CN103861614A - Metal soft carrier ternary catalyst with firm carrying layer - Google Patents
Metal soft carrier ternary catalyst with firm carrying layer Download PDFInfo
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- CN103861614A CN103861614A CN201210546805.7A CN201210546805A CN103861614A CN 103861614 A CN103861614 A CN 103861614A CN 201210546805 A CN201210546805 A CN 201210546805A CN 103861614 A CN103861614 A CN 103861614A
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Abstract
A metal soft carrier ternary catalyst with a firm carrying layer is provided, and belongs to the technical field of flue gas denitrification catalysts. The metal soft carrier ternary catalyst solves the problems that vehicle purifiers at present are poor in purification functions and have difficulty in meeting emission requirements. The metal soft carrier ternary catalyst comprises 38-46% by weight of a metal soft carrier, 8-12% by weight of a aluminized coating, 44-48% by weight of a catalyst carrying layer and 1-2% by weight of a catalyst component, wherein the catalyst component is one or more of platinum, palladium and rhodium. The catalyst is good in automobile exhaust gas purification effects, strong in plasticity, convenient and flexible to use, and wide in application scope. The carrying layer is firm, and therefore, the catalyst is good in catalyst durability and high in stability, and can achieve good purification effects after hydrothermal ageing.
Description
Technical field
The invention belongs to catalyst for denitrating flue gas technical field, particularly a kind of catalyst for tail-gas from gasoline automobiles.
Background technology
Motor vehicle exhaust emission severe contamination mankind's atmospheric environments of depending on for existence, and greatly threatening human body health.Along with the intensification of people to motor vehicle exhaust emission contamination hazard understanding, the stricter automobile exhaust emission standard scheme of the numerous and confused formulation in countries in the world.
For pusher motor-car pollution emission reduction, improve atmosphere quality, national environmental protection portion issues bulletin, requires various places strictly to implement immediately state IV standards to gasoline car.With respect to state III standard, state IV standards is further improved for the emission request of gasoline car, carbon monoxide must not exceed 1.0 grams/kilometer (EUROIII Emission Standard is 2.3 grams/kilometer), hydrocarbon must not exceed 0.1 gram/kilometer (EUROIII Emission Standard is 0.2 gram/kilometer), nitrogen oxide must not exceed 0.08 gram/kilometer (EUROIII Emission Standard is 0.15 gram/kilometer), and particle standard must not exceed 0.025 gram/kilometer.
Shown to environment, to the more and more higher requirement of quality of the life and the sense of duty to carrying out state IV standards from state III standard upgrade, but native country independent brand is in the face of the high-level discomfort of international joint.
From state III to state IV, be not only reaching of car load production technology, but the system engineering of the comprehensive requirements such as fuel oil quality, condition of road surface, traffic administration, driving technology, driving habit, operational maintenance.From current technology, the key of automobile environment-protection is to control exhaust emissions well by correlation technique, reduces the discharge of pernicious gas.
CN1454701A Rarefied-burning automobile exhaust gas catalyzing and purifying method and device, this disclosure of the invention a kind of Rarefied-burning automobile exhaust gas catalyzing and purifying method and device, relate to purifying vehicle exhaust technology.This invention is that two catalytic bed are set on the exhaust pipe of engine, and additional reducing agent nozzle is set between two reaction beds.The first reaction bed utilizes tail gas institute hydrocarbon-containiproducts nitrogen oxides reduction, makes the contained hydrocarbon of tail gas and carbon monoxide be converted into carbon dioxide and water simultaneously; The second reaction bed utilizes additional oxygen-bearing hydrocarbon reducing agent nitrogen oxides reduction, meanwhile, makes additional reducing agent be converted into carbon dioxide and water.This invention is compared with prior art scheme, can widen active temperature scope, improve purification of nitrogen oxides efficiency, assistance utilizes the effect of engine exhaust institute's hydrocarbon-containiproducts and additional oxygen-bearing hydrocarbon nitrogen oxides reduction, reduce the consumption of additional reducing agent, and Efficient Conversion hydrocarbon and carbon monoxide are carbon dioxide and water.
CN1872409A cleaning catalyst for tail gases of automobiles and preparation method thereof, this invention relates to a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof.This catalyst comprises carrier and is coated to the washcoat layer on carrier, taking the weight of washcoat layer as 100%, comprise following component: (1) 67～95% composite alumina carrier weighing, described composite alumina carrier is by aluminium oxide and be selected from lanthanum, cerium, praseodymium, neodymium, zirconium, magnesium, chromium, manganese, iron, cobalt, the oxide composition of one or more auxiliary agents in nickel: the active component of (2) 5～33 heavy %, described active component is by being selected from cobalt, molybdenum, nickel, tungsten, zirconium, titanium, lanthanum, cerium, praseodymium, one or more non-noble metal oxides in neodymium be selected from platinum, palladium, one or more metal oxide containing precious metals compositions of rhodium.The catalyst that this invention provides has good catalyzed conversion performance, can reduce the impact of tail gas medium sulphide content on catalyst poisoning, thus the tail gas clean-up efficiency that the higher gasoline combustion of sulfur content is discharged.
Mono-kind of CN1899690A removes the catalyst of nitrogen oxide and carbon monoxide in vehicle exhaust simultaneously, this invention relates to a kind of efficient, cheap non-precious metal catalyst and replaces the triple effect noble metal catalyst that is applied at present purifying vehicle exhaust, specially refers to a kind of catalyst that simultaneously removes nitrogen oxide and carbon monoxide in vehicle exhaust.It is characterized in that Ag is Your Majesty.Wherein, Co is co-catalyst, is jointly carried on support C eO
2adopt the sluggish precipitation preparation that urea is precipitating reagent; The introducing of active component A g and Co adopts dipping method, floods Co after first flooding Ag, and the best loading of Ag and Co is 4wt% and 0.4wt%.The effect of this invention and benefit be provided Catalysts for Reducing cleaning catalyst for tail gases of automobiles, metering oxygen cost.This catalyst is under the condition of 120000h-1 existence in air speed, interior 200～500 DEG C of lower temperature window, and when realizing NO and CO, catalysis is eliminated.
CN1772382A metal carrier for automobile tail gas purifier catalyst and preparation method thereof, this invention relates to a kind of for metal carrier for automobile tail gas purifier catalyst and preparation method thereof, solves existing metallic carrier complex forming technology and the higher technical problem of production cost.Metal carrier for automobile tail gas purifier catalyst, is characterized in that tridimensional network, and skeleton is that metallic nickel or core adopt metallic copper substantially, and skin comprises that the skeleton of metallic nickel is matrix, and porosity is 30～98%, and hole count is 20～60PPI, and aperture is 0.5～3mm.Preparation method comprises the following steps: conductive treatment is made on a. polyurethane or polyether foam surface, and conductive treatment can adopt electroless plating method or vaccum gas phase sedimentation method, applies carbon back electrically-conducting paint: b. electro-deposition parent metal, conventional nickel or copper clad nickel; C. in pyrolysis oven, foamed plastics matrix is burnt, removed.The main carrier as automobile tail gas purifier catalyst.
CN1600418A cleaning catalyst for tail gases of automobiles and preparation method thereof, this disclosure of the invention a kind of cleaning catalyst for tail gases of automobiles and preparation method thereof.Taking cordierite ceramic as carrier, taking aluminium glue and modenite as coated substrate, taking one or more oxides in the elements such as La-Ce-Zr solid solution or La, Ce, Zr, Mn or composite oxides as auxiliary agent, taking Pt, Pd, Rh as main active.The manufacture method of this catalyst is: one or more in aluminium glue powder, modenite powder, auxiliary agent are mixed into mixed powder and distilled water makes mixed coating material, cordierite honeycomb ceramic is impregnated in prepared mixed coating material, dipping, dry, roasting, the disposable coated carrier that makes coating load rate 10～30%, again the coated carrier making is immersed in the noble metal precursor solution of PH=2～7, dipping, dry, roasting, makes cleaning catalyst for tail gases of automobiles of the present invention.The catalyst of this invention has good low temperature activating characteristic and very high catalytic conversion efficiency, can effectively reduce the cold start emission of automobile.
The present invention relates to the firmly soft carrier three-way catalyst of metal of a kind of catalyst carrying layer, mainly solve in the soft carried catalyst of the existing metal of vehicle between the soft carrier of metal and catalyst carrying layer cohesive force poor, carrying layer is insecure, in the soft vector form deforming process of metal, holds caducous problem.The present invention adopts fluffy fe-cr-ni alloy wire, be wound in the spiral metal carrier that little spring is the same, then soft metal carrier is carried out to alitizing processing, improve the technical scheme of soft carrier top layer aluminium content, solve preferably this problem, the catalyst of preparation has the feature of catalyst carrying layer firmly, to the soft carrier strong adhesion of metal, can be used in the industrial production of the soft carried catalyst of metal.
Comprehensive relatively, powder method because investment is little, instant effect, applicability be wide, in ferrous materials, obtained comparatively successfully applying.
Summary of the invention
Technical problem to be solved by this invention is that the existing clarifier of vehicle existing in prior art still plays catharsis, but satisfy regulatory emission request completely, all replacings had both been wasted resource, the problem raising the cost again.Provide a kind of new metal soft carrier catalyst for tail-gas from gasoline automobiles, the soft carrier catalyst for tail-gas from gasoline automobiles of metal of the present invention has that the clean-up effect, plasticity of raising is strong, easy to use and flexible, the feature such as applied widely.
For solving the problems of the technologies described above, the invention provides the firmly soft carrier three-way catalyst of metal of a kind of carrying layer, its technical scheme is as follows:
Carrying layer is the soft carrier three-way catalyst of metal firmly, comprises the component of following percentage by weight:
38% ~ 46% the soft carrier of metal;
8% ~ 12% the aluminized coating forming at the soft carrier surface of described metal;
44% ~ 48% the catalyst carrying layer forming on described aluminized coating surface;
And 1% ~ 2% the catalysis composition forming on described catalyst carrying layer surface, described catalysis composition is one or more in platinum, palladium or rhodium.
Preferred version as the inventive method:
The aluminized coating of the soft carrier surface of described metal obtains by powder alitizing, hot-dip aluminizing using method or the processing of hot spray process alitizing.
Preferred version as the inventive method:
The aluminized coating of the soft carrier surface of described metal obtains by the processing of powder alitizing.
Preferred version as the inventive method:
The soft carrier of described metal is entwined by spiral helicine fe-cr-ni alloy wire.
Preferred version as the inventive method:
The monnolithic case of the soft carrier of described metal is spherical in shape, and volume is 0.05 ~ 2L.
Preferred version as the inventive method:
The volume of the soft carrier of described metal is 0.08 ~ 0.20L.
Preferred version as the inventive method:
In described catalyst carrying layer, contain one or more in aluminium oxide, cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide or manganese oxide.
Preferred version as the inventive method:
In described catalyst carrying layer, contain aluminium oxide, cerium oxide, zirconia and manganese oxide, wherein the weight percent content of aluminium oxide is 94%, and the weight percent content of cerium oxide, zirconia and manganese oxide is equal 2%;
The load capacity of described catalysis composition is 10 ~ 80g/ft
3, in catalysis composition, contain palladium catalyst, platinum catalyst and rhodium catalyst, wherein the weight ratio of palladium catalyst, platinum catalyst and rhodium catalyst is 1:0 ~ 1:0 ~ 1.
Preferred version as the inventive method:
The load capacity of described catalysis composition is 15 ~ 60g/ft
3, wherein the weight ratio of palladium catalyst, platinum catalyst and rhodium catalyst is 1:0 ~ 0.3:0.1 ~ 0.3.
The present invention also provides the firmly application of the soft carrier three-way catalyst of metal in tail-gas from gasoline automobiles purifies of a kind of above-mentioned carrying layer.
The preparation method of catalyst of the present invention comprises the following steps:
Step 1: adopt alitizing to process the soft carrier of metal, then clean up;
Step 2: quantitative aluminium oxide and distilled water are mixed, be made into alumina content and be 2040% slurry, add again one or more in quantitative cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide, manganese oxide, ball milling 24-72h in ball mill, obtains uniform combined oxidation aluminum slurry;
Step 3: by soft the metal cleaning up after surface treatment carrier, the slurry obtaining by step 2 applies, coated weight is 20 ~ 100g/L, then dry, roasting;
Step 4: carried noble metal: prepare quantitative platinum, palladium, rhodium soluble-salt solution, add appropriate complexing agent, competitive adsorbate, the carrier that step 3 is obtained floods, and then dry, roasting, obtains the firmly soft carrier three-way catalyst of metal of carrying layer.
The present invention adopts fluffy fe-cr-ni alloy wire, be wound in the spiral metal carrier that little spring is the same, adopt alitizing to process the soft carrier of metal, improve the soft carrier of metal top layer aluminium content, then apply firmly catalyst carrying layer, the technical scheme of carried noble metal at this carrier surface.Soft metal carried catalyst is filled in air vent of automobile engine pipeline, not only have that the purifying vehicle exhaust effect of raising, plasticity are strong, easy to use and flexible, the feature such as applied widely, and because carrying layer is firm, durability of catalyst is better, stability is stronger, after hydrothermal aging, still obtain good clean-up effect, can be used in the discharge improvement of existing vehicle.
Below by embodiment, the present invention is further elaborated, and these schemes are only to further illustrate instead of the scope of limit value claims.
Catalyst performance detects:
For the simulated automotive exhaust gas component measured in table 1, to the clean-up effect of fresh state three-way catalyst, hydrothermal aging state (quick aging in electric furnace, 1150 DEG C × 24h) three-way catalyst in table 2 and table 3.
Table 1: the vehicle exhaust composition of simulated determination
| Gas | NO | CO | C 8H 8 | O 2 | CO 2 | N 2 | Steam |
| Volume fraction % | 0～0.06 | 2～6 | 0.02～0.06 | 0.98～1.02 | 9～14 | 0～50 | 8～15 |
Detailed description of the invention
[embodiment 1]
Carrying layer is the soft carrier three-way catalyst of metal firmly, is made up of the component of following percentage by weight:
0.2L(0.007ft
3), 16.3g(43.6%) the soft carrier of metal, the soft carrier of metal is that fe-cr-ni alloy wire is wound in entirety in the shape of a spiral for spherical fluffy body;
The aluminized coating of 3.7 grams forming at the soft carrier surface of metal;
The 17g(45.5% forming on aluminized coating) catalyst carrying layer; In catalyst carrying layer, aluminium oxide accounts for 94%, and cerium oxide, zirconia, manganese oxide respectively account for 2%;
And 0.37g(1%) active component, the weight ratio of active component palladium, platinum, rhodium is 1:0.03:0.20.
Active component noble-metal-supported amount is 50g/ft
3.
The preparation method of above-mentioned catalyst comprises:
Step 1: adopt alitizing to process metal soft carrier, the content of top layer aluminium is total catalyst weight 10%, then cleans up;
Step 2: 15.98g(is accounted for to 94%) aluminium oxide and distilled water mixing, be made into alumina weight percentage composition and be 20% slurry, add again 0.34g(to account for 2%) cerium oxide, 0.34g(account for 2%) zirconia and 0.34g(account for 2%) manganese oxide, ball milling 24h in ball mill, obtains uniform combined oxidation aluminum slurry;
Step 3: the slurry obtaining by step 2 applies the soft carrier of metal after cleaning up in step 1, and coated weight is 20 ~ 100g/L, then dry, roasting;
Step 4: in the aqueous solution of ammonium chloroplatinate, palladium bichloride and chlorine rhodium acid potassium, drying and roasting, obtain the firmly soft carrier three-way catalyst of metal of carrying layer by soft the metal that is coated with catalyst carrying layer carrier impregnation; In ammonium chloroplatinate, palladium bichloride and chlorine rhodium acid potassium, the weight ratio of palladium, platinum, rhodium is 1:0.03:0.20, and the gross weight of palladium, platinum, rhodium is 0.37g.
[embodiment 2]
The soft carrier of metal of 16.3g, the aluminized coating of 3.7 grams, active component noble-metal-supported amount is 45g/ft
3, the weight relative amount of catalysis composition palladium, platinum, rhodium is 1:0.10:0.10, all the other are with embodiment 1.
[embodiment 3]
The soft carrier of metal of 17g, the aluminized coating of 3 grams, active component noble-metal-supported amount is 50g/ft
3, the weight relative amount of catalysis composition palladium, platinum, rhodium is 1:0.20:0.14, all the other are with embodiment 1.
[embodiment 4]
The soft carrier of metal of 15.5g, the aluminized coating of 4.5 grams, active component noble-metal-supported amount is 45g/ft
3, the weight relative amount of catalysis composition palladium, platinum, rhodium is 1:0.25:0.13, all the other are with embodiment 1.
Table 2: the clean-up effect of fresh catalyst
Table 3: the clean-up effect of hydrothermal aging state three-way catalyst
Claims (10)
1. the firmly soft carrier three-way catalyst of metal of carrying layer, is characterized in that, comprises the component of following percentage by weight: 38% ~ 46% the soft carrier of metal;
8% ~ 12% the aluminized coating forming at the soft carrier surface of described metal;
44% ~ 48% the catalyst carrying layer forming on described aluminized coating surface;
And 1% ~ 2% the catalysis composition forming on described catalyst carrying layer surface, described catalysis composition is one or more in platinum, palladium or rhodium.
2. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 1, is characterized in that:
The aluminized coating of the soft carrier surface of described metal obtains by powder alitizing, hot-dip aluminizing using method or the processing of hot spray process alitizing.
3. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 2, is characterized in that:
The aluminized coating of the soft carrier surface of described metal obtains by the processing of powder alitizing.
4. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 3, is characterized in that:
The soft carrier of described metal is entwined by spiral helicine fe-cr-ni alloy wire.
5. the soft carrier tail-gas from gasoline automobiles of metal according to claim 4 cleaning catalyst, is characterized in that:
The monnolithic case of the soft carrier of described metal is spherical in shape, and volume is 0.05 ~ 2L.
6. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 5, is characterized in that:
The volume of the soft carrier of described metal is 0.08～0.20L.
7. according to the firmly soft carrier three-way catalyst of metal of the carrying layer described in claim 1,2,3,4,5 or 6, it is characterized in that:
In described catalyst carrying layer, contain one or more in aluminium oxide, cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide or manganese oxide.
8. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 7, is characterized in that:
In described catalyst carrying layer, contain aluminium oxide, cerium oxide, zirconia and manganese oxide, wherein the weight percent content of aluminium oxide is 94%, and the weight percent content of cerium oxide, zirconia and manganese oxide is equal 2%;
The load capacity of described catalysis composition is 10 ~ 80g/ft
3, in catalysis composition, contain palladium catalyst, platinum catalyst and rhodium catalyst, wherein the weight ratio of palladium catalyst, platinum catalyst and rhodium catalyst is 1:0 ~ 1:0 ~ 1.
9. the firmly soft carrier three-way catalyst of metal of carrying layer according to claim 8, is characterized in that:
The load capacity of described catalysis composition is 15 ~ 60g/ft
3, wherein the weight ratio of palladium catalyst, platinum catalyst and rhodium catalyst is 1:0 ~ 0.3:0.1 ~ 0.3.
10. the firmly application of the soft carrier three-way catalyst of metal in tail-gas from gasoline automobiles purifies of carrying layer according to claim 8 or claim 9.
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|---|---|---|---|---|
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| CN101249444A (en) * | 2008-04-14 | 2008-08-27 | 长春吉大科诺科技有限责任公司 | Method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier |
| EP1985353A1 (en) * | 2007-04-27 | 2008-10-29 | N.E. Chemcat Corporation | Exhaust gas purification catalyst for automobile, exhaust gas purification catalyst system and purifying process of exhaust gas |
| CN102039146A (en) * | 2010-11-18 | 2011-05-04 | 华东理工大学 | Catalyst for purifying exhaust gas of natural gas engine and preparation method thereof |
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2012
- 2012-12-14 CN CN201210546805.7A patent/CN103861614A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1593756A (en) * | 2004-07-05 | 2005-03-16 | 南京大学 | Preparation method of metal honeycomb supported catalyst |
| CN1830566A (en) * | 2006-04-18 | 2006-09-13 | 天津大学 | Preparation method of coppor cerium catalyst coated on FeCrAl carrior |
| EP1985353A1 (en) * | 2007-04-27 | 2008-10-29 | N.E. Chemcat Corporation | Exhaust gas purification catalyst for automobile, exhaust gas purification catalyst system and purifying process of exhaust gas |
| CN101249444A (en) * | 2008-04-14 | 2008-08-27 | 长春吉大科诺科技有限责任公司 | Method for preparing nitrous oxides selectivity reduction catalyst on metal alloy carrier |
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Effective date of abandoning: 20190521 |