CN118950030A - Methanol fuel automobile exhaust purification catalyst - Google Patents
Methanol fuel automobile exhaust purification catalyst Download PDFInfo
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Abstract
本发明涉及汽车尾气净化技术领域，提出了甲醇燃料汽车尾气净化催化剂，包括前级催化剂和后级催化剂；前级催化剂的原料为前级稀土主料、前级活性料和前级辅料；后级催化剂的原料为后级稀土主料、后级活性料和后级辅料；前级稀土主料为高铈稀土、中铈中锆稀土、前级金属氧化物、前级贵金属和钴黑色料；后级稀土主料为高锆稀土、中铈中锆稀土、后级金属氧化物和后级贵金属；高铈稀土的铈含量为50wt%~60wt%；中铈中锆稀土的铈含量为30wt%~40wt%，锆含量为40wt%~50wt%；高锆稀土的锆含量为60wt%~70wt%。通过上述技术方案，解决了相关技术中的甲醇燃料汽车尾气净化催化剂的尾气净化性能较差的问题。The invention relates to the technical field of automobile exhaust purification, and proposes a methanol fuel automobile exhaust purification catalyst, including a front-stage catalyst and a rear-stage catalyst; the raw materials of the front-stage catalyst are a front-stage rare earth main material, a front-stage active material and a front-stage auxiliary material; the raw materials of the rear-stage catalyst are a rear-stage rare earth main material, a rear-stage active material and a rear-stage auxiliary material; the front-stage rare earth main material is high cerium rare earth, medium cerium and medium zirconium rare earth, a front-stage metal oxide, a front-stage precious metal and a cobalt black material; the rear-stage rare earth main material is high zirconium rare earth, medium cerium and medium zirconium rare earth, a rear-stage metal oxide and a rear-stage precious metal; the cerium content of the high cerium rare earth is 50wt%~60wt%; the cerium content of the medium cerium and medium zirconium rare earth is 30wt%~40wt%, and the zirconium content is 40wt%~50wt%; the zirconium content of the high zirconium rare earth is 60wt%~70wt%. Through the above technical scheme, the problem of poor exhaust purification performance of the methanol fuel automobile exhaust purification catalyst in the related art is solved.
Description
Technical Field
The invention relates to the technical field of automobile exhaust purification, in particular to a methanol fuel automobile exhaust purification catalyst.
Background
With the development of the automobile industry, methanol has been considered as the most promising and optimal alternative fuel for automobiles because of its physicochemical properties similar to those of gasoline and its very abundant raw materials (coal, natural gas, biomass, etc.) for production. At present, the development of methanol fuel automobiles plays an important role in the development of automobile industry in China, but the main pollutants discharged by methanol fuel automobiles are a large amount of unburned methanol and incompletely combusted products such as formaldehyde and the like, which form serious threat to the environment and human bodies and must be purified.
Catalysts installed in the exhaust system of automobiles can achieve purification of exhaust gas, and currently, these catalysts are generally three-way catalysts. The three-way catalyst consists of two parts: a support and an active catalytic material coated on the support; the active catalytic material is usually one or more noble metals such as platinum, palladium and rhodium, and additionally an oxidizing material and the like are added, so that the catalytic activity, the deep oxidation-reduction performance and the like of the existing methanol fuel automobile exhaust purification catalyst do not meet the actual practical requirements.
Therefore, the development of the methanol fuel automobile exhaust gas purifying catalyst with excellent exhaust gas purifying performance has important significance in various aspects of automobile industry, energy structure and the like in China.
Disclosure of Invention
The invention provides a methanol fuel automobile exhaust purification catalyst, which solves the problem of poor exhaust purification performance of the methanol fuel automobile exhaust purification catalyst in the related art.
The technical scheme of the invention is as follows:
The invention provides a methanol fuel automobile tail gas purifying catalyst, which comprises a front-stage catalyst and a rear-stage catalyst;
the raw materials of the pre-stage catalyst comprise a pre-stage rare earth main material, a pre-stage active material and a pre-stage auxiliary material;
The raw materials of the rear-stage catalyst comprise rear-stage rare earth main materials, rear-stage active materials and rear-stage auxiliary materials;
The front-stage rare earth main material comprises high cerium rare earth, middle cerium middle zirconium rare earth, front-stage metal oxide, front-stage noble metal and cobalt black;
The rear-stage rare earth main material comprises high-zirconium rare earth, middle-cerium middle-zirconium rare earth, rear-stage metal oxide and rear-stage noble metal;
the cerium content of the high-cerium rare earth is 50-60 wt%; the cerium content of the zirconium rare earth in the middle cerium is 30-40 wt% and the zirconium content is 40-50 wt%; the zirconium content of the high-zirconium rare earth is 60-70 wt%.
As a further technical scheme, the cobalt content of the cobalt black material is 40-50 wt%.
As a further technical scheme, the pre-stage metal oxide and the post-stage metal oxide each independently comprise one or more of nano titanium dioxide, nano aluminum oxide and lanthanum modified aluminum oxide.
As a further technical scheme, the nano titanium dioxide is nano titanium dioxide containing tungsten, and the tungsten content is 2-10 wt%.
As a further technical scheme, the pre-stage active material and the post-stage active material each independently comprise an organic acid and a metal salt.
As a further technical scheme, the organic acid is one or more of citric acid, malic acid, oxalic acid and tartaric acid;
the metal salt is one or more of cobalt salt, manganese salt, barium salt and nickel salt.
As a further technical scheme, the pre-stage auxiliary material and the post-stage auxiliary material each independently comprise a thickener, a pH regulator and water.
As a further technical scheme, the thickener is one or two of aluminum sol and cellulose thickener; the pH regulator is an acidic pH regulator.
The invention also provides a methanol fuel automobile exhaust purification catalyst, which comprises the following components in parts by weight:
the raw materials of the pre-stage catalyst comprise 1500-1520 parts of pre-stage rare earth main material, 80-111 parts of pre-stage active material and 3846-4210 parts of pre-stage auxiliary material;
The raw materials of the rear-stage catalyst comprise 1500 parts of rear-stage rare earth main materials, 90 parts of rear-stage active materials and 4210-4212 parts of rear-stage auxiliary materials;
The front-stage rare earth main material comprises 580-700 parts of high cerium rare earth, 300-400 parts of middle cerium zirconium rare earth, 500-510 parts of front-stage metal oxide and 5-30 parts of cobalt black material;
The rear-stage rare earth main material comprises 700-800 parts of high-zirconium rare earth, 200-300 parts of middle-cerium middle-zirconium rare earth and 500 parts of rear-stage metal oxide.
As a further technical scheme, the pre-stage noble metal comprises Pt, pd and Rh; the latter noble metal includes Pd and Rh.
As a further technical scheme, the aluminum sol comprises aluminum sol P4 (07), aluminum sol JHALH-15 and aluminum sol SRJ-01; the cellulose thickener is one or more of hydroxypropyl methylcellulose, hydroxyethyl cellulose, methylcellulose, hydroxyethyl methylcellulose and hydroxypropyl cellulose.
As a further technical scheme, the mass ratio of the aluminum sol P4 (07), the aluminum sol JHALH-15 and the aluminum sol SRJ-01 is 5-10:5:7.
As a further technical scheme, the mass ratio of the nano titanium dioxide to the nano aluminum oxide to the lanthanum modified aluminum oxide is 5-7:9-10:10.
As a further technical scheme, the mass ratio of the organic acid to the metal salt is 1-3:3.
As a further technical scheme, when the thickener is aluminum sol and cellulose thickener, the mass ratio of the aluminum sol to the cellulose thickener is 170:2-4.
As a further technical scheme, the metal salt in the pre-stage active material is cobalt salt, manganese salt and barium salt.
As a further technical scheme, the metal salt in the later-stage active material is barium salt and nickel salt.
As a further technical scheme, the preparation process of the pre-stage catalyst comprises the following steps:
And mixing the pre-stage active material solution, the pre-stage auxiliary material solution and the pre-stage rare earth main material to obtain the pre-stage catalyst.
As a further technical scheme, the preparation process of the post-catalyst comprises the following steps:
and mixing the rear-stage active material solution, the rear-stage auxiliary material solution and the rear-stage rare earth main material to obtain the rear-stage catalyst.
As a further technical scheme, the application method of the pre-stage catalyst comprises the following steps: the pre-catalyst is coated on the surface of a carrier, and can be applied to the tail gas purification of a methanol fuel automobile after being dried and roasted.
As a further technical scheme, the application method of the post-stage catalyst comprises the following steps: the catalyst of the later stage is coated on the surface of a carrier, and can be applied to the tail gas purification of a methanol fuel automobile after being dried and roasted.
As a further technical scheme, the temperature of the drying is 50-60 ℃;
The temperature is raised to 100 ℃ at a heating rate of 2.5 ℃/min during the roasting, and the temperature is kept for 60min;
heating from 100 ℃ to 150 ℃ at a heating rate of 1.25 ℃/min, and preserving heat for 60min;
then heating from 150 ℃ to 250 ℃ at a heating rate of 1.67 ℃/min, and preserving heat for 30min;
Then heating from 250 ℃ to 550 ℃ at a heating rate of 1.67 ℃/min, and preserving heat for 150-180min.
In the invention, a roasting method of stepwise heating is adopted during roasting, and the temperature is firstly raised to 100 ℃ and is kept for 60min; the adsorbed water on the surface of the coating material can be effectively discharged; then heating from 100 ℃ to 150 ℃ and preserving heat for 60min, so that the crystal water of the internal structure of the coating material can be effectively removed; heating from 150deg.C to 250deg.C, maintaining for 30min, and discharging organic components in the coating material; the temperature is raised from 250 ℃ to 550 ℃, and the temperature is kept for 150-180 min, so that the catalytic activity and stability of the catalyst can be fully ensured.
The working principle and the beneficial effects of the invention are as follows:
In the invention, the methanol fuel automobile exhaust purifying catalyst comprises a front-stage catalyst and a rear-stage catalyst. The pre-stage catalyst mainly purifies CO, THC, NMHC, CH 4 and other pollutants; the latter stage catalyst mainly purifies NOx and the like. By adding rare earth, cobalt black, metal oxide, metal salt and other components into the catalyst, the cobalt black is favorable for purifying CO, and the metal oxide and other components are favorable for purifying formaldehyde and methanol. The organic combination of the front stage and the rear stage and the mutual matching of the components finally obviously improve the purification performance of the catalyst on the tail gas of the methanol fuel automobile, and the methanol fuel automobile tail gas purification catalyst has excellent thermal shock resistance and can resist the high temperature of 1000 ℃.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, the information of the raw materials used is shown in table 1 below.
TABLE 1 raw material information
The preparation method of the cobalt black material comprises the following steps:
Mixing lanthanum nitrate, cerium nitrate, cobalt nitrate, ferric nitrate and deionized water at 80 ℃ under stirring until the lanthanum nitrate, the cerium nitrate, the cobalt nitrate and the ferric nitrate are dissolved, adding aluminum oxide, continuously stirring and mixing until the aluminum oxide becomes a thick block, and drying and roasting the thick block to obtain a cobalt black material; wherein the roasting temperature is 750-760 ℃ and the roasting time is 2.5h; the mass ratio of the aluminum oxide to the lanthanum nitrate to the cerium nitrate to the cobalt nitrate to the ferric nitrate is 26:4:12:46:12; the cobalt content of the cobalt black material was 46wt%.
Example 1
The methanol fuel automobile tail gas purifying catalyst comprises a front-stage catalyst and a rear-stage catalyst;
the raw materials of the pre-stage catalyst comprise the following components in parts by weight:
Front-stage rare earth main material: 700 parts of high cerium rare earth, 300 parts of middle cerium zirconium rare earth, 10 parts of cobalt black material, 120 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: 20 parts of barium acetate and 60 parts of citric acid,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 200 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 16 parts of nitric acid and 3460 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
the raw materials of the subsequent catalyst comprise the following components in parts by weight:
rear-stage rare earth main material: 800 parts of high-zirconium rare earth, 200 parts of middle-cerium middle-zirconium rare earth, 100 parts of nano titanium dioxide, 200 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Post-stage active material: 20 parts of barium acetate, 10 parts of nickel nitrate, 60 parts of citric acid,
Post-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 6 parts of hydroxypropyl methylcellulose, 14 parts of nitric acid and 3850 parts of deionized water;
post noble metal: pd 2.4 parts, rh 3.6 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH value to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
The preparation process of the post catalyst comprises the following steps:
t1, dissolving a later-stage active material in 500 parts of deionized water to obtain a later-stage active material solution;
T2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
T3, mixing the rear-stage active material solution and the aluminum sol solution for 20min, adding the rear-stage rare earth main material, stirring, adjusting the pH to 4.0-4.1, adding hydroxypropyl methyl cellulose, continuously stirring for 30min, adjusting the pH to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain rear-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
t4, mixing the rear noble metal with 63 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a rear noble metal solution;
and T5, dropwise adding a rear-stage noble metal solution into the rear-stage slurry A, and stirring and mixing to obtain the rear-stage catalyst.
Example 2
The difference between this example and example 1 is only that the pre-stage catalyst comprises the following raw materials in parts by weight:
Front-stage rare earth main material: 580 parts of high cerium rare earth, 400 parts of medium cerium zirconium rare earth, 30 parts of cobalt black material, 120 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: 20 parts of barium acetate and 60 parts of citric acid,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 6 parts of hydroxypropyl methylcellulose, 15 parts of nitric acid and 3848 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH to 4.0-4.1, adding hydroxypropyl methyl cellulose, continuously stirring for 30min, adjusting the pH to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
Example 3
The difference between this example and example 1 is only that the pre-stage catalyst comprises the following raw materials in parts by weight:
Front-stage rare earth main material: 700 parts of high cerium rare earth, 300 parts of middle cerium zirconium rare earth, 10 parts of cobalt black material, 120 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: 16 parts of manganese acetate, 30 parts of barium acetate and 60 parts of citric acid,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 4 parts of hydroxypropyl methylcellulose, 15 parts of nitric acid and 3851 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH to 4.0-4.1, adding hydroxypropyl methyl cellulose, continuously stirring for 30min, adjusting the pH to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
Example 4
The difference between this example and example 1 is only that the pre-stage catalyst comprises the following raw materials in parts by weight:
Front-stage rare earth main material: 700 parts of high cerium rare earth, 300 parts of middle cerium zirconium rare earth, 5 parts of cobalt black material, 120 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: 10 parts of cobalt nitrate, 20 parts of barium acetate and 60 parts of citric acid,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 6 parts of hydroxypropyl methylcellulose, 16 parts of nitric acid and 3832 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH to 4.0-4.1, adding hydroxypropyl methyl cellulose, continuously stirring for 30min, adjusting the pH to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
Example 5
The difference between this example and example 1 is only that the pre-stage catalyst comprises the following raw materials in parts by weight:
Front-stage rare earth main material: 700 parts of high cerium rare earth, 300 parts of medium cerium zirconium rare earth, 10 parts of cobalt black material, 130 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: cobalt nitrate 5 parts, manganese acetate 16 parts, barium acetate 30 parts, citric acid 60 parts,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 6.5 parts of hydroxypropyl methylcellulose, 16 parts of nitric acid and 3840 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH to 4.0-4.1, adding hydroxypropyl methyl cellulose, continuously stirring for 30min, adjusting the pH to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
Example 6
The difference between this example and example 4 is only that the raw materials of the latter stage catalyst, in parts by weight, include:
Rear-stage rare earth main material: 700 parts of high-zirconium rare earth, 300 parts of medium-cerium medium-zirconium rare earth, 100 parts of nano titanium dioxide, 200 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Post-stage active material: 20 parts of barium acetate, 10 parts of nickel nitrate, 60 parts of citric acid,
Post-stage auxiliary materials: JHALH-15 parts of aluminum sol, 100 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 6 parts of hydroxypropyl methylcellulose, 16 parts of nitric acid and 3860 parts of deionized water;
post noble metal: pd 2.4 parts and Rh 3.6 parts.
Comparative example 1
The difference between this comparative example and example 1 is only that the raw materials of the pre-stage catalyst, in parts by weight, include:
front-stage rare earth main material: 700 parts of high cerium rare earth, 300 parts of medium cerium zirconium rare earth, 120 parts of nano titanium dioxide, 180 parts of nano aluminum oxide and 200 parts of lanthanum modified aluminum oxide,
Pre-stage active material: 20 parts of barium acetate and 60 parts of citric acid,
Pre-stage auxiliary materials: JHALH-15 parts of aluminum sol, 200 parts of aluminum sol P4 (07), 140 parts of aluminum sol SRJ-01, 16 parts of nitric acid and 3390 parts of deionized water,
Front noble metal: pt 1.6 parts, pd 6 parts, rh 2.4 parts;
The preparation process of the pre-stage catalyst comprises the following steps:
s1, dissolving a pre-stage active material in 500 parts of deionized water to obtain a pre-stage active material solution;
s2, dissolving aluminum sol JHALH-15, aluminum sol P4 (07) and aluminum sol SRJ-01 in 2000 parts of deionized water to obtain an aluminum sol solution;
S3, mixing the pre-stage active material solution and the aluminum sol solution for 20min, adding the pre-stage rare earth main material, stirring, adjusting the pH value to 4.0-4.1, and grinding at a rotating speed of 2000r/min to obtain pre-stage slurry A; wherein nitric acid and deionized water are adopted for regulating the pH;
s4, mixing the pre-noble metal with 120 parts of citric acid aqueous solution (the mass ratio of citric acid to water is 1:10) to obtain a pre-noble metal solution;
S5, dripping the pre-stage noble metal solution into the pre-stage slurry A, and stirring and mixing to obtain the pre-stage catalyst.
WHTC test
The catalysts of the previous stage prepared in examples 1 to 6 and comparative example 1 were coated on a previous stage carrier, the catalyst of the next stage was coated on a next stage carrier, dried at 50 c, calcined, packaged, tested WHTC on a methanol engine 7L-state six-stage rack,
Wherein, the temperature is raised to 100 ℃ at a heating rate of 2.5 ℃/min during roasting, and the temperature is kept for 60min;
heating from 100 ℃ to 150 ℃ at a heating rate of 1.25 ℃/min, and preserving heat for 60min;
then heating from 150 ℃ to 250 ℃ at a heating rate of 1.67 ℃/min, and preserving heat for 30min;
Then the temperature is increased from 250 ℃ to 550 ℃ at the heating rate of 1.67 ℃/min, and the temperature is kept for 150min.
Engine model: a07N;
the pre-stage size is 10.5x4 inches, and the pre-stage carrier specification Φ266.7x101.6;
The post-stage dimensions were 10.5 x 4 inches, post-stage carrier gauge Φ266.7x101.6;
The technical route is as follows: equivalent combustion + EGR + TWC pre-stage + TWC post-stage.
The test results are summarized in tables 2 to 3.
Table 2WHTC test results
TABLE 3WHTC test results
As can be seen from tables 2-3 above, compared with comparative example 1, the catalysts prepared in examples 1-6 showed that the emission of CO was lower and the CO conversion was more than 95%, especially the CO conversion in example 5 was 98.49%, indicating that the addition of cobalt black to the pre-catalyst gave a stronger purification of CO.
The catalysts prepared in examples 1-6 are matched with each other in front and back stages, so that the emission values of methanol, formaldehyde, methane and NOx, THC, NMHC are far lower than the standard limit, the conversion rate of methanol can reach 99.99%, the conversion rate of formaldehyde can reach 99.93%, the conversion rate of NOx can reach 94.65%, the conversion rate of THC can reach 99.88%, the conversion rate of NMHC can reach 99.99%, the catalyst prepared in the invention has excellent purification performance on methanol fuel automobile exhaust, the emission value of the catalyst prepared in examples 1-3 and 5 can be as low as 0.001g/kwh, and the emission value of methanol can be as low as 0.004g/kwh.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
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