CN1042092A - A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof - Google Patents
A kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method thereof Download PDFInfo
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- CN1042092A CN1042092A CN 88107136 CN88107136A CN1042092A CN 1042092 A CN1042092 A CN 1042092A CN 88107136 CN88107136 CN 88107136 CN 88107136 A CN88107136 A CN 88107136A CN 1042092 A CN1042092 A CN 1042092A
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Abstract
A kind of doped fuel vehicle exhaust that is applicable to purifies the catalyst of usefulness, it is as first carrier with the cordierite honeycomb substrate, to include adhesive, the activated alumina slurries of stabilizing agent are second carrier coating, and composite oxides, the small amount of precious metals formed with base metal and rare earth element are catalytic active component.The present invention also provides this kind Preparation of catalysts method, promptly be coating liquid by the first carrier impregnation activated alumina after, drying, roasting again through the coating liquid of impregnation catalyst active component, are then carried out the drying second time, roasting, hydrogen reduction and are formed ABO
3The complex rare-earth oxidate containing valuable metal type honeycomb catalyst of structure.
Description
The present invention relates to the doped fuel vehicle exhaust and purify a kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst of usefulness and preparation method thereof.
Since the seventies rare earth composite catalyst comes out, it is used in the internal combustion engine purification aspect has carried out number of research projects, no matter it is aspect its composition proportioning or preparation method, of a great variety.
The catalyst that purifying internal combustion engine tail gas is used not only will possess Catalytic Oxygen such as the CO in the dusty gas, total hydrocarbon are changed into harmless CO
2And water, and to adapt to many exacting terms; Impact up to the thermal current more than 1000 ℃ as delivery temperature, components such as the sulphur that exists in the tail gas, lead, phosphorus are to the intoxication of catalyst; Stand the test of the driving of mileage more than 50,000 kilometers and guarantee minimum is reduced in the influence of engine power performance, promptly the device of catalytic cleaner is as far as possible little, active high, factor such as vapour lock is little and price is low.
The U.S., Japan are from late nineteen seventies, and the commercial catalyst of employing is noble metal type, as u.s.p 3,914,389, and Japan Patent 40,878(1976).Though the price of base metal and rare earth mixed oxide catalyst unit volume is lower, as CN85102282A, CN86103200A because their activity are low, uses air speed also little, and the loading amount of catalyst requires many, and is concerning purifying box, also also uneconomical.United States Patent (USP) 3,897 367(1975) adopts RE perovskite admixture Pt, Ru, can improve the performance of catalyst, but contains the Pt amount than higher; Report is also arranged in addition, as Pat.NoJ.57601443, J.61011140, adopt rare earth perovskite catalyst to add small amount of precious metals, but they are to be coated with to be loaded on the alumina globule, cause gas-flow resistance to increase, and, cause auxiliary air to pollute with prolonging and efflorescence service time.
The purpose of this invention is to provide a kind of complex rare-earth oxidate containing valuable metal type honeycomb catalyst and preparation method, make it to satisfy better the needs that the doped fuel vehicle exhaust purifies, further solve the serious problems of the environmental pollution that causes by automobile.
The present invention has ABO for a kind of by what carrier and catalytic active component constituted
3The complex rare-earth oxidate containing valuable metal type honeycomb catalyst of structure, it is characterized in that having parallel duct with inside, its hole density is that the cordierite cellular material of 40-64 hole/square centimeter is first carrier, with the activated alumina slurries that include adhesive, stabilizing agent is second carrier coating, and composite oxides, the small amount of precious metals formed with base metal and rare earth element are that catalytic active component constitutes A
X1A
X2A
X3B
Y1B
Y2B
Y3O
3The catalyst of structure, its A position is formed with alkali metal such as rare earth elements such as two or three La, Ce, Pr, Nd in the periodic table of elements and K, Na and Ca, Sr, alkali earth metals such as Ba, Mg, the B position is formed by metallic elements such as two or three Cu, Mn, Fe, Co, Ni, Cr, Pb, Zr, Pt, Pd in the periodic table of elements, wherein X
1, X
2, X
3Respectively between 0.1-0.9, Y
1, Y
2, Y
3Respectively between 0.999-0.001, and X
1+ X
2+ X
3=1, Y
1+ Y
2+ Y
3=1, Pt or the Pd content in catalytic active component is pressed atomic ratio between 0.001-0.2, and catalytic active component accounts for the 4-10% of whole vehicle weight.
Preparation of catalysts method of the present invention, mainly comprise carrier impregnation is applied liquid, drying, roasting, activation then, it is characterized in that having parallel duct as the inside of first carrier, its cell densities is that the cordierite cellular material of 40-64 hole/square centimeter is immersed in the resistant to elevated temperatures AL that contains stabilizing agent and adhesive
2O
3Slurries in, wherein stabilizing agent is mixed rare-earth oxide and alkaline-earth metal such as Ba, Sr such as La, Ce, Pr, Nd, the content of stabilizing agent accounts for the 1-8% of activated alumina weight.Adhesive is aluminium colloidal sol and hydrochloric acid, a kind of inorganic acid in the nitric acid, and the weight ratio of activated alumina and aluminium colloidal sol is 1: 0.5～2; The concentration of aluminium colloidal sol (is pressed AL
2O
3Meter) contains AL for every milliliter
2O
30.1～0.2 gram.Form second carrier through dry, roasting for the first time then, then honeycomb substrate of this coating activated alumina is immersed in the coating liquid of catalytic active component of the composite oxides formed with base metal and rare earth element, small amount of precious metals, afterwards again through drying for the second time, roasting, be ABO through hydrogen reduction formation structure again
3Catalyst.
The preparation of the second carrier coating slurries: the first step is a preparation aluminium colloidal sol, take by weighing a certain amount of aluminium flake (purity＞99.5%), the HCL that adds 8-15%, in temperature is to add hot reflux under the 60-100 ℃ of condition, treat that aluminium flake and Hcl complete reaction promptly make institute's palpus aluminium colloidal sol, then the active oxidation aluminium powder is mixed in the ball milling cylinder by a certain percentage with aluminium colloidal sol, on ball mill ball milling 18-24 hour again, it is characterized in that alumina powder needed at 500-600 ℃ of preroast 5-7 hour; La, the Ce, mixed rare-earth oxide and the alkaline-earth metal such as Ba, Sr such as Pr, Nd that contain 1-8% in the slurries; The concentration of aluminium colloidal sol (is pressed AL
2O
3) contain AL for every milliliter
2O
30.1-0.2 gram, the weight ratio of alumina powder and aluminium colloidal sol is 1: 0.5-2; The pH value of regulating aluminium colloidal sol with a kind of inorganic acid such as hydrochloric acid or nitric acid is 2-4.
To the gasoline car catalyst for clarifying, adopt the honeycomb ceramics of density 40-64 hole, hole/square centimeter, it has bigger geometric outer surface, the carrying out that helps catalytic reaction adds adhesive and can make second carrier coating even, firmly in the aluminium oxide slurries, unlikelyly under thermal shock, make coating shedding, to guarantee the carrying capacity that is coated with of catalytic active component, in the aluminium oxide slurries, add the heat endurance that stabilizing agent can improve second carrier, promptly improve the phase transition temperature of activated alumina and unlikely reduction surface area.
By catalyst A BO
3Structure form to calculate the aqueous solution of preparation nitrate mixture, add impregnating agent altogether simultaneously, impregnating agent can be oxalic acid altogether, tartaric acid, or citric acid etc., add above-mentioned these common impregnating agent and can make the active component mixed liquor stable, and improve catalyst activity, can reduce forming ABO simultaneously greatly
3The sintering temperature of structure catalyst and shortening roasting time.Generally do not add the above-mentioned solution of impregnating agent altogether and will form ABO
3The catalyst of structure must be at roasting a couple of days more than 1000 ℃ (as USP 3,897,367 reports), and has added common impregnating agent, need only be 700 ℃-800 ℃ following roasting a few hours, and this is that economic worth is very arranged in industrial production.
The preparation catalyst all will pass through redrying, roasting process, behind the first carrier impregnation activated alumina slurries, dry through for the first time, roasting, the coating liquid of the second carrier impregnation catalytic active component is after drying and roasting for the second time, its once, redrying all at room temperature, dried in the shade 2 hours, dried 10-30 minute down at 80 ℃-90 ℃ through micro-wave oven again, again through baking oven 100-120 ℃ of down oven dry 2-3 hour, bakes to burn the article is 850 ℃ of following roastings 3 hours in muffle furnace, after baking is 300 ℃ of-800 ℃ of roastings 2.5 hours in muffle furnace.Roasting can make active component be uniformly dispersed at carrier surface after the microwave drying, in case active component, influences catalytic activity and catalyst outward appearance in the carrier surface one-way flow.The catalyst good through roasting must promptly get required catalyst in 2 hours by logical hydrogen reducing under 350 ℃-450 ℃.
The present invention compared with prior art has following characteristics and good effect:
1, on structure is formed, adopt hole density be the cordierite honeycomb bodies of 40-64 hole/square centimeter as catalyst matrix, have bigger geometric jacquard patterning unit surface; Add adhesive and stabilizing agent in second alumina catalyst support, can make aluminum oxide coating layer firmly, evenly, high temperature resistant; It is that main complex rare-earth oxidate containing valuable metal partly replaces noble metal that the catalyst activity component adopts base metal, and cost is lower, and raw material is easy to get.
2, on preparation technology, in active component, add impregnating agent altogether, can make the solution stable for extended periods of time, can form ABO at a lower temperature fast
3The catalyst of crystal structure has shortened the Catalyst Production cycle greatly.
3, on catalyst performance, the present invention can match in excellence or beauty with noble metal catalyst.Be in particular in: (1) catalyst initiation temperature is low, and the initiation temperature of CO and HC (referring to that they transform 50% o'clock required minimum temperature) is respectively 250 ℃ and 270 ℃; (2) the air speed characteristic is good, can use air speed to reach 100,000-120,000 hr
-1Thereby, do not influence engine power performance reason catalyst loading amount more; (3) can stand high temperature thermal shocking, what maximum operation (service) temperature can reach that 1000 ℃ (4) particularly point out is that this catalyst has stronger anti-Pb, S, P poisoning performance, we use Pb content to be higher than in the gasoline of the actual use of China the above gasoline (i.e. every liter of gasoline of 6 gram Pb/) of 1 order of magnitude of Pb content to strengthen to poison and test, operation is nearly 300 hours continuously, and catalytic activity is not fallen as follows.These all are that similar catalyst institute is incomparable.(5) this catalyst life can stand above long-term continuous use of 50,000 KM, and activity does not have obviously decline.
Specifically describe this catalyst below in conjunction with embodiment, the test result of method for preparing catalyst and catalyst performance:
Embodiment 1
Prepare resistant to elevated temperatures Al
2O
3Slurries take by weighing 130 gram aluminium flakes earlier, and (purity＞99.5%), the HCL1000 milliliter of adding 10% adds hot reflux in conical flask, and temperature is controlled at 80～90 ℃, treats promptly to make standby aluminium colloidal sol after aluminium flake and the HCL complete reaction.Take by weighing 6 hours alumina powder of 550 ℃ of preroast, 910 grams then, add La respectively
2O
332g, CeO
23.6g and barium nitrate 46.5g, (elder generation dilutes the colloidal sol of the above-mentioned concentration of 800 grams with 600 ml distilled waters before adding to mix the above-mentioned aluminium colloidal sol for preparing 800 grams of back adding, and to regulate PH with HCL be 3-3.5), in the ball milling cylinder, use about 18 hours of ball mill ball milling then, promptly make Al
2O
3Slurries.
The cordierite cellular material that will have its hole density of parallel duct as the inside of first carrier and be 40-64 hole/square centimeter is immersed in the AL that makes above
2O
3After the slurries 10 minutes, under room temperature, dried in the shade 2 hours with the raffinate that compressed air is blown away in the duct, again through micro-wave oven 80 ℃ of oven dry 10 minutes, again through baking oven 100 ℃ of oven dry 2 hours, then 850 ℃ of roastings 3 hours in muffle furnace.
According to prescription La0.8 Sr0.2 Co0.98 Pt0.02 O
3Take by weighing La(NO
3)
36H
2O 13.86 grams, Sr(No
3)
21.6 gram, Co(NO
3)
26H
2O 11.52 grams mix the back and add the dissolving of 50 ml distilled waters, add 32 milliliters of the platinum solution and citric acid 16.8 grams of 4.9 grams per liters again, will scribble Al then
2O
3Cordierite honeycomb bodies immersed in this solution 15 minutes, take out with compressed air (0.3-0.5Kg/cm
2) blow away raffinate in the duct, dried in the shade under the room temperature 2 hours, 80 ℃ of dryings are 10 minutes in little stove, again in baking oven 100 ℃ the oven dry 2 hours, put into 300 ℃ of roastings of muffle furnace half an hour then, nitrate is decomposed, again 800 ℃ of roastings 2 hours, logical again hydrogen promptly obtains catalyst prod behind 400 ℃ of reductase 12s hour.This kind catalyst performance is measured as follows:
(1) estimate initial activity with the distribution method: use flow reactor, in containing the air of 0.5%CO, air speed is 30,000 hr
-1Condition under, the relation of its temperature and conversion ratio is as shown in table 1:
Table 1
| Catalyst inlet temperature ℃ | 158 | 175 | 180 |
| CO conversion ratio (%) | 21.6 | 74.0 | 100 |
(2) anti-So
2Poisoning performance: in flow reactor, feeding contains 0.4% CO and 50PPm So
2Air, feed 10% steam simultaneously, reaction temperature is used 350 ℃, turns round continuously 13 hours, the CO conversion ratio still remains on 100%.
(3) 6 ten thousand KM decide border driving examination, catalyst are installed on 212 jeeps of Beijing nearly 2 liters of catalyst loading amount, high-speed 120,000 hr
-1, CO and HC conversion ratio are as shown in table 2 with the variation of mileage.The average conversion of CO and HC is respectively 79.3% and 62.2%.
Table 2
| Ten thousand kilometers | 0.016 | 0.46 | 1.24 | 1.82 | 3.35 | 3.58 |
| CO conversion ratio (%) | 72 | 87 | 70 | 77 | 94 | 94 |
| HC conversion ratio (%) | 62 | 72 | 63 | 74 | 65 | 65 |
| Ten thousand kilometers | 3.74 | 4.21 | 6.03 |
| CO conversion ratio (%) | 86 | 67 | 67 |
| HC conversion ratio (%) | 45 | 73 | 41 |
The result shows that this catalyst is not feeding under the situation of auxiliary air, uses doped fuel, and through the long-time running of 60,000 KM, activity is still satisfactory.
Embodiment 2
According to prescription La
0.8Sr
0.2Mn
0.5Ni
0.48Pd
0.02O
3Take by weighing La(No
3)
36H
2O3.8 restrains Sr(NO
3)
22.54 gram, Mn(NO
3)
2(50% manganese nitrate solution) 8.6 milliliters, Ni(No
3)
24.6 gram adds citric acid 8.4 grams, uses dissolved in distilled water, as carrier in the example 1 at Al
2o
3Impregnation drying, roasting make second carrier in the slurries, example 1 was with this carrier impregnation catalyst solution 10 minutes for another example, take out drying, roasting, again it is immersed in the palladium solution of 0.79 gram Pd/ milliliter and to take out dryly in 1 minute, hour promptly get catalyst prod through logical hydrogen at 420 ℃ of reductase 12s 500 ℃ of roastings of muffle furnace 2 hours again.Table 3 listed this catalyst on the KG550B gasoline engine through nearly 300 hours life test result.The catalyst inlet temperature is 390 ℃, and air speed is 30,000 hr
-1, Pb content is 6 gram Pb/ liters in the gasoline.Comparing its life-span with some similar catalyst almost exceeds an order of magnitude.
Table 3
| Running time hr | Beginning | 30 | 115 | 129 | 142 | 165 |
| CO conversion ratio % | 99.8 | 99.5 | 99.5 | 97.7 | 99.4 | 91.4 |
| HC conversion ratio % | 88.5 | 90.2 | 92.2 | 70.6 | 71.5 | 68.4 |
| Running time hr | 189 | 232 | 260 |
| CO conversion ratio % | 91.4 | 99.7 | 99.8 |
| HC conversion ratio % | 67.6 | 94.8 | 87.3 |
Embodiment 3
According to prescription La0.8 Sr0.2 Mn0.5 Ni0.48 Pd0.02 O
3Take by weighing La(NO
3)
36H
2O 97.3 grams, Sr(NO
3)
26.34 gram, Mn(NO
3)
2(50% manganese nitrate) solution 211.2 grams, Ni(NO
3)
26H
2O 116.0 grams, after the adding distil water dissolving, 70 milliliters of palladium solution that add 0.015 gram Pd/ milliliter again, below make catalyst by example 1 described step, this catalyst that makes is investigated its air speed characteristic with KG-550B type gasoline engine tail gas, the stationary catalyst bed inlet temperature is 290 ℃ (lead tolerance is 6 gram Pb/ liters in the gasoline), and the result is as shown in table 4:
Table 4
| Air speed is worth ten thousand Hr -1 | CO conversion ratio (%) | HC conversion ratio (%) |
| 3 | 99.5 | 90.5 |
| 5 | 99.5 | 91.8 |
| 6 | 99.6 | 90.4 |
| 8 | 99.5 | 91.6 |
| 9 | 98.4 | 90.0 |
| 10 | 95.1 | 84.5 |
Embodiment 4
According to prescription La 0.8 Sr 0.2 Co0.098 Pt0.01 Pt0.01 O
3Take by weighing La(No
3)
36H
2O 13.86g, Sr(NO
3)
21.69g, Co(NO
3)
26H
2O 11.52g mixes the back dissolved in distilled water, 4.4 milliliters of palladium solution that add 16 milliliters of the platinum solution of 4.9 grams per liters and 9.67 grams per liters again, undertaken obtaining catalyst prod by the step of example 1, it is as shown in table 5 that the catalyst that makes is recorded under the different sintering temperatures 2 hours surface area result of roasting with BC-1 type specific surface analyzer:
Table 5
| Sintering temperature ℃ | 500 | 600 | 700 | 800 |
| Catalyst surface area m 2/g | 9.9 | 8.6 | 8.4 | 8.8 |
Measurement result shows: the roasting 2 hours under said temperature of this catalyst, surface area does not have significant change, again its heat ageing under 1000 ℃ of high temperature is measured its activity change, CO as a result in 3 hours
T90%(referring to that CO transforms 90% o'clock temperature) brought up to about 200 ℃ from 181 ℃, and The above results shows that this catalyst has good heat endurance.
Embodiment 5
According to K
0.2La
0.6Sr
0.2Zr
0.98Pd
0.02O
3Prescription is got KNO
30.81 gram, La(NO
3)
26H
2O 10.4 gram Sr(NO
3)
21.69 gram, ZrO(NO
3)
2.2H
2O 10.5 grams add dissolved in distilled water and add 0.04 gram PdCL again
23.6 milliliters of the solution of/milliliter mix the back and add 8.4 gram citric acids, make catalyst sample by example 1 method, carry out the catalyst activity evaluation by the method and the condition of example 1, the results are shown in table 6:
| Catalyst inlet temperature ℃ | 174 | 176 | 189 |
| CO conversion ratio (%) | 33 | 90.6 | 100 |
Claims (13)
1, a kind of have an ABO by what carrier and catalytic active component constituted
3The complex rare-earth oxidate containing valuable metal type honeycomb catalyst of structure, it is characterized in that having parallel duct with inside, its hole density is that the cordierite cellular material of 40-64 hole/square centimeter is first carrier, with the activated alumina slurries that include adhesive, stabilizing agent is second carrier coating, and composite oxides, the small amount of precious metals formed with base metal and rare earth element are that catalytic active component constitutes A
X1A
X2A
X3B
Y1B
Y2B
Y3O
3The catalyst of structure, its A position is formed with alkali metal such as rare earth elements such as two or three La, Ce, Pr, Nd, K, Na in the periodic table of elements and Mg, Ca, alkali earth metals such as Sr, Ba, the B position does not have to belong to by metals such as two or three Cu, Mn, Fe, Co, Ni, Cr, Pb, Zr, Pt, Pd in the periodic table and is formed, wherein X
1, X
2, X
3Respectively between 0.1-0.9, Y
1, Y
2, Y
3Respectively between 0.999-0.001, and X
1+ X
2+ X
3=1, Y
1+ Y
2+ Y
3=1.Pt or the Pd content in catalytic active component is pressed atomic ratio between 0.001-0.2.
2, according to the described catalyst of claim 1, it is characterized in that adhesive that the activated alumina slurries as second carrier coating include is a kind of inorganic acid in aluminium colloidal sol and hydrochloric acid, the nitric acid, the weight ratio of activated alumina and aluminium colloidal sol is 1: 0.5-2, the concentration of aluminium colloidal sol (is pressed AL
2O
3Meter) contains AL for every milliliter
2O
30.1-0.2 gram.
3, according to the described catalyst of claim 1, it is characterized in that the stabilizing agent that the activated alumina slurries as second carrier coating include is mixed rare-earth oxide and alkaline-earth metal such as Ba, Sr such as La, Ce, Pr, Nd, the content of stabilizing agent accounts for the 1-8% of activated alumina.
4,, it is characterized in that catalytic active component accounts for the 4-10% of whole vehicle weight according to claim 1,2,3 described catalyst.
5, a kind of according to the described Preparation of catalysts method of claim 1, mainly comprise carrier impregnation is applied liquid, drying, roasting, activation then, it is characterized in that having parallel duct as the inside of first carrier, its hole density is that the cordierite cellular material of 40-64 hole/square centimeter is immersed in the resistant to elevated temperatures AL that contains stabilizing agent, adhesive
2O
3Slurries in, form second carrier through dry, roasting for the first time then, then honeycomb substrate of this coating activated alumina is immersed in the coating liquid of catalytic active component of the composite oxides formed with base metal and rare earth element, small amount of precious metals, afterwards again through drying for the second time, roasting, be ABO through hydrogen reduction formation structure again
3Catalyst.
6, according to the described Preparation of catalysts method of claim 5, it is characterized in that AL
2O
3Contained adhesive is a kind of inorganic acid in aluminium colloidal sol and hydrochloric acid, the nitric acid in the slurries, and the weight ratio of activated alumina and aluminium colloidal sol is 1: 0.5-2; The concentration of aluminium colloidal sol (is pressed AL
2O
3Meter) contains AL for every milliliter
2O
30.1-0.2 gram.
7, according to the described Preparation of catalysts method of claim 5, it is characterized in that AL
2O
3Stabilizing agent contained in the slurries is mixed rare-earth oxide and alkaline-earth metal such as Ba, Sr such as La, Ce, Pr, Nd, and the content of stabilizing agent accounts for the 1-8% of activated alumina weight.
8,, it is characterized in that the activity of such catalysts component is according to A according to the described Preparation of catalysts method of claim 5
X1A
X2A
X3B
Y1B
Y2B
Y3O
3The chemical composition of structure is calculated and preparation, its A position is formed with alkali metal such as rare earth elements such as two or three La, Ce, Pr, Nd in the periodic table of elements and K, Na and Ca, Sr, alkali earth metals such as Mg, Ba, the B position is formed by metallic elements such as two or three Cu, Mn, Fe, Co, Ni, Cr, Pb, Zr, Pt, Pd in the periodic table, wherein X
1, X
2, X
3Respectively between 0.1-0.9, Y
1, Y
2, Y
3Respectively between 0.999-0.001, X
1+ X
2+ X
3=1, Y
1+ Y
2+ Y
3=1Pt or the Pd content in catalytic active component is pressed atomic ratio between 0.001-0.2.
9, according to claim 5,8 described Preparation of catalysts methods, it is characterized in that catalytic active component is the aqueous solution that is mixed with the nitrate mixture, add impregnating agent altogether simultaneously.
10,, it is characterized in that the common impregnating agent that adds is oxalic acid, tartaric acid or citric acid according to the method for making of the described catalyst of claim 9.
11,, it is characterized in that the first carrier impregnation active A L according to the method for making of the described catalyst of claim 5
2O
3Behind the slurries, through dry, roasting for the first time, second carrier carries out dry, the roasting second time behind the coating liquid of impregnation catalyst active component, it once, redrying is all through at room temperature drying in the shade 2 hours, dried 10-30 minute down at 80 ℃-90 ℃ through micro-wave oven again, again through baking oven 100 ℃-120 ℃ down oven dry 2-3 hour, bakes to burn the article is 850 ℃ of following roastings 3 hours in muffle furnace, after baking is 300 ℃ of-800 ℃ of roastings 2.5 hours in muffle furnace.
12, according to the method for making of the described catalyst of claim 5, the temperature that it is characterized in that hydrogen reduction is 350 ℃-450 ℃, and the time is 2 hours.
13,, it is characterized in that the time of the each dipping of carrier is several minutes to 1 hour, but the mode single-steeping of dipping also can be taked repeatedly repeated impregnations according to the method for making of the described catalyst of claim 5.
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|---|---|---|---|
| CN 88107136 CN1021412C (en) | 1988-10-26 | 1988-10-26 | Honeycomb catalyst of rare earth composite oxide type containing noble metal and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88107136 CN1021412C (en) | 1988-10-26 | 1988-10-26 | Honeycomb catalyst of rare earth composite oxide type containing noble metal and its preparing method |
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|---|---|
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| CN1021412C CN1021412C (en) | 1993-06-30 |
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ID=4834519
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|---|---|---|---|
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|---|---|
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| CN1045549C (en) * | 1993-11-26 | 1999-10-13 | 中国科学技术大学 | Three-effect catalyst and preparing method containing copper and lanthanum-oxides, platinum and rhodium |
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1988
- 1988-10-26 CN CN 88107136 patent/CN1021412C/en not_active Expired - Fee Related
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