CN101274216A - Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof - Google Patents
Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof Download PDFInfo
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- CN101274216A CN101274216A CNA200710304718XA CN200710304718A CN101274216A CN 101274216 A CN101274216 A CN 101274216A CN A200710304718X A CNA200710304718X A CN A200710304718XA CN 200710304718 A CN200710304718 A CN 200710304718A CN 101274216 A CN101274216 A CN 101274216A
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Abstract
The invention provides a catalyst active component coaxial radial symmetrical distribution method, a preparation method and a device thereof, which can obviously improve the utilization ratio of the catalyst active component and prolong the service life of the catalyst.
Description
Technical field
The present invention relates to the coaxial radial symmetric formula of a kind of catalyst activity component location mode, and the method and the device that prepare this coaxial radial symmetric formula distribution catalyst activity component.
Background technology
Catalytic purification is that one of effective method is polluted in the control of engine and vehicular emission tail gas (hereinafter to be referred as tail gas), and catalyst is the core of catalysis and purification technology.Catalyst can change into the carbon monoxide CO in the motor-vehicle tail-gas, hydrocarbon HC, dissolved organic matter SOF, nitrogen oxide NOx and even solid particulate matter the steam H of nuisanceless or low public hazards by catalytic oxidation and catalytic reduction reaction
2O, nitrogen N
2With carbon dioxide CO
2Deng.So not single, catalytic purification method also is one of most effectual way of various stationary source emission controls, and catalyst is more extensive in industrial application.
Catalyst, especially fixed bde catalyst, under service condition, owing to be subjected to the influence of waller effect, and fast more the closer to the moving speed of the position reaction logistics at beds center, slow more the closer to the position flow rate of tube wall.The catalysis task that corresponding beds centre is born is the heaviest, also the easiest inefficacy, and the position at bed edge, and the catalysis task of bearing is the lightest.The problem that causes thus is: behind the catalysqt deactivation of beds center, and the catalyst activity of edge is still very high, thereby causes edge's catalyst not to be fully utilized, thereby forms waste.
If adopt with the axial symmetry paint-on technique, by coating procedure is rationally regulated and control, make the last carrying capacity of catalyst, from beds (carrier) center, radially outwards constantly successively decrease by interior (center).This distributed architecture of catalyst, make the catalyst at beds center and peripheral position reach service life as much as possible simultaneously, thereby avoid the waste of catalyst, improve the utilization rate of catalyst, can reduce the manufacturing cost and use cost of catalyst accordingly, particularly in the motor vehicle tail-gas purifying technology, because catalyst generally all is that the utilization rate that improves catalyst just has remarkable economic efficiency and social benefit more by various noble metal preparations.
Summary of the invention
At the shortcoming and defect that existing catalyst-coated technology exists, one object of the present invention is to provide a kind of method that catalyst activity component is distributed according to coaxial radial symmetric formula.
Another object of the present invention is to provide a kind of method for preparing the catalyst of the coaxial radial symmetric formula distribution of above-mentioned active constituent.
Another object of the present invention is to provide a kind of device of realizing above-mentioned preparation method.
Technical scheme of the present invention is as follows:
The coaxial radial symmetric formula of a kind of catalyst activity component location mode, it is characterized in that: the catalyst activity component load capacity is successively decreased to edge by the center in the radial direction at carrier; The active constituent load capacity is identical on same axial direction.
The preparation method that the coaxial radial symmetric formula of a kind of catalyst activity component distributes, it is characterized in that: described preparation method is coated on the carrier according to the mode layering of successively decreasing successively from center course extracellular concentration by active matter slurry or the active constituent salting liquid in order to the adsorption activity component with previously prepared variable concentrations.
The preparation method that the coaxial radial symmetric formula of described catalyst activity component distributes may further comprise the steps:
The preparation method that the coaxial radial symmetric formula of described catalyst activity component distributes may further comprise the steps:
Among the described active constituent salting liquid P0, active constituent is platinum Pt, palladium Pd or rhodium Rh is wherein a kind of or several, and salting liquid is a nitrate solution.
Described carrier is for being honeycomb substrate, pelleted substrate, wall-flow type carrier or the semi-fluid general formula carrier of base material with pottery or metal.
Described oven dry calcining kiln is a net belt type continuous drying calcining kiln.
A kind of coating unit that distributes in order to the coaxial radial symmetric formula of preparation catalyst activity component, described coating unit comprises the cavity volume of ccontaining coating slurry or liquid and is positioned at cavity volume and nozzle and compressed air inlet, it is characterized in that: described nozzle has the ring section spout, spout internal cavities and carrier external diameter are suitable, are connected removably between nozzle and the cavity volume.
Described coating unit is equipped with serial nozzle, and described serial nozzle has the spout internal cavities of different bores.
Described ring section spout is circle or elliptical annular cross section spout.
Technique effect of the present invention is:
The coaxial radial symmetric formula of catalyst activity component of the present invention location mode, by the catalyst activity component load capacity is successively decreased to edge by the center along the carrier radial direction, and the active constituent load capacity is identical on same axial direction.Such active constituent distribution mode has overcome the defective that the existing catalyst activity component mode that is evenly distributed has fully, it is carrier center site catalysts premature failure, thereby the external catalyst active constituent that causes can not effectively utilize, and causes the waste of catalyst activity component and catalysis efficiency.The catalysis task that the present invention has utilized the carrier center site catalysts to bear just is the heaviest, also the easiest inefficacy, and the position at bed edge, the lightest characteristics of bearing of catalysis task, catalyst activity component is distributed in right amount, thereby significantly improve the utilization rate of catalyst, also prolonged the working life of catalyst converter accordingly.
The present invention also provides above-mentioned preparation method with coaxial radial symmetric formula distribution catalyst activity component, its active matter slurry or active constituent salting liquid in order to the adsorption activity component by having variable concentrations with previously prepared one group, active matter slurry that outside the course of center concentration is successively decreased successively again or the layering of active constituent salting liquid are coated on the carrier, prepare the above-mentioned catalyst activity component with coaxial radial symmetric formula distribution of the present invention.
Catalyst distribution mode by method for preparing can make full use of rare noble metal isoreactivity component, and helps the diabatic process of beds simultaneously, has much practical value.
Catalyst distribution mode of the present invention and preparation method thereof not only can be used for vehicle emission pollution control field, more can be used for not only can be used for the integrated catalyst in the industrial large-scale fixed bde catalyst preparation, more can be used for beaded catalyst.Its use on beaded catalyst has more advantage, and beaded catalyst that can preparation in quantity different activities component load capacity is filled on the fixed bed then on request, forms the catalyst that coaxial radial symmetric distributes.
The present invention also provides a kind of coating unit that distributes in order to the coaxial radial symmetric formula of preparation catalyst activity component, comprise the cavity volume of ccontaining coating slurry or liquid and be positioned at cavity volume and nozzle and compressed air inlet, its nozzle has the ring section spout, spout internal cavities and carrier external diameter are suitable, are connected removably between nozzle and the cavity volume.Utilize this coating unit can be very easily the active matter slurry or the layering of active constituent salting liquid of variable concentrations to be coated on the carrier, prepare the present invention above-mentioned have a catalyst activity component that coaxial radial symmetric formula distributes.
Description of drawings
Fig. 1 is the structural representation of coating unit of the present invention.
Fig. 2 is the structural representation of circular ring-shaped spout.
Fig. 3 is the structural representation of elliptical perimeter spout.
The specific embodiment
(1) takes by weighing activated alumina 40kg, cerium zirconium sosoloid 7kg, nitric acid 1kg and deionized water 52kg, put into ball grinder ball milling 8h, make alumina slurry C0.
(2) alumina slurry C0 is divided into each 20kg of 5 equal portions, adds deionized water 0kg respectively, 2kg, 4kg, 6kg, 8kg ground 1 hour again, and adding acid or alkali adjusting viscosity are suitable, make slurry C 1, C2, C3, C4 and C5 accordingly.
(3) slurry C 1, C2, C3, C4 and C5 are added respectively (as shown in Figure 1) in the applicator that different size ring section nozzle is installed, apply the compressed air of 2MPa, outside by carrier center successively, slurry C 1, C2, C3, C4 and C5 are pressed in the carrier, blow most residual slurry.
(4) the above-mentioned carrier that is coated with alumina slurry is put into net belt type continuous drying calcining kiln, heated 5 hours, the highest sintering temperature is controlled at 500 ℃, makes the catalyst semi-finished product.
(5) get concentration be 15% active constituent (Pd/Pt=10: 1) nitrate solution P0, above-mentioned catalyst semi-finished product be impregnated in wherein 5 minutes, take out, blow off raffinate.500 ℃ of roastings are 2 hours in the calcining kiln, naturally cool to room temperature, can make the coaxial radial symmetric distributed catalyst of desired active constituent.
(1) takes by weighing activated alumina 40kg, cerium zirconium sosoloid 7kg, nitric acid 1kg and deionized water 52kg, put into ball grinder ball milling 8h, make alumina slurry C0.
(2) metal beehive carrier that preliminary treatment is good was dipped in the above-mentioned slurry 10 seconds, took out the back and blew most residual slurry with 4MPa compressed air.
(3) the above-mentioned carrier that is coated with alumina slurry is put into net belt type continuous drying calcining kiln, heated 8 hours, the highest sintering temperature is controlled at 500 ℃, makes catalyst semi-finished product (being loaded with coating) G0.
(4) getting concentration is that (Pd/Pt=10: 1) nitrate solution P0 is totally 1 liter, is divided into 5 equal portions, is diluted to 100%, 80%, 60%, 50%, 40% with deionized water respectively, makes noble metal nitrate solution P1, P2, P3, P4 and P5 respectively for 20% active constituent.
(5) above-mentioned active constituent nitrate solution P1, P2, P3, P4 and P5 are added (as shown in Figure 1) in the coating machine that different size ring section nozzle is installed respectively, apply the compressed air of 0.04MPa, outside by carrier center successively, slurry C 1, C2, C3, C4 and C5 are pressed in the carrier, and the time that the control flow of solution is crossed carrier is 20 seconds.Compressed air with 4MPa blows most raffinate at last.500 ℃ roasting 2 hours naturally cools to room temperature in the calcining kiln, can make the coaxial radial symmetric distributed catalyst of desired active constituent.
Active constituent can be platinum Pt, palladium Pd or rhodium Rh is wherein a kind of or several among the above embodiment, but is not limited to platinum Pt, rhodium Rh, palladium Pd, and its salting liquid can also be an acetate solution.
Layering coating operation can be that continuously uninterrupted layering applies among the above embodiment, also can adopt the interruption layering to apply.
Though adopted 5 layers of coating method among the above embodiment, the catalyst activity component that is not limited to 5 layers in the practical application distributes.
Utilize this preparation method to implement noble metal layering paint-on technique, in noble metal active solution, add an amount of block copolymer, also can rely on the suction-operated of copolymer, make platinum, palladium, 3 kinds of different noble metal compositions of rhodium be distributed in the different degree of depth of coating as required, make different noble metals give full play to separately effect.
Figure 1 shows that the structural representation of coating unit of the present invention.Cavity 1 one ends are provided with nozzle 2, and the other end is connected with compressed air inlet 3.Wherein nozzle 2 front ends are the annular jet 5 with cavity 4, and annular jet 5 can be multiple shape, provides two kinds of embodiment in this specification, and a kind of is circular (as shown in Figure 2), and another kind is oval (as shown in Figure 3).Described annular jet 5 shapes can also be runway annular, trapezoidal annular, triangular ring or the like.
Wherein adopt dismountable mode to be connected between nozzle 2 and the cavity 1, as be threaded.Each cavity 1 all is furnished with one group of nozzle 2, has the cavity 4 of different bores on this group nozzle 2 respectively.Can change the nozzle 2 that adapts fast according to the radial dimension of carrier like this.
Carrier can be various materials, shape and size among the present invention, includes but not limited to pottery or metal, alloy or composite to be honeycomb substrate, pelleted substrate, wall-flow type carrier, the semi-fluid general formula carrier of matrix.
Catalyst activity component location mode of the present invention and preparation method thereof can extensive use, be applicable to gasoline engine, diesel engine, various alternative fuel engine, three-way catalyst TWC, the oxidation catalyst OC of various hybrid powers, catalyst for purification of nitrogen oxides DeNOx, and the industrial catalyst of other type, stationary source control catalyst, can also be applied to various types of particle trappers etc. that load has active constituent.
Claims (10)
1. the coaxial radial symmetric formula of catalyst activity component location mode, it is characterized in that: the catalyst activity component load capacity is successively decreased to edge by the center in the radial direction at carrier; The active constituent load capacity is identical on same axial direction.
2. the preparation method that distributes of the coaxial radial symmetric formula of a catalyst activity component, it is characterized in that: described preparation method is coated on the carrier according to the mode layering of successively decreasing successively from center course extracellular concentration by active matter slurry or the active constituent salting liquid in order to the adsorption activity component with previously prepared variable concentrations.
3. the preparation method that the coaxial radial symmetric formula of catalyst activity component as claimed in claim 2 distributes is characterized in that: the preparation method that the coaxial radial symmetric formula of described catalyst activity component distributes may further comprise the steps:
Step 1 is total to 100kg with activated alumina 20-50kg, cerium zirconium sosoloid 5-10kg, nitric acid 0.3-1kg and deionized water and puts into ball milling, ground and mixed 3-12 hour.Make alumina slurry C0, the total solid content of control slurry is 30-60%.
Step 2 is with prepared alumina slurry C0 break into portions, each part increases progressively the adding deionized water respectively, grinds 1-3 hour respectively, and adds acid or alkali adjusting viscosity, make accordingly serial slurry C 1, C2, C3 ... Cn, wherein activated alumina content C1＞C2＞C3＞...＞Cn.
Step 3 with slurry C 1, C2, C3, ... Cn outwards is coated on the carrier successively by carrier center.
Step 4 is put into the oven dry calcining kiln with the carrier of coating alumina slurry, under 300-600 ℃, heats 3-12 hour.Make semi-finished product G0.
Step 5 is got the active constituent salting liquid P0 that concentration is 5-20%, semi-finished product G0 be impregnated in taking-up after 5-25 minute among the active constituent salting liquid P0, under 300-500 ℃ in roasting roasting in kilns 1-3 hour, naturally cool to room temperature and get final product, wherein catalyst activity component has coaxial radial symmetric formula distribution.
4. the preparation method that the coaxial radial symmetric formula of catalyst activity component as claimed in claim 2 distributes,, it is characterized in that: the preparation method that the coaxial radial symmetric formula of described catalyst activity component distributes may further comprise the steps:
Step 1 is total to 100kg with activated alumina 20-50kg, cerium zirconium sosoloid 5-10kg, nitric acid 0.3-1kg and deionized water and puts into ball milling, ground and mixed 3-12 hour.Make alumina slurry C0, the total solid content of control slurry is 30-60%.
Step 2 immerses among the alumina slurry C0 carrier with the coating alumina slurry.
Step 3 is put into the oven dry calcining kiln with the carrier of coating alumina slurry, under 300-600 ℃, heats 3-12 hour.Make semi-finished product G0.
Step 4 is got the some equal portions of active constituent salting liquid P0 that concentration is 20-30%, increases progressively respectively to add the deionized water dilution, be prepared into serial active constituent salting liquid P1, P2, P3 ... Pn.
Step 5 with solution P1, P2, P3 ... Pn outwards is coated on the carrier successively by carrier center, moves into 300-500 ℃ roasting roasting in kilns 1-3hrs, naturally cools to room temperature and gets final product, and wherein catalyst activity component has coaxial radial symmetric formula and distributes.
5. as claim 3 or 4 described preparation methods, it is characterized in that: among the described active constituent salting liquid P0, active constituent is platinum Pt, palladium Pd or rhodium Rh is wherein a kind of or several, and salting liquid is a nitrate solution.
6. preparation method as claimed in claim 5 is characterized in that: described carrier is for being honeycomb substrate, pelleted substrate, wall-flow type carrier or the semi-fluid general formula carrier of base material with pottery or metal.
7. preparation method as claimed in claim 6 is characterized in that: described oven dry calcining kiln is a net belt type continuous drying calcining kiln.
8. coating unit that distributes in order to the coaxial radial symmetric formula of preparation catalyst activity component, described coating unit comprises the cavity volume of ccontaining coating slurry or liquid and is positioned at cavity volume and nozzle and compressed air inlet, it is characterized in that: described nozzle has the ring section spout, spout internal cavities and carrier external diameter are suitable, are connected removably between nozzle and the cavity volume.
9. coating unit as claimed in claim 8 is characterized in that: described coating unit is equipped with serial nozzle, and described serial nozzle has the spout internal cavities of different bores.
10. coating unit as claimed in claim 9 is characterized in that: described ring section spout is circle or elliptical annular cross section spout.
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| CN200710304718XA CN101274216B (en) | 2007-12-29 | 2007-12-29 | Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof |
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| CN200710304718XA CN101274216B (en) | 2007-12-29 | 2007-12-29 | Coaxial radial symmetrical type distribution method of catalyst activity component, preparation and device thereof |
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| CN101274216B CN101274216B (en) | 2011-08-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157520A (en) * | 2013-03-04 | 2013-06-19 | 上海云汇环保科技有限公司 | Radial gradient load three-way catalyst and preparation method |
| CN103191736A (en) * | 2013-04-07 | 2013-07-10 | 无锡威孚环保催化剂有限公司 | Preparation method of cyclic three-way catalyst |
| CN104399459A (en) * | 2014-10-31 | 2015-03-11 | 金华欧仑催化科技有限公司 | Catalyst for rear-stage three-way catalytic converter |
| CN107649126A (en) * | 2017-10-27 | 2018-02-02 | 南京依柯卡特排放技术股份有限公司 | Biradical noble metal DOC catalyst and preparation method for diesel exhaust purification |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10230330A1 (en) * | 2002-07-05 | 2004-01-22 | Audi Ag | Method and device for spatially inhomogeneous coating of a honeycomb body and inhomogeneously coated honeycomb body |
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2007
- 2007-12-29 CN CN200710304718XA patent/CN101274216B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103157520A (en) * | 2013-03-04 | 2013-06-19 | 上海云汇环保科技有限公司 | Radial gradient load three-way catalyst and preparation method |
| CN103191736A (en) * | 2013-04-07 | 2013-07-10 | 无锡威孚环保催化剂有限公司 | Preparation method of cyclic three-way catalyst |
| CN104399459A (en) * | 2014-10-31 | 2015-03-11 | 金华欧仑催化科技有限公司 | Catalyst for rear-stage three-way catalytic converter |
| CN107649126A (en) * | 2017-10-27 | 2018-02-02 | 南京依柯卡特排放技术股份有限公司 | Biradical noble metal DOC catalyst and preparation method for diesel exhaust purification |
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| CN101274216B (en) | 2011-08-03 |
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Granted publication date: 20110803 Termination date: 20161229 |