CN108273501A - A kind of vehicle maintenance service three-way catalyst and preparation method thereof - Google Patents
A kind of vehicle maintenance service three-way catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000012423 maintenance Methods 0.000 title claims abstract description 16
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 40
- 239000000654 additive Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 38
- 230000000996 additive effect Effects 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 35
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 34
- 238000000576 coating method Methods 0.000 claims abstract description 26
- 239000011248 coating agent Substances 0.000 claims abstract description 23
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011230 binding agent Substances 0.000 claims abstract description 19
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 15
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 9
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims abstract description 7
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum oxide Inorganic materials [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000004048 modification Effects 0.000 claims abstract description 5
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 4
- KTUFCUMIWABKDW-UHFFFAOYSA-N oxo(oxolanthaniooxy)lanthanum Chemical compound O=[La]O[La]=O KTUFCUMIWABKDW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002002 slurry Substances 0.000 claims description 76
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 52
- 238000003756 stirring Methods 0.000 claims description 50
- 239000010948 rhodium Substances 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- 229910001868 water Inorganic materials 0.000 claims description 31
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 24
- 238000000498 ball milling Methods 0.000 claims description 17
- VXNYVYJABGOSBX-UHFFFAOYSA-N rhodium(3+);trinitrate Chemical compound [Rh+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VXNYVYJABGOSBX-UHFFFAOYSA-N 0.000 claims description 12
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 238000010790 dilution Methods 0.000 abstract description 12
- 239000012895 dilution Substances 0.000 abstract description 12
- 239000006185 dispersion Substances 0.000 abstract description 10
- 230000005012 migration Effects 0.000 abstract description 10
- 238000013508 migration Methods 0.000 abstract description 10
- 239000010970 precious metal Substances 0.000 abstract description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052593 corundum Inorganic materials 0.000 abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 4
- 239000012266 salt solution Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 23
- 239000000243 solution Substances 0.000 description 19
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 8
- 239000003795 chemical substances by application Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical class [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910052763 palladium Inorganic materials 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical class [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 238000007865 diluting Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002927 oxygen compounds Chemical class 0.000 description 2
- -1 palladium nitrates Chemical class 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
Classifications
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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
-
- 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
-
- B01J35/60—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/90—Physical characteristics of catalysts
- B01D2255/908—O2-storage component incorporated in the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Abstract
A kind of vehicle maintenance service three-way catalyst, the three-way catalyst include hydrogen-storing material, modification γ Al2O3, rare-earth additive, binder, noble metal nitrate, the γ Al of the modification2O3The γ Al being modified for La2O3, the hydrogen-storing material is cerium zirconium compound oxide, hydrogen-storing material and modified γ Al2O3Weight ratio is 2：3~3：2, rare-earth additive include zirconium, praseodymium, neodymium, yttrium nitrate it is one or more, account for apply stratum total 1~5%.In coating preparation process, precious metal salt solution is added after dilution, and is stirred overnight, and effectively noble metal can be inhibited to reunite, and improves the dispersion degree of noble metal, to improve the utilization rate of noble metal；Low temperature drying is first used, can avoid in flash drying process, the migration of active component causes active component to be reunited, and avoids being sintered when roasting.Reduce the dosage of noble metal.
Description
Technical field
The present invention relates to vehicle maintenance services, and in particular to a kind of vehicle maintenance service three-way catalyst and its preparation side
Method.
Background technology
In recent years, China's car ownership gradually increases, a large amount of discharges of vehicle exhaust while offering convenience for the mankind
Also it brings and can not be ignored pollution.After automobile starting, due to fuel oil incomplete combustion or high temperature, will produce a large amount of CO, HC and
NOx, these pollutants seriously endanger ecological environment and health.Therefore, it is necessary to urgently solve the problems, such as automobile exhaust pollution.
Currently, the processing most effective method of vehicle exhaust is installation automobile exhaust purifier, key technology is that triple effect is urged
The preparation of agent.Three-way catalyst generally use ceramic honeycomb is matrix, and coating activated alumina is carrier, then carried noble metal
Pt, Pd, Rh etc. are prepared into integral catalyzer as active component, which has catalysis oxidation and catalysis two kinds of work(of reduction
Can, although the discharge of HC, CO and NOx can be reduced effectively, the preparation process of the catalyst is complicated, and noble metal cost is higher.
Traditional preparation process as described in patent CN200510062095.0, CN201510207711.0 and CN201310358641.X,
Using the coating method directly submerged, either carrier or active component is both needed to that catalysis is made through repeatedly impregnating, drying, roast
Agent, not only preparation process is complicated, and active component is easy to run off, and coating is easy to fall off, and through multiple drying and roasting, noble metal easy-sintering,
Utilization rate is low.
Invention content
For the deficiency in the presence of the prior art, the purpose of the present invention is to provide a kind of vehicle maintenance service triple effects to urge
Agent and preparation method thereof, preparation process of the invention is simple, and noble metal utilisation is high, content is low.
To achieve the above object, present invention employs the following technical solutions：
A kind of vehicle maintenance service three-way catalyst, the three-way catalyst include hydrogen-storing material, modification γ-Al2O3、
Rare-earth additive, binder, noble metal nitrate, the γ-Al of the modification2O3γ-the Al being modified for La2O3, the hydrogen-storing material
For cerium zirconium compound oxide, hydrogen-storing material and modified γ-Al2O3Weight ratio is 2：3~3：2, rare-earth additive include zirconium, praseodymium,
Neodymium, yttrium nitrate it is one or more, account for apply stratum total 1~5%.
The present invention also proposes a kind of vehicle maintenance service three-way catalyst preparation method, includes the following steps：
(1) Pd layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds hydrogen-storing material cerium
Zirconium mixed oxide and modified γ-Al2O3, after stirring evenly, palladium nitrate solution is added, stirs 12~24 hours, is added and bonds
Agent continues 30~60min of stirring, adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains
Pd layers of slurry；
(2) Rh layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds hydrogen-storing material cerium
Zirconium mixed oxide and modified γ-Al2O3, after stirring evenly, rhodium nitrate solution is added, stirs 12~24 hours, is added and bonds
Agent continues 30~60min of stirring, adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains
Rh layers of slurry；
(3) the coating materials bed of material：Pd layers of slurry are first coated, Rh layers of slurry are coated with after dry；
(4) dry and roasting：It after the coating materials bed of material, is placed in drying box and is dried, be subsequently placed in Muffle furnace and carry out
Roasting.
Above-mentioned three-way catalyst contains catalyst activity part i.e. palladium nitrate, rhodium nitrate, oxidations of the wherein Pd as CO, HC
Catalytic active component, Rh is as NOXReduction catalysts active constituent.γ-Al2O3It is to urge to have large specific surface area as carrier
Change reaction and reacting environment is provided.Hydrogen-storing material can overcome the atmosphere for the redox reaction that air-fuel ratio brings to change.Rare earth helps
Agent plays a relatively comprehensive effect here, can cocatalyst active part catalysis reaction, improve catalyst storage
Oxygen ability is put, and catalyst ageing resistance can be improved, increases dispersion degree of each section in three-way catalyst, can also prevent
Catalyst component and oxidation reactive aluminum, improve the activity of catalyst component.The addition of binder can make the coating where catalyst and bee
Nest combination is more secured.The three-way catalyst component of the present invention not only acts as above-mentioned respective effect, and by hydrogen-storing material and
Modified γ-Al2O3Ratio, the different rare-earth additives of addition, optimize technique so that catalyst becomes the entirety of a collaboration.
Compared with prior art, the present invention having the advantages that：
1, in coating preparation process, precious metal salt solution is added the present invention after dilution, long agitation, can effectively press down
Noble metal processed is reunited, and the dispersion degree of noble metal is improved, to improve the utilization rate of noble metal.
2, in containing Precious Metal, addition zirconium, praseodymium, neodymium, yttrium etc. are used as modified additive, can enhance γ-Al2O3's
Thermal stability reduces the loss of specific surface area, and can improve the dispersion degree of noble metal, prevents accumulation of metal, further increases expensive
Rate of metal, while reducing the dosage of precious metal palladium, in catalyst of the present invention the content of palladium 0.35~1.06g/L it
Between.
3, in drying process, low temperature drying is first used, can avoid in flash drying process, the migration of active component causes to live
Property component reunite, avoid roasting when be sintered.
4, in roasting process, first 300 DEG C of low-temperature bakes, then 550 DEG C of roastings can not only further decrease active component
Migration, can also make coating adhere on honeycomb more secured, improve the mechanical strength of catalyst.
5, coating uses vacuum suction mode, the slurry of identical or different type can be respectively coated at carrier both ends, and can
Accounting of the coating on honeycomb is adjusted, coating efficiency is high, and coating is combined more secured with honeycomb.
Specific implementation mode
Below by specific implementation mode, the present invention is described in further detail：
A kind of vehicle maintenance service three-way catalyst, the three-way catalyst include hydrogen-storing material, modification γ-Al2O3、
Rare-earth additive, binder, noble metal nitrate, the γ-Al of the modification2O3γ-the Al being modified for La2O3, the hydrogen-storing material
For cerium zirconium compound oxide, hydrogen-storing material and modified γ-Al2O3Weight ratio is 2：3~3：2, rare-earth additive include zirconium, praseodymium,
Neodymium, yttrium nitrate it is one or more, account for apply stratum total 1~5%.
A kind of vehicle maintenance service three-way catalyst preparation method, includes the following steps：
(1) Pd layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds cerium zirconium composite oxygen
Compound and modified γ-Al2O3, after stirring evenly, palladium nitrate solution is added, stirs 12~24 hours, binder is added, continues
30~60min is stirred, adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains Pd layers of slurry
Material；
(2) Rh layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds cerium zirconium composite oxygen
Compound and modified γ-Al2O3, after stirring evenly, rhodium nitrate solution is added, stirs 12~24 hours, binder is added, continues
30~60min is stirred, adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains Rh layers of slurry
Material；
(3) the coating materials bed of material：Pd layers of slurry are first coated, Rh layers of slurry are coated with after dry；
(4) dry and roasting：It after the coating materials bed of material, is placed in drying box and is dried, be subsequently placed in Muffle furnace and carry out
Roasting.
The dosage of Pd ratios Rh nitrate is big in the catalyst, and the mass ratio of palladium nitrate and rhodium nitrate is 9:1, both
It is dispersed in modified γ-Al2O3In, modified γ-Al2O3It provides a sufficiently large specific surface area and is provided for noble metal and urged
Changing reacting environment, Rh primarily serves the effect of Reduction of NO in catalyst, and Pd primarily serves CO catalytic oxidation and the effect of HC,
Due to NOXReduction, need CO and HC as reducing agent, therefore Pd is coated in bottom Rh and is coated in outer layer, can make NO first with
CO and HC reactions, extra CO and HC are catalytically oxidized to CO by Pd again2And H2O。
Modification γ-Al in catalyst2O3, hydrogen-storing material and rare-earth additive and noble metal impregnate long agitation jointly,
Noble metal reaches high degree of dispersion.
Noble metal after dilution is slowly added to be conducive to further to increase dispersity.
It is 3~4 that pH-value is adjusted described in step (1), and the adjusting pH-value described in step (2) is 3~4.
The effect for adjusting pH-value is equally to prevent from pulp layer from being formed to reunite, and keeps the components such as noble metal, rare-earth additive uniform
Dispersion.
Coating materials bed of material mode described in step (3) is vacuum suction.
When coating, slurry is placed in above honeycomb, by the way of vacuum suction, coats honeycomb both ends, it can be by containing admittedly
Amount coats height needed for adjusting, and improves coating efficiency, and it is more secured that slurry can be made to be combined with honeycomb.
Dry 80 DEG C of first low temperature dry 1~2h, the latter 120 DEG C dry 2~3h used described in step (3), (4), step
Suddenly the roasting described in (4) is using first 300 DEG C of 1~2h of low-temperature bake, then 550 DEG C of 2~4h of roasting.
In drying process, low temperature drying is first used, can avoid in flash drying process, the migration of active component leads to activity
Component is reunited, and avoids being sintered when roasting.
In roasting process, first 300 DEG C of low-temperature bakes, then 550 DEG C of roastings can not only further decrease moving for active component
It moves, coating can also be made to adhere on honeycomb more secured, improve the mechanical strength of catalyst.
Rare-earth additive nitrate described in step (1) is one or more in zirconium, praseodymium, neodymium, and additive amount is in terms of oxide
The score for accounting for solid gross mass in Pd layers of slurry is 1~5%；Rare-earth additive nitrate described in step (2) is in zirconium, praseodymium, yttrium
It is one or more, additive amount accounted in terms of oxide solid gross mass in Rh layers of slurry score be 1~5%.
Rare-earth additive can enhance γ-Al2O3Thermal stability, reduce the loss of specific surface area, and noble metal can be improved
Dispersion degree, prevent accumulation of metal, further increase noble metal utilisation.
Embodiment 1
It takes zirconium nitrate 1.8g after 70g water dissolutions, the γ-Al that 19g is modified by La is added2O3With 29g cerium-zirconium composite oxides
Object is uniformly mixed, and is slowly added dropwise into slurry after 2.2g palladium nitrates are diluted 1 times, is stirred 12 hours；It is added after stirring viscous
Agent 1.4g is tied, 30min is stirred, it is 3 to adjust pH value, and ball milling 30min after 18g water is added, obtains Pd layers of slurry；
After taking 1.4g zirconium nitrates to be dissolved in 55g water, the γ-Al that 15g is modified by La are added2O3With 23g cerium-zirconium composite oxides
Object is uniformly mixed, and is slowly added dropwise into slurry after 0.46g rhodium nitrates are diluted 2 times, is stirred 12 hours；It is added after stirring viscous
Agent 1.1g is tied, 30min is stirred, it is 3 to adjust pH value, and ball milling 30min after 16g water is added, obtains Rh layers of slurry；
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, are divided
Honeycomb both ends Zhen Kongchouxi be coated to, are put into air dry oven the dry 1h of first 80 DEG C of low temperature, then 120 DEG C of dry 2h spare.
Rh layers based on siccative coated weight 80g/L, Rh layers of slurry vacuum suction are coated in containing Pd layers of ceramic honeycomb both ends, drum is put into
The dry 1h of first 80 DEG C of low temperature in wind drying box, then 120 DEG C of dry 2h.First 300 DEG C low-temperature bake 1hs are put into Muffle furnace after drying,
550 DEG C of roasting 2h again, both obtain Pd-Rh double-layer catalysts.
Precious metal salt is slowly dropped into after dilution in slurry, after grinding for a long time, it is fully dispersed in the slurry.
Pd layers of slurry are first applied, apply Rh layers of slurry afterwards, Rh first is catalyzed HC, CO and restores NOXReaction, then Pd be catalyzed HC, CO
Oxidation reaction.The mode applied by way of vacuum suction, the height on honeycomb can be controlled, and then control noble metal
Utilization rate.It applies after Pd layer slurry in such a way that gradient is dried, first low temperature is dried, then with 120 DEG C of dryings, prevents your gold
The migration of category；Then the mode roasted with gradient, first low-temperature bake are roasted with 550 DEG C, further prevent the migration of noble metal,
It prevents from being sintered.
Embodiment 2
After taking 1.8g zirconium nitrates and 1.3g neodymium nitrates to be dissolved in 70g water, the γ-Al that 19g is modified by La are added2O3And 29g
Cerium zirconium compound oxide is uniformly mixed, and takes a concentration of 17.91% palladium nitrate solution 2.67g, be slowly added dropwise after dilution to
In slurry, stir 24 hours；Binder 1.4g is added after stirring, stirs 60min, it is 4 to adjust pH value, after 18g water is added
Ball milling 50min is added to obtain Pd layers of slurry；
After taking 1.4g zirconium nitrates and 1.0g praseodymium nitrates to be dissolved in 60g water, the γ-Al that 15g is modified by La are added2O3And 23g
Cerium zirconium compound oxide is uniformly mixed, and is taken a concentration of 9.47% rhodium nitrate solution 0.56g, is slowly added dropwise after dilution to slurry
In material, stir 24 hours；Binder 1.1g is added after stirring, stirs 60min, it is 4 to adjust pH value, and ball after 16g water is added
50min is ground, Rh layers of slurry are obtained.
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, are divided
Honeycomb both ends Zhen Kongchouxi be coated to, are put into air dry oven the dry 2h of first 80 DEG C of low temperature, then 120 DEG C of dry 3h spare.
Rh layers based on siccative coated weight 80g/L, Rh layers of slurry vacuum suction are coated in containing Pd layers of ceramic honeycomb both ends, drum is put into
The dry 2h of first 80 DEG C of low temperature in wind drying box, then 120 DEG C of dry 3h.First 300 DEG C low-temperature bake 2hs are put into Muffle furnace after drying,
550 DEG C of roasting 4h again, both obtain Pd-Rh double-layer catalysts.
Precious metal salt dilutes again after being configured to solution, is then slowly dropped into slurry, after grinding for a long time, more
It is fully dispersed in the slurry.Rare-earth additive ratio increases, and rare-earth additive role more highlights.The catalytic capability of catalyst
The utilization rate for being primarily due to noble metal is relatively high.1. the precious metal salt dispersion after dilution is in the slurry, no and modified
γ-Al2O3Reaction, does not assemble；②γ-Al2O3The required reacting environment of catalyst is provided with the ratio of hydrogen-storing material,
With the needs to oxygen；3. the addition of rare-earth additive makes effect become apparent from, the effect of catalyst each section is not simple phase
Add, but with synergistic effect.Pd layers of slurry are first applied, apply Rh layers of slurry afterwards, Rh first is catalyzed HC, CO and restores NOXIt is anti-
It answers, then Pd is catalyzed the oxidation reaction of HC, CO.The mode applied by way of vacuum suction, can control on honeycomb
Highly, and then the utilization rate of noble metal is controlled.After Pd layers of slurry of coating in the way of gradient drying, first low temperature drying,
Again with 120 DEG C of dryings, the migration of noble metal is prevented；Then the mode roasted with gradient, first low-temperature bake are roasted with 550 DEG C, into
One step prevents the migration of noble metal, prevents from being sintered.
Embodiment 3
After taking 2.6g praseodymium nitrates, 2.6g neodymium nitrates and 1.3g zirconium nitrates to be dissolved in 70g water, it is added what 27g was modified by La
γ-Al2O3It is uniformly mixed with 18g cerium zirconium compound oxides, takes a concentration of 17.91% palladium nitrate solution 2.67g, diluted
After be slowly added dropwise into slurry, stir 18 hours；Binder 1.4g is added after stirring, stirs 45min, it is 3 to adjust pH value,
Ball milling 45min after addition 18g water, is added to obtain Pd layers of slurry.
After taking 2.1g praseodymium nitrates, 2.7g yttrium nitrates and 1.4g zirconium nitrates to be dissolved in 60g water, it is added what 22g was modified by La
γ-Al2O3It is uniformly mixed with 15g cerium zirconium compound oxides, a concentration of 9.47% rhodium nitrate solution 0.56g is taken, after dilution
It is slowly added dropwise into slurry, stirs 18 hours；Binder 1.1g is added after stirring, stirs 45min, it is 3 to adjust pH value, and
Ball milling 45min after addition 16g water, obtains Rh layers of slurry；
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, are divided
Honeycomb both ends Zhen Kongchouxi be coated to, are put into air dry oven the dry 1h of first 80 DEG C of low temperature, then 120 DEG C of dry 2h spare.
Rh layers based on siccative coated weight 80g/L, Rh layers of slurry vacuum suction are coated in containing Pd layers of ceramic honeycomb both ends, drum is put into
The dry 1h of first 80 DEG C of low temperature in wind drying box, then 120 DEG C of dry 2h.First 300 DEG C low-temperature bake 1hs are put into Muffle furnace after drying,
550 DEG C of roasting 2h again, both obtain Pd-Rh double-layer catalysts.
Precious metal salt dilutes again after being configured to solution, is then slowly dropped into slurry, after grinding for a long time, more
It is fully dispersed in the slurry.Rare-earth additive ratio increases, and rare-earth additive role more highlights.The catalytic capability of catalyst
The utilization rate for being primarily due to noble metal is relatively high.1. the precious metal salt dispersion after dilution is in the slurry, no and modified
γ-Al2O3Reaction, does not assemble；②γ-Al2O3The required reacting environment of catalyst is provided with the ratio of hydrogen-storing material,
With the needs to oxygen；3. the addition of rare-earth additive makes effect become apparent from, the effect of catalyst each section is not simple phase
Add, but with synergistic effect.Pd layers of slurry are first applied, apply Rh layers of slurry afterwards, Rh first is catalyzed HC, CO and restores NOXIt is anti-
It answers, then Pd is catalyzed the oxidation reaction of HC, CO.The mode applied by way of vacuum suction, can control on honeycomb
Highly, and then the utilization rate of noble metal is controlled.After Pd layers of slurry of coating in the way of gradient drying, first low temperature drying,
Again with 120 DEG C of dryings, the migration of noble metal is prevented；Then the mode roasted with gradient, first low-temperature bake are roasted with 550 DEG C, into
One step prevents the migration of noble metal, prevents from being sintered.
Comparative example 1
γ-the Al for taking 19g to be modified by La2O3It is mixed with 29g cerium zirconium compound oxides, 70g water is added and stirs evenly, it will
2.2g palladium nitrates are slowly added dropwise after diluting 1 times into slurry, stir 12 hours；Binder 1.4g, stirring are added after stirring
30min, it is 3 to adjust pH value, and ball milling 30min after 19.8g water is added, obtains Pd layers of slurry；
γ-the Al for taking 15g to be modified by La2O3It is mixed with 23g cerium zirconium compound oxides, 55g water is added and stirs evenly, it will
0.46g rhodium nitrates are slowly added dropwise after diluting 2 times into slurry, stir 12 hours；Binder 1.1g, stirring are added after stirring
30min, it is 3 to adjust pH value, and ball milling 30min after 17.4g water is added, obtains Rh layers of slurry；
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, are divided
Honeycomb both ends Zhen Kongchouxi be coated to, are put into air dry oven the dry 1h of first 80 DEG C of low temperature, then 120 DEG C of dry 2h spare.
Rh layers based on siccative coated weight 80g/L, Rh layers of slurry vacuum suction are coated in containing Pd layers of ceramic honeycomb both ends, drum is put into
The dry 1h of first 80 DEG C of low temperature in wind drying box, then 120 DEG C of dry 2h.First 300 DEG C low-temperature bake 1hs are put into Muffle furnace after drying,
550 DEG C of roasting 2h again, both obtain Pd-Rh double-layer catalysts.
Comparative example 2
After taking 1.8g zirconium nitrates and 1.3g neodymium nitrates to be dissolved in 70g water, the γ-Al that 19g is modified by La are added2O3And 29g
Cerium zirconium compound oxide is uniformly mixed, and is taken a concentration of 17.91% palladium nitrate 2.67g, is slowly added dropwise into slurry, stirring
24 hours；Binder 1.4g is added after stirring, stirs 60min, it is 4 to adjust pH value, and ball milling 50min after 18g water is added, adds
Add and has obtained Pd layers of slurry；
After taking 1.4g zirconium nitrates and 1.0g praseodymium nitrates to be dissolved in 60g water, the γ-Al that 15g is modified by La are added2O3And 23g
Cerium zirconium compound oxide is uniformly mixed, and is taken a concentration of 9.47% rhodium nitrate solution 0.56g, is slowly added dropwise into slurry,
Stirring 24 hours；Binder 1.1g is added after stirring, stirs 60min, it is 4 to adjust pH value, and ball milling after 16g water is added
30min obtains Rh layers of slurry.
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, are divided
Honeycomb both ends Zhen Kongchouxi be coated to, are put into air dry oven the dry 1h of first 80 DEG C of low temperature, then 120 DEG C of dry 2h spare.
Rh layers based on siccative coated weight 80g/L, Rh layers of slurry vacuum suction are coated in containing Pd layers of ceramic honeycomb both ends, drum is put into
The dry 2h of first 80 DEG C of low temperature in wind drying box, then 120 DEG C of dry 3h.First 300 DEG C low-temperature bake 2hs are put into Muffle furnace after drying,
550 DEG C of roasting 4h again, both obtain Pd-Rh double-layer catalysts.
Comparative example 3
After taking 2.6g praseodymium nitrates, 2.6g neodymium nitrates and 1.3g zirconium nitrates to be dissolved in 70g water, it is added what 27g was modified by La
γ-Al2O3It is uniformly mixed with 18g cerium zirconium compound oxides, takes a concentration of 17.91% palladium nitrate solution 2.67g, diluted
After be slowly added dropwise into slurry, stir 18 hours；Binder 1.4g is added after stirring, stirs 45min, it is 3 to adjust pH value,
Ball milling 45min after addition 18g water, is added to obtain Pd layers of slurry.
After taking 2.1g praseodymium nitrates, 2.7g yttrium nitrates and 1.4g zirconium nitrates to be dissolved in 60g water, it is added what 22g was modified by La
γ-Al2O3It is uniformly mixed with 15g cerium zirconium compound oxides, a concentration of 9.47% rhodium nitrate solution 0.56g is taken, after dilution
It is slowly added dropwise into slurry, stirs 18 hours；Binder 1.1g is added after stirring, stirs 45min, it is 3 to adjust pH value, and
Ball milling 45min after addition 16g water, obtains Rh layers of slurry；
Honeycomb specification is diameter 101.6mm, high 62mm, 600 mesh of hole density.Pd layers based on siccative coated weight 100g/L, apply
Honeycomb is immersed in Pd pulp layer 20min when covering, extra raffinate in duct is removed after taking-up, the dry 2h at 120 DEG C, then at horse
Not 550 DEG C of roasting 2h in stove, then be impregnated in Rh layers of slurry and taken out after 20min, extra raffinate in duct is removed, at 120 DEG C
Dry 2h, 550 DEG C of roasting 2h, are made Pd-Rh catalyst in Muffle furnace.
Catalyst test：
Catalyst performance test carries out in stainless steel fixed bed reactors, and simulated automotive tail gas group becomes：CO
0.75%, C3H8300ppm、C3H6600ppm、NO 500ppm、O20.8%, CO210%, N2For Balance Air, air speed 40000h-1, gas is formed divides FGA-4100 exhaust gas analyzers to analyze by Buddhist.According to embodiment 1,2,3 three-way catalyst carry out
Contrast test, the results are shown in table below：(the ignition ability of reaction three-way catalyst and maximum detergent power)
Comparative example 1 is identical with the preparation process of embodiment 1, but that zirconium nitrate is not added in the Pd layer slurries of comparative example 1,
Also that zirconium nitrate is not added in Rh layers of slurry, by test result：The ignition ability of embodiment 1 and maximum detergent power are all
It is more with obvious effects than comparative example 1.It can be seen that rare-earth additive contributes to the raising of three-way catalyst performance.
Comparative example 2 is identical with the preparation process of embodiment 2, but the palladium nitrate solution that the Pd layer slurries of comparative example 2 are added
It is not diluted 17.91% palladium nitrate solution, the rhodium nitrate solution that Rh layers of slurry is added is also undiluted.Pass through test result
Known to：The effect of embodiment 2 is more with obvious effects than comparative example 2.So the noble metal after dilution is more dispersed, noble metal utilizes effect
The performance of rate higher, three-way catalyst is more preferable.
Comparative example 3 is identical with the preparation process of embodiment 3, but the coating method of comparative example 3 is impregnated, only with 120
DEG C dry 2 hours, Muffle furnace roasted 2 hours.By test result：By being sucked by vacuum coating method, low temperature drying, low
The preparation process of temperature roasting is better than with dipping, direct high temperature drying, the preparation process of high-temperature roasting.
The maximum difference of 1,2,3 preparation process of embodiment is the rare-earth additive type difference being added, and effect is most notably
Three kinds of rare-earth additives are added, the embodiment 3 of the precious metal solution after dilution is added,
Equally it is to add three kinds of rare-earth additives, comparative example 3 uses impregnation method to coat, high temperature drying, high temperature roasting
It burns, effect is a kind of mode that effect is worst in all comparative examples.It can be seen that coating method, drying temperature, calcination temperature.It influences
To the dispersity of noble metal, the utilization rate of noble metal is reduced, reduces the effect of three-way catalyst.
Catalyst especially noble metal component can be made to keep preferable dispersivity and dispersion energy as it can be seen that rare-earth additive is added
Power.Rare-earth additive is present in modified γ-Al2O3In, the thermal stability of catalyst can be enhanced, stablize the height point of noble metal
Bulk state improves conversion ratio.Gradient type drying temperature and calcination temperature contribute to the mechanical strength for increasing catalyst, carry simultaneously
High catalytic performance.Meanwhile the effect of each section in catalyst is not to be simply added, but make with certain collaboration
With, coordinate the present invention preparation method, reduce the dosage of noble metal so that the best results of three small catalysts.
Finally illustrate, the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although with reference to compared with
Good embodiment describes the invention in detail, it will be understood by those of ordinary skill in the art that, it can be to the skill of the present invention
Art scheme is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered at this
In the right of invention.
Claims (6)
1. a kind of vehicle maintenance service three-way catalyst, the three-way catalyst include hydrogen-storing material, modification γ-Al2O3, it is dilute
Native auxiliary agent, binder, noble metal nitrate, it is characterised in that：γ-the Al of the modification2O3γ-the Al being modified for La2O3, institute
It is cerium zirconium compound oxide, hydrogen-storing material and modified γ-Al to state hydrogen-storing material2O3Weight ratio is 2：3~3：2, rare-earth additive packet
Include zirconium, praseodymium, neodymium, yttrium nitrate it is one or more, account for apply stratum total 1~5%.
2. a kind of vehicle maintenance service three-way catalyst preparation method, it is characterised in that：Include the following steps：
(1) Pd layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds cerium zirconium compound oxide
With modified γ-Al2O3, after stirring evenly, palladium nitrate solution is added, stirs 12~24 hours, binder is added, continues to stir
30~60min adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains Pd layers of slurry；
(2) Rh layers of slurry are prepared：First rare-earth additive nitrate is dissolved with appropriate amount of deionized water, adds cerium zirconium compound oxide
With modified γ-Al2O3, after stirring evenly, rhodium nitrate solution is added, stirs 12~24 hours, binder is added, continues to stir
30~60min adjusts pH-value, and water is added to be adjusted to ball milling 30min~60min after required solid content, obtains Rh layers of slurry；
(3) the coating materials bed of material：Pd layers of slurry are first coated, Rh layers of slurry are coated with after dry；
(4) dry and roasting：It after the coating materials bed of material, is placed in drying box and is dried, be subsequently placed in Muffle furnace and roasted.
3. a kind of vehicle maintenance service three-way catalyst preparation method according to claim 2, it is characterised in that：Step
(1) it is 3~4 that pH-value is adjusted described in, and the adjusting pH-value described in step (2) is 3~4.
4. a kind of vehicle maintenance service three-way catalyst preparation method according to claim 2, it is characterised in that：Step
(3) the coating materials bed of material mode described in is vacuum suction.
5. a kind of vehicle maintenance service three-way catalyst preparation method according to claim 2, it is characterised in that：Step
(3), dry 80 DEG C of first the low temperature dry 1~2h, latter 120 DEG C dry 2~3h, described in step (4) used described in (4)
Roasting is using first 300 DEG C of 1~2h of low-temperature bake, then 550 DEG C of 2~4h of roasting.
6. a kind of vehicle maintenance service three-way catalyst preparation method according to claim 2, it is characterised in that：Step
(1) rare-earth additive nitrate described in is one or more in zirconium, praseodymium, neodymium, and additive amount is accounted in terms of oxide in Pd layers of slurry
The score of solid gross mass is 1~5%；Rare-earth additive nitrate described in step (2) is zirconium, praseodymium, one or more in yttrium,
The score that additive amount accounts for solid gross mass in Rh layers of slurry in terms of oxide is 1~5%.
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| CN108927168A (en) * | 2018-07-16 | 2018-12-04 | 山东艾泰克环保科技股份有限公司 | A kind of natural gas vehicle three-way catalyst and preparation method thereof |
| CN109174077A (en) * | 2018-10-17 | 2019-01-11 | 安徽菲扬新材料有限公司 | A kind of vehicle maintenance service catalyst and preparation method thereof |
| CN109225213A (en) * | 2018-10-08 | 2019-01-18 | 江苏几维环境科技有限公司 | A kind of preparation method of motor vehicle tail-gas purifying close coupling three-way catalyst |
| CN109351355A (en) * | 2018-10-17 | 2019-02-19 | 台州欧信环保净化器有限公司 | A kind of Motorcycle catalytic converter and preparation method thereof meeting motorcycle state four standard |
| CN109675557A (en) * | 2019-01-09 | 2019-04-26 | 无锡威孚环保催化剂有限公司 | Noble metal catalyst and preparation method thereof with high thermal stability |
| CN109876793A (en) * | 2019-03-17 | 2019-06-14 | 中自环保科技股份有限公司 | A kind of three-way catalyst preparation method and its catalyst with high CO detergent power |
| CN111437811A (en) * | 2019-01-17 | 2020-07-24 | 上海清气环保科技有限公司 | High-performance automobile exhaust purification catalyst and preparation method thereof |
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| CN202823403U (en) * | 2012-08-09 | 2013-03-27 | 上海歌地催化剂有限公司 | Double-deck coating structure of honeycomb ceramic carrier |
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| CN108927168A (en) * | 2018-07-16 | 2018-12-04 | 山东艾泰克环保科技股份有限公司 | A kind of natural gas vehicle three-way catalyst and preparation method thereof |
| CN109225213A (en) * | 2018-10-08 | 2019-01-18 | 江苏几维环境科技有限公司 | A kind of preparation method of motor vehicle tail-gas purifying close coupling three-way catalyst |
| CN109174077A (en) * | 2018-10-17 | 2019-01-11 | 安徽菲扬新材料有限公司 | A kind of vehicle maintenance service catalyst and preparation method thereof |
| CN109351355A (en) * | 2018-10-17 | 2019-02-19 | 台州欧信环保净化器有限公司 | A kind of Motorcycle catalytic converter and preparation method thereof meeting motorcycle state four standard |
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| CN109675557B (en) * | 2019-01-09 | 2022-03-18 | 无锡威孚环保催化剂有限公司 | Noble metal catalyst with high thermal stability and preparation method thereof |
| CN111437811A (en) * | 2019-01-17 | 2020-07-24 | 上海清气环保科技有限公司 | High-performance automobile exhaust purification catalyst and preparation method thereof |
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| CN111672509A (en) * | 2020-03-05 | 2020-09-18 | 王金波 | Nano noble metal catalyst for purifying automobile exhaust and preparation method thereof |
| CN112023986A (en) * | 2020-09-18 | 2020-12-04 | 无锡威孚环保催化剂有限公司 | Automobile exhaust purification catalyst and preparation method thereof |
| CN112023986B (en) * | 2020-09-18 | 2022-09-16 | 无锡威孚环保催化剂有限公司 | Automobile exhaust purification catalyst and preparation method thereof |
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Application publication date: 20180713 |