CN103028429A - Three-way catalyst and preparation method thereof - Google Patents
Three-way catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a three-way catalyst system, which comprises a catalyst carrier and an active material. The active material comprises a platinum group metal or an oxide of the platinum group metal and a mesoporous material of which the surface is modified by a metallic oxide; the catalyst carrier comprises a reinforced layer and a support layer; the reinforced layer is formed in a first carrier material; the support layer is formed in a second carrier material; the support layer is arranged in the surface of the reinforced layer; and the active material is attached to the surface of the support layer. The three-way catalyst system provided by the invention is mainly used in the field of automobile tail gas treatment; and the situation that a platinum group element or the oxide of the platinum group element is coated to lose activity caused by structural change of the mesoporous material at the instantaneous high temperature due to low heat stability of high temperature water is avoided. The three-way catalyst system improves the heat stability of the high temperature water, so that the service life and the catalytic efficiency of a catalyst are improved. The invention also provides a preparation method of the three-way catalyst system.
Description
Technical field
The present invention relates to catalyst field, relate in particular to a kind of three-way catalyst and preparation method thereof.
Background technology
Along with the development of science and technology, people's living standard improves constantly, and automobile has become the main flow walking-replacing tool and has been widely used.China's automobile pollution had reached 9,000 ten thousand in 2009, but, growth along with automobile pollution, vehicle exhaust is also day by day serious to the pollution of air, in especially big and big and medium-sized cities, the tail gas of motor vehicle emission progressively becomes the air-polluting principal element, therefore the improvement of automobile exhaust pollution has been become the problem that national governments pay much attention to.
To the improvement of automobile exhaust pollution, mainly take two kinds of approach of emission controls by improving combustion and external purification.External purification is the effective means of control automobile exhaust pollution.External purification refers to by the method for physics or chemistry the pollutant in the tail gas be processed.Chemical method by external widely used method at present, namely by the three-way emission control device being installed with the harmful substance CO in the tail gas, HC, NO
xChange into harmless CO
2, H
2O, and N
2Thereby, greatly reduce environmental pollution, improve air quality.
External three-way catalyst has passed through nearly 40 years development.The company that the at present research and development in this field maintain the leading position is the JM company of Britain, the BASF AG of the U.S., the Umicore Company in Europe.Develop the merchant as the large automobile exhaust systems in the world three, its altogether occupation rate of market more than 90%.In 20 century 70 mid-terms, the developed countries such as Europe, the United States, day just bring into use Exhaust Gas Catalytic Converter for Automobiles, and three-way catalyst is the vent gas treatment product that grows up the eighties, by process simultaneously CO, HC and the NO in the exhaust with a kind of catalyst
x, i.e. catalyst take Pt, Rh and Pd noble metal as main active component.
Three-way catalyst generally is comprised of catalyst carrier, coating and active component.Carrier surface scribbles very thin catalyst coat, and thickness is between 20～40 μ m.It is with γ-Al
2O
3Be main, other composite oxide material of doped portion, its effect is carried noble metal and makes its high degree of dispersion, strengthens the durability of noble metal; That directly play catalytic action in the coating mainly is platinum family noble metal (platinum Pt, rhodium Rh, palladium Pd), and current most of three-way catalysts adopt the combination of platinum, rhodium as the noble metal composition; The consumption of every liter of automotive exhaust catalysis device is 1.4～1.7g.In the process of exploitation catalyst, people recognize in order to make effectively effect of catalyst performance, and each in three kinds of noble metal platinums, rhodium, the palladium will occupy a special position in catalyst; But in order to reduce the cost of catalyst, the consumption of noble metal is crucial in the control catalyst, be key technology in the catalyst preparation and how can make noble metal nano particles keep high dispersion and keep stable, the science and technology staff concentration can make noble metal nano particles can reach Jie's poromerics application technology of polymolecularity in exploitation for this reason.
Chinese patent CN101433846 discloses a kind of cerium-based composite oxides supported precious metal three-effect catalyst and preparation method thereof, it be salt take solubility cerium, zirconates and aluminium salt and solubility modifying element as raw material, adopt coprecipitation to prepare carrier material γ-Al
2O
3With Ce
1-xZr
xM
yO
2, wherein x=0.25～0.75 (molar fraction), M=lanthanum, praseodymium, strontium or copper, y=0～0.1 (mass fraction), aluminium oxide and cerium Zirconium oxide mass ratio are 0.5～2; The equi-volume process load accounts for catalyst quality 0.25～3.0% noble metal on carrier, the high-performance three-effect catalyst of preparation cerium-based composite oxides supported precious metal, and its essence is the element doping of mesoporous material.
Chinese patent CN1792430 discloses a kind of cerium oxide/zirconia composite mesopore three-effect catalysis material and preparation method thereof.This cerium oxide/zirconia composite mesopore three-effect catalysis material, be that 15～40% nanocrystalline cerium oxide and nanometer crystal zirconium form the inorganic skeleton with meso-hole structure by mass content, obtain CO, HC and NO that prepared cerium oxide/zirconia composite mesopore catalysis material is used for purifying automobile tail gas simultaneously
x, and have good low temperature active and heat endurance, similar patent such as CN1212885C.
In above-mentioned patent, all used mesoporous material or molecular sieve as a kind of material of coating, but general mesoporous material or hydrothermal stability of molecular sieve are relatively poor, if when engine operation under the moment high-temperature condition, the destruction of catalyst coat material structure will occur and cause noble metal to be wrapped, so that the noble metal effective rate of utilization sharply descends, catalyst is of serious failure.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of high activity, high hydrothermal stability, three-way catalyst system and preparation method thereof cheaply.
In order to solve the prior art problem, the invention provides a kind of three-way catalyst system, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and surface are by the mesoporous material of metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; The first carrier material forms described enhancement Layer; The Second support material forms described supporting layer; Described supporting layer is arranged at described enhancement Layer surface, and described active material is attached to described support layer surface.
Preferably, described metal oxide is one or more in alundum (Al2O3), magnesia, calcium oxide, barium monoxide, strontium oxide strontia, zinc oxide, oxidation one, gallium oxide, indium oxide or the germanium oxide.
Preferably, one or more in described mesoporous material selected from cerium zirconium-oxygen solid solution, alumino-silicate or the amorphous silica.
Preferably, described the first carrier material is cordierite.
Preferably, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.
The present invention also provides a kind of preparation method of three-way catalyst system, comprising:
A) provide the first carrier material and Second support material;
B) slurry that described the first carrier material dipping is formed by the Second support slurry obtains catalyst carrier after for the first time roasting; Described the first carrier material forms the enhancement Layer of described catalyst carrier; Described Second support material forms the supporting layer of described catalyst carrier;
C) mesoporous material is mixed with metal salt solution, by backflow, infusion process or collosol and gel or coprecipitation method carry out that salt or oxide precursor with metal ion is attached on the mesoporous material surface, filtration, drying, carry out for the second time roasting and obtain the surface by the mesoporous material of metal oxide modified;
D) compounding agent solution, described surface are mixed with platinum group metal or platinum group metal salts by the mesoporous material of metal oxide modified, obtain active material slurry;
E) described catalyst carrier flooded in described active material slurry, carry out for the third time roasting after the drying and obtain the three-way catalyst system.
Preferably, described the first carrier material is cordierite.
Preferably, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.
Preferably, one or more in described mesoporous material selected from cerium zirconium-oxygen solid solution, alumino-silicate or the amorphous silica.
Preferably, described compounding agent solution is for making by one or more the aqueous solution in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and the yttrium nitrate.
The invention provides a kind of three-way catalyst system, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and surface are by the mesoporous material of metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; The first carrier material forms described enhancement Layer; The Second support material forms described supporting layer; Described supporting layer is arranged at described enhancement Layer surface, and described active material is attached to described support layer surface.Among the present invention the mesoporous material after the modification is incorporated into three-way catalyst, improves the decentralization of noble metal with modification high hydrothermal stability mesoporous material as coating material, the use consumption of decrease noble metal, the utilization rate of raising noble metal.The present invention also provide a kind of with modified mesoporous material as the high-performance of coating framework material, high hydrothermal stability and three-way catalyst preparation method cheaply.The method preparation condition easily realizes, raw material is easy to get, and operates controlledly, is fit to large-scale industrial production.
Description of drawings
Fig. 1,2 is for adding adsorption-desorption curve and the pore-size distribution of the obtained catalyst fines of mesoporous material;
The three-decker catalyst pattern SEM photo that Fig. 3 makes;
Fig. 4 catalyst is to the catalyzed conversion curve of simulated exhaust gas;
The adsorption/desorption curve of 00 ℃ of hydrothermal treatment consists rear catalyst of Figure 59 powder.
The specific embodiment
In order further to understand the present invention, below in conjunction with embodiment the preferred embodiments of the invention are described, but should be appreciated that the just restriction for further specifying the features and advantages of the present invention rather than patent of the present invention being required of these descriptions.
The invention provides a kind of three-way catalyst system, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and surface are by the mesoporous material of metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; The first carrier material forms described enhancement Layer; The Second support material forms described supporting layer; Described supporting layer is arranged at described enhancement Layer surface, and described active material is attached to described support layer surface.
According to the present invention, described three-way catalyst system comprises catalyst carrier and active material, the prior art of comparing, active material provided by the invention forms on the mesoporous material for the oxide with platinum group metal or platinum group metal is attached to, described mesoporous material passes through metal oxide modified, improve the high hydrothermal stability of mesoporous material, described metal oxide also can improve the stability of described catalyst in addition, when being applied to the vehicle exhaust process field, described catalyst makes, can keep NO in the tail gas at changeable environment, CO, the activation of the compounds such as CH and reaction, make the pernicious gas rapid conversion in the tail gas, if when engine operation under the moment high-temperature condition, active material is that stratiform is attached to described catalyst carrier surface, part is infiltrated in the supporting layer of Second support material formation, because the mesoporous material surface has metal oxide modified, so in the situation that moment high temperature, described mesoporous material structure can be not destroyed, the oxide of described platinum group metal or platinum group metal can not be wrapped by, and platinum group metal or the platinum group metal oxide having avoided causing because of coating lose activity.
According to the present invention, described mesoporous material is preferably selected from one or more in cerium-zirconium-oxygen solid solution, alumino-silicate or the amorphous silica.Ce more preferably
xZr
1-xO
2Among (0.1≤x≤0.8), SBA-15, SBA-16, MCM-21, MCM-41, MCM-48, MCM-50, ZSM-5 and the ZSM-35 one or more.Wherein SBA-15, SBA-16 are that the aperture is the amorphous silica mesoporous material of 2～30nm, a kind of mesopore material that it is synthesized in California, USA university santa barbara branch school for the former academician in Fudan University in Shanghai Zhao east." bagel ", " Egg-sausage ", " cashew nut " or the meso-hole structures such as " wheat heads " that generally have high-sequential.
MCM-41 (Mobil Composition of Matters), MCM-48 and MCM-50 are the aperture at the amorphous silica mesoporous material of 2～10nm.Wherein MCM-41 has hexagonal mesoporous structure, and MCM-48 has the pore passage structure of three-dimensional UNICOM, and MCM-50 has layer structure.
ZSM-5 (Zeolite Socony Mobil) is the alumino-silicate of U.S. Mobil oil company invention in 1975, and its general molecular formula is Na
nAl
nSi
96-nO
19216H
2O (0＜n＜27) generally has the 3 D pore canal system, and the hole dimension that is parallel to the axial linear of b duct is
The hole dimension that is parallel to the axial sinusoidal of a duct is
Can there be micropore and meso-hole structure in the aperture; ZSM-35 is the spherical cage that octatomic ring duct and hexatomic ring duct infall form 0.6～0.7nm.
According to the present invention, described metal oxide is preferably one or more in alundum (Al2O3), magnesia, calcium oxide, barium monoxide, strontium oxide strontia, zinc oxide, oxidation one, gallium oxide, indium oxide or the germanium oxide.These metal oxides make by mesoporous material being immersed in the soluble metal salting liquid corresponding with above-mentioned oxide, and then dry calcination obtains.And described soluble metal salting liquid can be solubility alkoxide, nitrate or the hydroxide of aluminium, magnesium, calcium, barium, strontium, zinc, yttrium, gallium, indium or germanium.Described metal oxide can adhere to or be filled in the space of mesoporous material, prevent that the pore structure that mesoporous material causes owing to external condition is unstable from caving in, these metal oxides also can play the effect that each gas reacts in certain activation tail gas in addition.
Comprise enhancement Layer and supporting layer according to catalyst carrier of the present invention.Described supporting layer is arranged at described enhancement Layer surface.Described enhancement Layer provides mechanical strength and toughness for catalyst system; Described supporting layer carrying and fixing described active material.According to enhancement Layer of the present invention by the first carrier material form, described supporting layer forms by described Second support material, described the first carrier material is preferably cordierite.
According to the present invention, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.Supporting layer is cellular, has increased specific area, has increased the contact area of catalyst and tail gas, thereby can improve the catalytic efficiency of catalyst.
The present invention also provides a kind of preparation method of three-way catalyst system, comprising: the first carrier material and Second support material a) are provided;
B) slurry that described the first carrier material dipping is formed by the Second support slurry obtains catalyst carrier after for the first time roasting; Described the first carrier material forms the enhancement Layer of described catalyst carrier; Described Second support material forms the supporting layer of described catalyst carrier;
C) mesoporous material is mixed with metal salt solution, by backflow, infusion process or collosol and gel or coprecipitation method carry out that salt or oxide precursor with metal ion is attached on the mesoporous material surface, filtration, drying, carry out for the second time roasting and obtain the surface by the mesoporous material of metal oxide modified;
D) compounding agent solution, described surface are mixed with platinum group metal or platinum group metal salts by the mesoporous material of metal oxide modified, obtain active material slurry;
E) described catalyst carrier flooded in described active material slurry, carry out for the third time roasting after the drying and obtain the three-way catalyst system.
According to the present invention, the preparation of described three-way catalyst system is specially:
1) with 600 orders and 400 order cordierite carrier ultrasonic cleaning and dry rear for subsequent use;
2) with activated alumina (γ-Al
2O
3) or common aluminium oxide and common cerium zirconium sosoloid one be 1: 0～4 to be mixed with slurry in mass ratio, regulate slurry pH value 1～6, obtain slurry A;
3) cordierite carrier with cleaning floods rear drying in the A slurry, and carries out the sample B that for the second time roasting obtains being covered with Second support under 100～500 ℃;
4) be mixed with modified solution C with in aluminum soluble salt, magnesium salts, calcium salt, barium salt, strontium salt, zinc salt, yttrium salt, gallium salt, indium salt or the germanium salt one or more for subsequent use;
5) mesoporous material that will make by oneself or buy is (such as Ce
xZr
1-xO
2(0.1≤x≤0.8), SBA-15, SBA-16, MCM-21, MCM-41, MCM-48, MCM-50, ZSM-5 and ZSM-35 etc.) join in the above-mentioned C solution, undertaken salt or the oxide precursor of metal ion are attached on the mesoporous material surface by backflow, infusion process or collosol and gel or coprecipitation method; With slurries filtration and after fully washing, 30～150 ℃ of dryings, and for subsequent use at the powder D that carries out under 100～500 ℃ after for the second time roasting obtained modification in 0.5～6 hour;
6) the preparing metal ion concentration is the compounding agent solution of 0.5mol/L～5mol/L, and regulating the pH value by acid or alkali is 1～6, the gained solution E;
7) other coating material of powder D or interpolation is joined together stir in the solution E or ball milling evenly after, add one or more soluble-salts in lower content (bullion content is the 0.7g/L calculated) catalyst activity component platinum, rhodium or the palladium in the slurry, and stir and obtain slurry F;
8) sample B is flooded certain hour in slurry F after, under 30～150 ℃ of dryings dry 0.5～48 hour, obtain three-way catalyst in carrying out for the third time roasting under 400～700 ℃ after 1～8 hour.
Described step 4) employed modification soluble-salt is alkoxide, nitrate or hydroxide;
Described step 6) acid described in is one or more of nitric acid, acetic acid or ethanedioic acid, and alkali is one or more of ammoniacal liquor, hydrazine or urea, and last, the drying mode in the described step is the electric heating forced air drying;
Described compounding agent solution preferably makes by one or more the aqueous solution in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and the yttrium nitrate.
It below is specific embodiment provided by the invention.
With the three-way catalyst of modified SBA-15 material as coating material
A, 400 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) as the Second support material, the preparation solid content is the slurry of 30wt%, regulating slurry PH is 2, obtains slurry A;
C, the cordierite carrier of cleaning flooded half an hour in the A slurry after, 110 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 600 ℃ of lower roastings;
D, aluminium secondary butylate is made into the modification toluene solution of content 10%, mesoporous material SBA-15 is added in the solution, room temperature refluxed 3 hours, and the powder C that filtration, alcohol wash, the rear 110 ℃ of dryings of washing obtain after the modification is for subsequent use;
It is the aqueous solution of auxiliary agent that f, preparation contain zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, and total concentration of metal ions is 5mol/L in the described aqueous solution.Regulating pH value by nitric acid is 2, the gained solution D;
G, with powder C join in the solution D stir 4 hours after, adding the catalyst activity component in the slurry is the soluble-salt of rhodium or palladium (bullion content is the 0.7g/L calculated), and stirs and obtain slurry E;
H, sample B flooded 30 minutes in slurry E after, 80 ℃ lower dry 24 hours, obtain three-way catalyst in 600 ℃ of lower roastings after 4 hours.
Catalyst has been carried out properties characterized shown in Fig. 1～4, catalyst is contained under 10% steam hydrothermal treatment consists at 900 ℃, and the adsorption/desorption curve is as shown in Figure 5 after 10 hours.
Fig. 1～5 are relevant characterization and performance test among the embodiment 1, P among Fig. 1
0/ P has obvious hysteresis loop at 0.4～0.8 place, so this material has obvious meso-hole structure; The mesoporous aperture of propping up calculating from the BHJ desorption of Fig. 2 is 3.8nm, and Fig. 3 is prepared three-decker catalyst pattern SEM photo; Fig. 4 is that catalyst is to the catalyzed conversion curve of simulated exhaust gas, catalyst T
50 (CO)Be 220 ℃, T
50 (CH)Be 260 ℃, T
50 (NOx)It is 220 ℃.Wherein a is the CH inversion cuver; B is the CO inversion cuver; C is the NO inversion cuver; Fig. 5 be catalyst through the adsorption/desorption curve of 900 ℃ of hydrothermal treatment consists rear catalyst powder, can draw material from figure and still have meso-hole structure, do not cause pore structure to be caved in because of long-time hydrothermal treatment consists.
Embodiment 2
With the three-way catalyst of modified SBA-15 material as coating material
A, 600 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) and Ce
0.2Zr
0.8O
2Preparation preparation solid content was the slurry of 30wt% to solid solution as the Second support material in 3: 2 in mass ratio, and regulating slurry PH is 2, obtains slurry A;
C, the cordierite carrier of cleaning flooded half an hour in the A slurry after, 80 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 650 ℃ of lower roastings;
D, tert-butyl alcohol magnesium is made into the modification toluene solution of content 15%, mesoporous material SBA-15 is added in the solution, constantly stir and by infusion process presoma is adhered on the mesoporous material surface; After the also abundant alcohol wash of slurries filtration, washing, obtain modified powder C 110 ℃ of lower dryings after 24 hours for subsequent use;
F, contain barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 1mol/L in the described aqueous solution.Regulating pH value by nitric acid is 3, the gained solution D;
G, with powder C and γ-Al
2O
3Powder joins in mass ratio in the solution D and to stir after 2 hours at 2: 1, and adding the catalyst activity component in the slurry is platinum, rhodium or palladium (bullion content is the 0.7g/L calculated) soluble-salt, and stirs and obtain slurry E;
H, sample B flooded 1 hour in slurry E after, 110 ℃ lower dry 10 hours, obtain three-way catalyst in 650 ℃ of lower roastings after 3 hours.
Embodiment 3
With the three-way catalyst of modified SBA-15 material as coating material
A, 400 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) as the Second support material, preparation preparation solid content is the slurry of 30wt%, regulating slurry PH is 2, obtains slurry A;
C, the cordierite carrier of cleaning flooded half an hour in the A slurry after, 110 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 600 ℃ of lower roastings;
D, aluminum nitrate is made into the modified solution of content 10%, mesoporous material SBA-15 is added in the solution, constantly stir and by sol-gal process the alumina precursor gel is adhered on the mesoporous material surface; With slurries filtration and fully after the washing, respectively 60 ℃ and 110 ℃ of lower dryings 24 hours, and the powder C after 500 ℃ of lower roastings obtained modification in 1 hour is for subsequent use;
F, contain zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 2mol/L in the described aqueous solution.Regulating pH value by nitric acid is 2, the gained solution D;
G, with powder C join in the solution D stir 4 hours after, adding the catalyst activity component in the slurry is the soluble-salt of rhodium or palladium (bullion content is the 0.7g/L calculated), and stirs and obtain slurry E;
H, sample B flooded 30 minutes in slurry E after, 80 ℃ lower dry 24 hours, obtain three-way catalyst in 600 ℃ of lower roastings after 4 hours.
Embodiment 4
With the three-way catalyst of modified SBA-15 material as coating material
A, 600 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) and Ce
0.2Zr
0.8O
2The preparation solid content was the slurry of 30wt% to solid solution as the Second support material in 3: 2 in mass ratio, and regulating slurry PH is 2, obtains slurry A;
C, the cordierite carrier of cleaning flooded half an hour in the A slurry after, 80 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 650 ℃ of lower roastings;
D, aluminum nitrate and magnesium nitrate be made into the modified solution of content 15%, mesoporous material SBA-15 is added in the solution, constantly stir and by infusion process presoma is adhered on the mesoporous material surface; With slurries filtration and fully after the washing, respectively 60 ℃ and 110 ℃ of lower dryings 24 hours, and the powder C after 450 ℃ of lower roastings obtained modification in 2 hours is for subsequent use;
F, contain barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 3mol/L in the described aqueous solution.Regulating pH value by nitric acid is 3, the gained solution D;
G, with powder C and γ-Al
2O
3Powder joins in mass ratio in the solution D and to stir after 2 hours at 2: 1, and adding the catalyst activity component in the slurry is platinum, rhodium or palladium (bullion content is the 0.7g/L calculated) soluble-salt, and stirs and obtain slurry E;
H, sample B flooded 1 hour in slurry E after, 110 ℃ lower dry 10 hours, obtain three-way catalyst in 650 ℃ of lower roastings after 3 hours.
With the three-way catalyst of the mesoporous cerium zirconium powder of modification end as coating material
A, 400 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) as the Second support material, the preparation solid content is the slurry of 30wt%, regulating slurry PH is 2, obtains slurry A;
C, the cordierite carrier of cleaning flooded half an hour in the A slurry after, 110 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 600 ℃ of lower roastings;
D, aluminium secondary butylate is made into the modification toluene solution of content 20%, mesoporous cerium zirconium is added in the solution, room temperature refluxed 1 hour, and the powder C that filtration, alcohol wash, the rear 110 ℃ of dryings of washing obtain after the modification is for subsequent use;
F, contain zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 4mol/L in the described aqueous solution.Regulating pH value by nitric acid is 2, the gained solution D;
G, with powder C join in the solution D stir 4 hours after, adding the catalyst activity component in the slurry is the soluble-salt of rhodium or palladium (bullion content is the 0.7g/L calculated), and stirs and obtain slurry E;
H, sample B flooded 30 minutes in slurry E after, 80 ℃ lower dry 24 hours, obtain three-way catalyst in 600 ℃ of lower roastings after 4 hours.
Embodiment 6
With the three-way catalyst of Modified MCM-41 material as coating material
A, 600 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with common aluminium oxide as the Second support material, the preparation solid content is the slurry of 30wt%, regulating slurry PH is 1, obtains slurry A after 24 hours through planetary ball mill;
C, the cordierite carrier of cleaning flooded 15 minutes in the A slurry after, 110 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 700 ℃ of lower roastings;
D, yttrium nitrate and barium hydroxide be made into the modified solution of mass content 8%, Mesoporous silica MCM 41 is added in the solution, constantly stir and by coprecipitation metal precursor is adhered on the mesoporous material surface; With slurries filtration and fully after the washing, respectively 80 ℃ and 120 ℃ of lower dryings 24 hours, and the powder C after 350 ℃ of lower roastings obtained modification in 1 hour is for subsequent use;
F, contain zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, neodymium nitrate, ferric nitrate, cobalt nitrate, copper nitrate and yttrium nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 5mol/L in the described aqueous solution.Regulating pH value by nitric acid is 4, the gained solution D;
G, with powder C and γ-Al
2O
3Powder joins in mass ratio in the solution D and to stir after 1 hour at 1: 1, and adding the catalyst activity component in the slurry is platinum, rhodium or palladium (bullion content is the 0.7g/L calculated) soluble-salt, and stirs and obtain slurry E;
H, sample B flooded 3 hours in slurry E after, 100 ℃ lower dry 24 hours, obtain three-way catalyst in 600 ℃ of lower roastings after 6 hours.
Embodiment 7
With the three-way catalyst of modified ZSM-5 mesoporous material as coating material
A, 400 order cordierite carrier ultrasonic cleaning and drying are rear for subsequent use;
B, with activated alumina (γ-Al
2O
3) as the Second support material, the preparation solid content is the slurry of 30wt%, regulating slurry PH is 3, obtains slurry A;
C, the cordierite carrier of cleaning flooded 30 minutes in the A slurry after, 115 ℃ of dryings 24 hours, obtain being covered with the sample B of Second support 600 ℃ of lower roastings;
D, aluminum nitrate and barium hydroxide be made into the modified solution of mass content 12%, mesoporous material ZSM-5 is added in the solution, constantly stir and by infusion process metal precursor is attached on the mesoporous material surface; With slurries filtration and fully after the washing, respectively 70 ℃ and 110 ℃ of lower dryings 24 hours, and the powder C after 380 ℃ of lower roastings obtained modification in 2 hours is for subsequent use;
F, contain zirconium nitrate, cerous nitrate, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate and copper nitrate as the aqueous solution of auxiliary agent take the preparation of certain proportioning, total concentration of metal ions is 2.5mol/L in the described aqueous solution.Regulating pH value by nitric acid is 5, the gained solution D;
G, with powder C join in the solution D stir 6 hours after, adding the catalyst activity component in the slurry is platinum, rhodium or palladium (bullion content is the 0.7g/L calculated) soluble-salt, and stirs and obtain slurry E;
H, sample B flooded 1 hour in slurry E after, 120 ℃ lower dry 24 hours, obtain three-way catalyst in 600 ℃ of lower roastings after 4 hours.
Above a kind of three-way catalyst system provided by the invention and preparation method thereof is described in detail; having used specific case herein sets forth principle of the present invention and embodiment; the explanation of above embodiment just is used for helping to understand method of the present invention and core concept thereof; should be understood that; for those skilled in the art; under the prerequisite that does not break away from the principle of the invention; can also carry out some improvement and modification to the present invention, these improvement and modification also fall in the protection domain of claim of the present invention.
Claims (10)
1. a three-way catalyst system is characterized in that, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and surface are by the mesoporous material of metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; The first carrier material forms described enhancement Layer; The Second support material forms described supporting layer; Described supporting layer is arranged at described enhancement Layer surface, and described active material is attached to described support layer surface.
2. three-way catalyst system according to claim 1, it is characterized in that, described metal oxide is one or more in alundum (Al2O3), magnesia, calcium oxide, barium monoxide, strontium oxide strontia, zinc oxide, oxidation one, gallium oxide, indium oxide or the germanium oxide.
3. three-way catalyst system according to claim 1 is characterized in that, one or more in described mesoporous material selected from cerium zirconium solid solution, alumino-silicate or the amorphous silica.
4. three-way catalyst system according to claim 1 is characterized in that, described the first carrier material is cordierite.
5. three-way catalyst system according to claim 1 is characterized in that, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.
6. the preparation method of a three-way catalyst system is characterized in that, comprising:
A) provide the first carrier material and Second support material;
B) slurry that described the first carrier material dipping is formed by the Second support slurry obtains catalyst carrier after for the first time roasting; Described the first carrier material forms the enhancement Layer of described catalyst carrier; Described Second support material forms the supporting layer of described catalyst carrier;
C) mesoporous material is mixed with metal salt solution, by backflow, infusion process or collosol and gel or coprecipitation method carry out that salt or oxide precursor with metal ion is attached on the mesoporous material surface, filtration, drying, carry out for the second time roasting and obtain the surface by the mesoporous material of metal oxide modified;
D) compounding agent solution, described surface are mixed with platinum group metal or platinum group metal salts by the mesoporous material of metal oxide modified, obtain active material slurry;
E) described catalyst carrier flooded in described active material slurry, carry out for the third time roasting after the drying and obtain the three-way catalyst system.
7. preparation method according to claim 6 is characterized in that, described the first carrier material is cordierite.
8. preparation method according to claim 6 is characterized in that, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.
9. preparation method according to claim 6 is characterized in that, one or more in described mesoporous material selected from cerium zirconium-oxygen solid solution, alumino-silicate or the amorphous silica.
10. preparation method according to claim 6, it is characterized in that, described compounding agent solution is for making by one or more the aqueous solution in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and the yttrium nitrate.
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