CN104148068B - Fast light-off ternary catalyst for automobile tail gas - Google Patents
Fast light-off ternary catalyst for automobile tail gas Download PDFInfo
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- CN104148068B CN104148068B CN201410385550.XA CN201410385550A CN104148068B CN 104148068 B CN104148068 B CN 104148068B CN 201410385550 A CN201410385550 A CN 201410385550A CN 104148068 B CN104148068 B CN 104148068B
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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
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- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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Abstract
The present invention relates to a kind of Fast light-off ternary catalyst for automobile tail gas, it is characterized in that: include honeycomb support, honeycomb support adheres to Pd coating, Pd coating is adhered to Rh coating；Pd in described Pd coating is supported on the first zirconia composite oxide and doping La2O3γ Al2O3On；Rh in described Rh coating is supported on the second zirconia composite oxide and doping La2O3γ Al2O3On.Three-way catalyst of the present invention is adapted for mount on the close coupling position of exhaust manifold outlet, has the highest HC, CO and NOx low-temperature catalytic activity, is particularly advantageous in reducing the HC pollutant emission of cold-start phase.
Description
Technical field
The present invention relates to a kind of ternary catalyst for automobile tail gas, especially a kind of Fast light-off vehicle exhaust ternary
Catalyst, belongs to purifying vehicle exhaust technical field.
Background technology
The major pollutants of vehicle exhaust are that carbon monoxide (CO), Hydrocarbon (HC) and nitrogen oxidation are closed
Thing (NOx).The catalyst being arranged on gas extraction system is utilized carbon monoxide, oxidizing hydrocarbon to be become
Carbon dioxide (CO2) and water (H2O), and simultaneously make oxynitride be reduced to nitrogen (N2), it is achieved tail
The purification of gas, this catalyst is commonly referred to three-way catalyst.Three-way catalyst is made up of two parts: honeycomb
The pottery of shape or metallic carrier, and it is attached to supported catalyst coating.Catalyst coat is generally by having
There is the inorganic oxide material of large specific surface area (such as γ-Al2O3And CeO2Deng) and be supported on oxide table
Noble metal active component (being often one or more in Pt (platinum), Pd (palladium), Rh (the rhodium)) group in face
Become.In NEDC test loop, during cold-starting automobile, the HC pollutant discharge amount of first 40 seconds operating modes is usual
Account for more than the 70% of whole test loop HC discharge capacity.Therefore, the conversion effect of cold-start phase HC is improved
Rate always is that three-way catalyst needs the important technological problems solved.HC during in order to improve cold-starting automobile
Transformation efficiency, on the one hand, three-way catalyst can be arranged close to enmgine exhaust outlet position
(commonly referred to Close-coupled catalyst), make reaction bed temperature can be rapidly achieved HC initiation temperature (T50,
The conversion ratio of HC reaches temperature when 50%)；On the other hand, optimize catalyst coat, improve the low of catalyst
Temperature activity, to reduce the T50 of HC.During additionally, high engine load is run, the bed of Close-coupled catalyst
Temperature can reach 900 DEG C～the high temperature of 1100 DEG C, and this just requires that catalyst remains to keep after standing high temperature ageing
Higher catalysis activity.
Current three-way catalyst the most all uses double coating structure, the lower coating being i.e. attached on honeycomb substrate
Loading Pd, and the upper coating being attached in lower coating supports Rh.Pd coating is typically by γ-Al2O3With containing CeO2
Cerium zirconium sosoloid composition, Rh coating is general also by γ-Al2O3With containing CeO2Cerium zirconium sosoloid composition.
Summary of the invention
It is an object of the invention to overcome the deficiencies in the prior art, it is provided that a kind of Fast light-off vehicle exhaust
Three-way catalyst, has higher HC low temperature active (the lowest T50) and high-temperature aging resisting performance.
The technical scheme provided according to the present invention, described Fast light-off ternary catalyst for automobile tail gas, including honeybee
Nest shape carrier, is characterized in that: adhere to Pd coating on described honeycomb support, adheres to Rh in Pd coating
Coating；Pd in described Pd coating is supported on the first zirconia composite oxide and doping La2O3γ
-Al2O3On, the component of the first zirconia composite oxide is: the ZrO of 60wt%～90wt%2With
The Pr of 10wt%～40wt%6O11, adulterate La2O3γ-Al2O3Component be: the La of 1wt%～8wt%2O3
Al with 92wt%～99wt%2O3；Rh in described Rh coating is supported on the second zirconium oxide combined oxidation
Thing and doping La2O3γ-Al2O3On, the component of the second zirconia composite oxide is:
The ZrO of 75wt%～95wt%2La with 5wt%～25wt%2O3、Y2O3、Nd2O3In one or more,
Doping La2O3γ-Al2O3Component be: the La of 1wt%～8wt%2O3Al with 92wt%～99wt%2O3。
Further, the first zirconia composite oxide and doping La in described Pd coating2O3γ-Al2O3
Mass ratio be 1:3～3:1.
Further, the second zirconia composite oxide in described Rh coating and doping La2O3γ
-Al2O3Mass ratio be 1:3～3:1.
Further, on described honeycomb support, the coated weight of Pd coating is 50～200g/L, Rh coating
Coated weight be 30～160g/L.
Further, in described Rh coating, the content of the Rh of load is 1～10g/ft3。
Further, in described Pd coating, the content of the Pd of load is 20～200g/ft3。
The invention have the advantage that the coating of three-way catalyst of the present invention is the double coating structure of Pd/Rh,
Pd is supported on a kind of by Pr6O11With ZrO2The zirconia composite oxide constituted and doping La2O3γ
-Al2O3On, and Rh is supported on a kind of by ZrO2With La2O3、Y2O3、Nd2O3In one or more structures
The zirconia composite oxide become and doping La2O3γ-Al2O3On, the design of this coating makes catalyst load
Pd and Rh nanoparticle has the highest high-temperature aging resisting ability, the most still possesses the highest low temperature HC
Catalysis activity, has lower HC initiation temperature compared to existing technology.
Detailed description of the invention
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: by the first zirconia composite oxide of 100g, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then Palladous nitrate. is molten
Liquid (containing 4.71g precious metals pd) joins in serosity；Finally take this coating slurry appropriate and be coated to honeycomb
On shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein,
The component of the first zirconia composite oxide is the ZrO of 75wt%2Pr with 25wt%6O11, adulterate La2O3
γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: by 100g the second zirconia composite oxide, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then rhodium nitrate is molten
Liquid (containing 0.353g noble metal Rh) joins in serosity；Finally take this coating slurry appropriate and be coated to coating
On the cellular structure ceramic carrier of Pd coating, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain
Rh coating；Wherein, the component of the second zirconia composite oxide is the ZrO of 90wt%2, the La of 5wt%2O3
Y with 5wt%2O3, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3With 96wt%'s
Al2O3。
Embodiment 2: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: by the first zirconia composite oxide of 100g, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then Palladous nitrate. is molten
Liquid (containing 4.71g precious metals pd) joins in serosity；Finally take this coating slurry appropriate and be coated to honeycomb
On shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein,
The component of the first zirconia composite oxide is the ZrO of 90wt%2Pr with 10wt%6O11, adulterate La2O3
γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: by 100g the second zirconia composite oxide, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then rhodium nitrate is molten
Liquid (containing 0.353g noble metal Rh) joins in serosity；Finally take this coating slurry appropriate and be coated to coating
On the cellular structure ceramic carrier of Pd coating, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain
Rh coating；Wherein, the component of the second zirconia composite oxide is the ZrO of 85wt%2, the La of 5wt%2O3、
The Y of 5wt%2O3Nd with 5wt%2O3, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3
Al with 96wt%2O3。
Embodiment 3: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: by the first zirconia composite oxide of 100g, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then Palladous nitrate. is molten
Liquid (containing 4.71g precious metals pd) joins in serosity；Finally take this coating slurry appropriate and be coated to honeycomb
On shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein,
The component of the first zirconia composite oxide is the ZrO of 60wt%2Pr with 40wt%6O11, adulterate La2O3
γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: by 100g the second zirconia composite oxide, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then rhodium nitrate is molten
Liquid (containing 0.353g noble metal Rh) joins in serosity；Finally take this coating slurry appropriate and be coated to coating
On the cellular structure ceramic carrier of Pd coating, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain
Rh coating；Wherein, the component of the second zirconia composite oxide is the ZrO of 95wt%2With 5wt%'s
La2O3, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
Embodiment 4: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: by the first zirconia composite oxide of 60g, 140g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then Palladous nitrate. is molten
Liquid (containing 4.71g precious metals pd) joins in serosity；Finally take this coating slurry appropriate and be coated to honeycomb
On shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein,
The component of the first zirconia composite oxide is the ZrO of 60wt%2Pr with 40wt%6O11, adulterate La2O3
γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: by 60g the second zirconia composite oxide, 140g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then rhodium nitrate is molten
Liquid (containing 0.353g noble metal Rh) joins in serosity；Finally take this coating slurry appropriate and be coated to coating
On the cellular structure ceramic carrier of Pd coating, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain
Rh coating；Wherein, the component of the second zirconia composite oxide is the ZrO of 95wt%2With 5wt%'s
La2O3, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
Comparative example 1: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: adulterate La by 100g cerium zirconium sosoloid, 100g2O3γ-Al2O3
Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then palladium nitrate solution is (expensive containing 4.71g
Metal Pd) join in serosity；Finally take this coating slurry appropriate to be coated on cellular structure ceramic carrier, and
450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein, the component of cerium zirconium sosoloid
CeO for 30wt%2, the ZrO of 60wt%2, the La of 5wt%2O3Pr with 5wt%6O11, adulterate La2O3
γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: adulterate La by 100g cerium zirconium sosoloid, 100g2O3γ-Al2O3
Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then by rhodium nitrate solution (containing 0.353g
Noble metal Rh) join in serosity；Finally take this coating slurry appropriate and be coated to be coated with the honeybee of Pd coating
On nest shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Rh coating；Wherein,
The component of cerium zirconium sosoloid is the CeO of 30wt%2, the ZrO of 60wt%2, the La of 5wt%2O3With 5wt%'s
Pr6O11, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
Comparative example 2: a kind of ternary catalyst for automobile tail gas, including cellular structure ceramic carrier, specification is Ф
118.4mm × 152.4mm, hole density is 600cpsi, and duct wall thickness is 4.3mil, and volume is 1.678L；?
Adhering to Pd coating on honeycomb support, the coated weight of Pd coating is 150g/L, adheres to Rh in Pd coating
Coating, the coated weight of Rh coating is 100g/L；Wherein, in Pd coating, the content of Pd is 100g/ft3, Rh
In coating, the content of Rh is 5g/ft3。
The coating procedure of described Pd coating is: by 100g the second zirconia composite oxide, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then Palladous nitrate. is molten
Liquid (containing 4.71g precious metal palladium Pd) joins in serosity；Finally take this coating slurry appropriate and be coated to honeybee
On nest shape ceramic monolith, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain Pd coating；Wherein,
The component of the second zirconia composite oxide is the ZrO of 90wt%2, the La of 5wt%2O3With 5wt%'s
Y2O3, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
The coating procedure of described Rh coating is: by the first zirconia composite oxide of 100g, 100g doping
La2O3γ-Al2O3Mix with appropriate amount of deionized water, after ball milling, obtain coating slurry, then rhodium nitrate is molten
Liquid (containing 0.353g noble metal Rh) joins in serosity；Finally take this coating slurry appropriate and be coated to coating
On the cellular structure ceramic carrier of Pd coating, and 450 DEG C～600 DEG C of roasting temperatures 1～5 hours, obtain
Rh coating；Wherein, the component of the first zirconia composite oxide is the ZrO of 75wt%2With 25wt%'s
Pr6O11, adulterate La2O3γ-Al2O3The La that component is 4wt%2O3Al with 96wt%2O3。
By the catalyst sample obtained by embodiment 1～embodiment 4, comparative example 1～comparative example 2 all at 1000 DEG C
High temperature Muffle furnace in condition aging 20 hours, aging after catalyst encapsulation after at the engine bed of 2.0L
HC, CO and NO is tested on framexInitiation temperature T50.Test result is as shown in table 1.
Table 1
As shown in table 1, the result of catalyst performance evaluation shows, compared with comparative example 1,2, the present invention is real
Execute the three-way catalyst disclosed in example 1～4 and there is the highest HC, CO and NOxLow-temperature catalytic activity, especially
It is adapted to be mounted within the close coupling position of exhaust manifold outlet, advantageously reduces the HC in cold-starting automobile stage and pollute
Thing discharges.
The test of engine pedestal initiation temperature is also a kind of characterizing method of catalyst activity, and initiation temperature is the lowest,
Represent that low temperature active is the best.So the data that table 1 is given be i.e. aging after low temperature active (including HC), table
Pd and the Rh nanoparticle that face this coating design makes catalyst load has the highest high-temperature aging resisting ability,
The most still possess the highest low temperature HC catalysis activity, have lower HC initiation temperature compared to existing technology.
Claims (3)
1. a Fast light-off ternary catalyst for automobile tail gas, including honeycomb support, is characterized in that: adhere to Pd coating on described honeycomb support, adheres to Rh coating in Pd coating；Pd in described Pd coating is supported on the first zirconia composite oxide and doping La2O3γ-Al2O3On, the component of the first zirconia composite oxide is: the ZrO of 60wt% ~ 90wt%2Pr with 10wt% ~ 40wt%6O11, adulterate La2O3γ-Al2O3Component be: the La of 1wt% ~ 8wt%2O3Al with 92wt% ~ 99wt%2O3；Rh in described Rh coating is supported on the second zirconia composite oxide and doping La2O3γ-Al2O3On, the component of the second zirconia composite oxide is: the ZrO of 75wt% ~ 95wt%2La with 5wt% ~ 25wt%2O3、Y2O3、Nd2O3In one or more, adulterate La2O3γ-Al2O3Component be: the La of 1wt% ~ 8wt%2O3Al with 92wt% ~ 99wt%2O3；
The first zirconia composite oxide and doping La in described Pd coating2O3γ-Al2O3Mass ratio be 1:3 ~ 3:1；The second zirconia composite oxide in described Rh coating and doping La2O3γ-Al2O3Mass ratio be 1:3 ~ 3:1；
On described honeycomb support, the coated weight of Pd coating be the coated weight of 50 ~ 200g/L, Rh coating be 30 ~ 160g/L.
2. Fast light-off ternary catalyst for automobile tail gas as claimed in claim 1, is characterized in that: in described Rh coating, the content of the Rh of load is 1 ~ 10g/ft3。
3. Fast light-off ternary catalyst for automobile tail gas as claimed in claim 1, is characterized in that: in described Pd coating, the content of the Pd of load is 20 ~ 200g/ft3。
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| CN105597748A (en) * | 2015-11-13 | 2016-05-25 | 无锡威孚环保催化剂有限公司 | Segmented type ternary catalyst and preparation method thereof |
| CN106362740A (en) * | 2016-08-31 | 2017-02-01 | 芜湖恒耀汽车零部件有限公司 | Catalyst for automobile exhaust purifier |
| CN106391429A (en) * | 2016-08-31 | 2017-02-15 | 芜湖恒耀汽车零部件有限公司 | Coating processing method of catalyst for automobile tail gas purifier |
| CN106285843A (en) * | 2016-08-31 | 2017-01-04 | 芜湖恒耀汽车零部件有限公司 | Automobile exhaust purifier |
| CN108126698A (en) * | 2018-01-05 | 2018-06-08 | 无锡威孚环保催化剂有限公司 | A kind of selective cleaning three-way catalyst and preparation method thereof |
| CN108940279B (en) * | 2018-07-20 | 2022-07-05 | 无锡威孚环保催化剂有限公司 | Gasoline vehicle tail gas purification three-way catalyst and preparation method thereof |
| CN108855072B (en) * | 2018-08-16 | 2021-10-22 | 无锡威孚环保催化剂有限公司 | High-temperature-aging-resistant three-way catalyst and preparation method thereof |
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| US7870724B2 (en) * | 2004-11-09 | 2011-01-18 | Ford Global Technologies, Llc | Lean NOx trap with PGM zoned axially |
| KR20100129465A (en) * | 2009-06-01 | 2010-12-09 | 희성촉매 주식회사 | Three way catalyst with triple layer coating structure |
| CN103143351B (en) * | 2013-03-15 | 2015-04-29 | 无锡威孚环保催化剂有限公司 | Ternary catalyst |
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