CN101214450A - Multifunctional composite oxides powder body and method for using the powder body to prepare catalyst for motor vehicle exhausting gas purification - Google Patents
Multifunctional composite oxides powder body and method for using the powder body to prepare catalyst for motor vehicle exhausting gas purification Download PDFInfo
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- CN101214450A CN101214450A CNA2007103047175A CN200710304717A CN101214450A CN 101214450 A CN101214450 A CN 101214450A CN A2007103047175 A CNA2007103047175 A CN A2007103047175A CN 200710304717 A CN200710304717 A CN 200710304717A CN 101214450 A CN101214450 A CN 101214450A
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Abstract
The invention provides a multi-functional complex oxide powder capable of absorbing and storing NOx, HC and O2 and a method of preparing emission and purification catalyst for motor vehicles with the powder. The catalyst of the invention is not easy to conglobe and age, is easy to disperse evenly, has very high specific surface area, can effectively improve the dispersion and stability of precious metal and other active components, and has very good high-temperature thermal stability.
Description
Technical field
The present invention relates to a kind ofly can adsorb and store NO simultaneously
x, HC and O
2The multifunctional composite oxides powder and adopt the method for this powder prepare automotive exhaust gas purification catalyst.
Background technology
For the better protection environment, Abgasgesetz is more and more stricter, and is also more and more higher to the requirement of engine and car load cold start emission limit value, objectively requires catalyst: have better HC absorption and memory function 1., with the discharge capacity of reduction engine HC under cold start; 2. has better NO
xAbsorption and memory function, increase catalyst under lean burn conditions to NO
xAbsorption and storage capacity and to NO
xThe selective reduction ability; 3. have the ability of better absorption and storage oxygen, guarantee that catalyst is under engine air-fuel ratio fluctuation range condition, to HC and NO
xDeng still having good catalyticing purifying effect.
The preparation method commonly used of catalyst coat is with various functional materials (as molecular sieve and cerium zirconium sosoloid etc.) and water mixed pulp at present, is coated on to prepare coating on the carrier again.Be subjected to the restriction of preparation condition, in the preparation of coating, each functional material is difficult to reach even mixing, thereby influences its effect.
Summary of the invention
The object of the present invention is to provide and a kind ofly can adsorb and store NO simultaneously
x, HC and O
2The multifunctional composite oxides powder.
Another object of the present invention is to provide a kind of method of utilizing above-mentioned multifunctional composite oxides powder as catalyst coat prepare automotive exhaust purifier.
Technical scheme of the present invention is:
A kind of multifunctional composite oxides powder is characterized in that: described multifunctional composite oxides powder adopts the following steps preparation: step (1) takes by weighing 100～120 parts of activated aluminas, brium carbonate BaCO according to weight
3100～300 parts of 100～250 parts, 100～200 parts of lanthanum yttrium-cerium-zirconium solid solutions, 65～105 parts in ZSM-5 molecular sieve and deionized waters, grind to form slurry C O, wherein the lanthanum yttrium-cerium-zirconium solid solution is a lanthanum yttrium cerium zirconium compound oxide, and wherein the percentage of the shared amount of substance of lanthanum, yttrium, cerium, zirconium is respectively 2～6%, 2～6%, 20～80%, 20～80%;
Step (2) is with slurry C O and 10～30 parts of surfactants of being made up of PEG400, lignocellulosic and starch, and ball milling to particle diameter is the slurry C 1 of 0.5～5 μ m in high energy ball mill;
Step (3) is carried out slurry C 1 after the fast spraying drying light-burned, promptly obtains described multifunctional composite oxides powder PO.
Slurry C O adopts ball grinder to grind in the step (1).
Described ball grinder is an agate ball milling cylinder.
Described slurry C O milling time is 1～3 hour.
Slurry C 1 was descended light-burned 1～3 hour at 300～500 ℃ in the described step (3).
100～120 parts of activated aluminas, brium carbonate BaCO in the step (1)
3220 parts of 200～250 parts, 180～200 parts of lanthanum yttrium-cerium-zirconium solid solutions, 65～85 parts in ZSM-5 molecular sieve and deionized waters.
100～120 parts of activated aluminas, brium carbonate BaCO in the step (1)
3230 parts of 100～150 parts, 100～120 parts of lanthanum yttrium-cerium-zirconium solid solutions, 95～105 parts in ZSM-5 molecular sieve and deionized waters.
A kind of method of prepare automotive exhaust gas purification catalyst is characterized in that: comprise following steps:
Step (1) takes by weighing 80 parts of boehmites, 100 parts of deionized waters and 25 parts of acetic acid according to weight and add thermal agitation under 80 ℃, and dispergation becomes C2;
Step (2) with slurry C 2, foregoing multifunctional composite oxides powder PO and deionized water in the stirring of homogenizer high speed, homogenizing, be mixed and made into slurry C 3;
Step (3) will be dipped in the slurry C 3 through pretreated honeycomb substrate, and airtight ageing is taken out in hanging, dries in vacuum drying box, makes catalyst coat through roasting again;
Step (4) is by the equivalent impregnation method, and it is light-burned that noble metal active component is carried on the above-mentioned catalyst coat back, and the load capacity of control noble metal active component is 2.5g/l, can make the purifying vehicle exhaust gas catalyst.
Described noble metal active component is platinum Pt, palladium Pd or rhodium Rh is wherein a kind of or several.
In the described step (3), in vacuum drying box in 110～120 ℃ of down oven dry, 450 ℃ of roastings 1.5 hours in the argon gas atmosphere that flows again.
Technique effect of the present invention is:
The present invention is synthetic a kind of storage oxygen, storage HC and storage NO of having concurrently
xIn the multifunctional composite oxides powder body material of one, can when slurrying, can select suitable content to carry out the preparation of coating as required, thereby reach the purpose of simplifying coating preparation process and technology.Because the granularity very thin (near nanoscale) of this multi-functional powder body material, and in preparation process, be added with distinctive dispersant with high efficiency, so each functional material is difficult for reuniting and is aging, and be easy to be uniformly dispersed, its coatings prepared also has very high specific area, can effectively improve decentralization and the stability of noble metal isoreactivity component on carrier.In addition, adopt the multifunctional composite oxides powder body material that makes through stable aluminium oxide, cerium zirconium sosoloid and molecular sieve, have good high high-temp stability.
The present invention also provides a kind of method of utilizing above-mentioned multifunctional composite oxides powder body material prepare automotive exhaust gas purification catalyst, adopt this method can make full use of the good characteristic of described multifunctional composite oxides powder body material, make prepared catalyst have better HC absorption and memory function, can significantly reduce the discharge capacity of engine HC under cold start; Has better NO
xAbsorption and memory function, can increase catalyst under lean burn conditions to NO
xAbsorption and storage capacity and to NO
xThe selective reduction ability; Have the ability of better absorption and storage oxygen, guarantee that catalyst is under engine air-fuel ratio fluctuation range condition, to HC and NO
xDeng still having good catalyticing purifying effect.
The specific embodiment
Embodiment 1
At first prepare multifunctional composite oxides powder PO:
Step 1. takes by weighing activated alumina Al
2O
3100～120g, brium carbonate BaCO
3200～250g, lanthanum yttrium-cerium-zirconium solid solution 180～200g, ZSM-5 molecular sieve 65～85g and deionized water 220g put into agate ball milling cylinder, grind and make slurry C O in 1.5 hours, and used lanthanum yttrium-cerium-zirconium solid solution is La
0.08Y
0.04Ce
0.31Zr
0.6O
2
Step 2. is poured above-mentioned slurry C O in the high energy ball mill into, adds the homemade surfactant SURF23 of 20g, and ball milling to particle diameter is 0.8～1 μ m, makes slurry C 1; Described SURF23 is the mixture of multiple organic surface active agent, and Main Ingredients and Appearance comprises PEG400, lignocellulosic and starch etc., and main effect is diminishing, dispersion and grinding aid etc.
Step 3. is carried out the fast spraying drying with slurry C 1, again in 450 ℃ light-burned 1.5 hours, promptly obtain desired multifunctional composite oxides powder PO.
Utilize prepared multifunctional composite oxides powder PO prepare automotive exhaust gas purification catalyst then:
Step 4. is got 80g boehmite, 100g deionized water and 25g acetic acid and add thermal agitation 6 hours under 80 ℃, dispergation form slurry C2.
Step 5. is poured above-mentioned slurry C 2, powder PO and deionized water 180g in the homogenizer into, and slurry C 3 was made in high-speed stirred, homogenizing, mixing in 2 hours under 2000rpm.
Step 6. will be dipped in the above-mentioned slurry C 3 10 seconds through pretreated metal beehive carrier, take out the back and blow most residual slurry with compressed air.Airtight ageing 12 hours places vacuum drying box in 110 ℃ of oven dry 5 hours, again in the argon gas atmosphere that flows 450 ℃ of following roastings 1.5 hours, make the multifunctional composite oxides coating.
Step 7. adopts the equivalent impregnation method, precious metal palladium Pd is carried on the above-mentioned multifunctional composite oxides coating, and the load capacity of control Pd is 2.5g/l, again in 350 ℃ light-burned 2 hours down, can make the purifying vehicle exhaust gas catalyst.
Embodiment 2
At first prepare multifunctional composite oxides powder PO:
Step 1. takes by weighing activated alumina 100～120g, brium carbonate 100～150g, lanthanum yttrium-cerium-zirconium solid solution 100～120g, ZSM-5 molecular sieve 95～105g and deionized water 230g, put into ball grinder, grind 1.5 hours form slurry CO, used lanthanum yttrium-cerium-zirconium solid solution is La
0.08Y
0.04Ce
0.6Zr
0.31O
2
Step 2. is poured above-mentioned slurry C O in the high energy ball mill into, adds 20g homemade surfactant SURF23 as described in example 1 above, and ball milling to particle diameter is about 0.5 μ m, makes slurry C 1.
Step 3 is carried out the fast spraying drying with slurry C 1, in 450 ℃ times light-burned 1.5 hours, promptly obtains desired multifunctional composite oxides powder PO again.
Utilize prepared multifunctional composite oxides powder PO prepare automotive exhaust gas purification catalyst then:
Step 4. is got 80g boehmite, 100g deionized water and 25g acetic acid and add thermal agitation 6 hours under 80 ℃, dispergation form slurry C2;
Step 5 is poured above-mentioned slurry C 2, powder PO and deionized water 160g in the homogenizer into, and slurry C 3 was made in high-speed stirred, homogenizing, mixing in 2 hours under 2000rpm.
Step 6 will be dipped in the above-mentioned slurry C 3 10 seconds through pretreated ceramic honeycomb carrier, take out the back and blow most residual slurry with compressed air.Airtight ageing 12 hours places vacuum drying box in 120 ℃ of down oven dry 6 hours, again in the argon gas atmosphere that flows 450 ℃ of following roastings 1.5 hours, make the multifunctional composite oxides coating;
Step 7 is by the equivalent impregnation method, with precious metal palladium Pd/ platinum Pt (=5: 1) be carried on the above-mentioned multifunctional composite oxides coating, the total load capacity of control noble metal is 2.5g/l.In 350 ℃ times light-burned 2 hours, can make available purifying vehicle exhaust gas catalyst again.
The above embodiment only is two kinds of preferred embodiments of the present invention, to help public understanding or understand spirit of the present invention or essence, but should by any way scope of authority of the presently claimed invention not twisted and limit.
Claims (10)
1. multifunctional composite oxides powder is characterized in that: described multifunctional composite oxides powder adopts the following steps preparation: step (1) takes by weighing 100～120 parts of activated aluminas, brium carbonate BaCO according to weight
3100～300 parts of 100～250 parts, 100～200 parts of lanthanum yttrium-cerium-zirconium solid solutions, 65～105 parts in ZSM-5 molecular sieve and deionized waters, grind to form slurry C O, wherein the lanthanum yttrium-cerium-zirconium solid solution is a lanthanum yttrium cerium zirconium compound oxide, and wherein the percentage of the shared amount of substance of lanthanum, yttrium, cerium, zirconium is respectively 2～6%, 2～6%, 20～80%, 20～80%;
Step (2) is with slurry C O and 10～30 parts of surfactants of being made up of PEG400, lignocellulosic and starch, and ball milling to particle diameter is the slurry C 1 of 0.5～5 μ m in high energy ball mill;
Step (3) is carried out slurry C 1 after the fast spraying drying light-burned, promptly obtains described multifunctional composite oxides powder PO.
2. a kind of multifunctional composite oxides powder as claimed in claim 1 is characterized in that: slurry C O adopts ball grinder to grind in the step (1).
3. a kind of multifunctional composite oxides powder as claimed in claim 2 is characterized in that: described ball grinder is an agate ball milling cylinder.
4. a kind of multifunctional composite oxides powder as claimed in claim 3 is characterized in that: described slurry C O milling time is 1-3 hour.
5. a kind of multifunctional composite oxides powder as claimed in claim 1 is characterized in that: slurry C 1 was descended light-burned 1-3 hour at 300～500 ℃ in the described step (3).
6. a kind of multifunctional composite oxides powder as claimed in claim 1 is characterized in that: 100～120 parts of activated aluminas, brium carbonate BaCO in the step (1)
3220 parts of 200～250 parts, 180～200 parts of lanthanum yttrium-cerium-zirconium solid solutions, 65～85 parts in ZSM-5 molecular sieve and deionized waters.
7. a kind of multifunctional composite oxides powder as claimed in claim 1 is characterized in that: 100～120 parts of activated aluminas, brium carbonate BaCO in the step (1)
3230 parts of 100～150 parts, 100～120 parts of lanthanum yttrium-cerium-zirconium solid solutions, 95～105 parts in ZSM-5 molecular sieve and deionized waters.
8. the method for a prepare automotive exhaust gas purification catalyst, it is characterized in that: comprise following steps: step (1) takes by weighing 80 parts of boehmites, 100 parts of deionized waters and 25 parts of acetic acid according to weight and add thermal agitation under 80 ℃, and dispergation becomes C2;
Step (2) with slurry C 2, multifunctional composite oxides powder PO as claimed in claim 1 and deionized water in the stirring of homogenizer high speed, homogenizing, be mixed and made into slurry C 3;
Step (3) will be dipped in the slurry C 3 through pretreated honeycomb substrate, and airtight ageing is taken out in hanging, dries in vacuum drying box, makes catalyst coat through roasting again;
Step (4) is by the equivalent impregnation method, and it is light-burned that noble metal active component is carried on the above-mentioned catalyst coat back, and the load capacity of control noble metal active component is 2.5g/l, can make the purifying vehicle exhaust gas catalyst.
9. the method for a kind of prepare automotive exhaust gas purification catalyst as claimed in claim 8 is characterized in that: described noble metal active component is platinum Pt, palladium Pd or rhodium Rh is wherein a kind of or several.
10. the method for a kind of prepare automotive exhaust gas purification catalyst as claimed in claim 9 is characterized in that: in the described step (3), in vacuum drying box in 110～120 ℃ of down oven dry, 450 ℃ of roastings 1.5 hours in the argon gas atmosphere that flows again.
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|---|---|---|---|
| CNB2007103047175A CN100566832C (en) | 2007-12-29 | 2007-12-29 | A kind of multifunctional composite oxides powder and adopt the method for this powder prepare automotive exhaust gas purification catalyst |
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|---|---|---|---|
| CNB2007103047175A CN100566832C (en) | 2007-12-29 | 2007-12-29 | A kind of multifunctional composite oxides powder and adopt the method for this powder prepare automotive exhaust gas purification catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091642A (en) * | 2010-12-20 | 2011-06-15 | 昆明理工大学 | Method for preparing composite oxide supported nano noble metal granule catalyst |
| CN102133546A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Preparation method of precious metal doped composite ABO3-type catalyst |
| CN107308952A (en) * | 2016-10-13 | 2017-11-03 | 南京德普瑞克催化器有限公司 | A kind of motor cycle method for preparing catalyst for meeting state four standard |
| CN113617380A (en) * | 2021-08-17 | 2021-11-09 | 安徽工业大学 | Preparation method of HZSM-5 molecular sieve modified high-performance cerium-based denitration catalyst |
-
2007
- 2007-12-29 CN CNB2007103047175A patent/CN100566832C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102091642A (en) * | 2010-12-20 | 2011-06-15 | 昆明理工大学 | Method for preparing composite oxide supported nano noble metal granule catalyst |
| CN102133546A (en) * | 2010-12-20 | 2011-07-27 | 昆明理工大学 | Preparation method of precious metal doped composite ABO3-type catalyst |
| CN102091642B (en) * | 2010-12-20 | 2012-10-31 | 昆明理工大学 | Method for preparing composite oxide supported nano noble metal granule catalyst |
| CN102133546B (en) * | 2010-12-20 | 2013-07-31 | 昆明理工大学 | Preparation method of precious metal doped composite ABO3-type catalyst |
| CN107308952A (en) * | 2016-10-13 | 2017-11-03 | 南京德普瑞克催化器有限公司 | A kind of motor cycle method for preparing catalyst for meeting state four standard |
| CN113617380A (en) * | 2021-08-17 | 2021-11-09 | 安徽工业大学 | Preparation method of HZSM-5 molecular sieve modified high-performance cerium-based denitration catalyst |
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| CN100566832C (en) | 2009-12-09 |
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