CN112221511B - Ternary metal oxide based diesel particulate oxidation catalyst and preparation method thereof - Google Patents

Ternary metal oxide based diesel particulate oxidation catalyst and preparation method thereof Download PDF

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CN112221511B
CN112221511B CN202011093153.7A CN202011093153A CN112221511B CN 112221511 B CN112221511 B CN 112221511B CN 202011093153 A CN202011093153 A CN 202011093153A CN 112221511 B CN112221511 B CN 112221511B
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coating
catalyst
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carrier
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CN112221511A (en
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李志军
孟雨
李振国
钟祥麟
宋金瓯
郑雪龙
申博玺
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Tianjin University
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
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    • 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
    • B01J37/0234—Impregnation and coating simultaneously
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    • B01D2255/30—Silica

Abstract

The invention discloses a ternary metal oxide-based diesel particulate oxidation catalyst and a preparation method thereof. Catalyst consisting of MoO3CuO and K2O is a main catalytic active ingredient, La2O3And V2O5Is a cocatalyst. The catalyst is coated in DOC, and can simultaneously and efficiently oxidize and purify PM, HC and CO in the exhaust gas of the diesel engine. The invention uses MoO3CuO and K2The O ternary composite oxide replaces the precious metal in the traditional DOC catalyst, reduces the raw material cost of the catalyst, and enhances the catalytic activity of the catalyst on the oxidation reaction of carbon components in PM. From La2O3And V2O5The formed cocatalyst further enhances the catalytic activity of the catalyst on PM oxidation reaction, and improves the sulfur resistance and thermal stability of the catalyst. The prior preparation of the main catalytic active ingredient precursor ensures the close combination of the components of the main catalytic active ingredient and promotes the exertion of the synergistic catalytic action among different components of the main catalytic active ingredient.

Description

Ternary metal oxide based diesel particulate oxidation catalyst and preparation method thereof
Technical Field
The invention belongs to the technology of purifying diesel engine tail gas pollutants, and particularly relates to a catalyst for oxidation purification reaction of diesel engine exhaust Particulate Matters (PM) and a preparation method thereof.
Background
Due to the limitation of working modes, the emission of PM and nitrogen oxides (NOx) of the diesel engine is high, and meanwhile, in the combustion process in a cylinder of the diesel engine, a 'trade-off' effect exists between the PM and the NOx, so that the control indexes of the emission regulations of China V and China VI aiming at the PM and the NOx of the diesel engine for vehicles cannot be met simultaneously by means of combustion optimization, and an exhaust aftertreatment system becomes necessary equipment of the diesel engine meeting the emission regulations of China V and China VI. At present, a Diesel Particulate Filter (DPF) is the most efficient and reliable post-treatment technology for purifying exhaust PM of a diesel engine, and is adopted by most diesel engines meeting national VI emission regulations. However, the DPF purifies the diesel exhaust PM mainly by physical interception, and a large amount of trapped PM is deposited in the DPF carrier pore channels, which causes the diesel exhaust to be pressurized, resulting in-cylinder combustion deterioration. Therefore, when the PM in the DPF is deposited to a certain extent, the diesel engine user is required to actively take measures to raise the diesel engine exhaust temperature to above the light-off temperature at which the PM undergoes a non-catalytic oxidation reaction, thereby realizing non-catalytic oxidation purification of the deposited PM. However, the regeneration process not only occupies the normal running time of the diesel engine, increases the maintenance cost of the whole engine and generates additional fuel consumption, but also seriously damages the reliability and the service life of the DPF carrier due to frequent high-temperature regeneration. If a Diesel Oxidation Catalyst (DOC) in front of the DPF is able to purify a part of the PM, the PM purification requirement of the DPF can be reduced, thereby reducing the regeneration frequency of the DPF. However, the precious metal main catalytic active component adopted by the traditional DOC has a good purification effect on gaseous pollutants such as carbon Hydrogen (HC) and carbon monoxide (CO) and a soluble organic component (SOF) in PM, and hardly has a purification effect on a carbonaceous component in PM. Therefore, the development of a high activity PM oxidation catalyst for DOC has become one of the technological bases for the design and optimization of low regeneration frequency diesel exhaust after-treatment systems.
Disclosure of Invention
Aiming at the prior art, the invention provides a ternary metal oxide-based diesel particulate oxidation catalyst and a preparation method thereof, aiming at improving the catalytic activity of DOC (catalyst oxygen degree) on the oxidation reaction of carbon components in PM (particulate matters) while efficiently purifying gaseous pollutants and SOF (soluble organic matters)3CuO and K2O as main catalytic active component and La2O3And V2O5The catalyst is used as a promoter, is coated in DOC, and can simultaneously and efficiently oxidize and purify PM, HC and CO in the exhaust gas of the diesel engine. The catalyst of the invention uses multi-element metal oxide to replace the main catalytic active component of noble metal in DOC, and combines with high-performance catalyst promoter to develop DOC oxidation catalyst with higher catalytic activity for oxidation reaction of SOF and carbonaceous components in HC, CO and PM. Including molybdenum trioxide (MoO)3) And copper oxide (CuO), have good catalytic properties for oxidation reactions. But MoO3MoO, which is easily sintered and lost when used alone with CuO, resulting in a shortened catalyst life3The CuO compound is used in combination with CuO, and the phenomena of sintering and loss can be slowed down or even avoided by mutual interference of crystal structures of two oxides. Further, potassium oxide (K) is added to the transition metal composite oxide2O) can enhance the mobility of catalytically active sites on the surface of the catalyst and can also provide for the oxidation of carbonaceous components to CO by the formation of intermediate carbonate species2These mechanisms of action are capable of significantly enhancing the catalytic activity of the oxidation reaction of the primary catalytically active component. On the other hand, lanthanum oxide (La) is added into the catalyst formula2O3) Can further promote the enhancement of the catalytic action of the main catalytic active component on the PM oxidation reaction, and can also improve the sulfur resistance of the catalyst. And vanadium pentoxide (V)2O5) As the catalyst promoter, the thermal stability of the multi-metal composite oxide can be improved, and the reliability and the service life of the catalyst can be prolonged.
In order to solve the technical problems, the invention provides a ternary metal oxide-based diesel particulate oxidation catalyst, which comprises a catalytic coating and a carrier, wherein the catalytic coating is coated on the carrier and consists of a main catalytic active component, a cocatalyst and a coating base material; the main catalytic active component consists of MoO3CuO and K2O composition of said MoO3CuO and K2The mass percentage of O is as follows: 30-40%/30-50%/20-30%, the MoO3CuO and K2The sum of the mass percentages of O is100 percent; the main catalytic active component, the cocatalyst and the coating base material comprise the following components in percentage by mass: 10-20%/20-30%/50-70%, wherein the sum of the mass percentages of the main catalytic active component, the cocatalyst and the coating base material is 100%.
Further, the catalyst of the present invention, wherein the cocatalyst is formed of La2O3And V2O5Composition of the La2O3And V2O5The mass percentage of the components is as follows: 80-90%/20-10%, the La2O3And V2O5The sum of the mass percentages of (A) and (B) is 100%.
The coating base material is made of TiO2、γ-Al2O3And SiO2Composition of the TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 20-40%/40-60%/10-20%, the TiO2、γ-Al2O3And SiO2The sum of the mass percentages of the components is 100 percent; the TiO is2From pure powdered TiO2Said gamma-Al2O3From pure powdery gamma-Al2O3Said SiO2From the product of silica gel calcination.
The mass percentages of the catalytic coating and the carrier are as follows: 15-30%/85-70%, wherein the sum of the mass percentages of the catalytic coating and the carrier is 100%; the carrier is 400-mesh cordierite honeycomb ceramic.
The preparation method of the catalyst comprises the following steps:
step 1) catalyst composition design: the composition of the catalyst is designed according to the proportion of each component in the catalyst, and the catalyst comprises MoO3CuO and K2Mass percent of O, La2O3And V2O5In mass percent of TiO2、γ-Al2O3And SiO2The mass percentages of the main catalytic active component, the cocatalyst and the coating base material, and the target mass percentage ranges of the catalytic coating and the carrierAnd planning the quality of the catalytic coating to be produced;
step 2) preparation of a precursor of the main catalytic active component: calculating MoO required by the preparation of the main catalytic active ingredient precursor according to the proportion of each component designed in the step 1) and the mass of the catalytic coating required to be generated by the planning in the step 1)3、CuO、K2O and TiO in coating base material2The mass of (c); combined per 1163.8g (NH)4)6Mo7O2Preparation 1008.0g MoO3241.6g of Cu (NO) per one gram3)2·3H2O preparation of 79.5g CuO per 202.2g KNO3Preparation 94.2g K2Calculating the (NH) required by the precursor of the main catalytic active ingredient by the conversion ratio of O4)6Mo7O2、Cu(NO3)2·3H2O and KNO3The mass of (c); weighing 4 raw materials with determined mass, namely pure powdery TiO2、(NH4)6Mo7O2、Cu(NO3)2·3H2O and KNO3Adding the 4 raw materials together to the mass equivalent to the TiO2Uniformly stirring the mixture in deionized water with the mass being 3-5 times that of the mixture to form slurry; grinding the slurry on a grinder to a median particle size, D50The particle size is within the range of 0.5-0.8 micron, and the ground slurry is stirred and heated at the temperature of 80-100 ℃ until the water in the slurry is evaporated to dryness and converted into solid; roasting the solid subjected to water evaporation at 500-600 ℃ for 2-3 h, wherein the roasted solid is a main catalytic active ingredient precursor;
step 3) preparation of a coating slurry for generating the catalytic coating: calculating La required for preparing coating slurry according to the proportion of each component designed in the step 1) and the quality of the catalytic coating required to be generated by the planning in the step 1)2O3、V2O5And gamma-Al2O3、SiO2The mass of (c); combined per 866.0g La (NO)3)3·6H2O preparation 325.8g La2O3Every 234.0g NH4VO3Preparation 182.0g V2O5Each 182.0g V2O5Adding oxalic acid 180.0-360.0 g, and SiO in silica gel2Calculating the mass percent of La (NO) required by preparing coating slurry3)3·6H2O、NH4VO3Mass of oxalic acid and silica gel; in addition, the mass of the polyethylene glycol and the nitric acid consumed for preparing the catalytic coating is calculated according to the proportion that every 100g of the catalytic coating needs 5-15 g of polyethylene glycol with the average molecular weight of 20000 and 25-50 g of nitric acid; weighing 8 materials with determined mass, namely La (NO)3)3·6H2O、NH4VO3Pure powder gamma-Al2O3Adding 8 raw materials into deionized water with the mass 2-4 times of that of the catalytic coating to be prepared, and uniformly stirring to form slurry; the slurry is then ground on a grinder to a median particle size, D50The particle size is within the range of 0.8-1.0 micron, and the ground pulp is stirred for 36-60 hours at the temperature of 70-90 ℃ to obtain coating pulp;
step 4) coating of coating slurry: designing the mass of said support to be coated with a catalytic coating; weighing the carrier with determined mass, immersing the carrier in the coating slurry at the temperature of 60-80 ℃, and ensuring that the upper end surface of the carrier is 0.2-1 cm higher than the liquid level of the coating slurry; after the coating slurry is naturally lifted to fill all pore channels of the carrier, taking the carrier out of the coating slurry, blowing off residual fluid in the pore channels, drying at 90-110 ℃ for 6-12 h, and roasting at 500-600 ℃ for 2-4 h; and repeating the processes of dipping, drying and roasting for 2-3 times to obtain the ternary metal oxide based diesel particulate oxidation catalyst.
The catalyst is packaged and then installed in an exhaust passage close to an exhaust manifold assembly of a diesel engine, so that the PM, HC and CO in the exhaust gas can be efficiently oxidized and purified at the same time.
Compared with the prior art, the invention has the beneficial effects that:
the invention uses MoO3CuO and K2The ternary composite oxide main catalytic active component formed by O replaces noble metal in the traditional DOC catalyst, so that the raw material cost of the DOC catalyst is reduced, the sulfur resistance and the thermal stability of the DOC catalyst are improved, and the catalytic activity of the novel DOC catalyst on the oxidation reaction of carbon components in PM is enhanced. From La2O3And V2O5The formed cocatalyst promotes the enhancement of the catalytic action of the main catalytic active component on the PM oxidation reaction, improves the sulfur resistance of the catalyst, improves the thermal stability of the multi-metal composite oxide, and prolongs the reliability and the service life of the catalyst. The prior preparation of the main catalytic active ingredient precursor ensures the close combination of all the components of the main catalytic active ingredient and promotes the exertion of the synergistic catalytic action among different components of the main catalytic active ingredient. In addition, made of TiO2、γ-Al2O3And SiO2The formed ternary coating base material provides a more suitable medium for the full play of the functions of the main catalytic active component and the cocatalyst.
Drawings
FIG. 1 is a schematic diagram of an engine evaluation system for diesel engine exhaust emission purification performance.
Wherein: 1-a dynamometer; 2-a coupler; 3-test diesel engine; 4-an intake air flow meter; 5-an air inlet processor; 6-oil injector; 7-a fuel injection control system; 8-exhaust sampling port A; 9-temperature sensor a; 10-DOC; 11-temperature sensor B; 12-exhaust sample port B; 13-double-channel temperature display instrument; 14-an exhaust sampling valve; 15-PM analyzer; 16-air pump.
FIG. 2 shows an engine evaluation system for evaluating the purification performance of exhaust pollutants of a diesel engine, wherein the average exhaust temperature in DOC is 350 ℃ and the airspeed is 60000h-1Under the steady-state working condition of (1), (3) the PM purification efficiency of the exhaust pollutant purification reaction in the DOC under the catalysis of the catalyst prepared in the embodiment is improved.
FIG. 3 shows an engine evaluation system for the purification performance of exhaust pollutants of a diesel engine, in which the DOC has an average exhaust temperature of 450 ℃ and a space velocity of 100000h-1In the steady state, examples 1 to 3PM purification efficiency of exhaust pollutant purification reaction in DOC under the catalysis of the prepared catalyst.
Fig. 4 shows PM purification efficiency of an exhaust pollutant purification reaction in DOC by using the diesel engine exhaust pollutant purification performance engine evaluation system in a european steady state test cycle (ESC) test under catalysis of the catalysts prepared in examples 1 to 3.
Detailed Description
The design idea of the invention is as follows: the utility model provides a PM oxidation purifies usefulness, ternary metal oxide base diesel engine particulate matter oxidation catalyst suitable for in DOC, includes catalytic coating and carrier, catalytic coating scribbles on the carrier, catalytic coating comprises main catalytic activity composition, cocatalyst and coating base material. With MoO3CuO and K2O is used as a main catalytic active ingredient, i.e. MoO3CuO and K2The O ternary composite oxide replaces the precious metal in the traditional DOC catalyst, reduces the raw material cost of the catalyst, and enhances the catalytic activity of the catalyst on the oxidation reaction of carbon components in PM. With La2O3And V2O5The catalyst is a cocatalyst, further enhances the catalytic activity of the catalyst on PM oxidation reaction, and also improves the sulfur resistance and thermal stability of the catalyst. In the preparation method, the prior preparation of the main catalytic active ingredient precursor ensures the close combination of the components of the main catalytic active ingredient and promotes the exertion of the synergistic catalytic action among different components of the main catalytic active ingredient. The catalyst prepared by the invention can be coated in DOC to simultaneously and efficiently oxidize and purify PM, HC and CO in the exhaust gas of a diesel engine.
In the ternary metal oxide-based diesel particulate oxidation catalyst of the present invention,
(1) from MoO3CuO and K2O constitutes the main catalytically active component, and the MoO3CuO and K2The mass percentage of O is as follows: 30-40%/30-50%/20-30%, the sum of the mass percentages being 100%.
(2) From La2O3And V2O5Constitute a cocatalyst, and the La2O3And V2O5The weight percentage of the components is as follows: 80-90%/20-10%, the sum of the mass percentages being 100%.
(3) From TiO2、γ-Al2O3And SiO2Constituting a coating base material, and the TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 20-40%/40-60%/10-20%, the sum of the mass percentages is 100%; the TiO is2From pure powdered TiO2The gamma-Al2O3From pure powdery gamma-Al2O3The SiO is2From the product of silica gel calcination.
(4) The catalytic coating of the catalyst comprises the main catalytic active component, the cocatalyst and a coating base material, and the main catalytic active component, the cocatalyst and the coating base material comprise the following components in percentage by mass: 10-20%/20-30%/50-70%, and the sum of the mass percentages is 100%.
(5) The catalyst of the invention is composed of the catalytic coating and 400-mesh cordierite honeycomb ceramic, the 400-mesh cordierite honeycomb ceramic is a carrier of the catalyst of the invention, the catalytic coating is required to be coated on the carrier, and the mass percentage ranges of the catalytic coating and the carrier are as follows: 15-30%/85-70%, and the sum of the mass percentages is 100%.
The preparation method of the ternary metal oxide-based diesel particulate oxidation catalyst mainly comprises the following 4 steps: designing the composition of a catalyst, preparing a precursor of a main catalytic active component, preparing coating slurry and coating the coating slurry.
The technical solution of the present invention is further described below by specific examples, and with reference to the accompanying drawings. It should be noted that the embodiments described above are illustrative and not restrictive, and the invention is not to be limited to the following embodiments.
The ternary metal oxide-based diesel particulate oxidation catalyst includes: MoO3、CuO、K2O、La2O3、V2O5、TiO2、γ-Al2O3And SiO2And 400 mesh cordierite honeycomb ceramic.
From MoO3CuO and K2O constitutes the main catalytically active component, and the MoO3CuO and K2The mass percentage of O is as follows: 30-40%/30-50%/20-30%, and the sum of the mass percentages is 100%.
From La2O3And V2O5Constitute a cocatalyst, and the La2O3And V2O5The mass percentage of the components is as follows: 80-90%/20-10%, and the sum of the mass percentages is 100%.
From TiO2、γ-Al2O3And SiO2Constituting a coating base material, and said TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 20-40%/40-60%/10-20%, the sum of the mass percentages being 100%; the TiO is2From pure powdered TiO2The gamma-Al2O3From pure powdery gamma-Al2O3Said SiO2From the product of silica gel calcination.
The catalytic coating of the catalyst comprises the main catalytic active component, the cocatalyst and a coating base material, and the main catalytic active component, the cocatalyst and the coating base material comprise the following components in percentage by mass: 10-20%/20-30%/50-70%, and the sum of the mass percentages is 100%.
The catalyst of the invention is composed of the catalytic coating and 400-mesh cordierite honeycomb ceramic, the 400-mesh cordierite honeycomb ceramic is a carrier of the catalyst of the invention, the catalytic coating is required to be coated on the carrier, and the mass percentages of the catalytic coating and the carrier are as follows: 15-30%/85-70%, and the sum of the mass percentages is 100%.
The method for preparing the catalyst of the present invention is described in detail below with reference to specific examples.
Example 1
(1) Catalyst composition design
The following proportions are respectively designed: MoO3CuO andK2the mass percentage of O is as follows: 40%/40%/20%, La2O3And V2O5The mass percentage of the components is as follows: 80%/20%, TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 40%/50%/10%, the mass percent of the main catalytic active component, the cocatalyst and the coating base material is as follows: 20%/20%/60%, the target mass percentage ranges of the catalytic coating and the carrier are: 19-21%/81-79%, the sum of the mass percentages being 100%; and the coating slurry was planned to produce 2000g of catalytic coating.
(2) Preparation of main catalytic active ingredient precursor
480g of powdered TiO were weighed2、184.7g(NH4)6Mo7O2、486.2g Cu(NO3)2·3H2O and 171.7g KNO3Adding the 4 raw materials into 1440g of deionized water, and uniformly stirring to form slurry; grinding the slurry on a grinder to a median particle size (D)50Particle size) is within the range of 0.5-0.8 micron, and the ground pulp is stirred and heated at the temperature of 80 ℃ until the water in the pulp is evaporated to dryness and converted into solid; and roasting the solid after the water is evaporated to dryness at 500 ℃ for 3 hours, wherein the roasted solid is the precursor of the main catalytic active ingredient.
(3) Preparation of coating slurries
850.6g La (NO) was weighed out3)3·6H2O、102.9g NH4VO3600g of pure powdery gamma-Al2O379.1g of oxalic acid, 480g of SiO2Adding 8 raw materials into 10000g of deionized water together, and uniformly stirring to form a slurry, wherein the mass content of the silica gel is 25%, 300g of polyethylene glycol with the molecular weight of 20000, 500g of nitric acid and the main catalytic active ingredient precursor prepared in the step (2); the slurry was then ground on a mill to a median particle size (D)50Particle size) is within the range of 0.8-1.0 micron, and the ground slurry is stirred for 60 hours at 70 ℃ to obtain coating slurry.
(4) Application of coating slurries
Weighing 1000g of the carrier, immersing the carrier in the coating slurry at 60 ℃, and ensuring that the upper end surface of the carrier is 0.2cm higher than the liquid level of the slurry; and after the slurry is naturally lifted to fill all pore channels of the carrier, taking the carrier out of the slurry, blowing off residual fluid in the pore channels, drying at 90 ℃ for 12h, and roasting at 500 ℃ for 4 h. Repeating the processes of dipping, drying and roasting for 2 times to obtain the ternary metal oxide-based diesel particulate oxidation catalyst.
Example 2
(1) Catalyst composition design
The following proportions are respectively designed: MoO3CuO and K2The mass percentage of O is as follows: 30%/40%/30%, La2O3And V2O5The mass percentage of the components is as follows: 90%/10%, TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 20%/60%/20%, the mass percent of the main catalytic active component, the cocatalyst and the coating base material is as follows: 20%/30%/50%, the target mass percentage ranges of the catalytic coating and the carrier are: 27-29%/73-71%, and the sum of the mass percentages is 100%; and it was planned that the coating slurry could be formulated to produce 2000g of catalytic coating.
(2) Preparation of main catalytic active ingredient precursor
Weighing 200g of powdered TiO2、138.5g(NH4)6Mo7O2、486.2g Cu(NO3)2·3H2O and 257.6g KNO3Adding the 4 raw materials into 1000g of deionized water, and uniformly stirring to form slurry; grinding the slurry on a grinder to a median particle size (D)50Particle size) is within the range of 0.5-0.8 micron, and the ground pulp is stirred and heated at the temperature of 100 ℃ until the water in the pulp is evaporated to dryness and converted into solid; and roasting the solid subjected to water evaporation at 600 ℃ for 2 hours, wherein the roasted solid is a precursor of the main catalytic active ingredient.
(3) Preparation of coating slurries
Weighing 1435.4g La (NO)3)3·6H2O、77.1g NH4VO3600g of pure powdery gamma-Al2O3118.7g of oxalic acid, 800g of SiO2Adding 8 raw materials into 15000g of deionized water together, and uniformly stirring to form a slurry, wherein the mass content of the silica gel is 25%, 100g of polyethylene glycol with the molecular weight of 20000, 1000g of nitric acid and the main catalytic active ingredient precursor prepared in the step (2); the slurry was then ground on a grinder to a median particle size (D)50Particle size) is within the range of 0.8-1.0 micron, and the ground slurry is stirred for 36 hours at 90 ℃ to obtain coating slurry.
(4) Application of coating slurries
Weighing 1000g of the carrier, immersing the carrier in the coating slurry at 80 ℃, and ensuring that the upper end surface of the carrier is 0.5cm higher than the liquid level of the slurry; after the slurry is naturally lifted to fill all pore channels of the carrier, taking the carrier out of the slurry, blowing off residual fluid in the pore channels, drying at 110 ℃ for 6h, and roasting at 600 ℃ for 2 h; repeating the processes of dipping, drying and roasting for 3 times to obtain the ternary metal oxide-based diesel particulate oxidation catalyst.
Example 3
(1) Catalyst composition design
The following proportions are respectively designed: MoO3CuO and K2The mass percentage of O is as follows: 30%/50%/20%, La2O3And V2O5The weight percentage of the components is as follows: 80%/20%, TiO2、γ-Al2O3And SiO2The weight percentage of the components is as follows: 30%/60%/10%, the mass percent of the main catalytic active component, the cocatalyst and the coating base material is as follows: 10%/20%/70%, the target mass percentage ranges of the catalytic coating and the carrier are: 22-24%/78-76%, the sum of the mass percentages is 100%; and it was planned that the coating slurry could be formulated to produce 2000g of catalytic coating.
(2) Preparation of main catalytic active ingredient precursor
420g of powdered TiO are weighed2、69.3g(NH4)6Mo7O2、303.9g Cu(NO3)2·3H2O、85.9g KNO3Adding the 4 raw materials into 1680g of deionized water, and uniformly stirring to form a slurry; grinding the slurry on a grinder to a median particle size (D)50Particle size) is within the range of 0.5-0.8 microns, and the ground slurry is stirred and heated at 90 ℃ until the water in the slurry is evaporated to dryness and converted into solid; and roasting the solid after the water is evaporated to dryness at the temperature of 600 ℃ for 2 hours, wherein the roasted solid is the precursor of the main catalytic active component.
(3) Preparation of coating slurries
Weighing 850.6g La (NO)3)3·6H2O、102.9g NH4VO3840g of pure powdery gamma-Al2O387.9g of oxalic acid, 560g of SiO2Adding 8 raw materials into 20000g of deionized water together, and uniformly stirring to form a slurry, wherein the mass content of the silica gel is 25%, the 200g of polyethylene glycol with the molecular weight of 20000, the 600g of nitric acid and the main catalytic active ingredient precursor prepared in the step (2) are mixed; the slurry was then ground on a grinder to a median particle size (D)50Particle size) is within the range of 0.8-1.0 micron, and the ground slurry is stirred for 48 hours at 80 ℃ to obtain coating slurry.
(4) Application of coating slurries
Weighing 1000g of the carrier, immersing the carrier in the coating slurry at 80 ℃, and ensuring that the upper end surface of the carrier is 1cm higher than the liquid level of the slurry; after the slurry is naturally lifted to fill all pore channels of the carrier, taking the carrier out of the slurry, blowing off residual fluid in the pore channels, drying at 100 ℃ for 9h, and roasting at 600 ℃ for 3 h; repeating the processes of dipping, drying and roasting for 3 times to obtain the ternary metal oxide-based diesel particulate oxidation catalyst.
The PM purification efficiency of the exhaust pollutant purification reaction in the DOC under the catalysis of the catalyst prepared in examples 1 to 3 was evaluated by using the diesel engine exhaust pollutant purification performance engine evaluation system shown in fig. 1. Before the test, the catalysts prepared in the embodiments 1 to 3 are respectively cut and respectively combined into an integral catalyst, and the cut and combined integral catalyst is packaged. The test method comprises the following steps:
(1) and (3) steady-state working condition test: as shown in figure 1, a dynamometer 1 and a coupling 2 are used for controlling the torque and the rotating speed of a test engine (CY4102 type diesel engine) 3, the fuel supply speed of a fuel injector 6 to the diesel engine is adjusted through a fuel injection control system 7, and the proportion of the exhaust flow of the engine to the volume of a catalyst is controlled to be 60000h-1And 100000h-1And controlling the average exhaust temperature in the DOC 10 to be 350 ℃ and 450 ℃ respectively in sequence to evaluate the PM purification performance. The intake air flow measurement value of the intake air flow meter 4 provides feedback parameters for the control strategy of the fuel injection control system; and the intake air processor 5 supplies the engine with clean air of a specific temperature and humidity. The temperature sensor A9 and the temperature sensor B11 measure the exhaust temperature at two ends of the DOC 10 respectively, the exhaust temperature is displayed by the dual-channel temperature display instrument 13, and the average temperature of the exhaust in the DOC 10 can be obtained by calculating the average value of the two temperatures. Exhaust samples before and after being processed by the DOC 10 enter the exhaust sampling valve 14 and the PM analyzer 15 through the exhaust sampling port A8 and the exhaust sampling port B12 respectively for PM emission analysis, and the exhaust after PM analysis is discharged out of a laboratory through the air pump 16. By utilizing the engine evaluation system for the purification performance of the diesel engine exhaust pollutants, the average exhaust temperature in DOC is 350 ℃, and the airspeed is 60000h-1The average exhaust temperature in time and DOC is 450 ℃ and the space velocity is 100000h-1In the meantime, the PM purification efficiency of the catalysts prepared in examples 1 to 3 is shown in fig. 2 and 3, respectively.
(2) ESC test: the evaluation system of the engine for the purification performance of the exhaust pollutants of the diesel engine shown in fig. 1 is adopted, and the PM purification efficiency of the purification reaction of the exhaust pollutants in the DOC under the catalysis of the catalyst prepared in the examples 1 to 3 is evaluated according to the ESC test regulations specified in the national standard GB 17691-2005, "emission limits of compression ignition type and gas fuel ignition type engines for vehicles and exhaust pollutants of automobiles, and the measurement method (stages III, IV, V), and the results are shown in fig. 4.
The ternary metal oxide-based diesel particulate oxidation catalyst provided by the inventionPM in exhaust gas of a diesel engine can be efficiently purified by a catalytic oxidation reaction mechanism. When the consumption of the main catalytic active component raw material is high and the proportion is proper (example 2), the PM purification efficiency under the normal and low exhaust temperature test working conditions exceeds 65%, the PM purification efficiency under the ESC circulation working condition test is also close to 65%, and the requirement of the tail gas aftertreatment system of the diesel engine in the VI can be met. The invention uses MoO3CuO and K2The ternary composite oxide main catalytic active component formed by O replaces noble metal in the traditional DOC catalyst, so that the raw material cost of the DOC catalyst is reduced, the sulfur resistance and the thermal stability of the DOC catalyst are improved, and the catalytic activity of the novel DOC catalyst on the oxidation reaction of carbon components in PM is enhanced. From La2O3And V2O5The formed cocatalyst promotes the enhancement of the catalytic action of the main catalytic active component on the PM oxidation reaction, improves the sulfur resistance of the catalyst, improves the thermal stability of the multi-metal composite oxide, and prolongs the reliability and the service life of the catalyst. The prior preparation of the main catalytic active ingredient precursor ensures the close combination of all the components of the main catalytic active ingredient and promotes the exertion of the synergistic catalytic action among different components of the main catalytic active ingredient. In the invention, the mass proportion of the main catalytic active component in the catalytic coating and the proportion of each component in the main catalytic active component are the most important influence factors on the PM purification performance of the catalyst, and the mass proportion and proportion of the cocatalyst in the catalytic coating are secondary factors influencing the PM purification performance of the catalyst.
Although the present invention has been described in connection with the accompanying drawings, the present invention is not limited to the above-described embodiments, which are intended to be illustrative rather than restrictive, and many modifications may be made by those skilled in the art without departing from the spirit of the present invention as disclosed in the appended claims.

Claims (4)

1. A ternary metal oxide-based diesel particulate oxidation catalyst comprises a catalytic coating and a carrier, wherein the catalytic coating is coated on the carrier and consists of a main catalytic active component, a cocatalyst and a coating base material; it is characterized in that the preparation method is characterized in that,
the main catalytic active component consists of MoO3CuO and K2O composition, said MoO3CuO and K2The mass percentage of O is as follows: 30-40%/30-50%/20-30%, the MoO3CuO and K2The sum of the mass percentages of O is 100 percent;
the main catalytic active component, the cocatalyst and the coating base material are as follows by mass percent: 10-20%/20-30%/50-70%, wherein the sum of the mass percentages of the main catalytic active component, the cocatalyst and the coating base material is 100%;
the cocatalyst is La2O3And V2O5Composition of the La2O3And V2O5The mass percentage of the components is as follows: 80-90%/20-10%, the La2O3And V2O5The sum of the mass percentages of the components is 100 percent;
the coating base material is made of TiO2、γ-Al2O3And SiO2Composition of said TiO2、γ-Al2O3And SiO2The mass percentage of the components is as follows: 20-40%/40-60%/10-20%, the TiO2、γ-Al2O3And SiO2The sum of the mass percentages of the components is 100 percent; the TiO is2From pure powdered TiO2The gamma-Al2O3From pure powdery gamma-Al2O3Said SiO2From the product of silica gel calcination.
2. The three-way metal oxide-based diesel particulate oxidation catalyst of claim 1, wherein: the mass percentages of the catalytic coating and the carrier are as follows: 15-30%/85-70%, wherein the sum of the mass percentages of the catalytic coating and the carrier is 100%; the carrier is 400-mesh cordierite honeycomb ceramic.
3. A method for preparing a ternary metal oxide-based diesel particulate oxidation catalyst according to any one of claims 1 or 2, comprising the steps of:
step 1) catalyst composition design:
the composition of the catalyst is designed according to the ratio of each component in the catalyst according to any one of claims 1 or 2, comprising MoO3CuO and K2Mass percent of O, La2O3And V2O5In mass percent of TiO2、γ-Al2O3And SiO2The mass percentages of the main catalytic active component, the cocatalyst and the coating base material, the target mass percentage range of the catalytic coating and the carrier, and the mass of the catalytic coating required to be generated in plan;
step 2) preparation of a precursor of a main catalytic active component:
calculating MoO required by the preparation of the precursor of the main catalytic active component according to the proportion of each component designed in the step 1) and the mass of the catalytic coating required to be generated by the planning in the step 1)3、CuO、K2O and TiO in coating base material2The mass of (c); combined per 1163.8g (NH)4)6Mo7O2Preparation 1008.0g of MoO3Each 241.6g of Cu (NO)3)2·3H2O preparation of 79.5g CuO per 202.2g KNO3Preparation 94.2g K2Calculating the (NH) required by the precursor of the main catalytic active ingredient by the conversion ratio of O4)6Mo7O2、Cu(NO3)2·3H2O and KNO3The mass of (c); weighing 4 raw materials with determined mass, namely pure powdery TiO2、(NH4)6Mo7O2、Cu(NO3)2·3H2O and KNO3Adding the 4 raw materials together to the mass equivalent to the TiO2Uniformly stirring the mixture in deionized water with the mass being 3-5 times that of the mixture to form slurry;
grinding the slurry on a grinder to a median particle size, D50Particle size of 0.5EWithin the range of 0.8 micron, stirring and heating the ground slurry at 80-100 ℃ until the water in the slurry is evaporated to dryness and converted into a solid; roasting the solid after the water is evaporated to dryness at 500-600 ℃ for 2-3 h, wherein the roasted solid is a main catalytic active ingredient precursor;
step 3) preparation of a coating slurry for generating the catalytic coating:
calculating the La required for preparing the coating slurry according to the proportion of each component designed in the step 1) and the mass of the catalytic coating required to be generated by the planning in the step 1)2O3、V2O5And gamma-Al2O3、SiO2The mass of (c); bound per 866.0gLa (NO)3)3·6H2O preparation 325.8g La2O3Every 234.0g NH4VO3Preparation 182.0g V2O5Each 182.0g V2O5Adding oxalic acid 180.0-360.0 g, and SiO in silica gel2Calculating the mass percent of La (NO) required by preparing coating slurry3)3·6H2O、NH4VO3Mass of oxalic acid and silica gel; in addition, the mass of the polyethylene glycol and the nitric acid consumed for preparing the catalytic coating is calculated according to the proportion that every 100g of the catalytic coating needs 5-15 g of polyethylene glycol with the average molecular weight of 20000 and 25-50 g of nitric acid;
weighing 8 kinds of raw materials, La (NO) with determined mass3)3·6H2O、NH4VO3Pure powder gamma-Al2O3Adding 8 raw materials into deionized water with the mass 2-4 times of that of the catalytic coating prepared in the step 2) together, and uniformly stirring to form slurry;
the slurry is then ground on a mill to a median particle size, D50The particle size is within the range of 0.8-1.0 micron, and the ground pulp is stirred for 36-60 hours at the temperature of 70-90 ℃ to obtain coating pulp;
step 4) coating of coating slurry:
designing the mass of said support to be coated with a catalytic coating; weighing the carrier with determined mass, immersing the carrier in the coating slurry at the temperature of 60-80 ℃, and ensuring that the upper end surface of the carrier is 0.2-1 cm higher than the liquid level of the coating slurry; after the coating slurry is naturally lifted to fill all pore channels of the carrier, taking the carrier out of the coating slurry, blowing off residual fluid in the pore channels, drying at 90-110 ℃ for 6-12 h, and roasting at 500-600 ℃ for 2-4 h; and repeating the processes of dipping, drying and roasting for 2-3 times to obtain the ternary metal oxide based diesel particulate oxidation catalyst.
4. The use of the ternary metal oxide-based diesel particulate oxidation catalyst prepared by the preparation method of claim 3, wherein the catalyst is packaged and then installed in an exhaust passage close to an exhaust manifold assembly of a diesel engine, so that the simultaneous efficient oxidation and purification of PM, HC and CO in exhaust gas is realized.
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CN113797915B (en) * 2021-10-24 2023-11-21 合肥神舟催化净化器股份有限公司 Diesel oxidation catalyst based on metal oxide nano particles, preparation method and application
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0724260A (en) * 1993-07-15 1995-01-27 I C T:Kk Catalyst for purification of exhaust gas from diesel engine
CN101056692A (en) * 2004-10-14 2007-10-17 催化溶液公司 Platinum group metal-free catalysts for reducing the ignition temperature of particulates on a diesel particulate filter
CN105944749A (en) * 2016-05-05 2016-09-21 合肥神舟催化净化器有限公司 Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines
CN106582794A (en) * 2016-11-18 2017-04-26 天津大学 Catalyst based on modified molecular sieve and hydrotalcite derived oxides and applied to diesel engine, preparation and application
CN106622348A (en) * 2016-11-14 2017-05-10 天津大学 Ferrous modified molecular sieve type diesel engine selective catalytic reduction catalyst
CN109201052A (en) * 2018-09-30 2019-01-15 中自环保科技股份有限公司 A kind of diesel soot particle oxidation catalyst and preparation method thereof
CN109589988A (en) * 2018-12-31 2019-04-09 天津大学 The double coated catalysts of diesel engine based on hydrotalcite Derived Oxides and preparation method
CN109589976A (en) * 2018-12-31 2019-04-09 天津大学 Use for diesel engine catalyst and preparation method based on oxide compound primary catalysts

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0724260A (en) * 1993-07-15 1995-01-27 I C T:Kk Catalyst for purification of exhaust gas from diesel engine
CN101056692A (en) * 2004-10-14 2007-10-17 催化溶液公司 Platinum group metal-free catalysts for reducing the ignition temperature of particulates on a diesel particulate filter
CN105944749A (en) * 2016-05-05 2016-09-21 合肥神舟催化净化器有限公司 Modified molecular sieve main catalyst based composite oxidation catalyst for diesel engines
CN106622348A (en) * 2016-11-14 2017-05-10 天津大学 Ferrous modified molecular sieve type diesel engine selective catalytic reduction catalyst
CN106582794A (en) * 2016-11-18 2017-04-26 天津大学 Catalyst based on modified molecular sieve and hydrotalcite derived oxides and applied to diesel engine, preparation and application
CN109201052A (en) * 2018-09-30 2019-01-15 中自环保科技股份有限公司 A kind of diesel soot particle oxidation catalyst and preparation method thereof
CN109589988A (en) * 2018-12-31 2019-04-09 天津大学 The double coated catalysts of diesel engine based on hydrotalcite Derived Oxides and preparation method
CN109589976A (en) * 2018-12-31 2019-04-09 天津大学 Use for diesel engine catalyst and preparation method based on oxide compound primary catalysts

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