CN1473651A - Noble metal-rare-earth catalyst for purifying waste gas and its preparation - Google Patents
Noble metal-rare-earth catalyst for purifying waste gas and its preparation Download PDFInfo
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- CN1473651A CN1473651A CNA021287562A CN02128756A CN1473651A CN 1473651 A CN1473651 A CN 1473651A CN A021287562 A CNA021287562 A CN A021287562A CN 02128756 A CN02128756 A CN 02128756A CN 1473651 A CN1473651 A CN 1473651A
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Abstract
The catalyst includes alumina, RE metal oxide, composite Al-La oxide, and active metal Pt, Pd and Rh. It features that the mixed oxide grain with aluina, cerium oxide and Al-La oxide carries at least one of Pt and Pd as well as Rh. The mixed oxide grain is prepared through dissolving salt of Al, Ce and La in water, adding NH3OH to produce precipitate, and heating to decompose the precipitate. The catalyst preparing process includes carrying mixed oxide grains onto the carrier, carrying least one of Pt and Pd onto the mixed oxide grains, and carrying Rh finally. The catalyst is especially suitable for purifying automobile tail gas of gasoline engine near the theoretical air/fuel ratio, and has the features of lasting use, less noble metal consumption, high purifying efficiency and powerful sulfur poison resistance.
Description
Technical field
The present invention relates to noble metal one rare earth oxide exhaust gas purifying catalyst and preparation method thereof, be specially adapted near the purifying vehicle exhaust of petrol engine chemically correct fuel.
Background technology
Vehicle exhaust is the important pollution sources of atmospheric environment.Catalyst is applied to automobile tail gas purification system, makes carbon monoxide CO, the hydrocarbon HC and the nitrogen oxide NO that produce in the engine working process
xBe converted into innocuous gas carbon dioxide, steam and nitrogen, remain now and an important topic of catalytic field from now on.Press stoichiometric air-fuel ratio or lower slightly air-fuel ratio when petrol engine, when for example working between 14.7～14.4, the catalyst that contains noble metals such as rare earth, platinum, palladium and rhodium can effectively transform above-mentioned three kinds of gases simultaneously.Therefore, this catalyst is often referred to as " three-way catalyst ".Typical this catalyst adopts higher noble metal loading to reach higher transformation efficiency usually, to satisfy more and more harsher discharge standard.This catalyst is comparatively expensive.US Patent specification US4843056 (on June 27th, 1989) discloses a kind of exhaust gas purifying catalyst.Its formation comprises successively: be loaded with at least a rare earth oxide on the alumina particle, the intermediate layer supports rhodium, supports at least a of platinum, palladium at last.Its preparation method is followed successively by corresponding to formation: support alumina particle on the carrier, support at least a rare earth oxide on the alumina particle, support rhodium on the rare earth oxide, support at least a of platinum, palladium at last.This catalyst bullion content is higher, has increased financial cost, and its anti-lead poisoning performance has much room for improvement, and is narrower to the gasoline adaptability that sulphur and rare hydrocarbon content are high.
Summary of the invention
The object of the invention is to provide the gasoline engine car tai-gas clean-up catalyst that low, the anti-lead poisoning ability of a kind of bullion content is strong, sulphur and rare hydrocarbon content scope had the broad adaptive capacity.
Another object of the present invention provides aforementioned gasoline engine car tai-gas clean-up catalyst preparation method.
The tai-gas clean-up catalyst composition of the object of the invention one comprises aluminium oxide, rare-earth oxide, aluminium lanthanium complex oxide, reactive metal platinum, palladium, rhodium, characteristics are to have supported at least a of platinum, palladium on the mixed oxide particle that includes aluminium oxide, cerium oxide, aluminium lanthanium complex oxide, support rhodium subsequently, adopt the following order coprecipitation technology to prepare mixed oxide particle: 1. the soluble salt with aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment; 2. add 1. gained sediment of thermal decomposition steps.
For the better exhaust gas purifying catalyst of obtained performance, can do following further adjustment to the catalyst technology scheme.
Mixed oxide particle is coated on the honeycomb substrate mixed oxide particle weight: vehicle weight=0.1～0.3: 1.
With respect to the carrier of unit volume, the gross weight that supports of reactive metal platinum, palladium, rhodium is 5～35g/ft
3, this supports gross weight can further be adjusted into 10～16g/ft
3, can support any of platinum or palladium on the mixed oxide particle, platinum, palladium, rhodium weight ratio are rhodium: platinum or palladium=1: 2～10; Perhaps supported the mixture of platinum and palladium on the mixed oxide particle, platinum, palladium, rhodium weight ratio are: platinum: palladium=1: 0.3～3, rhodium: (platinum+palladium)=1: 2～10.
Can include titanium oxide TiO in the mixed oxide particle
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a, titanium oxide TiO
2And/or zirconia ZrO
2And/or barium monoxide BaO and/or magnesia MgO: contain titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a mixed oxide particle=0～8: 100, this ratio can further be adjusted into 0.5～8: 100, and this mixed oxide particle that contains additive is by step 2. gained co-precipitation mixed oxide particle and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO directly mix and obtain; Can also include praseodymium oxide PrO in the mixed oxide particle
2, europium oxide Eu
2O
3At least a, praseodymium oxide PrO
2And/or europium oxide Eu
2O
3: contain praseodymium oxide PrO
2And/or europium oxide Eu
2O
3Mixed oxide particle=0～2: 100, this praseodymium oxide PrO that contains
2, europium oxide Eu
2O
3Mixed oxide particle by step 2. gained co-precipitation mixed oxide particle and praseodymium oxide PrO
2, europium oxide Eu
2O
3Directly mix and obtain.
Weight ratio with the oxide metering before the 1. middle aluminium of step, cerium, the dissolving of lanthanum soluble salt is CeO
2: (CeO
2+ La
2O
3)=0.4～0.7: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.3～0.7: 1; The step heat decomposition temperature that adds 2. is 500～700 ℃.
Realize that the object of the invention two technical measures comprise following process steps successively: 1. on catalyst carrier, support mixed oxide particle, 2. on the mixed oxide particle coating, support at least a of platinum, palladium, 3. support rhodium at last.
Above-mentioned method for preparing catalyst is done following further improvement, can obtain better invention effect.
The catalyst carrier that invention is used can be a honeycomb.Can include aluminium oxide, cerium oxide, aluminium lanthanium complex oxide in preparation method's step mixed oxide particle 1., its preparation adopts following process steps in sequence: A that the soluble salt of aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment, and B adds thermal decomposition steps A gained sediment for 500～700 ℃.Also can include aluminium oxide, cerium oxide, aluminium lanthanium complex oxide and titanium oxide TiO in preparation method's step mixed oxide particle 1.
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a, titanium oxide TiO
2With or zirconia ZrO
2And/or barium monoxide BaO and/or magnesia MgO: contain titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a mixed oxide particle=0～8: 100, its preparation adopts following process steps in sequence: A that the soluble salt of aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment, and B adds thermal decomposition steps A gained sediment for 500～700 ℃, and C is with step B gained analyte and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO mix.Can also include aluminium oxide, cerium oxide, aluminium lanthanium complex oxide and praseodymium oxide PrO in preparation method's step mixed oxide particle 1.
2, europium oxide Eu
2O
3At least a, praseodymium oxide PrO
2And/or europium oxide Eu
2O
3: contain praseodymium oxide PrO
2And/or europium oxide Eu
2O
3Mixed oxide particle=0～2: 100, its preparation adopts following process steps in sequence: A that the soluble salt of aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment, and B adds the 1. described sediment of thermal decomposition steps for 500～700 ℃, and C is with step B gained analyte and praseodymium oxide PrO
2, europium oxide Eu
2O
3Mix.
The method for preparing catalyst step 1. support can with mixed oxide particle water sample sluny impregnation or the spray carrier, step 2. support the carrier that the mixed oxide particle coating can be arranged with the chloro-complex aqueous solution of platinum, palladium dipping or spray load, step 3. support the carrier that can 2. handle through step with the chloro-complex aqueous solution dipping or the spray of rhodium.
The present invention has following advantage:
(1) the three-way catalyst good endurance of the present invention's preparation, the entrucking experiment life-span is above 80,000 kilometers.
(2) invention adopts coprecipitation method to prepare mixed oxide particle, and with alkaline solution co-precipitation aluminium, cerium, lanthanum three's soluble salt, aluminium, lanthanum enter in the same compound when co-precipitation, and the product that obtains after adding thermal decomposition is an aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThree's mixed oxide.The X-ray diffraction is observed and to be shown and do not have La in the co-precipitation thermal decomposition product
2O
3Oxide illustrates the three kinds of possibilities that have of lanthanum: 1. form and stablize the lanthana crystal formation, 2. lanthanum enters in other oxide lattices, but owing to calcining heat is not enough, does not form the product type, is 3. wrapped up by other oxides in precipitation process.The X-ray diffraction was found after 700 ℃ of calcinings supported the carrier of coating, included activated alumina, cerium oxide and aluminium lanthanium complex oxide in the coating material.This explanation lanthanum is deposited in precipitation process on the alpha-alumina crystals surface, has an effect in the entering part aluminium oxide lattice with adsorb oxygen or Lattice Oxygen.Lanthanum enters the aluminium oxide lattice slows down the alpha-alumina crystals speed of growth, thereby obtains tiny crystal grain, has improved aluminium oxide crystal transfer temperature.The catalyst of this compound mixed oxide preparation with only with aluminium oxide and rare earth oxide directly mixed must catalyst compare, greatly improved catalyst to HC, CO, NO
xCatalytic conversion efficiency.Compare with direct mixed method, the inventor thinks that this coprecipitation method can also make the even mixability that reaches molecular level between component, can quicken the reaction between component greatly when calcining, thereby improve catalytic activity and durability.
(3) mixed-metal oxides and the additive material of use average grain diameter 500～700 dusts, the collision probability when having improved the specific surface of catalyst and having contacted with tail gas has promoted the catalyst transformation efficiency.
(4) layering supports platinum and/or palladium, rhodium, has reached with traditional three-way catalyst and has compared the purpose that reduces noble metal dosage to greatest extent, and catalyst is still possessed excellent tail gas clean-up performance simultaneously.Noble metal loading mode of the present invention at first contacts tail gas with the rhodium layer, realize the catalytic reduction of NOx.HC and CO are diffused in the catalyst coat subsequently, carry out catalyzed conversion by platinum and/or palladium.Discharge duplet in the NOx reduction process, accept proton, these duplets just in time are that platinum and/or palladium catalyzed conversion HC and CO are used, and therefore, it has served as reducing agent to a certain extent.Just because of this, this arrangement mode that supports of noble metal has improved the transformation efficiency of catalyst to NOx, HC, CO effectively.
(5) skin supports rhodium, has reduced the sensitiveness of palladium to sulphur, has improved the anti-poisoning capability of catalyst, helps keeping the high-effect of catalyst integral body.
(6) in catalyst, add rare earth metal the cost of catalyst is descended, the anti-lead poisoning ability of catalyst is strengthened.
(7) catalyst transformation efficiency height of the present invention, the CO transformation efficiency reaches 90～99%, and the HC transformation efficiency reaches 90～95%, and the NOx transformation efficiency reaches 85～90%.
(8) the car load discharge performance of installation catalyst of the present invention reaches European II standard.
The specific embodiment
Triple effect exhaust gas purifying catalyst provided by the invention and preparation method thereof has high relatively rare earth element loading and low noble metal loading characteristics, to HC, CO, NO in the petrol engine tail gas
xThe catalyzed conversion excellent performance.It constitutes with the aluminium oxide Al that includes with the coprecipitation method preparation
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZMixed oxide particle be that basic selectivity adds titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO at least a or praseodymium oxide PrO
2, europium oxide Eu
2O
3At least a, support at least a of platinum, palladium subsequently thereon, support rhodium at last, through calcining, decompose and to obtain catalyst.The key of invention is aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThree's mixed oxide.The inventor finds when adopting coprecipitation method to prepare oxide particle.During with alkaline solution co-precipitation aluminium Al, cerium Ce, lanthanum La three's soluble salt, aluminium Al and lanthanum La enter in the same compound when co-precipitation, and what obtain after adding thermal decomposition is aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThere is not La in three's mixed oxide in the co-precipitation thermal decomposition product
2O
3Oxide.The inventor guesses, and this is owing to the approximation and relative homogeneous distributivity of neighbour's metallic atom in the oxide lattice, causes the change of compound structure, forms the aluminium lanthanium complex oxide after thermal decomposition.Here use aluminium lanthanium complex oxide La
XAl
YO
2Form of presentation, show that the inventor still makes co-precipitation gained aluminium lanthanum compound and thermal decomposition gained aluminium lanthanum compound and determine to characterize, so have the uncertain footnote X of numerical value, Y, Z in the chemical formula.Among the present invention, adopt the chemical coprecipitation technology to prepare aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThree's mixed oxide is about to aluminium oxide Al
2O
3, cerium oxide CeO
2, lanthana La
2O
3Three's the soluble salt for example nitrate of nitrate, sulfate, chlorate or band chlorion is dissolved in the water, and reaches about 10 with ammonium hydroxide adjusting ph value and realizes co-precipitation, and 500～700 ℃ add the mixed oxide particle that thermal decomposition obtains the three subsequently.For the purpose that realization chemical coprecipitation technique of the present invention will reach, the form of aluminium Al, cerium Ce, lanthanum La soluble salt includes but not limited to above-mentioned several, the solvent that uses is not limited to water, precipitating reagent includes but not limited to ammonium hydroxide, and the temperature range that adds thermal decomposition can also be done the adjustment that exceeds the scope of the invention.In addition, follow principle of the present invention, can also find the preparation aluminium oxide Al except that the chemical coprecipitation technology
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZOther technology of three's mixed oxide.
As mentioned above, the metallic element that constitutes mixed-metal oxides will contain aluminium, cerium and lanthanum at least, but can comprise other rare earth metal such as europium and praseodymium.In mixed-metal oxides, the relative amount between various metallic elements must keep the balance in the certain limit.Preparing aluminium oxide Al with chemical coprecipitation technique
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZDuring three's mixed oxide, the proportioning of aluminium Al, cerium Ce, lanthanum La soluble salt is the benchmark metering with its metal oxide total weight percent, and promptly aluminium Al, cerium Ce, lanthanum La soluble salt are respectively through aluminium oxide Al
2O
3, lanthana La
2O
3, cerium oxide CeO
2Conversion obtains.With aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThe three is in master's the mixed oxide, the europium oxide Eu that selectivity contains
2O
3, praseodymium oxide PrO
2At least a and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO at least a, be mete-wand with the mixed oxide gross weight that includes these additives or rare earth oxide additive, with aluminium oxide Al
2O
3, cerium oxide CeO
2, aluminium lanthanium complex oxide La
XAl
YO
ZThe method that these additives of three's mixed oxide and this or rare earth oxide additive directly mix.Europium oxide Eu
2O
3, praseodymium oxide PrO
2, titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO can obtain by market.
For formation is applied to the coating of carrier surface, the grain diameter of mixed-metal oxides and stabiliser materials is on average better less than 1000 dusts, and is on average better at 200～900 dusts, and granular size is best at 500～700 dusts.Along with the reduction of grain graininess, catalyst has higher transformation efficiency when contacting with tail gas.
For the purpose of the present invention, carrier may be to exist with any one configuration state, and that often uses is integral honeycomb structure, textile fabric shape structure, corrugated flake structure or layer structure.In order effectively catalyst to be applied to automobile tail gas purification system, the catalyst of invention is deposition or is coated in by the good material of a kind of high-temperature stable, electrical insulation capability for example on the mechanical honeycomb substrate made such as cordierite, mullite.The preferred mechanical honeycomb substrate comprises a kind of alumina silicate list lithium salts structure, i.e. cordierite.Preferred every liter cordierite can provide with N
250～1000m of absorption measurement
2Surface area.The carrier hole gap density should be consistent to greatest extent with the pressure reduction, and is preferable so that 200～800 holes to be arranged on this carrier cross-sectional area per square inch.But this structure is not crucial to catalyst of the present invention, can find to also have a lot of other materials and structure to can be used for the present invention by the present invention for those skilled in the art.
The present invention adopts carrier surface oxide coating well known to those skilled in the art to support technology, and the mixed slurry that is about to mixed-metal oxides particle and/or oxide stabilizer particle is coated on the carrier.For example, on carrier, apply mixed slurry, then unnecessary slip in the carrier duct is blown away,, and, make the oxide in the coating obtain complete ceramic structure in 700 ℃ of following calcinings of temperature commonly used 3 hours afterwards with its oven dry by dipping or spraying method.For making the mixed oxide coatings amount reach 10～30wt.% of vehicle weight, may support in the process through repeatedly coating in coating.
According to the present invention, calculate with carrier outward appearance volume, with respect to containing gross weight 5～35g/ft on the carrier outward appearance volume carrier coating
3(ft in the formula
3Be the carrier bulk dimension: noble metal cubic feet), noble metal loading 10～30g/ft
3The time catalytic effect preferable, 10～16g/ft
3The time the most desirable.Here, carrier outward appearance volume is meant, according to the volume that the monnolithic case size of carrier calculates, do not consider the volume part that carrier inside is got rid of because of containing duct, pipeline, hole or similar spaces.For example to the cylindrical honeycomb carrier, carrier outward appearance volume is cylindrical cross-section area and the high product of post, does not consider the part of getting rid of because of preparation honeycomb duct.Among the present invention, noble metal supports and is divided into two stages.Phase I supports at least a of platinum, palladium on the mixed oxide coatings with impregnation method, and the loading mode during mixture can be platinum, palladium random order.Second stage supports rhodium with impregnation method finishing on the carrier coating that platinum and/or palladium support.Last gained catalyst only contains rhodium and does not contain above-mentioned other noble metal from the outside outermost layer of carrier, and platinum and/or palladium support in the layer not rhodium-containing.The present invention adopts noble metal soluble precursor compound wet impregnation to finish noble metal and supports, and the noble metal soluble compound includes but not limited to chlorate, nitrate.Those skilled in the art can find that other precursor compound of noble metal is also applicable to the present invention.Behind the cated carrier of noble metal precursor liquid solution dip coating, dry and thermal decomposition precursor compound obtains noble metal or metal oxide containing precious metals.In addition, except that this liquid phase is mixed the method that supports noble metal, also can use the method for precious metal salt solid-state conversion under 300～500 ℃ to realize that noble metal supports.
The aluminum nitrate purity that the present invention uses is technical pure, by the aluminium oxide Al of aluminum nitrate acquisition
2O
3Can be α, γ, β type.Cerium, lanthanum soluble salt purity are not less than 99% and are technical grade.Europium oxide Eu
2O
3, praseodymium oxide PrO
2, titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO purity be technical pure.Ammoniacal liquor purity technical grade.Deionized water is used in invention.Aforementioned agents, raw material all can obtain from market channel.Noble metal platinum, palladium, rhodium purity are all greater than 99.99%, and precious metal raw material can obtain from legitimate channels.Embodiment 1
Weigh 10kg Al (NO
3)
3, 3.8kg La (NO
3)
36H
2O and 3.8kg Ce (NO
3)
36H
2O is dissolved in 200 liters of deionized waters, up to whole dissolvings under constantly stirring.Under constantly stirring, slowly add 35wt%NH
4The OH aqueous solution is about 10.0 to the ph value, produces sediment.With the sediment ageing after 24 hours, filter and with deionized water drip washing sediment 5 times.Calcined filter cake 3 hours down, obtain mixed-metal oxides for 500 ℃.Press the oxide metering of aluminium, cerium, lanthanum, this coprecipitation reaction proportion relation is: CeO
2: (CeO
2+ La
2O
3)=0.514: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.552: 1.This coprecipitation reaction proportion relation obtains by following conversion: W (kg)
Al2O3=W (kg)
Al (NO3) 3* MW
Al2O3/ 2MW
Al (NO3) 3=10kg * 102/426=2.39kgW (kg)
La2O3=W (kg)
La (NO3) 36H2O* MW
La2O3/ 2MW
La (NO3) 36H2O=3.8kg * 326/866=1.43kgW (kg)
CeO2=W (kg)
Ce (NO3) 36H2O* MW
CeO2/ MW
Ce (NO3) 36H2O=3.8kg * 172/434=1.51kg
This mixed-metal oxides is transferred in the ball mill, grinds 72 hours in water to about 800 dusts of average grain diameter, water is sized mixing to density 200g/l.
To have 400cell/in
2Honeycomb substrate mass-impregnation in above-mentioned slip about 30 seconds, move up and down carrier simultaneously.Take out carrier and, remove excessive coating slip with the compressed air purging.With the carrier that scribbles slip 110～150 ℃ of dryings 2 hours in air, in a continuous tunnel furnace, calcined 3 hours under 700 ℃ then, according to (vehicle weight after the coating-original vector weight)/original vector weight, calculate and also to realize mixed oxide particle weight: the coating of vehicle weight=0.2: 1 supports.
By supporting gross weight 16f/ft
3The noble metal loading that is scaled every liter of carrier is 0.56g/L, wherein Rh: (Pt+Pd)=1: 4.6, Pt: Pd=1: 0.31, Rh 0.10g/L, Pt 0.35g/L, Pd 0.11g/L.Presoma salt H with Pt, Pd, Rh
2PtCl
6, H
2PdCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.The precursor solution of Pt, Pd is mixed and is used for impregnated carrier.Then in 110 ℃ of following dry supports.Use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pt, Pd precursor compound dipping 2 hours.As a result, the Pt of 0.46g/L and Pd support on carrier by dipping.Afterwards, flood the carrier that supports Pt and Pd with the Rh precursor solution and realize supporting of 0.10g/L Rh.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃.
Embodiment 2
Weigh 1.8kg Al (NO
3)
3, 0.7kg La (NO
3)
36H
2O and 0.7kg Ce (NO
3)
36H
2O is dissolved in 200 liters of deionized waters, up to whole dissolvings under constantly stirring.Under constantly stirring, slowly add 35wt%NH
4The OH aqueous solution is about 10.0 to the ph value, produces sediment.With the sediment ageing after 24 hours, filter and with deionized water drip washing sediment 5 times.Calcined filter cake 3 hours down, obtain mixed-metal oxides for 700 ℃.Press the oxide metering of aluminium, cerium, lanthanum, this coprecipitation reaction proportion relation is: W
Al2O30.43kg, W
La2O30.26kg, W
CeO20.28kg, CeO
2: (CeO
2+ La
2O
3)=0.52: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.56: 1.
With above-mentioned co-precipitation mixed-metal oxides and stabilizing agent ZrO
2Directly mix with BaO, add the water wet-milling afterwards and make slip, slip is coated on the honeycomb ceramic carrier by the technology in the example 1.Calculate by weight, contain in the carrier coating: co-precipitation mixed-metal oxides 96.0wt%, 3.0wt%ZrO
2, 1.0wt%BaO.Adopt the method for embodiment 1, realize coating weight: the coating of vehicle weight=0.1: 1 supports.
By supporting gross weight 16g/ft
3The noble metal loading that is scaled every liter of carrier is 0.56g/L, wherein Rh: (Pt+Pd)=1: 4.6, Pt: Pd=1: 0.31, Rh 0.10g/L, Pt 0.35g/L, Pd 0.11g/L.Presoma salt H with Pt, Pd, Rh
2PtCl
6, H
2PdCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.The precursor solution of Pt, Pd is mixed and is used for impregnated carrier.Then in 110 ℃ of following dry supports.Use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pt, Pd precursor compound dipping 2 hours.As a result, the Pt of 0.46g/L and Pd support on carrier by dipping.Afterwards, flood the carrier that supports Pt and Pd with the Rh precursor solution and realize supporting of 0.10g/L Rh.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃.
Embodiment 3
Weigh 144.5kg Al (NO
3)
3, 15.2kg La (NO
3)
36H
2O and 23 kgCe (NO
3)
36H
2O is dissolved in 200 liters of deionized waters, up to whole dissolvings under constantly stirring.Under constantly stirring, slowly add 35wt%NH
4The OH aqueous solution is about 10.0 to the ph value, produces sediment.With the sediment ageing after 24 hours, filter and with deionized water drip washing sediment 5 times.Calcined filter cake 3 hours down, obtain mixed-metal oxides for 600 ℃.Press the oxide metering of aluminium, cerium, lanthanum, this coprecipitation reaction proportion relation is: W
Al2O334.6kg, W
La2O35.72kg, W
Ceo29.11kg, CeO
2: (CeO
2+ La
2O
3)=0.62: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.3: 1.
By the technology in the example 1 this co-precipitation mixed-metal oxides being made slip is coated on the honeycomb ceramic carrier.Adopt the method for embodiment 1, realize coating weight: vehicle weight=0.15: 1.
By supporting gross weight 20g/ft
3The noble metal loading that is scaled every liter of carrier is 0.7g/L, wherein Rh: (Pt+Pd)=1: 5, Pt: Pd=1: 3, Rh is about 0.12g/L, and Pt is about 0.44g/L, and Pd is about 0.14g/L.Presoma salt H with Pt, Pd, Rh
2PtCl
6, H
2PdCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.The precursor solution of Pt, Pd is mixed and is used for impregnated carrier.Then in 110 ℃ of following dry supports.Use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pt, Pd precursor compound dipping 2 hours.As a result, the Pt of 0.58g/L and Pd support on carrier by dipping.Afterwards, flood the carrier that supports Pt and Pd with the Rh precursor solution and realize supporting of 0.12g/L Rh.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃.
Embodiment 4
Reference example 1 is with 50kg Al (NO
3)
3, 15.2kg La (NO
3)
36H
2O and 23kg Ce (NO
3)
36H
2O obtains mixed-metal oxides through co-precipitation.Reaction ratio closes: W
Al2O312kg, W
La2O35.72kg, W
CeO29.11kg, CeO
2: (CeO
2+ La
2O
3)=0.62: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.55: 1.
With above-mentioned co-precipitation mixed-metal oxides and stabilizing agent PrO
2And Eu
2O
3Directly mix, add the water wet-milling afterwards and make slip, slip is coated on the honeycomb ceramic carrier by the technology in the example 1.Calculate by weight, contain in the carrier coating: co-precipitation mixed-metal oxides 98.0wt%, 1.0wt%PrO
2And 1.0wt%Eu
2O
3Adopt the method for embodiment 1, realize coating weight: the coating of vehicle weight=0.3: 1 supports.
By supporting gross weight 10g/ft
3The noble metal loading that is scaled every liter of carrier is 0.35g/L, wherein Rh: (Pt+Pd)=1: 10, Pt: Pd=1: 1, Rh is about 0.03g/L, and Pt is about 0.16g/L, and Pd is about 0.16g/L.Presoma salt H with Pt, Pd, Rh
2PtCl
6, H
2PdCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.The precursor solution of Pt, Pd is mixed and is used for impregnated carrier.Then in 110 ℃ of following dry supports.Use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pt, Pd precursor compound dipping 2 hours.As a result, the Pt of 0.32g/L and Pd support on carrier by dipping.Afterwards, flood the carrier that supports Pt and Pd with the Rh precursor solution and realize supporting of 0.03g/L Rh.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃.
Embodiment 5
Reference example 1 is with 50kg Al (NO
3)
3, 15.2kg La (NO
3)
36H
2O and 23kg Ce (NO
3)
36H
2O obtains mixed-metal oxides through co-precipitation.Reaction ratio closes: W
Al2O312kg, W
La2O35.72kg, W
CeO29.11kg, CeO
2: (CeO
2+ La
2O
3)=0.62: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.55: 1.
With above-mentioned co-precipitation mixed-metal oxides and stabilizer T iO
2, MgO, ZrO
2, BaO directly mixes, and adds the water wet-milling afterwards and makes slip, by the technology in the example 1 slip is coated on the honeycomb ceramic carrier.Calculate by weight, contain in the carrier coating: co-precipitation mixed-metal oxides 92.0wt%, 2.0wt%TiO
2, 0.7wt%MgO, 5.0wt%ZrO
2, 0.3wt%BaO.Adopt the method for embodiment 1, realize coating weight: the coating of vehicle weight=0.15: 1 supports.
By supporting gross weight 20g/ft
3The noble metal loading that is scaled every liter of carrier is 0.7g/L, wherein Rh: Pd=1: 5, and Rh 0.12g/L, Pd 0.58g/L.Presoma salt H with Pd, Rh
2PdCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.With the precursor solution impregnated carrier of Pd, then in 110 ℃ down dry, use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pd precursor compound dipping 2 hours.As a result, 0.58g/L Pd supports on carrier by dipping.Afterwards, flood the carrier that supports Pd, realize supporting of 0.12g/L Rh with the Rh precursor solution.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃
Embodiment 6
Reference example 1 is with 50kg Al (NO
3)
3, 15.2kg La (NO
3)
36H
2O and 23kg Ce (NO
3)
36H
2O obtains mixed-metal oxides through co-precipitation.Reaction ratio closes: W
Al2O312kg, W
La2O35.72kg, W
CeO29.11kg, CeO
2: (CeO
2+ La
2O
3)=0.62: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.55: 1.
With above-mentioned co-precipitation mixed-metal oxides and stabilizing agent ZrO
2Directly mix, add the water wet-milling afterwards and make slip, slip is coated on the honeycomb ceramic carrier by the technology in the example 1.Calculate by weight, contain in the carrier coating: co-precipitation mixed-metal oxides 98.0wt%, 2.0w%ZrO
2Adopt the method for embodiment 1, realize coating weight: the coating of vehicle weight=0.25: 1 supports.
By supporting gross weight 20g/ft
3The noble metal loading that is scaled every liter of carrier is 0.7g/L, wherein Rh: Pt=1: 10, and Rh is about 0.06g/L, and Pt is about 0.64g/L.Presoma salt H with Pt, Rh
2PtCl
4, H
3RhCl
6Be dissolved in the deionized water respectively.With the precursor solution impregnated carrier of Pt, then in 110 ℃ down dry, use H under 500 ℃
2And N
2Gaseous mixture reduction through the carrier of Pt precursor compound dipping 2 hours.As a result, 0.64g/L Pt supports on carrier by dipping.Afterwards, flood the carrier that supports Pt, realize supporting of 0.06g/L Rh with the Rh precursor solution.This catalyst is dry under 110 ℃, calcines 1 hour down, promptly gets product for 500 ℃.
Claims (16)
1. exhaust gas purifying catalyst, composition comprises aluminium oxide, rare-earth oxide, aluminium lanthanium complex oxide, reactive metal platinum, palladium, rhodium, it is characterized in that on the mixed oxide particle that includes aluminium oxide, cerium oxide, aluminium lanthanium complex oxide, supporting at least a of platinum, palladium, support rhodium subsequently, described mixed oxide particle adopts the preparation of following order coprecipitation technology: 1. the soluble salt with aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment; 2. add the 1. described sediment of thermal decomposition steps.
2. exhaust gas purifying catalyst according to claim 1 is characterized in that described mixed oxide particle is positioned on the honeycomb substrate, mixed oxide particle weight: vehicle weight=0.1～0.3: 1.
3. exhaust gas purifying catalyst according to claim 2 is characterized in that the gross weight that supports with respect to the described reactive metal platinum of the described carrier of unit volume, palladium, rhodium is 5～35g/ft
3, having supported any of platinum or palladium on the mixed oxide particle, platinum, palladium, rhodium weight ratio are rhodium: platinum or palladium=1: 2～10.
4. exhaust gas purifying catalyst according to claim 2 is characterized in that the gross weight that supports with respect to the described reactive metal platinum of the described carrier of unit volume, palladium, rhodium is 5～35g/ft
3, having supported platinum and palladium on the mixed oxide particle, platinum, palladium, rhodium weight ratio are platinum: palladium=1: 0.3～3, rhodium: (platinum+palladium)=1: 2～10.
5. according to claim 3 or 4 described exhaust gas purifying catalysts, it is characterized in that the gross weight that supports with respect to the described reactive metal platinum of the described carrier of unit volume, palladium, rhodium is 10～16g/ft
3
6. exhaust gas purifying catalyst according to claim 2 is characterized in that including in the described mixed oxide particle titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a, titanium oxide TiO
2And/or zirconia ZrO
2And/or barium monoxide BaO and/or magnesia MgO: mixed oxide particle=0～8 that contains additive: 100, the mixed oxide particle that contains additive is by 2. described co-precipitation mixed oxide particle of step and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO directly mix and obtain.
7. exhaust gas purifying catalyst according to claim 2 is characterized in that including in the described mixed oxide particle praseodymium oxide PrO
2, europium oxide Eu
2O
3At least a, praseodymium oxide PrO
2And/or europium oxide Eu
2O
3: contain praseodymium oxide PrO
2And/or europium oxide Eu
2O
3Mixed oxide particle=0～2: 100, contain praseodymium oxide PrO
2And/or europium oxide Eu
2O
3Mixed oxide particle by 2. described co-precipitation mixed oxide particle of step and praseodymium oxide PrO
2, europium oxide Eu
2O
3Directly mix and obtain.
8. exhaust gas purifying catalyst according to claim 2 is characterized in that the weight ratio of measuring with oxide before the 1. described aluminium of step, cerium, the dissolving of lanthanum soluble salt is CeO
2: (CeO
2+ La
2O
3)=0.4～0.7: 1, (CeO
2+ La
2O
3): (Al
2O
3+ CeO
2+ La
2O
3)=0.3～0.7: 1.
9. exhaust gas purifying catalyst according to claim 1 is characterized in that the 2. described heating-up temperature of step is 500～700 ℃.
10. exhaust gas purifying catalyst according to claim 1 is characterized in that including in the described mixed oxide particle titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a, titanium oxide TiO
2And/or zirconia ZrO
2And/or barium monoxide BaO and/or magnesia MgO: mixed oxide particle=0.5～8 that contains additive: 100, the mixed oxide particle that contains additive is by 2. described co-precipitation mixed oxide particle of step and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO directly mix and obtain and be positioned on the honeycomb substrate, the mixed oxide particle weight that contains additive: vehicle weight=0.1～0.3: 1, be 10～16g/ft with respect to the gross weight that supports of the described reactive metal platinum of unit volume honeycomb substrate, palladium, rhodium
3, containing on the mixed oxide particle of additive and supported platinum and palladium, platinum, palladium, rhodium weight ratio are platinum: palladium=1: 0.3～3, rhodium: (platinum+palladium)=1: 2～10, the weight ratio with the oxide metering before the 1. described aluminium of step, cerium, the dissolving of lanthanum soluble salt is CeO
2: (CeO
2+ La
2O
3)=0.4～0.7: 1, (CeO
2+ La
2O
3): (Al2O3+CeO
2+ La
2O
3)=0.3～0.7: 1, the 2. described heating-up temperature of step is 500～700 ℃.
11. the preparation method of the described exhaust gas purifying catalyst of claim 1 comprises following process steps successively: 1. on catalyst carrier, support mixed oxide particle, 2. on the mixed oxide particle coating, support at least a of platinum, palladium, 3. support rhodium subsequently.
12., it is characterized in that described catalyst carrier is a honeycomb according to the described exhaust gas purifying catalyst preparation method of claim 11.
13. according to the described exhaust gas purifying catalyst preparation method of claim 12, it is characterized in that including in the described mixed oxide particle aluminium oxide, cerium oxide, aluminium lanthanium complex oxide, following process steps in sequence is adopted in its preparation: 1. the soluble salt with aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment; 2. 500～700 ℃ add the 1. described sediment of thermal decomposition steps.
14., it is characterized in that including in the described mixed oxide particle aluminium oxide, cerium oxide, aluminium lanthanium complex oxide and titanium oxide TiO according to the described exhaust gas purifying catalyst preparation method of claim 12
2, zirconia ZrO
2, barium monoxide BaO, four kinds of additives of magnesia MgO at least a, titanium oxide TiO
2And/or zirconia ZrO
2And/or barium monoxide BaO and/or magnesia MgO: mixed oxide particle=0～8: 100, following process steps in sequence is adopted in its preparation: 1. the soluble salt with aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment; 2. 500～700 ℃ add the 1. described sediment of thermal decomposition steps; 3. with step 2. gained analyte and titanium oxide TiO
2, zirconia ZrO
2, barium monoxide BaO, magnesia MgO mix.
15., it is characterized in that including in the described mixed oxide particle aluminium oxide, cerium oxide, aluminium lanthanium complex oxide and praseodymium oxide PrO according to the described exhaust gas purifying catalyst preparation method of claim 12
2, europium oxide Eu
2O
3At least a, praseodymium oxide PrO
2And/or europium oxide Eu
2O
3: mixed oxide particle=0～2: 100, following process steps in sequence is adopted in its preparation: 1. the soluble salt with aluminium, cerium, lanthanum is dissolved in the water, and adds NH
3OH produces sediment; 2. 500～700 ℃ add the 1. described sediment of thermal decomposition steps; 3. with step 2. gained analyte and praseodymium oxide PrO
2, europium oxide Eu
2O
3Mix.
16. according to claim 11,12,13,14, one of 15 described exhaust gas purifying catalyst preparation methods, it is characterized in that step is 1. described supports to mixed oxide particle water sample sluny impregnation or spray described carrier, the 2. described carrier that the mixed oxide particle coating is arranged for chloro-complex aqueous solution dipping or spray load that supports of step with platinum, palladium, the 3. described carrier of 2. handling through step for the chloro-complex aqueous solution dipping or the spray of rhodium that supports of step.
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|---|---|---|---|
| CN 02128756 CN1234453C (en) | 2002-08-07 | 2002-08-07 | Noble metal-rare-earth catalyst for purifying waste gas and its preparation |
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|---|---|---|---|
| CN 02128756 CN1234453C (en) | 2002-08-07 | 2002-08-07 | Noble metal-rare-earth catalyst for purifying waste gas and its preparation |
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