respectively sial composite oxides, β-molecular sieve,
CeO2, powder total amount is 980g, and sial composite oxides and β-molecular sieve are well mixed;
(2) noble metal is weighed:The total amount of precious metals pt and precious metals pd is 30g/ft3, precious metals pt and precious metals pd
Ratio be 1:1, coated weight is 40g/L, calculates the amount of precious metals pt for 13.243g, weighs precious metals pt solution
It is 111.28g to measure, and the amount of precious metals pd is 13.243g, and the amount for weighing precious metals pd solution is 90.62g;
(3) load of noble metal:By precious metals pd (NO3)2Solution is diluted with water to 144g, and incipient wetness impregnation is in CeO2On, will
[Pt(NH3)4](OH)2Solution is diluted with water to 673g, and incipient wetness impregnation is in sial composite oxides and β-molecular sieve mixture material
On, it is aged 12h;
(4) treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial for being loaded with precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined, 110 DEG C of drying temperature, drying time 8h, sintering temperature 550
DEG C, roasting time 5h;
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing
Uniformly, zirconium glue caking agent is eventually adding, the solidfied material dry weight of zirconium glue caking agent accounts for the 0.02 of total material solidfied material, i.e. 20g powders
Zirconium glue;
(6) ball milling of slurries:By ball mill grinding, the final granularity of slurries to D90 is 3.8um to slurries;
(7) in slurries solid content measure:10g slurries are taken in dry pot, dry pot is placed in 550 DEG C of Muffle kiln roastings
20min, is cooled to room temperature, weighs its amount of powder matter 2.4, with the quality divided by 10g, just obtains slurry solid content 24%;
(8) slurries pH regulations:The pH to 4.4 of slurries is adjusted using dust technology;
(9) slurry coating coating:It is coated with quantitative coating special plane, carrier is positioned over the application chamber of coating special plane
Place, be 40g/L requirements according to coated weight and the solid content that measures to calculate the wet weightening of target be 475g, the slurries that will be calculated are added
To in slurry disk, quantitative coating is carried out, slurries are coated on the duct inwall of carrier;
(10) slurries drying:By 150 DEG C of flash bakings, drying time is 4h by the water in coating to the catalyst for having coated
Evaporate, drying rear catalyst is put into Muffle furnace, 550 DEG C of roasting 2h, insulation is cooled to room temperature, weighs catalyst after terminating
Weight 2374g.
Embodiment two:
A kind of preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
(1) material is weighed:By weight 0.59:0.1:0.3 weigh respectively sial composite oxides, β-molecular sieve,
CeO2, powder total amount is 990g, and sial composite oxides and β-molecular sieve are well mixed;
(2) noble metal is weighed:The total amount of precious metals pt and precious metals pd is 10g/ft3, precious metals pt and precious metals pd
Ratio be 1:4, coated weight is 20g/L, calculates the amount of precious metals pt for 3.5315g, weighs precious metals pt solution
It is 29.67g to measure, and the amount of precious metals pd is 14.1262g, and the amount for weighing precious metals pd solution is 96.67g;
(3) load of noble metal:By precious metals pd (NO3)2Solution is diluted with water to 216g, and incipient wetness impregnation is in CeO2On, will
[Pt(NH3)4](OH)2Solution is diluted with water to 584g, and incipient wetness impregnation is in sial composite oxides and β-molecular sieve mixture material
On, it is aged 12h;
(4) treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial for being loaded with precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined, 110 DEG C of drying temperature, drying time 8h, sintering temperature 550
DEG C, roasting time 5h.
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing
Uniformly, zirconium glue caking agent is eventually adding, the solidfied material dry weight of zirconium glue caking agent accounts for the 0.01 of total material solidfied material, i.e. 10g powders
Zirconium glue caking agent;
(6) ball milling of slurries:By ball mill grinding, the final granularity of slurries to D90 is 4.7um to slurries;
(7) in slurries solid content measure:10g slurries are taken in dry pot, dry pot is placed in 580 DEG C of Muffle kiln roastings
20min, is cooled to room temperature, weighs its amount of powder matter 2.3, with the quality divided by 10g, just obtains slurry solid content 15%;
(8) slurries pH regulations:The pH to 4.5 of slurries is adjusted using dilute nitric acid solution;
(9) slurry coating coating:It is coated with quantitative coating special plane, carrier is positioned at coating special plane application chamber,
Be 20g/L requirements according to coated weight and the solid content that measures to calculate the wet weightening of target be 380g, the slurries that will be calculated are added to
In slurry disk, quantitative coating is carried out, slurries are coated on the duct inwall of carrier;
(10) slurries drying:By 120 DEG C of flash bakings, drying time is 6h by the water in coating to the catalyst for having coated
Evaporate;Drying rear catalyst is put into Muffle furnace, 500 DEG C of roasting 2h, insulation is cooled to room temperature, weighs catalyst after terminating
Weight 2316g.
Embodiment three:
A kind of preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
The load step of noble metal
(1) material is weighed:By weight 0.68:0.15:0.15 weigh respectively sial composite oxides, β-molecular sieve,
CeO2, powder total amount is 980g, and sial composite oxides and β-molecular sieve are well mixed;
(2) noble metal is weighed:The total amount of precious metals pt and precious metals pd is 20g/ft3, precious metals pt and precious metals pd
Ratio be 1:1, coated weight is 30g/L, calculates the amount of precious metals pt for 11.7g, weighs the amount of precious metals pt solution
It is 98.3g, the amount of precious metals pd is 11.7g, the amount for weighing precious metals pd solution is 80.1g;
(3) load of noble metal:By precious metals pd (NO3)2Solution is diluted with water to 108g, and incipient wetness impregnation is in CeO2On, will
[Pt(NH3)4](OH)2Solution is diluted with water to 673g, and incipient wetness impregnation is in sial composite oxides and β-molecular sieve mixing material
On, it is aged 12h;
(4) treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial for being loaded with precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined, 130 DEG C of drying temperature, drying time 5h, sintering temperature 500
DEG C, roasting time 4h;
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing
Uniformly, zirconium glue caking agent is eventually adding, the solidfied material dry weight of zirconium glue caking agent accounts for the 0.02 of total material solidfied material, i.e. 20g powders
Zirconium glue;
(6) ball milling of slurries:By ball mill grinding, the final granularity of slurries to D90 is 4.5um to slurries;
(7) in slurries solid content measure:10g slurries are taken in dry pot, dry pot is placed in 600 DEG C of Muffle kiln roastings
20min, is cooled to room temperature, weighs its amount of powder matter 1.8, with the quality divided by 10g, just obtains slurry solid content 18%;
(8) slurries pH regulations:The pH to 4.3 of slurries is adjusted using dust technology;
(9) slurry coating coating:It is coated with quantitative coating special plane, carrier is positioned at coating special plane application chamber,
Be 30g/L requirements according to coated weight and the solid content that measures to calculate the wet weightening of target be 475g, the slurries that will be calculated are added to
In slurry disk, quantitative coating is carried out, slurries are coated on the duct inwall of carrier;
(10) slurries drying:By 130 DEG C of flash bakings, drying time is 5h by the water in coating to the catalyst for having coated
Evaporate;Drying rear catalyst is put into Muffle furnace, 500 DEG C of roasting 4h, insulation is cooled to room temperature, weighs catalyst after terminating
Weight 2345.5g.
Example IV:
A kind of preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
(1) material is weighed:By weight 0.525:0.15:0.3 weigh respectively sial composite oxides, β-molecular sieve,
CeO2, and sial composite oxides and β-molecular sieve are mixed;
(2) noble metal is weighed:The coated weight of coating is 10g/L, and the coated weight of precious metals pt and precious metals pd is 5g/
The mass ratio of ft3, wherein precious metals pt and precious metals pd is 1:5, the size according to carrier calculates coating aequum and your gold
Category Pt and precious metals pd aequum;
(3) load of noble metal:By Pd (NO3)2Solution presses CeO2The 90% of water absorption rate be diluted with water rear incipient wetness impregnation in
CeO2On, by [Pt (NH3)4](OH)2Solution is diluted with water rear incipient wetness impregnation in silicon by the 90% of sial composite oxides water absorption rate
On aluminium composite oxide and β-molecular sieve mixture material, 12h is aged respectively;
(4) treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial for being loaded with precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined;
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing are equal
It is even, it is eventually adding zirconium glue caking agent and is made slurries, the solidfied material dry weight of zirconium glue caking agent accounts for total material solidfied material in slurries
0.025, slurries add dust technology to adjust the pH to less than 4.5 of slurries after ball milling;
(6) slurry coating coating:The coating of coating is carried out with quantitative coating special plane, carrier is positioned over the painting of coating special plane
Cover at chamber, according to the coated weight of coating for the slurries that 10g/L will be calculated are added in slurry disk, carry out quantitative coating, will starch
Liquid is coated on the duct inwall of carrier;
(7) slurries drying and roasting:By 100 DEG C of flash bakings, drying time is 6h by coating to the catalyst for having coated
In water evaporation fall;Drying rear catalyst is put into Muffle furnace, 450 DEG C of roasting 2h prepare diesel vehicle particle oxidisability
Catalyst.
Embodiment five:
A kind of preparation method of diesel vehicle particle oxidative catalyst, comprises the following steps:
(1) material is weighed:By weight 0.84:0.1:0.05 weigh respectively sial composite oxides, β-molecular sieve,
CeO2, and sial composite oxides and β-molecular sieve are mixed;
(2) noble metal is weighed:The coated weight of coating is 40g/L, and the coated weight of precious metals pt and precious metals pd is 90g/
The mass ratio of ft3, wherein precious metals pt and precious metals pd is 3:1, the size according to carrier calculates coating aequum and your gold
Category Pt and precious metals pd aequum;
(3) load of noble metal:By Pd (NO3)2Solution presses CeO2The 90% of water absorption rate be diluted with water rear incipient wetness impregnation in
CeO2On, by [Pt (NH3)4](OH)2Solution is diluted with water rear incipient wetness impregnation in silicon by the 90% of sial composite oxides water absorption rate
On aluminium composite oxide and β-molecular sieve mixture material, 12h is aged respectively;
(4) treatment of precious metal material:The CeO2 of precious metals pd will be loaded with respectively and is loaded with the sial of precious metals pt
Composite oxides, β-molecular sieve mixture material are dried, are calcined;
(5) preparation of slurries:Material after roasting in step (4) is added separately in deionized water, stirring, mixing are equal
It is even, it is eventually adding zirconium glue caking agent and is made slurries, the solidfied material dry weight of zirconium glue caking agent accounts for total material solidfied material in slurries
0.01, slurries add dust technology to adjust the pH to less than 4.5 of slurries after ball milling;
(6) slurry coating coating:The coating of coating is carried out with quantitative coating special plane, carrier is positioned over the painting of coating special plane
Cover at chamber, according to the coated weight of coating for the slurries that 40g/L will be calculated are added in slurry disk, carry out quantitative coating, will starch
Liquid is coated on the duct inwall of carrier;
(7) slurries drying and roasting:By 150 DEG C of flash bakings, drying time is 3h by coating to the catalyst for having coated
In water evaporation fall;Drying rear catalyst is put into Muffle furnace, 550 DEG C of roasting 1h prepare diesel vehicle particle oxidisability
Catalyst.
Catalytically active assessment and back pressure test are carried out to the catalyst that embodiment three is prepared
(1) fresh state catalyst activity is evaluated
Test is carried out in pipe reaction stove.
Method of testing:By prepared catalyst cut growth 13mm* 13mm* wide 60mm high, catalyst center section is taken,
NO, CO will be contained2、H2O、C3H8, CO gaseous mixture be passed through in tubular type reacting furnace, wherein NO:300ppm, CO:1000ppm, C3H8:
300ppm, H2O:10%, CO2:6%, O2:10%;Heating rate is every 10 DEG C of intensification, is eventually raised to 500 DEG C.
Test result is as shown in table 1.
The fresh state catalyst activity evaluation result of table 1
As shown in Table 1, the initiation temperature T of the HC and CO of the catalyst prepared by embodiment three50Respectively 249 DEG C and 86
℃;NO is converted into NO2Conversion ratio highest is reached at 300 DEG C, conversion ratio is 92.7%.(2) heat ageing state catalyst activity
Evaluate
Pre-treatment:Catalyst prepared by embodiment three is placed in first it is aging in Muffle furnace, aging temperature be 800 DEG C, always
The change time is 16h, and then NOx, CO and HC again in simulated automotive tail gas carries out active investigation,
Test is carried out in pipe reaction stove.
Method of testing:NO, CO will be contained2、H2O、C3H8, CO gaseous mixture be passed through in high temperature reaction stove, wherein NO:
300ppm, CO:1000ppm, C3H8:300ppm, H2O:10%, CO2:6%, O2:10%;Heating rate is that every min heats up 10 DEG C,
It is eventually raised to 500 DEG C.
Test result is as shown in table 2.
The aging state catalyst activity evaluation result of table 2
As shown in Table 2, the initiation temperature T of the HC and CO of the catalyst prepared by embodiment three50Respectively 298 DEG C and 97
℃;NO is converted into NO2At 300 DEG C, conversion ratio reaches highest, and conversion ratio is 89.9%.(3) the back pressure test of catalyst
Surveyed back pressure be the DPF catalyst for preparing mounted in the embodiment three of the four cylinder engine that discharge capacity is 2.8 liters and
Overall pressure difference when DOC catalyst is combined, the size of DOC catalyst is 143.8*101.6, mesh number 400.
As shown in Figure 1, with the increase of flow, overall pressure difference in gradually increased trend, when flow reaches 50kg/,
Overall pressure difference remains to control within 10kpa.The magnitude of back pressure of catalyst directly affects the oil consumption size of diesel car engine, the back of the body
Pressure is bigger, and the oil consumption of engine is higher, therefore catalyst should as far as possible reduce back pressure in preparation process, wherein, catalyst
In coating coated weight, the granularity of coating slurry and coating coating position all be influence catalyst magnitude of back pressure it is important
Factor, the granularity D90 of floating coat slurries of the present invention is coating coated weight on 3~6um, and coating to the duct inwall of carrier
Fully ensured that catalyst has less back pressure for 10~40g/L so that using the method for the present invention prepare catalyst and
DOC catalyst has less overall pressure difference when being combined.
Claims (8)
1. a kind of diesel vehicle particle oxidative catalyst, it is characterised in that:Including carrier, coating, institute are coated with the carrier
The coated weight of coating is stated for 10 ~ 40g/L, the coating includes sial composite oxides, Rare-Earth Ce O2, β-molecular sieve and zirconium it is gluing
Knot agent, containing precious metals pt and precious metals pd in the coating, the coated weight of precious metals pt and precious metals pd is 5 ~ 90g/ft3,
The mass ratio of precious metals pt and precious metals pd is 1:5~3:1.
2. diesel vehicle particle oxidative catalyst as claimed in claim 1, it is characterised in that:Sial composite oxygen in the coating
Compound, Rare-Earth Ce O2, the mass ratio between β-molecular sieve be 0.525 ~ 0.84:0.1~0.15:0.05~0.3.
3. diesel vehicle particle oxidative catalyst as claimed in claim 1, it is characterised in that:The carrier is carborundum honeycomb
Carrier, its structure is wall-flow type structure, and the mesh number of the carrier is 200 ~ 300 mesh.
4. diesel vehicle particle oxidative catalyst as claimed in claim 1, it is characterised in that:In the sial composite oxides
The mass percent of silicon is 1.5 ~ 8%, and remaining is Al2O3。
5. the preparation method of the diesel vehicle particle oxidative catalyst described in claim 1, it is characterised in that:Including following step
Suddenly:
(1)Material is weighed:By weight 0.525 ~ 0.84:0.1~0.15:0.05 ~ 0.3 weighs sial combined oxidation respectively
Thing, β-molecular sieve, CeO2, and sial composite oxides and β-molecular sieve are mixed;
(2)Noble metal is weighed:The coated weight of coating is 10 ~ 40g/L, and the coated weight of precious metals pt and precious metals pd is 5 ~ 90g/
ft3, the wherein mass ratio of precious metals pt and precious metals pd is 1:5~3:1, size according to carrier calculate coating aequum and
Precious metals pt and precious metals pd aequum;
(3)The load of noble metal:By Pd(NO3)2Solution presses CeO2The 90% of water absorption rate is diluted with water rear incipient wetness impregnation in CeO2On,
By [Pt (NH3)4](OH)2Solution is diluted with water rear incipient wetness impregnation in sial composite oxygen by the 90% of sial composite oxides water absorption rate
In compound and β-molecular sieve mixture material, 10 ~ 12h is aged respectively;
(4)The treatment of precious metal material:The CeO of precious metals pd will be loaded with respectively2With the sial composite oxygen for being loaded with precious metals pt
Compound, β-molecular sieve mixture material are dried, are calcined;
(5)The preparation of slurries:By step(4)Material after middle roasting is added separately in deionized water, is stirred, is well mixed,
Be eventually adding zirconium glue caking agent and be made slurries, in slurries the solidfied material dry weight of zirconium glue caking agent account for total material solidfied material 0.01 ~
0.025%, slurries add dust technology to adjust the pH to less than 4.5 of slurries after ball milling;
(6)Slurry coating is coated:The coating of coating is carried out with quantitative coating special plane, carrier is positioned over the application chamber of coating special plane
Place, according to the coated weight of coating for the slurries that 10 ~ 40g/L will be calculated are added in slurry disk, carries out quantitative coating, and slurries lead to
Coating special plane is crossed to coat to the hole wall inner side of carrier;
(7)Slurries are dried and are calcined:The catalyst for having coated will be applied by 100 ~ 150 DEG C of flash bakings, drying time for 3 ~ 6h
Water evaporation in layer is fallen;Drying rear catalyst is put into Muffle furnace, 450 ~ 550 DEG C of 1 ~ 4h of roasting prepare diesel vehicle
Grain oxidative catalyst.
6. the preparation method of diesel vehicle particle oxidative catalyst as claimed in claim 5, it is characterised in that:The step
(3)Middle CeO2Water absorption rate be 80g water/100g CeO2, the water absorption rate of the sial composite oxides is 110g water/100g silicon
Aluminium composite oxide.
7. the preparation method of diesel vehicle particle oxidative catalyst as claimed in claim 5, it is characterised in that:The step
(4)Middle drying temperature is 100 ~ 150 DEG C, drying time 3-8h, and sintering temperature is 450 ~ 550 DEG C, 1 ~ 5h of roasting time.
8. the preparation method of diesel vehicle particle oxidative catalyst as claimed in claim 5, it is characterised in that:The step
(5)The granularity of middle ball milling rear slurry to D90 be 3 ~ 6um.
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CN114534486B (en) * | 2020-11-26 | 2023-03-31 | 长城汽车股份有限公司 | Method for purifying nitrogen oxide |
CN115387886A (en) * | 2022-09-23 | 2022-11-25 | 惠州市瑞合环保科技有限公司 | Diesel locomotive particle filter with catalyst slurry coating |
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