CN101284233A - Exhaust gas purifying catalyst and method of producing the same - Google Patents

Exhaust gas purifying catalyst and method of producing the same Download PDF

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Publication number
CN101284233A
CN101284233A CNA2008100916737A CN200810091673A CN101284233A CN 101284233 A CN101284233 A CN 101284233A CN A2008100916737 A CNA2008100916737 A CN A2008100916737A CN 200810091673 A CN200810091673 A CN 200810091673A CN 101284233 A CN101284233 A CN 101284233A
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catalyst
slurry
particle
compound
micropore
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CN101284233B (en
Inventor
菊地博人
菅克雄
中村雅纪
若松广宪
白鸟一幸
宫村利春
池泽纯
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Renault SAS
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Nissan Motor Co Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2370/00—Selection of materials for exhaust purification
    • F01N2370/02—Selection of materials for exhaust purification used in catalytic reactors

Abstract

Disclosed is an exhaust gas purifying catalyst exhibiting excellent purification performance for a long period of time by suppressing coagulation of a noble metal. A catalyst powder comprises a noble metal and first and second compounds. In the catalyst powder, the first compound carries the noble metal and is separated from another first compound carrying a noble metal by the second compound. At least one catalyst layer comprising the catalyst powder is formed on an inner surface of a substrate. The catalyst layer has fine pores. A fine pore volume of fine pores having a fine pore diameter of greater than 0.1 mum to less than or equal to 1 mum is 10% to 60% of the fine pore volume of fine pores having a fine pore diameter of 0.1 mum or less.

Description

Exhaust gas purification catalyst and manufacture method thereof
Technical field
The present invention relates to exhaust gas purification catalyst and manufacture method thereof, described exhaust gas purification catalyst is applicable to exhaust gas of internal combustion engines is purified.
Background technology
Exhaust gas purification catalyst generally is to form at the particle surface carried noble metal particle that is made of metal oxide, it is by the harmful components in this noble metal oxidation gaseous effluent for example unburned hydro carbons (HC), carbon monoxide (CO), and being translated into harmless composition is water and CO 2Gas.
In recent years, more and more stricter to the restriction of automobile exhaust gas, also require exhaust gas purification catalyst that above-mentioned unburned hydro carbons (HC), carbon monoxide (CO) are purified more efficiently simultaneously.In order to adapt to this requirement, various improvement have been carried out.For example, utilize the detergent power of catalyst generally to improve this phenomenon with the increase of noble metal surface area, increase the surface area of this noble metal by the particle diameter that reduces the noble metal in the exhaust gas purification catalyst, to increase the surface energy, improve the performance of exhaust gas purification catalyst.
At this moment, the stage is the following ultramicron state of number nm to the noble metal of exhaust gas purification catalyst in the early stage.But, the problem that exists is: exhaust gas purification catalyst in actual use, along with it is exposed in the oxidation atmosphere gas of high temperature, noble metal surperficial oxidized, adjacent noble metal condenses each other, merges, thickly turn to tens of nm, the surface area of noble metal reduces, and the purifying rate of harmful substance reduces in time.
For preventing the cohesion of noble metal, in some exhaust gas purification catalyst, make noble metal be dispersed in whole catalyst layer, described catalyst layer is to form on the inner face of the carrier that has connected many minute apertures cellularly, about such exhaust gas purification catalyst, the method that following manufacturing catalyst fines is arranged: mixed noble metal colloid and metal alkoxide, this metal alkoxide of hydrolysis are made catalyst fines (patent documentation 1).
In addition, for the surface area of the described noble metal that prevents to cause because of thickization reduces, realizes more high activityization,, developing reverse micelle method as the manufacture method that can make the high surface area noble metal.In the process of the manufacturing step of this reverse micelle method; preparation has formed the emulsion solution of the reverse micelle of the aqueous solution that contains the noble metal raw material; after micronized noble metal is separated out in this reverse micelle; destroy reverse micelle; through the gained sediment is filtered, drying, pulverizing, each step of sintering, make catalyst.
About reverse micelle method, the method that following manufacturing heat-resistant catalyst is arranged, the inverse micellar solution of the precious metal colloid aqueous solution, inverse micellar solution and the metal alkoxide mixing that the metal hydroxides aqueous solution is contained in micella inside, the mixture of sintering gained (patent documentation 2) are contained in micella inside.In addition, also have the manufacture method of following highly heat-resistant catalyst, this method comprises that modulation makes the step (patent documentation 2) of the inverse micellar solution of the precious metal salt aqueous solution and at least a above aqueous metal salt coexistence as co-catalyst component.
Patent documentation 1: the spy opens the 2000-15097 communique
Patent documentation 2: the spy opens the 2005-111336 communique
Patent documentation 3: the spy opens the 2005-185969 communique
Summary of the invention
The problem that invention will solve
Yet, employing is made the exhaust gas purification catalyst that the method for catalyst obtains by the mixture of precious metal colloid and metal alkoxide, though thickization of noble metal is improved, but the micropore volume of catalyst fines is little, in addition, the catalyst layer that catalyst fines is coated on the carrier and forms is very fine and close, and waste gas is difficult to spread in catalyst layer.
In addition, the exhaust gas purification catalyst that the method for employing application reverse micelle method obtains, manufacturing step is loaded down with trivial details, and manufacturing cost rises, therefore, existing problems aspect output.
Solve the method for problem
The main points of exhaust gas purification catalyst of the present invention are: its structure is to comprise carrier and be formed at the catalyst layer of one deck at least on the inner face of carrier, described catalyst layer contains catalyst fines, this catalyst fines comprises noble metal, first compound and second compound, and by the noble metal of the first compound loaded catalyst fines, this load separate each other by second compound between first compound of noble metal; Described catalyst layer has micropore, and in the micropore below micropore diameter is 1 μ m, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is 10%～60%.
In addition, the main points of exhaust gas purification catalyst manufacture method of the present invention are: it is used to make the exhaust gas purification catalyst of the invention described above, this method comprises the step for preparing catalyst fines, with the step that on the carrier inner face, forms this catalyst fines, wherein, the step of described preparation catalyst fines comprises: the step of carried noble metal on first compound, with precursor with second compound or second compound be dispersed in carry out in the water step of slurryization and then with load first compound of noble metal be dispersed in the slurry of described second compound, after drying, carry out sintering and obtain the step of catalyst fines; Described step at formation catalyst fines on the carrier inner face comprises: the compound that can disappear when adding sintering in the catalyst fines that is obtaining, slurryization, be coated on carrier, dry then, sintering have the step of the catalyst layer of micropore in the zone of 0.1 μ m～1 μ m in the micropore of formation catalyst layer.
The invention effect
According to exhaust gas purification catalyst of the present invention, can guarantee the diffusivity of waste gas, catalyst activity is maintained high level.
According to the manufacture method of exhaust gas purification catalyst of the present invention, can make exhaust gas purification catalyst of the present invention by design.
Description of drawings
Fig. 1 (a) and (b) be the key diagram that is formed with exhaust gas purification catalyst carrier of the present invention.
Fig. 2 (a) and (b) be the schematic diagram of exhaust gas purification catalyst of the present invention.
Fig. 3 is the schematic graph of the catalyst layer pore distribution curve of the exhaust gas purification catalyst that the present invention relates to.
Fig. 4 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Fig. 5 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Fig. 6 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Fig. 7 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Fig. 8 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Fig. 9 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Figure 10 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Figure 11 is the chart that the T50 result of the HC of sample among the embodiment is shown.
Symbol description
1 carrier
10 catalyst layers
11 catalyst fineses
12 noble metals
13 first compounds
14 second compounds
The specific embodiment
Below, the embodiment of accompanying drawings exhaust gas purification catalyst of the present invention.
Fig. 1 is carried on exhaust gas purification catalyst of the present invention for explanation the accompanying drawing of the situation of carrier.As an example, in Fig. 1 (a), represent carrier 1 with the stereogram of signal, it is essentially drum, is made of hear resistance materials such as potteries, has to be cellular by a plurality of minute apertures of a side perforation to the another side.The enlarged cross section figure in a hole of this carrier 1 of B region representation is shown in Fig. 1 (b) among Fig. 1 (a).Shown in Fig. 1 (b), surround on the inner face 1a in a hole of carrier 1 and be formed with catalyst layer 10.And, the thickness of the catalyst layer 10 that the profile of the carrier 1 that Fig. 1 (a) illustrates, the size of minute aperture and Fig. 1 (b) illustrate, different with the carrier 1 and the catalyst layer 10 of reality, this is for the ease of understanding the present invention.Thereby exhaust gas purification catalyst of the present invention is not limited to profile, the size of minute aperture and the thickness of the catalyst layer 10 that Fig. 1 (b) illustrates of the carrier 1 that Fig. 1 (a) illustrates.
The exhaust gas purification catalyst of present embodiment possesses this catalyst layer 10 of one deck at least.This catalyst layer 10 contains catalyst fines.Use Fig. 2 that the structure of catalyst fines of the present invention is described.Fig. 2 (a), Fig. 2 (b) are the ideograph of the catalyst fines of exhaust gas purification catalyst of the present invention.Shown in Fig. 2 (a), Fig. 2 (b), catalyst fines 11 comprises noble metal 12, first compound 13 and second compound 14, and its structure is: this noble metal 12 of first compound, 13 loads, load separate each other by second compound 14 between the single or aggregation of first compound 13 of this noble metal 12.In exhaust gas purification catalyst of the present invention, catalyst layer 10 with catalyst fines of this class formation has the micropore P1 that contains catalyst fines and as the micropore P2 in the space between catalyst fines, in the micropore below micropore diameter is 1 μ m, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is 10%～60%.
In the exhaust gas purification catalyst of the present embodiment of Figure 1 and Figure 2, about the catalyst fines 11 that contains in the catalyst layer 10, as shown in Figure 2, by first compound, 13 carried noble metals 12.Thus, this first compound 13 is used as and noble metal 12 chemically combined sticking agents (ア Application カ one material).Therefore, first compound 13 suppresses moving of noble metal 12.In addition, load be coated with second compound 14 such as aluminium oxide around first compound 13 of this noble metal 12.Thus, second compound 14 has suppressed noble metal 12 physically and has broken away from first compound 13 and mobile.And this second compound 14 will physically separate between first compound 13, suppress to move between this first compound 13, contact and condense, and its result, the noble metal 12 that inhibition is carried on this first compound 13 condenses.
For the catalyst fines 11 with said structure, waste gas must spread and arrive noble metal 12, discoveries such as inventor: second compound 14 that covers the noble metal 12 and first compound 13 in catalyst fines 11 must have the space of certain limit.Particularly, the initial stage micropore volume of catalyst is 0.24cm 3/ g～0.8cm 3About/g.If the not enough 0.24cm of initial stage micropore volume of catalyst 3About/g, then the gas diffusibility of waste gas is insufficient; In addition, if surpass 0.8cm 3About/g, then gas diffusibility can not change.
In addition, possess such as with regard to the catalyst layer 10 of the catalyst fines 11 of said structure with regard to containing, the important document of the exhaust gas purification catalyst of present embodiment is: this catalyst layer has micropore, and in the micropore below micropore diameter is 1 μ m, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is 10%～60%.
Fig. 3 is the schematic diagram of micropore distribution curve of the catalyst layer of exhaust gas purification catalyst of the present invention.In micropore distribution curve shown in Figure 3, the micropore volume of scope that micropore diameter surpasses 1 μ m by surface blemish, chap (Network ラ Star Network) etc. cause, do not represent the micropore of catalyst layer.Thereby the micropore of catalyst layer is that micropore volume below the 1 μ m illustrates by micropore diameter.The exhaust gas purification catalyst of present embodiment is that scope and micropore diameter below the 0.1 μ m is that 0.1 μ m～scope of 1 μ m has the peak of micropore volume respectively at micropore diameter.Micropore diameter is that the small micropore P1 that catalyst fines had shown in Fig. 2 (b) can be thought in the peak of the micropore volume of the following scope of 0.1 μ m.In addition, micropore diameter is that the micropore P2 as the space between catalyst fines shown in Fig. 2 (b) can be thought in the peak of micropore volume of the scope of 0.1 μ m～1 μ m.In the present invention, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is 10%～60%, can fully guarantee the micropore P2 as space between catalyst fines like this.Thus, fully guarantee the path (path) that gas spreads in catalyst layer, so can improve the gas diffusibility energy.And, in the prior art shown in dotted lines in Figure 3, be the peak that scope below the 0.1 μ m has single micropore volume only at micropore diameter.In a word, be that 0.1 μ m～scope of 1 μ m does not have the peak of micropore volume at micropore diameter in the prior art.In such prior art, micropore diameter is the micropore volume less than 10% of the micropore of 0.1 μ m～1 μ m, its catalyst layer densification, and waste gas is difficult to spread in catalyst layer.
In the exhaust gas purification catalyst of the present embodiment, when this catalyst fines 11 being coated on carrier 1 when making catalyst layer 10, in order to make waste gas extremely apply the depths of the catalyst layer 10 that forms from the diffusion into the surface of catalyst layer 10, limit following ranges: in the micropore diameter of catalyst layer 10 was micropore below the 1 μ m, micropore diameter was that the micropore of 0.1 μ m～1 μ m must account for 10%～60%.When micropore diameter is the micropore volume of the micropore of 0.1 μ m～1 μ m when being in 10%～60% scope, can obtain good catalyst performance.If micropore diameter is the not enough micropore diameter of micropore volume of micropore of the scope of 0.1 μ m～1 μ m be the following micropore of 1 μ m micropore volume 10%, there is following hidden danger in then not fully diffusion of gas: can't obtain improving effect by the obtainable sufficient catalyst performance of catalyst pellets minor structure institute of the present invention.In addition, in the micropore below micropore diameter is 1 μ m, if micropore diameter is the micropore volume of the micropore of 0.1 μ m～1 μ m surpass micropore diameter be the following micropore of 1 μ m micropore volume 60%, though it is no problem aspect the gas diffusion, but have following hidden danger: the amount in the space in the diffusion layer is too much, and the intensity of this diffusion layer descends.
In the described catalyst layer, the micropore volume of establishing micropore diameter and be the following micropore of 0.1 μ m is A, and micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is B, and then preferred B is that micropore diameter is 10%～60% of the following micropore volume of 1 μ m, and B/A 〉=0.1.B/A is more than 0.1, and then the waste gas in the catalyst layer is easy to circulation, can obtain the effect of improving of the desirable gas diffusibility energy of the present invention
More preferably this micropore diameter the micropore volume (B) of the micropore of 0.1 μ m～1 μ m for micropore diameter be below the 1 μ m micropore volume 20%～60%.Be in 20%～60% scope, can further improve the gas diffusibility energy, improve catalyst performance.
More preferably this micropore diameter is 30%～50% of the micropore volume of micropore diameter below 1 μ m at the micropore volume (B) of the micropore of 0.1 μ m～1 μ m.Be in 30%～50% scope, can obtain good especially gas diffusibility energy, and can balance have both good catalyst layer intensity well, can realize good especially catalyst performance as exhaust gas purification catalyst.
And the micropore that adopts known method such as mercury penetration method to measure catalyst layers distributes, and can investigate micropore diameter in such catalyst layer in the ratio of the micropore volume of the micropore of certain limit.
First compound 13 in the catalyst fines 11 can comprise the CeO of 70wt%～85wt% 2And the ZrO of 15wt%～30wt% 2When first compound 13 mainly contains CeO 2The time, in first compound 13, consist of the CeO of 70wt%～85wt% 2And the ZrO of 15wt%～30wt% 2The compound of (total amount is 100%) is applicable to the purification of waste gas.Particularly, when load during, and only use CeO as the Pt of noble metal 12 2Compare during load, with containing CeO 2And ZrO 2Complex chemical compound carry out load, can improve performance.This is because by containing ZrO 2Increased storage oxygen performance.In addition, by adopting complex chemical compound, the absorption affinity enhancing of Pt and first compound 13, can suppress the cohesion of the Pt that thermal history causes.Contain the above ZrO of 15wt% 2Can significantly show the effect of this employing complex chemical compound, but ZrO 2Content surpasses 30wt%, then CeO 2Storage oxygen performance become a little less than.
In addition, first compound 13 can be to remove CeO 2And ZrO 2Also contain La outward, 2O 3Complex chemical compound.
First compound 13 in the catalyst fines 11 can comprise the ZrO of 90wt%～99wt% 2And the La of 1wt%～10wt% 2O 3When first compound 13 mainly contains ZrO 2The time, in first compound 13, consist of ZrO 2Be 90wt%～99wt% and La 2O 3Be applicable to the purification of waste gas for the compound of 1wt%～10wt% (total amount is 100%).Particularly, load is during as the Rh of noble metal 12, with first compound 13 only be ZrO 2The time load compare, with containing ZrO 2And La 2O 3Complex chemical compound to carry out load more suitable.This be because: first compound 13 removes ZrO 2Also contain La outward 2O 3, can suppress ZrO like this 2Cohesion, bury at ZrO thereby suppress Rh 2Between particle.Contain the above La of 1wt% 2O 3Can significantly show the effect of this employing complex chemical compound, but contain La 2O 3Surpass 10wt%, then have following hidden danger: La 2O 3Stripping covers Rh.
Second compound 14 in the catalyst fines 11 preferably comprises aluminium oxide.For the purification of waste gas, waste gas must diffuse to noble metal by second compound 14, and aluminium oxide particularly gama-alumina be porous mass, its gas diffusibility can be good, in addition, its hear resistance is also outstanding, therefore is suitable for second compound 14.
Second compound 14 in the catalyst fines 11 can be the CeO that contains 5wt%～15wt% 2, 3wt%～10wt% ZrO 2Aluminium oxide.Contain CeO in the aluminium oxide 2, ZrO 2, can suppress the performance of catalyst undergoes after long-time and descend.This be because: in aluminium oxide, add CeO 2, ZrO 2, can suppress gama-alumina and change Alpha-alumina into, can suppress the deterioration (sintering phenomenon) of the aluminium oxide that thermal history causes thus.Contain CeO in the aluminium oxide 2And ZrO 2One of can suppress the performance of catalyst undergoes after long-time and descend, but contain CeO 2And ZrO 2Both can more effectively suppress the performance of catalyst undergoes after long-time and descend.CeO in the aluminium oxide 2And ZrO 2Amount preferably at CeO 2Be 5wt%～15wt%, ZrO 2Be the scope of 3wt%～10wt%,, then lack and add CeO if do not reach the lower limit of described scope 2, ZrO 2Effect, if surpass the upper limit of described scope in addition, then have following hidden danger: the performance after catalyst undergoes is long-time descends serious all the better.
Second compound 14 in the catalyst fines 11 can be for containing the La of 3wt%～10wt% 2O 3Aluminium oxide.Contain La in the aluminium oxide 2O 3, can suppress the performance of catalyst undergoes after long-time and descend.This be because: in aluminium oxide, add La 2O 3, can suppress the deterioration (sintering phenomenon) of the aluminium oxide that thermal history causes.La in the aluminium oxide 2O 3If the not enough 3wt% of content then lacks and adds La 2O 3Effect, in addition, if surpass 10wt%, then have following hidden danger: the performance after catalyst undergoes is long-time descends serious all the better.Thereby, the La in the aluminium oxide 2O 3Content be preferably the scope of 3wt%～10wt%.
Noble metal 12 in the catalyst fines 11 is preferably and is selected from least a among Pt, Pd and the Rh.Pt, Pd and Rh are the metal that waste gas is had catalyst activity, are suitable as noble metal 12, and described noble metal 12 is carried on Compound C e-Zr-Ox, the Zr-LaOx that is suitable as first compound 13.
Can on the inner face 1a of carrier 1, form one deck and contain catalyst layer 10 as above-mentioned catalyst fines 11, but the preferred diverse a plurality of layers of noble metal that on the inner face 1a of carrier 1, form.Particularly preferred mode is to form substrate layer described later on the inner face 1a of carrier 1, forms the diverse two catalyst layers of noble metal on this basalis.By forming the diverse a plurality of layers of noble metal, noble metal contained in each catalyst layer is brought into play good exhaust-gas purifying performance respectively, as the catalyst integral body that is formed on the carrier 1, purifying exhaust air effectively.
When forming multi-layer catalyst layer 10 on the inner face 1a at carrier 1, preferably between the inner face 1a of carrier 1 and catalyst layer 10, has the substrate layer that does not contain noble metal.By having the substrate layer that does not contain noble metal in the inner face 1a side of comparing more close carrier 1 with catalyst layer 10, four jiaos (four corners) in a hole (セ Le) of the quadrangular section that this substrate layer landfill is crossed by the inner face 1a of carrier 1.Thereby, in multi-layer catalyst,, can bring into play the waste gas purification effect of these catalyst layers effectively with the thickness homogeneous of the contacted catalyst layer of this substrate layer.
This basalis preferably comprises at least a in aluminium oxide and the hydro carbons adsorptivity compound.Aluminium oxide is the general material of the noble metal in the supported catalyst layer, can be suitably as the substrate layer that does not contain noble metal.In addition, be substrate layer with hydro carbons adsorptivity compound, can be when petrol engine start, be contained in hydro carbons in this waste gas by the hydro carbons adsorptivity compound absorption of this substrate layer.Thereby, the exhaust-gas purifying performance in the time of can improving so-called cold start-up.The example of this hydro carbons adsorptivity compound has zeolite, middle porous silica (メ ソ Port one ラ ス シ リ カ).
When forming multi-layer catalyst layer 10 on the inner face 1a at carrier 1, be contained in suitable being combined as that the catalyst fines in the catalyst layer of carrier inner face side constitutes: noble metal is the CeO that at least a, first compound among Pt and the Pd comprises 70wt%～85wt% 2And the ZrO of 15wt%～30wt% 2, second compound is the CeO that contains 5wt%～15wt% 2, 3wt%～10wt% ZrO 2Aluminium oxide.When not having substrate layer on the inner face of carrier and forming two catalyst layers, the catalyst layer of carrier inner face side is meant the ground floor catalyst layer of carrier inner face side; When forming substrate layer on the inner face at carrier and forming on this substrate layer when forming three layers on the inner face that two catalyst layers promptly is aggregated in carrier, the catalyst layer of carrier inner face side is meant the intermediate layer (one deck of the carrier inner face side in the two catalyst layers) in these three layers.The catalyst fines of the catalyst layer of this inner face side adopts such noble metal, first compound and second combination of compounds, can give full play to the catalyst performance of Pt and Pd, is preferred therefore.
When forming multi-layer catalyst layer 10 on the inner face 1a at carrier 1, be contained in other suitable being combined as of formation of catalyst fines of the catalyst layer of carrier inner face side: noble metal is at least a among Pt and the Pd, and first compound comprises the CeO of 70wt%～85wt% 2And the ZrO of 15wt%～30wt% 2, second compound is the La that contains 3wt%～10wt% 2O 3Aluminium oxide.To contain the La of 3wt%～10wt% 2O 3Aluminium oxide replace the above-mentioned CeO that contains 5wt%～15wt% 2, 3wt%～10wt% ZrO 2Aluminium oxide as second compound of the catalyst fines of the catalyst layer that inner face side comprised, such combination can be given full play to the catalyst performance of Pt and Pd equally, is preferred therefore.
When forming multi-layer catalyst layer 10 on the inner face 1a at carrier 1, the suitable of formation of catalyst fines that is contained in the catalyst layer of carrier surface side is combined as: noble metal is Rh, first compound ZrO by 90wt%～99wt% 2And the La of 1wt%～10wt% 2O 3, second compound is aluminium oxide.When not having substrate layer on the inner face of carrier and forming two catalyst layers, the catalyst layer of carrier surface side is meant the second layer catalyst layer away from that side of carrier inner face; When forming basalis on the inner face at carrier and form on this basalis when forming three layers on the inner face that two catalyst layers promptly is aggregated in carrier, the catalyst layer of carrier surface side is meant the top layer (one deck of the face side in the two catalyst layers) in these three layers.The catalyst fines of the catalyst layer of this face side adopts such noble metal, first compound and second combination of compounds, can give full play to the catalyst performance of Rh, is preferred therefore.
In the catalyst fines of the catalyst layer of above-mentioned face side, load first compound of noble metal be preferably 40wt%～75wt%, second compound is preferably 25wt%～60wt%.The content ratio of first compound and second compound is in above-mentioned scope, and the catalyst layer of face side is purifying exhaust air effectively.
Below, an example of the suitable manufacture method of exhaust gas purification catalyst of the present invention is described.The example of this manufacture method comprises step for preparing catalyst fines and the step that forms this catalyst fines on the inner face of carrier.
Wherein, the step of described preparation catalyst fines comprises: the step of carried noble metal on first compound, be dispersed in the water with precursor second compound or second compound, if necessary in wherein dissolving at least a compound in cerium compound, zirconium compounds and the lanthanum compound and carrying out the step of slurryization, and, then with load first compound of noble metal be dispersed in the slurry of described second compound, after drying, carry out sintering and obtain the step of catalyst fines.
In the step of carried noble metal, the carrying method that noble metal is carried on first compound can adopt known method, is not particularly limited on described first compound.For example, can be suitable for impregnation method etc.
With described on first compound step of carried noble metal carry out following step dividually: the precursor of second compound or second compound is dispersed in the water, if necessary at least a compound that wherein dissolves in cerium compound, zirconium compounds and the lanthanum compound, carry out slurryization.This step and between the step of carried noble metal on first compound, do not have mutual order.Being scattered in the water can be second compound, also can be the precursor of second compound.In addition, when second compound in the catalyst of desire manufacturing is when containing the compound of cerium, zirconium, lanthanum, in the water of the precursor that has disperseed second compound or second compound, dissolve at least a compound in cerium compound, zirconium compounds and the lanthanum compound.
With load first compound of noble metal be dispersed in the slurry of described second compound or its precursor, described slurry has optionally dissolved at least a in cerium compound, zirconium compounds and the lanthanum compound.Such dispersion treatment, i.e. size degradation load the agglomerate of first compound of noble metal, and it is scattered in processing in second compound, can adopt the method for using the organic compound dispersant.The physical method of the abrasive power (ズ リ power) that in addition, also can adopt refiner, obtains by high-speed stirred.
After the above-mentioned dispersion treatment, carry out drying.Drying means can be such as the method for having used spray dryer, vacuum freeze-drying method etc., but should keep with second compound covering load state of first compound of noble metal, and guarantees that necessary micropore volume is 0.24cm 3/ g～0.8cm 3/ g.
Thereafter, thus carrying out sintering obtains catalyst fines.Sintering condition gets final product by the sintering condition of general exhaust gas purification catalyst.
After above-mentioned catalyst fines preparation process, on the inner face of carrier, form catalyst fines as catalyst layer.The compound that this formation step can disappear when comprising the steps: to add sintering in the catalyst fines that obtains, slurryization, be coated on carrier, dry then, sintering have the step of the catalyst layer of micropore in the zone of 0.1 μ m～1 μ m in the micropore of formation catalyst layer.
Catalyst layer through the formation of this step is necessary it is following catalyst layer, and in the micropore of catalyst layer, the micropore in the zone of 0.1 μ m～1 μ m accounts for certain proportion.For this reason, prepare following slurry: when with above-mentioned catalyst fines slurryization, when being coated on carrier, the compound (to call " disappearance compound " in the following text) that can disappear when in slurry, being added in the sintering after the coating.The disappearance compound that adds disappears when the slurry coating with preparation carries out sintering behind carrier.Wherein the part of Xiao Shiing has participated in effectively that micropore diameter is the formation of the micropore of 0.1 μ m～1 μ m in the catalyst layer.As this disappearance compound, can be material arbitrarily, as long as it disappears, toner, starch, carbon black, active carbon etc. are for example arranged when sintering.The disappearance compound can use the following powder of particle diameter 1 μ m, in addition, also can use the above powder of particle diameter 1 μ m, because it can be pulverized to below the particle diameter 1 μ m when pulp preparation.In addition, can also use liquid material such as methylcellulose.
Embodiment
Embodiment 1～8 is the different example of ratio of the micropore of 0.1 μ m～1 μ m of being formed at the supported catalyst layer.
(embodiment 1)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In beaker, add 118.42g acicular boehmite (10nm φ * 100nm) (moisture 24%) makes it to be scattered in the water, carries out dispergation (Xie Rubber with acid), add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 9.21g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-1) of average grain diameter 3 μ m.
Then, to the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared with alumina-coated the powder b-1 that particle B obtains thereafter.
This powder of 168g b-1,7g boehmite alumina and 9.21g active carbon powder are added ball milling, thereafter, in ball milling, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-1) of average grain diameter 3 μ m.
Slurry a-1 is coated on diameter 36 φ (being 36mm), 400 holes (セ Le), 6 mils (ミ Le) (promptly, the wall thickness of honeycomb is 6/1000 inch, 400 holes are arranged on 1 square inch) honeycomb substrate (capacity 0.04L) on, dry, sintering, made the catalyst layer that has applied 140g/L (that is, the amount of powder in the slurry that adheres on every 1L honeycomb substrate is 140g).Thereafter, coating coating slurry b-1, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 1.The sample of the embodiment 1 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 2)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) makes it to be scattered in the water, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, preparation powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 19.44g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-2) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 19.44g active carbon powder are added ball milling, thereafter, in ball milling, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-2) of average grain diameter 3 μ m.
Slurry a-2 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-2, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 2.The sample of the embodiment 2 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 3)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) makes it to be scattered in the water, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, preparation powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This 168g powder a-1,7g boehmite alumina and 33.33g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-3) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 33.33g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-3) of average grain diameter 3 μ m thereafter.
Slurry a-3 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-3, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 3.The sample of the embodiment 3 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 4)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) makes it to be scattered in the water, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 46.51g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 makes the slurry (slurry a-4) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 46.51g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-4) of average grain diameter 3 μ m thereafter.
Slurry a-4 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-4, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 4.The sample of the embodiment 4 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 5)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) makes it to be scattered in the water, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 61.48g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-5) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and active carbon powder 61.48g are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-5) of average grain diameter 3 μ m thereafter.
Slurry a-5 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-5, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 5.The sample of the embodiment 5 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 6)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) makes it to be scattered in the water, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 75g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-6) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), make it to be scattered in the water, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 75g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-6) of average grain diameter 3 μ m thereafter.
Slurry a-6 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-6, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 6.The sample of the embodiment 6 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 7)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is cerium zirconium compound oxide particle A2).
(118.42g (moisture 24%) of 10nm φ * 100nm) uses aqueous dispersion, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A2 that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-2, the cerium zirconium compound oxide particle A2 that wherein used alumina-coated thereafter.
This powder of 168g a-2,7g boehmite alumina and 33.3g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-2 makes the slurry (slurry a-7) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 33.3g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-7) of average grain diameter 3 μ m thereafter.
Slurry a-7 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-7, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 7.The sample of the embodiment 7 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
(embodiment 8)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.To these particle impregnation dinitro two ammino palladiums, prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is cerium zirconium compound oxide particle A2).
(118.42g (moisture 24%) of 10nm φ * 100nm) uses aqueous dispersion, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A2 that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-2, the cerium zirconium compound oxide particle A2 that wherein used alumina-coated thereafter.
This powder of 168g a-2,7g boehmite alumina and 46.51g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-2 has made the slurry (slurry a-8) of average grain diameter 3 μ m.
Then, to impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20mm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 46.51g active carbon powder are added ball milling.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-8) of average grain diameter 3 μ m.
Slurry a-8 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-8, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 8.The sample of the embodiment 8 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
Embodiment 9～14 is the different example of micropore volume of catalyst fines.
(embodiment 9)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(118.42g (moisture 24%) of 10nm φ * 100nm) uses aqueous dispersion, carries out dispergation with acid, adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred to add acicular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-1, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-1 has made the slurry (slurry a-11) of average grain diameter 3 μ m.
Then, to the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-11 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 9.The sample of the embodiment 9 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 10)
As first compound, used the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(20 * 20 * 10nm) 113.92g (moisture 21%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred to add tabular boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-4, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-4,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-4 makes the slurry (slurry a-12) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add tabular boehmite 113.92g (moisture 21%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-3, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-3,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-12) of average grain diameter 3 μ m thereafter.
Slurry a-12 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-12, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 10.The sample of the embodiment 10 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 11)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder a-5, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-5,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-5 makes the slurry (slurry a-13) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add cubic boehmite 105.88g (moisture 15%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-4, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-4,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-13) of average grain diameter 3 μ m thereafter.
Slurry a-13 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-13, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 11.The sample of the embodiment 11 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 12)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
(20 * 20 * 60nm) 102.27g (moisture 12%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred to add the prism-shaped boehmite in beaker., this slurry carried out drying, sintering, prepared powder a-6, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-6,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-6 makes the slurry (slurry a-14) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add prism-shaped boehmite 102.27g (moisture 12%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-5, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-5,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-14) of average grain diameter 3 μ m thereafter.
Slurry a-14 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-14, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 12.The sample of the embodiment 12 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 13)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is cerium zirconium compound oxide particle A2).
(20 * 20 * 10nm) 113.92g (moisture 21%) use aqueous dispersion, make it to be acid, add the cerium zirconium compound oxide particle A2 that 90g prepares previously, disperse by high-speed stirred to add tabular boehmite in beaker., this slurry carried out drying, sintering, preparation powder a-7, the cerium zirconium compound oxide particle A2 that wherein used alumina-coated thereafter.
This powder of 168g a-7,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-7 has made the slurry (slurry a-15) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.(20 * 20 * 10nm) 113.92g (moisture 21%) use aqueous dispersion, make it to be acid, add the particle B that 90g prepares previously then, disperse by high-speed stirred to add tabular boehmite in beaker., this slurry carried out drying, sintering, prepared powder b-3, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-3,7g boehmite alumina and 52.27g active carbon powder are added in the ball milling.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-12) of average grain diameter 3 μ m.
Slurry a-15 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-12, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 13.The sample of the embodiment 13 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
(embodiment 14)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.At these particle impregnation dinitro two ammino palladiums, prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is cerium zirconium compound oxide particle A2).
(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A2 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder a-8, the cerium zirconium compound oxide particle A2 that wherein used alumina-coated thereafter.
This powder of 168g a-8,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-8 has made the slurry (slurry a-16) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of preparation load 0.814% rhodium.(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the particle B that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder b-4, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-4,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-13) of average grain diameter 3 μ m thereafter.
Slurry a-16 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-13, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 14.The sample of the embodiment 14 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
Among the embodiment 15～17, first compound comprises CeO 2And ZrO 2, but CeO 2With ZrO 2Compoundization than different separately.
(embodiment 15)
As first compound, use the cerium zirconium compound oxide particle of 70% cerium, 30% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A3).
(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the particle A3 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, preparation powder a-11, the particle A3 that wherein used alumina-coated thereafter.
This powder of 168g a-11,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-11 makes the slurry (slurry a-19) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of 90% zirconium, 10% lanthanum, the particle B2 of 0.814% rhodium that prepared load.(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the particle B2 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder b-8, the particle B2 that wherein used alumina-coated thereafter.
This powder of 168g b-8,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-17) of average grain diameter 3 μ m thereafter.
Slurry a-19 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-17, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 15.The sample of the embodiment 15 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 16)
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.To these particle impregnation dinitro two ammino platinum, prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder a-12, the particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-12,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-12 has made the slurry (slurry a-20) of average grain diameter 3 μ m.
Then, the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of 95% zirconium, 5% lanthanum, the particle B3 of 0.814% rhodium that prepared load.(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the particle B3 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder b-9, the particle B3 that wherein used alumina-coated thereafter.
This powder of 168g b-9,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-18) of average grain diameter 3 μ m thereafter.
Slurry a-20 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-18, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 16.The sample of the embodiment 16 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 17)
As first compound, used the cerium zirconium compound oxide particle of 85% cerium, 15% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A5).
(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the cerium zirconium compound oxide particle A5 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder a-13, the particle A5 that wherein used alumina-coated thereafter.
This powder of 168g a-13,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-13 has made the slurry (slurry a-21) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of 99% zirconium, 1% lanthanum, the preparation load particle B4 of 0.814% rhodium.(20 * 20 * 20nm) boehmite 105.88g (moisture 15%) use aqueous dispersion, carry out dispergation with acid, add the particle B4 that 90g prepares previously then, disperse by high-speed stirred to add cubic in beaker., this slurry carried out drying, sintering, prepared powder b-10, the particle B4 that wherein used alumina-coated thereafter.
This powder of 168g b-10,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-19) of average grain diameter 3 μ m thereafter.
Slurry a-21 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-19, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 17.The sample of the embodiment 17 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Among the embodiment 18～20, second compound is for containing CeO 2And ZrO 2Aluminium oxide, but this CeO 2And ZrO 2Amount have nothing in common with each other.
(embodiment 18)
As first compound, used the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 4.5g with cerium oxide, disperse to count the zirconium nitrate of 9g in this outside water with zirconia, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-16, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-16,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-16 has made the slurry (slurry a-24) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-24 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 18.The sample of the embodiment 18 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 19)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 9g with cerium oxide, disperse to count the zirconium nitrate of 4.5g in this outside water with zirconia, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-17, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-17,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-17 has made the slurry (slurry a-25) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, preparation powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-25 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 19.The sample of the embodiment 19 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 20)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (111.14g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 13.5g with cerium oxide, disperse to count the zirconium nitrate of 2.7g in this outside water with zirconia, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-18, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-18,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-18 makes the slurry (slurry a-26) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, preparation powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-26 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 20.The sample of the embodiment 20 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Among the embodiment 21～23, second compound is for containing La 2O 3Aluminium oxide, but La 2O 3Content have nothing in common with each other.
(embodiment 21)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (115.78g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 2.7g with lanthana, with aqueous dispersion, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-21, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-21,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-21 makes the slurry (slurry a-29) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-29 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 21.The sample of the embodiment 21 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 22)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, with aqueous dispersion, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-22, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-22,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-22 has made the slurry (slurry a-30) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-11) of average grain diameter 3 μ m thereafter.
Slurry a-30 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 22.The sample of the embodiment 22 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 23)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
In being housed, the beaker of water adds the acicular boehmite (107.43g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 9g with lanthana, with aqueous dispersion, add the cerium zirconium compound oxide particle A that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-23, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
This powder of 168g a-23,7g boehmite alumina and 52.27g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-23 has made the slurry (slurry a-31) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 52.27g active carbon powder are added in the ball mill.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g again, pulverize, made the slurry (slurry b-11) of average grain diameter 3 μ m.
Slurry a-31 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-11, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 23.The sample of the embodiment 23 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Embodiment 24～27 possesses substrate layer, and wherein, second compound of the catalyst in intermediate layer is for containing CeO 2And ZrO 2Aluminium oxide.
(embodiment 24)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the acicular boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 9g with cerium oxide, disperse to count the zirconium nitrate of 4.5g in this outside water with zirconia, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-26, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-26,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-26 has made the slurry (slurry a-34) of average grain diameter 3 μ m.
Then, to the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the alumina layer of 50g/L.Then, coating coating slurry a-34, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 24.The sample of the embodiment 24 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 25)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, made the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the acicular boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 9g with cerium oxide, disperse to count the zirconium nitrate of 4.5g in this outside water with zirconia, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-26, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-26,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-26 makes the slurry (slurry a-34) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-34, dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 25.The sample of the embodiment 25 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 26)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.To these particle impregnation dinitro two ammino palladiums, prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the acicular boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 9g with cerium oxide, disperse to count the zirconium nitrate of 4.5g in this outside water with zirconia, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-27, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-27,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-27 makes the slurry (slurry a-35) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.Add acicular boehmite 118.42g (moisture 24%) in beaker, use aqueous dispersion, carry out dispergation with acid, 90g adds the particle B for preparing previously then, disperses by high-speed stirred., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-35, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 26.The sample of the embodiment 26 of gained the has been load catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
(embodiment 27)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, make the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the needle-like boehmite (101.46g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the cerous nitrate of counting 9g with cerium oxide, disperse to count the zirconium nitrate of 4.5g in this outside water with zirconia, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-27, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-27,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-27 has made the slurry (slurry a-35) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-35, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 27.The sample of the embodiment 27 of gained the has been load catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
Embodiment 28～31 possesses substrate layer, and wherein, second compound of the catalyst in intermediate layer is for containing La 2O 3Aluminium oxide.
(embodiment 28)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-30 has made the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-38, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 28.The sample of the embodiment 28 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 29)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, make the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-30 makes the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-38, dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 29.The sample of the embodiment 29 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 30)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
Used the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium as first compound.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-31, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-31,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-31 makes the slurry (slurry a-39) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.Add acicular boehmite 118.42g (moisture 24%) in beaker, use aqueous dispersion, carry out dispergation with acid, 90g adds the particle B for preparing previously then, disperses by high-speed stirred., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-31) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-39, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 30.The sample of the embodiment 30 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 31)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, make the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-31, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-31,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-31 has made the slurry (slurry a-39) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.In beaker, add acicular boehmite 118.42g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B that 90g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-1, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-1,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-31) of average grain diameter 3 μ m.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-39, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-31, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 31.The sample of the embodiment 31 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
Embodiment 28～31 possesses substrate layer, and wherein, second compound of the catalyst in intermediate layer is for containing La 2O 3Aluminium oxide.
Embodiment 32～37 possesses substrate layer, but the ratio of first compound of top layer catalyst and second compound has nothing in common with each other.
(embodiment 32)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-30 makes the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B13 of 1.0175% rhodium.In beaker, add acicular boehmite 142.1g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B 13 that 72g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-13, the particle B that wherein used alumina-coated thereafter.
This powder of 168g b-13,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-41) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-38, dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-41, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 32.The sample of the embodiment 32 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 33)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, made the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-30 has made the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B14 of 0.5814% rhodium.In beaker, add acicular boehmite 71.1g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B14 that 126g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-14, the particle B14 that wherein used alumina-coated thereafter.
This powder of 168g b-14,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-42) of average grain diameter 3 μ m.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-38, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-42, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 33.The sample of the embodiment 33 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 34)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, made the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, used the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, comminuted powder a-30 has made the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B15 of 0.5426% rhodium.In beaker, add acicular boehmite 59.21g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B15 that 135g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-15, the particle B15 that wherein used alumina-coated thereafter.
This powder of 168g b-15,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-43) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-38, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-43, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 34.The sample of the embodiment 34 of gained the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 35)
In ball milling, add gamma-alumina powder 180g and boehmite alumina 20g, and then add entry 282.5g and 10% nitric acid 17.5g, pulverize, make the slurry (slurry c-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-31, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-31,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-31 has made the slurry (slurry a-39) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B14 of 0.5814% rhodium.In beaker, add acicular boehmite 71.1g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B14 that 126g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-14, the particle B14 that wherein used alumina-coated thereafter.
This powder of 168g b-14,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-42) of average grain diameter 3 μ m thereafter.
Slurry c-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the alumina layer of 50g/L.Then, coating coating slurry a-39, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-42, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 35.The sample of the embodiment 35 of gained for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
(embodiment 36)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, make the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, use the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A4).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A4 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, preparation powder a-30, the cerium zirconium compound oxide particle A4 that wherein used alumina-coated thereafter.
This powder of 168g a-30,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-30 has made the slurry (slurry a-38) of average grain diameter 3 μ m.
Then, at zirconium lanthanum (99: 1) the composite oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the preparation load particle B 14 of 0.5814% rhodium.In beaker, add acicular boehmite 71.1g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B14 that 126g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-14, the particle B14 that wherein used alumina-coated thereafter.
This powder of 168g b-14,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-42) of average grain diameter 3 μ m thereafter.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-38, dry, sintering have been made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-42, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as embodiment 36.The sample of the embodiment 36 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(embodiment 37)
In ball milling, add β zeolite 180g, Ludox (SiO 2: 15%) 288g and water 32g, pulverize then, made the slurry (slurry d-1) of average grain diameter 3 μ m.
As first compound, used the cerium zirconium compound oxide particle of 78% cerium, 22% zirconium.Impregnation dinitro two ammino palladiums in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pd (this is particle A8).
In being housed, the beaker of water adds the needle-like boehmite (113.40g (moisture 24.6%) of 10nm φ * 100nm), to wherein adding the lanthanum nitrate of counting 4.5g with lanthana, be scattered in the water, add the cerium zirconium compound oxide particle A8 that 90g prepares previously then, disperse by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-31, the cerium zirconium compound oxide particle A8 that wherein used alumina-coated thereafter.
This powder of 168g a-31,7g boehmite alumina and 38.41g active carbon powder are added ball milling.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-31 makes the slurry (slurry a-39) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B14 of 0.5814% rhodium.In beaker, add acicular boehmite 71.1g (moisture 24%), use aqueous dispersion, carry out dispergation, add the particle B14 that 126g prepares previously then, disperse by high-speed stirred with acid., this slurry carried out drying, sintering, prepared powder b-14, the particle B 14 that wherein used alumina-coated thereafter.
This powder of 168g b-14,7g boehmite alumina and 38.41g active carbon powder are added ball milling., to ball milling in add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-42) of average grain diameter 3 μ m thereafter.
Slurry d-1 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering have been made the β zeolite layer of 50g/L.Then, coating coating slurry a-39, dry, sintering are made the catalyst layer that has applied 140g/L.Thereafter, coating coating slurry b-42, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as embodiment 37.The sample of the embodiment 37 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 1,2 is an example of doing contrast with embodiment 1～8.
(comparative example 1)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this cerium zirconium compound oxide particle have been made load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding 90g cerium zirconium compound oxide particle A, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder a-3, the particle A that wherein used alumina-coated.The particle diameter of this aluminium oxide is 7～8nm.
In ball milling, add 168g this powder a-3 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-3 makes the slurry (slurry a-9) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g this powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-9 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, after the drying, coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, as the sample of comparative example 1.The sample of the comparative example 1 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 2)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this cerium zirconium compound oxide particle have been made load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding 90g cerium zirconium compound oxide particle A, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-3, the particle A that wherein used alumina-coated.The particle diameter of this aluminium oxide is 7～8nm.
In ball milling, add this powder of 168g a-3,7g boehmite alumina and 94.23g active carbon powder.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-3 makes the slurry (slurry a-10) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add this powder of 168g b-2,7g boehmite alumina and 94.23g active carbon powder, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-10) of average grain diameter 3 μ m.
Honeycomb substrate (capacity 0.04L) in diameter 36 φ, 400 holes, 6 mils is gone up coating coating slurry a-10, and dry, sintering are made the catalyst layer that has applied 140g/L, thereafter, coating coating slurry b-10, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as comparative example 2.The sample of the comparative example 2 of gained for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 3,4 is an example of doing contrast with embodiment 9～14.
(comparative example 3)
As first compound, use micropore volume 0.15cm 3The cerium zirconium compound oxide particle of/g.Impregnation dinitro two ammino platinum in to this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle Aa).
Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the described particle Aa of 90g, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-9, the particle Aa that wherein used alumina-coated.
In ball milling, add 168g this powder a-9 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-9 has made the slurry (slurry a-17) of average grain diameter 3 μ m.
Then, at micropore volume 0.16cm 3Impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of/g, the preparation load particle Bb of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds the described particle Bb of 90g therein, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-6, the particle of wherein having used alumina-coated.
In ball milling, add 168g this powder b-6 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-15) of average grain diameter 3 μ m.
Slurry a-17 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Then, coating coating slurry b-15, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as comparative example 3.The sample of gained comparative example 3 for load respectively the catalyst of Pd:0.5712g/L, Rh:0.2344g/L.
(comparative example 4)
As first compound, used the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this cerium zirconium compound oxide particle have been made load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Add the aluminium oxide nano particle 90.9g (moisture 1%) of average grain diameter 130nm in beaker, use aqueous dispersion, furnishing acidity adds the cerium zirconium compound oxide particle A that 90g prepares previously then, disperses by high-speed stirred., this slurry carried out drying, sintering, prepared powder a-10, the cerium zirconium compound oxide particle A that wherein used alumina-coated thereafter.
In ball milling, add 168g this powder a-10 and 7g boehmite alumina.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-10 makes the slurry (slurry a-18) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Add the aluminium oxide nano particle 90.9g (moisture 1%) of average grain diameter 130nm in beaker, use aqueous dispersion, furnishing acidity adds the particle B that 90g prepares previously then, disperses by high-speed stirred., this slurry carried out drying, sintering, prepared powder b-7, the particle B that wherein used alumina-coated thereafter.
In ball milling, add 168g this powder b-7 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-16) of average grain diameter 3 μ m.
Slurry a-18 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Then, coating coating slurry b-16, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as comparative example 4.The sample of gained comparative example 4 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 5,6 is an example of doing contrast with embodiment 15～17.
(comparative example 5)
As first compound, used the cerium zirconium compound oxide particle of 60% cerium, 40% zirconium.Impregnation dinitro two ammino platinum in this particle have been made load the cerium zirconium compound oxide particle of 0.85%Pt (particle A6 in addition).
Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the described particle A6 of 90g, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-14, the particle A6 that wherein used alumina-coated.
In ball milling, add 168g this powder a-14 and 7g boehmite alumina.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-14 makes the slurry (slurry a-22) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of zirconium 80%, lanthanum 20%, the preparation load particle B5 of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the described particle B5 of 90g, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-11, the particle B5 that wherein used alumina-coated.
In ball milling, add 168g this powder b-11 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-20) of average grain diameter 3 μ m.
Slurry a-22 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Then, coating coating slurry b-20, dry, sintering have been made the catalyst layer that has applied 60g/L.Sample as comparative example 5.The sample of gained comparative example 5 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 6)
As first compound, used the cerium zirconium compound oxide particle of 90% cerium, 10% zirconium.Impregnation dinitro two ammino platinum in this particle have been made load the cerium zirconium compound oxide particle of 0.85%Pt (particle A7 in addition).
Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the described particle A7 of 90g, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-15, the particle A7 that wherein used alumina-coated.
In ball milling, add 168g this powder a-15 and 7g boehmite alumina.Then, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-15 makes the slurry (slurry a-23) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the particle of 100% zirconium, the preparation load particle B6 of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the described particle B6 of 90g, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-12, the particle B6 that wherein used alumina-coated.
In ball milling, add 168g this powder b-12 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-21) of average grain diameter 3 μ m.
Slurry a-23 is coated on the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, and dry, sintering are made the catalyst layer that has applied 140g/L.Then, coating coating slurry b-21, dry, sintering are made the catalyst layer that has applied 60g/L.Sample as comparative example 6.The sample of gained comparative example 6 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 7,8 is an example of doing contrast with embodiment 18～20.
(comparative example 7)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 87.3g is dissolved in 2-methyl-2, and the 4-pentanediol is to wherein adding the acetyl acetone cerium of counting 1.8g with cerium oxide, in addition, adding is counted the acetyl acetone zirconium of 0.9g with zirconia, to wherein adding the described particle A of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-19, wherein with alumina-coated particle A.
In ball milling, add 168g this powder a-19 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-19 has made the slurry (slurry a-27) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of rhodium 0.814%.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-27 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, makes the sample of comparative example 7.The sample of gained comparative example 7 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 8)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 58.5g is dissolved in 2-methyl-2, and the 4-pentanediol is to wherein adding the acetyl acetone cerium of counting 18g with cerium oxide, in addition, adding is counted the acetyl acetone zirconium of 13.5g with zirconia, to wherein adding the described particle A of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-20, wherein with alumina-coated particle A.
In ball milling, add 168g this powder a-20 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-20 makes the slurry (slurry a-28) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-28 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, makes the sample of comparative example 8.The sample of gained comparative example 8 the has been load catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 9,10 is an example of doing contrast with embodiment 21～23.
(comparative example 9)
As first compound, use the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 89.1g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 0.9g with lanthana, to wherein adding the described particle A of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-24, wherein with alumina-coated particle A.
In ball milling, add 168g this powder a-24 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-24 makes the slurry (slurry a-32) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of rhodium 0.814%.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-32 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, has made the sample of comparative example 9.The sample of gained comparative example 9 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 10)
As first compound, used the cerium zirconium compound oxide particle of average grain diameter 30nm.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is cerium zirconium compound oxide particle A).
Will be with Al 2O 3The aluminium isopropoxide of counting 76.5g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 13.5g with lanthana, to wherein adding the described particle A of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder a-25, wherein with alumina-coated particle A.
In ball milling, add 168g this powder a-25 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-25 has made the slurry (slurry a-33) of average grain diameter 3 μ m.
Then, to the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the particle B of rhodium 0.814% that prepared load.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-33 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, makes the sample of comparative example 10.The sample of gained comparative example 10 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 11,12 is an example of doing contrast with embodiment 24～27.
(comparative example 11)
As first compound, used the cerium zirconium compound oxide particle of 60% cerium, 40% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A6).
Will be with Al 2O 3The aluminium isopropoxide of counting 87.3g is dissolved in 2-methyl-2, and the 4-pentanediol is to wherein adding the acetyl acetone cerium of counting 1.8g with cerium oxide, in addition, adding is counted the acetyl acetone zirconium of 0.9g with zirconia, to wherein adding the described particle A6 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-28, the particle A6 that wherein used alumina-coated.
In ball milling, add 168g this powder a-28 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-28 makes the slurry (slurry a-36) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-36 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, after the drying, coating 60g/L slurry b-9 after the drying, carries out sintering in 400 ℃, makes the sample of comparative example 11.The sample of gained comparative example 11 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 12)
As first compound, use the cerium zirconium compound oxide particle of 90% cerium, 10% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A7).
Will be with Al 2O 3The aluminium isopropoxide of counting 58.5g is dissolved in 2-methyl-2, and the 4-pentanediol is to wherein adding the acetyl acetone cerium of counting 18g with cerium oxide, in addition, adding is counted the acetyl acetone zirconium of 13.5g with zirconia, to wherein adding the described particle A7 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-29, the particle A7 that wherein used alumina-coated.
In ball milling, add 168g this powder a-29 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-29 makes the slurry (slurry a-37) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of 0.814% rhodium.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-37 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, has made the sample of comparative example 12.The sample of gained comparative example 12 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 13,14 is an example of doing contrast with embodiment 28～31.
(comparative example 13)
As first compound, used the cerium zirconium compound oxide particle of 60% cerium, 40% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A6).
Will be with Al 2O 3The aluminium isopropoxide of counting 89.1g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 0.9g with lanthana, to wherein adding the described particle A6 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-32, the particle A6 that wherein used alumina-coated.
In ball milling, add 168g this powder a-32 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-32 makes the slurry (slurry a-40) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in the zirconium lanthanium complex oxide particle of average grain diameter 20nm, the preparation load particle B of rhodium 0.814%.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, make the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-40 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, makes the sample of comparative example 9.The sample of gained comparative example 9 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 14)
As first compound, use the cerium zirconium compound oxide particle of 90% cerium, 10% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A7).
Will be with Al 2O 3The aluminium isopropoxide of counting 76.5g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 13.5g with lanthana, to wherein adding the described particle A7 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-33, the particle A7 that wherein used alumina-coated.
In ball milling, add 168g this powder a-33 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-33 has made the slurry (slurry a-41) of average grain diameter 3 μ m.
Then, to the zirconium lanthanium complex oxide particle impregnation rhodium nitrate of average grain diameter 20nm, the particle B of 0.814% rhodium that prepared load.Will be with Al 2O 3The aluminium isopropoxide of counting 90g is dissolved in 2-methyl-2, and the 4-pentanediol adds 90g particle B, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-2, the particle B that wherein used alumina-coated.
In ball milling, add 168g powder b-2 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-9) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-41 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-9, sintering is carried out in 400 ℃ in dry back, has made the sample of comparative example 14.The sample of gained comparative example 14 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Comparative example 15,16 is an example of doing contrast with embodiment 32～37.
(comparative example 15)
As first compound, use the cerium zirconium compound oxide particle of 60% cerium, 40% zirconium.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A6).
Will be with Al 2O 3The aluminium isopropoxide of counting 89.1g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 0.9g with lanthana, to wherein adding the described particle A6 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder a-32, the particle A6 that wherein used alumina-coated.
In ball milling, add 168g this powder a-32 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-32 makes the slurry (slurry a-40) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B16 of 0.50875% rhodium.
Will be with Al 2O 3The aluminium isopropoxide of counting 36g is dissolved in 2-methyl-2, and the 4-pentanediol adds 144g particle B16, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, preparation powder b-16, the particle B 16 that wherein used alumina-coated.
In ball milling, add 168g powder b-16 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-44) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-40 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-44, sintering is carried out in 400 ℃ in dry back, has made the sample of comparative example 15.The sample of gained comparative example 15 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
(comparative example 16)
As first compound, use the cerium zirconium compound oxide particle of cerium 90%, zirconium 10%.Impregnation dinitro two ammino platinum in this particle have prepared load the cerium zirconium compound oxide particle of 0.85%Pt (this is particle A7).
Will be with Al 2O 3The aluminium isopropoxide of counting 76.5g is dissolved in 2-methyl-2, and the 4-pentanediol to wherein adding the lanthanum acetate of counting 13.5g with lanthana, to wherein adding the described particle A7 of 90g, adds water and is hydrolyzed again.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder a-33, the particle A7 that wherein used alumina-coated.
In ball milling, add 168g this powder a-33 and 7g boehmite alumina.Thereafter, add entry 307.5g and 10% aqueous solution of nitric acid 17.5g in ball milling, comminuted powder a-33 has made the slurry (slurry a-41) of average grain diameter 3 μ m.
Then, impregnation rhodium nitrate in zirconium lanthanum (99: the 1) composite oxide particle of average grain diameter 20nm, the preparation load particle B17 of 1.356% rhodium.
Will be with Al 2O 3The aluminium isopropoxide of counting 126g is dissolved in 2-methyl-2, and the 4-pentanediol adds 54g particle B17, adds water and is hydrolyzed.Evaporation drying water, 2-methyl-2, organic matters such as 4-pentanediol carry out sintering then, have prepared powder b-17, the particle B17 that wherein used alumina-coated.
In ball milling, add 168g powder b-17 and 7g boehmite alumina, and then add entry 307.5g and 10% aqueous solution of nitric acid 17.5g, pulverize, made the slurry (slurry b-45) of average grain diameter 3 μ m.
Go up coating 140g/L slurry a-41 at the honeycomb substrate (capacity 0.04L) of diameter 36 φ, 400 holes, 6 mils, dry back coating 60g/L slurry b-45, sintering is carried out in 400 ℃ in dry back, has made the sample of comparative example 16.The sample of gained comparative example 16 for load respectively the catalyst of Pt:0.5712g/L, Rh:0.2344g/L.
Will be by the catalyst of the foregoing description 1～embodiment 37 and comparative example 1～comparative example 16 preparations, be installed on capacity and be in the gas extraction system of V-type engine of 3500cc, whenever single-row (sheet バ Application Network) installs 5 catalyst.Use normal benzine in Japan, the catalyst inlet temperature is set to 650 ℃, turns round 30 hours, is used for implementing thermal history by making for a long time.
Further, will be assembled in through each catalyst of long-time use in the simulated exhaust circulation device, in the simulated exhaust circulation device, feed the simulated exhaust of forming shown in the table 1,, investigate NO with 30 ℃/minute speed rising catalytic temperature x, CO, HC (C 3H 6) purifying rate be 50% temperature (T50).
(table 1)
Figure A20081009167300571
Illustrated in table 2～9: the micropore volume of the catalyst fines of each catalyst of adopted use that gas adsorption method measures embodiment 1～embodiment 37 and comparative example 1～comparative example 16, simultaneously, the sample that is obtained by coating catalyst layer on honeycomb substrate cuts the test section, adopt mercury penetration method to measure micropore volume, in the micropore below micropore diameter shown in table 2～9 is 1 μ m, micropore diameter is that the micropore volume (A) of the following micropore of 0.1 μ m is the ratio of the micropore volume (B) of 0.1 μ m～1 μ m with micropore diameter.Show evaluation result in the lump.
In addition, illustrated in Fig. 4～11: the HC (C of each catalyst of embodiment 1～embodiment 37 and comparative example 1～comparative example 16 3H 6) purifying rate is the relation of 50% temperature.
Figure A20081009167300581
Figure A20081009167300591
Figure A20081009167300601
Figure A20081009167300611
Figure A20081009167300621
Figure A20081009167300631
Figure A20081009167300641
Figure A20081009167300651
In the catalyst of table 2 and comparative example 1 shown in Figure 4, second compound of ground floor catalyst has used the aluminium oxide that comes from aluminium isopropoxide, in addition, second compound of second layer catalyst has used aluminium isopropoxide, the micropore volume minimum of its ground floor, second layer catalyst fines, the ratio of the micropore of the 0.1 μ m～1 μ m of the catalyst layer that is coated with is very little, only is 9.3%.Utilize the Pt particle after tem observation uses for a long time, the Pt particle diameter is about 10nm, and the cohesion of Pt particle is few.In addition, the cohesion of Rh is also few.Yet catalyst activity is low.Can think, this be because: though the Pt particle diameter is little, micropore volume is little, waste gas be difficult to by, waste gas is difficult to arrive Pt.
In table 2 and the comparative example 2 shown in Figure 4, used the powder identical with comparative example 1, the ratio of the micropore of the 0.1 μ m～1 μ m of overlay increases to 65%, but after long-time the use, investigates coating, and coating is disintegrated, and can't estimate.Can think, this be because: the space of coating is too much, and the intensity of coating descends.
Relative thus, at the noble metal of ground floor is in each catalyst of embodiment 1～embodiment 6, embodiment 9～embodiment 12, embodiment 15～embodiment 25, embodiment 28,29, embodiment 32～embodiment 34, embodiment 36 of Pt, Pt particle diameter after long-time the use as 10nm about, the cohesion of Pt particle is few.In addition, the Rh particle is about 6nm, and cohesion is few.
In addition, the noble metal of ground floor is among embodiment 7, embodiment 8, embodiment 13, embodiment 14, embodiment 26, embodiment 27, embodiment 30, embodiment 31, embodiment 35, the embodiment 37 of Pd, Pd particle diameter after long-time the use is little, only be that the cohesion of Pd particle is few about 7nm～8nm.In addition, the Rh particle is about 6nm, and cohesion is few.
The catalyst activity of these embodiment, it is very good to compare with comparative example, has obtained high activity.
In the catalyst of table 3 and comparative example 3 shown in Figure 5, first compound of ground floor catalyst is a cerium zirconium compound oxide, and its micropore volume is 0.15cm 3/ g, first compound of second layer catalyst is the zirconium lanthanium complex oxide, its micropore volume is 0.16cm 3/ g, the catalyst activity of this catalyst is low.
In the catalyst of table 3 and comparative example 4 shown in Figure 5, second compound of ground floor and second layer catalyst has used the big grain aluminium oxide particles of 130nm.Therefore, the micropore volume value also becomes big.To the catalyst after the long-time use, utilize tem observation Pt particle, the Pt particle diameter becomes greatly, is about more than the 20nm, has found the cohesion of Pt particle, in addition, has also observed the cohesion of cerium zirconium compound oxide particle.Can think: aluminium oxide particles is big, and the space between aluminium oxide particles is big, and the cerium zirconium compound oxide particle that adheres to Pt shifts out from this space in long-time the use, condenses between the cerium zirconium compound oxide particle.In addition, can think: Pt also condenses with the cohesion of cerium zirconium compound oxide particle, and it is big that the Pt particle diameter becomes.In addition, for the Rh particle of the second layer, same visible its particle diameter increases to 15nm.Therefore, can think: though its micropore volume is big, catalyst activity is low.
In table 4 and comparative example 5 shown in Figure 6, the comparative example 6, compoundization of the cerium oxide in first compound of the ground floor and the second layer and zirconia etc. is than different.In the comparative example 5, the cerium oxide of ground floor and zirconic compoundization ratio are 60% and 40%, and the compoundization ratio of the zirconia of the second layer and lanthana is 80% and 20%, but compare with embodiment 15,16,17, and catalyst activity is low.The Pt particle diameter of ground floor that utilized tem observation is for about 10nm.The Rh particle of the second layer is little, for about 6nm, has observed it and has buried state between the zirconium lanthanium complex oxide particle that has condensed.
In addition, the cerium oxide of ground floor and zirconic compoundization ratio are 90% and 10% in the comparative example 6, and the second layer is a zirconia 100%, but compare with embodiment 15,16,17, and catalyst activity is low.The Pt particle diameter of ground floor that utilized tem observation is for about 10nm.The Rh particle of the second layer is little, be about 6nm, observed it and buried state between the Zirconia particles that has condensed.
Can think that except the micropore volume of the catalyst of comparative example 6 was little, this was also owing to the oxygen evolution ability deterioration of cerium oxide and zirconic composite oxides.In addition, can also think, this be because: in the relation of the compoundization ratio of such zirconia and lanthana, the zirconium lanthanium complex oxide easily condenses, and the Rh particle buries in zirconium lanthanium complex oxide particle, Zirconia particles, and it is difficult to contact with waste gas.
In addition, can also think: the micropore of catalyst layer is little, so the difficult arrival of waste gas, and catalyst activity is low.
In table 5 and comparative example 7 shown in Figure 7, the comparative example 8, compare with embodiment 18,19,20, catalyst activity is low.In this comparative example 7, comparative example 8, the Pt particle after the long-time use that utilized tem observation, the Pt particle diameter is about 10nm, the cohesion of Pt particle is few.In addition, the cohesion of Rh is also few.Yet catalyst activity is low.
Among the embodiment 18,19,20,, improved the hear resistance of the aluminium oxide behind the sintering, also kept big micropore volume after long-time the use by adding cerium compound, zirconium compounds to alumina precursor.In addition, can think: guaranteed the micropore of the 0.1 μ m～1 μ m of catalyst layer, so the diffusivity of waste gas is good, has kept catalyst activity.
Relative therewith, can think: in comparative example 7, the comparative example 8, do not have the additive effect of cerium compound, zirconium compounds, can not guarantee the micropore volume after long-time the use, the micropore of catalyst layer is little, so waste gas is difficult to arrive, and catalyst activity is low.
In table 6 and the comparative example 9,10 shown in Figure 8, compare with embodiment 21,22,23, catalyst activity is low.In comparative example 9,10, the Pt particle after the long-time use that utilized tem observation, the Pt particle diameter is about 10nm, the cohesion of Pt particle is few.In addition, the cohesion of Rh is also few.Yet catalyst activity is low.
Among the embodiment 21,22,23,, improved the hear resistance of the aluminium oxide behind the sintering, kept the micropore volume after the big long-time use by adding lanthanum compound to alumina precursor.In addition, can think: guaranteed the micropore of the 0.1 μ m～1 μ m of catalyst layer, the diffusivity of waste gas is good, has therefore kept catalyst activity.
Relative therewith, in comparative example 9,10, there is not the additive effect of lanthanum compound, micropore volume is little, the micropore volume after can't guaranteeing to use for a long time, in addition, can think: the micropore of catalyst layer is little, and waste gas is difficult to arrive, and catalyst activity is low.
In table 7 and comparative example 11 shown in Figure 9, the comparative example 12, compare with embodiment 24,25,26,27, catalyst activity is low.In comparative example 11, comparative example 12, the Pt particle after the long-time use that utilized tem observation, the Pt particle diameter is about 10nm, the cohesion of Pt particle is few.In addition, the cohesion of Rh is also few.Yet catalyst activity is low.
In embodiment 24,25,26,27, catalyst layer is three layers, has carried out bottom coating (ア Application ダ one コ one ト) at orlop, and is coated with the catalyst layer on intermediate layer, top layer.Therefore, the coating layer thickness of the catalyst in intermediate layer is even, and catalyst is worked effectively.The top layer also is same.In addition, add cerium compound, zirconium compounds, improved the hear resistance of the aluminium oxide behind the sintering, also can keep big micropore volume after long-time the use by the compoundization ratio of cerium oxide and zirconia etc. and to alumina precursor.In addition, can think: guaranteed the micropore of the 0.1 μ m～1 μ m of catalyst layer, so the diffusivity of waste gas is good, has kept catalyst activity.
Relative therewith, can think: in comparative example 11, comparative example 12, because the oxygen evolution ability deterioration of the zirconic composite oxides of cerium oxide, in addition, also because not do not add the effect of cerium compound, zirconium compounds to alumina precursor, can't guarantee the micropore volume after long-time the use, the micropore of catalyst layer is little, waste gas is difficult to arrive, so catalyst activity is low.
In table 8 and comparative example 13 shown in Figure 10, the comparative example 14, compare with embodiment 28,29,30,31, catalyst activity is low.In comparative example 13, comparative example 14, the Pt particle after the long-time use that utilized tem observation, the Pt particle diameter is about 10nm, the cohesion of Pt particle is few.In addition, the cohesion of Rh is also few.Yet catalyst activity is low.
In embodiment 28,29,30,31, catalyst layer is three layers, has carried out the bottom coating at orlop, and is coated with the catalyst layer on intermediate layer, top layer.Therefore, the coating layer thickness of the catalyst in intermediate layer is even, and catalyst is worked effectively.The top layer also is same.In addition, compoundization by cerium oxide and zirconia etc. than and in alumina precursor, add lanthanum compound, improved the hear resistance of the aluminium oxide behind the sintering, also can keep big micropore volume after long-time the use.In addition, can think: guaranteed the micropore of the 0.1 μ m～1 μ m of catalyst layer, the diffusivity of good waste gas has kept catalyst activity.
Relative therewith, can think: in comparative example 13, comparative example 14, because the oxygen evolution ability deterioration of cerium oxide and zirconic composite oxides, in addition, also because not do not add the effect of lanthanum compound to alumina precursor, can't guarantee the micropore volume after long-time the use, the micropore of catalyst layer is little, waste gas is difficult to arrive, so catalyst activity is low.
In table 9 and comparative example 15 shown in Figure 11, the comparative example 16, compare with embodiment 32,33,34,35,36,37, catalyst activity is low.
For the comparative example after the long-time use 15, utilize tem observation Pt particle, the Pt particle diameter is about 10nm, the Rh particle is little, for about 6nm, observes it and buries state between the zirconium lanthanium complex oxide particle that has condensed.Yet catalyst activity is low.
For the comparative example after the long-time use 16, utilize tem observation Pt particle, the Pt particle diameter is about 10nm, the Rh particle is little, for about 6nm.Yet catalyst activity is low.
In embodiment 32,33,34,35,36,37, catalyst layer is three layers, has carried out the bottom coating at orlop, and is coated with the catalyst layer on intermediate layer, top layer.Therefore, the coating layer thickness of the catalyst in intermediate layer is even, and catalyst is worked effectively.The top layer also is same.In addition, compoundization of cerium oxide by the intermediate layer and zirconia etc. than and in alumina precursor, add lanthanum compound, improved the hear resistance of the aluminium oxide behind the sintering, also can keep big micropore volume after long-time the use.In addition, the mixed proportion of the zirconium mixed oxide on top layer and aluminium oxide is also suitable.Can think: guaranteed the micropore of the 0.1 μ m～1 μ m of catalyst layer, so the diffusivity of waste gas is good, has kept catalyst activity.
Relative therewith, can think that in comparative example 15, catalyst activity is low, this be because: the oxygen evolution ability deterioration of the cerium oxide in intermediate layer and zirconic composite oxides; The effect that does not add lanthanum compound to alumina precursor, the micropore volume after can't guaranteeing to use for a long time; Micropore volume after long-time the use can't be guaranteed in the top layer; The amount of aluminium oxide is few, can not suppress the cohesion of zirconium mixed oxide, and Rh imbeds in the zirconium mixed oxide, and waste gas can't arrive; The micropore of catalyst layer is also little, and waste gas is difficult to arrive.
In addition, can think that in comparative example 16, catalyst activity is low, this be because: the oxygen evolution ability deterioration of the cerium oxide in intermediate layer and zirconic composite oxides; The effect that does not add lanthanum compound to alumina precursor, the micropore volume after can't guaranteeing to use for a long time; Micropore volume after long-time the use can't be guaranteed in the top layer; The amount of aluminium oxide is many, has suppressed the cohesion of zirconium mixed oxide, has also suppressed the cohesion of Rh, but because aluminium oxide is many, waste gas is difficult to arrive; The micropore of catalyst layer is little, and waste gas is difficult to arrive.

Claims (19)

1. exhaust gas purification catalyst, it comprises carrier and is formed at the catalyst layer of one deck at least on the carrier inner face, wherein,
The structure of described catalyst layer is: described catalyst layer contains catalyst fines, this catalyst fines comprises noble metal, first compound and second compound, and by the noble metal of the first compound loaded catalyst fines, load separate each other by second compound between first compound of this noble metal;
Described catalyst layer has micropore, and in the micropore below micropore diameter is 1 μ m, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is 10%～60%.
2. the exhaust gas purification catalyst of claim 1, wherein, in described catalyst layer, if micropore diameter is that the micropore volume of the following micropore of 0.1 μ m is A, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is B, in the micropore volume below micropore diameter is 1 μ m, B accounts for 10%～60%, and B/A 〉=0.1.
3. the exhaust gas purification catalyst of claim 1, wherein, in described catalyst layer, if micropore diameter is that the micropore volume of the following micropore of 0.1 μ m is A, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is B, and in the micropore volume below micropore diameter is 1 μ m, B accounts for 20%～60%.
4. the exhaust gas purification catalyst of claim 1, wherein, in described catalyst layer, if micropore diameter is that the micropore volume of the following micropore of 0.1 μ m is A, micropore diameter is that the micropore volume of the micropore of 0.1 μ m～1 μ m is B, and in the micropore volume below micropore diameter is 1 μ m, B accounts for 30%～50%.
5. the exhaust gas purification catalyst of claim 1, wherein, the micropore volume of described catalyst fines is 0.24cm 3/ g～0.8cm 3/ g.
6. the exhaust gas purification catalyst of claim 1, wherein, first compound of described catalyst fines comprises the CeO of 70wt%～85wt% 2And the ZrO of 15wt%～30wt% 2
7. the exhaust gas purification catalyst of claim 1, wherein, first compound of described catalyst fines comprises the ZrO of 90wt%～99wt% 2And the La of 1wt%～10wt% 2O 3
8. the exhaust gas purification catalyst of claim 1, wherein, second compound of described catalyst fines comprises aluminium oxide.
9. the exhaust gas purification catalyst of claim 1, wherein, second compound of described catalyst fines is the CeO that contains 5wt%～15wt% 2, 3wt%～10wt% ZrO 2Aluminium oxide.
10. the exhaust gas purification catalyst of claim 1, wherein, second compound of described catalyst fines is the La that contains 3wt%～10wt% 2O 3Aluminium oxide.
11. each exhaust gas purification catalyst of claim 1 to 10, wherein, the noble metal of described catalyst fines is to be selected from least a among Pt, Pd and the Rh.
12. the exhaust gas purification catalyst of claim 1 wherein, forms the described catalyst layer of multilayer on the carrier inner face.
13. the exhaust gas purification catalyst of claim 12 wherein, possesses the substrate layer that does not contain noble metal in the side than the more close carrier inner face of described catalyst layer.
14. the exhaust gas purification catalyst of claim 13, wherein, described substrate layer comprises at least a in aluminium oxide and the hydro carbons adsorptivity compound.
15. the exhaust gas purification catalyst of claim 12, wherein, the catalyst fines of the catalyst layer that is arranged in the carrier inner face side in described multi-layer catalyst layer, noble metal is at least a among Pt and the Pd, first compound is described first compound of claim 6, and second compound is described second compound of claim 9.
16. the exhaust gas purification catalyst of claim 12, wherein, in described multi-layer catalyst layer, be arranged in the catalyst fines of the catalyst layer of carrier inner face side, noble metal is at least a among Pt and the Pd, first compound is described first compound of claim 6, and second compound is described second compound of claim 10.
17. the exhaust gas purification catalyst of claim 12, wherein, in described multi-layer catalyst layer, be arranged in the catalyst fines of the catalyst layer of face side, noble metal is Rh, first compound is described first compound of claim 7, and second compound is described second compound of claim 8.
18. the exhaust gas purification catalyst of claim 17, wherein, in described multi-layer catalyst layer, be arranged in the catalyst fines of the catalyst layer of face side, load first compound of noble metal be 40wt%～75wt%, second compound is 25wt%～60wt%.
19. the manufacture method of exhaust gas purification catalyst, this method comprises: the step of preparation catalyst fines and on the carrier inner face, form the step of this catalyst fines, wherein:
The step of described preparation catalyst fines comprises:
On first compound step of carried noble metal and
With the precursor of second compound or second compound be dispersed in the step of carrying out slurryization in the water and
Then with load first compound of noble metal be dispersed in the slurry of described second compound, after drying, carry out sintering and obtain the step of catalyst fines;
The described step that forms catalyst fines on the carrier inner face comprises:
The compound that can disappear when in the catalyst fines that obtains, adding sintering, slurryization is coated on carrier, and dry then, sintering form the step of the catalyst layer of the micropore that has 0.1 μ m～1 μ m in the micropore of catalyst layer.
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CN102470348A (en) * 2009-11-17 2012-05-23 日产自动车株式会社 Exhaust gas purifying catalyst and method for manufacturing the same
CN104039443A (en) * 2012-02-07 2014-09-10 本田技研工业株式会社 Catalyst structure for treating exhaust gas
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