CN103028429B - A kind of three-way catalyst and preparation method thereof - Google Patents
A kind of three-way catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention provides a kind of ternary catalyst systems, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and the surperficial mesoporous material by metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; First carrier material forms described enhancement Layer; 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.Ternary catalyst systems provided by the invention is mainly used in vehicle maintenance service field, avoid mesoporous material under instantaneous high-temperature bad due to high-temperature hydrothermal stability and cause structure change, cause the oxide of platinum family element or platinum family element be wrapped by and lose activity.So described ternary catalyst systems improves high-temperature hydrothermal stability, thus improve life-span and the catalytic efficiency of catalyst.Present invention also offers a kind of preparation method of ternary catalyst systems.
Description
Technical field
The present invention relates to catalyst field, particularly relate to a kind of three-way catalyst and preparation method thereof.
Background technology
Along with the development of science and technology, the living standard of people improves constantly, and automobile has become main flow walking-replacing tool and has been widely used.Within 2009, China's automobile pollution has reached 9,000 ten thousand, but, along with the growth of 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 air-polluting principal element, has therefore become to the improvement of automobile exhaust pollution the problem that national governments pay much attention to.
To the improvement of automobile exhaust pollution, mainly take emission controls by improving combustion and external purification two kinds of approach.External purification is the most effective means controlling automobile exhaust pollution.External purification refers to the method by physics or chemistry, is processed by the pollutant in tail gas.Chemical method by external widely used method at present, namely by installing three-way emission control device by the harmful substance CO in tail gas, HC, NO
xchange into harmless CO
2, H
2o and N
2, thus greatly reduce environmental pollution, improve air quality.
External three-way catalyst is through the development of nearly 40 years.The company that research and development at present 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 business as the large automobile exhaust system in the world three, its altogether occupation rate of market more than 90%.In 20 century 70 mid-terms, Europe, the United States, Deng developed country just bring into use Exhaust Gas Catalytic Converter for Automobiles, and three-way catalyst is the vent gas treatment product grown up the eighties, by processing the CO in exhaust with a kind of catalyst, HC and NO simultaneously
x, namely with the catalyst that Pt, Rh and Pd noble metal is main active component.
Three-way catalyst is generally made up of catalyst carrier, coating and active component.Carrier surface scribbles very thin catalyst coat, and thickness is between 20 ~ 40 μm.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; Directly play the mainly platinum-group noble metals (platinum Pt, rhodium Rh, palladium Pd) of catalytic action in coating, current most of three-way catalyst adopts the combination of platinum, rhodium as noble metal component; The consumption of often liter of automotive exhaust catalysis device is 1.4 ~ 1.7g.In the process of exploitation catalyst, people recognize to make catalyst play effective effect, and each in three kinds of noble metal platinums, rhodium, palladium will occupy a special position in the catalyst; But in order to reduce the cost of catalyst, the consumption controlling noble metal in catalyst is crucial, and noble metal nano particles how can be made to keep high dispersion and keep stable to be key technology in catalyst preparing, 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 is with the salt of solubility cerium, zirconates and aluminium salt and solubility modifying element for raw material, adopts 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; On carrier, equi-volume process load accounts for catalyst quality 0.25 ~ 3.0% noble metal, prepares the high-performance three-effect catalyst of 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, by mass content be 15 ~ 40% nanocrystalline cerium oxide and nanometer crystal zirconium form the inorganic skeleton with meso-hole structure, obtain prepared cerium oxide/zirconia composite mesopore catalysis material simultaneously for CO, HC and the NO in purifying automobile tail gas
x, and there is excellent low temperature active and heat endurance, similar patent is as CN1212885C.
Mesoporous material or the molecular sieve a kind of material as coating is all employed in above-mentioned patent, but general mesoporous material or hydrothermal stability of molecular sieve poor, if when engine operation in instantaneous high-temperature situation, noble metal is caused to be wrapped the destruction that there will be catalyst coat material structure, noble metal effective rate of utilization is sharply declined, and catalyst is of serious failure.
Summary of the invention
The technical problem to be solved in the present invention is ternary catalyst systems providing a kind of high activity, high hydrothermal stability, low cost and preparation method thereof.
In order to solve prior art problem, the invention provides a kind of ternary catalyst systems, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and the surperficial mesoporous material by metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; First carrier material forms described enhancement Layer; 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 germanium oxide.
Preferably, one or more in described mesoporous material selected from cerium zirconium-oxygen solid solution, alumino-silicate or amorphous silica.
Preferably, described first carrier material is cordierite.
Preferably, described Second support material be aluminium oxide, activated alumina and cerium zirconium sosoloid one or more.
Present invention also offers a kind of preparation method of ternary catalyst systems, comprising:
A) first carrier material and Second support material are provided;
B) described first carrier material is flooded the slurry formed by Second support slurry, after first time roasting, obtain catalyst carrier; Described 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, undertaken the salt of metal ion or oxide precursor to be attached to by backflow, infusion process or collosol and gel or coprecipitation method mesoporous material on the surface, filter, dry, carry out second time roasting and obtain the mesoporous material of surface by 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 third time roasting after drying and obtain ternary catalyst systems.
Preferably, described 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 amorphous silica.
Preferably, described compounding agent solution is obtained by the aqueous solution of one or more in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and yttrium nitrate.
The invention provides a kind of ternary catalyst systems, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and the surperficial mesoporous material by metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; First carrier material forms described enhancement Layer; 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.In the present invention, modified mesoporous material is incorporated into three-way catalyst, improves the decentralization of noble metal using modification high hydrothermal stability mesoporous material as coating material, significantly reduce the use consumption of noble metal, improve the utilization rate of noble metal.Present invention also offers a kind of three-way catalyst preparation method of high-performance, high hydrothermal stability and low cost using modified mesoporous material as coating framework material.The method preparation condition easily realizes, and raw material is easy to get, and operates controlled, is applicable to large-scale industrial production.
Accompanying drawing explanation
Fig. 1,2 is for adding adsorption-desorption curve and the pore-size distribution of catalyst fines obtained by mesoporous material;
The three-decker catalyst pattern SEM photo that Fig. 3 obtains;
Fig. 4 catalyst is to the catalyzed conversion curve of simulated exhaust gas;
The adsorption/desorption curve of Figure 59 00 DEG C of hydrothermal treatment consists rear catalyst powder.
Detailed description of the invention
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiments of the invention are described, but should be appreciated that these describe just as further illustrating the features and advantages of the present invention instead of the restriction to patent requirements of the present invention.
The invention provides a kind of ternary catalyst systems, comprising: catalyst carrier and active material; Wherein said active material comprises: the oxide of platinum group metal or platinum group metal and the surperficial mesoporous material by metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; First carrier material forms described enhancement Layer; 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 ternary catalyst systems comprises catalyst carrier and active material, to compare prior art, active material provided by the invention is be attached to by the oxide of platinum group metal or platinum group metal mesoporous material is formed, 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 described catalyst application makes in vehicle maintenance service field, NO in tail gas can be kept at changeable environment, CO, the activation of the compounds such as CH and reaction, make the pernicious gas rapid conversion in tail gas, if when engine operation in instantaneous high-temperature situation, active material is that stratiform is attached to described catalyst support surface, part is infiltrated in the supporting layer of Second support material formation, because mesoporous material surface has metal oxide modified, so when instantaneous high-temperature, described mesoporous material structure can not be destroyed, the oxide of described platinum group metal or platinum group metal can not be wrapped by, avoid the platinum group metal of causing because of coated or platinum group metal oxide loses 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 amorphous silica.Be more preferably Ce
xzr
1-xo
2one or more in (0.1≤x≤0.8), SBA-15, SBA-16, MCM-21, MCM-41, MCM-48, MCM-50, ZSM-5 and ZSM-35.The wherein amorphous silica mesoporous material of SBA-15, SBA-16 to be aperture be 2 ~ 30nm, it is a kind of mesopore material that the former academician in Fudan University in Shanghai Zhao east is synthesized in California, USA university santa barbara branch school.Generally there is the meso-hole structures such as " bagel ", " Egg-sausage ", " cashew nut " or " wheat head " of high-sequential.
MCM-41 (Mobil Composition of Matters), MCM-48 and MCM-50 is the amorphous silica mesoporous material of aperture at 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 Mobil oil company of U.S. invention in 1975, and its general molecular formula is Na
nal
nsi
96-no
19216H
2o (0 < n < 27), generally have 3 D pore canal system, the hole dimension being parallel to the axial linear duct of b is
the hole dimension being parallel to the axial sinusoidal duct of a is
can there be micropore and meso-hole structure in 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 be preferably in alundum (Al2O3), magnesia, calcium oxide, barium monoxide, strontium oxide strontia, zinc oxide, oxidation one, gallium oxide, indium oxide or germanium oxide one or more.These metal oxides make by being immersed in by mesoporous material in the soluble metal salt solution corresponding with above-mentioned oxide, and then dry calcination obtains.And described soluble metal salt solution can be the solubility alkoxide of aluminium, magnesium, calcium, barium, strontium, zinc, yttrium, gallium, indium or germanium, nitrate or hydroxide.Described metal oxide can adhere to or be filled in the space of mesoporous material, the pore structure preventing mesoporous material from causing due to external condition instability is caved in, and these metal oxides also can play the effect that in certain activation tail gas, each gas reacts in addition.
Enhancement Layer and supporting layer is comprised 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.Formed by the first carrier material according to enhancement Layer of the present invention, described supporting layer formed by described Second support material, described 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, adds specific area, adds the contact area of catalyst and tail gas, thus can improve the catalytic efficiency of catalyst.
Present invention also offers a kind of preparation method of ternary catalyst systems, comprising: the first carrier material and Second support material a) are provided;
B) described first carrier material is flooded the slurry formed by Second support slurry, after first time roasting, obtain catalyst carrier; Described 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, undertaken the salt of metal ion or oxide precursor to be attached to by backflow, infusion process or collosol and gel or coprecipitation method mesoporous material on the surface, filter, dry, carry out second time roasting and obtain the mesoporous material of surface by 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 third time roasting after drying and obtain ternary catalyst systems.
According to the present invention, the preparation of described ternary catalyst systems is specially:
1) by 600 orders and 400 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
2) by activated alumina (γ-Al
2o
3) or common aluminium oxide and common cerium zirconium sosoloid one be 1: 0 ~ 4 be mixed with slurry in mass ratio, regulate slurry pH value 1 ~ 6, obtain slurry A;
3) dry after the cordierite carrier of cleaning being flooded in A slurry, and at 100 ~ 500 DEG C, carry out the sample B that second time roasting obtains being covered with Second support;
4) modified solution C is mixed with one or more in aluminum soluble salt, magnesium salts, calcium salt, barium salt, strontium salt, zinc salt, yttrium salt, gallium salt, indium salt or germanium salt for subsequent use;
5) by self-control or buy mesoporous material (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 above-mentioned C solution, undertaken the salt of metal ion or oxide precursor to be attached to mesoporous material on the surface by backflow, infusion process or collosol and gel or coprecipitation method; By slurries filtration and fully after washing, 30 ~ 150 DEG C of dryings, and at 100 ~ 500 DEG C, carrying out second time roasting, within 0.5 ~ 6 hour, to obtain modified powder D for subsequent use;
6) preparing metal ion concentration is the compounding agent solution of 0.5mol/L ~ 5mol/L, is 1 ~ 6 by acid or alkali adjust ph, gained solution E;
7) other coating material of powder D or interpolation is joined in solution E together stir or ball milling evenly after, in slurry, add one or more soluble-salts in lower content (bullion content is 0.7g/L calculated) catalyst activity component platinum, rhodium or palladium, and stir and obtain slurry F;
8), after sample B being flooded certain hour in slurry F, under 30 ~ 150 DEG C of dryings, drying 0.5 ~ 48 hour, carries out third time roasting and obtains three-way catalyst after 1 ~ 8 hour at 400 ~ 700 DEG C.
Described step 4) the modification soluble-salt that uses is alkoxide, nitrate or hydroxide;
Described step 6) described in acid be one or more of nitric acid, acetic acid or ethanedioic acid, alkali is one or more of ammoniacal liquor, hydrazine or urea, and finally, the drying mode in described step is electric heating forced air drying;
Described compounding agent solution obtains preferably by the aqueous solution of one or more in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and yttrium nitrate.
It is below specific embodiment provided by the invention.
Embodiment 1
Using modified SBA-15 material as the three-way catalyst of coating material
A, by 400 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) as Second support material, preparation solid content is the slurry of 30wt%, regulates slurry PH to be 2, obtains slurry A;
C, the cordierite carrier of cleaning is flooded half an hour in A slurry after, 110 DEG C of dryings 24 hours, at 600 DEG C, roasting obtained the sample B being covered with Second support;
D, aluminium secondary butylate is made into the modified toluene solution of content 10%, added by mesoporous material SBA-15 in solution, room temperature refluxes 3 hours, and filtration, alcohol wash, that the rear 110 DEG C of dryings of washing obtain modified powder C is for subsequent use;
F, preparation are the aqueous solution of auxiliary agent containing zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, and in the described aqueous solution, total concentration of metal ions is 5mol/L.PH value is regulated to be 2 by nitric acid, gained solution D;
G, powder C joined in solution D and stir after 4 hours, in slurry, add the soluble-salt that catalyst activity component is rhodium or palladium (bullion content is 0.7g/L calculated), and stir and obtain slurry E;
H, sample B is flooded 30 minutes in slurry E after, at 80 DEG C dry 24 hours, at 600 DEG C, roasting obtained three-way catalyst after 4 hours.
Carried out properties to catalyst to characterize as shown in figures 1-4, by catalyst, at 900 DEG C, containing hydrothermal treatment consists under 10% steam, after 10 hours, adsorption/desorption curve is as shown in Figure 5.
Fig. 1 ~ 5 are relevant characterization and performance test in embodiment 1, P in Fig. 1
0/ P has obvious hysteresis loop at 0.4 ~ 0.8 place, and therefore this material has obvious meso-hole structure; The mesoporous pore size propping up calculating from the BHJ desorption of Fig. 2 is 3.8nm, Fig. 3 is obtained three-decker catalyst pattern SEM photo; Fig. 4 is the catalyzed conversion curve of catalyst to simulated exhaust gas, catalyst T
50 (CO)be 220 DEG C, T
50 (CH)be 260 DEG C, T
50 (NOx)it is 220 DEG C.Wherein a is CH inversion cuver; B is CO inversion cuver; C is NO inversion cuver; Fig. 5 is the adsorption/desorption curve of catalyst through 900 DEG C of hydrothermal treatment consists rear catalyst powder, can show that material still has meso-hole structure from figure, not because of long-time hydrothermal treatment consists causing hole structure collapses.
Embodiment 2
Using modified SBA-15 material as the three-way catalyst of coating material
A, by 600 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) and Ce
0.2zr
0.8o
2solid solution is in mass ratio 3: 2 as Second support material, and preparation preparation solid content is the slurry of 30wt%, regulates slurry PH to be 2, obtains slurry A;
C, the cordierite carrier of cleaning is flooded half an hour in A slurry after, 80 DEG C of dryings 24 hours, at 650 DEG C, roasting obtained the sample B being covered with Second support;
D, tert-butyl alcohol magnesium is made into the modified toluene solution of content 15%, mesoporous material SBA-15 is added in solution, constantly stir and also by infusion process, presoma is adhered to mesoporous material on the surface; After slurries filtration also abundant alcohol wash, washing, at 110 DEG C, obtain modified powder C after dry 24 hours for subsequent use;
F, the aqueous solution being auxiliary agent containing barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 1mol/L.PH value is regulated to be 3 by nitric acid, gained solution D;
G, by powder C and γ-Al
2o
3powder joins in solution D stirs 2 hour after in mass ratio at 2: 1, adds that catalyst activity component is platinum, rhodium or palladium (bullion content is 0.7g/L calculated) soluble-salt in slurry, and stirs and obtain slurry E;
H, sample B is flooded 1 hour in slurry E after, at 110 DEG C dry 10 hours, at 650 DEG C, roasting obtained three-way catalyst after 3 hours.
Embodiment 3
Using modified SBA-15 material as the three-way catalyst of coating material
A, by 400 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) as Second support material, preparation preparation solid content is the slurry of 30wt%, regulates slurry PH to be 2, obtains slurry A;
C, the cordierite carrier of cleaning is flooded half an hour in A slurry after, 110 DEG C of dryings 24 hours, at 600 DEG C, roasting obtained the sample B being covered with Second support;
D, aluminum nitrate is made into the modified solution of content 10%, mesoporous material SBA-15 is added in solution, constantly stir also by sol-gal process by alumina precursor gel attachment mesoporous material on the surface; By slurries filtration and fully after washing, drying 24 hours at 60 DEG C and 110 DEG C respectively, and at 500 DEG C roasting within 1 hour, to obtain modified powder C for subsequent use;
F, the aqueous solution being auxiliary agent containing zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 2mol/L.PH value is regulated to be 2 by nitric acid, gained solution D;
G, powder C joined in solution D and stir after 4 hours, in slurry, add the soluble-salt that catalyst activity component is rhodium or palladium (bullion content is 0.7g/L calculated), and stir and obtain slurry E;
H, sample B is flooded 30 minutes in slurry E after, at 80 DEG C dry 24 hours, at 600 DEG C, roasting obtained three-way catalyst after 4 hours.
Embodiment 4
Using modified SBA-15 material as the three-way catalyst of coating material
A, by 600 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) and Ce
0.2zr
0.8o
2solid solution is in mass ratio 3: 2 as Second support material, and preparation solid content is the slurry of 30wt%, regulates slurry PH to be 2, obtains slurry A;
C, the cordierite carrier of cleaning is flooded half an hour in A slurry after, 80 DEG C of dryings 24 hours, at 650 DEG C, roasting obtained the sample B being covered with Second support;
D, aluminum nitrate and magnesium nitrate are made into the modified solution of content 15%, mesoporous material SBA-15 are added in solution, constantly stir and also by infusion process, presoma is adhered to mesoporous material on the surface; By slurries filtration and fully after washing, drying 24 hours at 60 DEG C and 110 DEG C respectively, and at 450 DEG C roasting within 2 hours, to obtain modified powder C for subsequent use;
F, the aqueous solution being auxiliary agent containing barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 3mol/L.PH value is regulated to be 3 by nitric acid, gained solution D;
G, by powder C and γ-Al
2o
3powder joins in solution D stirs 2 hour after in mass ratio at 2: 1, adds that catalyst activity component is platinum, rhodium or palladium (bullion content is 0.7g/L calculated) soluble-salt in slurry, and stirs and obtain slurry E;
H, sample B is flooded 1 hour in slurry E after, at 110 DEG C dry 10 hours, at 650 DEG C, roasting obtained three-way catalyst after 3 hours.
Embodiment 5
Using the mesoporous cerium zirconium powder end of modification as the three-way catalyst of coating material
A, by 400 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) as Second support material, preparation solid content is the slurry of 30wt%, regulates slurry PH to be 2, obtains slurry A;
C, the cordierite carrier of cleaning is flooded half an hour in A slurry after, 110 DEG C of dryings 24 hours, at 600 DEG C, roasting obtained the sample B being covered with Second support;
D, aluminium secondary butylate is made into the modified toluene solution of content 20%, add in solution by mesoporous cerium zirconium, room temperature refluxes 1 hour, and filtration, alcohol wash, that the rear 110 DEG C of dryings of washing obtain modified powder C is for subsequent use;
F, the aqueous solution being auxiliary agent containing zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 4mol/L.PH value is regulated to be 2 by nitric acid, gained solution D;
G, powder C joined in solution D and stir after 4 hours, in slurry, add the soluble-salt that catalyst activity component is rhodium or palladium (bullion content is 0.7g/L calculated), and stir and obtain slurry E;
H, sample B is flooded 30 minutes in slurry E after, at 80 DEG C dry 24 hours, at 600 DEG C, roasting obtained three-way catalyst after 4 hours.
Embodiment 6
Using Modified MCM-41 material as the three-way catalyst of coating material
A, by 600 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, using common aluminium oxide as Second support material, preparation solid content is the slurry of 30wt%, regulates slurry PH to be 1, obtains slurry A through planetary ball mill after 24 hours;
C, the cordierite carrier of cleaning is flooded 15 minutes in A slurry after, 110 DEG C of dryings 24 hours, at 700 DEG C, roasting obtained the sample B being covered with Second support;
D, yttrium nitrate and barium hydroxide are made into the modified solution of mass content 8%, Mesoporous silica MCM 41 are added in solution, constantly stir and also by coprecipitation, metal precursor is adhered to mesoporous material on the surface; By slurries filtration and fully after washing, drying 24 hours at 80 DEG C and 120 DEG C respectively, and at 350 DEG C roasting within 1 hour, to obtain modified powder C for subsequent use;
F, the aqueous solution being auxiliary agent containing zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, neodymium nitrate, ferric nitrate, cobalt nitrate, copper nitrate and yttrium nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 5mol/L.PH value is regulated to be 4 by nitric acid, gained solution D;
G, by powder C and γ-Al
2o
3powder joins in solution D stirs 1 hour after in mass ratio at 1: 1, adds that catalyst activity component is platinum, rhodium or palladium (bullion content is 0.7g/L calculated) soluble-salt in slurry, and stirs and obtain slurry E;
H, sample B is flooded 3 hours in slurry E after, at 100 DEG C dry 24 hours, at 600 DEG C, roasting obtained three-way catalyst after 6 hours.
Embodiment 7
Using modified ZSM-5 mesoporous material as the three-way catalyst of coating material
A, by 400 order cordierite carrier ultrasonic cleaning and dry after for subsequent use;
B, by activated alumina (γ-Al
2o
3) as Second support material, preparation solid content is the slurry of 30wt%, regulates slurry PH to be 3, obtains slurry A;
C, the cordierite carrier of cleaning is flooded 30 minutes in A slurry after, 115 DEG C of dryings 24 hours, at 600 DEG C, roasting obtained the sample B being covered with Second support;
D, aluminum nitrate and barium hydroxide are made into the modified solution of mass content 12%, mesoporous material ZSM-5 are added in solution, constantly stirs and also by infusion process, metal precursor is attached to mesoporous material on the surface; By slurries filtration and fully after washing, drying 24 hours at 70 DEG C and 110 DEG C respectively, and at 380 DEG C roasting within 2 hours, to obtain modified powder C for subsequent use;
F, the aqueous solution being auxiliary agent containing zirconium nitrate, cerous nitrate, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate and copper nitrate with certain proportioning preparation, in the described aqueous solution, total concentration of metal ions is 2.5mol/L.PH value is regulated to be 5 by nitric acid, gained solution D;
G, powder C joined in solution D and stirs after 6 hours, in slurry, add that catalyst activity component is platinum, rhodium or palladium (bullion content is 0.7g/L calculated) soluble-salt, and stir and obtain slurry E;
H, sample B is flooded 1 hour in slurry E after, at 120 DEG C dry 24 hours, at 600 DEG C, roasting obtained three-way catalyst after 4 hours.
Above a kind of ternary catalyst systems provided by the invention and preparation method thereof is described in detail; apply specific case herein to set forth principle of the present invention and embodiment; the explanation of above embodiment just understands method of the present invention and core concept thereof for helping; should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention; can also carry out some improvement and modification to the present invention, these improve and modify and also fall in the protection domain of the claims in the present invention.
Claims (4)
1. a ternary catalyst systems, 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 the surperficial mesoporous material by metal oxide modified; Described catalyst carrier comprises enhancement Layer and supporting layer; First carrier material forms described enhancement Layer; 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;
One or more in described mesoporous material selected from cerium zirconium solid solution, alumino-silicate or amorphous silica;
Described first carrier material is cordierite;
Described Second support material be activated alumina and cerium zirconium sosoloid one or more.
2. ternary catalyst systems 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, yittrium oxide, gallium oxide, indium oxide or germanium oxide.
3. a preparation method for ternary catalyst systems, is characterized in that, comprising:
A) first carrier material and Second support material are provided;
B) described first carrier material is flooded the slurry formed by Second support slurry, after first time roasting, obtain catalyst carrier; Described 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 the salt of metal ion or oxide precursor to be attached to mesoporous material on the surface, filter, dry, carry out second time roasting and obtain the mesoporous material of surface by 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 third time roasting after drying and obtain ternary catalyst systems;
One or more in described mesoporous material selected from cerium zirconium solid solution, alumino-silicate or amorphous silica;
Described first carrier material is cordierite;
Described Second support material be activated alumina and cerium zirconium sosoloid one or more.
4. preparation method according to claim 3, it is characterized in that, described compounding agent solution is obtained by the aqueous solution of one or more in zirconium nitrate, cerous nitrate, barium hydroxide, lanthanum nitrate, praseodymium nitrate, neodymium nitrate, nickel nitrate, Titanium Nitrate, ferric nitrate, cobalt nitrate, copper nitrate and yttrium nitrate.
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| JP6236995B2 (en) | 2013-08-28 | 2017-11-29 | マツダ株式会社 | Exhaust gas purification catalyst, method for producing the same, and exhaust gas purification method using the same |
| CN105642269B (en) * | 2016-02-26 | 2018-07-27 | 江西国瓷博晶新材料科技有限公司 | A kind of compound cerium zirconium sosoloid and preparation method thereof |
| EP3266519A1 (en) * | 2016-06-16 | 2018-01-10 | Pacific Industrial Development Corporation | Doped ceria-zirconia-alumina catalyst support materials with oxygen storage capacity (osc) and method of making thereof |
| CN106268915A (en) * | 2016-07-15 | 2017-01-04 | 武汉市三合中天科技有限公司 | Minute amount of noble metal modification cerium zirconium meso-porous molecular sieve material and synthesis technique thereof and application |
| CN106540688B (en) * | 2016-12-06 | 2020-07-10 | 绍兴正开智能设备有限公司 | Ternary composite noble metal catalyst |
| CN108452809B (en) * | 2018-01-30 | 2020-01-10 | 中国科学院长春应用化学研究所 | Supported noble metal catalyst with high-temperature sintering resistance and preparation method thereof |
| CN108435211B (en) * | 2018-04-04 | 2021-03-19 | 四川理工学院 | Preparation method of Ce-doped Ni-Fe-Ce ternary sulfide oxygen evolution catalyst |
| CN111206978A (en) * | 2020-02-09 | 2020-05-29 | 太仓丹妮尔模塑汽配有限公司 | Automobile exhaust pipe with high purification efficiency and low air resistance |
| CN113376310A (en) * | 2021-06-17 | 2021-09-10 | 上海松柏传感技术有限公司 | Preparation method of gas-sensitive material for combustible gas sensor and product |
| WO2023090303A1 (en) * | 2021-11-16 | 2023-05-25 | 株式会社フルヤ金属 | Catalyst carrier, catalyst, and methods respectively for producing those products |
| CN117414821B (en) * | 2023-12-08 | 2024-03-15 | 中自环保科技股份有限公司 | High-temperature-resistant sintering Pt-based three-way catalyst and preparation method thereof |
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