CN101560900B - Vehicle exhaust catalytic cleaner and cold start pollution control application - Google Patents
Vehicle exhaust catalytic cleaner and cold start pollution control application Download PDFInfo
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- CN101560900B CN101560900B CN200810104184A CN200810104184A CN101560900B CN 101560900 B CN101560900 B CN 101560900B CN 200810104184 A CN200810104184 A CN 200810104184A CN 200810104184 A CN200810104184 A CN 200810104184A CN 101560900 B CN101560900 B CN 101560900B
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- bearing alloy
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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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- 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
The invention relates to a vehicle exhaust catalytic cleaner which comprises a three-way catalyst, a gasket and a vacuum interlayer shell. At least one of hydrogen storing alloys and gettering materials is contained in a vacuum interlayer, and the interlayer internally comprises one or more following distribution modes: powdery hydrogen storing alloys are is uniformly plated in the interlayer, powdery gettering material is uniformly plated in the interlayer, nubby hydrogen storing alloys are uniformly distributed in the interlayer, or nubby gettering materials are uniformly distributed in the interlayer. The interlayer of the catalytic cleaner is in a high vacuum state at room temperature or low temperature. The vehicle exhaust catalytic cleaner has the characteristics of high response speed, simple device structure and strong stability. The catalytic cleaner can be used for controlling the discharge of cold start contaminants of the vehicle exhaust and/or controlling the working temperature of the three-way catalyst of the vehicle exhaust, and can be used for prolonging the service life of the catalyst and the catalytic cleaner.
Description
Technical field
The present invention relates to automobile exhaust pollution control technique field, more particularly, relate to method and technology that control is polluted in a kind of vehicle exhaust cold start-up, and relate to the raising catalyzer and the technology in catalytic cleaner life-span.
Background technique
Vehicle exhaust has become human society one big mobile pollution source, and the harm people's is healthy.Vehicle tail gas triple effect catalytic cleaner and EFI closed loop control are effectively to solve one of measure of automobile exhaust pollution.Usually the vehicle tail gas triple effect catalytic cleaner partly is made up of three-way catalyst, liner, shell etc., and what wherein play the catalytic purification effect is three-way catalyst.Because the vehicle tail gas triple effect catalyzer is only in uniform temperature (250～400 ℃) down behind the ignition, the effect of competence exertion catalytic purification in the vehicle exhaust cold start-up stage, can cause a large amount of tail gas to produce and discharging (account for vehicle exhaust total release 60～80%).Control is polluted in the vehicle exhaust cold start-up has become the key problem in technology that satisfies stricter automobile exhaust emission standard.Also there be the overtemperature deterioration problem of three-way catalyst in the automobile driving process in common in addition catalytic cleaner, shortens the working life of catalyzer and catalytic cleaner.
US5850734-A, EP796137-A, CN1799689 disclose the close-coupled precatalyst, and close coupled catalyst is nearer from motor, and ignition shortens the cold start-up time fast, thereby reduces cold start emission; But close coupled catalyst need tolerate very high operating temperature, and at high temperature easy inactivation.US2002187893, US6953769, US2002139112 etc. disclose the HC grabber, and the hydrocarbon with discharging when cold start-up adsorbs, after reaching initiation temperature, with HC release the carrying out catalytic purification of absorption.But because the introducing of HC grabber makes catalytic purification system become complicated.US5070694, US5512789 etc. have reported the three-way catalyst electric-heating technology, but there are shortcomings such as complex design, manufacture cost height, operational reliability difference in electric-heating technology, thereby technical application has received considerable restraint.
The tail gas catalyzing unit of US5477676 invention comprises vacuum sandwich and phase-changing energy storage material layer; And at the outside hydrogen gas supplying apparatus of installing of catalytic cleaner; According to the catalytic cleaner operating temperature,, control degree of vacuum in the interlayer through initiatively importing or absorbing hydrogen in the interlayer; Thereby realize that low temperature is heat insulation, the high temperature heat transfer effect.But because ACTIVE CONTROL, make this system quite complicated, exist controlling component more, shortcoming such as damage, malfunctioning easily.In the US6203764 report catalytic cleaner, hydrogen storage material is inserted in the vacuum sandwich, and contacts with phase-change material, carries out passive heating through phase-change material temperature.Although the use of phase-change material can effectively absorb the storage tail gas heat quantity, increased the cost and the complexity of purifier system.
Summary of the invention
The purpose of this invention is to provide a kind of install simple, processing cost is low and have the car tail-gas catalytic purifier that speed of response is fast, stability is strong.Another object of the present invention provides car tail-gas catalytic purifier of the present invention and uses as cold start-up pollutant emission control; And/or as Control of Automobile tail gas three-way catalyst operating temperature, and improve the application in catalyzer and catalytic cleaner working life.The present invention can effectively solve auto-exhaust catalyst and be difficult to quick ignition in the cold start-up stage, auto-exhaust catalyst easy inactivation and problem such as scrap under excessive temperature.
In order to realize the foregoing invention purpose, the present invention takes following technological scheme:
The technological scheme that the present invention adopts is the vacuum sandwich structure that the car tail-gas catalytic purifier shell is made into similar Dewar ampuliform; At least a in hydrogen bearing alloy and the getter material contained in vacuum sandwich inside, and is in the following manner one or more in the inner mode that distributes of interlayer: evenly be coated with the powdery hydrogen bearing alloy, evenly be coated with powdery getter material, evenly distribute block hydrogen bearing alloy, the even block getter material that distributes; And contain in described vacuum sandwich inside under two kinds of situation of hydrogen bearing alloy and getter material, described hydrogen bearing alloy is the hydrogen bearing alloy of hydrogenation; Contain in described vacuum sandwich inside under a kind of situation of hydrogen bearing alloy or getter material, described hydrogen bearing alloy is the hydrogen bearing alloy of hydrogenation, or described getter material is the getter material of hydrogenation.Hydrogen bearing alloy carries out passive suction hydrogen, puts the hydrogen behavior according to the temperature of tail gas and catalyzer, changes the degree of vacuum in the vacuum sandwich simultaneously, changes the heat dissipation rate of catalytic cleaner, thereby simplifies the structure and the controlling component of car tail-gas catalytic purifier.This catalytic cleaner can keep under room temperature and the low temperature condition of high vacuum degree in (＜400 ℃) interlayer, guarantees that the catalytic cleaner vacuum sandwich stops phenomenons such as transmission of heat, thermoconvection fully in the cold start-up stage, impels the catalyzer ignition that is rapidly heated; After guaranteeing that on the other hand automobile stops, the catalytic purification actuator temperature is in keeping warm mode when dropping near the initiation temperature, starts ignition next time fast to help automobile catalyst.
Because hydrogen itself has the very strong capacity of heat transmission, only keeping under the high vacuum state in the purifier interlayer (greater than 10
-5Torr), just can have good heat preservation effect.Deterioration causes layer vacuum to descend to general hydrogen bearing alloy owing to material property or after repeatedly the hydrogen circulation is put in suction.Getter material has good at a lower temperature multiple gases absorptivity, like O
2, N
2, CO, CO
2, H
2, H
2O etc.The present invention promptly is one or both in employing high-performance hydrogen bearing alloy, the getter material, to reach and to keep the condition of high vacuum degree and the working life of improving purifier of purifier interlayer under the low temperature.This catalytic cleaner does not need other accessories, and device is simple, and processing cost is low, and has the advantages that speed of response is fast, stability is strong.
Hydrogen is the good conductor of heat; When reaching operating temperature behind the car tail-gas catalytic purifier ignition; Hydrogen bearing alloy discharges small quantity of hydrogen can make the increase of former vacuum conductivity nearly a hundred times, makes former vacuum insulation system become a heat conductor, and heat can distribute through modes such as conduction, convection current.When automobile stopped back catalytic cleaner greenhouse cooling, hydrogen was absorbed, when dropping to the catalyzer initiation temperature; The hydrogen fundamental absorption finishes; Simultaneously further inhale hydrogen by getter material, vacuum sandwich recovers high vacuum state again, stops transmission of heat, thermoconvection in the interlayer; Reduce thermal loss, play insulation effect.Also can adopt the getter material of hydrogen bearing alloy or the hydrogenation of high-performance hydrogenation to reach the cryogenic vacuum adiabatic heat-insulation in addition in the vacuum sandwich separately and high temperature is released hydrogen heat conduction purpose.
Content of the present invention is a kind of vehicle exhaust cold start-up groundwater pollution control and technology specifically, and relates to the raising catalyzer and the technology in catalytic cleaner life-span.A kind of car tail-gas catalytic purifier is promptly disclosed; This purifier is made up of three-way catalyst, liner, vacuum sandwich shell three parts; And at least a in hydrogen bearing alloy, the getter material contained in vacuum sandwich inside; It is the hydrogen bearing alloy that getter material and hydrogenation are contained in vacuum sandwich inside; Or vacuum sandwich contains the hydrogen bearing alloy of hydrogenation, or vacuum sandwich contains the getter material of hydrogenation, and is in the following manner one or more in the inner mode that distributes of interlayer: evenly be coated with the powdery hydrogen bearing alloy, evenly be coated with powdery getter material, evenly distribute block hydrogen bearing alloy, the even block getter material that distributes.The catalytic cleaner interlayer can keep high vacuum under room temperature or low temperature, between-10 ℃～400 ℃, degree of vacuum is greater than 10
-5Torr between 400 ℃～800 ℃, is filled with hydrogen in the shell interlayer, and degree of vacuum is less than 10
-2Torr.Car tail-gas catalytic purifier according to the invention can be applicable to pollutant of vehicle exhaust control, accelerates catalyzer ignition (250 ℃～400 ℃) specifically, reduces the cold start-up pollutant emission; Car tail-gas catalytic purifier according to the invention also can be applicable to effective control of three-way catalyst operating temperature (600～950 ℃), prevents catalyzer overtemperature inactivation, thereby improves catalyzer and purifier working life.
Hydrogen bearing alloy or getter material can adopt alloy of different nature according to demands of different; Hydrogen bearing alloy or getter material are homogeneous bulky distribution or even powdery coating in interlayer inside, make catalytic cleaner have the advantages that speed of response is fast, stability is strong, and do not need other accessories, and the purifier device is simple, low cost of manufacture.
The car tail-gas catalytic purifier of being mentioned among the present invention is triple effect main catalytic purifier or preposition close even catalytic cleaner.The hydrogen bearing alloy that the present invention mentions has good hydrogen-absorbing ability between 300～700 ℃, between 400 ℃～800 ℃, have and well put the hydrogen characteristic; And the alloy serviceability temperature is greater than 200 ℃, no phase-splitting under 500～1000 ℃ of high temperature.The getter material that the present invention mentions has good hydrogen-absorbing ability between-10～400 ℃; Do not have hydrogen-absorbing ability more than 400 ℃; Can put hydrogen more than 400 ℃; Be used to keep catalytic cleaner shell interlayer under room temperature and low temperature, to have the condition of high vacuum degree state, help the quick ignition of vehicle tail gas triple effect catalyzer, reduce cold start emission; Help car tail-gas catalytic purifier and after stopping, having near the insulation effect the initiation temperature, the quick ignition of auto-exhaust catalyst when promoting next cold start-up.
In car tail-gas catalytic purifier of the present invention, it is that alloy, Zr are that alloy, Mg are at least a in the alloy that hydrogen bearing alloy and getter material are respectively rare earth RE alloy, Ti.Rare earth RE is at least a among La, Ce, Pr, Nd, Sm, Gd, Y, Tb, Tm, Yb, Dy, Ho, Er, the Lu.
In car tail-gas catalytic purifier of the present invention, it is that alloy, Zr are at least a in the alloy that hydrogen bearing alloy and getter material are preferably Ti respectively.
The hydrogen bearing alloy representation is A among the present invention
1-xB
xWherein A is at least a among Ti, Zr, rare earth RE, the Mg; B is at least a among Hf, Nb, Cr, Fe, Ca, Ni, Mn, Mo, the Al, and x is a mol ratio: 0.05～0.90, and rare earth RE comprises at least a among La, Ce, Sm, Nd, Gd, Y, Tb, Tm, the Yb; Its alloy serviceability temperature is greater than 200 ℃, no phase-splitting under 500～1000 ℃ of high temperature.Hydrogen bearing alloy is inhaled hydrogen at 300～700 ℃, puts hydrogen at 400 ℃～800 ℃.
The getter material representation is C among the present invention
1-xD
xWherein C is at least a among Ti, Zr, rare earth RE, the Mg; D is at least a among Nb, Cu, Mo, Fe, Co, V, Al, Mn, the Si, and x is a mol ratio: 0.05～0.90, and rare earth RE comprises at least a among La, Pr, Nd, Y, Dy, Ho, Er, the Lu.Getter material is inhaled hydrogen at-10～400 ℃, is not inhaling hydrogen more than 400 ℃ and can put hydrogen.
Rare earth has unique electronic structure, and the introducing of rare earth metal can improve the performance of hydrogen bearing alloy or getter material.
Three-way catalyst is the tai-gas clean-up catalyst that contains precious metal M among the present invention, and M is at least a in platinum, palladium, the rhodium; Contain at least a in aluminium oxide, cerium oxide, the zirconium oxide in the catalyzer; Precious metal can effectively be eliminated carbon monoxide, hydrocarbon and the nitrogen oxide in the tail gas, and aluminium oxide, cerium oxide, zirconium oxide can be as the activity of such catalysts coating.
Car tail-gas catalytic purifier according to the invention, owing to contain getter material, interlayer can keep high vacuum under room temperature or low temperature, as between-10 ℃～400 ℃, degree of vacuum is greater than 10 in the shell interlayer
-5Torr.Catalytic cleaner can effectively reduce the cold start-up pollutant emission, prevents three-way catalyst excess temperature inactivation, improves the working life of catalyzer and catalytic cleaner.
Description of drawings
Fig. 1 is a car tail-gas catalytic purifier structural representation of the present invention.
Wherein, the label among Fig. 1 is: 1: vacuum sandwich; 2: block hydrogen bearing alloy; 3: block getter material; 4: catalyzer; 5: liner
Embodiment
Further specify technological scheme of the present invention through embodiment below.But protection domain is not limited to embodiment, anyly all belongs to protection domain of the present invention with the similar or identical technology of above-mentioned invention thought.Numeral in hydrogen bearing alloy among the embodiment, the representation of getter material is mol ratio.
The comparative example:
Get certain cellular Pt-Pd-Rh/Al is housed
2O
3The general-utility car vent gas catalytic cleaner of noble metal triple effect catalyst, catalyzer initiation temperature are 340 ℃, and automobile starting needs 130 second time to the catalyzer ignition; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, 857 ℃ of catalyzer and purifier true temperatures.
Embodiment 1:
With above-mentioned comparative example Pt-Pd-Rh/Al
2O
3Noble metal triple effect catalyst; But adopt the catalytic cleaner of band vacuum sandwich shell of the present invention, car tail-gas catalytic purifier structure of the present invention is as shown in Figure 1, and the vent gas catalytic cleaner shell adopts the vacuum sandwich structure of Dewar ampuliform; Be that the vent gas catalytic cleaner shell has vacuum sandwich 1; At inner block hydrogen bearing alloy 2, the block getter material 3 of evenly distributing of vacuum sandwich 1, catalyzer 4 is housed in vent gas catalytic cleaner, between catalyzer and the vacuum sandwich shell liner 5 is housed.Also can in vacuum sandwich 1, be coated with powdery hydrogen bearing alloy or powdery getter material (figure does not show).In present embodiment 1, the vacuum sandwich 1 inner block hydrogen bearing alloy 2 that only evenly distributes promptly is Zr0.5-Fe0.3-Al0.2 hydrogen bearing alloy 25 grams of the interior block hydrogenation that evenly distributes of interlayer, maintenance high vacuum in 30 ℃ of following interlayers, and degree of vacuum is 9.5 * 10
-6Torr.Between catalyzer and the vacuum sandwich liner is housed.Cold-starting automobile needs 100 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 7.5 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 810 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 9.6 * 10 under the room temperature
-6Torr.
Embodiment 2:
Test operation is with embodiment 1, but outside Zr0.5-Fe0.3-Al0.2 hydrogen bearing alloy 25 grams of the even block hydrogenation that distributes in the interlayer, other is the block 10 gram Ti0.7-La0.1-Mo0.2 getter materials of distribution evenly, and 25 ℃ of interior degree of vacuum of following interlayers are 5.7 * 10
-6Torr.Cold-starting automobile needs 65 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 3.0 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 797 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 5.8 * 10 under the room temperature
-6Torr.
Embodiment 3:
Test operation is with embodiment 1, but evenly is coated with Ti0.75-Cu0.05-Mo0.2 getter material 28 grams of powdery hydrogenation in the interlayer, and degree of vacuum are 9.0 * 10 in 25 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 98 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 6.5 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 809 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 9.1 * 10 under the room temperature
-6Torr.
Embodiment 4:
Test operation is with embodiment 1, but evenly is coated with Ti0.65-La0.1-Cu0.05-Mo0.2 getter material 28 grams of powdery hydrogenation in the interlayer, and degree of vacuum are 7.5 * 10 in 25 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 87 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 7.0 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 803 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 7.6 * 10 under the room temperature
-6Torr.
Embodiment 5:
Test operation is with embodiment 1, but Zr0.4-Nd0.2-Fe0.2-Al0.2 hydrogen bearing alloy 25 grams of the block hydrogenation that evenly distributes in the interlayer, degree of vacuum is 7.4 * 10 in 25 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 85 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 7.2 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 802 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 7.4 * 10 under the room temperature
-6Torr.
Embodiment 6:
Test operation is with embodiment 1, but outside Mg0.5-Nd0.3-Al0.2 hydrogen bearing alloy 20 grams of the block hydrogenation that evenly distributes in the interlayer, other evenly is coated with powdery 15 gram Zr0.4-Y0.4-Fe0.2 getter materials, and degree of vacuum is 6.3 * 10 in 50 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 70 seconds time; During 600 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 9.5 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 602 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 6.5 * 10 under the room temperature
-6Torr.
Embodiment 7:
Test operation is with embodiment 1, but evenly is coated with in the interlayer outside Ti0.6-Mo0.4 hydrogen bearing alloy 25 grams of powdery hydrogenation, evenly is coated with powdery 10 gram Ti0.1-V0.7-Al0.2 getter materials in addition, and degree of vacuum are 6.0 * 10 in 400 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 75 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 1.5 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 799 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 6.1 * 10 under the room temperature
-6Torr.
Embodiment 8:
Test operation is with embodiment 1, the cellular Pt-Rh/CeO but purifier is packed into
2-Al
2O
3Noble metal triple effect catalyst, and evenly be coated with in the interlayer outside Ti0.7-Nb0.3 hydrogen bearing alloy 30 grams of powdery hydrogenation, the block 15 gram La0.5-Ti0.3-Al0.2 getter materials that evenly distribute in addition, degree of vacuum is 4.1 * 10 in-10 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 50 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 4.0 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 795 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 4.3 * 10 under the room temperature
-6Torr.
Embodiment 9:
Test operation is with embodiment 1, the cellular Pd/CeO but purifier is packed into
2-ZrO
2-Al
2O
3Noble metal triple effect catalyst, and outside Zr0.6-La0.3-Mn0.1 hydrogen bearing alloy 30 grams of the block hydrogenation that evenly distributes in the interlayer, evenly be coated with powdery 12 gram Ti0.5-Mg0.1-Fe0.2-Al0.2 getter materials in addition, degree of vacuum is 2.7 * 10 in 200 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 30 seconds time; During 700 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 9.5 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 698 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 2.4 * 10 under the room temperature
-6Torr.
Embodiment 10:
Test operation is with embodiment 1, the cellular Pd-Rh/CeO but purifier is packed into
2-ZrO
2-Al
2O
3Noble metal triple effect catalyst, and evenly be coated with La0.1-Ti0.1-Ni0.5-Hf0.3 hydrogen bearing alloy 35 gram of powdery hydrogenation in the interlayer, degree of vacuum are 8.3 * 10 in 25 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 90 seconds time; During 400 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 8.5 * 10 in the interlayer
-6Torr, the catalyzer true temperature is 406 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 8.4 * 10 under the room temperature
-6Torr.
Embodiment 11:
Test operation is with embodiment 1, the cellular Pd-Rh/CeO but purifier is packed into
2-ZrO
2-Al
2O
3Noble metal triple effect catalyst, and Ti0.6-Y0.1-Mo0.3 getter material 30 grams of the block hydrogenation that evenly distributes in the interlayer, degree of vacuum is 8.0 * 10 in 100 ℃ of following interlayers
-6Torr, degree of vacuum is 8.1 * 10 in 400 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 80 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 8.5 * 10 in the interlayer
-2Torr, the catalyzer true temperature is 803 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 8.2 * 10 under the room temperature
-6Torr.
Embodiment 12:
Test operation is with embodiment 1, the cellular Pt-Rh/CeO but purifier is packed into
2-Al
2O
3Noble metal triple effect catalyst, and evenly be coated with in the interlayer outside Ti0.1-Y0.5-Cr0.4 hydrogen bearing alloy 25 grams of powdery hydrogenation, the block 13 gram Zr0.3-Nd0.3-Mn0.4 getter materials that evenly distribute in addition, degree of vacuum is 5.3 * 10 in 30 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 55 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 4.3 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 796 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 5.4 * 10 under the room temperature
-6Torr.
Embodiment 13:
Test operation is with embodiment 1, the cellular Pd-Rh/CeO but purifier is packed into
2-ZrO
2-Al
2O
3Noble metal triple effect catalyst; And evenly be coated with in the interlayer outside Ti0.4-Ce0.2-Sm0.2-Ca0.2 hydrogen bearing alloy 30 grams of powdery hydrogenation, evenly be coated with the powder 10 gram Zr0.4-Pr0.1-Dy0.2-Si0.3 getter materials and the block 8 gram Ti0.5-Ho0.2-Lu0.1-Co0.2 getter materials that evenly distribute in addition.Degree of vacuum is 4.5 * 10 in 50 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 50 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 4.8 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 795 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 4.6 * 10 under the room temperature
-6Torr.
Embodiment 14:
Test operation is with embodiment 1, the cellular Pd-Rh/CeO but purifier is packed into
2-Al
2O
3Noble metal triple effect catalyst; Evenly be coated with in the interlayer outside Ti0.5-Tm0.1-Yb0.1-Cr0.3 hydrogen bearing alloy 20 grams of Ti0.5-Gd0.2-Tb0.1-Ca0.2 hydrogen bearing alloy 20 grams of powdery hydrogenation and the block hydrogenation that evenly distributes, other is coated with powdery 15 gram Zr0.4-Er0.1-Nb0.2-Si0.3 getter materials.Degree of vacuum is 4.8 * 10 in 30 ℃ of following interlayers
-6Torr.Cold-starting automobile needs 52 seconds time; During 800 ℃ of catalyzer proper functioning vehicle exhaust temperature, degree of vacuum is 5.0 * 10 in the interlayer
-1Torr, the catalyzer true temperature is 796 ℃.After automobile stopped, the interior degree of vacuum of interlayer was 5.0 * 10 under the room temperature
-6Torr.
Embodiment 15:
Different hydrogen bearing alloys and getter material are inhaled hydrogen, put the hydrogen test, and the result is following:
| Sample | Inhale hydrogen temperature ℃ | Hydrogen discharging temperature ℃ |
| Hydrogen bearing alloy Ti0.5-Tm0.1-Yb0.1-Cr0.3 | 650 | 756 |
| Hydrogen bearing alloy Zr0.6-La0.3-Mn0.1 | 580 | 650 |
| Hydrogen bearing alloy Mg0.5-Nd0.3-Al0.2 | 455 | 490 |
| Hydrogen bearing alloy Zr0.5-Fe0.3-Al0.2 | 385 | 450 |
| Hydrogen bearing alloy Ti0.7-Nb0.3 | 554 | 683 |
| Getter material Ti0.6-Y0.1-Mo0.3 | 390 | 605 |
| Getter material Ti0.5-Mg0.1-Fe0.2-Al0.2 | 280 | 738 |
| Getter material Zr0.4-Y0.4-Fe0.2 | 80 | 476 |
Embodiment 16:
Block Ti0.6-Mo0.4 hydrogen bearing alloy is carried out quick phase-splitting degradation testing (being equivalent at least 10000 hydrogen sucting discharging hydrogen circulations).The phase-splitting degradation testing adopts document G.D.Sandrock, P.D.Goodell, E.L.Huston and P.M.Golben fast; On the Disproportionation of Intermetallic Hydrides, Z.Phys.Chem.NF, Vol.164; 1989, at is reported method p.1285, and wherein temperature is 600 ℃; 80 barometric pressure of hydrogen pressure, ageing time 20 hours.Find that alloy still is former bulk, no phase-splitting, hydrogen storage property funeral 18%.
Embodiment 17:
Block Ti0.5-Tm0.1-Yb0.1-Cr0.3 hydrogen bearing alloy is carried out quick phase-splitting degradation testing (method is with embodiment 16), but temperature is 900 ℃, 80 barometric pressure of hydrogen pressure, ageing time 12 hours.Find that alloy still is former bulk, no phase-splitting, hydrogen storage property forfeiture 10%.
Claims (6)
1. car tail-gas catalytic purifier; It is characterized in that forming by three-way catalyst, liner, vacuum sandwich shell three parts; The hydrogen bearing alloy of getter material and hydrogenation is contained in vacuum sandwich inside, and is in the following manner one or more in the inner mode that distributes of interlayer: evenly be coated with the powdery hydrogen bearing alloy, evenly be coated with powdery getter material, evenly distribute block hydrogen bearing alloy, the even block getter material that distributes; Said hydrogen bearing alloy representation is A
1-xB
x, wherein A is at least a among Ti, Zr, the Mg, and B is at least a among Hf, Nb, Cr, Fe, Ca, the Ni, and x is a mol ratio: 0.05～0.90, its alloy serviceability temperature is greater than 200 ℃, no phase-splitting under 500～1000 ℃ of high temperature; Hydrogen bearing alloy is inhaled hydrogen at 300～700 ℃, puts hydrogen at 400 ℃～800 ℃; Said getter material representation is C
1-xD
x, wherein C is at least a among Ti, Zr, the rare earth RE, and D is at least a among Cu, Mo, Co, V, Al, Mn, the Si, and x is a mol ratio: 0.05～0.90, rare earth RE comprises at least a among La, Pr, Nd, Y, Dy, Ho, Er, the Lu; Getter material is inhaled hydrogen at-10～400 ℃, is not inhaling hydrogen more than 400 ℃ and can put hydrogen; Getter material can absorb O
2, N
2, CO, CO
2, H
2, H
2The O multiple gases.
2. according to the said car tail-gas catalytic purifier of claim 1, it is characterized in that catalytic cleaner is triple effect main catalytic purifier or preposition close even catalytic cleaner.
3. according to claim 1 or 2 said car tail-gas catalytic purifiers, it is characterized in that three-way catalyst contains precious metal M, M is at least a in platinum, palladium, the rhodium; And contain at least a in aluminium oxide, cerium oxide, the zirconium oxide.
4. according to claim 1 or 2 said car tail-gas catalytic purifiers, it is characterized in that between-10 ℃～400 ℃ that keep vacuum in the shell interlayer, degree of vacuum is greater than 10
-5Torr between 400 ℃～800 ℃, is filled with hydrogen in the shell interlayer, and degree of vacuum is less than 10
-2Torr.
5. any said car tail-gas catalytic purifier in the use claim 1,2,3,4 is as the application of Control of Automobile tail gas cold start-up pollutant emission.
6. use any said car tail-gas catalytic purifier in the claim 1,2,3,4 as Control of Automobile tail gas three-way catalyst operating temperature, and improve the application in catalyzer and catalytic cleaner working life.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810104184A CN101560900B (en) | 2008-04-16 | 2008-04-16 | Vehicle exhaust catalytic cleaner and cold start pollution control application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200810104184A CN101560900B (en) | 2008-04-16 | 2008-04-16 | Vehicle exhaust catalytic cleaner and cold start pollution control application |
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| Publication Number | Publication Date |
|---|---|
| CN101560900A CN101560900A (en) | 2009-10-21 |
| CN101560900B true CN101560900B (en) | 2012-09-19 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103191608B (en) * | 2013-04-01 | 2015-03-25 | 中国市政工程西北设计研究院有限公司 | Air pipe type garage purifier |
| CN106401706A (en) * | 2016-04-25 | 2017-02-15 | 安庆职业技术学院 | Purification device for automobile tail gas |
| CN110180602A (en) * | 2019-06-27 | 2019-08-30 | 高化学（江苏）化工新材料有限责任公司 | Low-temperature denitration catalyst and preparation method thereof |
| CN110374725B (en) * | 2019-08-09 | 2020-09-22 | 浙江圣纳智能科技有限公司 | Cold start heating device for automobile three-way catalyst |
| CN112627950B (en) * | 2020-12-17 | 2022-09-27 | 宁波科森净化器制造有限公司 | Exhaust gas purifier |
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2008
- 2008-04-16 CN CN200810104184A patent/CN101560900B/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
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| JP特开平11-141329A 1999.05.25 |
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