CN103182305A - Three-way catalyst and preparation method for same - Google Patents
Three-way catalyst and preparation method for same Download PDFInfo
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- CN103182305A CN103182305A CN2011104432566A CN201110443256A CN103182305A CN 103182305 A CN103182305 A CN 103182305A CN 2011104432566 A CN2011104432566 A CN 2011104432566A CN 201110443256 A CN201110443256 A CN 201110443256A CN 103182305 A CN103182305 A CN 103182305A
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Abstract
The invention provides a three-way catalyst, wherein porous ceramic is used as a matrix, a catalysis layer is arranged on the porous ceramic; the catalysis layer comprises a first catalysis layer and a second catalysis layer; the first catalysis layer comprises a first catalysis part and a second catalysis part, and the second catalysis layer comprises a third catalysis part and a fourth catalysis part; and the third catalysis part is located just below the first catalysis part, and the fourth catalysis part is located just below the second catalysis part. The invention further provides a preparation method for the catalyst. The catalyst prepared by the preparation method provided by the invention is good in the catalytic performances of HC, CO and NOx before being aged, and still good in the catalytic performances after being aged under certain conditions, thus reflecting a good anti-ageing capacity.
Description
Technical field
The present invention relates to automobile exhaust pollution thing (CO, HC, NO
X) play complex rare-earth oxidate containing valuable metal-noble metal honeycomb catalyst of three-way emission control effect and preparation method thereof.
Background technology
The purpose of catalytic cleaning of car tail gas is exactly that harmful CO and HC are oxidized to CO
2And H
2O is with NO
XBe reduced into N
2Because the chemical composition of vehicle exhaust is very complicated, its conversion ratio be that oxidizing gas or reducibility gas are relevant with reaction gas also, so catalyst is divided into oxidized form and reduced form two parts in function except outside the Pass having with activity of such catalysts.
The oxidation reaction of the main catalysis CO of oxidation catalyst and HC, key reaction is as follows:
2CO+O
2——2CO
2
4HC+5O
2——4CO
2+2H
2O
HC+NO
2——CO
2+H
2O
The main catalyzing N O of reduction catalyst
XReduction reaction:
2NO+CO——N
2+CO
2
2NO+HC——N
2+H
2O+CO
2
Because of the chemical environment difference of two kinds of reaction requirements, so early stage catalyst is discrete with both.Owing to the improvement of engine, realized to make the chemical environment of two kinds of function compatibilities afterwards; Because the improvement of catalyst preparation technology coexists as on the same catalyst two kinds of activated centres of oxidation and reduction, three-way catalyst TWC(Three – way catalyst finally occurred).
Present three-way catalyst preparation mainly is to apply one deck at cordierite honeycomb ceramic carrier to have the aluminum oxide coating layer of high-specific surface area with better carried noble metal, as patent of invention CN101161337A with the cordierite honeycomb ceramics as matrix, be matrix with the porous ceramics, which is provided with Catalytic Layer, wherein, the ground floor Catalytic Layer is that activated alumina supports rare earth metal, the mixing of one or more in the alkaline-earth metal, second layer Catalytic Layer is that aluminium oxide supports first active noble metals with mithridatism and non-zero residual activity, comprise that also the 3rd layer of Catalytic Layer is second noble metal with catalytic activity, the 4th layer of Catalytic Layer is rare earth, the oxide of alkaline earth or transition metal.
This catalyst has catalytic performance and heat endurance preferably, and adapt to wideer air-fuel ratio scope, namely can be in wideer scope the efficient of oxidation and reduction all than higher, but the oxide of alkaline-earth metal and rare earth metal is in different layers respectively with noble metal, and total number of plies is 4 layers, and general thickness is bigger, the gas diffusion slowly, being quick on the draw property difference and the whole carrier surface of each layer covering can not utilize when catalysis fully, and utilization rate is not high.
Summary of the invention
The present invention exists thickness big for solving existing three-way catalyst, and the gas diffusion is slow, and the technical problem that being quick on the draw property difference and utilization rate are not high provides the Catalysts and its preparation method that a kind of thickness is little, the gas diffusion is slow, being quick on the draw property is poor, utilization rate is high.
The invention discloses a kind of three-way catalyst, is matrix with the porous ceramics, which is provided with Catalytic Layer, and described Catalytic Layer comprises first Catalytic Layer and second Catalytic Layer; Described first Catalytic Layer comprises first catalysed partial and second catalysed partial, and described second Catalytic Layer comprises the 3rd catalysed partial and the 4th catalysed partial; Wherein, the 3rd catalysed partial be positioned at first catalysed partial under, the 4th catalysed partial be positioned at second catalysed partial under, described first catalysed partial is that first support oxide supports second active noble metals with mithridatism, second catalysed partial is that second support oxide supports the 3rd active noble metals with mithridatism, the 3rd catalysed partial is that the 3rd support oxide supports the 3rd active noble metals with mithridatism, and the 4th catalysed partial is that the 4th support oxide supports first active noble metals with mithridatism; Described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide independently are one or more oxide and activated alumina of rare earth metal, alkaline-earth metal separately.
The invention also discloses a kind of preparation method of this three-way catalyst, may further comprise the steps:
The coating feed liquid that S1, preparation the 3rd catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to first solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains second solution; In boehmite, add second solution and first solution, stir and obtain the 3rd solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make first and apply feed liquid;
S2, the preparation-obtained coating feed liquid of step S1 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Get ceramic matrix and put into Flat bottom container, put vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 3rd catalysed partial;
The coating feed liquid that S3, preparation the 4th catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 4th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 5th solution; In boehmite, add the 5th solution and the 4th solution, stir and obtain the 6th solution; The nitrate solution that adds first active noble metals again mixes with ball milling method and to make second and apply feed liquid;
S4, the preparation-obtained coating feed liquid of step S3 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S2 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S5, preparation first catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 7th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 8th solution; In boehmite, add the 8th solution and the 7th solution, stir and obtain the 9th solution; The nitrate solution that adds second active noble metals again mixes with ball milling method and to make the 3rd and apply feed liquid;
S6, the preparation-obtained coating feed liquid of step S5 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S4 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S7, preparation second catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the tenth solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 11 solution; In boehmite, add the 11 solution and the tenth solution, stir and obtain the 12 solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make the 4th and apply feed liquid;
S8, the preparation-obtained coating feed liquid of step S7 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S6 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial.
Three-way catalyst of the present invention has only two-layer, the thin thickness of three-way catalyst, be conducive to the diffusion of gas, improved reaction sensitivity, and the three-way catalyst of double-layer structure of the present invention contains four catalysed partials, and first catalysed partial and second catalysed partial are positioned at first Catalytic Layer, and the 3rd catalysed partial and the 4th catalysed partial are positioned at second Catalytic Layer, can when catalysis, the utilization of maximum possible not have a catalysed partial, improve the utilization rate of three-way catalyst.
Description of drawings
Fig. 1 is the schematic diagram of three-way catalyst of the present invention.
The specific embodiment
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explaining the present invention, and be not used in restriction the present invention.
The invention discloses a kind of three-way catalyst, is matrix with the porous ceramics, which is provided with Catalytic Layer, and described Catalytic Layer comprises first Catalytic Layer and second Catalytic Layer; Described first Catalytic Layer comprises first catalysed partial and second catalysed partial, and described second Catalytic Layer comprises the 3rd catalysed partial and the 4th catalysed partial; Wherein, the 3rd catalysed partial be positioned at first catalysed partial under, the 4th catalysed partial be positioned at second catalysed partial under, described first catalysed partial is that first support oxide supports second active noble metals with mithridatism, second catalysed partial is that second support oxide supports the 3rd active noble metals with mithridatism, the 3rd catalysed partial is that the 3rd support oxide supports the 3rd active noble metals with mithridatism, and the 4th catalysed partial is that the 4th support oxide supports first active noble metals with mithridatism; Described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide independently are one or more oxide and activated alumina of rare earth metal, alkaline-earth metal separately.
According to three-way catalyst provided by the invention, preferably, described first active noble metals is Rh, and second noble metal is Pt, and the 3rd active noble metals is Pd.Three-way catalyst of the present invention contains three kinds of active noble metals, has reduced the consumption of metal Pt, reduces cost.Active noble metals Rh, Pt and Pd branch are opened load, and Rh is in the more even distribution of alumina layer.
According to three-way catalyst provided by the invention, can better bring into play its catalytic action for the active noble metals that makes each catalysed partial, preferably, the addition of the first active noble metals Rh is the 0.05-0.2g/L of ceramic matrix; The addition of the second active noble metals Pt is the 0.05-0.2g/L of ceramic matrix, and the addition of the 3rd active noble metals Pd is the 0.02-0.5g/L of ceramic matrix, and Rh, Pt are Rh:Pt:Pd=1:1-5:1-10 with the element wt ratio of Pd.
According to three-way catalyst provided by the invention, for the active noble metals that makes each catalysed partial can better be brought into play its catalytic action, preferably, the weight of each catalysed partial is the 5-20wt% of ceramic matrix weight not all.
According to three-way catalyst provided by the invention, for the active noble metals that makes each catalysed partial can better be brought into play its catalytic action, preferably, described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide, wherein, rare earth metal is one or more the mixing of La, Ce, Zr, Pr, Nd, Pm and Sm, and alkaline-earth metal is one or more the mixing among Ba, Mg, Ca, the Sr.
According to three-way catalyst provided by the invention, for the active noble metals that makes each catalysed partial can better be brought into play its catalytic action, preferably, described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide, rare earth metal is La, Ce, Zr, and each element wt is than being Al:Ce:Zr:La=15-70:5-30:5-30:5-20 in each catalysed partial.
The used ceramic matrix of the present invention is cordierite honeycomb ceramic carrier.
The present invention also provides the preparation method of this three-way catalyst, and this method may further comprise the steps:
The coating feed liquid that S1, preparation the 3rd catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to first solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains second solution; In boehmite, add second solution and first solution, stir and obtain the 3rd solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make first and apply feed liquid;
S2, the preparation-obtained coating feed liquid of step S1 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Get ceramic matrix and put into Flat bottom container, put vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 3rd catalysed partial;
The coating feed liquid that S3, preparation the 4th catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 4th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 5th solution; In boehmite, add the 5th solution and the 4th solution, stir and obtain the 6th solution; The nitrate solution that adds first active noble metals again mixes with ball milling method and to make second and apply feed liquid;
S4, the preparation-obtained coating feed liquid of step S3 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S2 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S5, preparation first catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 7th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 8th solution; In boehmite, add the 8th solution and the 7th solution, stir and obtain the 9th solution; The nitrate solution that adds second active noble metals again mixes with ball milling method and to make the 3rd and apply feed liquid;
S6, the preparation-obtained coating feed liquid of step S5 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S4 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S7, preparation second catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the tenth solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 11 solution; In boehmite, add the 11 solution and the tenth solution, stir and obtain the 12 solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make the 4th and apply feed liquid;
S8, the preparation-obtained coating feed liquid of step S7 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S6 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial.
Preparation method of the present invention, the weight concentration of described first solution, the 4th solution, the 7th solution, the tenth solution is 25-55%.
Preparation method of the present invention, the pH of described the 3rd solution, the 6th solution, the 9th solution and ground 12 solution is 2-5.
Preparation method of the present invention, the condition that vacuumizes among described step S2, S4, S6 and the S8 is: vacuum is 0.08-0.2Mpa, pumpdown time is 3-10s, and control first apply feed liquid, second viscosity that applies feed liquid and the 3rd coating material is 200-2000mPa.s.
Preparation method of the present invention, the condition of described drying is: baking temperature 80-130 ℃, dry 3-4 hour.The condition of described roasting is: sintering temperature 600-800 ℃, and roasting 4-6 hour.
Structure below by description of drawings three-way catalyst of the present invention.
As shown in Figure 1, described three-way catalyst comprises first Catalytic Layer 1 and second Catalytic Layer 2, and is clear in order to describe, set the first Catalytic Layer position for " on ", the external D score that is set in the second Catalytic Layer place.First Catalytic Layer comprises first catalysed partial 3 and second catalysed partial 4, second Catalytic Layer comprises the 3rd catalysed partial 5 and the 4th catalysed partial 6, and the 3rd catalysed partial 5 be positioned at first catalysed partial 3 under, the 4th catalysed partial 6 be positioned at second catalysed partial 4 under.
Also the present invention is described in further detail by reference to the accompanying drawings as example below by concrete experiment several times.
Embodiment 1
1,The preparation of the coating feed liquid of the 3rd catalysed partial takes by weighing AlNO
330g makes concentration and is 30% solution 100ml.Take by weighing Ce-Zr composite oxides (Shandong Zibo China celebrating powder technology Co., Ltd) 100g, add deionized water 200g, the amount of adding PEG600 is 4g, and stirring obtains Ce-Zr mixed oxide feed liquid.Take by weighing 130g boehmite (Chinese Aluminium Co., Ltd) and add Ce-Zr mixed oxide feed liquid.The aluminum nitrate solution that makes before getting is regulated pH value to 3.Take by weighing concentration and be 3% Pd(NO3)
2It is that rotational speed of ball-mill is the coating feed liquid that 400r/min makes the 3rd catalysed partial in 3 the feed liquid that (expensive grind platinum industry) solution 20ml adds pH value, and controlling the viscosity of sludge scope is 1000mPa.s.
2, the prepared feed liquid injection that contains the 3rd precious metals pd is had in the Flat bottom container of scale, liquid surface height controlling is at the 65mm scale; Get cordierite honeycomb ceramic carrier and put into Flat bottom container, put vacuum extractor on the top of cordierite honeycomb ceramic carrier; Suction 0.08MPa, pumpdown time 7s makes the liquid level of slurry in cordierite honeycomb ceramic carrier arrive a half and stops to vacuumize; Carrier is taken out, and the catalyst above-below direction is constant in the taking-up process, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; 120 ℃ of dryings 4 hours, 700 ℃ of roastings 5 hours namely obtain the 3rd catalysed partial.
3, the coating feed liquid for preparing the 4th catalysed partial according to the method for step 1 takes by weighing concentration and is 0.5% Rh(NO3)
3Solution 20ml is prepared into the feed liquid that contains the first noble metal Rh by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 2000mPa.s.
4, honeycomb ceramic carrier be inverted come, a side that will not apply down, the technology coating that contains the feed liquid of Pd by coating contains the feed liquid of Rh, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained the 4th catalysed partial in 5 hours.
5, the coating feed liquid for preparing first catalysed partial according to the method for step 1 takes by weighing concentration and is 1% Pt(NO3)
2Solution 20ml is prepared into the feed liquid that contains second precious metals pt by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 1500mPa.s.
6, an end that will be coated with Pd down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pt, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained first catalysed partial in 5 hours.
7, the coating feed liquid for preparing second catalysed partial according to the method for step 1 takes by weighing concentration and is 1.8% Pd(NO3)
2Solution 20ml, the technology that contains the feed liquid of the 3rd precious metals pd by preparation is prepared into the feed liquid that contains the 3rd precious metals pd, and control viscosity of sludge scope is 500mPa.s.
8, an end that will be coated with Rh down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pd, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained second catalysed partial in 5 hours.
Can obtain three-way catalyst A1.
1,The preparation of the coating feed liquid of the 3rd catalysed partial takes by weighing AlNO
330g makes concentration and is 30% solution 100ml.Take by weighing Ce-Zr composite oxides (Shandong Zibo China celebrating powder technology Co., Ltd) 200g, add deionized water 300g, the amount of adding PEG600 is 6g, and stirring obtains Ce-Zr mixed oxide feed liquid.Take by weighing 150g boehmite (Chinese Aluminium Co., Ltd) and add Ce-Zr mixed oxide feed liquid.The aluminum nitrate solution that makes before getting is regulated pH value to 5.Take by weighing concentration and be 4% Pd(NO3)
2It is that rotational speed of ball-mill is the coating feed liquid that 300r/min makes the 3rd catalysed partial in 4 the feed liquid that (expensive grind platinum industry) solution 40ml adds pH value, and controlling the viscosity of sludge scope is 200mPa.s.
2, the prepared feed liquid injection that contains the 3rd precious metals pd is had in the Flat bottom container of scale, liquid surface height controlling is at the 65mm scale; Get cordierite honeycomb ceramic carrier and put into Flat bottom container, put vacuum extractor on the top of cordierite honeycomb ceramic carrier; Suction 0.10MPa, pumpdown time 5s makes the liquid level of slurry in cordierite honeycomb ceramic carrier arrive a half and stops to vacuumize; Carrier is taken out, and the catalyst above-below direction is constant in the taking-up process, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; 120 ℃ of dryings 4 hours, 700 ℃ of roastings 4 hours namely obtain the 3rd catalysed partial.
3, the coating feed liquid for preparing the 4th catalysed partial according to the method for step 1 takes by weighing concentration and is 1.0% Rh(NO3)
3Solution 25ml is prepared into the feed liquid that contains the first noble metal Rh by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 1000mPa.s.
4, honeycomb ceramic carrier be inverted come, a side that will not apply down, the technology coating that contains the feed liquid of Pd by coating contains the feed liquid of Rh, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained the 4th catalysed partial in 5 hours.
5, the coating feed liquid for preparing first catalysed partial according to the method for step 1 takes by weighing concentration and is 1.5% Pt(NO3)
2Solution 30ml is prepared into the feed liquid that contains second precious metals pt by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 500mPa.s.
6, an end that will be coated with Pd down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pt, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained first catalysed partial in 5 hours.
7, the coating feed liquid for preparing second catalysed partial according to the method for step 1 takes by weighing concentration and is 4% solution 10ml, and the technology that contains the feed liquid of the 3rd precious metals pd by preparation is prepared into the feed liquid that contains the 3rd precious metals pd, and control viscosity of sludge scope is 500mPa.s.
With the end that is coated with Rh down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pd, 130 ℃ of dryings 3 hours, and 600 ℃ of roastings namely obtained second catalysed partial in 6 hours.
Can obtain three-way catalyst A2.
1,The preparation of the coating feed liquid of the 3rd catalysed partial takes by weighing AlNO
330g makes concentration and is 30% solution 100ml.Take by weighing Ce-Zr composite oxides (Shandong Zibo China celebrating powder technology Co., Ltd) 200g, add deionized water 300g, the amount of adding PEG600 is 6g, and stirring obtains Ce-Zr mixed oxide feed liquid.Take by weighing 150g boehmite (Chinese Aluminium Co., Ltd) and add Ce-Zr mixed oxide feed liquid.The aluminum nitrate solution that makes before getting is regulated pH value to 5.Take by weighing concentration and be 3% Pd(NO3)
2It is that rotational speed of ball-mill is the coating feed liquid that 300r/min makes the 3rd catalysed partial in 2 the feed liquid that (expensive grind platinum industry) solution 5ml adds pH value, and controlling the viscosity of sludge scope is 200mPa.s.
2, the prepared feed liquid injection that contains the 3rd precious metals pd is had in the Flat bottom container of scale, liquid surface height controlling is at the 65mm scale; Get cordierite honeycomb ceramic carrier and put into Flat bottom container, put vacuum extractor on the top of cordierite honeycomb ceramic carrier; Suction 0.20MPa, pumpdown time 3s makes the liquid level of slurry in cordierite honeycomb ceramic carrier arrive a half and stops to vacuumize; Carrier is taken out, and the catalyst above-below direction is constant in the taking-up process, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; 120 ℃ of dryings 4 hours, 700 ℃ of roastings 4 hours namely obtain the 3rd catalysed partial.
3, the coating feed liquid for preparing the 4th catalysed partial according to the method for step 1 takes by weighing concentration and is 1.0% Rh(NO3)
3Solution 25ml is prepared into the feed liquid that contains the first noble metal Rh by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 1000mPa.s.
4, honeycomb ceramic carrier be inverted come, a side that will not apply down, the technology coating that contains the feed liquid of Pd by coating contains the feed liquid of Rh, 80 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained the 4th catalysed partial in 5 hours.
5, the coating feed liquid for preparing first catalysed partial according to the method for step 1 takes by weighing concentration and is 1% Pt(NO3)
2Solution 14ml is prepared into the feed liquid that contains second precious metals pt by the technology that preparation contains the feed liquid of the 3rd precious metals pd, and control viscosity of sludge scope is 500mPa.s.
6, an end that will be coated with Pd down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pt, 120 ℃ of dryings 4 hours, 700 ℃ of roastings namely obtained first catalysed partial in 5 hours.
7, the coating feed liquid for preparing second catalysed partial according to the method for step 1 takes by weighing concentration and is 2% solution 5ml, and the technology that contains the feed liquid of the 3rd precious metals pd by preparation is prepared into the feed liquid that contains the 3rd precious metals pd, and control viscosity of sludge scope is 500mPa.s.
With the end that is coated with Rh down, the technology that contains the feed liquid of Pd by coating applies the feed liquid that contains Pd, 80 ℃ of dryings 4 hours, and 800 ℃ of roastings namely obtained second catalysed partial in 4 hours.
Can obtain three-way catalyst A3.
Comparative Examples 1
Take by weighing 100g boehmite and 100gCe-Zr composite oxides, add deionized water 300ml, add PEG600 4g, ball milling makes the activated alumina coating material liquid that ground floor supports alkaline-earth metal and rare earth metal.
Take by weighing concentration and be 0.2% RhCl3 solution 100ml, take by weighing 100g boehmite and its and mix and stir.
With honeycomb ceramic carrier, the dipping ground floor supports the oxygen content coating material liquid 3min of rare earth metal and alkaline-earth metal, takes out, and blows the through hole road with purger, 110 ℃ of dry 5h, and 700 ℃ of roasting 5h namely apply the oxygen content that ground floor supports rare earth metal and alkaline-earth metal.
Honeycomb ceramic carrier floods the oxygen content coating material liquid 3min that the second layer supports Rh again, and take out and blow the hole, 100 ℃ of oven dry 6h, 750 ℃ of roastings namely are coated with and are covered with the oxygen content that supports noble metal Rh.
Take by weighing concentration and be 0.8% PtCl2 solution 150ml, get the above-mentioned ceramic monolith that has applied the aluminium oxide of Rh, flood this solution, 100 ℃ of dry 4h, 600 ℃ of roastings, i.e. carried noble metal Pt.
Be impregnated into 3min in the feed liquid of the activated alumina that supports alkaline-earth metal and rare earth metal with applying ceramic monolith behind the Pt, blow the hole, 100 ℃ of dry 4h, 700 ℃ of roasting 5h obtain three-way catalyst B1.
The catalytic performance test
Adopt GB14761-1999, implant the sensor of gas analyzer at the blast pipe of catalyst rear and front end, detect gas and change through the composition before and after the catalyst, calculate catalyst to the conversion ratio of CO, HC, NOx.The results are shown in Table 1.
The ageing resistace test
Adopt GB18352.3, test its ageing resistace.The results are shown in Table 1.
Table 1
As can be seen from Table 1, the catalytic performance of HC, the CO of the catalyst that the present invention makes before aging, NOx is good, and after the wearing out of certain condition, catalytic performance is still good, has embodied good ageing resistance.
Claims (12)
1. a three-way catalyst is characterized in that, is matrix with the porous ceramics, which is provided with Catalytic Layer, and described Catalytic Layer comprises first Catalytic Layer and second Catalytic Layer; Described first Catalytic Layer comprises first catalysed partial and second catalysed partial, and described second Catalytic Layer comprises the 3rd catalysed partial and the 4th catalysed partial; Wherein, the 3rd catalysed partial be positioned at first catalysed partial under, the 4th catalysed partial be positioned at second catalysed partial under, described first catalysed partial is that first support oxide supports second active noble metals with mithridatism, second catalysed partial is that second support oxide supports the 3rd active noble metals with mithridatism, the 3rd catalysed partial is that the 3rd support oxide supports the 3rd active noble metals with mithridatism, and the 4th catalysed partial is that the 4th support oxide supports first active noble metals with mithridatism; Described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide independently are one or more oxide and activated alumina of rare earth metal, alkaline-earth metal separately.
2. three-way catalyst according to claim 1, it is characterized in that: first active noble metals is Rh, and second noble metal is Pt, and the 3rd active noble metals is Pd.
3. three-way catalyst according to claim 2, it is characterized in that: the addition of the first active noble metals Rh is the 0.05-0.2g/L of ceramic matrix; The addition of the second active noble metals Pt is the 0.05-0.2g/L of ceramic matrix, and the addition of the 3rd active noble metals Pd is the 0.02-0.5g/L of ceramic matrix, and Rh, Pt are Rh:Pt:Pd=1:1-5:1-10 with the element wt ratio of Pd.
4. three-way catalyst according to claim 1, it is characterized in that: the weight of each catalysed partial is the 5-20wt% of ceramic matrix weight.
5. three-way catalyst according to claim 1, it is characterized in that: described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide, wherein, rare earth metal is one or more the mixing of La, Ce, Zr, Pr, Nd, Pm and Sm, and alkaline-earth metal is one or more the mixing among Ba, Mg, Ca, the Sr.
6. three-way catalyst according to claim 5, it is characterized in that: described first support oxide, second support oxide, the 3rd support oxide and the 4th support oxide, rare earth metal is La, Ce, Zr, and each element wt is than being Al:Ce:Zr:La=15-70:5-30:5-30:5-20 in each catalysed partial.
7. according to the preparation method of the described three-way catalyst of claim 1, it is characterized in that, may further comprise the steps:
The coating feed liquid that S1, preparation the 3rd catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to first solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains second solution; In boehmite, add second solution and first solution, stir and obtain the 3rd solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make first and apply feed liquid;
S2, the preparation-obtained coating feed liquid of step S1 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Get ceramic matrix and put into Flat bottom container, put vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 3rd catalysed partial;
The coating feed liquid that S3, preparation the 4th catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 4th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 5th solution; In boehmite, add the 5th solution and the 4th solution, stir and obtain the 6th solution; The nitrate solution that adds first active noble metals again mixes with ball milling method and to make second and apply feed liquid;
S4, the preparation-obtained coating feed liquid of step S3 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S2 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S5, preparation first catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the 7th solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 8th solution; In boehmite, add the 8th solution and the 7th solution, stir and obtain the 9th solution; The nitrate solution that adds second active noble metals again mixes with ball milling method and to make the 3rd and apply feed liquid;
S6, the preparation-obtained coating feed liquid of step S5 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S4 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial;
The coating feed liquid that S7, preparation second catalysed partial are used: with the nitrate of rare earth metal and alkaline-earth metal, add deionized water, be configured to the tenth solution; Composite oxide power to rare earth metal adds deionized water then, and the interpolation polyethylene glycol mixes and obtains the 11 solution; In boehmite, add the 11 solution and the tenth solution, stir and obtain the 12 solution; The nitrate solution that adds the 3rd active noble metals again mixes with ball milling method and to make the 4th and apply feed liquid;
S8, the preparation-obtained coating feed liquid of step S7 injected have in the Flat bottom container of scale, liquid surface height controlling is in half position of ceramic matrix height; Ceramic matrix among the step S6 is inverted in the Flat bottom container, puts vacuum extractor on the top of ceramic matrix, the condition that control vacuumizes makes the liquid level of coating feed liquid in ceramic matrix arrive a half and stops to vacuumize; Carrier is taken out, in the taking-up process, keeps the ceramic matrix above-below direction constant, utilize purger never an end of slurry blow to the end that slurry is arranged, until there not being liquid to flow out; Final drying, roasting prepare the 4th catalysed partial.
8. preparation method according to claim 7 is characterized in that, the weight concentration of described first solution, the 4th solution, the 7th solution, the tenth solution is 25-55%.
9. preparation method according to claim 7 is characterized in that, the pH of described the 3rd solution, the 6th solution, the 9th solution and ground 12 solution is 2-5.
10. preparation method according to claim 7, it is characterized in that, the condition that vacuumizes among described step S2, S4, S6 and the S8 is: vacuum is 0.08-0.2Mpa, pumpdown time is 3-10s, and control first apply feed liquid, second viscosity that applies feed liquid and the 3rd coating material is 200-2000mPa.s.
11. preparation method according to claim 7 is characterized in that, the condition of described drying is: baking temperature 80-130 ℃, and dry 3-4 hour.
12. preparation method according to claim 7 is characterized in that, the condition of described roasting is: sintering temperature 600-800 ℃, and roasting 4-6 hour.
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Cited By (8)
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| CN104307513A (en) * | 2014-11-12 | 2015-01-28 | 贵州大学 | RhPdPt metal nanoalloy catalyst and application thereof |
| CN104759281A (en) * | 2015-03-11 | 2015-07-08 | 江苏大学 | Preparation method of composite oxide catalyst used for purifying diesel engine |
| CN106807369A (en) * | 2017-02-13 | 2017-06-09 | 安徽新态环保科技有限公司 | A kind of automobile three-way catalysts catalyst |
| CN106807370A (en) * | 2017-03-22 | 2017-06-09 | 无锡威孚环保催化剂有限公司 | A kind of three-way catalyst |
| CN107206360A (en) * | 2015-02-05 | 2017-09-26 | 庄信万丰股份有限公司 | Three-way catalyst |
| WO2017204008A1 (en) * | 2016-05-24 | 2017-11-30 | 株式会社キャタラー | Exhaust gas purifying catalyst |
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| CN104307513A (en) * | 2014-11-12 | 2015-01-28 | 贵州大学 | RhPdPt metal nanoalloy catalyst and application thereof |
| CN107206360A (en) * | 2015-02-05 | 2017-09-26 | 庄信万丰股份有限公司 | Three-way catalyst |
| CN104759281A (en) * | 2015-03-11 | 2015-07-08 | 江苏大学 | Preparation method of composite oxide catalyst used for purifying diesel engine |
| WO2017204008A1 (en) * | 2016-05-24 | 2017-11-30 | 株式会社キャタラー | Exhaust gas purifying catalyst |
| JPWO2017204008A1 (en) * | 2016-05-24 | 2019-03-22 | 株式会社キャタラー | Exhaust gas purification catalyst |
| US10960389B2 (en) | 2016-05-24 | 2021-03-30 | Cataler Corporation | Exhaust gas purification catalyst |
| CN106807369B (en) * | 2017-02-13 | 2019-06-18 | 安徽新态环保科技有限公司 | A kind of automobile three-way catalysts catalyst |
| CN106807369A (en) * | 2017-02-13 | 2017-06-09 | 安徽新态环保科技有限公司 | A kind of automobile three-way catalysts catalyst |
| CN106807370A (en) * | 2017-03-22 | 2017-06-09 | 无锡威孚环保催化剂有限公司 | A kind of three-way catalyst |
| CN106807370B (en) * | 2017-03-22 | 2019-05-24 | 无锡威孚环保催化剂有限公司 | A kind of three-way catalyst |
| CN110898829A (en) * | 2019-07-24 | 2020-03-24 | 南京工业大学 | Composite filter material with synergistic removal function of nitrogen oxides and dioxins and preparation method thereof |
| CN110586088A (en) * | 2019-10-12 | 2019-12-20 | 无锡威孚环保催化剂有限公司 | Preparation method of segmented national six natural gas equivalence ratio catalyst |
| CN110586088B (en) * | 2019-10-12 | 2022-06-24 | 无锡威孚环保催化剂有限公司 | Preparation method of segmented national six natural gas equivalence ratio catalyst |
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