CN1120748C - Catalyst for catalytic purifying car tail gas and preparation process thereof - Google Patents

Catalyst for catalytic purifying car tail gas and preparation process thereof Download PDF

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Publication number
CN1120748C
CN1120748C CN 01119168 CN01119168A CN1120748C CN 1120748 C CN1120748 C CN 1120748C CN 01119168 CN01119168 CN 01119168 CN 01119168 A CN01119168 A CN 01119168A CN 1120748 C CN1120748 C CN 1120748C
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hours
catalyst
roastings
tail gas
dryings
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CN1385239A (en
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王心葵
王浩静
田东旭
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

The present invention relates to a catalyst for the catalytic purification of automobile tail gas and a preparation process thereof, wherein the catalyst is composed of the following materials in a weight ratio that honeycomb ceramics: gamma-Al2 O3: La2 O3: CeO2: Pd =(16 to 18.35): (1.65 to 4): (0.165 to 1.25): (0.0825 to 1): (0.02 to 0.2). The catalyst of the present invention has favorable low-temperature activity and favorable high-temperature stability, and the problems of cold starting and sintering in the exhaust of the automobile tail gas are solved in a large degree; the present invention is suitable for a wider range of air-fuel ratio, and an operation window is enlarged.

Description

A kind of catalyst for catalytic purifying car tail gas and preparation technology thereof
The invention belongs to a kind of catalyst, relate in particular to a kind of catalyst for catalytic purifying car tail gas and preparation technology thereof.
As everyone knows, the motor vehicle exhaust emission severe contamination human atmospheric environment of depending on for existence, and greatly threatening human healthy.Along with the intensification of people to motor vehicle exhaust emission contamination hazard understanding, the numerous and confused automobile exhaust emission standard bill of strictness more of formulating in countries in the world, strict more discharging bill, i.e. transition low emission vehicle (TLEV), low emission (LEV) and ultra-low emission vehicle (ULEV) standard are implemented in decision 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 are all at active research and exploitation cleaning catalyst for tail gases of automobiles since the seventies, existing at present much about Study on Automobile Exhaust Catalysts and patent, as CN97120101, this patent has been described a kind of paste liquid with the hydrated alumina dry glue powder and has been made dipping stoste, add the catalyst that various ingredients is made, this catalyst inner layer is a perovskite structure, skin is a spinel structure, 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 US5013705, this patent has been described a kind of to contain γ~Al 2O 3Make dipping stoste, the noble metal catalyst made from the suspension of other auxiliary agent.Its initiation temperature is still too high, more than 310 ℃.And measure 60~80% CO discharging in cold start-up two minutes according to FTP method (Federal Government assay method).This needs catalyst to have very low ignition.Because vehicle operational mode is very complicated, the automobile exhaust temperature can reach about 1050 ℃, needs catalyst to have good high-temperature stability simultaneously.
Purpose of the present invention just provides a kind of the have good low ignition and the catalyst and the preparation technology thereof of high-temperature stability.
Catalyst weight ratio of the present invention consists of: ceramic honey comb: γ~Al 2O 3: La 2O 3: CeO 2: Pd=16~18.35: 1.65~4: 0.165~1.25: 0.0825~1: 0.02~0.2.
Preparation of catalysts technology 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, wherein the mol ratio of metallic aluminium and aluminium chloride is 2~8: 1,1 mole metal aluminium correspondence, 200~1000ml distilled water, under 50~100 ℃ temperature, refluxed 2~48 hours, and made alumina sol;
(2) preparation of dipping stoste: in alumina sol, the organic solution that adds a kind of mass percent concentration and be 15-30% is made dispersant, and the volume ratio of dispersant and alumina sol is 1: 1-3; Add organic matter and make tackifier, the percent by volume that tackifier account for dipping stoste is 1-5%, and it is mixed, promptly get to flood and use stoste,
(3) Preparation of catalysts: will ceramic honey comb immerse in the dipping stoste dipping about 1~2 hour, and,, promptly on the ceramic honey comb surface, formed γ~Al2O3 coating again in 300~550 ℃ of roastings 3~5 hours 120 ℃ of dryings 1~4 hour; Consist of by the catalyst weight ratio: ceramic honey comb: γ~Al 2O 3: La 2O 3: CeO 2: Pd=16~18.35: 1.65~4: 0.165~1.25: 0.0825~1: 0.02~0.2 is immersed the coating honeycomb ceramic carrier in the lanthanum nitrate hexahydrate earlier, flood after 2~4 hours and take out, 120 ℃ of dryings 2~4 hours, and 300~600 ℃ of roastings 2~10 hours, thereafter immerse in the cerous nitrate solution, flood after 2~4 hours and to take out, 120 ℃ of dryings 2~4 hours, and 300~600 ℃ of roastings 2~10 hours; To contain auxiliary agent La 2O 3And CeO 2The coating ceramic honey comb immerse the PdCl of Ph=1~7 2In the solution,, and, promptly obtain catalyst 550 ℃ of roastings 2~10 hours 120 ℃ of dryings 2~5 hours.
Described dispersant is polyvinyl alcohol, methylcellulose or organic amine etc.
Described tackifier are poly-oxireme or methyl fiber etc.
Catalyst of the present invention is with CeO 2And La 2O 3Make 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, simultaneously La with precious metals pd 2O 3Be good heat-resisting stabilizing agent, by with Al 2O 3Formation has the perovskite-type compounds LaAlO of high heat stability 3Thereby, stablized catalyst carrier.Catalyst of the present invention had both had good cryogenic property, had higher heat-resistant stability again.
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 boehmite colloidal sol and γ~Al commonly used 2O 3The made slurry of powder is compared, and has homogeneous, the stability of height, and this colloidal sol is placed and gelatin phenomenon can not be taken place in 2 years.
(2) adopt the so-gel technology 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 uniform and stable on the ceramic honey comb surface, help active component high degree of dispersion, improved dispersion degree of active components, thereby improved activity of such catalysts.
(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 firm attached to the ceramic honey comb surface, in roasting process, help the formation in hole, the 10nm left and right sides equally, play an important role to improving activity of such catalysts.
(5) catalyst of the present invention is introduced La 2O 3Make auxiliary agent, at high temperature La 2O 3With Al 2O 3Generate heat-staple perovskite-type compounds LaAlO 3Thereby, stoped the sintering of catalyst.
(6) 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, simultaneously because Ce CO 4+Variable valency, higher storage oxygen effect is arranged, this catalyst also is applicable to the air-fuel ratio scope of broad, has enlarged action pane.
(7) catalyst of the present invention has good low temperature active and high-temperature stability, has solved the cold start-up and the sintering 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,, promptly make transparent, stable alumina sol 70 ℃ of reactions 20 hours.In alumina sol and dispersant solution volume ratio be 1: 1 ratio to add mass percent concentration be 25% dispersant solution, and add binding agent 5ml, mix, promptly get and flood stoste.Ceramic honey comb matrix 18 gram immersed in the dipping stostes took out in 2 hours, 120 ℃ of dryings 2 hours, then 550 ℃ of roastings 5 hours.γ~Al 2O 3Coating quality is 1.62 grams.It is in 7.92% the lanthanum nitrate hexahydrate that the coating honeycomb ceramic carrier is immersed mass percent concentration, 120 ℃ of dryings 2 hours, then 550 ℃ of roastings 5 hours.Then it is immersed mass percent concentration and be in 5.5% the cerous nitrate solution, flood taking-up after 2 hours, then 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours.With the carrier after the surface preparation, immersion Ph=6, mass percent concentration are 0.1% PdCl 2In the solution 3 hours, and in 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours promptly made final catalyst.
Embodiment 2:
135 gram aluminium flakes, 242 gram aluminium chloride and 1100ml distilled water are mixed,, promptly make transparent, stable alumina sol 75 ℃ of reactions 24 hours.In alumina sol and dispersant solution volume ratio be 2: 1 ratio to add mass concentration be 20% dispersant solution, binding agent 3ml.Promptly get after mixing and flood stoste.16 gram ceramic honey comb matrixes are immersed wherein, take out the back 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours repeat aforesaid operations, γ~Al 2O 3Coating quality is 3.2 grams, immerses mass percent concentration then and be in 19.5% lanthanum nitrate hexahydrate dipping 2 hours, 120 ℃ of dryings 3 hours, and 550 ℃ of roastings 5 hours.Thereafter immersed mass percent concentration and be in 16.9% the cerous nitrate solution 4 hours, 120 ℃ of dryings 4 hours, 550 ℃ of roastings 5 hours were immersed mass percent concentration and are 0.2%, the PdCl of Ph=2 at last 2In the solution 4 hours, and 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours promptly got final catalyst.
Embodiment 3:
165 gram aluminium flakes, 242 gram aluminium chloride and 1300ml distilled water are mixed, 80 ℃ were reacted 30 hours, promptly make transparent, stable alumina sol, in alumina sol and dispersant solution volume ratio is that to add mass percent concentration be 30% dispersant solution for 3: 1 ratio, and adding binding agent 2ml, after mixing, promptly get and flood stoste.16 gram ceramic honey comb matrixes were immersed in the dipping stostes 3 hours,, and, repeat aforesaid operations 550 ℃ of roastings 5 hours 120 ℃ of dryings 3 hours.γ~Al 2O 3Coating quality is 3.92 grams, immersed mass percent concentration and be in 20.53% lanthanum nitrate hexahydrate 4 hours, and 550 ℃ of roastings 4 hours, immersed mass percent concentration then and be in 17.63% cerous nitrate solution 4 hours, and, immerse Ph=4, mass percent concentration at last and be 0.3% PdCl 550 ℃ of roastings 4 hours 2In the solution 4 hours, through 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours promptly made final catalyst.
Embodiment 4:
75.6 gram aluminium flakes, 122 gram aluminium chloride and 550ml distilled water are mixed,, promptly make transparent, stable alumina sol 90 ℃ of reactions 26 hours.In alumina sol and dispersant solution volume ratio be 2.5: 1 ratio to add mass percent concentration be 30% dispersant solution, promptly get after mixing and flood stoste.16.5 gram ceramic honey comb bodies were immersed in the dipping stostes 4 hours,, and, repeat aforesaid operations 550 ℃ of roastings 5 hours 120 ℃ of dryings 4 hours.γ~Al 2O 3Coating quality is 2.64 grams, immersed mass percent concentration and be in 20.53% lanthanum nitrate hexahydrate 4 hours, and 550 ℃ of roastings 4 hours, immersed mass percent concentration then and be in 17.63% cerous nitrate solution 4 hours, and, immerse Ph=3, mass percent concentration thereafter and be 0.3% PdCl 550 ℃ of roastings 4 hours 2In the solution 4 hours, through 120 ℃ of dryings 2 hours, 550 ℃ of roastings 5 hours promptly made final catalyst.
Catalyst of the present invention has good low temperature active, and under the air speed of 15000/h, (volumn concentration of CO is 1.35%, N in simulation gas 2Be carrier gas) descend detection can get following result:
Catalyst Initiation temperature T 50%/℃ Minimum complete conversion temperature T 100%/℃
Embodiment 1 53 87
Embodiment 2 46 85
Embodiment 3 41 78
Embodiment 4 44 80
Above-mentioned catalyst not only has good low temperature active but also has good heat-resistant stability, and catalyst is through 1050 ℃, and behind 24 hours the senile experiment, (volumn concentration of CO is 1.35%, N in simulation gas 2Be carrier gas) descend detection can get following result:
Catalyst Initiation temperature T 50%/℃ Minimum complete conversion temperature T 100%/℃
Embodiment 1 157 170
Embodiment 2 155 171
Embodiment 3 146 164
Embodiment 4 149 169

Claims (4)

1. a catalyst for catalytic purifying car tail gas is characterized in that the weight ratio of catalyst consists of: ceramic honey comb: γ~Al 2O 3: La 2O 3: CeO 2: Pd=16~18.35: 1.65~4: 0.165~1.25: 0.0825~1: 0.02~0.2.
2. the preparation technology of a catalyst for catalytic purifying car tail gas is characterized in that Preparation of catalysts technology comprises the steps:
(1) preparation of alumina sol: metallic aluminium is mixed according to a certain percentage with aluminium chloride, distilled water, wherein the mol ratio of metallic aluminium and aluminium chloride is 2~8: 1,1 mole metal aluminium correspondence, 200~1000ml distilled water, under 50~100 ℃ temperature, refluxed 2~48 hours, and made alumina sol;
The preparation of (2) proofing stoste: in alumina sol, the organic solution that adds a kind of mass percent concentration and be 15-30% is made dispersant, and the volume ratio of dispersant and alumina sol is 1: 1-3; Add organic matter and make tackifier, the percent by volume that tackifier account for dipping stoste is 1-5%, and it is mixed, promptly get to flood and use stoste,
(3) Preparation of catalysts: will ceramic honey comb immerse in the dipping stoste dipping about 1~2 hour, and, in 300~550 ℃ of roastings 3~5 hours, promptly on the ceramic honey comb surface, formed γ~Al again 120 ℃ of dryings 1~4 hour 2O 3Coating; Consist of by the catalyst weight ratio: ceramic honey comb: γ~Al 2O 3: La 2O 3: CeO 2: Pd=16~18.35: 1.65~4: 0.165~1.25: 0.0825~1: 0.02~0.2 is immersed the coating honeycomb ceramic carrier in the lanthanum nitrate hexahydrate earlier, flood after 2~4 hours and take out, 120 ℃ of dryings 2~4 hours, and 300~600 ℃ of roastings 2~10 hours, thereafter immerse in the cerous nitrate solution, flood after 2~4 hours and to take out, 120 ℃ of dryings 2~4 hours, and 300~600 ℃ of roastings 2~10 hours; To contain auxiliary agent La 2O 3And CeO 2The coating ceramic honey comb immerse the PdCl of Ph=1~7 2In the solution,, and, promptly obtain catalyst 550 ℃ of roastings 2~10 hours 120 ℃ of dryings 2~5 hours.
3. the preparation technology of a kind of catalyst for catalytic purifying car tail gas as claimed in claim 2 is characterized in that described dispersant is polyvinyl alcohol, methylcellulose or organic amine.
4. the preparation technology of a kind of catalyst for catalytic purifying car tail gas as claimed in claim 2 is characterized in that described tackifier are poly-oxireme or methyl fiber.
CN 01119168 2001-05-14 2001-05-14 Catalyst for catalytic purifying car tail gas and preparation process thereof Expired - Fee Related CN1120748C (en)

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Publication number Priority date Publication date Assignee Title
JP3843090B2 (en) * 2003-09-12 2006-11-08 本田技研工業株式会社 Exhaust gas purification catalyst, method for producing the same, and exhaust gas purification catalyst device for vehicles
CN103861589B (en) * 2014-03-12 2015-10-21 浙江师范大学 For the mullite Pt-supported catalyst and preparation method thereof of purifying industrial organic waste gas
CN104289229A (en) * 2014-10-27 2015-01-21 北京碧水源环境工程有限公司 Preparation method for load transition metal catalyst for ozone oxidation as well as load transition metal catalyst and application thereof
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
CN109201053B (en) * 2018-10-11 2021-11-05 成都信息工程大学 Pd/CeO based on base metal doping2-Al2O3Catalyst and preparation method thereof
CN113318726B (en) * 2020-02-28 2023-08-01 中科粤能净(山东)新材料有限公司 Photocatalyst with function of releasing negative oxygen ions and preparation method and application thereof

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