CN100338341C - Vehicle tail-gas catalytic converter - Google Patents
Vehicle tail-gas catalytic converter Download PDFInfo
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- CN100338341C CN100338341C CNB031143997A CN03114399A CN100338341C CN 100338341 C CN100338341 C CN 100338341C CN B031143997 A CNB031143997 A CN B031143997A CN 03114399 A CN03114399 A CN 03114399A CN 100338341 C CN100338341 C CN 100338341C
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- catalytic converter
- automobiles
- gas catalytic
- exhaust gas
- foaming
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- 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
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- Catalysts (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The present invention relates to a vehicle tail gas catalytic converter. The present invention comprises a casing, a vibration damping layer, a metal carrier and a catalyst coating layer, wherein the metal carrier is manufactured by adopting a foamed metal material with 50 to 1200 microns of hole diameters, and 80 to 90% of porosity factors; through the hot corrosion of organic acid, and dipping and sintering processes, the metal carrier is firmly combined with catalyst coating constituents. The present invention has the advantages of heat shock and mechanical shock resistance, high purification efficiency and long service life.
Description
[technical field]
The present invention relates to a kind of Exhaust Gas Catalytic Converter for Automobiles, relate in particular to its catalyst carrier.
[background technique]
In automobile tail gas purification system, catalyzer is the critical component of catalyst, and its carrier material is pottery and metal two classes.Compare shortcoming such as at present general honeycomb ceramic carrier exists temperature lower (1400 ℃ softening), element wall is thicker, preheating is slow, exhaust resistance is bigger with metallic carrier.Therefore, each state is all in the exploitation of carrying out metallic carrier.The metallic carrier wall thickness only is 1/4 of a ceramic monolith, thereby can reduce exhaust resistance.And make the catalyst carrier miniaturization become possibility; The thermal capacity of metallic carrier is little, and its pre-thermal characteristics is good, helps the enforcement that the electric preheating catalyzer is realized the zero-emission measure of HC, also has advantages such as thermal adaptability is good in addition.
And the various structures that the metallic carrier of catalyzer is combined into based on the wavy metal net in the present Exhaust Gas Catalytic Converter for Automobiles, its heat shock resistance and mechanical shock performance are lower, oxidation resistance deficiency during high temperature has particularly influenced Exhaust Gas Catalytic Converter for Automobiles working life.In addition, the metallic carrier that this ripple is netted, its specific surface area is limited, and adsoption catalyst active component scarce capacity has limited the further raising of Exhaust Gas Catalytic Converter for Automobiles purification efficiency.
[summary of the invention]
The purpose of this invention is to provide a kind of heat shock resistance and mechanical shock, purification efficiency height, the Exhaust Gas Catalytic Converter for Automobiles of long service life.
The objective of the invention is to be achieved through the following technical solutions:
A kind of Exhaust Gas Catalytic Converter for Automobiles comprises housing, vibration damping layer, metallic carrier and catalyst coat, and wherein said metallic carrier is the foaming metal material, and the foaming aperture of foaming metal is 50～1200 microns, and porosity ratio is 80～98%.The aperture of wherein foaming is an average pore size, that is: with certain-length divided by the foaming hole count that radially links to each other continuous in this length; Porosity ratio is a material mesopore volume and the percentaeg of the ratio of the volume of material under nature; Described foaming metal material, its component can be expressed as AB, and the A component is a nickel, and its content accounts for 60～90wt% of foaming metal material; The B component comprises one or more among chromium Cr, aluminium Al, iron Fe, cobalt Co, molybdenum Mo, zinc Zn, zirconium Zr, vanadium V, titanium Ti, cerium Ce, lanthanum La, the neodymium Nu, and its content accounts for 10～40wt% of foaming metal material.
The foaming aperture of described further foaming metal material is 400～800 microns, and porosity ratio is 95～98%.
Described catalyst coat component comprises metallic element, rare earth metal and small amount of precious metals, and wherein metallic element comprises one or more among calcium Ca, barium Ba, magnesium Mg, zirconium Zr, zinc Zn, the aluminium Al; Rare earth metal comprises one or more among cerium Ce, lanthanum La, praseodymium Pr, the neodymium Nu; Precious metal comprises one or more among palladium Pb, platinum Pt, rhodium Rh, the ruthenium Ru.
Also can add in gama-alumina, zirconium oxide, the cerium oxide one or more in the described catalyst coat component.
Described foaming metal material prepares by electro-plating method.
The foam hole wall surface of described foaming metal material is formed with compact oxidation layer.
The advantage of Exhaust Gas Catalytic Converter for Automobiles of the present invention is: heat shock resistance and mechanical shock, and specific surface area is big, the purification efficiency height, carrier and catalyst coat combination force are strong, long service life.
The present invention is further illustrated in conjunction with example with reference to the accompanying drawings.
[description of drawings]
Fig. 1 is an Exhaust Gas Catalytic Converter for Automobiles cross-sectional view of the present invention.
Fig. 2 is an Exhaust Gas Catalytic Converter for Automobiles carrier material foam hole amplification assumption diagram of the present invention.
Fig. 3 is carrier foaming metal aperture and conversion ratio performance diagram among the Exhaust Gas Catalytic Converter for Automobiles embodiment of the present invention.
[embodiment]
Please refer to Fig. 1, Exhaust Gas Catalytic Converter for Automobiles provided by the invention, comprise housing 1, vibration damping layer 2, metallic carrier 3 and be coated on supported catalyst coating 4, the material of wherein said metallic carrier 3 is the foaming metal material, and the foaming aperture of foaming metal is 50～1200 microns (for average pore size), and porosity ratio is 80～98%.
Fig. 2 is the foam hole amplification assumption diagram (with the JSM-5610 test of JEOL company) of Exhaust Gas Catalytic Converter for Automobiles foaming metal carrier material of the present invention, can know among the figure and see that foaming metal has tridimensional network, skeleton is connected with each other, all holes communicate, and have very high porosity ratio and higher mechanical strength.In the present invention, use it for the Exhaust Gas Catalytic Converter for Automobiles carrier, preferably its aperture is 50～1200 microns, and porosity ratio is 80～98%.
Among the present invention, the pore size of foaming metal carrier is very big to the performance impact of adsoption catalyst.The aperture too hour, active substance concentrates on carrier surface, carrier inside is filled out to enter, and gas fluidity reduces.When the aperture was too big, specific surface area reduced, and active material utilization is low.The uniformity in aperture is good more, in the hole active substance distribute good more, its utilization ratio equilibrium, and playing one's part to the full, the efficient of tail gas clean-up can be good more.Through test, when foaming metal was elected 50～1200 microns as the catalytic-converter substrate aperture, effect was better, was optimum when the aperture is 400～800 microns.
Among the present invention, when foaming metal carrier porosity ratio 80～98%, promptly can be used as catalytic-converter substrate.Porosity ratio is big more in general, and carrier property is good more.Preferable porosity 95～98% in the practical application.
Prepare in the Exhaust Gas Catalytic Converter for Automobiles of the present invention, adopting electro-plating method to prepare the aperture is 50～1200 microns, the foaming metal of porosity ratio 80～98%, again through as the pretreatment of high temperature oxidation, electrochemical anodic oxidation, organic acid heat erosion with the thin oxide layer of formation surface compact.So not only strengthen the combination force with catalyst coat component and catalyst coat oxide such as aluminium oxide, zirconium oxide, cerium oxide, also improved the oxidation-resistance property of carrier material, purification efficiency and the working life that can improve catalyzer.
In the preparation process of Exhaust Gas Catalytic Converter for Automobiles of the present invention, the technology that the foaming metal carrier combines with the catalyst activity component comprises the manufacturing process of organic acid heat burn into immersion coating and sintering.Such combination makes and forms the MULTILAYER COMPOSITE oxidation film at carrier surface, strengthened the soundness that the foaming metal carrier combines with the catalyst activity component.And then make catalyzer have better heat-resisting impact and mechanical shock performance, and the purification efficiency raising, obtain working life prolonging.
Adopt stainless steel tubular housing 1, damping pad 2, with above-mentioned foaming metal as carrier, catalyzer with method for preparing is made into Exhaust Gas Catalytic Converter for Automobiles as inner core, has heat shock resistance and mechanical shock, and specific surface area is big, the purification efficiency height, the advantage of long service life.
[embodiment 1]
(1), the preparation and the pretreatment of foaming nickel metal: adopt known electroplating technology to prepare 1.5～3.0 millimeters of thickness, porosity ratio is 95～98%, the foaming nichrome that the aperture is 400 microns, its even aperture distribution, no sealing of hole, no fenestra has certain mechanical property and softness.Wherein nichrome electroplating technology and prescription are as following table 1:
Table 1 is electroplated foaming nickel alloy technology and prescription
| Form and process conditions | (g/L) |
| CrCl3·6H2O | 50～80 |
| NiCl2·6H2O | 20～75 |
| Formic acid (mL/L) | 10～95 |
| H3BO3 | 20～50 |
| NaBr | 40～90 |
| The pH value | 1～4 |
| Temperature (℃) | 20～60 |
| Jk(A/dm2) | 2～10 |
Anode adopts the inert stone electrode ink, and negative electrode adopts the conductive foaming plastics.Simultaneously, for the quality of improving coating has also been added a small amount of additive, as dodecyl sodium sulfate and coumarin, coated metal nickel content is 60～90%, chromium content 10～40%.
The foaming nichrome of galvanoplastic preparation after 1～5 hour, just can directly be used as the Exhaust Gas Catalytic Converter for Automobiles carrier through the organic acid heat erosion.
(2), the preparation of Exhaust Gas Catalytic Converter for Automobiles: catalyst coat contains the mixed component (wherein aluminium oxide and zirconic ratio are 0: 3～3: 0) of nanometer gama-alumina and nano zircite.Is a certain proportion of aluminium oxide and zirconia blend powder impregnation 30～80 ℃ to temperature, contains in the saturated solution of cerium salt to form emulsion, and dip time was controlled at 2～5 hours.Under this temperature, this emulsion is immersed on the metal alloy carrier of organic acid heat erosion then, dip time is 2～4 hours, and blows off or centrifugally get rid of unnecessary emulsion by pressurized air stream.The metal alloy carrier that dipping is good is heated to 400～600 ℃, and is incubated 1～8 hour, is cooled to room temperature then.
The metal alloy of load being crossed another carrier sinters, and after the cooling, with the further heat treatment of organic acid, and then it is impregnated in the solution that contains soluble cerium salt, rhodium salt and a small amount of magnesium salts.Keeping temperature is 30～80 ℃, 2～4 hours time.The catalyzer that finally is used for Exhaust Gas Catalytic Converter for Automobiles then through processing procedure sintering same as described above.
Adopt stainless steel tubular housing 1, damping pad 2, with the catalyzer of method for preparing reel or lamination after be made into Exhaust Gas Catalytic Converter for Automobiles as inner core.
[embodiment 2]
(1), the preparation and the pretreatment of foaming nickel metal: with embodiment 1.
(2), the preparation of Exhaust Gas Catalytic Converter for Automobiles: will handle 1～5 hour foaming nichrome through organic acid, direct impregnation is in the mixed solution that contains certain proportion aluminum soluble salt, zirconates, cerium salt, rhodium salt and an amount of other component, remove unnecessary solvent, after the drying, be heated to 400～600 ℃, kept 2～6 hours.After being cooled to room temperature, carry out organic acid burn into dipping, oven dry and sintering more repeatedly, form the MULTILAYER COMPOSITE oxidation film at carrier surface, till reaching technical requirements.
Adopt stainless steel tubular housing 1, damping pad 2 is made into Exhaust Gas Catalytic Converter for Automobiles with the catalyzer of method for preparing as inner core.
[embodiment 3]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 50 microns, preparation process is with embodiment 1.
[embodiment 4]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 200 microns, preparation process is with embodiment 1.
[embodiment 5]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 600 microns, preparation process is with embodiment 1
[embodiment 6]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 800 microns, preparation process is with embodiment 1.
[embodiment 7]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 1000 microns, preparation process is with embodiment 1.
[embodiment 8]
Make Exhaust Gas Catalytic Converter for Automobiles, its carrier adopts 1.5～3.0 millimeters of thickness, through-hole rate 95～98%, and the foaming nichrome that the aperture is 1200 microns, preparation process is with embodiment 1.
With the Exhaust Gas Catalytic Converter for Automobiles that the foregoing description is made, through 30000 kilometers road complete vehicle test, the conversion ratio of its CO, HC, NOx (%) test result sees the following form:
| Example | Embodiment 1 | | | | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 |
| Aperture (micron) | 400 | 400 | 50 | 200 | 600 | 800 | 1000 | 1200 |
| CO conversion ratio % | 91 | 94 | 80 | 83 | 95 | 93 | 87 | 75 |
| HC conversion ratio % | 94 | 93 | 75 | 76 | 93 | 90 | 83 | 70 |
| NOx conversion ratio % | 72 | 70 | 50 | 55 | 74 | 73 | 71 | 60 |
Claims (7)
1, a kind of Exhaust Gas Catalytic Converter for Automobiles comprises housing, vibration damping layer, metallic carrier and catalyst coat, it is characterized in that: described metallic carrier is the foaming metal material, and the foaming aperture of foaming metal is 50～1200 microns, and porosity ratio is 80～98%; Described foaming metal material, its component is expressed as AB, then:
The A component is a nickel, and its content accounts for 60～90wt% of foaming metal material;
The B component comprises one or more among chromium Cr, aluminium Al, iron Fe, cobalt Co, molybdenum Mo, zinc Zn, zirconium Zr, vanadium V, titanium Ti, cerium Ce, lanthanum La, the neodymium Nu, and its content accounts for 10～40wt% of foaming metal material.
2, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 1 is characterized in that: the foaming aperture of described foaming metal material is 400～800 microns, and porosity ratio is 95～98%.
3, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 1, it is characterized in that: described catalyst coat, its component comprises metallic element, rare earth metal and small amount of precious metals, and wherein metallic element comprises one or more among calcium Ca, barium Ba, magnesium Mg, zirconium Zr, zinc Zn, the aluminium Al; Rare earth metal comprises one or more among cerium Ce, lanthanum La, praseodymium Pr, the neodymium Nu; Precious metal comprises one or more among palladium Pb, platinum Pt, rhodium Rh, the ruthenium Ru.
4, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 3 is characterized in that: described catalyst coat also can add in gama-alumina, zirconium oxide, the cerium oxide one or more in its component.
5, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 1 is characterized in that: described foaming metal material prepares by electro-plating method.
6, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 1 is characterized in that: the foam hole wall surface of described foaming metal material is formed with compact oxidation layer.
7, Exhaust Gas Catalytic Converter for Automobiles as claimed in claim 6 is characterized in that: the oxide layer of described foaming metal material foam hole wall surface is by high temperature oxidation or electrochemical anodic oxidation or organic acid heat erosion formation.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031143997A CN100338341C (en) | 2003-04-30 | 2003-04-30 | Vehicle tail-gas catalytic converter |
| US10/816,753 US20040211172A1 (en) | 2003-04-24 | 2004-04-02 | Muffler and catalytic converter devices |
| EP04728502A EP1616083B1 (en) | 2003-04-24 | 2004-04-21 | Muffler and catalytic converter devices |
| PCT/CN2004/000380 WO2004094793A1 (en) | 2003-04-24 | 2004-04-21 | Muffler and catalytic converter devices |
| JP2006500460A JP2006526726A (en) | 2003-04-24 | 2004-04-21 | Muffler and catalytic converter device |
| KR1020057020136A KR100659398B1 (en) | 2003-04-24 | 2004-04-21 | Muffler and catalytic converter devices |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031143997A CN100338341C (en) | 2003-04-30 | 2003-04-30 | Vehicle tail-gas catalytic converter |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1542265A CN1542265A (en) | 2004-11-03 |
| CN100338341C true CN100338341C (en) | 2007-09-19 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031143997A Expired - Lifetime CN100338341C (en) | 2003-04-24 | 2003-04-30 | Vehicle tail-gas catalytic converter |
Country Status (1)
| Country | Link |
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| CN (1) | CN100338341C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2009072764A (en) * | 2007-09-21 | 2009-04-09 | Waertsilae Schweiz Ag | Exhaust gas particle filter and method for manufacturing exhaust gas particle filter |
| CN102430336B (en) * | 2011-09-14 | 2015-08-12 | 中国第一汽车股份有限公司 | Eliminate the preprocessor of nitrogen oxide |
| JPWO2015159698A1 (en) * | 2014-04-18 | 2017-04-13 | 株式会社アツミテック | Exhaust gas purification system, catalyst, and exhaust gas purification method |
| CN104001556B (en) * | 2014-06-10 | 2016-03-02 | 中国科学院山西煤炭化学研究所 | A kind of high-termal conductivity egg-shell catalyst carrier and preparation method and application |
| CN106677865A (en) * | 2015-11-11 | 2017-05-17 | 赖宜铭 | Metal carrier and catalytic converter device for diesel engine |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5710319A (en) * | 1980-06-23 | 1982-01-19 | Toyota Motor Corp | Exhaust gas filter for internal combustion engine |
| CN1202570A (en) * | 1997-06-13 | 1998-12-23 | 山东工程学院 | Tail gas purifying silencer for internal combustion engine |
-
2003
- 2003-04-30 CN CNB031143997A patent/CN100338341C/en not_active Expired - Lifetime
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5710319A (en) * | 1980-06-23 | 1982-01-19 | Toyota Motor Corp | Exhaust gas filter for internal combustion engine |
| CN1202570A (en) * | 1997-06-13 | 1998-12-23 | 山东工程学院 | Tail gas purifying silencer for internal combustion engine |
Non-Patent Citations (7)
| Title |
|---|
| 发泡镍生产工艺探讨 刘辰忠，电镀与涂饰，第17卷第2期 1998 * |
| 多孔金属材料制备方法 刘培生，黄林国，功能材料，第33卷第1期 2002 * |
| 材料大辞典 师昌绪，727，化学工业出版社 1994 * |
| 汽油车用催化转化器综述 马亚琴，小型内燃机，第27卷第5期 1998 * |
| 汽车排放污染物控制实用技术 蔡凤田，139.142，人民交通出版社 1999 * |
| 泡沫镍的制备工艺及性能参数 汤宏伟，陈宗璋，钟发平，电池工业，第7卷第6期 2002 * |
| 高孔隙度金属—泡沫镍的研制 戎旭滨，陈立佳，崔思霖，李卫利，沈阳工业大学学报，第13卷第4期 1991 * |
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| CN1542265A (en) | 2004-11-03 |
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