CN106423158A - Hollow spherical three-way catalyst - Google Patents
Hollow spherical three-way catalyst Download PDFInfo
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- CN106423158A CN106423158A CN201610651702.5A CN201610651702A CN106423158A CN 106423158 A CN106423158 A CN 106423158A CN 201610651702 A CN201610651702 A CN 201610651702A CN 106423158 A CN106423158 A CN 106423158A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 22
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 13
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 13
- 230000000694 effects Effects 0.000 claims abstract description 11
- 239000006255 coating slurry Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000010970 precious metal Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N EtOH Substances CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- 238000002360 preparation method Methods 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 17
- 239000008187 granular material Substances 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 229910000765 intermetallic Inorganic materials 0.000 claims description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 8
- 239000004793 Polystyrene Substances 0.000 claims description 8
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 8
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004816 latex Substances 0.000 claims description 8
- 229920000126 latex Polymers 0.000 claims description 8
- 229910052763 palladium Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 229920002223 polystyrene Polymers 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 229910052703 rhodium Inorganic materials 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 4
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 229910052878 cordierite Inorganic materials 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000012423 maintenance Methods 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium oxide Inorganic materials [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 239000000725 suspension Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 101150003085 Pdcl gene Proteins 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 239000011247 coating layer Substances 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 239000002923 metal particle Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002637 Pr6O11 Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 2
- 241000264877 Hippospongia communis Species 0.000 claims 3
- 239000000919 ceramic Substances 0.000 claims 1
- 239000006104 solid solution Substances 0.000 abstract description 4
- 230000033116 oxidation-reduction process Effects 0.000 abstract description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract 1
- 230000000977 initiatory effect Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 229910052726 zirconium Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 239000010948 rhodium Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910001868 water Inorganic materials 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- 229910002666 PdCl2 Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 description 2
- 241000256844 Apis mellifera Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention relates to a hollow spherical three-way catalyst for automobile exhaust treatment. The hollow spherical three-way catalyst is characterized by being prepared by the following steps: preparing a micron-size opening hollow metal spherical precious metal as an active component of the three-way catalyst by an oxidation-reduction method; mixing with a cerium-zirconium solid solution and the ball-milling liquid of La2O3-Al2O3 to obtain a coating slurry; applying the slurry to a honeycomb zirconium carrier; and roasting for 1-5 hours at 400-600 DEG C to obtain a novel automobile exhaust three-way catalyst. The three-way catalyst provided by the invention is easy to prepare and has the advantages of high activity, low initiation temperature, good high-temperature stability and the like.
Description
Technical field
The present invention relates to hollow ball-type three-way catalyst, belong to purifying vehicle exhaust technical field.
Background technology
Ternary catalyzing unit is mounted in most important outer purifier in automobile exhaust system, and vehicle exhaust can be arranged by it
The harmful gass such as CO, HC and the NOx going out are changed into harmless carbon dioxide, water and nitrogen by oxidation and reduction.Work as height
When the vehicle exhaust of temperature passes through purifier, the cleanser in ternary catalyzing unit will strengthen the work of tri- kinds of gases of CO, HC and NOx
Property, promote it to carry out certain oxidation-reduction chemical reaction, wherein CO is oxidized into colourless, nontoxic titanium dioxide at high temperature
Carbon gas；HC compound is oxidized to water (H20) and carbon dioxide at high temperature；NOx is reduced into nitrogen and oxygen.Three kinds of harmful gas
Body becomes innocuous gas, so that vehicle exhaust is purified.
Three-way catalyst is made up of two parts：Cellular pottery or metallic carrier, and it is attached to the catalysis on carrier
Agent coating.Catalyst coat is generally by oxide material (as aluminium oxide), hydrogen-storing material and the dispersion with large specific surface area
Noble metal active component on oxide or hydrogen-storing material surface is (often for one of Pt (platinum), Pd (palladium), Rh (rhodium) or several
Kind) composition.Hydrogen-storing material therein generally contains the composite oxides of cerium zirconium, and it passes through oxygen or release in adsorption storage tail gas
Go out oxygen to adjust the ratio of oxidizing component and reproducibility component in tail gas, make carbon monoxide and oxidized same of Hydrocarbon
When oxynitride be reduced.In order to improve the transformation efficiency of pollutant during cold-starting automobile, three-way catalyst is often installed in
Near the position of enmgine exhaust outlet, in galloping, the bed temperature of three-way catalyst can reach 900～
1100 DEG C of high temperature.
In order to suppress the alloying action of Rh and Pd under hot conditionss to make catalyst activity reduction, current three-element catalytic
Agent generally all adopts double coating structures, that is, be attached to the lower coating loading Pd on honeycomb substrate, coating material generally comprises cerium zirconium
Solid solution, aluminium oxide and other auxiliary agents；And the upper coating being attached in lower coating supports Rh, coating material typically also includes cerium zirconium
Solid solution, aluminium oxide and other auxiliary agents.But, this bilayer coated structure, lead to gas diffusion slow, draw property difference is simultaneously
And each layer of whole carrier surface of covering, can not utilize completely in catalysis, utilization rate is not high.Additionally, single precious metal atom
Energy highest, under the conditions of high-temperature oxygen-enriched, the Rh of upper coating still coating can be migrated and be interacted with Pd gradually downward,
Lead to high temperature sintering, and make the activity decrease of catalyst.
Content of the invention
The purpose of the present invention is to overcome the deficiencies in the prior art, provides a kind of ternary for vehicle maintenance service
Catalyst, single layer coating process advan, in the directly contact of gas and catalyst, has higher Hydrocarbon, carbon monoxide
With oxynitride disposal ability；Meanwhile, hollow ball shape structural metal minimum energy, volume is larger, can effectively inhibitory activity gold
The heat inactivation that metal particles migration leads to.
In order to realize the above-mentioned purpose of the present invention, the present invention adopts the following technical scheme that：
Open hollow ball-type three-way catalyst for vehicle maintenance service is it is characterised in that with precious metals pt, Rh and Pd
As active constituent, active metal is open hollow metal ball-type, and all active metals are located at same coating；Cordierite-base honeybee
Nest pottery is as first vector；Using aluminum oxide coating layer as Second support；Urge using rare-earth oxides such as cerium oxide as helping
Agent.
In described catalyst, the weight of metal active component is the 0～4% of total catalyst weight, the weight of promoter
Measure 0～6% for total catalyst weight.
The preparation method of catalyst, comprises the steps of：
(1) preparation of catalyst activity granule
Under room temperature, the Polystyrene latex spheres of appropriate size are added to the active metallic compound H of formula ratio2PtCl6's
Ethanol solution, this solution supersound process 10～80 minutes obtains homogeneous suspension liquid；Continue stirring 3～8 hours, be warmed up to 40
～80 DEG C, the ethanol in solution is vapored away, obtain dry powder ball.This dry powder ball is dried 8～15 hours at 50～60 DEG C, weight
Newly it is dispersed in 1000ml ethanol, adds appropriate hydrazine hydrate solution (0.1M), metallic compound is reduced, centrifugation obtains black
Color solid particle, distilled water wash 1～3 time, then use absolute ethanol washing 1～3 time again, be dried 3～8 at 30～60 DEG C little
When, obtain PStPt granule.
According to formula, it is respectively configured the PdCl of 1000ml2And RhCl3Ethanol solution, with reference to above step, obtain PStPd and
PStRh granule.
(2) catalyst preparation
500～1000g cerium zirconium sosoloid, the La2O3-Al2O3 of 200～500g and appropriate amount of deionized water are mixed, and warp
Prepare after ball milling and obtain coating slurry；PStPt, PStPd and PStRh granule of the formula ratio that step (1) and (2) are obtained is placed in
This solution, under room temperature stir 1～4 hour, then this coating slurry is coated on honeycomb cordierite carrier, and 400 DEG C～
600 DEG C of roasting temperatures 1～5 hour, obtain three-way catalyst.
The Polystyrene latex spheres of the appropriate size described in step (1), a size of 0.5～10um.
The active metallic compound of the formula ratio described in step (1), part by weight is Polystyrene latex spheres:Activity gold
Belong to compound=1:0.1～10
Active metallic compound described in step (1) includes the compound of Pt, Rh, Pd, mainly includes H2PtCl6, Rh and
The chloride of Pd.
Appropriate hydrazine hydrate solution described in step (1), mol ratio is active metal:Hydrazine hydrate=1:0.5～3.
Cerium zirconium sosoloid described in step (2) and La2O3-Al2O3Mass ratio be 1:0.3～3.
The component (weight ratio) of the cerium zirconium sosoloid described in step (2) is：15～50%CeO2,10～50%ZrO2 and
One or more of 5～12% La2O3, Y2O3, Pr6O11, Nd2O3.
PStPt, PStPd and PStRh granule of the formula ratio described in step (2), mol ratio is Pd:Rh:Pt=1:0.5
～4:0～0.5, the load capacity of active metal particles is 2～100g/ft3.
In La2O3-Al2O3 described in step (2), doping in Al2O3 for the La2O3 is 1～8%
Beneficial effects of the present invention：
Catalyst provided by the present invention has the advantages that high activity, low light-off temperature, good high-temperature stability, has
Very strong practical value.
Specific embodiment
Embodiment 1
(1) catalyst activity component PStPt preparation
Under room temperature, 1 gram of Polystyrene latex spheres (PSt, 3um) is added to 3 grams of H2PtCl61000ml ethanol solution,
By this solution supersound process 30 minutes, obtain homogeneous suspension liquid；Continue stirring 5 hours, be warmed up to 60 DEG C, by the ethanol in solution
Vapor away, obtain dry powder ball.This dry powder ball is dried 10 hours at 60 DEG C, is again dispersed in 1000ml ethanol, add
200ml hydrazine hydrate solution (0.1M), by H2PtCl6Reduction, centrifugation acquisition black solid particle, distilled water wash 2 times, so
Use twice of absolute ethanol washing more afterwards, be dried 5 hours at 40 DEG C, obtain PStPt granule.
(2) catalyst activity component PStPt and PStRh preparation
Weigh 3.5 grams of PdCl respectively2With 4 grams of RhCl3, the ethanol solution of configuration 1000ml is with reference to step (1), acquisition PStPd
With PStRh granule.
(3) coating procedure of coating
La by 900g cerium zirconium sosoloid, 300g2O3-Al2O3Mix with appropriate amount of deionized water, and prepare after ball milling
To coating slurry；PStPt, PStPd and PStRh granule that step (1) and (2) are obtained is placed in this solution, and under room temperature, stirring 2 is little
When, (specification is Ф 101.6mm × 123.3mm, and hole density is then this coating slurry to be coated to honeycomb cordierite carrier
600cpsi, duct wall thickness is 4.3mil, and volume is 1.0L) on, and in 480～600 DEG C of roasting temperatures 1～5 hour, obtain
Three-way catalyst.Wherein, the component of cerium zirconium sosoloid is：40%CeO2, 40%ZrO2, 6%La2O3And 6%Nd2O3, cerium zirconium is solid
Solution average pore size be 30nm, La2O3Content account for La-Al2O33%.
Embodiment 2
(1) catalyst activity component PStPt preparation
Under room temperature, 2 grams of Polystyrene latex spheres (PSt, 3um) are added to 5 grams of PdCl21000ml ethanol solution,
By this solution supersound process 30 minutes, obtain homogeneous suspension liquid；Continue stirring 5 hours, be warmed up to 60 DEG C, by the ethanol in solution
Vapor away, obtain dry powder ball.This dry powder ball is dried 10 hours at 60 DEG C, is again dispersed in 1000ml ethanol, add
600ml hydrazine hydrate solution (0.1M), by PdCl2Reduction, centrifugation acquisition black solid particle, distilled water wash 2 times, then
Use twice of absolute ethanol washing again, be dried 5 hours at 40 DEG C, obtain PStPd granule.
(2) catalyst activity component PStRh preparation
Weigh 4 grams of RhCl3, the ethanol of configuration 1000ml, solution, with reference to step (1), obtains PStRh granule.
(3) coating procedure of coating
La by 900g cerium zirconium sosoloid, 300g2O3-Al2O3Mix with appropriate amount of deionized water, and prepare after ball milling
To coating slurry；PStPd the and PStRh granule that step (1) and (2) are obtained is placed in this solution, stirring 2 hours under room temperature, so
Afterwards by this coating slurry be coated to honeycomb cordierite carrier (specification be Ф 101.6mm × 123.3mm, hole density be 600cpsi,
Duct wall thickness is 4.3mil, and volume is 1.0L) on, and in 480～600 DEG C of roasting temperatures 1～5 hour, obtain three-element catalytic
Agent.Wherein, the component of cerium zirconium sosoloid is：40%CeO2,40%ZrO2,6%La2O3And 6%Nd2O3, cerium zirconium sosoloid
Average pore size is 30nm, La2O3Content account for La-Al2O33%.
Embodiment 3
Catalytic performance test
With reference to automotive emissions limit value and method of testing GB14761, the exhaustor implantation in catalyst rear and front end
The sensor of gas analyser, composition transfer before and after catalyst for the detected gas, calculate catalyst and CO, HC, NOx are turned
Rate.The results are shown in Table 1.
Claims (10)
1. it is used for the open hollow ball-type three-way catalyst of vehicle maintenance service it is characterised in that cordierite-base ceramic honey comb conduct
First vector；Using aluminum oxide coating layer as Second support；Using rare-earth oxides such as cerium oxide as promoter；With your gold
Belong to Pt, Rh and Pd as active constituent, active metal is open hollow metal ball-type；Only one layer of coating.Described catalyst
In, the weight of metal active component is the 0～3% of total catalyst weight, the weight of promoter be total catalyst weight 0～
5%.
Open hollow ball-type three-way catalyst for vehicle maintenance service is it is characterised in that made with precious metals pt, Rh and Pd
For active constituent, active metal is open hollow metal ball-type, and all active metals are located at same coating；Cordierite-base honeycomb
Pottery is as first vector；Using aluminum oxide coating layer as Second support；Using rare-earth oxides such as cerium oxide as co-catalysis
Agent.
In described catalyst, the weight of metal active component is the 0～4% of total catalyst weight, and the weight of promoter is
The 0～5% of total catalyst weight.
2. open hollow ball-type three-way catalyst preparation method according to claim 1 it is characterised in that：
(1) preparation of catalyst activity granule
Under room temperature, the Polystyrene latex spheres of appropriate size are added to the active metallic compound H of formula ratio2PtCl6Ethanol
Solution, this solution supersound process 10～80 minutes obtains homogeneous suspension liquid；Continue stirring 3～8 hours, be warmed up to 40～80
DEG C, the ethanol in solution is vapored away, obtains dry powder ball.This dry powder ball is dried 8～15 hours at 50～50 DEG C, again divides
It is dispersed in 1000ml ethanol, adds appropriate hydrazine hydrate solution (0.1M), metallic compound is reduced, it is solid that centrifugation obtains black
Body granule, distilled water wash 1～3 time, then use absolute ethanol washing 1～3 time again, be dried 3～8 hours at 30～50 DEG C, obtain
Obtain PStPt granule.
According to formula, it is respectively configured the PdCl of 1000ml2And RhCl3Ethanol solution, with reference to above step, obtain PStPd and
PStRh granule.
(2) catalyst preparation
800～1000g cerium zirconium sosoloid, the La2O3-Al2O3 of 200～500g and appropriate amount of deionized water are mixed, and through ball milling
Prepare afterwards and obtain coating slurry；It is molten that PStPt, PStPd and PStRh granule of the formula ratio that step (1) and (2) are obtained is placed in this
Liquid, stirs 1～4 hour under room temperature, then this coating slurry is coated on honeycomb cordierite carrier, and at 400 DEG C～600 DEG C
Roasting temperature 1～5 hour, obtains three-way catalyst.
3. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (1)
The Polystyrene latex spheres of appropriate size, a size of 1.0～8.0um.
4. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (1)
The active metallic compound of formula ratio, part by weight is Polystyrene latex spheres:Active metallic compound=1:0.1～10.
5. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (1)
Active metallic compound includes the compound of Pt, Rh, Pd, mainly includes H2PtCl6, the chloride of Rh and Pd.
6. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (1)
Appropriate hydrazine hydrate solution, mol ratio is active metal:Hydrazine hydrate=1:0.5～3.
7. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (2)
Cerium zirconium sosoloid and La2O3-Al2O3Mass ratio be 1:0.3～3.
8. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (2)
The component (weight ratio) of cerium zirconium sosoloid is：The La2O3 of 15～50%CeO2,10～50%ZrO2 and 5～12%, Y2O3,
One or more of Pr6O11, Nd2O3.
9. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (2)
PStPt, PStPd and PStRh granule of formula ratio, mol ratio is Pd:Rh:Pt=1:0.5～4:0～0.5, active metal particles
Load capacity be 2～100g/ft3.
10. hollow ball-type three-way catalyst according to claim 2 preparation it is characterised in that：Described in step (2)
In La2O3-Al2O3, doping in Al2O3 for the La2O3 is 1～6%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110653006A (en) * | 2019-10-14 | 2020-01-07 | 安徽省全天卫环保科技有限公司 | Nano catalyst for high-efficiency pyrolysis of gasoline |
| CN112588288A (en) * | 2020-11-20 | 2021-04-02 | 湖南省吉安特技术有限公司 | Preparation method of rhodium-aluminum composite oxide nano hollow powder |
-
2016
- 2016-08-03 CN CN201610651702.5A patent/CN106423158A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110653006A (en) * | 2019-10-14 | 2020-01-07 | 安徽省全天卫环保科技有限公司 | Nano catalyst for high-efficiency pyrolysis of gasoline |
| CN112588288A (en) * | 2020-11-20 | 2021-04-02 | 湖南省吉安特技术有限公司 | Preparation method of rhodium-aluminum composite oxide nano hollow powder |
| CN112588288B (en) * | 2020-11-20 | 2022-06-14 | 湖南省吉安特技术有限公司 | Preparation method of rhodium-aluminum composite oxide nano hollow powder |
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