CN1304792A - Catalyst for catalytic cleaning of car tail gas and its preparing process - Google Patents
Catalyst for catalytic cleaning of car tail gas and its preparing process Download PDFInfo
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- CN1304792A CN1304792A CN 00124740 CN00124740A CN1304792A CN 1304792 A CN1304792 A CN 1304792A CN 00124740 CN00124740 CN 00124740 CN 00124740 A CN00124740 A CN 00124740A CN 1304792 A CN1304792 A CN 1304792A
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Abstract
A catalyst for the catalytic cleaning of car's tail gas contains cellular ceramics, gamma-Al2O3, CeO2 and Pb in ratio of (16-18.35):(1.65-4):(0.0025-1):(0.02-0.2), and is prepared through immersing the cellular ceramics in Al2O3 sol containing disperser and adhesive for coating Al2O3, and adding CeO2 and Pd. Its advantages include low-temp ignition nature, high activity and simple preparing process.
Description
The invention belongs to a kind of catalyst of handling waste gas, relate in particular to a kind of Catalysts and its preparation method of catalytic cleaning of car tail gas.
As everyone knows, the atmospheric environment that the motor vehicle exhaust emission severe contamination mankind depend on for existence, and great threat the healthy of the mankind.Along with the intensification of people to motor vehicle exhaust emission contamination hazard understanding, the stricter automobile exhaust emission standard bill of the numerous and confused formulation in countries in the world, determine to implement stricter discharging bill, i.e. transition low emission vehicle (TLEV), low emission (LEV) and ultra-low emission vehicle (ULEV) standard such as California.Reduce motor vehicle exhaust emission to greatest extent and become the difficult problem urgent to be solved that China and international community face jointly.At present, catalytic purification converter and closed-loop control BBG technology become the mainstream technology of control motor vehicle exhaust emission.
Catalytic conversion technique is the simple but effective method that reduces automobile gas emission pollution.Many countries all at active research and exploitation cleaning catalyst for tail gases of automobiles, have many research and patents about cleaning catalyst for tail gases of automobiles at present since the seventies.As Chinese patent CN97120101, this patent has been described a kind of paste liquid with the hydrated alumina dry glue powder and has been made dipping stoste, adds various ingredients as the catalyst that La, Mn, Cu etc. make.This catalyst inner layer is a perovskite structure, and skin is a spinel structure, and the deadly defect of the oxide catalyst of this special construction is that initiation temperature (being that reaction-ure conversion-age is 50% o'clock a reaction temperature) is too high, generally about 250-300 ℃.For another US 5013705, this patent has been described a kind of to contain γ-Al
2O
3Contain Pd, Pt catalyst with the suspension of the Multicomponents such as Zr, La does that dipping stoste makes, the initiation temperature of this catalyst is explained still too high, more than 310 ℃, and measure according to FTP (Federal Government determination method), the CO of 60-80% is discharging in cold start-up 2 minutes, this shows that the cold start-up problem is ubiquitous serious problems.
Goal of the invention of the present invention provides a kind of Catalysts and its preparation method with low temperature ignition and highly active catalytic cleaning of car tail gas.
Catalyst each component weight ratio of the present invention is as follows:
Ceramic honey comb: γ-Al
2O
3: CeO
2: Pd=16-18.35: 1.65-4: 0.0025-1: 0.02-0.2
Preparation of catalysts method of the present invention comprises the steps:
(1) preparation of alumina sol
Metallic aluminium is mixed according to a certain percentage with aluminium chloride, distilled water, and wherein the mol ratio of metallic aluminium and aluminium chloride is 2-8: 1,1 mole metal aluminium needs 200-1000ml distilled water; Under 50-100 ℃ temperature backflow 2-48 hour, make stable, transparent alumina sol;
(2) a certain amount of organic dispersing agent solution of adding and organic tackifier mix in alumina sol, make dipping stoste, the weight percent concentration of this organic dispersing agent solution is 15-30%, the volume ratio of dispersant solution and alumina sol is 1: 1-3, and the addition of binding agent accounts for the 1-5% of dipping with the stoste volume;
(3) press ceramic honey comb: γ-Al
2O
3: CeO
2: the Pd weight ratio is the ratio of 16-18.35: 1.65-4: 0.0825-1: 0.02-0.2, ceramic honey comb is joined dipping with flooding 1-2 hour in the stoste, take out ceramic honey comb at 120 ℃ of dry 1-4 hours, in 300-500 ℃ of roasting 3-5 hour, make the surface and scribble γ-Al again
2O
3Honeycomb ceramic carrier;
(4) by the proportioning that provides in (3) step, the surface is scribbled γ-Al
2O
3Ceramic honey comb immerse in the cerous nitrate solution, flood 2-4 hour, take out afterwards at 120 ℃ of dry 2-4 hours, and at 300-600 ℃ of roasting 2-10 hour, make the surface and scribble CeO
2And γ-Al
2O
3Honeycomb ceramic carrier;
(5) by the proportioning that provides in (3) step, the surface is scribbled CeO
2And γ-Al
2O
3Ceramic honey comb immerse the PdCl of pH=1-7
2In the solution, flooded 2-6 hour, taking-up is rear at 120 ℃ of dry 2-5 hours, and at 550 ℃ of roasting 2-10 hours, makes catalyst.
Aforesaid organic dispersing agent is polyvinyl alcohol, methylcellulose, organic amine etc.
Aforesaid organic tackifier is poly-oxireme, methylcellulose etc.
Catalyst of the present invention is with CeO
2Make auxiliary agent, CeO in auto-exhaust catalyst
2Have the effect of tangible storage oxygen, and interact, stablized the dispersion of noble metal, promoted the transmission of oxygen with precious metals pd.While CeO
2It also is good heat-resisting stabilizing agent.CeO
2The adding of auxiliary agent had not only improved activity of such catalysts but also had improved the heat-resistant stability of catalyst.Catalyst of the present invention has good cryogenic property.
This catalyst is applicable to the air speed scope and the temperature range of broad, is 10000-50000h in air speed
-1, normal pressure, serviceability temperature is in the 45-1000 ℃ of interval, and initiation temperature is at 45-90 ℃, and catalyst has higher low temperature active.
Catalyst commonly used is compared and is had following advantage in catalyst of the present invention and the prior art:
(1) homemade alumina sol and the boehmite colloidal sol and the γ-Al that commonly use
2O
3The made slurry of powder is compared, and has the homogeneous of height, stability, and this colloidal sol is placed and gelatin phenomenon can not be taken place in 2 years.
(2) adopt sol-gel technique to prepare γ-Al
2O
3Coating is with use boehmite colloidal sol and γ-Al
2O
3The made slurry of powder is made dipping stoste and is compared, and this technology makes γ-Al
2O
3Coating is stable at the ceramic honey comb surface uniform, is conducive to the high degree of dispersion of active component, has improved the decentralization of active component, thereby has improved the activity of catalyst.
(3) in alumina sol, add organic matter and make dispersant, the adding of this dispersant makes aluminium oxide obtain good dispersion at the ceramic honey comb matrix surface, and coating layer thickness is even, in roasting process, to form the suitable aperture about 10nm on the ceramic honey comb surface, play an important role.
(4) in alumina sol, add another kind of organic matter and make binding agent, make aluminum oxide coating layer firmly be attached to the ceramic honey comb surface, in roasting process, be conducive to equally the formation of 10nm left and right sides micropore, the activity that improves catalyst is played an important role.
(5) catalyst of the present invention is introduced CeO
2Make auxiliary agent, improved the decentralization of precious metals pd, promoted the transmission of oxygen, improved the oxidation activity of catalyst CO.Simultaneously because Ce
4+Variable valency, have storage oxygen effect, this catalyst also is applicable to the air-fuel ratio scope of broad, has enlarged action pane.
(6) catalyst of the present invention has extremely low ignition and higher low temperature active, has solved the cold start-up problem of motor vehicle exhaust emission to a great extent.
Embodiments of the invention are as follows:
Embodiment 1
108 gram aluminium flakes, 242 gram aluminium chloride and 1000ml distilled water are mixed, 70 ℃ of reactions 20 hours, namely make transparent, stable alumina sol; In alumina sol and dispersant solution volume ratio be 1: 1 ratio to add mass percent concentration be 25% hexamethylenetetramine solution, and add methylcellulose 5ml, mix, namely get dipping stoste.Ceramic honey comb matrix 18 gram immersed in the dipping stostes took out in 2 hours, 120 ℃ of dryings 2 hours, then at 550 ℃ of roastings 5 hours, γ-Al
2O
3Coating quality is 1.62 grams, obtains the surface and scribbles γ-Al
2O
3Honeycomb ceramic carrier immerses it then mass percent concentration and is in 3.92% the cerous nitrate solution, flood taking-up after 2 hours, and then 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours obtain the surface and scribble γ-Al
2O
3, CeO
2Honeycomb ceramic carrier, it is immersed pH=6, mass percent concentration is 0.1% PdCl
2In the solution 3 hours, and in 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours namely made final catalyst.
Embodiment 2
135 gram aluminium flakes, 242 gram aluminium chloride and 1100ml distilled water are mixed, 75 ℃ of reactions 24 hours, namely make transparent, stable alumina sol; In alumina sol and dispersant solution volume ratio be 2: 1 ratio to add mass percent concentration be 20% methocel solution, and add Pluronic F-127 solution 3ml, mix, namely get dipping stoste.Ceramic honey comb matrix 16 gram is immersed the dipping stostes immerses wherein, after taking out 120 ℃ of dryings 2 hours, then at 550 ℃ of roastings 5 hours, γ-Al
2O
3Coating quality is 3.2 grams, obtains the surface and scribbles γ-Al
2O
3Honeycomb ceramic carrier immersed it mass percent concentration and is in 16.9% the cerous nitrate solution 4 hours then, and 120 ℃ of dryings 4 hours, 550 ℃ of roastings 5 hours obtained the surface and scribble γ-Al
2O
3, CeO
2Honeycomb ceramic carrier, it is immersed mass percent concentration is 0.2%, the PdCl of pH=2
2In the solution 4 hours, and in 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours namely made final catalyst.
Embodiment 3
165 gram aluminium flakes, 242 gram aluminium chloride and 1300ml distilled water are mixed, 80 ℃ of reactions 30 hours, namely make transparent, stable alumina sol; In alumina sol and dispersant solution volume ratio be 3: 1 ratio to add mass percent concentration be 30% hexamethylenetetramine solution, and add Pluronic F-127 2ml, mix, namely get dipping stoste.Ceramic honey comb matrix 16 gram is immersed the dipping stostes immersed in the dipping stostes 3 hours, 120 ℃ of dryings 3 hours, then at 550 ℃ of roastings 5 hours, γ-Al
2O
3Coating quality is 3.92 grams, obtains the surface and scribbles γ-Al
2O
3Honeycomb ceramic carrier immersed it then mass percent concentration and is in 17.63% the cerous nitrate solution 4 hours, and 550 ℃ of roastings 4 hours, obtains the surface and scribble γ-Al
2O
3, CeO
2Honeycomb ceramic carrier, it is immersed pH=4, mass percent concentration is 0.3% PdCl
2In the solution 4 hours, through 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours namely made final catalyst.
Embodiment 4
75.6 gram aluminium flakes, 122 gram aluminium chloride and 550ml distilled water are mixed, 90 ℃ of reactions 26 hours, namely make transparent, stable alumina sol; In alumina sol and dispersant solution volume ratio be 2.5: 1 ratio to add mass percent concentration be 30% poly-vinyl alcohol solution, add methylcellulose 2ml, namely get dipping stoste after mixing.Ceramic honey comb matrix 16.5 gram is immersed the dipping stostes immersed in the dipping stostes 4 hours, 120 ℃ of dryings 4 hours, and at 550 ℃ of roastings 5 hours, γ-Al
2O
3Coating quality is 2.64 grams, obtains the surface and scribbles γ-Al
2O
3Honeycomb ceramic carrier immersed it mass percent concentration and is in 17.63% the cerous nitrate solution 4 hours then, and 550 ℃ of dryings 4 hours, obtained the surface and scribble γ-Al
2O
3, CeO
2Honeycomb ceramic carrier, it is immersed pH=3, mass percent concentration is 0.3% PdCl
2In the solution 4 hours, through 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours namely made final catalyst.
Above-mentioned catalyst is applicable to wider air speed scope and temperature range, and (volumn concentration of CO is 1.35%, N in simulation gas
2Be carrier gas) descend detection can get following result:
| Catalyst | Air speed (h -1) | Initiation temperature T 50%/ ℃ | Minimum complete conversion temperature T 100%/ ℃ |
| Embodiment 1 | 15000 | 45 ℃ | 88 ℃ |
| Embodiment 2 | 30000 | 65 ℃ | 101 ℃ |
| Embodiment 3 | 45000 | 74 ℃ | 112 ℃ |
| Embodiment 4 | 50000 | 90 ℃ | 135 ℃ |
Claims (4)
1. the catalyst of a catalytic cleaning of car tail gas is characterized in that the weight ratio of each component is:
Ceramic honey comb: γ-Al
2O
3: CeO
2: Pd=16-18.35: 1.65-4: 0.0025-1: 0.02-0.2.
2. the Preparation of catalysts method of a catalytic cleaning of car tail gas is characterized in that the Preparation of catalysts method comprises the steps:
(1) preparation of alumina sol
Metallic aluminium is mixed according to a certain percentage with aluminium chloride, distilled water, and wherein the mol ratio of metallic aluminium and aluminium chloride is 2-8: 1,1 mole metal aluminium needs 200-1000ml distilled water; Under 50-100 ℃ temperature backflow 2-48 hour, make stable, transparent alumina sol;
(2) a certain amount of organic dispersing agent solution of adding and organic tackifier mix in alumina sol, make dipping stoste, the weight percent concentration of this organic dispersing agent solution is 15-30%, the volume ratio of dispersant solution and alumina sol is 1: 1-3, and the addition of binding agent accounts for the 1-5% of dipping with the stoste volume;
(3) press ceramic honey comb: γ-Al
2O
3: CeO
2: the Pd weight ratio is the ratio of 16-18.35: 1.65-4: 0.0825-1: 0.02-0.2, ceramic honey comb is joined dipping with flooding 1-2 hour in the stoste, take out ceramic honey comb at 120 ℃ of dry 1-4 hours, in 300-500 ℃ of roasting 3-5 hour, make the surface and scribble γ-Al again
2O
3Honeycomb ceramic carrier;
(4) by the proportioning that provides in (3) step, the surface is scribbled γ-Al
2O
3Ceramic honey comb immerse in the cerous nitrate solution, flood 2-4 hour, take out afterwards at 120 ℃ of dry 2-4 hours, and at 300-600 ℃ of roasting 2-10 hour, make the surface and scribble CeO
2And γ-Al
2O
3Honeycomb ceramic carrier;
(5) by the proportioning that provides in (3) step, the surface is scribbled CeO
2And γ-Al
2O
3Ceramic honey comb immerse the PdCl of pH=1-7
2In the solution, flooded 2-6 hour, taking-up is rear at 120 ℃ of dry 2-5 hours, and at 550 ℃ of roasting 2-10 hours, makes catalyst.
3. the Preparation of catalysts method of a kind of catalytic cleaning of car tail gas according to claim 2 is characterized in that described organic dispersing agent is polyvinyl alcohol, methylcellulose, organic amine.
4. the Preparation of catalysts method of a kind of catalytic cleaning of car tail gas according to claim 2 is characterized in that described organic tackifier is poly-oxireme, methylcellulose.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00124740A CN1088400C (en) | 2000-09-14 | 2000-09-14 | Catalyst for catalytic cleaning of car tail gas and its preparing process |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN00124740A CN1088400C (en) | 2000-09-14 | 2000-09-14 | Catalyst for catalytic cleaning of car tail gas and its preparing process |
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| Publication Number | Publication Date |
|---|---|
| CN1304792A true CN1304792A (en) | 2001-07-25 |
| CN1088400C CN1088400C (en) | 2002-07-31 |
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ID=4590629
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|---|---|---|---|
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Cited By (12)
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| CN100391599C (en) * | 2005-07-31 | 2008-06-04 | 浙江师范大学 | Carried by CeO2 based composite oxides coated carrier Pd catalyst, its prepn. method |
| CN102247840A (en) * | 2011-05-19 | 2011-11-23 | 武汉大学 | Catalyst used for sodium formate process and preparation method thereof |
| CN1630556B (en) * | 2002-02-15 | 2012-10-03 | 株式会社Ict | Catalyst for clarifying exhaust emission from internal combustion engine, method for preparation thereof and method for clarifying exhaust emission from internal combustion engine |
| CN103464152A (en) * | 2013-09-29 | 2013-12-25 | 福州大学 | Catalyst for tail gas purification and preparation method thereof |
| CN104203400A (en) * | 2012-03-30 | 2014-12-10 | 三井金属矿业株式会社 | Palladium catalyst |
| CN104689817A (en) * | 2014-12-12 | 2015-06-10 | 湖北航特科技有限责任公司 | Composite oxide catalyst for purification of vehicle tail gas and method for preparing composite oxide catalyst for purification of vehicle tail gas |
| CN105200480A (en) * | 2015-10-30 | 2015-12-30 | 苏州莲池环保科技发展有限公司 | Preparation method of automobile exhaust catalyst |
| CN108607552A (en) * | 2018-05-07 | 2018-10-02 | 华北电力大学（保定） | A kind of high-efficient purification auto-exhaust catalyst |
| CN109158104A (en) * | 2018-07-28 | 2019-01-08 | 裴泽民 | A kind of preparation method of automobile exhaust detergent |
| CN109513452A (en) * | 2018-11-29 | 2019-03-26 | 东莞东阳光科研发有限公司 | Film catalyst, its presoma and carrier and preparation method thereof |
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| ATE78717T1 (en) * | 1987-10-30 | 1992-08-15 | Degussa | PLATINUM-FREE THREE-WAY CATALYST. |
| JPH0941469A (en) * | 1995-08-04 | 1997-02-10 | Inax Corp | Feed water pipe connecting structure to western style toilet bowl |
| CN1070385C (en) * | 1997-05-14 | 2001-09-05 | 中国石油化工总公司 | Improved segregation fractionating column system |
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- 2000-09-14 CN CN00124740A patent/CN1088400C/en not_active Expired - Fee Related
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| CN102247840A (en) * | 2011-05-19 | 2011-11-23 | 武汉大学 | Catalyst used for sodium formate process and preparation method thereof |
| CN102247840B (en) * | 2011-05-19 | 2013-03-06 | 武汉大学 | Catalyst used for sodium formate process and preparation method thereof |
| CN104203400A (en) * | 2012-03-30 | 2014-12-10 | 三井金属矿业株式会社 | Palladium catalyst |
| CN103464152B (en) * | 2013-09-29 | 2015-03-04 | 福州大学 | Catalyst for tail gas purification and preparation method thereof |
| CN103464152A (en) * | 2013-09-29 | 2013-12-25 | 福州大学 | Catalyst for tail gas purification and preparation method thereof |
| CN104689817A (en) * | 2014-12-12 | 2015-06-10 | 湖北航特科技有限责任公司 | Composite oxide catalyst for purification of vehicle tail gas and method for preparing composite oxide catalyst for purification of vehicle tail gas |
| CN105200480A (en) * | 2015-10-30 | 2015-12-30 | 苏州莲池环保科技发展有限公司 | Preparation method of automobile exhaust catalyst |
| CN108607552A (en) * | 2018-05-07 | 2018-10-02 | 华北电力大学（保定） | A kind of high-efficient purification auto-exhaust catalyst |
| CN109158104A (en) * | 2018-07-28 | 2019-01-08 | 裴泽民 | A kind of preparation method of automobile exhaust detergent |
| CN109513452A (en) * | 2018-11-29 | 2019-03-26 | 东莞东阳光科研发有限公司 | Film catalyst, its presoma and carrier and preparation method thereof |
| CN109513452B (en) * | 2018-11-29 | 2019-10-18 | 东莞东阳光科研发有限公司 | Film catalyst, its presoma and carrier and preparation method thereof |
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