CN103861613A - Metal soft carrier gasoline vehicle tail gas cleaning catalyst - Google Patents
Metal soft carrier gasoline vehicle tail gas cleaning catalyst Download PDFInfo
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- CN103861613A CN103861613A CN201210545839.4A CN201210545839A CN103861613A CN 103861613 A CN103861613 A CN 103861613A CN 201210545839 A CN201210545839 A CN 201210545839A CN 103861613 A CN103861613 A CN 103861613A
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- soft carrier
- metal
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- tail
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Abstract
The invention discloses a metal soft carrier gasoline vehicle tail gas cleaning catalyst. The metal soft carrier gasoline vehicle tail gas cleaning catalyst comprises, by weight, 40 to 60% of a metal soft carrier, 38 to 59% of a catalyst carrying layer formed on the metal soft carrier, and 1 to 2% of a catalyst ingredient; the catalyst ingredient is one or more selected from platinum, palladium, and rhodium. The metal soft carrier gasoline vehicle tail gas cleaning catalyst is capable of increasing purifying effect, is high in plasticity, is convenient and flexible to use, and is wide in application range.
Description
Technical field
The present invention relates to tail-gas from gasoline automobiles field of purification, be specifically related to the soft carrier tail-gas from gasoline automobiles of a kind of metal cleaning catalyst.
Background technology
Gasoline motor car exhausted gas severe contamination mankind's atmospheric environments of depending on for existence, and greatly threatening human body health.Along with the intensification of people to gasoline motor car exhausted gas contamination hazard understanding, the stricter gasoline motor car exhausted gas 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 there are numerous discomforts in the face of the high standard of international joint in native country independent brand.
From state's III standard to state IV standards, be not only reaching of requirement 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 gasoline car environmental protection is to control exhaust emissions well by correlation technique, reduces the discharge of pernicious gas, generally adopts tail-gas from gasoline automobiles cleaning catalyst and/or purifier to realize.
Publication number is that the Chinese patent application of CN1454701A discloses a kind of lean burn type tail-gas from gasoline automobiles catalytic purification method and device, relates to tail-gas from gasoline automobiles purification techniques.Two catalytic bed are specifically set on the exhaust pipe of engine, 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.But its step complexity.
Publication number is that the Chinese patent of CN1872409A discloses a kind of tail-gas from gasoline automobiles cleaning catalyst 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, thereby improves the tail gas clean-up efficiency that the higher gasoline combustion of sulfur content is discharged.But its cost is high, pressure drop is high.
Publication number is that the Chinese patent of CN1899690A discloses a kind of catalyst that simultaneously removes nitrogen oxide and carbon monoxide in tail-gas from gasoline automobiles, is that Ag is Your Majesty.Wherein, Co is co-catalyst, is jointly carried on support C eO
2upper, wherein 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 are that provided catalyst cost is low, have and do not measure under the condition of oxygen, and this catalyst is 120000h in air speed
-1, interior 200～500 DEG C of lower temperature window, when realizing NO and CO, catalysis is eliminated.
Publication number is that the Chinese patent of CN1772382A discloses a kind of tail-gas from gasoline automobiles purifier catalyst metallic carrier and preparation method thereof, solves existing metallic carrier complex forming technology and the higher technical problem of production cost.This tail-gas from gasoline automobiles purifier catalyst metallic carrier, is 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 tail-gas from gasoline automobiles purifier catalyst.
Publication number is that the Chinese patent of CN1600418A discloses a kind of tail-gas from gasoline automobiles cleaning catalyst 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 combination chart layer 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 tail-gas from gasoline automobiles cleaning catalyst.This catalyst has good low temperature activating characteristic and very high catalytic conversion efficiency, can effectively reduce the cold start emission of gasoline car.
Although the existing clarifier that meets the In-Use Motor Vehicles of state III discharge standard existing still can play catharsis, satisfy regulatory emission request completely, and all resource had both been wasted in replacing, had again the problem raising the cost.If work out and can make exhaust emissions meet cleaning catalyst or the catalysis process that state IV standards is applicable to again existing clarifier will to have broad application prospects in conjunction with existing clarifier.
Summary of the invention
The present invention is directed to the existing clarifier of the vehicle existing in prior art and still play catharsis, but satisfy regulatory emission request completely, all resource had both been wasted in replacing, the problem raising the cost again, the soft carrier tail-gas from gasoline automobiles of a kind of new metal cleaning catalyst is provided, and the soft carrier tail-gas from gasoline automobiles of metal of the present invention cleaning catalyst has that the clean-up effect, plasticity of raising is strong, easy to use and flexible, the feature such as applied widely.
The present invention adopts the soft carrier of metal being entwined in the shape of a spiral by fluffy fe-cr-ni alloy wire, then on the soft carrier of this metal, form the technical scheme of catalyst carrying layer carrying transition metal, solve preferably this problem, can be used in the discharge improvement of existing vehicle.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
The soft carrier tail-gas from gasoline automobiles of a kind of metal cleaning catalyst, comprises the component of following percentage by weight:
40% ~ 60% the soft carrier of metal;
38% ~ 59% the catalyst carrying layer forming on the soft carrier of described metal;
And 1% ~ 2% catalysis composition (being active component), described catalysis composition is one or more in platinum, palladium, rhodium.
The soft carrier tail-gas from gasoline automobiles of described metal cleaning catalyst, is preferably made up of the component of following percentage by weight:
53.5% the soft carrier of metal;
45.5% the catalyst carrying layer forming on the soft carrier of described metal;
And 1% catalysis composition (being active component), described catalysis composition is one or more in platinum, palladium, rhodium.
The soft carrier of described metal is the fluffy body being entwined in the shape of a spiral by fe-cr-ni alloy wire, can be wound in as required the soft carrier of metal that entirety is arbitrary shape, prepare very conveniently, and in fluffy body, have a large amount of gaps to exist, be beneficial to the load of catalysis composition.Described fe-cr-ni alloy wire can directly adopt commercially available prod.
The shape of the described soft carrier of metal is preferably spherical, and volume is 0.05L ~ 2L, more preferably 0.08L ~ 0.2L.
The composition of described catalyst carrying layer is one or more in aluminium oxide, cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide, manganese oxide.When selecting when two or more, the ratio between each composition can be any ratio.The composition of described catalyst carrying layer is preferably aluminium oxide, cerium oxide, zirconia and manganese oxide, is further preferably made up of 94% aluminium oxide, 2% cerium oxide, 2% zirconia and 2% manganese oxide, and wherein % is weight percentage.
Described catalysis composition is preferably three kinds of palladium, platinum and rhodiums.
In described catalysis composition, palladium, platinum and rhodium three's weight ratio is 1: be greater than 0 and be less than or equal to 1: be greater than 0 and be less than or equal to 1, be preferably 1: be greater than 0 and be less than or equal to 0.3:0.1 ~ 0.3, more preferably 1:0.03 ~ 0.25:0.13 ~ 0.2.
The load capacity of described catalysis composition is 10g/ft
3~ 80g/ft
3, more preferably 15g/ft
3~ 60g/ft
3, ft is foot.The load capacity of catalysis composition refers to every ft
3the grams of the catalysis composition of the soft carrier tail-gas from gasoline automobiles of metal cleaning catalyst kind load.
The preparation method of the soft carrier tail-gas from gasoline automobiles of described metal cleaning catalyst, comprises the following steps:
(1) one or both and water in metal oxide, transition metal oxide are mixed, ball milling 24h-72h in ball mill, obtains uniform slurry;
(2) slurry step (1) being obtained is evenly coated on the soft carrier of metal, and coated weight is 20 ~ 100g/L, and drying and roasting obtain the soft carrier of metal of catalyst carrying layer;
(3) the soft carrier of the metal that has catalyst carrying layer of putting into step (2) in the soluble-salt solution of catalysis composition floods, and drying and roasting obtain the soft carrier tail-gas from gasoline automobiles of metal cleaning catalyst.
Described coated weight refers to the grams of the slurry applying on every liter of soft carrier of metal.
In the soluble-salt solution of described catalysis composition, also can add appropriate complexing agent and competitive adsorbate, described complexing agent and competitive adsorbate are selected commercially available prod.
Described metal oxide is selected one or more in aluminium oxide, magnesia, barium monoxide.Described transition metal oxide is selected one or more in cerium oxide, zirconia, nickel oxide, manganese oxide.
The preferred preparation method of one of the soft carrier tail-gas from gasoline automobiles of described metal cleaning catalyst, comprises the following steps:
(1) aluminium oxide and water are mixed, be made into the slurry that alumina weight percentage composition is 20%-40%, add one or more in cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide, manganese oxide, ball milling 24h-72h in ball mill, obtains uniform slurry again;
(2) slurry step (1) being obtained is evenly coated on the soft carrier of metal, and coated weight is 20 ~ 100g/L, and drying and roasting obtain the soft carrier of metal of catalyst carrying layer;
(3) the soft carrier of the metal that has catalyst carrying layer of putting into step (2) in the soluble-salt solution of catalysis composition floods, and drying and roasting obtain the soft carrier tail-gas from gasoline automobiles of metal cleaning catalyst.
Described catalyst can be used for purifying gasoline car tail, while specifically use, catalyst can be placed in to gasoline motor car exhausted gas pipe.Can place in use one or more, described multiplely be preferably 2-8.The flexibility of there is installation, arranging.
The present invention has following beneficial effect:
The soft carrier tail-gas from gasoline automobiles of metal of the present invention cleaning catalyst has solved preferably the existing clarifier of vehicle and has still played catharsis, but satisfy regulatory emission request completely, all resource had both been wasted in replacing, and the problem raising the cost again can be used in the discharge improvement of existing vehicle.
Soft metal of the present invention catalyst has that the clean-up effect, plasticity of raising is strong, easy to use and flexible, the feature such as applied widely, can adjust flexibly according to the gap of the existing emission status of vehicle and state IV discharge standard the quantity of the soft carried catalyst of placement metal.
Detailed description of the invention
The present invention is described above, in order to obtain further understanding, will tell about specific embodiment below, these schemes are only the scopes that further illustrates instead of limit claims.Wherein % is all weight percentage.
Embodiment 1
The soft carrier tail-gas from gasoline automobiles of metal cleaning catalyst, the component by following percentage by weight:
0.2L(0.007ft
3), 20g(53.5%) 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 17g(45.5% forming on the soft carrier of metal) 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.
Preparation method comprises:
(1) 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;
(2) adopt the clean fe-cr-ni alloy wire of surface clean to be wound in the shape of a spiral entirety for spherical fluffy body, volume is 0.2L, weight is 20g, taking this fluffy body as the soft carrier of metal, combined oxidation aluminum slurry is evenly coated on the soft carrier of metal, drying and roasting, obtain being coated with the soft carrier of metal of catalyst carrying layer;
(3) by soft the metal that is coated with catalyst carrying layer carrier impregnation in the aqueous solution of ammonium chloroplatinate, palladium bichloride and chlorine rhodium acid potassium, drying and roasting, obtain the soft carrier tail-gas from gasoline automobiles of metal cleaning catalyst; 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
Except the weight ratio of active component palladium, platinum, rhodium is 1:0.10:0.10, all the other are with embodiment 1.
Embodiment 3
Except the weight ratio of active component palladium, platinum, rhodium is 1:0.20:0.14, all the other are with embodiment 1.
Embodiment 4
Except the weight ratio of active component palladium, platinum, rhodium is 1:0.25:0.13, all the other are with embodiment 1.
Catalyst performance detects: the catalyst of respectively being prepared by embodiment 1-4 is placed in gasoline motor car exhausted gas pipe, the volume fraction (Vol) of hydrocarbon (HC), carbon monoxide (CO) and nitric oxide (NO) in tail-gas from gasoline automobiles while moving 1000 kilometers by the method test gasoline car (taking unleaded gas as fuel) of GB18285-2005 Appendix B, the results are shown in Table 1, in table 1,5025 represent ASM5025 operating mode, and 2540 represent ASM2540 operating mode.Gasoline car adopts manual forerunner's gasoline car that discharge capacity is 1.60L, and gasoline car discharge testing result adopts steady state condition method exhaust detection system.Two soft carried catalysts of metal are installed.
The experimental result that the operation of table 1 catalyst is 1000 kilometers
Claims (10)
1. the soft carrier tail-gas from gasoline automobiles of a metal cleaning catalyst, is characterized in that, comprises the component of following percentage by weight: 40% ~ 60% the soft carrier of metal;
38% ~ 59% the catalyst carrying layer forming on the soft carrier of described metal;
And 1% ~ 2% catalysis composition, described catalysis composition is one or more in platinum, palladium, rhodium.
2. the soft carrier tail-gas from gasoline automobiles of metal according to claim 1 cleaning catalyst, is characterized in that, the soft carrier of described metal is the fluffy body being entwined in the shape of a spiral by fe-cr-ni alloy wire.
3. the soft carrier tail-gas from gasoline automobiles of metal according to claim 2 cleaning catalyst, is characterized in that, the soft carrier of described metal is spherical, and volume is 0.05L ~ 2L.
4. the soft carrier tail-gas from gasoline automobiles of metal according to claim 3 cleaning catalyst, is characterized in that, the volume of the described soft carrier of metal is 0.08L ~ 0.2L.
5. the soft carrier tail-gas from gasoline automobiles of metal according to claim 1 cleaning catalyst, is characterized in that, described catalyst carrying layer is one or more in aluminium oxide, cerium oxide, zirconia, magnesia, barium monoxide, nickel oxide, manganese oxide.
6. the soft carrier tail-gas from gasoline automobiles of metal according to claim 1 cleaning catalyst, is characterized in that, described catalysis composition is three kinds of palladium, platinum and rhodiums.
7. the soft carrier tail-gas from gasoline automobiles of metal according to claim 6 cleaning catalyst, is characterized in that, in described catalysis composition, palladium, platinum and rhodium three's weight ratio is 1: be greater than 0 and be less than or equal to 1: be greater than 0 and be less than or equal to 1.
8. the soft carrier tail-gas from gasoline automobiles of metal according to claim 7 cleaning catalyst, is characterized in that, in described catalysis composition, palladium, platinum and rhodium three's weight ratio is 1: be greater than 0 and be less than or equal to 0.3:0.1 ~ 0.3.
9. the soft carrier tail-gas from gasoline automobiles of metal according to claim 8 cleaning catalyst, is characterized in that, in described catalysis composition, palladium, platinum and rhodium three's weight ratio is 1:0.03 ~ 0.25:0.13 ~ 0.2.
10. the application in tail-gas from gasoline automobiles purifies according to the soft carrier tail-gas from gasoline automobiles of the metal cleaning catalyst described in claim 1 ~ 9 any one.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210545839.4A CN103861613A (en) | 2012-12-14 | 2012-12-14 | Metal soft carrier gasoline vehicle tail gas cleaning catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210545839.4A CN103861613A (en) | 2012-12-14 | 2012-12-14 | Metal soft carrier gasoline vehicle tail gas cleaning catalyst |
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| CN103861613A true CN103861613A (en) | 2014-06-18 |
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| CN201210545839.4A Pending CN103861613A (en) | 2012-12-14 | 2012-12-14 | Metal soft carrier gasoline vehicle tail gas cleaning catalyst |
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Cited By (1)
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| CN111346637A (en) * | 2018-12-24 | 2020-06-30 | 上海萃励电子科技有限公司 | Preparation method of Pd-Ir supported manganese oxide nanotube |
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Effective date of abandoning: 20181102 |