CN108126698A - A kind of selective cleaning three-way catalyst and preparation method thereof - Google Patents

A kind of selective cleaning three-way catalyst and preparation method thereof Download PDF

Info

Publication number
CN108126698A
CN108126698A CN201810010016.9A CN201810010016A CN108126698A CN 108126698 A CN108126698 A CN 108126698A CN 201810010016 A CN201810010016 A CN 201810010016A CN 108126698 A CN108126698 A CN 108126698A
Authority
CN
China
Prior art keywords
coatings
composite oxide
zirconia composite
coating
catalyst
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201810010016.9A
Other languages
Chinese (zh)
Inventor
王卫东
贾莉伟
李晓坤
浦琦伟
陈同同
谢鼎峰
王德冰
岳军
韩婷婷
韩飞
林帅帅
方建荣
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Wuxi Weifu Environmental Protection Catalyst Co Ltd
Original Assignee
Wuxi Weifu Environmental Protection Catalyst Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Wuxi Weifu Environmental Protection Catalyst Co Ltd filed Critical Wuxi Weifu Environmental Protection Catalyst Co Ltd
Priority to CN201810010016.9A priority Critical patent/CN108126698A/en
Publication of CN108126698A publication Critical patent/CN108126698A/en
Pending legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1023—Palladium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1026—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • 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
    • 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 present invention relates to a kind of selective cleaning three-way catalysts and preparation method thereof, three-way catalyst includes honeycomb support, one end of honeycomb support is inlet end, the other end is outlet side, inlet end is provided with the first Pd coatings and the first Rh coatings from bottom to up, outlet side is provided with the 2nd Pd coatings and the 2nd Rh coatings from bottom to up, and the first Pd coatings include the La of load Pd2O3‑Al2O3With the first zirconia composite oxide, the first Rh coatings include the second zirconia composite oxide and La of load Rh2O3‑Al2O3, La of the 2nd Pd coatings including loading Pd2O3‑Al2O3, the first zirconia composite oxide or third zirconia composite oxide, the 2nd Rh coatings are load the second zirconia composite oxide of Rh or the 4th zirconia composite oxide, La2O3‑Al2O3.Preparation method of the present invention is simple to operation, and the three-way catalyst prepared still has very high carbon monoxide conversion capability after weathering.

Description

A kind of selective cleaning three-way catalyst and preparation method thereof
Technical field
The present invention relates to a kind of selective cleaning three-way catalysts and preparation method thereof, belong to catalyst preparation technology neck Domain.
Background technology
The major pollutants of vehicle exhaust are carbon monoxide (CO), hydrocarbon (HC) and oxynitrides (NOx).With The increase year by year of car ownership, motor vehicle exhaust emission has become the main source of air pollution.Mounted on tail-gas from gasoline automobiles Three-way catalyst in after-treatment system can be by carbon monoxide, oxidizing hydrocarbon into carbon dioxide (CO2) and water (H2O), oxynitrides and is made to be reduced to nitrogen (N2) simultaneously, so as to fulfill in tail gas three kinds of major pollutants synchronize it is net Change.The three-way catalyst is usually made of two parts：Cellular ceramics or metallic carrier and the catalysis being attached on carrier Agent coating.Catalyst coat is usually by the inorganic oxide material with large specific surface area (such as γ-Al2O3 and containing CeO2 Cerium zirconium sosoloid etc.) and to be supported on the noble metal active component of oxide surface (be often Pt (platinum), in Pd (palladium), Rh (rhodium) It is one or more of) composition.
With the continuous of emission regulation plus sternly, China will come into effect " six a of state " discharge standard in the year two thousand twenty.With before compared with It is compared for known NEDC test loops, the WLTC test loop transient conditions that " six a of state " is used are more, and F-Zero exists More than 130km/h, and the high-speed working condition duration is longer so that and the purification of CO is extremely difficult.Traditional three-way catalyst Anti- fluctuation of operating conditions ability is weaker, cannot effectively meet " six a of state " more harsh CO emission requests, therefore carry out highly selective The research of the three-way catalyst of CO is purified for solving " six a of state " stage automobile aftertreatment products upgrade problem with particularly significant Meaning.
Invention content
The purpose of the present invention is to solve the anti-fluctuation of operating conditions ability of three-way catalyst in the prior art is weaker, CO conversion ratios The problem of being not high enough to provides a kind of selective cleaning three-way catalyst and preparation method thereof, the three-element catalytic being prepared Agent has preferable CO catalytic activity.
The present invention adopts the following technical scheme that：A kind of selective cleaning three-way catalyst, including honeycomb support (1), institute The one end for stating honeycomb support (1) is inlet end, and the other end of honeycomb support is outlet side, and the inlet end is set from bottom to up The first Pd coatings (2) and the first Rh coatings (3) are equipped with, the outlet side is provided with the 2nd Pd coatings (4) and second from bottom to up Rh coatings (5), the first Pd coatings include the La of load Pd2O3-Al2O3With the first zirconia composite oxide, described first Rh coatings include the second zirconia composite oxide and La of load Rh2O3-Al2O3, the 2nd Pd coatings are including loading Pd's La2O3-Al2O3, the first zirconia composite oxide or third zirconia composite oxide, the 2nd Rh coatings include load The second zirconia composite oxide of Rh or the 4th zirconia composite oxide, the La for loading Rh2O3-Al2O3, the first Pd The load capacity of Pd is 5~350g/ft in coating3, the load capacity of Pd is 5~350g/ft in the 2nd Pd coatings3, described first The load capacity of Rh is 0.1~50g/ft in Rh coatings3, the load capacity of Rh is 0.1~50g/ft in the 2nd Rh coatings3。
Further, La in the first Pd coatings, the first Rh coatings, the 2nd Pd coatings and the 2nd Rh coatings2O3-Al2O3 Mass ratio with zirconia composite oxide is 1:6~6:1.
Further, the component of first zirconia composite oxide is by weight percentage：40~60wt%'s CeO2, 25~55wt% ZrO2With the La of 5~15wt%2O3、Y2O3、Pr6O11、Nd2O3One or more of.
Further, the component of second zirconia composite oxide is by weight percentage：65~95wt%'s ZrO2With the CeO of 5~35wt%2、La2O3、Y2O3、Pr6O11、Nd2O3One or more of.
Further, the component of the third zirconia composite oxide is by weight percentage：60~90wt%'s CeO2, 5~35wt% ZrO2With the La of 5~15wt%2O3、Y2O3、Pr6O11、Nd2O3One or more of.
Further, the component of the 4th zirconia composite oxide is by weight percentage：20~40wt%'s CeO2, 45~75wt% ZrO2With the La of 5~15wt%2O3、Y2O3、Pr6O11、Nd2O3One or more of.
Further, the La2O3-Al2O3Component be by weight percentage：The La of 1~8wt%2O3With 92~ The Al of 99wt%2O3。
Further, the coated weight of the first Pd coatings and the 2nd Pd coatings is 60~200g/L.
Further, the coated weight of the first Rh coatings and the 2nd Rh coatings is 50~180g/L.
The preparation method of selective cleaning three-way catalyst, includes the following steps：
The coating of (1) the first Pd coatings：Honeycomb support is taken, is 5~350g/ by the load capacity of Pd in the first Pd coatings ft3The quality of Pd needed for calculating, the second zirconium oxide composite oxygen as needed for the coated weight of the first Pd coatings for 60~200g/L calculating Compound and La2O3-Al2O3Quality, successively by Pd precious metal solutions, La2O3-Al2O3, the first zirconia composite oxide and go Ionized water mixes, and coating slurry is configured to after ball milling；Slurries are coated on the inlet end of carrier, by the catalyst after coating At a temperature of 80~150 DEG C drying 0.2~for 24 hours；
The coating of (2) the 2nd Pd coatings：It is 5~350g/ft by the load capacity of Pd in the 2nd Pd coatings3Pd needed for calculating Quality, La2O3-Al2O3, the first zirconia composite oxide as needed for the coated weight of the 2nd Pd coatings for 60~200g/L calculating Or the quality of third zirconia composite oxide, by Pd precious metal solutions, La2O3-Al2O3, the first zirconia composite oxide or Third zirconia composite oxide and deionized water mixing, are configured to coating slurry after ball milling；Slurries are coated to carrier On outlet side, the catalyst after coating dried at a temperature of 80~150 DEG C to 0.2~for 24 hours；Then the catalyst of drying is existed 350~650 DEG C of 1~5h of roasting temperature；
The coating of (3) the first Rh coatings：It is 0.1~50g/ft by the load capacity of Rh in the first Rh coatings3Rh needed for calculating Quality, as the first Rh coatings coated weight for 50~180g/L calculate needed for the second zirconia composite oxide and La2O3- Al2O3Quality, by Rh precious metal solutions, the second zirconia composite oxide, La2O3-Al2O3It mixes, and passes through with deionized water Coating slurry is configured to after ball milling；Slurries are coated on the first Pd coatings of catalyst inlet end, by the catalyst after coating At a temperature of 80~150 DEG C drying 0.2~for 24 hours；
The coating of (4) the 2nd Rh coatings：The Rh as needed for the load capacity of Rh in the 2nd Rh coatings for 0.1~50g/ft3 calculating Quality, as the 2nd Rh coatings coated weight for 50~180g/L calculate needed for the second zirconia composite oxide or the 4th oxidation Zirconium mixed oxide, La2O3-Al2O3Quality, by Rh precious metal solutions, the second zirconia composite oxide or the 4th zirconium oxide Composite oxides, La2O3-Al2O3It is mixed with deionized water, and coating slurry is configured to after ball milling；Slurries are coated to catalysis On 2nd Pd coatings of agent outlet side, the catalyst after coating dried at a temperature of 80~150 DEG C to 0.2~for 24 hours, then it will dry Dry catalyst is in 350~650 DEG C of 1~5h of roasting temperature.
Preparation method of the present invention is simple, and step is easily operated, using the different zirconia composite oxide of oxygen storage capacity into Row optimum organization effectively improves the oxygen storage capacity of catalyst, and the three-way catalyst being prepared still has very high after weathering CO conversion capabilities.
Description of the drawings
Fig. 1 is the structural diagram of the present invention.
Reference numeral：Honeycomb support 1, the first Pd coatings 2, the first Rh coatings 3, the 2nd Pd coatings 4, the 2nd Rh coatings 5.
Specific embodiment
Comparative example 1：
A kind of three-way catalyst, including cellular structure ceramic carrier, specification is Ф 118.4mm × 152.4mm, and hole density is 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support by gas into outgoing direction one end be inlet end, separately One end is outlet side, and the length ratio of inlet end and outlet side is 1:1, the first Pd coatings of attachment are (including load Pd's on inlet end La2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the mass ratio of the first zirconia composite oxide It is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；Adhere to the 2nd Pd coatings on outlet side (including load Pd's La2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the mass ratio of the first zirconia composite oxide It is 1：1) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd coatings of inlet end and the 2nd Pd of outlet side are applied Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on layer respectively2O3-Al2O3, wherein the second oxygen Change zirconium mixed oxide and La2O3-Al2O3Mass ratio be 1：1), coated weight is 120g/L, and the content of Rh is 4g/ft3。
The preparation method of three-way catalyst, using following processing step：
The coating procedure of (1) the first Pd coatings：By the palladium nitrate solution containing 58.86g precious metals pds, 1000g La2O3- Al2O3, the first zirconia composite oxides of 1000g and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed The coating slurry is coated on the inlet end of cellular structure ceramic carrier by coated weight for 120g/L；Wherein, the first zirconium oxide is compound The component of oxide is CeO250wt%, ZrO240wt%, La2O35wt%, Pr6O115wt%, La2O3-Al2O3In contain The La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (2) the 2nd Pd coatings：By the palladium nitrate solution containing 5.89g precious metals pds, 1000g La2O3- Al2O3, the first zirconia composite oxides of 1000g and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed The coating slurry is coated to outlet side by coated weight for 120g/L；Catalyst after coating is dried into 5h at a temperature of 120 DEG C, so Afterwards by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, the component of the first zirconia composite oxide is CeO2 50wt%, ZrO240wt%, La2O35wt%, Pr6O115wt%, La2O3-Al2O3In have the La of 5wt%2O3With 95wt%'s Al2O3。
(3) coating procedure of inlet end and outlet side Rh coatings：By the rhodium nitrate solution containing 2.35g noble metals Rh, The second zirconia composite oxides of 1000g, 1000g La2O3-Al2O3It is mixed with appropriate amount of deionized water, coating is obtained after ball milling Then the coating slurry is coated to the air inlet for the cellular structure ceramic carrier for being coated with Pd coatings by slurries by coated weight for 120g/L On end, then coating slurry is coated on outlet side for 120g/L by coated weight；By the catalyst after coating in 120 DEG C of temperature Lower drying 5h, then by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, the group of the second zirconia composite oxide Part is CeO210wt%, ZrO285wt%, La2O35wt%, La2O3-Al2O3Component be 5wt% La2O3With 95wt%'s Al2O3.Comparative example 2：
A kind of three-way catalyst, including cellular structure ceramic carrier, specification is Ф 118.4mm × 152.4mm, and hole density is 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support by gas into outgoing direction one end be inlet end, separately One end is outlet side, and the length ratio of inlet end and outlet side is 1:1, the first Pd coatings of attachment are (including load Pd's on inlet end La2O3-Al2O3With third zirconia composite oxide, wherein La2O3-Al2O3With the mass ratio of third zirconia composite oxide It is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；Adhere to the 2nd Pd coatings on outlet side (including load Pd's La2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the mass ratio of the first zirconia composite oxide It is 1：1) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd coatings of inlet end and the 2nd Pd of outlet side are applied Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on layer respectively2O3-Al2O3, wherein the second oxygen Change zirconium mixed oxide and La2O3-Al2O3Mass ratio be 1：1), coated weight is 120g/L, and the content of Rh is 4g/ft3。
The preparation of 2 catalyst exemplar of comparative example：Each parameter, composition and preparation process are identical with comparative example 1, in addition to inlet end The first Pd coatings in the first zirconia composite oxide become third zirconia composite oxide, form and be CeO270wt%, ZrO220wt%, La2O35wt%, Pr6O115wt%.
Embodiment 1：
A kind of selective cleaning three-way catalyst, including cellular structure ceramic carrier 1, specification for Ф 118.4mm × 152.4mm, hole density 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support 1 presses gas disengaging side It is inlet end to one end, the other end is outlet side, and the length ratio of inlet end and outlet side is 1:1, is attached on inlet end The one Pd coatings (La including loading Pd2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the first oxidation The mass ratio of zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；It is attached on outlet side The 2nd Pd coatings (La including loading Pd2O3-Al2O3With third zirconia composite oxide, wherein La2O3-Al2O3With third oxygen The mass ratio for changing zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd of inlet end The first Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on coating2O3-Al2O3, wherein second Zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1) content of, coated weight 120g/L, Rh are 4g/ft3；Go out The 2nd Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on the 2nd Pd coatings at gas end2O3- Al2O3, wherein the second zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1), coated weight 120g/L, Rh's contains It measures as 4g/ft3。
The preparation method of the selective cleaning three-way catalyst, using following processing step：
(1) the first Pd coating application procedures：By the palladium nitrate solution containing 58.86g precious metals pds, 1000g La2O3- Al2O3, the first zirconia composite oxides of 1000g and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed Coating slurry is coated on the inlet end of cellular structure ceramic carrier by coated weight for 120g/L.Wherein, the first zirconium oxide composite oxygen The component of compound is CeO250wt%, ZrO240wt%, La2O35wt%, Pr6O115wt%, La2O3Stable aluminium oxide Component is the La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (2) the 2nd Pd coatings：By the palladium nitrate solution containing 5.89g precious metals pds, 1000g La2O3- Al2O3, 1000g thirds zirconia composite oxide and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed The coating slurry is coated to the outlet side of cellular structure ceramic carrier for 120g/L by coated weight；By the catalyst after coating 120 5h is dried at a temperature of DEG C, then by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, third oxidation zirconium composite oxide The component of object is CeO270wt%, ZrO220wt%, La2O35wt%, Pr6O115wt%, La2O3-Al2O3Component be The La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (3) the first Rh coatings：Rhodium nitrate solution containing 2.35g noble metals Rh, 1000g second are aoxidized Zirconium mixed oxide, 1000g La2O3-Al2O3It is mixed with appropriate amount of deionized water, coating slurry is obtained after ball milling, then by painting The coating slurry is coated to for 120g/L on the inlet end for the cellular structure ceramic carrier for being coated with the first Pd coatings by the amount of covering.Its In, the component of the second zirconia composite oxide is CeO210wt%, ZrO285wt%, La2O35wt%, La2O3-Al2O3's Component is the La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (4) the 2nd Rh coatings：Rhodium nitrate solution containing 2.35g noble metals Rh, 1000g second are aoxidized Zirconium mixed oxide, 1000g La2O3-Al2O3It is mixed with appropriate amount of deionized water, coating slurry is obtained after ball milling, then by painting The coating slurry is coated to for 120g/L on the outlet side for the cellular structure ceramic carrier for being coated with the 2nd Pd coatings by the amount of covering；It will apply Catalyst after covering dries 5h at a temperature of 120 DEG C, then by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, The component of zirconium dioxide composite oxides is CeO210wt%, ZrO285wt%, La2O35wt%, La2O3Stable aluminium oxide Component be 5wt% La2O3With the Al of 95wt%2O3。
Embodiment 2：
A kind of selective cleaning three-way catalyst, including cellular structure ceramic carrier 1, specification for Ф 118.4mm × 152.4mm, hole density 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support 1 presses gas disengaging side It is inlet end to one end, the other end is outlet side, and the length ratio of inlet end and outlet side is 1:1, is attached on inlet end The one Pd coatings (La including loading Pd2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the first oxidation The mass ratio of zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；It is attached on outlet side The 2nd Pd coatings (La including loading Pd2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the first oxygen The mass ratio for changing zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd of inlet end The first Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on coating2O3-Al2O3, wherein second Zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1) content of, coated weight 120g/L, Rh are 4g/ft3；Go out The 2nd Rh coatings (the 4th zirconia composite oxide and La including loading Rh are attached on the 2nd Pd coatings at gas end2O3- Al2O3, wherein the 4th zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1), coated weight 120g/L, Rh's contains It measures as 4g/ft3。
The preparation of 2 catalyst exemplar of embodiment：Each parameter, composition and preparation process are same as Example 1, in addition to outlet side The first Pd coatings in third zirconia composite oxide become the first zirconia composite oxide, form as CeO2 50wt%, ZrO240wt%, La2O35wt%, Pr6O115wt%；The second zirconia composite oxide in 2nd Rh coatings Become the 4th zirconia composite oxide, form CeO230wt%, ZrO260wt%, La2O35wt%, Pr6O115wt%.
Embodiment 3：
A kind of selective cleaning three-way catalyst, including cellular structure ceramic carrier 1, specification for Ф 118.4mm × 152.4mm, hole density 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support 1 presses gas disengaging side It is inlet end to one end, the other end is outlet side, and the length ratio of inlet end and outlet side is 1:1, is attached on inlet end The one Pd coatings (La including loading Pd2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the first oxidation The mass ratio of zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；It is attached on outlet side The 2nd Pd coatings (La including loading Pd2O3-Al2O3With third zirconia composite oxide, wherein La2O3-Al2O3With third oxygen The mass ratio for changing zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd of inlet end The first Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on coating2O3-Al2O3, wherein second Zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1) content of, coated weight 120g/L, Rh are 4g/ft3；Go out The 2nd Rh coatings (the 4th zirconia composite oxide and La including loading Rh are attached on the 2nd Pd coatings at gas end2O3- Al2O3, wherein the 4th zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1), coated weight 120g/L, Rh's contains It measures as 4g/ft3。
The preparation of 3 catalyst exemplar of embodiment：Each parameter, composition and preparation process are same as Example 2, in addition to outlet side The first Pd coatings in the first zirconia composite oxide become third zirconia composite oxide, form and be CeO270wt%, ZrO220wt%, La2O35wt%, Pr6O115wt%.
Embodiment 4：
A kind of selective cleaning three-way catalyst, including cellular structure ceramic carrier 1, specification for Ф 118.4mm × 152.4mm, hole density 600cpsi, duct wall thickness are 4.3mil, volume 1.678L；Honeycomb support 1 presses gas disengaging side It is inlet end to one end, the other end is outlet side, and the length ratio of inlet end and outlet side is 1:1, is attached on inlet end The one Pd coatings (La including loading Pd2O3-Al2O3With the first zirconia composite oxide, wherein La2O3-Al2O3With the first oxidation The mass ratio of zirconium mixed oxide is 1：1) content of, coated weight 120g/L, Pd are 100g/ft3；It is attached on outlet side The 2nd Pd coatings (La including loading Pd2O3-Al2O3With third zirconia composite oxide, wherein La2O3-Al2O3With third oxygen The mass ratio for changing zirconium mixed oxide is 1：4) content of, coated weight 120g/L, Pd are 10g/ft3；First Pd of inlet end The first Rh coatings (the second zirconia composite oxide and La including loading Rh are attached on coating2O3-Al2O3, wherein second Zirconia composite oxide and La2O3-Al2O3Mass ratio be 1：1) content of, coated weight 120g/L, Rh are 4g/ft3；Go out The 2nd Rh coatings (the 4th zirconia composite oxide and La including loading Rh are attached on the 2nd Pd coatings at gas end2O3- Al2O3, wherein the 4th zirconia composite oxide and La2O3-Al2O3Mass ratio be 4：1), coated weight 120g/L, Rh's contains It measures as 4g/ft3。
The preparation of 4 catalyst exemplar of embodiment uses following processing step：
(1) the first Pd coating application procedures：By the palladium nitrate solution containing 58.86g precious metals pds, 1000g La2O3- Al2O3, the first zirconia composite oxides of 1000g and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed Coating slurry is coated on the inlet end of cellular structure ceramic carrier by coated weight for 120g/L.Wherein, the first zirconium oxide composite oxygen The component of compound is CeO250wt%, ZrO240wt%, La2O35wt%, Pr6O115wt%, La2O3Stable aluminium oxide Component is the La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (2) the 2nd Pd coatings：By the palladium nitrate solution containing 14.71g precious metals pds, 1000g La2O3- Al2O3, 4000g thirds zirconia composite oxide and appropriate amount of deionized water mixing, coating slurry is obtained after ball milling, is then pressed The coating slurry is coated to the outlet side of cellular structure ceramic carrier for 120g/L by coated weight；By the catalyst after coating 120 5h is dried at a temperature of DEG C, then by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, third oxidation zirconium composite oxide The component of object is CeO270wt%, ZrO220wt%, La2O35wt%, Pr6O115wt%, La2O3-Al2O3Component be The La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (3) the first Rh coatings：Rhodium nitrate solution containing 2.35g noble metals Rh, 1000g second are aoxidized Zirconium mixed oxide, 1000g La2O3-Al2O3It is mixed with appropriate amount of deionized water, coating slurry is obtained after ball milling, then by painting The coating slurry is coated to for 120g/L on the inlet end for the cellular structure ceramic carrier for being coated with the first Pd coatings by the amount of covering.Its In, the component of the second zirconia composite oxide is CeO210wt%, ZrO285wt%, La2O35wt%, La2O3-Al2O3's Component is the La of 5wt%2O3With the Al of 95wt%2O3。
The coating procedure of (4) the 2nd Rh coatings：Rhodium nitrate solution containing 5.86g noble metals Rh, 4000g the 4th are aoxidized Zirconium mixed oxide, 1000g La2O3-Al2O3It is mixed with appropriate amount of deionized water, coating slurry is obtained after ball milling, then by painting The coating slurry is coated to for 120g/L on the outlet side for the cellular structure ceramic carrier for being coated with the 2nd Pd coatings by the amount of covering；It will apply Catalyst after covering dries 5h at a temperature of 120 DEG C, then by the catalyst of drying in 500 DEG C of roasting temperature 3h.Wherein, The component of four zirconia composite oxides is CeO230wt%, ZrO260wt%, La2O35wt%, Pr6O115wt%, La2O3 The component of stable aluminium oxide is the La of 5wt%2O3With the Al of 95wt%2O3。
By 1~embodiment of embodiment 4,1 and 2 obtained catalyst sample of comparative example in 1050 DEG C of high temperature Muffle furnace With condition aging 20h, clarifier is then encapsulated into, is recycled by WLTC and carries out vehicle emission test, tests the engine row of vehicle It measures as 1.6L, the results are shown in Table 1 for emission test.
Table 1
Low speed Middling speed At a high speed Ultrahigh speed
CO(g) CO(g) CO(g) CO(g)
Comparative example 1 7.17 3.45 2.45 5.13
Comparative example 2 7.51 3.03 2.09 4.52
Embodiment 1 6.76 2.95 1.98 4.15
Embodiment 2 6.80 3.04 2.06 4.22
Embodiment 3 6.58 2.71 1.81 3.59
Embodiment 4 6.33 2.30 1.62 3.04
As shown in table 1, catalyst vehicle emission test the result shows that, compared with comparative example, 1~4 institute of the embodiment of the present invention The three-way catalyst of preparation has excellent CO detergent powers in each transient condition especially ultrahigh speed operating mode.

Claims (10)

1. a kind of selective cleaning three-way catalyst, it is characterised in that：Including honeycomb support（1）, the honeycomb support（1） One end for inlet end, the other end of honeycomb support is outlet side, and the inlet end is provided with the first Pd coatings from bottom to up （2）With the first Rh coatings（3）, the outlet side is provided with the 2nd Pd coatings from bottom to up（4）With the 2nd Rh coatings（5）, it is described First Pd coatings include the La of load Pd2O3-Al2O3With the first zirconia composite oxide, the first Rh coatings include load The second zirconia composite oxide and La of Rh2O3-Al2O3, La of the 2nd Pd coatings including loading Pd2O3-Al2O3, first Zirconia composite oxide or third zirconia composite oxide, the second zirconium oxide that the 2nd Rh coatings include load Rh are answered It closes oxide or loads the 4th zirconia composite oxide, the La of Rh2O3-Al2O3, the load capacity of Pd in the first Pd coatings For 5 ~ 350g/ft3, the load capacity of Pd is 5 ~ 350g/ft in the 2nd Pd coatings3, the load capacity of Rh in the first Rh coatings For 0.1 ~ 50g/ft3, the load capacity of Rh is 0.1 ~ 50g/ft in the 2nd Rh coatings3。
2. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The first Pd coatings（2）, first Rh coatings（3）, the 2nd Pd coatings（4）With the 2nd Rh coatings（5）Middle La2O3-Al2O3With the mass ratio of zirconia composite oxide It is 1:6~6:1.
3. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The first oxidation zirconium composite oxide The component of object is by weight percentage：The CeO of 40 ~ 60wt%2, 25 ~ 55wt% ZrO2With the La of 5 ~ 15wt%2O3、Y2O3、 Pr6O11、Nd2O3One or more of.
4. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The second oxidation zirconium composite oxide The component of object is by weight percentage：The ZrO of 65 ~ 95wt%2With the CeO of 535wt%2、La2O3、Y2O3、Pr6O11、Nd2O3In It is one or more of.
5. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The third aoxidizes zirconium composite oxide The component of object is by weight percentage：The CeO of 60 ~ 90wt%2, 5 ~ 35wt% ZrO2With the La of 5 ~ 15wt%2O3、Y2O3、 Pr6O11、Nd2O3One or more of.
6. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The 4th oxidation zirconium composite oxide The component of object is by weight percentage：The CeO of 20 ~ 40wt%2, 45 ~ 75wt% ZrO2With the La of 5 ~ 15wt%2O3、Y2O3、 Pr6O11、Nd2O3One or more of.
7. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The La2O3-Al2O3Component press Weight percent is calculated as：The La of 1 ~ 8wt%2O3With the Al of 92 ~ 99wt%2O3。
8. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The first Pd coatings and the 2nd Pd The coated weight of coating is 60 ~ 200g/L.
9. selective cleaning three-way catalyst as described in claim 1, it is characterised in that：The first Rh coatings and the 2nd Rh The coated weight of coating is 50 ~ 180g/L.
10. the preparation method of selective cleaning three-way catalyst described in claim 1, it is characterised in that：Include the following steps：
（1）The coating of first Pd coatings：Honeycomb support is taken, is 5 ~ 350g/ft by the load capacity of Pd in the first Pd coatings3It calculates The quality of required Pd, as the first Pd coatings coated weight for 60 ~ 200g/L calculate needed for the second zirconia composite oxide and La2O3-Al2O3Quality, successively by Pd precious metal solutions, La2O3-Al2O3, the first zirconia composite oxide and deionized water Mixing, is configured to coating slurry after ball milling；Slurries are coated on the inlet end of carrier, by the catalyst after coating 80 ~ At a temperature of 150 DEG C drying 0.2 ~ for 24 hours；
（2）The coating of 2nd Pd coatings：It is 5 ~ 350g/ft by the load capacity of Pd in the 2nd Pd coatings3The quality of Pd needed for calculating, La2O3-Al2O3, the first zirconia composite oxide or third as needed for the coated weight of the 2nd Pd coatings for 60 ~ 200g/L calculating The quality of zirconia composite oxide, by Pd precious metal solutions, La2O3-Al2O3, the first zirconia composite oxide or third oxygen Change zirconium mixed oxide and deionized water mixing, coating slurry is configured to after ball milling；Slurries are coated to the outlet side of carrier On, the catalyst after coating dried at a temperature of 80 ~ 150 DEG C to 0.2 ~ for 24 hours；Then by the catalyst of drying at 350 ~ 650 DEG C 1 ~ 5 h of roasting temperature；
（3）The coating of first Rh coatings：It is 0.1 ~ 50g/ft by the load capacity of Rh in the first Rh coatings3The quality of Rh needed for calculating, The second zirconia composite oxide and La as needed for the coated weight of the first Rh coatings for 50 ~ 180g/L calculating2O3-Al2O3Matter Amount, by Rh precious metal solutions, the second zirconia composite oxide, La2O3-Al2O3It mixes with deionized water, and matches after ball milling Coating slurry is made；Slurries are coated on the first Pd coatings of catalyst inlet end, by the catalyst after coating 80 ~ 150 At a temperature of DEG C drying 0.2 ~ for 24 hours；
（4）The coating of 2nd Rh coatings：The matter of the Rh as needed for the load capacity of Rh in the 2nd Rh coatings for 0.1 ~ 50g/ft3 calculating Amount, the second zirconia composite oxide or the 4th zirconium oxide are answered as needed for the coated weight of the 2nd Rh coatings for 50 ~ 180g/L calculating Close oxide, La2O3-Al2O3Quality, Rh precious metal solutions, the second zirconia composite oxide or the 4th zirconium oxide is compound Oxide, La2O3-Al2O3It is mixed with deionized water, and coating slurry is configured to after ball milling；Slurries are coated to catalyst to go out On the 2nd Pd coatings at gas end, the catalyst after coating dried at a temperature of 80 ~ 150 DEG C to 0.2 ~ for 24 hours, then urging drying Agent is in 350 ~ 650 DEG C of 1 ~ 5 h of roasting temperature.
CN201810010016.9A 2018-01-05 2018-01-05 A kind of selective cleaning three-way catalyst and preparation method thereof Pending CN108126698A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810010016.9A CN108126698A (en) 2018-01-05 2018-01-05 A kind of selective cleaning three-way catalyst and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810010016.9A CN108126698A (en) 2018-01-05 2018-01-05 A kind of selective cleaning three-way catalyst and preparation method thereof

Publications (1)

Publication Number Publication Date
CN108126698A true CN108126698A (en) 2018-06-08

Family

ID=62400399

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810010016.9A Pending CN108126698A (en) 2018-01-05 2018-01-05 A kind of selective cleaning three-way catalyst and preparation method thereof

Country Status (1)

Country Link
CN (1) CN108126698A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940279A (en) * 2018-07-20 2018-12-07 无锡威孚环保催化剂有限公司 A kind of tail-gas from gasoline automobiles three-effect catalyst for purifying and preparation method thereof
CN109985624A (en) * 2019-04-29 2019-07-09 无锡威孚环保催化剂有限公司 Catalysts for Motorcycles coated three times and preparation method thereof
CN110586088A (en) * 2019-10-12 2019-12-20 无锡威孚环保催化剂有限公司 Preparation method of segmented national six natural gas equivalence ratio catalyst

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507590A1 (en) * 1991-04-05 1992-10-07 Nippon Shokubai Co., Ltd. Catalyst for purifying exhaust gas
WO2008091004A1 (en) * 2007-01-24 2008-07-31 Nippon Steel Materials Co., Ltd. Exhaust gas purification catalyst, and catalytic honey-comb structure for exhaust gas purification
CN101479023A (en) * 2006-06-29 2009-07-08 乌米科雷股份两合公司 Three-way catalyst
CN102400745A (en) * 2011-10-26 2012-04-04 浙江吉利汽车研究院有限公司 Ternary catalytic converter and method for coating catalytic layers thereof
CN104148068A (en) * 2014-08-06 2014-11-19 无锡威孚环保催化剂有限公司 Three-way catalyst capable of quickly igniting automobile exhaust
CN105536782A (en) * 2015-12-15 2016-05-04 重庆海特汽车排气***有限公司 Back segment coating of ternary catalyst for purifying automobile exhaust
CN105536786A (en) * 2015-12-15 2016-05-04 重庆海特汽车排气***有限公司 Ternary catalyst for purifying automobile exhaust
CN105772023A (en) * 2016-03-31 2016-07-20 湖南省吉安特技术有限公司 Manufacturing method for efficient three-component catalyst coating
CN105964253A (en) * 2016-05-13 2016-09-28 无锡威孚环保催化剂有限公司 Gasoline car particle capturing catalyst and preparation method thereof
CN106944047A (en) * 2017-03-06 2017-07-14 无锡威孚环保催化剂有限公司 A kind of four coatings three-way catalyst and preparation method thereof

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507590A1 (en) * 1991-04-05 1992-10-07 Nippon Shokubai Co., Ltd. Catalyst for purifying exhaust gas
CN101479023A (en) * 2006-06-29 2009-07-08 乌米科雷股份两合公司 Three-way catalyst
WO2008091004A1 (en) * 2007-01-24 2008-07-31 Nippon Steel Materials Co., Ltd. Exhaust gas purification catalyst, and catalytic honey-comb structure for exhaust gas purification
CN102400745A (en) * 2011-10-26 2012-04-04 浙江吉利汽车研究院有限公司 Ternary catalytic converter and method for coating catalytic layers thereof
CN104148068A (en) * 2014-08-06 2014-11-19 无锡威孚环保催化剂有限公司 Three-way catalyst capable of quickly igniting automobile exhaust
CN105536782A (en) * 2015-12-15 2016-05-04 重庆海特汽车排气***有限公司 Back segment coating of ternary catalyst for purifying automobile exhaust
CN105536786A (en) * 2015-12-15 2016-05-04 重庆海特汽车排气***有限公司 Ternary catalyst for purifying automobile exhaust
CN105772023A (en) * 2016-03-31 2016-07-20 湖南省吉安特技术有限公司 Manufacturing method for efficient three-component catalyst coating
CN105964253A (en) * 2016-05-13 2016-09-28 无锡威孚环保催化剂有限公司 Gasoline car particle capturing catalyst and preparation method thereof
CN106944047A (en) * 2017-03-06 2017-07-14 无锡威孚环保催化剂有限公司 A kind of four coatings three-way catalyst and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王学中等: ""Pd基三效催化剂在实际排气体系中的应用性研究"", 《2001全国机动车排气和工业废气催化治理学术研讨会论文集》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108940279A (en) * 2018-07-20 2018-12-07 无锡威孚环保催化剂有限公司 A kind of tail-gas from gasoline automobiles three-effect catalyst for purifying and preparation method thereof
CN109985624A (en) * 2019-04-29 2019-07-09 无锡威孚环保催化剂有限公司 Catalysts for Motorcycles coated three times and preparation method thereof
CN110586088A (en) * 2019-10-12 2019-12-20 无锡威孚环保催化剂有限公司 Preparation method of segmented national six natural gas equivalence ratio catalyst
CN110586088B (en) * 2019-10-12 2022-06-24 无锡威孚环保催化剂有限公司 Preparation method of segmented national six natural gas equivalence ratio catalyst

Similar Documents

Publication Publication Date Title
CN107715875B (en) GPF quaternary catalyst and preparation method thereof
KR101868181B1 (en) Advanced catalyzed soot filters and method of making and using the same
EP2542339B1 (en) Carbon monoxide conversion catalyst
CN102039205B (en) Monolithic nitrogen oxide selective reduction catalyst and preparation method thereof
CN102909020B (en) Sulfur-resistant catalytic-combustion catalyst and preparation method thereof
KR101593244B1 (en) Improving adhesion and coating integrity of washcoats and overcoats
CN103157470B (en) Ternary catalyst for automobile tail gas
US9120077B2 (en) Surface-coated zeolite materials for diesel oxidation applications
US20100104491A1 (en) Multilayered Catalyst Compositions
CN104148068B (en) Fast light-off ternary catalyst for automobile tail gas
KR20100053636A (en) Catalyst compositions
CN108126698A (en) A kind of selective cleaning three-way catalyst and preparation method thereof
CN108979798A (en) A kind of gasoline car granule capturing catalyst converter and preparation method thereof
JP2015525123A (en) Three-way catalyst system
CN107790124A (en) Three-component Catalytic Converters for Automobiles
CN109794240A (en) A kind of bis- coated catalysts of Pd-Rh and preparation method thereof
CN109046348A (en) A kind of gasoline vehicle tail gas multicomponent catalyst and preparation method thereof
CN106268970A (en) Three-way catalyst for vehicle maintenance service
CN108837829A (en) A kind of layer-stepping natural gas vehicle three-way catalyst preparation method
JP2023505657A (en) Thermal aging resistant oxidation catalyst for diesel emissions control
CN113600188A (en) Catalyst for purifying tail gas of gasoline vehicle and preparation method thereof
CN105597748A (en) Segmented type ternary catalyst and preparation method thereof
CN108940279A (en) A kind of tail-gas from gasoline automobiles three-effect catalyst for purifying and preparation method thereof
CN106925266A (en) Single coating three-way catalyst
CN101444734A (en) Catalyst for purifying exhaust gas from non-road miniature diesel engine, and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180608