CN103157520A - Radial gradient load three-way catalyst and preparation method - Google Patents
Radial gradient load three-way catalyst and preparation method Download PDFInfo
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- CN103157520A CN103157520A CN201310067986XA CN201310067986A CN103157520A CN 103157520 A CN103157520 A CN 103157520A CN 201310067986X A CN201310067986X A CN 201310067986XA CN 201310067986 A CN201310067986 A CN 201310067986A CN 103157520 A CN103157520 A CN 103157520A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention discloses a radial gradient load three-way catalyst and a preparation method, the catalyst comprises a carrier with a regular structure and a coating material attached on the surface of the carrier, the coating material presents gradient load along the radial direction of the carrier with the regular structure, and the load is gradually reduced from an axis area to a marginal area of the carrier. Compared with the uniformly loaded three-way catalyst, the provided catalyst can reduce the amount of the coating material by 5-15wt%, and the catalytic activity is equal.
Description
Technical field
The present invention relates to the catalytic cleaning of car tail gas field, specifically, relate to the radially three-effect catalyst for purifying tail gas of car and preparation method thereof of load in gradient of a kind of coating material.
Background technology
Automotive emissions mainly comprise carbon monoxide (CO), hydrocarbon (HC), nitrogen oxide (NO
x), its major polluting atmosphere environment.NO particularly
xProduce photochemical fog and NO with HC under the ultraviolet ray irradiation
xForm acid rain and all ecological environment is produced serious destruction.At present mainly utilize three-way catalyst with pollutant CO, HC and the NO of motor vehicle emission
xBe converted into harmless nitrogen G﹠W.Three-way catalyst is installed in the catalytic converter of gas extraction system, and catalytic converter due to the diffusion of air-flow, causes the air-flow skewness in catalytic converter on its expansion pipeline section.The throughput in catalyst axis zone is large, and fringe region throughput less.At present the coating material of three-way catalyst all adopts the equally loaded mode, and this will cause the catalyst edge zone not play one's part to the full, thereby causes the waste of coating material.
For this problem, mainly make the catalyst internal gas flow even by structure or the auxiliary equipment that changes catalyst at present, improve the utilization rate in catalyst edge zone.Adopt respectively the mode of dividing plate shunting and turbine bypass that the air-flow in catalytic converter is evenly distributed as patent US2010/0050598A1 and US3964875.
Although said apparatus can make the catalytic converter internal gas flow be evenly distributed, take full advantage of the fringe region of catalyst, reach good catalyticing purifying effect, but the catalytic converter apparatus volume is large, cost is high, and part flow arrangement can make exhaust be pressed increase, causes the waste of fuel oil.
Summary of the invention
Purpose of the present invention provides a kind of three-way catalyst for purifying vehicle exhaust and preparation method thereof, and this catalyst can reduce the consumption of coating material on the basis that does not reduce catalytic activity.
For achieving the above object, the invention provides a kind of gradient load three-way catalyst, this catalyst comprises the carrier with ordered structure and the coating material that is attached to carrier surface, described coating material is along the radially load in gradient of ordered structure carrier, and reduced gradually by axis zone to the fringe region load capacity of carrier.
Above-mentioned gradient load three-way catalyst, wherein, described catalyst is comprised by axis zone to fringe region: the first area of 25-35%, the second area of 25-35%, and the 3rd zone of 35-45%, above percentage number average refers to that it accounts for the percentage by volume of whole catalyst.
Above-mentioned gradient load three-way catalyst, wherein, the carrier of described ordered structure refers to have the regular parallel duct of mesopore of macro-scale and the catalyst carrier of structured surface.
Above-mentioned gradient load three-way catalyst, wherein, described pore structure is shaped as square, hexagon, circle or other are irregularly shaped.
Above-mentioned gradient load three-way catalyst, wherein, the carrier of described ordered structure is cellular.
Above-mentioned gradient load three-way catalyst, wherein, the carrier of described ordered structure refers to any one in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier, metal alloy honeycomb substrate.
The present invention also provides a kind of preparation method of above-mentioned gradient load three-way catalyst, and the method comprises following concrete steps:
Step 1 is mixed cerium zirconium aluminum composite oxides and precious metal salt in quality 100:0.5～1.0 ratios, add deionized water, make solid content by weight percentage count the mixture of 30～40wt%, the pH value is adjusted to 2～6, ball milling was made slurry in 3～6 hours;
Step 2 take above-mentioned stock quality as benchmark, is calculated in mass percent, and adds polyvinyl alcohol 1～3wt% to stir in the slurry of step 1 preparation, and the slurry that then will contain polyvinyl alcohol radially is carried on carrier surface in gradient along the ordered structure carrier;
Step 3 is dried the carrier product of step 2 under the shady and cool environment that ventilates, then in 100～120 ℃ of dryings 10～20 hours, 500～600 ℃ of roastings 3～6 hours, heating rate be 2～4 ℃ per minute;
Step 4 passes into H with the carrier product of step 3 at 400～450 ℃
2/ N
2Mist reduced 1～4 hour, namely obtained the target catalyst.
The preparation method of above-mentioned gradient load three-way catalyst, wherein, the load capacity of the coating material of described uniform load three-way catalyst is 60～70wt%, take catalyst quality as benchmark.
The preparation method of above-mentioned gradient load three-way catalyst, wherein, take uniform load three-way catalyst load capacity as benchmark, the coating material load capacity of first area is the load capacity of uniform load three-way catalyst, the coating material load capacity of second area is 95～85wt% of uniform load three-way catalyst load capacity, and the coating material load capacity in the 3rd zone is 85～75wt% of uniform load three-way catalyst load capacity.
The preparation method of above-mentioned gradient load three-way catalyst, wherein, described H
2/ N
2In mist, H
2Content accounts for the 4.5-5.5vol% of mist percentage by volume meter.
The present invention is carried on the ordered structure honeycomb support with the coating material gradient surperficial, in the situation that do not reduce the catalytic activity graded that the catalyst activity realizes catalyst according to air-flow distribution characteristics in catalytic converter.Regional gas stream amount around the axis of regular texture catalyst is large, the coating material that load is more, and the fringe region throughput is little, the coating material that load is less.The air-flow in the zone around the catalyst converter axis is discharged than multizone via the catalyst cupport coating material, and the edge air-flow is via the less zone discharge of catalyst cupport coating material.Three-way catalyst of the present invention comprises the ordered structure honeycomb support and is attached to the coating material of carrier surface, the distribution that the catalyst with ordered structure that the present invention adopts only relates to coating material improves, and therefore coating material is had no particular limits.Catalyst of the present invention is compared with the uniform load three-way catalyst, can make the consumption of coating material reduce by 5～15wt%, and catalytic activity is suitable.
Description of drawings
Fig. 1 is the structural representation of the coating material gradient load of a kind of gradient load three-way catalyst of the present invention.
Fig. 2 is the initiation temperature indicatrix of the catalyst A that makes of embodiments of the invention 1.
Fig. 3 is the initiation temperature indicatrix of the catalyst B that makes of Comparative Examples 1 of the present invention.
The specific embodiment
The invention provides a kind of gradient load three-way catalyst and preparation method thereof.This catalyst comprises the carrier and the coating material that is attached to carrier surface of ordered structure, and described coating material has no particular limits coating material along the radially load in gradient of ordered structure honeycomb support.The catalyst of the present invention's preparation can reduce the consumption of coating material on the basis that does not reduce catalytic activity.
Catalyst of the present invention is the gradient ordered structure catalyst, and this catalyst comprises the ordered structure honeycomb support and is attached to the supported catalyst coating material.
The present invention has no particular limits the gradient distribution of coating material, as long as the load capacity of coating material radially changing in gradient along the ordered structure carrier.(the coating material load capacity of uniform load three-way catalyst is preferably 67wt% take uniform load three-way catalyst load capacity as benchmark, take catalyst quality as benchmark, be that coating material weight is the 67wt% of vehicle weight), wherein, the coating material load capacity of first area 10 is preferably the load capacity (being 67wt%) of uniform load three-way catalyst, the percentage by volume of first area 10 shared whole catalyst is 25-35%, second area 20 coating material load capacity are preferably the 90wt% of uniform load three-way catalyst load capacity, the percentage by volume of second area 20 shared whole catalyst is 25-35%, the coating material load capacity in the 3rd zone 30 is preferably the 80wt% of uniform load three-way catalyst load capacity, and the percentage by volume of the 3rd zone 30 shared whole catalyst is 35-45%, as shown in Figure 1.
The carrier of ordered structure of the present invention refers to have the regular parallel duct of mesopore of macro-scale and the catalyst carrier of structured surface.The carrier of described ordered structure includes but not limited to cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier, metal alloy honeycomb substrate.The present invention has no particular limits described pore structure shape, is not limited to square, hexagon, circle or other are irregularly shaped.
The distribution that the catalyst with ordered structure that adopts due to the present invention only relates to coating material improves, and coating material is had no particular limits.For example, described cerium zirconium aluminum composite oxides and precious metal salt can be commercially available, and also can adopt the whole bag of tricks to prepare.
In the present invention, the contact conditions of described catalyst and tail gas is the contact conditions of industrial three-way catalyst and tail gas, and namely the volume space velocity of tail gas is 40000～80000h
-1, excess air factor is 0.90～1.10.
Embodiment 1:
The present embodiment is used for illustrating the preparation of catalyst of the present invention.Take 695g cerium zirconium aluminum composite oxides (55wt% γ-Al
2O
3, 13wt%CeO
2, 16wt%ZrO
2, 3.5wt%BaO, 11wt%MgO, 1.5wt%Pr
6O
11, take the cerium zirconium aluminum composite oxides quality as benchmark), 0.65g Rh (NO
3)
3, 4.43g Pd (NO
3)
3Mix with the 1291g deionized water, make the mixture that solid content is 35wt%, with nitric acid, the pH value is adjusted to 3, wet ball grinding was made slurry in 4 hours.Add again the 7g poly-vinyl alcohol solution to stir, adopt the catalyst gradient apply instrument with slurry radially distribution gradient be carried on cylindrical cordierite honeycomb ceramic carrier surface.Take uniform load three-way catalyst load capacity as benchmark, the coating material load capacity of its first area 10 is that (load capacity of the coating material of uniform load three-way catalyst is 67wt% for the load capacity of uniform load three-way catalyst, take catalyst quality as benchmark), the coating material load capacity of second area 20 is the 90wt% of uniform load three-way catalyst load capacity, the coating material load capacity in the 3rd zone 30 is the 80wt% of uniform load three-way catalyst load capacity, as shown in Figure 1.Then catalyst is placed in the shady and cool environment 12 hours of ventilating, then in 120 ℃ of dryings 12 hours, and at 600 ℃ of lower roastings 4 hours (heating rate be 3 ℃ per minute), then uses H for 450 ℃
2/ N
2(H
2Content is 5.0vol%) process and namely to obtain catalyst of the present invention in 4 hours.
Comparative Examples 1:
This Comparative Examples is used for the preparation of explanation prior art uniform load catalyst.
According to the step Kaolinite Preparation of Catalyst of embodiment 1, different is that coating procedure floating coat material adopts uniform load.Take catalyst quality as benchmark, the coating material load capacity is 67wt%.
Test case 1: for the catalyst A of embodiment 1 and the catalyst B of Comparative Examples 1.The catalyst A that above-described embodiment 1 is made and comparative example catalyst B fill respectively and are packaged in catalytic converter.Test is engine works of EQ49li(Dongfeng Automobile Co., Ltd with engine model), load sample 1.0L, excess air factor is 1.01, tail gas was with 50000 hours
-1Volume space velocity pass through catalyst.Detect the concentration value of catalyst inlet temperature and carbon monoxide, hydrocarbons and nitrogen oxide, then calculate the catalytic conversion efficiency of catalyst according to following formula:
Gained catalyst A light off characteristics curve is seen Fig. 2, and catalyst B light off characteristics curve is seen Fig. 3.Temperature when catalytic conversion efficiency is 50% is initiation temperature T
50, the temperature when catalytic conversion efficiency is 90% is maximum conversion efficient temperature T
90, the T of catalyst A and B
50And T
90See Table 1.
Table 1 catalyst A and B ignition activity data
Can be found out by Fig. 2-3 and table 1: apply the product of instrument production (coating) with the catalyst gradient, in the situation that reduce the 5-15% coating material, its performance and control sample are suitable, namely do not reduce the performance of catalyst.
Although content of the present invention has been done detailed introduction by above preferred embodiment, will be appreciated that above-mentioned description should not be considered to limitation of the present invention.After those skilled in the art have read foregoing, for multiple modification of the present invention with to substitute will be all apparent.Therefore, protection scope of the present invention should be limited to the appended claims.
Claims (10)
1. gradient load three-way catalyst, this catalyst comprises the carrier with ordered structure and the coating material that is attached to carrier surface, it is characterized in that, described coating material is along the radially load in gradient of ordered structure carrier, and reduced gradually by axis zone to fringe region load capacity.
2. gradient load three-way catalyst as claimed in claim 1, it is characterized in that, described catalyst is comprised by axis zone to fringe region: the first area of 25-35% (10), the second area of 25-35% (20), and the 3rd zone (30) of 35-45%, above percentage refers to that each zone accounts for the percentage by volume of whole catalyst.
3. gradient load three-way catalyst as claimed in claim 1, is characterized in that, the carrier of described ordered structure refers to have the regular parallel duct of mesopore of macro-scale and the catalyst carrier of structured surface.
4. gradient load three-way catalyst as claimed in claim 3, is characterized in that, described pore structure is shaped as square, hexagon, circle or other are irregularly shaped.
5. gradient load three-way catalyst as claimed in claim 3, is characterized in that, the carrier of described ordered structure is cellular.
6. gradient load three-way catalyst as claimed in claim 5, is characterized in that, the carrier of described ordered structure refers to any one in cordierite honeycomb carrier, mullite honeycomb substrate, cellular alumina carrier, metal alloy honeycomb substrate.
7. the preparation method of the described gradient load of any one three-way catalyst in a kind according to claim 1-6, is characterized in that, the method comprises following concrete steps:
Step 1 is mixed cerium zirconium aluminum composite oxides and precious metal salt in quality 100:0.5～1.0 ratios, add deionized water, make solid content by weight percentage count the mixture of 30～40wt%, the pH value is adjusted to 2～6, ball milling was made slurry in 3～6 hours;
Step 2 take above-mentioned stock quality as benchmark, adds polyvinyl alcohol 1～3wt% to stir in the slurry of step 1 preparation, and the slurry that then will contain polyvinyl alcohol radially is carried on carrier surface in gradient along the ordered structure carrier;
Step 3 is dried the carrier product of step 2 under the shady and cool environment that ventilates, then in 100～120 ℃ of dryings 10～20 hours, 500～600 ℃ of roastings 3～6 hours, heating rate be 2～4 ℃ per minute;
Step 4 passes into the H2/N2 mist with the carrier product of step 3 at 400～450 ℃, reduces 1～4 hour, namely obtains the target catalyst.
8. the preparation method of gradient load three-way catalyst as claimed in claim 7, is characterized in that, the load capacity of the coating material of described uniform load three-way catalyst is 60～70wt%, take catalyst quality as benchmark.
9. the preparation method of gradient load three-way catalyst as claimed in claim 8, it is characterized in that, take uniform load three-way catalyst load capacity as benchmark, the coating material load capacity of first area (10) is the load capacity of uniform load three-way catalyst, the coating material load capacity of second area (20) is 95～85wt% of uniform load three-way catalyst load capacity, and the coating material load capacity of the 3rd zone (30) is 85～75wt% of uniform load three-way catalyst load capacity.
10. the preparation method of gradient load three-way catalyst as claimed in claim 7, is characterized in that, described H
2/ N
2In mist, H
2Content accounts for the 4.5-5.5vol% of mist percentage by volume meter.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226295A (en) * | 2014-09-10 | 2014-12-24 | 济南大学 | Cerium-zirconium-aluminum composite oxide and gasoline car tail gas three-way catalyst as well as preparation methods of composite oxide and catalyst |
| CN107126975A (en) * | 2017-04-01 | 2017-09-05 | 四川群青新材料科技有限公司 | A kind of liquid-solid reaction catalyst of high surface area |
| CN109641195A (en) * | 2016-08-11 | 2019-04-16 | 优美科股份公司及两合公司 | Particulate filter with SCR activity coating |
| CN110605114A (en) * | 2019-10-15 | 2019-12-24 | 南开大学 | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration |
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| CN101224423A (en) * | 2008-02-04 | 2008-07-23 | 北京英泰世纪环境科技有限公司 | Active component block distributed catalyst and preparing method thereof |
| CN101274216A (en) * | 2007-12-29 | 2008-10-01 | 北京英泰世纪环境科技有限公司 | Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof |
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2013
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR100781726B1 (en) * | 2006-09-15 | 2007-12-03 | 한국중부발전(주) | Method for manufacturing de-nox scr coating catalyst using porous ceramic substrate |
| CN101274216A (en) * | 2007-12-29 | 2008-10-01 | 北京英泰世纪环境科技有限公司 | Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104226295A (en) * | 2014-09-10 | 2014-12-24 | 济南大学 | Cerium-zirconium-aluminum composite oxide and gasoline car tail gas three-way catalyst as well as preparation methods of composite oxide and catalyst |
| CN109641195A (en) * | 2016-08-11 | 2019-04-16 | 优美科股份公司及两合公司 | Particulate filter with SCR activity coating |
| CN109641195B (en) * | 2016-08-11 | 2023-01-10 | 优美科股份公司及两合公司 | Particulate filter with SCR active coating |
| CN107126975A (en) * | 2017-04-01 | 2017-09-05 | 四川群青新材料科技有限公司 | A kind of liquid-solid reaction catalyst of high surface area |
| CN107126975B (en) * | 2017-04-01 | 2020-06-30 | 四川群青新材料科技有限公司 | High-surface-area catalyst for liquid-solid reaction |
| CN110605114A (en) * | 2019-10-15 | 2019-12-24 | 南开大学 | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration |
| CN110605114B (en) * | 2019-10-15 | 2022-04-01 | 南开大学 | Application of mullite oxide supported catalyst in low-temperature selective catalytic reduction denitration |
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Application publication date: 20130619 |