CN102614874A - Preparation method of alumina slurry, automobile exhaust purification catalyst containing the alumina slurry and preparation method of the automobile exhaust purification catalyst containing the alumina slurry - Google Patents
Preparation method of alumina slurry, automobile exhaust purification catalyst containing the alumina slurry and preparation method of the automobile exhaust purification catalyst containing the alumina slurry Download PDFInfo
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Abstract
The invention discloses a preparation method of alumina slurry. The preparation method comprises the following steps of I, carrying out stepwise dipping of an adsorbent and carrying out centrifugal filtration to obtain an active adsorbent, and II, carrying out a process II1 through carrying out calcination of the active adsorbent obtained by the step I under oxygen insulation, heating to improve oxygen concentration, carrying out calcination to obtain active powder, mixing the active powder, alumina, ceria-zirconia powder and at least one binder, and carrying out ball milling of the mixture to obtain the alumina slurry, or carrying out a process II2 through mixing the active adsorbent, alumina and ceria-zirconia powder, carrying out calcination of the mixture under oxygen insulation, heating to improve oxygen concentration, carrying out calcination to obtain mixed powder, mixing the mixed powder and at least one binder, and carrying out ball milling to obtain the alumina slurry. The invention also discloses an automobile exhaust purification catalyst and a preparation method thereof. The preparation method of the automobile exhaust purification catalyst comprises the following steps of coating the alumina slurry on a honeycomb ceramic carrier, drying and carrying out calcination. Through the preparation method of the automobile exhaust purification catalyst and the alumina slurry, an active ingredient utilization rate and catalytic performances of the automobile exhaust purification catalyst are improved.
Description
Technical field
The invention relates to preparation method and a kind of cleaning catalyst for tail gases of automobiles of a kind of preparation method of slurry containing aluminum oxide, a kind of cleaning catalyst for tail gases of automobiles.
Background technology
Along with developing of automobile industry, the auto output surge, the tail gas of motor vehicle emission has become one of primary pollution source of atmosphere.CO in the motor vehicle emission tail gas, hydrocarbon (HC), NO
xVery harmful to health and PE.In order to eliminate this severe contamination, countries in the world have been formulated strict Abgasgesetz in succession, therefore, reduce motor vehicle exhaust emission to greatest extent, have become global environmental protection field key subjects anxious to be solved.Perfect day by day along with China's motor vehicle exhaust emission rules, more and more stricter to emission of automobile wastes control, therefore, require cleaning catalyst for tail gases of automobiles to have excellent catalytic performance and good resistant to thermal aging endurance quality.
Traditional load Preparation of catalysts method has: the precipitation method, ion exchange adsorption and traditional infusion process (directly with metal impregnation on carrier).These methods all are the capillarity absorption that active component is directly relied on carrier (like aluminium oxide) micropore, and drying and calcining becomes oxide attached on the carrier then.And these methods exist active component to be difficult to be uniformly dispersed, and the active particle thing size of preparation is restive, the shortcoming that active component can't oriented load.General catalytic reaction all is contact catalysis, so require carrier to have enough big specific surface.But the carrier that specific surface is big is not suitable for active component and directly contacts under some catalytic conditions, or need contact simultaneously with other materials that plays promoting catalysis, and traditional preparation method seems and is difficult to realize in this case.
Summary of the invention
The objective of the invention is in order to overcome in the prior art, the active component utilization rate was low when cleaning catalyst for tail gases of automobiles prepared, and catalytic performance is bad, the shortcoming of resistant to thermal aging endurance quality difference.A kind of preparation method of alumina slurry of cleaning catalyst for tail gases of automobiles is provided.
A kind of alumina slurry preparation method comprises: I is prepared multiple maceration extract, and the active component of every kind of maceration extract is different, with the adsorbent step impregnation in maceration extract, behind the step impregnation again centrifugal filtration get hypersober, carry out the step II again
1Or carry out the step II
2Said step II
1Be the hypersober oxygen barrier roasting that the step I is obtained, calcining obtains active powder under oxygen atmosphere again, and active powder that will obtain again and aluminium oxide, cerium zirconium powder body, binding agent mix, and ball milling obtains alumina slurry; Said step II
2For after hypersober that the step I is obtained and aluminium oxide, cerium zirconium powder body mix, with the mixture oxygen barrier roasting that obtains, under oxygen atmosphere, calcine again mixed powder, mixed powder mixes with binding agent again, ball milling gets alumina slurry.
A kind of preparation method of cleaning catalyst for tail gases of automobiles, this method comprise the slurry that contains aluminium oxide are coated on the honeycomb ceramic carrier, drying, and roasting, wherein, the slurry that contain aluminium oxide of said alumina slurry for preparing through above-mentioned preparation method.
A kind of cleaning catalyst for tail gases of automobiles is prepared by the preparation method of above-mentioned cleaning catalyst for tail gases of automobiles, wherein, and the slurry that contain aluminium oxide of said alumina slurry for preparing through above-mentioned preparation method.
The active material of catalytic reaction; Owing to the difference of valence state, catalytic performance has evident difference, like the application of palladium (being Pd) in vehicle exhaust in catalysis;, Pd shows relatively poor catalytic performance when existing with simple substance, when Pd shows best reactivity with simple substance and oxidation state and when depositing.So when the preparation catalyst, we seem most important to preparation technology's reasonable control.The oxygen barrier of the present invention when the preparation alumina slurry handled, and can well overcome the limitation that conventional method prepares catalyst, and improve the utilization rate of active component (like Pt, Pd, Rh), improves the catalytic performance of catalyst.
Compared with prior art; Method provided by the invention; In preparation slurry process, adopt step impregnation adsorbent and oxygen barrier roasting to calcine again and removed carbon base body, can guarantee the high degree of dispersion of noble metal in the pulp preparation process; Avtive spot is highly stable simultaneously, but also can play facilitation to the performance of catalyst." high degree of dispersion " described here and " avtive spot is highly stable " are and well known to a person skilled in the art technical term.
The specific embodiment
A kind of alumina slurry preparation method comprises: I is prepared multiple maceration extract, and the active component of every kind of maceration extract is different, with the adsorbent step impregnation in maceration extract, behind the step impregnation again centrifugal filtration get hypersober, carry out the step II again
1Or carry out the step II
2Said step II
1Be the hypersober oxygen barrier roasting that the step I is obtained, calcining obtains active powder under oxygen atmosphere again, and active powder that will obtain again and aluminium oxide, cerium zirconium powder body, binding agent mix, and ball milling obtains alumina slurry; Said step II
2For after hypersober that the step I is obtained and aluminium oxide, cerium zirconium powder body mix, with the mixture oxygen barrier roasting that obtains, under oxygen atmosphere, calcine again mixed powder, mixed powder mixes with binding agent again, ball milling gets alumina slurry.
Above-mentioned preparation method comprises that also the adsorbent that centrifugal filtration is obtained carries out drying, and baking temperature is preferably 100-120 ℃.
Above-mentioned preparation method also comprises, carries out the step II
1Or step II
2In mixing the time also add co-catalyst and be mixed together.
A kind of alumina slurry preparation method of the present invention; Can be described as: adsorbent is carried out step impregnation in active ingredient solution; Dried active adsorbent and secluding air calcining is again controlled oxygen concentration then and is calcined the adsorbent carbon carrier, to obtain active powder.Can first dry adsorbent in the step impregnation process also can be moist.Wherein, oxygen concentration control is exactly bubbling air in the blanket of nitrogen, is benchmark with the cumulative volume of gaseous mixture, and the air of feeding accounts for 10-20 volume %, and increases oxygen concentration gradually, eliminates so that carbon is ablated.Can prepare auto-exhaust catalyst with this active powder.
Above-mentioned preparation method, said dipping adsorption time is 1-6h; Temperature is controlled to be 500 ± 10 ℃ during the oxygen barrier roasting, and roasting time is 0.5-3h, and temperature control is 600-650 ℃ during calcining, and calcination time is 2-6h, increases oxygen concentration during calcining gradually; Rotational speed of ball-mill is 180-270 rev/min, and the ball milling time is 1.5-4h; Said baking temperature is 100-120 ℃, and be 1-3h drying time.
Maceration extract according to the invention is preferably the nitrate or the acetate solution of reactive metal, and its active component is one or more in palladium nitrate, rhodium nitrate, platinum nitrate, cerous nitrate, zirconium nitrate, lanthanum nitrate, praseodymium nitrate, zirconyl nitrate, barium nitrate and barium acetate preferably.Contained metallic element is that catalyst can not lack in the said maceration extract; Form adding with nitrate or acetate mainly is that nitrate ion or acetate ion have acidity; Can keep pH value of slurry a lower scope; The PH of said maceration extract＜4, the mass concentration of active component are 1.5%-15%.
Isolated oxygen roasting is to be in order progressively to remove carbon base body and to make the reduction of part metals oxide in order to make slaine tentatively resolve into oxide, to increase the oxygen concentration calcining then.High-temperature calcination and carbon base body exist down, make rhodium nitrate and platinum nitrate be reduced to simple substance Rh and Pt respectively; Palladium nitrate partly is reduced to simple substance Pd, and part is reduced to palladium oxide; Other active components of residue are reduced into corresponding oxide in the maceration extract.The purpose of doing like this is to prevent that metal oxide crystal grain from becoming big.Said active powder is to contain among precious metals pt, Pd, the Rh one or more above one group of combination oxide powder.
In the step impregnation, (in the described precious metal salt solution, the noble metal of indication is the known palladium nitrate of those skilled in the art, rhodium nitrate, platinum nitrate to precious metal salt solution.So) because the few final impregnating of use amount, all the other metal salt solutions can be according to the atomic mass size, and the dipping atomic weight is little earlier.Because the general big metal ion of atomic weight is adsorbed more easily.Every kind of maceration extract adsorption time is preferably 0.3-1h, total adsorption time 1-6h.
Adsorbent according to the invention is a graininess or fibrous, and the specific surface of said granular adsorption agent is preferably 500-1700m
2/ g, granularity D50 are preferably the 0.5-5 micron, and the length of said fibrous adsorbent is the 1-6 micron, and said adsorbent is a kind of in active carbon, mesoporous carbon, amorphous carbon preferably, and its addition accounts for 5 weight %-10 weight % of maceration extract.The granularity D90 of said granular adsorption agent is preferably the 1-5 micron, and the length of said fibrous adsorbent further is preferably the 3-6 micron.The specific surface of said granular adsorption agent further is preferably 500-1000m
2/ g.Simultaneously, among the present invention, adsorbent need be in follow-up calcination process ablated removing, to reach the object of the invention.
Binding agent according to the invention is one or more in polyvinyl alcohol, polyethylene glycol, ammonium polyacrylate, methylcellulose, ethyl cellulose, HPMC, APES preferably.
Aluminium oxide average pore size according to the invention is preferably 10-30nm, further is preferably 10-20nm, and average pore volume is preferably 0.1-1.0mL/g, further is preferably 0.3-0.6mL/g.Said aluminum oxide grain size D50 is preferably the 1-3 micron, and cerium zirconium powder body granularity D50 is preferably the 1-2 micron.
Co-catalyst according to the invention is an alkaline earth oxide, one or more in preferred autoxidation barium, magnesia, calcium oxide, the strontium oxide strontia.Barium monoxide adds to and works to stablize aluminium oxide in the slurry, is added into co-catalyst and mainly works to improve powder body material character.
A kind of preparation method of cleaning catalyst for tail gases of automobiles, this method comprise the slurry that contains aluminium oxide are coated on the honeycomb ceramic carrier, drying, and roasting, wherein, the slurry that contain aluminium oxide of said alumina slurry for preparing through above-mentioned preparation method.
Said coating is carried out once, compares with the honeycomb ceramic carrier before applying, and the weight of roasting rear catalyst increases 30-40 weight %.
Said baking temperature is preferably 100-150 ℃, is preferably 2-5h drying time; Said sintering temperature is preferably 450-550 ℃, and roasting time is preferably 2-3 hour.
A kind of cleaning catalyst for tail gases of automobiles is prepared by the preparation method of above-mentioned cleaning catalyst for tail gases of automobiles, wherein, and the slurry that contain aluminium oxide of said alumina slurry for preparing through above-mentioned preparation method.
For a better understanding of the present invention, explain with concrete steps below:
(1) at first prepare multiple maceration extract, the active component of every kind of maceration extract is different, with the adsorbent step impregnation in maceration extract;
(2) then above-mentioned maceration extract is joined in the container that adsorbent is housed in order or adsorbent is joined in the above-mentioned maceration extract that contains the different activities composition successively, all should keep one section dipping adsorption time after whenever joining in a kind of maceration extract;
(3) behind the step impregnation again centrifugal filtration obtain adsorbent, and 100-120 ℃ down fully dry, again under blanket of nitrogen 500 ± 10 ℃ handle a period of times, regulate air concentration and also be warming up to 600-650 ℃ of calcining to remove carbon base body, obtain active powder;
(4) then active powder is joined in the slurry with aluminium oxide, cerium zirconium powder body, binding agent and co-catalyst preparation, ball milling is prepared into active slurry, and being coated on the honeycomb ceramic carrier of cordierite is worth catalyst through drying and roasting.
Adopt the catalyst of this method preparation; Have catalytic conversion efficiency height, ageing resistace excellent characteristics; Can selectively active component be distributed; Accurately prepare the needed active nano of reaction center, here " active component is distributed " is for well known to a person skilled in the art technical term.And can prepare the catalyst of superior performance through regulating calcination reaction air inlet and relying on the reproducibility of CO and C in the discharge gas that calcination generates to control the chemical valence state of active component.
In order to make the object of the invention, technical scheme and advantage clearer,, the present invention is further elaborated below in conjunction with specific embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
Use method of the present invention to prepare concrete catalyst below, but be not limited in this several kinds of catalyst.
Embodiment 1
The preparation of slurry
(1) preparation contains the maceration extract 100g (PH of maceration extract is 3) of 15wt% cerous nitrate and 10wt% zirconyl nitrate, and (D50 is 3um, and specific surface is 1500 m to add the spheric active carbon of 10g then
2/ g), centrifugal filtration behind the dipping 60min joins the adsorbent that obtains among the palladium nitrate solution 100g of 1.3wt% (PH of palladium nitrate solution is 2), dipping 60min, and centrifugal filtration obtains hypersober once more;
(2) with hypersober 500 ℃ of roasting 1.5h under blanket of nitrogen, be warming up to 600 ℃ then and also feed the nitrogen mixture calcining 30min that contains air 10 volume %, feed pure air-treatment 1.5h again and obtain active powder;
(3) with above-mentioned active powder and 50g aluminium oxide (company of Boyang Chemical Co., Ltd., Zibo; Average pore size is 20nm, and average pore volume is 0.5mL/g), 50g cerium zirconium powder body (cerium-zirconium mixed oxide, Zibo Huaqing Powder Material Techn Co., Ltd. produces; Average pore size is 19.4nm; Average pore volume is 0.21mL/g), the binding agent (APES, Hai'an, Jiangsu petrochemical plant is produced) of 1.0g, surplus is supplied (control solid content 30%) with deionized water; With above-mentioned mixed system rotating speed ball milling 4h with 200r/min in ball mill, obtain slurry then.
Preparation of catalysts
Go up the said slurry of absorption through vacuum suction at cordierite honeycomb ceramic matrix (the cylindrical cordierite honeycomb ceramic matrix of Φ 93 * 125mm type that Corning Incorporated produces), the adsorbance of slurry is 300g.With the cordierite honeycomb ceramic matrix that has adsorbed slurry in 120 ℃ of dry 3h, again in Muffle furnace (the holy glad scientific instrument in Shanghai Co., Ltd produces) in 550 ℃ of following roasting 3h, obtain loaded catalyst S1.
Embodiment 2
The preparation of slurry
(1) preparation contains the maceration extract 100g (PH of maceration extract is 3) of 15wt% cerous nitrate and 10wt% zirconyl nitrate, and (D50 is 3um, and specific surface is 1500 m to add the spheric active carbon of 10g then
2/ g), dipping 60min.Centrifugal filtration joins the adsorbent that obtains among the palladium nitrate solution 100g of 1.3wt% (PH of palladium nitrate solution is 2), dipping 60min, and centrifugal filtration obtains hypersober once more;
(2) with hypersober and 50g aluminium oxide (company of Boyang Chemical Co., Ltd., Zibo; Average pore size is 20nm; Average pore volume is 0.5mL/g), 50g cerium zirconium powder body (cerium-zirconium mixed oxide; Zibo Huaqing Powder Material Techn Co., Ltd. produces, and average pore size is 19.4nm, and average pore volume is 0.21mL/g) be blended in the following 500 ℃ of roasting 1h of blanket of nitrogen; Be warming up to 600 ℃ then and also feed the nitrogen mixture calcining 30min that contains air 10 volume %, feed pure air-treatment 1h again and obtain mixed powder;
(3) with the binding agent (APES of mixed powder and 1.0 g; Hai'an, Jiangsu petrochemical plant is produced); Surplus is supplied (control solid content 30%) with deionized water, with above-mentioned mixed system rotating speed ball milling 4h with 200r/min in ball mill, obtains slurry then.
Preparation of catalysts
Go up the said slurry of absorption through vacuum suction at cordierite honeycomb ceramic matrix (the cylindrical cordierite honeycomb ceramic matrix of Φ 93 * 125mm type that Corning Incorporated produces), the adsorbance of slurry is 300g.With the cordierite honeycomb ceramic matrix that has adsorbed slurry in 120 ℃ of dry 3h, again in Muffle furnace (the holy glad scientific instrument in Shanghai Co., Ltd produces) in 550 ℃ of following roasting 3h, obtain loaded catalyst S2.
Embodiment 3
Compare with embodiment 1, (D50 is 3um, and specific surface is 1500 m to replace spheric active carbon to use carbon fiber active carbon (the clear and rich Science and Technology Ltd. in Qingdao produces for length 5um, specific surface 900 ㎡/g) in the preparation of slurry
2/ g), other steps are identical with embodiment 1, obtain loaded catalyst S3.
Embodiment 4
Compare with embodiment 1, in the preparation of slurry, comprise that also the adsorbent that centrifugal filtration is obtained carries out drying, baking temperature is 110 ℃, and be 2h drying time.Other are identical with embodiment 1, obtain product S4.
Embodiment 5
The preparation of slurry
(1) preparation contains the maceration extract 100g (PH of maceration extract is 3) of 15wt% cerous nitrate, 10wt% strontium nitrate and 5wt% barium acetate, and (D50 is 6um, and specific surface is 700 m to add the 10g spheric active carbon then
2/ g), dipping 2h.Centrifugal filtration joins 100g with the adsorbent that obtains and contains in the solution of palladium nitrate 1.3wt% (PH of palladium nitrate solution is 2), dipping absorption 1h, and centrifugal filtration obtains hypersober once more;
(2) the 120 ℃ of following dry 1h of hypersober that centrifugal filtration obtained; 510 ℃ of roasting 0.5h under blanket of nitrogen again; Be warming up to 650 ℃ then and also feed the nitrogen mixture calcining 30min that contains air 20 volume %, feed pure air-treatment 2.5h again and obtain active powder;
(3) with above-mentioned active powder and 50g aluminium oxide (company of Boyang Chemical Co., Ltd., Zibo; Average pore size is 20nm; Average pore volume is 0.5mL/g), 45g cerium zirconium powder body (cerium-zirconium mixed oxide, Zibo Huaqing Powder Material Techn Co., Ltd. produces, average pore size is 19.4nm; Average pore volume is 0.21mL/g), 1.2g co-catalyst (magnesia), 1.5g binding agent (APES); Surplus is supplied (control solid content 30%) with deionized water, with above-mentioned mixed system rotating speed ball milling 2.5h with 270r/min in ball mill, obtains alumina slurry then.
Preparation of catalysts
Go up the said slurry of absorption through vacuum suction at cordierite honeycomb ceramic matrix (the cylindrical cordierite honeycomb ceramic matrix of Φ 93 * 125mm type that Corning Incorporated produces), the adsorbance of slurry is 300g.With the cordierite honeycomb ceramic matrix that has adsorbed slurry in 100 ℃ of dry 5h, again in Muffle furnace (bright and beautiful stove industry equipment Co., Ltd produces before the Yixing City) in 500 ℃ of following roasting 2h, obtain loaded catalyst S5.
Embodiment 6
The preparation of slurry
(1) each 100g of palladium nitrate solution (its PH is 3) of cerous nitrate, 10wt% strontium nitrate, 5wt% barium acetate and the 1.3wt% of preparation 15wt%, (D50 is 3um, and specific surface is 1500 m to use the 10g mesoporous carbon then
2/ g) substep immerses in the above-mentioned solution and adsorbs 1.5h at every turn successively, and last centrifugal filtration obtains hypersober;
(2) with the above-mentioned hypersober that obtains dry 3h under 100 ℃; With hypersober 490 ℃ of roasting 3h under blanket of nitrogen; Be warming up to 620 ℃ then and also feed the nitrogen mixture calcining 1h that contains air 15 volume %, feed pure air-treatment 5h again and obtain active powder;
(3) with above-mentioned active powder and 40g aluminium oxide (company of Boyang Chemical Co., Ltd., Zibo; Average pore size is 20nm; Average pore volume is 0.5mL/g), 50g cerium zirconium powder body (cerium-zirconium mixed oxide, Zibo Huaqing Powder Material Techn Co., Ltd. produces, average pore size is 19.4nm; Average pore volume is 0.21mL/g), 1.2g co-catalyst (magnesia), 1.5g binding agent (containing 1g HPMC, 0.5g APES); Surplus is supplied (control solid content 30%) with deionized water, with above-mentioned mixed system rotating speed ball milling 1.5h with 180r/min in ball mill, obtains slurry then.
Preparation of catalysts
Go up the said slurry of absorption through vacuum suction at cordierite honeycomb ceramic matrix (the cylindrical cordierite honeycomb ceramic matrix of Φ 93 * 125mm type that Corning Incorporated produces), the adsorbance of slurry is 300g.With the cordierite honeycomb ceramic matrix that has adsorbed slurry in 150 ℃ of dry 2h, again in Muffle furnace (bright and beautiful stove industry equipment Co., Ltd produces before the Yixing City) in 450 ℃ of following roasting 2.5h, obtain loaded catalyst S6.
Embodiment 7
Compare with embodiment 1, in the preparation of slurry, sintering temperature is 450 ℃, and roasting time is 3h.Other are identical with embodiment 1, obtain product S7.
Comparative Examples 1
The preparation of slurry
Take by weighing 25g γ part aluminium oxide, 25g cerium zirconium powder, 1g polyvinyl alcohol, 3g boehmite, the remainder water is supplied (control solid content 30%).The frequency ball milling 4h with 35HZ in ball mill obtains first slurry with above-mentioned mixed system.
Preparation of catalysts
(1) go up the said slurry of absorption through vacuum suction at cordierite honeycomb ceramic matrix (the cylindrical cordierite honeycomb ceramic matrix of Φ 93 * 125mm type that Corning Incorporated produces), the adsorbance of slurry is 340g.After the cordierite honeycomb ceramic that has adsorbed slurry purged with compressed air, matrix was in 120 ℃ of dry 3h, and in 500 ℃ of following roasting 2h, then adsorption activity composition solution (concentration is the palladium nitrate solution of 1.3wt%).Soaked carrier at 120 ℃ of dry 3h, again in 500 ℃ of following roasting 1.5h, is made the ground floor of catalyst.
(2) take by weighing 25g cerium zirconium powder body, 20g aluminium oxide, 1.5g methyl cellulose ether, 6g boehmite, the remainder water is supplied (control solid content 30%).The frequency ball milling 4h with 35HZ in ball mill obtains second slurry with above-mentioned mixed system.Adopting as previously mentioned, way applies the second layer and drying and roasting, adsorption activity composition solution (rhodium nitrate of 0.2wt%), the catalyst D1 of drying and roasting system more then.
Comparative Examples 2
Compare with embodiment 1, do not adopt step impregnation and blanket of nitrogen to handle, other steps are all identical with embodiment 1.Adopt all active components of disposable dipping, calcine in the air then, make powder after, make catalyst D2 by embodiment 1 method again.
Performance test
The above loaded catalyst S1-S6 for preparing, D1, D2 are carried out following performance test:
Laboratory simulation tail gas is HC (C
3H
8): 1500ppm, CO:1.5 volume %, NO:1500ppm, CO
210.0 volume %, O
21.05 volume %, water vapour 10 volume %, all the other are nitrogen, nitrogen is balance gas: control N voluntarily
2And O
2Flow make λ=1 (λ is an air-fuel ratio), or change in very among a small circle in λ=1 front and back, unaged experiment condition: air speed is 6 * 104 h
-1, 350 ℃ of reaction temperatures.Test load type catalyst is to the initiation temperature T50 of HC, CO, NO; And the catalyst of test after wearing out in 4 hours 1000 ℃ of following roastings is to the initiation temperature T50 of HC, CO, NO; The reaction temperature of test fresh sample and aged samples conversion ratio is 350 ℃, and testing procedure is following:
1, with in the exhaust analyzer test simulation tail gas, under the situation of not adorning catalyst, record HC, CO, NO
xThe initial concentration value, be designated as the numerical value that C0 represents CO, NO, HC respectively.
2, catalyst carrier is put into quartz tube reactor, through quartz ampoule, control quartz ampoule temperature is 350 ℃, and control N with simulated exhaust gas
2And O
2Flow make λ=1 (λ is an air-fuel ratio), or change in very among a small circle in λ=1 front and back, activation is after 30 minutes, record is through behind the catalyst action, the concentration value of CO, NO, HC is designated as the numerical value that C1 represents CO, NO, HC respectively;
And according to following formula calculating conversion ratio;
η (conversion ratio) %=((C0-C1)/C0) * 100%
The result is as shown in table 1.
The test result of table 1 can find out that the catalytic efficiency of the loaded catalyst that method disclosed by the invention prepares is higher, and anti-poisoning performance is better, resistant to thermal aging excellent in durability, long service life.
Claims (13)
1. alumina slurry preparation method, comprising: I is prepared multiple maceration extract, the active component of every kind of maceration extract is different, with the adsorbent step impregnation in maceration extract, behind the step impregnation again centrifugal filtration obtain hypersober, carry out the step II again
1Or carry out the step II
2Said step II
1Be the hypersober oxygen barrier roasting that the step I is obtained, calcining obtains active powder under oxygen atmosphere again, and active powder that will obtain again and aluminium oxide, cerium zirconium powder body, binding agent mix, and ball milling obtains alumina slurry; Said step II
2For after hypersober that the step I is obtained and aluminium oxide, cerium zirconium powder body mix, with the mixture oxygen barrier roasting that obtains, under oxygen atmosphere, calcine again mixed powder, mixed powder mixes with binding agent again, ball milling gets alumina slurry.
2. method according to claim 1 is characterized in that, this method comprises that also the hypersober that centrifugal filtration is obtained carries out drying.
3. method according to claim 1 is characterized in that, this method also comprises, carries out the step II
1Or step II
2In mixing the time also add co-catalyst and be mixed together.
4. method according to claim 2 is characterized in that, said dip time is 1-6h; Temperature is controlled to be 500 ± 10 ℃ during the oxygen barrier roasting, and roasting time is 0.5-3h, and temperature control is 600-650 ℃ during calcining, and calcination time is 2-6h; Rotational speed of ball-mill is 180-270 rev/min, and the ball milling time is 1.5-4h; Said baking temperature is 100-120 ℃, and be 1-3h drying time.
5. method according to claim 1; It is characterized in that said adsorbent is a graininess or fibrous, the specific surface of said granular adsorption agent is 500-1700 m2/g; Granularity D50 is the 0.5-6 micron; The length of said fibrous adsorbent is the 1-6 micron, and adsorbent is selected from a kind of in active carbon, mesoporous carbon, the amorphous carbon, and its addition accounts for 5 weight %-10 weight % of maceration extract total amount.
6. method according to claim 1; It is characterized in that; Said maceration extract is nitrate or the acetate solution that contains reactive metal, and its active component is selected from one or more in palladium nitrate, rhodium nitrate, platinum nitrate, cerous nitrate, zirconium nitrate, lanthanum nitrate, praseodymium nitrate, zirconyl nitrate, barium nitrate and the barium acetate, the PH of said maceration extract＜4; Total amount with maceration extract is a benchmark, and the mass percent concentration of active component is 1.5%-15%.
7. method according to claim 1 is characterized in that said binding agent is selected from one or more in polyvinyl alcohol, polyethylene glycol, ammonium polyacrylate, methylcellulose, ethyl cellulose, HPMC, the APES.
8. method according to claim 1 is characterized in that, said aluminium oxide average pore size is 10-30nm, and average pore volume is 0.1-1.0mL/g.
9. method according to claim 3 is characterized in that said co-catalyst is an alkaline earth oxide, is selected from barium monoxide, magnesia, calcium oxide, the strontium oxide strontia one or more.
10. the preparation method of a cleaning catalyst for tail gases of automobiles; This method comprises and the slurry that contains aluminium oxide is coated on the honeycomb ceramic carrier drying, roasting; It is characterized in that said alumina slurry is prepared by any described method among the claim 1-9.
11. method according to claim 10, wherein, said coating is carried out once, compares with the honeycomb ceramic carrier before applying, and the weight of roasting rear catalyst increases 30-40 weight %.
12. method according to claim 11, wherein, said baking temperature is 100-150 ℃, and be 2-5h drying time; Said sintering temperature is 450-550 ℃, and roasting time is 2-3 hour.
13. a cleaning catalyst for tail gases of automobiles is characterized in that, said catalyst is prepared by each said method of claim 10-12.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103193512A (en) * | 2013-04-01 | 2013-07-10 | 景德镇陶瓷学院 | Film modified material for wall-flow honeycomb ceramic and method for modifying ceramic filter by utilizing same |
| CN104500186A (en) * | 2015-01-11 | 2015-04-08 | 温州泓呈祥科技有限公司 | Motor vehicle tail gas purifying silencer |
| CN104624205A (en) * | 2015-02-25 | 2015-05-20 | 孙高雷 | Method for regenerating three-way catalyst Pd/Na2O/K2O/C |
| CN105833921A (en) * | 2016-03-12 | 2016-08-10 | 江阴华音陶瓷机电科技有限公司 | Quantified mixing and coating process for wall-flow ceramic carrier DPF catalyst |
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| CN107570200A (en) * | 2017-08-14 | 2018-01-12 | 无锡市永兴金属软管有限公司 | A kind of automobile exhaust purifier catalyst and preparation method thereof |
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| CN103193512A (en) * | 2013-04-01 | 2013-07-10 | 景德镇陶瓷学院 | Film modified material for wall-flow honeycomb ceramic and method for modifying ceramic filter by utilizing same |
| CN103193512B (en) * | 2013-04-01 | 2014-11-05 | 景德镇陶瓷学院 | Film modified material for wall-flow honeycomb ceramic and method for modifying ceramic filter by utilizing same |
| CN104500186A (en) * | 2015-01-11 | 2015-04-08 | 温州泓呈祥科技有限公司 | Motor vehicle tail gas purifying silencer |
| CN104624205A (en) * | 2015-02-25 | 2015-05-20 | 孙高雷 | Method for regenerating three-way catalyst Pd/Na2O/K2O/C |
| CN105833921A (en) * | 2016-03-12 | 2016-08-10 | 江阴华音陶瓷机电科技有限公司 | Quantified mixing and coating process for wall-flow ceramic carrier DPF catalyst |
| CN105903465A (en) * | 2016-04-28 | 2016-08-31 | 常州大学 | Load type hydrodeoxygenation catalyst and preparation method thereof |
| CN105903465B (en) * | 2016-04-28 | 2019-07-09 | 常州大学 | A kind of load hydrogenation dehydrogenation catalyst and preparation method thereof |
| CN107570200A (en) * | 2017-08-14 | 2018-01-12 | 无锡市永兴金属软管有限公司 | A kind of automobile exhaust purifier catalyst and preparation method thereof |
| CN109569627A (en) * | 2018-12-19 | 2019-04-05 | 中自环保科技股份有限公司 | One kind catalyst containing Pd and preparation method thereof |
| CN109569627B (en) * | 2018-12-19 | 2020-10-23 | 中自环保科技股份有限公司 | Pd-containing catalyst and preparation method thereof |
| CN112547133A (en) * | 2020-12-18 | 2021-03-26 | 宁波科森净化器制造有限公司 | Preparation method of carrier catalyst of catalytic converter |
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