CN1436592A - Prepn process of catalyst for purfying automobile tail gas - Google Patents
Prepn process of catalyst for purfying automobile tail gas Download PDFInfo
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Abstract
The present invention discloses the preparation process of catalyst for purifying automobile tail gas. In the wet process, La, Zr, Ce and Pr element components are added into the alumina matrix to obtain composite alumina, and active noble metal component is then carried to obtain the catalyst. The catalyst thus prepared has ever high heat stability and ever high catalytic activity.
Description
Technical field
The invention relates to a kind of preparation method of cleaning catalyst for tail gases of automobiles, the preparation method who further says so and contain the cleaning catalyst for tail gases of automobiles of noble metal about a kind of.
Background technology
The waste gas that engine produces contains a large amount of pernicious gases in the tail gas as automobile, these pernicious gases mainly are made up of carbon monoxide/hydro carbons and nitrogen oxide.The increasingly stringent that need require motor exhaust along with environmental protection increases day by day to the demand of exhaust gas purifying catalyst, and the requirement of catalyst performance is also improved constantly.Along with the promulgation of Environmental Protection in China rules and progressively strict, the utilization of cleaning catalyst for tail gases of automobiles becomes the highly effective external purification means of a kind of improvement motor vehicle exhaust emission.
A kind of preparation method who contains the exhaust gas purifying catalyst of noble metal is disclosed in CN1239017A, this method comprises a kind of preparation of base coating material, be that part boehmite in the scheduled volume and deionized water are mixed, adding a kind of its pH value of acid accent is 1.5-4.0, the boehmite that adds surplus, be stirred to slurries and be equal colloid shape, the hydroxide and the aluminium colloidal sol that under agitation add a kind of auxiliary agent, 30-100 ℃ of aging slurries are more than 0.5 hour, dry also roasting, obtain a kind of composite alumina, the composite alumina that obtains with the solution impregnation that contains noble metal again, dry and roasting.This method complicated operation, prepared slurries uniformity is bad, through at high temperature active not high enough of the catalyst of this method preparation.
Technical scheme
The objective of the invention is at the deficiencies in the prior art, the preparation method of the higher cleaning catalyst for tail gases of automobiles that contains noble metal of a kind of catalytic activity is provided.
The preparation method of cleaning catalyst for tail gases of automobiles provided by the invention comprises the following steps:
(1) gets the soluble-salt that contains one or more elements in lanthanum, zirconium, cerium, yttrium or the praseodymium of scheduled volume and deionized water and form the solution that concentration is the heavy % of 10-20, after stirring under 40-90 ℃, regulating pH with alkali is 7.5-12.5,60-85 ℃ was stirred 20-120 minute, and filtering and washing is the wet cake of 40-80% to moisture content;
(2) boehmite and the deionized water with scheduled volume mixes, 40-90 ℃ is stirred down, forming alumina content is the uniform sizing material of the heavy % of 15-25, after taking out the slurry of the heavy % of 10-90, remaining slurry with acid for adjusting pH=0.5-5.5 and stirred 20-80 minute, is added slurry that takes out and the wet cake that step (1) obtains again, and stirring is 20-80 minute under 40-90 ℃, drying and roasting obtain composite alumina;
(3) composite alumina that obtains with the solution impregnation that contains noble metal, dry and roasting.
The preparation method of cleaning catalyst for tail gases of automobiles provided by the present invention, being by wet chemistry method, is matrix with the aluminium oxide, adds a kind of or wherein several elemental constituent in lanthanum, zirconium, cerium, yttrium or the praseodymium, after being prepared into composite alumina, the carried noble metal active component forms again.In said composite alumina, it forms the Al that counts the heavy % of 50-90 with oxide
2O
3, the heavy % of 0-15 La
2O
3, the heavy % of 0-18 CeO
2, the heavy % of 0-15 ZrO
2, the heavy % of 0-15 Y
2O
3Or the Pr of the heavy % of 0-15
2O
3
In the preparation method of cleaning catalyst for tail gases of automobiles provided by the invention, the used alkali of said adjusting pH value is selected from one or more in magnesium carbonate, ammoniacal liquor, urea, sodium acid carbonate or the aqueous sodium carbonate in the step (1).
In preparation method provided by the invention, the used acid of said adjusting pH value is selected from one or more in citric acid, watery hydrochloric acid, tartaric acid or the carbonic acid in the step (2); The ratio of the said taking-up slurry of step (2) is preferably the heavy % of 25-75; Said drying and roasting are carried out under normal condition in the step (2), dry temperature can be from room temperature to 300 ℃, preferred 90-130 ℃, drying time is more than 0.5 hour, preferred 1-4 hour, sintering temperature 500-900 ℃, preferred 600-850 ℃, roasting time is more than 0.5 hour, preferred 3-10 hour.
In preparation method provided by the invention, the process that said usefulness contains the solution impregnation composite alumina of noble metal in the step (3) can adopt conventional infusion process.Drying and roasting under normal condition behind the dipping noble metal, dry temperature can be from room temperature to 300 ℃, preferred 100-200 ℃, drying time is more than 0.5 hour, and preferred 1-10 hour, sintering temperature 400-700 ℃, preferred 500-700 ℃, roasting time is more than 0.5 hour, preferred 1-10 hour.Said noble metal is selected from one or more in platinum, palladium or the rhodium, and the consumption of noble metal should make to contain the heavy % of noble metal 0.1-30 in the catalyst.
Method provided by the invention has overcome existing preparation method's complexity, the inhomogeneities of slurries, and prepared cleaning catalyst for tail gases of automobiles has following characteristics:
(1) good heat endurance, for example, as the composite alumina through modification of catalyst substrates, after 6 hours, its BET specific area still can reach 126 meters through 850 ℃ of roastings
2/ restrain and 144 meters
2/ gram, pore volume are respectively 0.33 milliliter/gram and 0.37 milliliter/gram, and water absorption rate is respectively 47% and 50%, and the aluminium oxide that adopts prior art to make, after 6 hours, its BET specific area is respectively 118 meters through 800 ℃ of roastings
2/ restrain and 109 meters
2/ gram, pore volume are respectively 0.27 milliliter/gram and 0.25 milliliter/gram, and water absorption rate is respectively 38% and 36%.
(2) higher catalytic activity:, try to achieve the purification temperature T that CO, HC and NOx purifying rate were respectively at 50% o'clock with the function construction of purifying rate as temperature
50Value, when what adopt according to method preparation provided by the invention, when the catalyst of 850 ℃ of roastings after 6 hours, the T of CO
50Be 165 ℃ and 182 ℃, the T of HC
50Be 189 ℃ and 202 ℃, the T of NOx
50Be 167 ℃ and 183 ℃, and when adopting catalyst through the prior art for preparing of 850 ℃ of roastings after 6 hours, the T of CO
50Be 188 ℃ and 190 ℃, the T of HC
50Be 222 ℃ and 221 ℃, NOx is 186 ℃ and 189 ℃.
The specific embodiment
Following example will the present invention is further illustrated.
The preparation process of example 1 and 2 explanation composite aluminas.
Example 1
In 3000 milliliters beaker, add deionized water, add 50 gram LaCl
37H
2O (wherein contains La
2O
316.28 gram, Pr
6O
118.5 gram) (chemical pure, the Beijing Chemical Plant produces), 80 gram CeCl
36H
2O (contains CeO
238.816 gram) (chemical pure, the Beijing Chemical Plant produces), 70 gram ZrOCl
28H
2O (contains Zr
2O
326.768 gram, Y
2O
35.93 gram) (chemical pure, Beijing Chemical Plant produce) makes its complete solvent soln concentration 12 heavy %, regulates pH=9 with ammoniacal liquor (chemical pure, the Beijing Chemical Plant produces), constant temperature stirred 60 minutes for 65 ℃, and suction filtration to moisture content is that 50% wet cake is stand-by.
Get 437.7 gram boehmites (alumina content is 33%, and Qilu Petrochemical company catalyst plant is produced) and add deionized water, 50 ℃ are stirred homogenizing and get the uniform sizing material that alumina content is 18 heavy % after 30 minutes.The slurry of taking-up part 30 heavy % is regulated pH=2.0 with remaining slurry with watery hydrochloric acid, stirs 40 minutes with slurry that takes out and the wet cake adding that obtains above and at 50 ℃ afterwards; 130 ℃ of oven dry 4 hours, 850 ℃ of roastings 6 hours obtain composite alumina.
Resulting composite alumina after 6 hours, is measured its BET specific surface and pore volume with low-temperature nitrogen adsorption method through 850 ℃ of roastings, and surveys its saturated water absorption.Measurement result is listed in table 1.
Example 2
In 3000 milliliters beaker, add deionized water, add 70 gram LaCl
37H
2O (contains La
2O
322.792 gram, Pr
6O
1111.9 60 gram ZrOCl gram),
28H
2O (contains Zr
2O
322.944 gram, Y
2O
35.08 gram) make its complete solvent soln concentration 18 heavy %, regulate pH=10.5 with sodium acid carbonate (chemical pure, the Beijing Chemical Plant produces), constant temperature stirred 110 minutes for 80 ℃, and suction filtration to moisture content is that 70% wet cake is stand-by.
Get 950.24 gram boehmites and add deionized water, 80 ℃ are stirred homogenizing and get the uniform sizing material that alumina content is 23 heavy % after 30 minutes.Take out the slurry of part 70 heavy %, remaining slurry is regulated pH=4.0 with citric acid, afterwards slurry that takes out and the wet cake that obtains are above added and be stirred in 80 ℃ and stirred 70 minutes; 130 ℃ of oven dry 4 hours, 850 ℃ of roastings 6 hours obtain composite alumina.
Resulting composite alumina after 6 hours, is measured its BET specific surface and pore volume with low-temperature nitrogen adsorption method through 850 ℃ of roastings, and surveys its saturated water absorption.Measurement result is listed in table 1.
The preparation of the aluminium oxide in Comparative Examples 1 and the 2 explanation prior aries in the preparation process of cleaning catalyst for tail gases of automobiles (add the content of oxide and aluminium oxide identical with example 1,2 respectively).
Comparative Examples 1
This Comparative Examples is the process for preparing composite alumina according to the CN1239017A disclosed method.
In 3000 milliliters of there-necked flasks, add and add 50 gram LaCl under 1500 ml deionized water, the stirring
37H
2O, 80 gram CeCl
36H
2O and 70 gram ZrOCl
28H
2O makes it to dissolve fully.Add ammoniacal liquor under the room temperature, adjust its pH=11, wait to precipitate fully, be warming up to 80 ℃, aging slurries are 6 hours under this temperature, filter, wash the gained filter cake to there not being acid group, and the mixture that gets hydroxide is stand-by.
Get 225.13 gram boehmites and add deionized water, stirred 30 minutes, being made into solid content is the slurries of 19 heavy %, and the hydrochloric acid adjust pH that added 1: 1 is 3.5; Add the above-mentioned mixture that is prepared into lanthanum, cerium, zirconium hydroxide; Under agitation continue to add 112.57 gram boehmites and 150 gram aluminium colloidal sols (salic 22 heavy %, the Shandong catalyst plant is produced), continue to stir, make slurries be uniform colloid shape.50 ℃ aging 1.5 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roasting temperatures 5 hours make composite alumina.
Resulting composite alumina, is measured BET specific surface and pore volume with low-temperature nitrogen adsorption method, and is surveyed its saturated water absorption after 6 hours through 800 ℃ of roastings.The results are shown in table 1.
Comparative Examples 2
In 3000 milliliters of there-necked flasks, add and add 70 gram LaCl under 1500 ml deionized water, the stirring
37H
2O and 60 gram ZrOCl
28H
2O makes it to dissolve fully.Add ammoniacal liquor under the room temperature, adjust its pH=11, wait to precipitate fully, be warming up to 80 ℃, aging slurries are 6 hours under this temperature, filter, wash the gained filter cake to there not being acid group, and the mixture that gets lanthanum, cerium, zirconium hydroxide is stand-by.
Get 544.61 gram boehmites and add deionized water, stirred 30 minutes, being made into solid content is the slurries of 19 heavy %, and the hydrochloric acid adjust pH that added 1: 1 is 3.5; Add the above-mentioned mixture that is prepared into lanthanum, cerium, zirconium hydroxide; Under agitation continue to add 273.30 gram boehmites and 200 gram aluminium colloidal sols, continue to stir, make slurries be uniform colloid shape.50 ℃ aging 1.5 hours, 120 ℃ of dryings 4 hours, 500 ℃ of roasting temperatures 5 hours make composite alumina.
Resulting composite alumina, is measured BET specific surface and pore volume with low-temperature nitrogen adsorption method, and is surveyed its saturated water absorption after 6 hours through 800 ℃ of roastings.The results are shown in table 1.
Table 1
| BET specific area (rice 2/ gram) | Pore volume (milliliter/gram) | Water absorption rate (%) | |
| Example 1 | ????126 | ?????0.33 | ????47 |
| Example 2 | ????144 | ?????0.37 | ????50 |
| Comparative Examples 1 | ????118 | ?????0.27 | ????38 |
| Comparative Examples 2 | ????109 | ?????0.25 | ????36 |
As can be seen from Table 1, though through 850 ℃ of roastings after 6 hours, specific surface, pore volume and the saturated water absorption of prepared combined oxidation aluminum matrix but are higher than the alumina host in 6 hours prior art for preparing of 800 ℃ of roastings comprehensively in the inventive method, illustrate that it has good heat endurance.
The dipping preparation process and the activity rating result thereof of the noble metal of example 3 and 4 explanation catalyst.
In example, the evaluation of catalyst performance is carried out as follows: with catalyst cupport 20 millimeters of diameters, (Corning Incorporated on long 30 millimeters the cordierite carrier, 400 hole/square feet, 0.65 millimeter of wall thickness), the monoblock internal diameter of packing into is in 30 millimeters the quartz tube reactor respectively, with the slit between expansion block sealed silica envelope reactor and the catalyst, and the empty combustion of analog theory.
With containing CO9000ppm, H
22000ppm, HC600ppm, CO
210800ppm, NOx900ppm, O
2The mist of 16000ppm and surplus nitrogen is the purifying property that reaction raw materials is estimated its tail gas.This mist was with 12000 hours
-1Volume space velocity by quartz tube reactor, from room temperature temperature programming to 500 ℃, 20 ℃ of assaying reaction devices of every intensification exit generates CO, HC and the NO in the gas to quartz tube reactor with 11 ℃/minute speed
xThe change in concentration value, then, calculate the purifying rate of pernicious gas according to following formula.
With the function construction of purifying rate, try to achieve the purification temperature T that CO, HC and NOx purifying rate were respectively at 50% o'clock as temperature
50Value, this value can be used as the standard of evaluation catalyst to the tail gas catalytic purification activity.
The composition of the generation gas of reactor exit is by following Instrument measuring:
Carbon monoxide (CO): QGS-08B type CO infrared spectrum analyser, Sino-German co-partnership company of Beijing Analytical Instrument Factory;
Carbon dioxide (CO
2): QGS-08B type CO infrared spectrum analyser, Sino-German co-partnership company of Beijing Analytical Instrument Factory;
Oxygen (O
2): GXH-500 type O
2Analyzer, Sino-German co-partnership company of Beijing Analytical Instrument Factory;
Hydrocarbon (HC): 3110 RES type exhaust-gas analyzers, Japan produces;
Nitrogen oxide (NO
x): Model-10 type chemiluminescence NO
xAnalyzer, U.S. Thermo Electron Corp..
Example 3
With the composite alumina of chloroplatinic acid (non-ferrous metal research institute product) solution impregnation 30 gram examples 1 preparation of 13.5 milliliters of platiniferous 0.02082 grams per milliliters, 120 ℃ dry 2 hours down, 600 ℃ of following roastings 2 hours.Use radium chloride (the non-ferrous metal research institute product) solution impregnation of 13.5 milliliters of rhodium-containing 0.0038 grams per milliliters again, 120 ℃ dry 2 hours down, 600 ℃ of following roastings 2 hours obtain catalyst.
20 millimeters of diameters, on long 30 millimeters the cordierite carrier (Corning Incorporated, 400 hole/square feet, 0.65 millimeter of wall thickness), through 850 ℃ of roastings after 6 hours, the monoblock internal diameter of packing into is in 30 millimeters the quartz tube reactor, mensuration T with catalyst cupport
50Conversion temperature.The results are shown in table 2.Contain noble metal 1.1 heavy %.
Example 4
With the composite alumina in the example 2 dipping precious metal solution, different is with the chloroplatinic acid in 13.5 milliliters of chlorine palladium acid solution replacement examples 3 that contain Pd 0.3904 grams per milliliter, and other noble metal kind is all identical with example 3 with consumption and preparation method.Measure T
50Conversion temperature.The results are shown in table 2.Contain noble metal 15.1 heavy %.
The Preparation of catalysts process and the catalytic activity of prior art for preparing adopted in Comparative Examples 3 and 4 explanations.
Comparative Examples 3
With the dipping of the composite alumina in the Comparative Examples 1 precious metal solution, noble metal kind, consumption and dipping process are identical with example 3.Measure T
50Conversion temperature.The results are shown in table 2.Contain noble metal 1.1 heavy %.
Comparative Examples 4
With the dipping of the composite alumina in the Comparative Examples 2 precious metal solution, noble metal kind, consumption and dipping process are identical with example 4.Measure T
50Conversion temperature.The results are shown in table 2.Contain noble metal 15.1 heavy %.
Table 2
| ?CO-T 50(℃) | ?HC-T 50(℃) | ?NO x-T 50(℃) | |
| Example 3 | ????182 | ????202 | ????183 |
| Example 4 | ????165 | ????189 | ????167 |
| Comparative Examples 3 | ????190 | ????221 | ????189 |
| Comparative Examples 4 | ????188 | ????222 | ????186 |
As seen from Table 2, according to the catalyst of method preparation provided by the invention, its detergent power is apparently higher than the catalyst of prior art for preparing.
Claims (5)
1, a kind of preparation method of cleaning catalyst for tail gases of automobiles is characterized in that this method comprises the steps:
(1) gets the soluble-salt that contains one or more elements in lanthanum, zirconium, cerium, yttrium or the praseodymium of scheduled volume and deionized water and form the solution that concentration is the heavy % of 10-20, after stirring under 40-90 ℃, regulating pH with alkali is 7.5-12.5,60-85 ℃ was stirred 20-120 minute, and filtering and washing is the wet cake of 40-80% to moisture content;
(2) boehmite and the deionized water with scheduled volume mixes, 40-90 ℃ is stirred down, forming alumina content is the uniform sizing material of the heavy % of 15-25, after taking out the slurry of the heavy % of 10-90, remaining slurry is with acid for adjusting pH=0.5-5.5 and stirred 20-80 minute, and the wet cake that the slurry that takes out and step (1) are obtained adds again, 40-90 ℃ of stirring 20-80 minute down, drying and roasting obtain composite alumina;
(3) composite alumina that obtains with the solution impregnation that contains noble metal, dry and roasting.
2, in accordance with the method for claim 1, it is characterized in that the used alkali of said adjusting pH value in the step (1) is selected from a kind of or its mixture in magnesium carbonate, ammoniacal liquor, urea, sodium acid carbonate or the aqueous sodium carbonate.
3, in accordance with the method for claim 1, it is characterized in that the used acid of said adjusting pH value in the step (2) is selected from a kind of or its mixture in citric acid, watery hydrochloric acid, tartaric acid or the carbonic acid.
4, in accordance with the method for claim 1, the ratio that it is characterized in that the said taking-up slurry of step (2) is the heavy % of 25-75.
5, in accordance with the method for claim 1, it is characterized in that the said noble metal of step (3) is selected from one or more in platinum, palladium or the rhodium, content is the heavy % of the 0.1-30 of catalyst.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB02103902XA CN1171673C (en) | 2002-02-07 | 2002-02-07 | Prepn process of catalyst for purfying automobile tail gas |
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|---|---|---|---|
| CNB02103902XA CN1171673C (en) | 2002-02-07 | 2002-02-07 | Prepn process of catalyst for purfying automobile tail gas |
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|---|---|
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| CN1171673C CN1171673C (en) | 2004-10-20 |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1915485B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Alumina containing additive |
| CN1915486B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
| CN101066533B (en) * | 2007-05-24 | 2010-05-19 | 威海佰德信新材料有限公司 | Production process of catalyst carrier material suitable for high temperature condition |
| CN102000558A (en) * | 2010-10-27 | 2011-04-06 | 重庆海特汽车排气系统有限公司 | Composite oxide for automobile exhaust catalytic purification and preparation method thereof |
| CN103007955A (en) * | 2012-12-26 | 2013-04-03 | 湖南稀土金属材料研究院 | Cleaning catalyst for automobile exhaust and preparation method of cleaning catalyst carrier |
| CN101087651B (en) * | 2004-12-22 | 2013-04-17 | 日产自动车株式会社 | Exhaust gas purification catalyst and method for producing exhaust gas purification catalyst |
| CN103831100A (en) * | 2014-03-05 | 2014-06-04 | 浙江达峰汽车技术有限公司 | POC (particle oxidation catalyst) coating with high adhesive strength |
| CN105008046A (en) * | 2013-02-25 | 2015-10-28 | 优美科触媒日本有限公司 | Exhaust gas purifying catalyst and exhaust gas purification method using same |
| CN107051435A (en) * | 2017-01-13 | 2017-08-18 | 十堰贵元通环保科技有限公司 | A kind of manufacture method of vehicle exhaust exhaust gas catalyst |
| CN109675557A (en) * | 2019-01-09 | 2019-04-26 | 无锡威孚环保催化剂有限公司 | Noble metal catalyst and preparation method thereof with high thermal stability |
| CN110124659A (en) * | 2019-06-20 | 2019-08-16 | 中自环保科技股份有限公司 | A kind of cerium zirconium aluminum matrix composite, cGPF catalyst and preparation method thereof |
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2002
- 2002-02-07 CN CNB02103902XA patent/CN1171673C/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101087651B (en) * | 2004-12-22 | 2013-04-17 | 日产自动车株式会社 | Exhaust gas purification catalyst and method for producing exhaust gas purification catalyst |
| CN1915485B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Alumina containing additive |
| CN1915486B (en) * | 2005-08-17 | 2010-05-12 | 中国石油化工股份有限公司 | Hydrated alumina with structure of similar to thin diaspore of containing additive |
| CN101066533B (en) * | 2007-05-24 | 2010-05-19 | 威海佰德信新材料有限公司 | Production process of catalyst carrier material suitable for high temperature condition |
| CN102000558A (en) * | 2010-10-27 | 2011-04-06 | 重庆海特汽车排气系统有限公司 | Composite oxide for automobile exhaust catalytic purification and preparation method thereof |
| CN103007955A (en) * | 2012-12-26 | 2013-04-03 | 湖南稀土金属材料研究院 | Cleaning catalyst for automobile exhaust and preparation method of cleaning catalyst carrier |
| CN103007955B (en) * | 2012-12-26 | 2016-05-25 | 湖南稀土金属材料研究院 | A kind of preparation method of cleaning catalyst and carrier thereof for vehicle exhaust |
| CN105008046A (en) * | 2013-02-25 | 2015-10-28 | 优美科触媒日本有限公司 | Exhaust gas purifying catalyst and exhaust gas purification method using same |
| CN103831100B (en) * | 2014-03-05 | 2016-03-23 | 浙江达峰汽车技术有限公司 | A kind of high bond strength POC coating |
| CN103831100A (en) * | 2014-03-05 | 2014-06-04 | 浙江达峰汽车技术有限公司 | POC (particle oxidation catalyst) coating with high adhesive strength |
| CN107051435A (en) * | 2017-01-13 | 2017-08-18 | 十堰贵元通环保科技有限公司 | A kind of manufacture method of vehicle exhaust exhaust gas catalyst |
| CN109675557A (en) * | 2019-01-09 | 2019-04-26 | 无锡威孚环保催化剂有限公司 | Noble metal catalyst and preparation method thereof with high thermal stability |
| CN109675557B (en) * | 2019-01-09 | 2022-03-18 | 无锡威孚环保催化剂有限公司 | Noble metal catalyst with high thermal stability and preparation method thereof |
| CN110124659A (en) * | 2019-06-20 | 2019-08-16 | 中自环保科技股份有限公司 | A kind of cerium zirconium aluminum matrix composite, cGPF catalyst and preparation method thereof |
| WO2020253726A1 (en) * | 2019-06-20 | 2020-12-24 | 中自环保科技股份有限公司 | Cerium-zirconium-aluminium-based composite material, cgpf catalyst and preparation method therefor |
| CN110124659B (en) * | 2019-06-20 | 2021-03-23 | 中自环保科技股份有限公司 | Cerium-zirconium-aluminum-based composite material, cGPF catalyst and preparation method thereof |
| CN111632589A (en) * | 2020-06-09 | 2020-09-08 | 合肥神舟催化净化器股份有限公司 | Preparation method of high-stability automobile exhaust purification catalyst |
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| CN1171673C (en) | 2004-10-20 |
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