CN1171682C - Coating method of automobile tail gas purifying catalyst - Google Patents
Coating method of automobile tail gas purifying catalyst Download PDFInfo
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- CN1171682C CN1171682C CNB021005982A CN02100598A CN1171682C CN 1171682 C CN1171682 C CN 1171682C CN B021005982 A CNB021005982 A CN B021005982A CN 02100598 A CN02100598 A CN 02100598A CN 1171682 C CN1171682 C CN 1171682C
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Abstract
The present invention relates to a method for coating automobile exhaust gas purifying catalysts, which comprises: serous fluid which comprises noble metal catalysts and takes assistant modified composite alumina as a matrix is coated on a cordierite honeycomb carrier processed with a non-ionic surfactant solution. With the coating method, a coating has the advantages of hard cracking and peeling-off and less coating loss.
Description
Technical field
The invention relates to a kind of painting method of catalyst, further say so about a kind of painting method of cleaning catalyst for tail gases of automobiles.
Background technology
Along with the promulgation of Environmental Protection in China rules and progressively strict, it is to administer the highly effective external purification means of motor vehicle exhaust emission that cleaning catalyst for tail gases of automobiles is installed, the purifying vehicle exhaust effect how, closely related with bond strength of catalyst coat and carrier etc., only guaranteed catalyst coat difficult drop-off just can make attached to its lip-deep noble metal continuously effective ground harmful substance is catalytically conveted to innocuous substance.
The durability that is used for the preliminary treatment of cordierite honeycomb carrier of cleaning catalyst for tail gases of automobiles and catalyst coat is closely related, if carrier and Bond Strength of Coating are low, coating easily chaps, peels off, and will directly influence catalytic activity.Thereby to choosing of carrier preliminary treatment and coating processes be improve carrier and anchoring strength of coating, improve the coating microstructure, the key of raising catalytic activity and durability, also be the key of whole technology of preparing.
The disclosed method of JP59039346 is to use organic polymer aqueous solution precoatings such as polyethylene, polypropylene, polystyrene, polyurethane, polyvinyl alcohol or cellulose derivative earlier, applies activated alumina afterwards.The deficiency of this method is that organic polymer is not modified, and does not bring into play the effect that it strengthens intensity between catalyst coat and carrier as yet.
The method that discloses among the JP56124442 does not relate to the content of modified organic polymers precoating, just with containing unmodified polyethylene alcohol, ZrO
2, CeO
2, pure Al
2O
3The salt solution impregnation honeycomb substrate of (aluminum nitrate), magnesium aluminate spinel and Pt, Pd.
The preparation method of disclosed catalyst-coated slurry among the CN1103010 does not include the content of organic polymer precoating, is intending the thin dried glue (Al of water
2O
33H
2O), ceria, talcum powder, rare nitric acid and 5% polyvinyl alcohol simultaneously ball milling form glue, directly cure after the vacuum covering, afterwards dipping 2-60 minute and cure preparation in Cu, La nitrate and among the Pt, the Rh aqueous solution respectively.Organic polymer in this method does not relate to the modification preliminary treatment, and catalyst coat divided for three steps finished, and at first the coated catalysts carrier floods base metal and noble metal afterwards respectively.
We find that in the catalyst-coated method that is provided in the prior art, resulting coating easily chaps and peels off, and causes the loss of measuring on the catalyst coat.
Technical scheme
It is little to the purpose of this invention is to provide on a kind of coating the amount loss, is difficult for be full of cracks and the painting method of the cleaning catalyst for tail gases of automobiles that peels off.
The painting method of tai-gas clean-up catalyst provided by the present invention comprises that with the composite alumina through a kind of additive modification be the catalyst slurry that matrix makes, and applies the process of the cordierite honeycomb carrier of handling with nonionic surfactant solution again.
Specifically, this painting method comprises the steps:
(1) preparation of catalyst pulp: the salt that contains one or more elements in zirconium, cerium or the lanthanum of getting scheduled volume is dissolved in the deionized water, obtaining concentration is the aqueous solution of the heavy % of 10-20, be heated to 40-90 ℃, regulate pH=7.5-12.5 with alkali, 60-85 ℃ was stirred 20-120 minute, through suction filtration, wash to moisture content be the 40-80% wet cake; Mix in boehmite and the deionized water, stir under the 40-90 ℃ of temperature, making alumina content is the uniform sizing material of the heavy % of 15-25, take out the wherein slurry of the heavy % of 10-90, remaining slurry is regulated pH=0.5-5.5, stir the slurry of adding taking-up after 20-80 minute and above-mentioned wet cake, 40-90 ℃ is stirred after 20-80 minute down, dry, roasting obtain composite alumina; Adopt conventional method dip loading noble metal, dry, roasting obtains catalyst; The catalyst that obtains is mixed with deionized water, regulates pH=1-7,, it is the heavy % of 20-45 that wet ball grinding obtains solid content, grain diameter is the catalyst pulp of 1-10 μ m;
(2) processing of cordierite honeycomb carrier: as a weight, add the deionized water dissolving of 9 parts of-99 parts of weight with nonionic surface active agent, get unmodified nonionic surface active agent solution;
(3) after pH value of solution is 0.5-6.0 or 7.5-9.5 in the adjusting (2), get modification nonionic surface active agent solution, dipping cordierite honeycomb carrier, and dry 1-5 hour.
(4) with catalyst pulp the cordierite honeycomb carrier of handling is applied, make on the catalyst amount reach the heavy % of 10-25 after, through the drying and the roasting of routine.
In the painting method of cleaning catalyst for tail gases of automobiles provided by the present invention, said adjusting pH is that the used alkaline solution of 7.5-12.5 is selected from one or more the mixture in magnesium carbonate, ammoniacal liquor, urea, sodium acid carbonate or the sodium carbonate liquor in the step (1); Regulate pH and be the used acid solution of 0.5-6.0 and be selected from one or more mixture in citric acid, watery hydrochloric acid, tartaric acid or the carbonic acid.
The said noble metal of step (1) 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; The process that said usefulness contains the solution impregnation composite alumina of noble metal can adopt conventional infusion process.Under normal condition, carry out drying and roasting behind the dipping noble metal, said baking temperature can be from room temperature to 300 ℃, preferred 100-200 ℃, drying time is more than 0.5 hour, preferred 1-10 hour, sintering temperature 400-700 ℃, preferred 500-700 ℃, roasting time is more than 0.5 hour, preferred 1-10 hour.
In the painting method of cleaning catalyst for tail gases of automobiles provided by the present invention, said adjusting pH is that the used acid of 0.5-6.0 is selected from one or more the mixture in formic acid, acetate, hydrochloric acid, citric acid, phosphoric acid or the nitric acid in the step (2); Said adjusting pH is that the used alkali of 7.5-9.5 is selected from one or more the mixture in ammoniacal liquor, sodium carbonate or the NaOH.
Said nonionic surface active agent is meant and does not generate ion that in water the surfactant of polyhydroxy or polyoxyethylene groups isoreactivity gene is arranged in the molecule, and this surfactant is all more stable to bronsted lowry acids and bases bronsted lowry, mainly contains polyalcohol type and polyoxyethylene-type.Preferred nonionic is selected from one or more the mixture in polyethylene glycol, glycerine, carboxymethyl cellulose, polyvinyl alcohol or the polyacrylic acid.
The painting method of cleaning catalyst for tail gases of automobiles provided by the present invention applies effect by the evaluation of aqueous vapor erosion test.This method is to take by weighing carrier behind a certain amount of coated catalysts with the one thousandth balance, with air purge 5-15 minute of 5atm, use the identical time of water erosion of 1000-2000 ml/min, pH=5-8 afterwards, use 5atm again air purge 5-15 minute, 90-130 ℃ of oven dry, 500-700 ℃ roasting 1-3 hour, use the vehicle weight of this coated catalysts behind the one thousandth balance weighing aqueous vapor erosion test again, with η (%)=(1-W
After/ W
Before) * 100% calculates amount loss rate on the catalyst coat, wherein, and W
BeforeBe the weight (g) of carrier before the erosion experiment, W
AfterWeight (g) for erosion experiment back carrier.
The painting method of cleaning catalyst for tail gases of automobiles provided by the present invention than the painting method that prior art provided, applies the resulting catalyst coat in back and does not see be full of cracks and peeling phenomenon, and the amount loss is littler on the coating.For example, amount is lost in 2.3-3.5% on the painting method coating provided by the invention, and adopts prior art to apply, and the amount loss is up to 23-56% on the catalyst coat of gained; From to the stereoscan photograph of catalyst coat as can be seen, the resulting catalyst coat of painting method provided by the invention surface does not have crack performance to occur, and the catalyst coat surface of adopting prior art to apply has tangible be full of cracks to produce.
Description of drawings
The stereoscan photograph of the catalyst coat that Fig. 1 obtains for example 1 described method.
The stereoscan photograph of the catalyst coat that Fig. 2 obtains for Comparative Examples 1 described method.
The specific embodiment
Below by example method provided by the invention is further described.
Example 1
(1) in 3000 ml beakers, adds deionized water, add the 50g lanthanum rich rare earth and (contain La
2O
316.28 gram, Pr
6O
118.5 gram, chemical pure, Beijing Chemical Plant's production), 80g cerous chlorate (chemical pure, the Beijing Chemical Plant produces), 70g zirconium oxychloride (contain yittrium oxide 5.93 grams, chemical pure, the Beijing Chemical Plant produces), being dissolved into concentration is to change in 2000 milliliters of there-necked flasks behind the 11 heavy % solution, and heating is stirred to 45 ℃, regulates pH=9 with ammoniacal liquor, 65 ℃ of constant temperature stirred 40 minutes, suction filtration, wash the wet cake of moisture content 40%.
Add deionized water and 650g boehmite (alumina content is 33%, and the Shandong catalyst plant is produced) in 3500 milliliters making beating jar, 45 ℃ of homogenizing become the slurries of salic 16 heavy % after 30 minutes.Take out 20% slurry, after remaining slurry is regulated pH=1.0 and stirred 25 minutes with 20% watery hydrochloric acid in jar, add and take out slurry and wet cake, 45 ℃ stir 25 minutes even after, 3 hours, 600 ℃ roastings of 120 ℃ of dryings obtained composite alumina after 4 hours.
With the composite alumina of platinum acid chloride solution dipping preparation, 120 ℃ dry 2 hours down, 600 ℃ of following roastings 2 hours.Again with rhodium chloride solution dipping, 120 ℃ dry 2 hours down, 600 ℃ of following roastings 2 hours.Prepare catalyst.
Get the 100g catalyst and add deionized water and an amount of zirconia ball grinding media, wet ball grinding obtains pH=1.5, solid content is the slurries of 23 heavy %, and grain diameter obtains catalyst pulp less than 3 μ m.
(2) in 3000 milliliters beaker, claim 200g polyvinyl alcohol (Beijing Chemical Plant, the degree of polymerization 1000), add deionized water and make its dissolving, getting concentration is the unmodified polyethylene alcoholic solution of 2 heavy %, add concentrated hydrochloric acid afterwards, obtain the modified poly ethylene alcoholic solution of pH=2.0 after the dissolving.
Get 20g cordierite honeycomb carrier (Corning Incorporated, 400 hole/square feet), dipping took out dry 3 hours after 5 minutes in above-mentioned modified poly ethylene alcoholic solution.
(3) with catalyst slurry the cordierite honeycomb carrier is applied, last amount is 13 heavy %, 130 ℃ of dryings 2 hours, 650 ℃ of roastings 2 hours.
Coating effect by aqueous vapor erosion test evaluation catalyst:
After the carrier of the air purge coated catalysts of 5atm 10 minutes, use the identical time of water erosion of 1500 ml/min, pH=6.8 instead, use the air purge 10 minutes of 5atm again, 130 ℃ of oven dry, 650 ℃ of roastings 2 hours, with the weight of the honeycomb substrate of the forward and backward coated catalysts of one thousandth balance weighing aqueous vapor erosion test, according to formula η (%)=(1-W
After/ W
Before) * 100% calculates amount loss rate on the catalyst coat, in the formula, and W
Before: the weight (g) of carrier before the erosion experiment, W
After: the weight (g) of erosion experiment back carrier is calculated amount loss η on the catalyst coat
1
The analysis of catalyst coat surface topography is carried out with the ISI-60 ESEM that American I Si Corporation produces, and analysis condition is: accelerating potential 20KV, inclination angle 30, operating distance 15mm.
The surface topography photo of the catalyst coat after this example applies is seen Fig. 1.
Example 2
The parameter of (1) preparation wet cake in the example 1 is changed into: concentration of salt solution is 14 heavy %, and heating is stirred to 60 ℃, regulates pH=10 with urea, and constant temperature stirred 60 minutes for 70 ℃, suction filtration, wash the wet cake of moisture content 50%.
The parameter of preparation composite alumina changes into: the slurries that obtain salic 18 heavy % under 60 ℃, take out 40% slurry, remaining slurry is regulated the pH=2.0 stirring after 35 minutes with citric acid, add and take out slurry and above-mentioned wet cake, 60 ℃ stir 35 minutes evenly after, 100 ℃ of dryings 6 hours, 500 ℃ of roastings 6 hours.
Mechanical milling process changes into: pH=3.0, wet ball grinding obtain solid content and attach most importance to 30%, and grain diameter is less than the catalyst pulp of 5 μ m.
(2) with glycerine (chemical pure, Beijing Chemical Plant), concentration is the unmodified glycerine solution of 4 heavy %, adds formic acid, obtains the modification glycerine solution of pH=4.0.
With modification glycerine solution impregnation cordierite honeycomb carrier, amount is 17% on the catalyst-coated.
Other parameters are identical with example 1 with step.
After the air purge catalyst of 5atm 10 minutes, use the identical time of water erosion of 1500 ml/min, pH=6.8 instead, use the air purge catalyst 10 minutes of 5atm again, 130 ℃ of oven dry, 650 ℃ of roastings 2 hours, with the weight of the honeycomb substrate of the forward and backward coated catalysts of one thousandth balance weighing aqueous vapor erosion test, calculate amount loss η on the catalyst coat
2
The surface topography photo of the catalyst coat after this example applies has the feature of Fig. 1.
Example 3
The parameter of (1) preparation wet cake in the example 1 is changed into: concentration of salt solution is 16 heavy %, and heating is stirred to 75 ℃, regulates pH=11 with sodium acid carbonate, and constant temperature stirred 80 minutes for 80 ℃, suction filtration, wash the wet cake of moisture content 60%.
The preparation composite alumina changes into: the slurries that obtain salic 21 heavy % under 75 ℃.Take out 60% slurry, remaining regulate pH=3.0 and stir 50 minutes with tartaric acid after, add and take out slurry and above-mentioned wet cake, 75 ℃ stir 50 minutes evenly after, 120 ℃ of dryings 4 hours, 600 ℃ of roastings 3 hours.
Mechanical milling process changes into: it is 40 heavy % that pH=5.0, wet ball grinding obtain solid content, and grain diameter is less than the catalyst pulp of 7 μ m.
(2) with carboxymethyl cellulose (chemical pure, Beijing Chemical Plant), concentration is the unmodified cmc soln of 6 heavy %, adds ammoniacal liquor, obtains the modified carboxy methyl cellulose solution of pH=8.0.
Use the modified carboxy methyl cellulose solution impregnating carrier.Amount is 21% on the catalyst-coated.
Other parameters are identical with example 1 with step.
After the air purge catalyst of 5atm 12 minutes, use the identical time of water erosion of 1800 ml/min, pH=7.5 instead, use the air purge catalyst 12 minutes of 5atm again, 130 ℃ of oven dry, 650 ℃ of roasting 2h, with the forward and backward vehicle weight that is coated with catalyst of one thousandth balance weighing aqueous vapor erosion test, calculate amount loss η on the catalyst coat
3
The surface topography photo of the catalyst coat after this example applies has the feature of Fig. 1.
Example 4
The parameter of (1) preparation wet cake in the example 1 is changed into: concentration of salt solution is 18 heavy %, and heating is stirred to 85 ℃, regulates pH=12 with magnesium carbonate, and constant temperature stirred 100 minutes for 84 ℃, suction filtration, wash the wet cake of moisture content 70%.
The system composite alumina changes into: 85 ℃ down the slurries of salic 24 heavy %.Take out 80% slurry, remaining regulate pH=4.0 and stir 70 minutes with carbonic acid after, add and take out slurry and above-mentioned wet cake, 85 ℃ stir 70 minutes evenly after, 110 ℃ of dryings 5 hours, 550 ℃ of roastings 5 hours.
Mechanical milling process changes into: it is 43 heavy % that pH=7.0, wet ball grinding obtain solid content, and grain diameter is less than the catalyst pulp of 9 μ m.
(2) with polyethylene glycol (Beijing Chemical Plant, the degree of polymerization 200), concentration is the unmodified polyglycol solution of 8 heavy %, adds NaOH, obtains the modified poly (ethylene glycol) solution of pH=9.0.
Use the modified poly (ethylene glycol) solution impregnating carrier.Amount is 23% on the catalyst-coated.
Other parameters are identical with example 1 with step.
After the air purge catalyst of 5atm 15 minutes, use the identical time of water erosion of 2000 ml/min, pH=8 instead, use the air purge catalyst 15 minutes of 5atm again, 130 ℃ of oven dry, 650 ℃ of roasting 2h, with the forward and backward vehicle weight that is coated with catalyst of one thousandth balance weighing aqueous vapor erosion test, calculate amount loss η on the catalyst coat according to formula
4
The surface topography photo of the catalyst coat after this example applies has the feature of Fig. 1.
Comparative Examples 1
Get the homemade cordierite honeycomb carrier of 20g, in the catalyst slurry of example 1 step (1) preparation, add the unmodified polyethylene alcoholic solution of step (2) preparation, apply then, 130 ℃ of oven dry, 650 ℃ of roastings 2 hours.With with example 1 in the evaluation of identical method, calculate amount loss η on the catalyst coat
5
The surface topography photo of the coated catalyst coat of this Comparative Examples is seen Fig. 2.
Comparative Examples 2
Get the homemade cordierite honeycomb carrier of 20g, in example 2 steps (2), flooded 5 minutes in the unmodified glycerine solution of preparation, use the catalyst slurry of example 2 steps (1) preparation to apply 130 ℃ of oven dry, 650 ℃ of roasting 2h after the oven dry again.With with example 2 in the evaluation of identical method, calculate amount loss η on the catalyst coat
6
The surface topography photo of the catalyst coat after this Comparative Examples applies has the feature of Fig. 2.
Comparative Examples 3
Get the homemade cordierite honeycomb carrier of 20g, in the catalyst slurry of example 3 steps (1) preparation, add the unmodified cmc soln of step (2) preparation, apply 130 ℃ of oven dry, 650 ℃ of roasting 2h then.With with example 3 in the evaluation of identical method, calculate amount loss η on the catalyst coat
7
The surface topography photo of the catalyst coat after this Comparative Examples applies has the feature of Fig. 2.
Comparative Examples 4
Get the homemade cordierite honeycomb carrier of 20g, in example 4 steps (2), flooded 5 minutes in the unmodified polyglycol solution of preparation, again the catalyst slurry of example 4 steps (1) preparation is applied 130 ℃ of oven dry, 650 ℃ of roasting 2h after the oven dry.With with example 4 in the evaluation of identical method, calculate amount loss η on the catalyst coat
8
The surface topography photo of the catalyst coat after this Comparative Examples applies has the feature of Fig. 2.
Amount loss η sees Table on the catalyst coat in above-mentioned example and the Comparative Examples.
Table
Example number 1234 Comparative Examples 1 Comparative Examples 2 Comparative Examples 3 Comparative Examples 4
Measure η on the coating
1η
2η
3η
4η
5η
6η
7η
8
Loss (%) 2.7 2.3 3.5 2.8 56.0 26.5 37.0 23.0
Claims (6)
1, a kind of painting method of cleaning catalyst for tail gases of automobiles comprises that with the process of catalyst-coated in the cordierite honeycomb carrier it is characterized in that, this painting method comprises the steps:
(1) preparation of catalyst pulp: the salt that contains one or more elements in zirconium, cerium or the lanthanum of getting scheduled volume is dissolved in the deionized water, obtaining concentration is the aqueous solution of the heavy % of 10-20, be heated to 40-90 ℃, regulate pH=7.5-12.5 with alkali, 60-85 ℃ was stirred 20-120 minute, through suction filtration, wash to moisture content be the 40-80% wet cake; Boehmite is mixed with deionized water, stir under the 40-90 ℃ of temperature, making alumina content is the uniform sizing material of the heavy % of 15-25, take out the wherein slurry of the heavy % of 10-90, remaining slurry is continued with acid for adjusting pH=0.5-5.5, stir the slurry of adding taking-up after 20-80 minute and above-mentioned wet cake, 40-90 ℃ is stirred after 20-80 minute down, dry, roasting obtain composite alumina; Adopt conventional method dip loading noble metal, dry, roasting obtains catalyst; The catalyst that obtains is mixed with deionized water, regulate pH=1-7, wet ball grinding obtains the heavy % of solid content 20-45, grain diameter is the catalyst pulp of 1-10 μ m;
(2) processing of cordierite honeycomb carrier: as a weight, add the deionized water dissolving of 9 parts of-99 parts of weight with non-ionic surface active agent, after adjusting pH is 0.5-6.0 or 7.5-9.5, dipping cordierite honeycomb carrier, and dry 1-5 hour;
(3) with catalyst pulp the cordierite honeycomb carrier of handling is applied, make on the catalyst amount reach the heavy % of 10-25 after, through the drying and the roasting of routine.
2, in accordance with the method for claim 1, it is characterized in that said adjusting pH in the step (1) is that the used alkali of 7.5-12.5 is selected from one or more the mixture in magnesium carbonate, ammoniacal liquor, urea, sodium acid carbonate or the sodium carbonate liquor.
3, in accordance with the method for claim 1, it is characterized in that said adjusting pH in the step (1) is that the used acid of 0.5-6.0 is selected from one or more the mixture in citric acid, hydrochloric acid, tartaric acid or the carbonic acid.
4, in accordance with the method for claim 1, it is characterized in that said non-ionic surface active agent in the step (2) is selected from one or more the mixture in polyethylene glycol, glycerine, carboxymethyl cellulose, polyvinyl alcohol or the polyacrylic acid.
5, in accordance with the method for claim 1, it is characterized in that said adjusting pH in the step (2) is that the used acid of 0.5-6.0 is selected from one or more the mixture in formic acid, acetate, hydrochloric acid, citric acid, phosphoric acid or the nitric acid.
6, in accordance with the method for claim 1, it is characterized in that said adjusting pH in the step (2) is that the used alkali of 7.5-9.5 is selected from one or more the mixture in ammoniacal liquor, sodium carbonate or the NaOH.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021005982A CN1171682C (en) | 2002-02-07 | 2002-02-07 | Coating method of automobile tail gas purifying catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB021005982A CN1171682C (en) | 2002-02-07 | 2002-02-07 | Coating method of automobile tail gas purifying catalyst |
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|---|---|
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| CN1171682C true CN1171682C (en) | 2004-10-20 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448541C (en) * | 2006-12-13 | 2009-01-07 | 北京英泰世纪环境科技有限公司 | High specific surface area alumina coating preparation method and coating prepared therefrom and metal carrier three-effect catalyzing device |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100427208C (en) * | 2006-01-19 | 2008-10-22 | 清华大学 | Method for preparing catalyst to purify automobile tail gas |
| CN101491776B (en) * | 2008-01-23 | 2010-12-01 | 中国石油化工股份有限公司 | Alumina coats pulp and preparation method thereof |
| CN105597750B (en) * | 2016-01-06 | 2017-12-29 | 中自环保科技股份有限公司 | A kind of flawless three-way catalyst coating paste, catalyst and preparation method thereof |
| CN109026303A (en) * | 2018-07-24 | 2018-12-18 | 苏州水木康桥环境工程技术有限公司 | A kind of preparation method of oxidized form catalysed particulate bed filter device and its catalysis oxidation particle |
| CN109225315A (en) * | 2018-09-05 | 2019-01-18 | 华东理工大学 | Molecular screen base integral catalyzer and preparation method for propane waste gas catalytic combustion |
| 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 |
-
2002
- 2002-02-07 CN CNB021005982A patent/CN1171682C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100448541C (en) * | 2006-12-13 | 2009-01-07 | 北京英泰世纪环境科技有限公司 | High specific surface area alumina coating preparation method and coating prepared therefrom and metal carrier three-effect catalyzing device |
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