CN106076330A - A kind of automotive catalyst coating paste adding Graphene and preparation method thereof - Google Patents
A kind of automotive catalyst coating paste adding Graphene and preparation method thereof Download PDFInfo
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- CN106076330A CN106076330A CN201610414279.7A CN201610414279A CN106076330A CN 106076330 A CN106076330 A CN 106076330A CN 201610414279 A CN201610414279 A CN 201610414279A CN 106076330 A CN106076330 A CN 106076330A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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Abstract
The present invention relates to a kind of automotive catalyst coating paste adding Graphene, it is characterised in that: it is interpolation 0.1～the Graphene of 2% mass percent in catalyst coat slurry.The addition manner of Graphene the most formerly adds, and contributes to obtaining bigger specific surface area Magnification, and catalyst coat slurry is to be supported on honeycomb ceramic carrier by hybrid mode, and drying, roasting make graphen catalyst coating.By adding Graphene powder in catalyst coat slurry, making the specific surface area of the catalyst coat being finally supported on honeycomb ceramic carrier be increased, the Magnification of specific surface area can reach 30%；Meanwhile, the application discovery is not that the increment rate of the most specific surface areas of addition of Graphene is the biggest, and when in catalyst coat slurry, the interpolation content of Graphene is about 1%, the increment rate of catalyst coat specific surface area is maximum.
Description
Technical field
The present invention relates to tail gas cleaning catalyst for vehicles coating, be specifically related to a kind of car with bigger contact gear ratio surface area
Use catalyst coat.
Background technology
The tail gas of motor vehicle emission is one of urban climate polluter, and reducing the maximally effective means of automobile exhaust pollution is to install
Vehicle tail gas triple effect catalyst, mainly comprising of catalyst includes that (cordierite consists of 5SiO2 2Al2O3 to carrier
2MgO), coating (aluminium oxide, Ce, Zr, La etc.) and platinum group metal (Pt, Pd and Rh).
Coating is mainly comprising of catalyst, affects the biggest on activity, stability and the service life etc. of catalyst.Pottery
The specific surface area of honeycomb substrate is less than 1m2/ g, it is impossible to meet the effective gas-solid interface needed for three-effect catalysis process, needs at pottery
On ceramic carrier, one layer of porous material with more bigger serface of coating is as Second support, to increase reacting gas and catalyst
Contact area, improve three-effect catalysis reaction efficiency；The specific surface area of coating is to evaluate the Chief index of coating quality,
It is directly connected to the activity of three-way catalyst.
At present, automotive catalyst overwhelming majority catalyst coatings (aluminium oxide, Ce, Zr, La RE composite and platinum family gold
Belong to) as Second support, coating typically constitutes from the 5～15% of vehicle weight, and applying coating can make carrier specific surface area increase to 50
～150m2/ more than g, thus provide catalyst sufficiently large surface area, specific surface area of catalyst is the biggest, reactant and catalyst
The chance of active sites contact is the most, and the efficiency of catalytic reaction is the highest.
Along with country is more and more higher to the requirement of automobile exhaust emission standard, the clean-up effect improving catalyst further becomes
For a big technical barrier of vehicle tail gas triple effect catalyst industry, the primary work that will solve this difficult problem strengthens coating
Specific surface area, this also becomes the emphasis of continuous research and innovation of those skilled in the art.
Summary of the invention
The technical problem to be solved is to provide a kind of for above-mentioned prior art to add the automobile-used of Graphene and urge
Agent coating paste and preparation method thereof, it is possible to increase the specific surface area of final coating, it is thus achieved that preferably catalytic effect.
Graphene is a kind of to be formed, with sp2 hybrid orbital, the flat film that hexangle type is honeycomb lattice by carbon atom, only
The two-dimensional material of one carbon atom thickness.Graphene is the thinnest material, is also the most tough material, and fracture strength ratio is best
Taller 200 times of steel.It has again good elasticity simultaneously, and stretch range can reach the 20% of own dimensions.It is current from
The material that so boundary is the thinnest, intensity is the highest,
Graphene has high heat conductivity, and heat conductivility is better than CNT, and thermal conductivity is up to 977 W/m K, hot strength
More than 15 MPa.
The present invention solves the technical scheme that the problems referred to above are used: a kind of automotive catalyst coating slurry adding Graphene
Material, is interpolation 0.1～the Graphene of 2% mass percent in catalyst coat slurry.
Further, catalyst coat slurry is to be supported on honeycomb ceramic carrier by hybrid mode, drying, roasting
Make graphen catalyst coating.
According to the difference of Graphene addition manner, the present invention provides the preparation method of the following two kinds catalyst coat slurry
The preparation method of a kind of automotive catalyst coating paste at rear interpolation Graphene, comprises the steps,
(1) cerium zirconium composite, modified aluminas, catalyst aid being mixed in proportion grinding, each raw material accounts for final catalyst coat
The weight/mass percentage composition of slurry be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalyst aid 20～40 %；
Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) Graphene powder is added to above-mentioned gained mixed solution, the quality hundred of Graphene in final catalyst coat slurry
Dividing content is 0.1～2%；The solid content of regulation catalyst coat slurry is 25～35%.
The preparation method of a kind of automotive catalyst coating paste formerly adding Graphene, comprises the steps.
(1) cerium zirconium composite, modified aluminas, catalyst aid, Graphene powder being mixed in proportion grinding, each raw material accounts for
The weight/mass percentage composition of whole catalyst coat slurry be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalysis helps
Agent 20～40 %, Graphene powder 0.1～2%；Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) solid content of regulation catalyst coat slurry is 25～35%.
Preferably, described cerium zirconium composite is the complex of cerium Zirconium oxide.
Preferably, described modified aluminas is lanthanum modified aluminas.
Preferably, the mixed oxidization of two or more element during described catalyst aid includes copper, ferrum, nickel, manganese, chromium
Thing.
The preparation method of the automotive catalyst coating adding Graphene of the present invention is to be coated in by catalyst coat pulp spraying
On honeycomb ceramic carrier, honeycomb ceramic carrier is sent into baking oven and dries at a temperature of 60～120 DEG C, after drying send into Muffle furnace in
Roasting 2-5 hour under the conditions of 400～600 DEG C, i.e. obtains the catalyst coat being supported on honeycomb ceramic carrier.
Compared with prior art, it is an advantage of the current invention that: by adding Graphene powder in catalyst coat slurry, make
The specific surface area being finally supported on the catalyst coat on honeycomb ceramic carrier is increased, the Magnification of specific surface area up to
To 30%；Meanwhile, the application discovery is not that the increment rate of the most specific surface areas of addition of Graphene is the biggest, works as catalyst
When in coating paste, the interpolation content of Graphene is about 1%, the increment rate of catalyst coat specific surface area is maximum；And for adding
Adding the situation of same amount Graphene, the mode at rear interpolation Graphene can obtain bigger than the mode formerly adding Graphene
Specific surface area Magnification.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
The present embodiment adds the automotive catalyst coating paste of Graphene be add in catalyst coat slurry 0.1～
The Graphene powder of 2% mass percent.According to the difference of Graphene addition manner, including the following two kinds catalyst coat slurry
Preparation method:
One, in the preparation method of automotive catalyst coating paste of rear interpolation Graphene, comprise the steps,
(1) cerium zirconium composite, modified aluminas, catalyst aid being mixed in proportion grinding, each raw material accounts for final catalyst coat
The weight/mass percentage composition of slurry be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalyst aid 20～40 %；
Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) Graphene powder is added to above-mentioned gained mixed solution, the quality hundred of Graphene in final catalyst coat slurry
Dividing content is 0.1～2%；The solid content of regulation catalyst coat slurry is 25～35%.
Two, formerly add the preparation method of the automotive catalyst coating paste of Graphene, comprise the steps.
(1) cerium zirconium composite, modified aluminas, catalyst aid, Graphene powder being mixed in proportion grinding, each raw material accounts for
The weight/mass percentage composition of whole catalyst coat slurry be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalysis helps
Agent 20～40 %, Graphene powder 0.1～2%；Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) solid content of regulation catalyst coat slurry is 25～35%.
Above-mentioned gained catalyst coat pulp spraying is coated on honeycomb ceramic carrier, honeycomb ceramic carrier is sent into baking oven in
Dry at a temperature of 60～120 DEG C, send into Muffle furnace roasting 2-5 hour under the conditions of 400～600 DEG C after drying, i.e. obtain load
Catalyst coat on honeycomb ceramic carrier.
Ceramic honey comb: specification ￠ 101.6mm × 68mm, hole density 400cpsi, wall thickness 0.20mm.
On JW-04 full-automatic N2 adsorption specific surface instrument, by UOP874-88 (International Standards Method) standard, make with nitrogen
For Adsorbate Gas, rear addition and front addition 0#-20# totally 21 kinds of slurries are carried out specific surface area (S.A), total pore volume and average hole
Footpath (T.P.V) (A.P.S) is analyzed.
The Graphene test result to catalyst coat specific surface area Magnification:
Sample state: at the catalyst coat of rear interpolation Graphene.
Test data:
Sample state: formerly add the catalyst coat of Graphene.
Test data:
As seen from the table, adding the automotive catalyst coating of Graphene, the increment rate of specific surface area is 30.01% to the maximum；Graphene
Add the increment rate of specific surface area when weight is 1% maximum；Same amount rear interpolation Graphene catalyst coat ratio formerly
The specific surface area increment rate of the catalyst coat adding Graphene wants height.
Above-mentioned cerium zirconium composite is the complex of commercially available cerium Zirconium oxide.Modified aluminas is commercially available lanthanum modified aluminas.
Catalyst aid includes the mixed oxide of two or more element in copper, ferrum, nickel, manganese, chromium, can be the most existing urging
Change auxiliary agent.
The graphen catalyst coating of the present invention has bigger specific surface area, and preparation technology is fairly simple, operation side
Just, it is simple to amplify and produce.
Claims (8)
1. the automotive catalyst coating paste adding Graphene, it is characterised in that: it is to add in catalyst coat slurry
0.1～2% Graphene of mass percent.
The automotive catalyst coating paste of interpolation Graphene the most according to claim 1, it is characterised in that: catalyst coat
Slurry is to be supported on honeycomb ceramic carrier by hybrid mode, and drying, roasting make graphen catalyst coating.
3. the preparation method of the automotive catalyst coating paste adding Graphene, it is characterised in that: comprise the steps,
(1) cerium zirconium composite, modified aluminas, catalyst aid being mixed in proportion grinding, each raw material accounts for final catalyst coat
The weight/mass percentage composition of slurry be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalyst aid 20～40 %；
Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) Graphene powder is added to above-mentioned gained mixed solution, the quality hundred of Graphene in final catalyst coat slurry
Dividing content is 0.1～2%；The solid content of regulation catalyst coat slurry is 25～35%.
4. the preparation method of the automotive catalyst coating paste adding Graphene, it is characterised in that: comprise the steps:
(1) cerium zirconium composite, modified aluminas, catalyst aid, Graphene powder being mixed in proportion grinding, each raw material accounts for finally urges
The weight/mass percentage composition of agent coating paste be cerium zirconium composite 10～40%, modified aluminas 10～60 %, catalyst aid 20
～40 %, Graphene powder 0.1～2%；Add appropriate water, mix and blend 2～8 hours；
(2) being added by the nitrate solution of noble metal in the mixture of step 1, mix and blend 2～5 hours, final catalyst is coated with
In layer slurry, the weight/mass percentage composition of noble metal nitrate is 1～2%, and wherein the mol ratio of Pd:Rh is 5:1；
(3) add aluminium glue, mix and blend 2～4 hours, in final catalyst coat slurry the weight/mass percentage composition of aluminium glue be 5～
10%；
(4) solid content of regulation catalyst coat slurry is 25～35%.
5., according to the preparation method of the automotive catalyst coating paste adding Graphene described in claim 3 or 4, its feature exists
In: described cerium zirconium composite is the complex of cerium Zirconium oxide.
6., according to the preparation method of the automotive catalyst coating paste adding Graphene described in claim 3 or 4, its feature exists
In: described modified aluminas is lanthanum modified aluminas.
7., according to the preparation method of the automotive catalyst coating paste adding Graphene described in claim 3 or 4, its feature exists
In: described catalyst aid includes the mixed oxide of two or more element in copper, ferrum, nickel, manganese, chromium.
8. the preparation method of the automotive catalyst coating adding Graphene, it is characterised in that: it is by catalyst coat slurry
It is sprayed on honeycomb ceramic carrier, honeycomb ceramic carrier is dried at a temperature of 60～120 DEG C, in 400～600 DEG C of bars after drying
Roasting 2-5 hour under part, i.e. obtains the catalyst coat being supported on honeycomb ceramic carrier.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610414279.7A CN106076330A (en) | 2016-06-14 | 2016-06-14 | A kind of automotive catalyst coating paste adding Graphene and preparation method thereof |
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| CN201610414279.7A CN106076330A (en) | 2016-06-14 | 2016-06-14 | A kind of automotive catalyst coating paste adding Graphene and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109638290A (en) * | 2018-12-25 | 2019-04-16 | 佛山科学技术学院 | A kind of phthalein cyanogen cobalt Ceramic Composite catalyst and the preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413769A (en) * | 2002-06-28 | 2003-04-30 | 福州大学 | Ternary catalyst for automobile tail gas and its preparation method |
| CN101653730A (en) * | 2009-08-26 | 2010-02-24 | 南京英斯威尔环保科技有限公司 | Three-way catalyst taking cordierite honeycomb ceramics as carrier |
| CN102728383A (en) * | 2012-02-22 | 2012-10-17 | 华东理工大学 | Preparation method of high temperature stable monolithic catalyst for purifying tail gas of automobile |
| CN105413674A (en) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | Preparation method of denitration catalyst carrier with graphene |
-
2016
- 2016-06-14 CN CN201610414279.7A patent/CN106076330A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1413769A (en) * | 2002-06-28 | 2003-04-30 | 福州大学 | Ternary catalyst for automobile tail gas and its preparation method |
| CN101653730A (en) * | 2009-08-26 | 2010-02-24 | 南京英斯威尔环保科技有限公司 | Three-way catalyst taking cordierite honeycomb ceramics as carrier |
| CN102728383A (en) * | 2012-02-22 | 2012-10-17 | 华东理工大学 | Preparation method of high temperature stable monolithic catalyst for purifying tail gas of automobile |
| CN105413674A (en) * | 2015-11-30 | 2016-03-23 | 安徽省元琛环保科技有限公司 | Preparation method of denitration catalyst carrier with graphene |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109638290A (en) * | 2018-12-25 | 2019-04-16 | 佛山科学技术学院 | A kind of phthalein cyanogen cobalt Ceramic Composite catalyst and the preparation method and application thereof |
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Application publication date: 20161109 |
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