CN104857974A - Palladium-only catalyst for purifying automobile tail gas and preparation method of palladium-only catalyst - Google Patents
Palladium-only catalyst for purifying automobile tail gas and preparation method of palladium-only catalyst Download PDFInfo
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- CN104857974A CN104857974A CN201510274727.3A CN201510274727A CN104857974A CN 104857974 A CN104857974 A CN 104857974A CN 201510274727 A CN201510274727 A CN 201510274727A CN 104857974 A CN104857974 A CN 104857974A
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- catalyst
- palladium
- coating
- base composite
- composite oxidate
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Abstract
The invention relates to a palladium-only catalyst for purifying an automobile tail gas and a preparation method of the palladium-only catalyst. The palladium-only catalyst is characterized by adopting a double-layer structure, wherein the bottom layer is a CeO2-ZrO2-based composite oxide oxygen storage material loaded with Pd, and the upper layer is an Al2O3-based composite oxide loaded with Pd. The palladium-only catalyst provided by the invention is high in reaction property and good in thermal stability.
Description
Technical field
The present invention relates to catalytic cleaning of car tail gas field, relate to a kind of purifying vehicle exhaust list Pd Catalysts and its preparation method.
Background technology
Along with increasing of automobile pollution, the tail gas of motor vehicle emission also more and more affects the living standard of people, and the most directly impact is exactly haze.Have a strong impact on the healthy of people.The major measure controlling motor vehicle exhaust emission develops the purification techniques of efficient auto-exhaust catalyst.Generally when the scope control of air-fuel ratio is when (14.6 ± 0.3), just NO can be made
x, CO and CH catalytic purification ability reach maximum.
Zhou Renxian etc. are at impact (the The effect of La doping on the structure of Ce of La doped with cerium zirconium solid solution on three-way catalytic performance
0.2zr
0.8o
2and the catalytic performance of its supported Pd-only three-way catalyst. Applied CatalysisB:Environmental.2010, have studied 101:150-159) and by coprecipitation, rare-earth elements La is doped in cerium zirconium sosoloid, at equi-volume impregnating load P d, after research finds doping La, the catalytic activity of catalyst is improved.
CN201210041024 discloses a kind of preparation method of integral automobile exhaust purification catalyst of high-temperature stable, it is characterized in that in coating paste preparation process, with the addition of appropriate complexed surfactant (Tween-80, this dish-20 and polyethylene glycol-200), thus improve the performance of slurry and whole coating procedure.
CN201010259503 discloses a kind of integral automobile exhaust purification catalyst and preparation method thereof, adopts cordierite honeycomb ceramic as carrier, adopts vacuum impregnation technology by La
2o
3, CeO
2, BaO, SrO, CaO, ZrO
2, CuO and SiO
2deng in the Alumina gel of one or more modifications load on cordierite honeycomb ceramic carrier, then adopt vacuum impregnation technology to be loaded on modified oxidized aluminized coating by La, Sr, Co, Cu, Mn, Fe and Pd isoreactivity composition.
CN200810233850 discloses a kind of anti-sulfur poisoning and preparation method thereof, it take cordierite honeycomb ceramic as matrix, with Pd, Pt and Rh noble metal for main active component, with the composite alumina of alumina powder, rare earth metal, alkaline-earth metal, transition metal and La-Y-Ce-Zr solid solution composition for coating, the compositions such as the prepreg layer formed with rare earth metal and transition metal.
CN200810020034 discloses a kind of metallic composite oxides material that can be used for the three layer structure of cleaning catalyst for tail gases of automobiles coating, it is characterized in that internal layer is aluminium oxide, intermediate layer and outermost layer are cerium Zirconium oxide, but intermediate layer is different with the composition of outermost layer cerium used Zirconium oxide.This powder body material adopts sol-gel method preparation.
(the Byungchul CHOI such as Byungchul CHOI, Jongwoo JEONG, Geonseog SON, Myunggun JUNG, Conversiion Characteristics of Double-Layer Washcoat Tri-Metal Three-Way Catalyst Using High Cell Density Substrate, JSME International Journal, 2005,48 (5): 874-881) catalyst of a series of different noble-metal-supported amount, different coating composition has been prepared, lower floor's load of catalyst metal Pd, upper strata load Pt metal and Rh.
The Chan-Soon Kang such as Chan-Soon Kang, Young-Jae You, Ki-Joong Kim, Tae-hee Kim, Seong-Jun Ahn, Kyong-Hwan Chung, Nam-Cook Park, Shoichi Kimura and Ho-Geun Ahn. Selective catalytic reduction of NO
xwith propene over double wash-coat monolith catalysts. Catalysis Today, 2006,111:229-235 does lower floor with the Pt catalyst of alumina load, and molecular sieve does upper strata, has prepared C
3h
6selective reduction NO
xdouble-layer catalyst.
Summary of the invention
Object of the present invention is exactly for purifying vehicle exhaust, develops and has low cost, high performance three-way catalyst and preparation method thereof.Three-way catalyst prepared by the inventive method avoids the use of the noble metals such as Pt and Rh, reduces the cost of catalyst, and has good tail gas clean-up reactivity worth.
Three-way catalyst of a kind of wide triple effect window of the present invention and preparation method thereof, utilizes the performance of different carriers Pt-supported catalyst in triple effect purification different, prepares and have double-deck single Pd tai-gas clean-up catalyst, comprise the following steps:
(1) carrier selects cordierite ceramic honeycomb carrier, and active coating is respectively CeO
2-ZrO
2base composite oxidate hydrogen-storing material and Al
2o
3base composite oxidate, active metal is metal Pd;
(2) the single Pd catalyst for purifying vehicle exhaust prepared by, have double-decker, bottom is Al
2o
3base composite oxidate, upper strata is CeO
2-ZrO
2base composite oxidate hydrogen-storing material.Wherein Al
2o
3base composite oxidate consist of M " O
x-Al
2o
3, the weight content of wherein M " being one or more in La and Ba, M " O is Al
2o
3in 3%-10%; CeO
2-ZrO
2base composite oxidate hydrogen-storing material consist of Ce
xzr
ym
zo
2, wherein the Ce/Zr one that to be 2:8 ~ 7:3, M be in La, Y, Al, Ba and more than one, the weight content of M is the 3%-10% in hydrogen-storing material;
(3) equi-volume impregnating is adopted to prepare M " O respectively
x-Al
2o
3and Ce
xzr
ym
zo
2pt-supported catalyst, the presoma of selected Pd is the one in palladium nitrate, palladium, the acid of chlorine palladium, palladium ammonia, palladium acetylacetonate.After having flooded, through 100-150 DEG C of drying, 300-550 DEG C of roasting.The weight content of Pd is 0.5%-3%;
(4) with the made M " O got ready
x-Al
2o
3pt-supported catalyst and boehmite mix with water, add the pH to 2-5 that appropriate nitric acid regulates feed liquid, then through ball grinding stirring, and obtained coating slurry A.With the made Ce got ready
xzr
ym
zo
2pt-supported catalyst and boehmite mix with water, add the pH to 2-5 that appropriate nitric acid regulates feed liquid, then through ball grinding stirring, and obtained coating slurry B;
(5) adopt the method for airless spraying, first coating material liquid A is coated on carrier cordierite ceramic, has applied rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 100-350 DEG C of heat treatment, prepare M " O
x-Al
2o
3the coating of Pt-supported catalyst; Then coating material liquid B is applied existing M " O
x-Al
2o
3on the carrier cordierite ceramic of the coating of Pt-supported catalyst, applied rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 100-350 DEG C of drying, 350-550 DEG C of roasting is prepared has double-deck single Pd integral catalyzer.
Beneficial effect of the present invention is: Pd only three way catalyst prepared by the inventive method, have active high, stability is high.The feature that cost is low, can the pollutant of high-efficient purification motor vehicle exhaust emission.
Detailed description of the invention
Below in conjunction with instantiation, the invention will be further described, and the present invention does not limit by following example.
Embodiment 1: carrier selects cordierite ceramic honeycomb carrier, active metal is metal Pd, and active coating is Al
2o
3.Take palladium nitrate as presoma, adopt infusion process to prepare Pd/Al
2o
3catalyst, after having flooded, through 120 DEG C of dryings, 550 DEG C of roastings, obtained catalyst is for subsequent use, and the content of Pd is 1%.Then by prepared Pd/Al
2o
3catalyst, boehmite and water mix, and by nitric acid adjust ph to 3-4, then prepare slurry through ball milling.Adopt the method for airless spraying, first prepared coating material liquid is coated on carrier cordierite ceramic, apply rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 150 DEG C of oven dry, 550 DEG C of roastings, prepare single Pd integral catalyzer, and in catalyst, the loading of Pd is 1.2g/L.
Embodiment 2: by the Al in embodiment 1
2o
3change La-Al into
2o
3, wherein La
2o
3weight content be 3%, all the other steps are identical.
Embodiment 3: by the Al in embodiment 1
2o
3change CeZrO into
2, wherein Ce/Zr mol ratio is 1:1, and all the other steps are identical.
Embodiment 4: by the Al in embodiment 1
2o
3change Ce into
0.65zr
0.30la
0.05o
δ, all the other steps are identical.
Embodiment 5: prepare Pd/Al respectively by the method in embodiment 1
2o
3with Pd/ CeZrO
2after catalyst, mix with boehmite and water respectively, by nitric acid adjust ph to 3-4, prepare slurry A(Pd/Al through ball milling
2o
3) and B(Pd/CeZrO
2).Adopt the method for airless spraying, be first coated on carrier cordierite ceramic by prepared coating material liquid A, applied rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 150 DEG C of oven dry, 350 DEG C of roastings, preparing coating is Pd/Al
2o
3catalyst; Then continue the method adopting airless spraying, it is Pd/Al that prepared coating material liquid B is coated in coating
2o
3catalyst on, then through 150 DEG C of oven dry, 550 DEG C of roastings, prepare and have double-deck single Pd catalyst, Pd loading is 1.2g/L, and wherein Pd is distributed as 1:1 between upper strata and the coating of bottom.
Embodiment 6: with embodiment 5, difference is that upper strata coating is Pd/Al
2o
3, lower floor's coating is Pd/CeZrO
2.
Embodiment 7: with embodiment 5, difference is that Pd is at Pd/Al
2o
3coating and Pd/CeZrO
2between be distributed as 1:2.
Catalyst reaction performance evaluation adopts fixed bed reactors, and reaction gas consists of CO (1%), NO (1000ppm), C
3h
8(1000ppm), O
2and N (0.95%)
2for Balance Air, CO and C in reaction gas after reaction
3h
8conversion ratio adopt gas chromatographic analysis, NO
xconversion ratio adopt nitrogen-oxide analyzer, measure.
Catalyst activity evaluation result:
Claims (5)
1. for a single Pd catalyst for purifying vehicle exhaust, it is characterized in that catalyst by carrier, active coating and active metal three part form, wherein: carrier is cordierite ceramic honeycomb carrier, active coating consist of CeO
2-ZrO
2base composite oxidate hydrogen-storing material and Al
2o
3base composite oxidate, active metal is metal Pd.
2. a kind of single Pd catalyst for purifying vehicle exhaust according to claim 1, it is characterized in that active coating has double-decker, wherein bottom is Al
2o
3base composite oxidate, upper strata is CeO
2-ZrO
2base composite oxidate hydrogen-storing material.
3. a kind of single Pd catalyst for purifying vehicle exhaust according to claim 1, is characterized in that upper strata CeO
2-ZrO
2base composite oxidate hydrogen-storing material consist of Ce
xzr
ym
zo
2, wherein the Ce/Zr one that to be 2:8 ~ 7:3, M be in La, Y, Al, Ba and more than one, the weight content of M is the 3%-10% in hydrogen-storing material; Bottom Al
2o
3base composite oxidate consist of M " O
x-Al
2o
3, the weight content of wherein M " being one or more in La and Ba, M " O is Al
2o
3in 3%-10%.
4. a kind of single Pd catalyst for purifying vehicle exhaust according to claim 1, is characterized in that Pd content is in the catalyst 0.8g/L ~ 3g/L, wherein at upper strata CeO
2-ZrO
2base composite oxidate hydrogen-storing material and bottom Al
2o
3in base composite oxidate, weight content ratio is 1:1 ~ 4:1.
5. a kind of according to claim 2 have double-deck single Pd catalyst for purifying vehicle exhaust, it is characterized in that preparation method adopts with the following method:
(1) equi-volume impregnating is adopted to prepare M " O
x-Al
2o
3pt-supported catalyst, the presoma of selected Pd is the one in palladium nitrate, palladium, the acid of chlorine palladium, palladium ammonia, palladium acetylacetonate; After having flooded, through 100-150 DEG C of drying, 300-550 DEG C of roasting, the weight content of Pd is 0.5%-3%;
(2) equi-volume impregnating is adopted to prepare Ce
xzr
ym
zo
2pt-supported catalyst, the presoma of selected Pd is the one in palladium nitrate, palladium, the acid of chlorine palladium, palladium ammonia, palladium acetylacetonate; After having flooded, through 100-150 DEG C of drying, 300-550 DEG C of roasting, the weight content of Pd is 0.5%-3%;
(3) with the made M " O got ready
x-Al
2o
3pt-supported catalyst and boehmite mix with water, add the pH to 2-5 that appropriate nitric acid regulates feed liquid, then through ball grinding stirring, and obtained coating slurry A; With the made Ce got ready
xzr
ym
zo
2pt-supported catalyst and boehmite mix with water, add the pH to 2-5 that appropriate nitric acid regulates feed liquid, then through ball grinding stirring, and obtained coating slurry B;
(4) adopt the method for airless spraying, first coating material liquid A is coated on carrier cordierite ceramic, has applied rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 100-350 DEG C of heat treatment, prepare M " O
x-Al
2o
3the coating of Pt-supported catalyst; Then coating material liquid B is coated in existing M " Ox-Al
2o
3on the carrier cordierite ceramic of Pt-supported catalyst coating, applied rear employing vacuum extraction, remove feed liquid unnecessary in duct, then through 100-350 DEG C of drying, 350-650 DEG C of roasting is prepared has double-deck single Pd integral catalyzer.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510274727.3A CN104857974A (en) | 2015-05-27 | 2015-05-27 | Palladium-only catalyst for purifying automobile tail gas and preparation method of palladium-only catalyst |
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|---|---|---|---|
| CN201510274727.3A CN104857974A (en) | 2015-05-27 | 2015-05-27 | Palladium-only catalyst for purifying automobile tail gas and preparation method of palladium-only catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106732585A (en) * | 2017-03-06 | 2017-05-31 | 西南化工研究设计院有限公司 | A kind of VOCs catalytic burning integral types catalyst and preparation method thereof |
| CN108607552A (en) * | 2018-05-07 | 2018-10-02 | 华北电力大学（保定） | A kind of high-efficient purification auto-exhaust catalyst |
| CN109395742A (en) * | 2018-12-21 | 2019-03-01 | 无锡威孚环保催化剂有限公司 | A kind of oxidation catalyst and preparation method thereof of catalysis burning VOCs |
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Cited By (4)
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|---|---|---|---|---|
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| CN106732585B (en) * | 2017-03-06 | 2019-05-07 | 西南化工研究设计院有限公司 | A kind of VOCs catalytic burning integral type catalyst and preparation method thereof |
| CN108607552A (en) * | 2018-05-07 | 2018-10-02 | 华北电力大学（保定） | A kind of high-efficient purification auto-exhaust catalyst |
| CN109395742A (en) * | 2018-12-21 | 2019-03-01 | 无锡威孚环保催化剂有限公司 | A kind of oxidation catalyst and preparation method thereof of catalysis burning VOCs |
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Application publication date: 20150826 |