CN110404536A - The preparation method of the three-way catalyst of bilayer coating - Google Patents
The preparation method of the three-way catalyst of bilayer coating Download PDFInfo
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Abstract
The present invention relates to a kind of preparation methods of the three-way catalyst of double-deck coating, it is the following steps are included: preparing wet gel step, preparing catalyst fines step, platiniferous coating coating step and coating step containing rhodium coatings.Prepared Pt/CeZr catalyst powder has chemical composition uniformity, high-purity, the ultra-fine property of height by means of the present invention, can improve the dispersibility of Pt active component;Meanwhile there are strong metal-support interactions for Pt and carrier cerium zirconium compound oxide, form Pt-O key and Pt-O-Ce key during high temperature ageing, greatly improve the stability of catalyst high temperature ageing.
Description
Technical field
The present invention relates to a kind of preparation methods of the three-way catalyst of double-deck coating, and the invention belongs to catalyst preparation technologies
Field.
Background technique
Gasoline car three-way catalyst refers to carbon monoxide (CO), hydrocarbon (HC) and the nitrogen oxygen that vehicle exhaust is discharged
Compound (NOx) by high-temperature catalytic reaction be converted into harmless carbon dioxide (CO2), water (H2) and nitrogen (N O2) automobile-used urge
Agent.Continuous with China's vehicle guaranteeding organic quantity is risen, and the pollutant of vehicle exhaust has become the main of urban air pollution
Source, this not only causes great harm to the health of the mankind, while also having huge destruction to ecological environment.Therefore,
Each state has all formulated harsh motor vehicle exhaust emission regulation, to limit the discharge of gaseous pollutant.With " state six " code enforcement
Close on, to the preparation of three-way catalyst, higher requirements are also raised.
Three-way catalyst generallys use Pt, Pd, Rh noble metal active component.With the continuous reduction of nearest Pt price, mesh
Its preceding market price has been significantly less than the price of Pd, and the ratio that Pt is improved in three-way catalyst even replaces Pd that can be conducive to it
Reduce the production cost of catalyst.It grows up, migrate in addition, noble metal active component is easy to happen crystal grain during high temperature ageing
Coking seriously affects catalytic performance.Therefore, it improves stability of active component during high temperature ageing and greatly improves ternary
The aging activity of catalyst.
Summary of the invention
The purpose of the present invention is overcoming the deficiencies in the prior art, a kind of three-way catalyst of double-deck coating is provided
Preparation method.
According to technical solution provided by the invention, the preparation method of the three-way catalyst of the double-deck coating includes following step
It is rapid:
A, cerous nitrate, zirconium nitrate and deionized water are mixed and are dissolved, then sequentially add platinum nitrate and rare earth element
Chelating agent is added after being sufficiently stirred in the presoma of oxide, pH value of solution is adjusted to 8~12 with ammonium hydroxide, then at 50~90 DEG C
Water-bath in heating stirring, so that moisture is sufficiently volatilized and aged overnight, obtain wet gel;
B, wet gel is put into drying 5~12 hours in 80~200 DEG C of baking ovens, is placed into after drying in Muffle furnace with 0.5
The heating rate of~20 DEG C/min is warming up to 500~800 DEG C and keeps the temperature roasting 1~8 hour, and it is low that catalyst is ground to granularity
Catalyst fines are obtained in 100 μm;
C, it takes catalyst fines to be added in deionized water, alumina material is added after being sufficiently stirred, is vigorously stirred to mixing
Uniformly, platiniferous coating slurry is formed, 1~5g/l Aluminum sol is added in platiniferous coating slurry after ball milling, and applies by 50~200g/l
It covers to honeycomb support, the load capacity of platinum element is 1~50g/ft3, the honeycomb support after coating is dried at 80~200 DEG C
It is 0.2~8 hour dry in case, and the catalyst after drying is warming up to 500~800 with the heating rate of 0.5~20 DEG C/min
DEG C and keep the temperature roasting 1~8 hour;
D, rhodium nitrate is loaded on the mixed powder of alumina material and cerium zirconium compound oxide using infusion process, first
Through drying 5~12 hours in 80~200 DEG C of baking ovens, places into Muffle furnace and be warming up to the heating rate of 0.5~20 DEG C/min
It 500~800 DEG C and keeps the temperature roasting 1~8 hour, obtained catalyst is ground to granularity lower than 100 μm, by catalyst fines
It is added in deionized water and forms rhodium-containing catalyst slurries, rhodium-containing catalyst slurries are coated in step by 50~200g/l after ball milling
On the catalyst of c, platiniferous coating is covered, the load capacity of rhodium element is 0.5~30g/ft3, the honeycomb support after coating is existed
It is 0.2~8 hour dry in 80~200 DEG C of baking ovens, and by the honeycomb support after drying with the heating rate of 0.5~20 DEG C/min
It is warming up to 500~800 DEG C and keeps the temperature roasting 1~8 hour, obtain finished catalyst.
As preferred: in step a, the rare earth oxide is La2O3、Y2O3、Nd2O3One of.
As preferred: in step a, the presoma of the rare earth oxide is rare earth element nitrate.
As preferred: in step a, the chelating agent is one of citric acid, EDTA, glycine.
As preferred: in step a, the molar ratio of platinum element and chelating agent is 0.5~20:0.25~24.
As preferred: in step c, the molar ratio Ce:Zr:Al:Pt: rare earth element 20 of each element in the platiniferous coating
~300:50~410:2200~3000:0.5~20:4~80.
As preferred: in step c, the alumina material is La2O3-Al2O3, and La2O3With Al2O3Mass ratio be 1:
99。
As preferred: in step d, it is described containing each element molar ratio Ce:Zr:Al:Rh in rhodium coatings be 20~300:50~
410:470~1000:0.5~35.
As preferred: in step d, the alumina material is La2O3-Al2O3, and La2O3With Al2O3Mass ratio be 1:
99。
Prepared Pt/CeZr catalyst powder has the chemical composition uniformity of height, height by means of the present invention
Purity, ultra-fine property, can improve the dispersibility of Pt active component;Meanwhile there are metallic carriers with carrier cerium zirconium compound oxide by Pt
Strong interaction forms Pt-O key and Pt-O-Ce key during high temperature ageing, greatly improves the stabilization of catalyst high temperature ageing
Property.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1
A kind of preparation method of the three-way catalyst of the double-deck coating the following steps are included:
A, 800g cerous nitrate, 1300g zirconium nitrate are mixed with 2000g deionized water, stirring and dissolving.Then it sequentially adds
The EDTA of 5g is added in 37.5g platinum nitrate (Pt containing 10mass%) and 200g neodymium nitrate after being sufficiently stirred, using ammonium hydroxide by solution
PH is adjusted to 10,90 DEG C of heating water bath stirrings, so that moisture sufficiently volatilize simultaneously aged overnight, obtains wet gel;
B, wet gel is put into drying 8 hours in 120 DEG C of baking ovens, Muffle furnace is placed into after drying with the heating of 10 DEG C/min
Rate program is warming up to 550 DEG C and keeps the temperature roasting 2 hours, and catalyst is ground to 80 μm of granularity and obtains catalyst fines;
C, it takes catalyst fines 192g to be added in 1200g deionized water, the La of 308g is added after being sufficiently stirred2O3-Al2O3
(La2O3With Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, it is molten that 2g/l aluminium is added in solution after ball milling
Glue, and coat by 100g/l to honeycomb support, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and will dry
Catalyst after dry to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 10 DEG C/min;
D, 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3(La2O3
With Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:1)
On mixed powder, first through drying 5 hours in 150 DEG C of baking ovens, places into Muffle furnace and be warming up to the heating rate of 5 DEG C/min
500 DEG C and keep the temperature roasting 2 hours, obtained catalyst is ground to 50 μm of granularity, deionized water is added in catalyst fines
Middle formation rhodium-containing catalyst slurries, rhodium-containing catalyst slurries are coated by 80g/l to catalyst prepared by step c after ball milling
On, platiniferous coating is covered, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and by the catalyst after drying with 10
DEG C/the heating rate temperature programming of min to 500 DEG C and keeps the temperature roasting 2 hours, obtain finished catalyst.
Embodiment 2
A kind of preparation method of the three-way catalyst of the double-deck coating the following steps are included:
A, 500g cerous nitrate, 1600g zirconium nitrate are mixed with 2000g deionized water, stirring and dissolving.Then it sequentially adds
12g citric acid is added in 75g platinum nitrate (Pt containing 10mass%) and 200g lanthanum nitrate after being sufficiently stirred, using ammonium hydroxide by solution
PH is adjusted to 8,65 DEG C of heating water bath stirrings, so that moisture sufficiently volatilize simultaneously aged overnight, obtains wet gel;
B, wet gel is put into drying 8 hours in 100 DEG C of baking ovens, Muffle furnace is placed into after drying with the heating of 25 DEG C/min
Rate program is warming up to 500 DEG C and keeps the temperature roasting 2 hours, and catalyst is ground to 60 μm of granularity and obtains catalyst fines;
C, it takes catalyst fines 100g to be added in 1200g deionized water, the La of 400g is added after being sufficiently stirred2O3-Al2O3
(La2O3With Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, it is molten that 2g/l aluminium is added in solution after ball milling
Glue, and coat by 100g/l to honeycomb support, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and will dry
Catalyst after dry to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 25 DEG C/min;
D, 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3(La2O3
With Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:1)
On mixed powder, first through drying 2 hours in 200 DEG C of baking ovens, places into Muffle furnace and be warming up to the heating rate of 0.5 DEG C/min
600 DEG C and keep the temperature roasting 1 hour, obtained catalyst is ground to 50 μm of granularity, deionized water is added in catalyst fines
Middle formation rhodium-containing catalyst slurries, rhodium-containing catalyst slurries are coated by 80g/l to catalyst prepared by step c after ball milling
On, platiniferous coating is covered, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and by the catalyst after drying with 25
DEG C/the heating rate temperature programming of min to 500 DEG C and keeps the temperature roasting 2 hours, obtain finished catalyst.
Embodiment 3
A kind of preparation method of the three-way catalyst of the double-deck coating the following steps are included:
A, 1000g cerous nitrate, 1100g zirconium nitrate are mixed with 2000g deionized water, stirring and dissolving.Then it sequentially adds
2g citric acid is added in 21g platinum nitrate (Pt containing 10mass%) and 80g yttrium nitrate after being sufficiently stirred, using ammonium hydroxide by pH value of solution
It is adjusted to 9.90 DEG C of heating water bath stirring, make moisture sufficiently volatilize simultaneously aged overnight, obtain wet gel;
B, wet gel is put into drying 5 hours in 180 DEG C of baking ovens, Muffle furnace is placed into after drying with the heating of 20 DEG C/min
Rate program is warming up to 800 DEG C and keeps the temperature roasting 1 hour, and catalyst is ground to 20 μm of granularity and obtains catalyst fines;
C, it takes catalyst fines 180g to be added in 1200g deionized water, the La of 320g is added after being sufficiently stirred2O3-Al2O3
(La2O3、Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, 2g/l Aluminum sol is added in solution after ball milling,
And coat by 100g/l to honeycomb support, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and will drying
Catalyst afterwards to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 20 DEG C/min;
D, 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3
(La2O3、Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:
1) on mixed powder, first through drying 5 hours in 80 DEG C of baking ovens, the heating rate liter in Muffle furnace with 0.5 DEG C/min is placed into
Temperature to 500 DEG C and keep the temperature roasting 4 hours, obtained catalyst is ground to 75 μm of granularity, by catalyst fines addition go from
Rhodium-containing catalyst slurries are formed in sub- water, rhodium-containing catalyst slurries are coated by 80g/l to catalysis prepared by step c after ball milling
In agent, cover platiniferous coating, by the catalyst after coating dry 1 hour in 120 DEG C of baking ovens, and by the catalyst after drying with
The heating rate temperature programming of 20 DEG C/min is to 500 DEG C and keeps the temperature roasting 2 hours, obtains finished catalyst.
Embodiment 4
A kind of preparation method of the three-way catalyst of the double-deck coating the following steps are included:
A, 1500g cerous nitrate, 600g zirconium nitrate are mixed with 2000g deionized water, stirring and dissolving.Then it sequentially adds
3.2g glycine is added in 32g platinum nitrate (Pt containing 10mass%) and 150g yttrium nitrate after being sufficiently stirred, using ammonium hydroxide by solution
PH is adjusted to 10.60 DEG C of heating water bath stirring, make moisture sufficiently volatilize simultaneously aged overnight, obtain wet gel;
B, wet gel is put into drying 12 hours in 80 DEG C of baking ovens, Muffle furnace is placed into after drying with the heating of 10 DEG C/min
Rate program is warming up to 650 DEG C and keeps the temperature roasting 1 hour, and catalyst is ground to 60 μm of granularity and obtains catalyst fines;
C, it takes catalyst fines 167g to be added in 1200g deionized water, the La of 333g is added after being sufficiently stirred2O3-Al2O3
(La2O3、Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, 2g/l Aluminum sol is added in solution after ball milling,
And coat by 100g/l to honeycomb support, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and will drying
Catalyst afterwards to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 20 DEG C/min;
D, 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3
(La2O3、Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:
1) on mixed powder, first through drying 8 hours in 160 DEG C of baking ovens, the heating rate liter in Muffle furnace with 10 DEG C/min is placed into
Temperature to 700 DEG C and keep the temperature roasting 4 hours, obtained catalyst is ground to 40 μm of granularity, by catalyst fines addition go from
Rhodium-containing catalyst slurries are formed in sub- water, rhodium-containing catalyst slurries are coated by 80g/l to catalysis prepared by step c after ball milling
In agent, cover platiniferous coating, by the catalyst after coating dry 1 hour in 120 DEG C of baking ovens, and by the catalyst after drying with
The heating rate temperature programming of 20 DEG C/min is to 500 DEG C and keeps the temperature roasting 2 hours, obtains finished catalyst.
Embodiment 5
A kind of preparation method of the three-way catalyst of the double-deck coating the following steps are included:
A, 1200g cerous nitrate, 900g zirconium nitrate are mixed with 2000g deionized water, stirring and dissolving.Then it sequentially adds
60g platinum nitrate (Pt containing 10mass%) and 330g lanthanum nitrate, are added 8gEDTA after being sufficiently stirred, using ammonium hydroxide by pH value of solution tune
It saves to 12.75 DEG C of heating water bath stirring, make moisture sufficiently volatilize simultaneously aged overnight, obtain wet gel;
B, wet gel is put into drying 6 hours in 150 DEG C of baking ovens, Muffle furnace is placed into after drying with the heating of 5 DEG C/min
Rate program is warming up to 700 DEG C and keeps the temperature roasting 1 hour, and catalyst is ground to 80 μm of granularity and obtains catalyst fines;
C, it takes catalyst fines 125g to be added in 1200g deionized water, the La of 375g is added after being sufficiently stirred2O3-Al2O3
(La2O3With Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, it is molten that 2g/l aluminium is added in solution after ball milling
Glue, and coat by 100g/l to honeycomb support, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and will dry
Catalyst after dry to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 20 DEG C/min;
D, 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3(La2O3
With Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:1)
On mixed powder, first through drying 7 hours in 120 DEG C of baking ovens, places into Muffle furnace and be warming up to the heating rate of 5 DEG C/min
600 DEG C and keep the temperature roasting 6 hours, obtained catalyst is ground to 90 μm of granularity, deionized water is added in catalyst fines
Middle formation rhodium-containing catalyst slurries, rhodium-containing catalyst slurries are coated by 80g/l to catalyst prepared by step c after ball milling
On, platiniferous coating is covered, the catalyst after coating is 1 hour dry in 120 DEG C of baking ovens, and by the catalyst after drying with 20
DEG C/the heating rate temperature programming of min to 500 DEG C and keeps the temperature roasting 2 hours, obtain finished catalyst.
Comparative example 1
(1) 3g platinum nitrate solution (Pt containing 10mass%) is added in 400ml deionized water.It is added into solution
The La of 540g2O3-Al2O3(La2O3With Al2O3Mass ratio be 1:99) and 60g cerium zirconium compound oxide material (ZrO2、CeO2、
Pr6O11Mass ratio be 47:51:2), be stirred well to uniformly mixed;
(2) step (1) described solution is put into drying 8 hours in 150 DEG C of baking ovens, by the powder after drying with 20 DEG C/min
Heating rate temperature programming to 500 DEG C and keep the temperature roasting 2 hours.It is spare after gained powder is ground to 30 μm of granularity;
(3) it takes step (2) the powder 500g to be added in 1200g deionized water, is vigorously stirred to being uniformly mixed, solution passes through
2g/l Aluminum sol is added after ball milling, coats by 100g/l to honeycomb support, by the catalyst after coating in 150 DEG C of baking ovens
Dry 2 hours, and by the catalyst after drying with the heating rate temperature programming of 20 DEG C/min to 500 DEG C and to keep the temperature roasting 2 small
When;
(4) the catalyst coat solution of rhodium-containing is prepared in the same way, and is coated by 80g/l to prepared by step (4)
Catalyst on, platiniferous coating is covered, by the catalyst after coating dry 2 hours in 150 DEG C of baking ovens, and by urging after drying
Agent to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 20 DEG C/min, obtains finished catalyst.
Comparative example 2
(1) 3g platinum nitrate solution (Pt containing 10mass%) is added in 400ml deionized water.It is added into solution
60g cerium zirconium compound oxide material (ZrO2、CeO2、Pr6O11Mass ratio be 47:51:2), be stirred well to uniformly mixed;
(2) step (1) described solution is put into drying 8 hours in 150 DEG C of baking ovens, by the powder after drying with 20 DEG C/min
Heating rate temperature programming to 500 DEG C and keep the temperature roasting 2 hours.It is spare after gained powder is ground to 30 μm of granularity;
(3) it takes step (2) the powder 55g to be added in 1200g deionized water, the La of 445g is added after being sufficiently stirred2O3-
Al2O3(La2O3With Al2O3Mass ratio be 1:99) material, be vigorously stirred to be uniformly mixed, 2g/l aluminium is added in solution after ball milling
Colloidal sol is coated by 100g/l to honeycomb support, and the catalyst after coating is 2 hours dry in 150 DEG C of baking ovens, and will be dried
Catalyst after dry to 500 DEG C and keeps the temperature roasting 2 hours with the heating rate temperature programming of 20 DEG C/min;
(4) 5g rhodium nitrate (Rh containing 10mass%) is loaded to the La of 135g using infusion process2O3-Al2O3
(La2O3With Al2O3Mass ratio be 1:99) and 15g cerium zirconium compound oxide (ZrO2、CeO2、Pr6O11Mass ratio be 44:55:
1) on mixed powder, the catalyst slurry coating of rhodium-containing is prepared after drying roasting by step (3) the method, and presses 80g/l
On coating to catalyst prepared by step (3), platiniferous coating is covered, by the catalyst after coating dry 1 in 120 DEG C of baking ovens
Hour, and by the catalyst after drying with the heating rate temperature programming of 20 DEG C/min to 500 DEG C and keep the temperature roasting 2 hours, obtain
To finished catalyst.
High temperature horse by embodiment 1 to embodiment 5, comparative example 1 and the obtained catalyst sample of comparative example 2 at 1050 DEG C
It not is then encapsulated into clarifier with condition aging 20h in furnace, is recycled by WLTC and carries out vehicle emission test, test the hair of vehicle
Motivation discharge capacity is 1.6L, and the results are shown in Table 1 for emission test.
Table 1
THC(mg/km) | CO(mg/km) | NOX(mg/km) | |
Embodiment 1 | 18.7 | 140.9 | 25.2 |
Embodiment 2 | 27.7 | 246.4 | 30.9 |
Embodiment 3 | 33.1 | 263.2 | 33 |
Embodiment 4 | 22.6 | 178 | 29.5 |
Embodiment 5 | 25.2 | 215.6 | 29.8 |
Comparative example 1 | 33.8 | 266.5 | 35.4 |
Comparative example 2 | 35.1 | 271.3 | 37.7 |
As shown in table 1, catalyst performance evaluation the result shows that, compared with comparative example 1, comparative example 1, the embodiment of the present invention
1 has excellent tail gas clean-up ability in each transient condition to three-way catalyst prepared by embodiment 5.
Claims (9)
1. a kind of preparation method of the three-way catalyst of the double-deck coating, it is characterized in that the preparation method the following steps are included:
A, cerous nitrate, zirconium nitrate and deionized water are mixed and are dissolved, then sequentially add platinum nitrate and rare earth element oxidation
Chelating agent is added after being sufficiently stirred in the presoma of object, pH value of solution is adjusted to 8 ~ 12 with ammonium hydroxide, then in 50 ~ 90 DEG C of water-bath
Middle heating stirring makes moisture sufficiently volatilize and aged overnight, obtains wet gel;
B, wet gel is put into 80 ~ 200 DEG C of baking ovens it is 5 ~ 12 hours dry, placed into after drying in Muffle furnace with 0.5 ~ 20 DEG C/
The heating rate of min is warming up to 500 ~ 800 DEG C and keeps the temperature roasting 1 ~ 8 hour, and catalyst is ground to granularity and is obtained lower than 100 μm
To catalyst fines;
C, take catalyst fines be added deionized water in, alumina material is added after being sufficiently stirred, be vigorously stirred to be uniformly mixed,
Platiniferous coating slurry is formed, 1 ~ 5g/l Aluminum sol is added in platiniferous coating slurry after ball milling, and coats by 50 ~ 200g/l to honeycomb
On shape carrier, the load capacity of platinum element is 1 ~ 50g/ft3, the honeycomb support after coating is dry in 80 ~ 200 DEG C of baking ovens
0.2 ~ 8 hour, and the catalyst after drying is warming up to 500 ~ 800 DEG C with the heating rate of 0.5 ~ 20 DEG C/min and keeps the temperature roasting
1 ~ 8 hour;
D, rhodium nitrate is loaded on the mixed powder of alumina material and cerium zirconium compound oxide using infusion process, first through 80
It is 5 ~ 12 hours dry in ~ 200 DEG C of baking ovens, it places into Muffle furnace and is warming up to 500 ~ 800 with the heating rate of 0.5 ~ 20 DEG C/min
DEG C and keep the temperature roasting 1 ~ 8 hour, obtained catalyst is ground to granularity lower than 100 μm, by catalyst fines addition go from
Rhodium-containing catalyst slurries are formed in sub- water, rhodium-containing catalyst slurries are coated in the catalyst of step c after ball milling by 50 ~ 200g/l
On, platiniferous coating is covered, the load capacity of rhodium element is 0.5 ~ 30g/ft3, the honeycomb support after coating is dried at 80 ~ 200 DEG C
It is 0.2 ~ 8 hour dry in case, and the honeycomb support after drying is warming up to 500 ~ 800 with the heating rate of 0.5 ~ 20 DEG C/min
DEG C and keep the temperature roasting 1 ~ 8 hour, obtain finished catalyst.
2. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step a, it is described dilute
Earth elements oxide is La2O3、Y2O3、Nd2O3One of.
3. the preparation method of the three-way catalyst of the double-deck coating as claimed in claim 2, it is characterized in that: in step a, it is described dilute
The presoma of earth elements oxide is rare earth element nitrate.
4. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step a, the chela
Mixture is one of citric acid, EDTA, glycine.
5. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step a, platinum element
Molar ratio with chelating agent is 0.5 ~ 20:0.25 ~ 24.
6. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step c, it is described to contain
The molar ratio Ce:Zr:Al:Pt: rare earth element of each element is 20 ~ 300:50 ~ 410:2200 ~ 3000:0.5 ~ 20 in platinum coating:
4~80。
7. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step c, the oxygen
Change aluminum material is La2O3-Al2O3, and La2O3With Al2O3Mass ratio be 1:99.
8. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step d, it is described to contain
Each element molar ratio Ce:Zr:Al:Rh is 20 ~ 300:50 ~ 410:470 ~ 1000:0.5 ~ 35 in rhodium coatings.
9. the preparation method of the three-way catalyst of the double-deck coating as described in claim 1, it is characterized in that: in step d, the oxygen
Change aluminum material is La2O3-Al2O3, and La2O3With Al2O3Mass ratio be 1:99.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110918092A (en) * | 2019-11-14 | 2020-03-27 | 江门市大长江集团有限公司 | Sectional catalyst and preparation method thereof |
CN112221494A (en) * | 2020-11-11 | 2021-01-15 | 中自环保科技股份有限公司 | Pt-containing catalyst suitable for gasoline vehicle tail gas purification and preparation method thereof |
CN112316961A (en) * | 2020-11-27 | 2021-02-05 | 中自环保科技股份有限公司 | Automobile exhaust treatment catalyst and preparation method thereof |
Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04161248A (en) * | 1990-10-24 | 1992-06-04 | Nissan Motor Co Ltd | Exhaust gas purification catalyst |
DE50106490D1 (en) * | 2000-03-28 | 2005-07-21 | Umicore Ag & Co Kg | Single-layer high-performance catalyst |
CN101168126A (en) * | 2007-10-18 | 2008-04-30 | 清华大学 | Method for in-situ preparing three-effect catalyst by sol-gel method on honeycomb ceramic carrier |
CN101224424A (en) * | 2008-02-04 | 2008-07-23 | 北京英泰世纪环境科技有限公司 | Double layer noble metal active component catalyst and preparing 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 |
CN107790124A (en) * | 2016-08-31 | 2018-03-13 | 重庆辉虎催化剂有限公司 | Three-component Catalytic Converters for Automobiles |
CN109012665A (en) * | 2018-08-16 | 2018-12-18 | 无锡威孚环保催化剂有限公司 | A kind of double coating three-way catalysts and preparation method thereof |
CN109046348A (en) * | 2018-08-24 | 2018-12-21 | 无锡威孚环保催化剂有限公司 | A kind of gasoline vehicle tail gas multicomponent catalyst and preparation method thereof |
CN109225213A (en) * | 2018-10-08 | 2019-01-18 | 江苏几维环境科技有限公司 | Preparation method of close-coupled three-way catalyst for motor vehicle exhaust purification |
CN109794240A (en) * | 2018-12-26 | 2019-05-24 | 中自环保科技股份有限公司 | A kind of bis- coated catalysts of Pd-Rh and preparation method thereof |
-
2019
- 2019-08-08 CN CN201910730190.5A patent/CN110404536A/en active Pending
Patent Citations (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH04161248A (en) * | 1990-10-24 | 1992-06-04 | Nissan Motor Co Ltd | Exhaust gas purification catalyst |
DE50106490D1 (en) * | 2000-03-28 | 2005-07-21 | Umicore Ag & Co Kg | Single-layer high-performance catalyst |
CN101168126A (en) * | 2007-10-18 | 2008-04-30 | 清华大学 | Method for in-situ preparing three-effect catalyst by sol-gel method on honeycomb ceramic carrier |
CN101224424A (en) * | 2008-02-04 | 2008-07-23 | 北京英泰世纪环境科技有限公司 | Double layer noble metal active component catalyst and preparing 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 |
CN107790124A (en) * | 2016-08-31 | 2018-03-13 | 重庆辉虎催化剂有限公司 | Three-component Catalytic Converters for Automobiles |
CN109012665A (en) * | 2018-08-16 | 2018-12-18 | 无锡威孚环保催化剂有限公司 | A kind of double coating three-way catalysts and preparation method thereof |
CN109046348A (en) * | 2018-08-24 | 2018-12-21 | 无锡威孚环保催化剂有限公司 | A kind of gasoline vehicle tail gas multicomponent catalyst and preparation method thereof |
CN109225213A (en) * | 2018-10-08 | 2019-01-18 | 江苏几维环境科技有限公司 | Preparation method of close-coupled three-way catalyst for motor vehicle exhaust purification |
CN109794240A (en) * | 2018-12-26 | 2019-05-24 | 中自环保科技股份有限公司 | A kind of bis- coated catalysts of Pd-Rh and preparation method thereof |
Non-Patent Citations (1)
Title |
---|
黄剑锋等编著: ""溶胶-凝胶法制备纳米粉体"", 《溶胶-凝胶原理与技术》 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN110918092A (en) * | 2019-11-14 | 2020-03-27 | 江门市大长江集团有限公司 | Sectional catalyst and preparation method thereof |
CN110918092B (en) * | 2019-11-14 | 2022-07-15 | 江门市大长江集团有限公司 | Sectional catalyst and preparation method thereof |
CN112221494A (en) * | 2020-11-11 | 2021-01-15 | 中自环保科技股份有限公司 | Pt-containing catalyst suitable for gasoline vehicle tail gas purification and preparation method thereof |
CN112221494B (en) * | 2020-11-11 | 2023-10-20 | 中自环保科技股份有限公司 | Pt-containing catalyst suitable for purifying tail gas of gasoline vehicle and preparation method thereof |
CN112316961A (en) * | 2020-11-27 | 2021-02-05 | 中自环保科技股份有限公司 | Automobile exhaust treatment catalyst and preparation method thereof |
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