CN101745375B - Cerium zirconium aluminum based multiple oxide material and preparing method thereof - Google Patents
Cerium zirconium aluminum based multiple oxide material and preparing method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 113
- -1 Cerium zirconium aluminum Chemical compound 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 21
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims abstract description 42
- 229910000420 cerium oxide Inorganic materials 0.000 claims abstract description 29
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 10
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 10
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 89
- 239000002243 precursor Substances 0.000 claims description 59
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 44
- 238000002360 preparation method Methods 0.000 claims description 43
- 230000006641 stabilisation Effects 0.000 claims description 23
- 238000011105 stabilization Methods 0.000 claims description 23
- 239000011259 mixed solution Substances 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 19
- 239000002131 composite material Substances 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000013049 sediment Substances 0.000 claims description 10
- 238000005245 sintering Methods 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 8
- 239000003153 chemical reaction reagent Substances 0.000 claims description 7
- 239000002244 precipitate Substances 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 239000008187 granular material Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000003795 chemical substances by application Substances 0.000 abstract 2
- 230000003712 anti-aging effect Effects 0.000 abstract 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 abstract 1
- 229910001928 zirconium oxide Inorganic materials 0.000 abstract 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 14
- 239000003381 stabilizer Substances 0.000 description 11
- 238000003860 storage Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 8
- 229910001593 boehmite Inorganic materials 0.000 description 7
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 6
- 238000004364 calculation method Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000007863 gel particle Substances 0.000 description 6
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229910052771 Terbium Inorganic materials 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000008240 homogeneous mixture Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical class [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004643 material aging Methods 0.000 description 1
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 1
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- RGRFMLCXNGPERX-UHFFFAOYSA-L oxozirconium(2+) carbonate Chemical compound [Zr+2]=O.[O-]C([O-])=O RGRFMLCXNGPERX-UHFFFAOYSA-L 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The present invention provides cerium zirconium aluminum based multiple oxide material and a preparing method thereof, wherein on the basis of the total amount of the cerium zirconium aluminum based multiple oxide material, the cerium zirconium aluminum based multiple oxide material is composed of the following components by weight: 25 to 70 shares of aluminum oxide, 20 to 60 shares of cerium oxide, 5 to 25 shares of zirconium oxide, 2 to 4.9 shares of lanthanum oxide and 2 to 15 shares of stable addition agent which is one or more oxides selected from Y, Eu, Gd and Sm. The cerium zirconium aluminum based multiple oxide material has high specific surface area. After the cerium zirconium aluminum based multiple oxide material is roasted in 450 DEG C to 550 DEG C for two to four hours, the specific surface area is all larger than 100m2/g; after the cerium zirconium aluminum based multiple oxide material is roasted in 1000 DEG C for ten hours, the specific surface area at least can reach 60 m2/g; after the cerium zirconium aluminum based multiple oxide material is roasted in 1100 DEG C for five hours, the specific surface area at least can reach 40m2/g. thus, the cerium zirconium aluminum based multiple oxide material is superior to the anti-aging performance of multiple oxide material of the prior art, and can be used as an addition agent or carrier for vehicle tail gas purifying three-way catalyst.
Description
Technical field
The present invention relates to a kind of composite oxide material, relate in particular to a kind of cerium zirconium aluminum based multiple oxide material and preparation method thereof.
Background technology
Along with the fast development of China's economy and increasing sharply of automobile pollution, motor vehicle exhaust emission has become a main source of atmosphere pollution, particularly urban atmospheric pollution, so purifying vehicle exhaust has become an importance of environmental pollution prevention and control.Along with the progressively attention of national environmental pollution, local also correspondingly put into effect more strict exhaust emission standard, this just requires to improve the clean-up effect of vehicle exhaust.
The normal noble metal three-way catalyst that uses is as cleaning catalyst for tail gases of automobiles at present, the noble metal three-way catalyst mainly is comprised of honeycomb ceramic carrier, hydrogen-storing material, aluminum oxide coating layer and some other stabilizing agents etc., and hydrogen-storing material, aluminum oxide coating layer and some other stabilizing agents load on the honeycomb ceramic carrier.Cerium oxide is a kind of hydrogen-storing material commonly used, it under oxidizing atmosphere with CeO
2Form exists, and is converted into CeO under reducing atmosphere
2-δThereby, three-way catalyst is remained in the more stable air-fuel ratio atmosphere, thereby widens the operation window of catalyst.In order to improve CeO
2High-temperature stability and oxygen storage capacity, often to wherein mixing ZrO
2, form cerium zirconium sosoloid.The storage oxygen performance of cerium zirconium sosoloid and heat endurance are much larger than CeO
2Because the specific area of honeycomb ceramic carrier is very little, normal by applying γ-Al
2O
3Come increasing specific surface area.The effect that cerium zirconium aluminum based multiple oxide can play simultaneously storage oxygen/oxygen release and improve the honeycomb ceramic carrier specific area is part important in the three-way catalyst.
CN1200954A discloses a kind of hydrogen-storing material of high thermal stability, it contains the cerium oxide of 5～60 % by weight, 0.1 at least a as stabilizing agent in the praseodymium oxide of～10 % by weight, lanthana, yittrium oxide and the neodymia, aluminium oxide, zirconia, titanium oxide, silica or its mixed oxide are carrier.By pore volume impregnation method and sluggish precipitation hydrogen-storing material and stabilizing agent are coated with and are loaded on the active aluminum oxide carrier.Through 900 ℃ of roastings after 10 hours, specific area is at 21～47m in air for this material
2/ g.Specific area behind this material aging is less, and this is unfavorable for storing up the performance of oxygen performance, and high-temperature stability is not ideal enough.
CN1695798A discloses a kind of Ce-Zr-Al based oxygen stored material and preparation method, this Ce-Zr-Al based oxygen stored material contains the cerium oxide of 10～70 % by weight, the zirconia of 10～45 % by weight, at least a as stabilizing agent in the aluminium oxide of 10～75 % by weight and 5～15 % by weight rare earths or the alkali earth metal oxide.Zirconia, aluminium oxide and stabilizer oxide exist with the solid solution form of cerium oxide.After 5 hours, specific area is 38～110m to this material through 1000 ℃ of roastings
2/ g, lanthana exists as optional stabilizing agent in this invention, does not introduce the specific area under the higher aging temperature.
CN1817447A discloses a kind of hydrogen-storing material with low-cerium, and its chief component component comprises at least a as auxiliary agent in lanthana, strontium oxide strontia and the yittrium oxide of being selected from of the zirconia of cerium oxide, 50～85mol% of 15～40mol% and 5～15mol%.This material adopts the coprecipitation preparation, and after 500～600 ℃ of calcinings, specific area reaches 120m
2/ g, oxygen storage capacity is not less than 300 μ mol/g at 200 ℃.Through 1000 ℃ after aging 10 hours, specific area is greater than 60m
2/ g, oxygen storage capacity is not less than 200 μ mol/g at 200 ℃.Do not contain aluminium oxide in the solvent of this material.
CN1116965A discloses a kind of aluminium oxide, cerium oxide and zirconia base composition, its preparation method and catalyst applications, the chief component component of said composition comprises the oxide of aluminium oxide, cerium oxide, zirconia, praseodymium oxide, iron oxide and/or lanthana and another kind of element, and this element is selected from the element of group VIII in bismuth, rare earth element, barium, silicon and the periodic table of elements.Preparation process prepares respectively first lanthanum-stabilized alumina and cerium zirconium gel precipitation, aluminium oxide is added in the precipitation carry out spray-drying again, last roasting.This preparation process needs separately preparation lanthanum-stabilized alumina, has prolonged manufacturing cycle.Specific area after this material wore out 3 hours through 940 ℃ is at 32～123m
2Between/the g.But do not introduce 1100 ℃ of specific areas of aging 5 hours.
Yet, experiment showed, that the specific area of above-mentioned hydrogen-storing material after 1100 ℃ of lower wearing out 5 hours all significantly descends, and all be no more than 20m
2/ g.This shows, the ageing resistace of the hydrogen-storing material of above-mentioned prior art is still waiting further raising.
Summary of the invention
To the objective of the invention is the poor shortcoming of hydrogen-storing material ageing resistace that is used for three-effect catalyst for purifying tail gas of car in order overcoming in the prior art, good cerium zirconium aluminum based multiple oxide material of a kind of ageing resistace and preparation method thereof to be provided.
The invention provides a kind of cerium zirconium aluminum based multiple oxide material, wherein, take the composite oxide material total amount as benchmark, this composite oxide material is comprised of the aluminium oxide of 25～70 % by weight, the cerium oxide of 20～60 % by weight, the zirconia of 5～25 % by weight, the lanthana of 2～4.9 % by weight and the stabilization aid of 2～10 % by weight, and described stabilization aid is selected from one or more in the oxide of Y, Eu, Gd, Tb and Sm.
The present invention also provides the preparation method of above-mentioned cerium zirconium aluminum based multiple oxide material, wherein, the method comprises the cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the precursor mixed solution of lanthana precursor and stabilization aid precursor contacts with precipitating reagent, sintering will be carried out after the gained washing of precipitate, described cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the consumption of lanthana precursor and stabilization aid precursor makes the gained cerium zirconium aluminum based multiple oxide material by the aluminium oxide of 25～70 % by weight, the cerium oxide of 20～60 % by weight, the zirconia of 5～25 % by weight, the stabilization aid of the lanthana of 2～4.9 % by weight and 2～15 % by weight forms, and described stabilization aid is selected from Y, Eu, Gd, in the oxide of Tb and Sm one or more.
Compare with the hydrogen-storing material that is used for three-effect catalyst for purifying tail gas of car in the prior art, cerium zirconium aluminum based multiple oxide material provided by the invention has the ageing resistace of obvious raising, for example, the initial specific surface of cerium zirconium aluminum based multiple oxide material provided by the invention is greater than 100 meters squared per gram, the specific area of 1000 ℃ of roastings after 5 hours is greater than 60 meters squared per gram, and the specific area of 1100 ℃ of roastings after 5 hours is greater than 40 meters squared per gram; And the storage oxygen performance of cerium zirconium aluminum based multiple oxide material provided by the invention is good.In addition, the preparation method of cerium zirconium aluminum based multiple oxide material provided by the invention can make the cerium zirconium aluminum based multiple oxide material of spheric granules, help further to improve the specific area of powder, this sphere composite oxide material is particularly suitable for cleaning catalyst for tail gases of automobiles.
Description of drawings
The X-ray diffractogram of Fig. 1 Powdered cerium zirconium aluminum based multiple oxide material sample that to be the present invention prepare after 4 hours 550 ℃ of roastings.
The X-ray diffractogram of Fig. 2 sample that is the Powdered cerium zirconium aluminum based multiple oxide material for preparing of the present invention after 10 hours burin-in process of 1000 ℃ of roastings.
The X-ray diffractogram of Fig. 3 sample that is the Powdered cerium zirconium aluminum based multiple oxide material for preparing of the present invention after 5 hours burin-in process of 1100 ℃ of roastings.
In accompanying drawing 1, accompanying drawing 2 and accompanying drawing 3, a, b, c, d, e, f curve represent respectively Comparative Examples 1, embodiment 1,2,3,4,5.
The specific embodiment
The invention provides a kind of cerium zirconium aluminum based multiple oxide material, wherein, take the composite oxide material total amount as benchmark, this composite oxide material is comprised of the aluminium oxide of 25～70 % by weight, the cerium oxide of 20～60 % by weight, the zirconia of 5～25 % by weight, the lanthana of 2～4.9 % by weight and the stabilization aid of 2～10 % by weight, and described stabilization aid is selected from one or more in the oxide of Y, Eu, Gd, Tb and Sm.
All can realize purpose of the present invention although meet the cerium zirconium aluminum based multiple oxide material of above-mentioned composition, but under the preferable case, take the composite oxide material total amount as benchmark, this composite oxide material is comprised of the aluminium oxide of 30～50 % by weight, the cerium oxide of 30～50 % by weight, the zirconia of 10～25 % by weight, the lanthana of 2～4.5 % by weight and the stabilization aid of 2～10 % by weight.The cerium zirconium aluminum based multiple oxide material that satisfies above-mentioned condition can obtain obviously higher ageing resistace.
In addition, the present inventor finds, when described stabilization aid is Tb
4O
7Or Tb
4O
7During with one or more mixture in the oxide of Y, Eu, Gd and Sm, in the situation that other condition is identical, the ageing resistace of cerium zirconium aluminum based multiple oxide material and storage oxygen performance all are significantly improved, and therefore, the preferred stabilization aid of the present invention is Tb
4O
7Or Tb
4O
7With one or more the mixture in the oxide of Y, Eu, Gd and Sm.
In order to make cerium zirconium aluminum based multiple oxide reach better high-temperature stability, cerium oxide and zirconic weight ratio are 1.5～10.5: 1 described in the preferred described cerium zirconium aluminum based multiple oxide material of the present invention, more preferably 1～2: 1.
Because spheric granules has obviously higher specific area, therefore described cerium zirconium aluminum based multiple oxide material is preferably spheric granules, and particle diameter can be 0.6～9.0 micron, is preferably 0.6～2.5 micron.
In above-mentioned composite oxide material, aluminium oxide, cerium oxide and zirconia are the basic composition components of composite oxides, and cerium oxide and zirconia play the effect of storage oxygen/oxygen release, and aluminium oxide provides higher specific area.Gama-alumina namely begins to undergo phase transition at 900 ℃, and specific area sharply reduces, and 1100 ℃ change fully that specific surface is actively low (to only have tens m into
2/ g) Alpha-alumina affects the performance of composite oxide material performance greatly.But lanthana is the generation of establishment gama-alumina phase transformation then, thereby stablizes the specific area of composite oxide material, and therefore, lanthana exists as the stabilizing agent of aluminium oxide.Described zirconia and stabilization aid are mainly used to stablize cerium oxide, suppress the thermal sintering of cerium oxide, improve its storage oxygen.Zirconium and stabilizer element exist with the form of cerium oxide solid solution in cerium zirconium aluminum based multiple oxide of the present invention.
Preparation method according to described cerium zirconium aluminum based multiple oxide material provided by the invention, owing to can realize purpose of the present invention as long as guarantee the composition of cerium zirconium aluminum based multiple oxide material of the present invention, therefore can realize purpose of the present invention as long as control forms the raw material composition of described cerium zirconium aluminum based multiple oxide material, there is no particular limitation to the concrete operations in the preparation process.For example, described cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the precursor mixed solution of lanthana precursor and stabilization aid precursor can be the cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the solution of the mixture of lanthana precursor and stabilization aid precursor, it also can be the cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the mixture of the separately solution of lanthana precursor and stabilization aid precursor, the precursor of described cerium oxide can be the various water soluble salts of cerium, such as cerous nitrate, one or more of cerous nitrate and cerous carbonate.Described zirconic precursor can be one or more in zirconium nitrate, zirconium oxychloride, zirconyl nitrate and the zirconyl carbonate.The precursor of described aluminium oxide can be one or more in boehmite, meta-aluminic acid and the aluminum nitrate.The precursor of described stabilization aid can be their separately corresponding water soluble salts.In the described precursor mixed solution, the total concentration of preferable alloy ion is no more than 0.3 mol/L, more preferably 0.1～0.2 mol/L.Described precipitating reagent can be various alkaline matters, does not more preferably introduce the alkaline matter of other metal ion, such as in ammoniacal liquor, ammonium carbonate, the carbonic hydroammonium one or more.The concentration of described precipitating reagent preferably is not less than 20 % by weight, more preferably 25～35 % by weight.
The mode of described contact can be that precipitant solution is added drop-wise in the described precursor mixed solution, but in order to make precipitating reagent more even with contacting of precursor, and reduce the granularity of gained composite oxide material, improve the specific area of gained composite oxide material, under the preferable case, the method of contact of the present invention comprises precipitant solution is injected in the described precursor mixed solution with vaporific under stirring condition, The faster the better for the speed that stirs, preferred mixing speed is 1200～2400 rev/mins, the speed that sprays into is 30～80 ml/min, is preferably 40～70 ml/min.The pH value of gained solution was preferably 9～14 after the amount that sprays into preferably made contact, and more preferably 10～12.Can be by realize the above-mentioned speed that sprays into spray gun.
In order further to reduce the granularity of gained composite oxide material, under the preferable case, method provided by the invention also comprises carried out ageing 5～15 hours with gained solution after the contact.The method of ageing generally comprises gained solution after the contact is left standstill under 20～40 ℃ environment temperature.
In order to make the gained composite oxide material be shaped to sphere, method provided by the invention is carried out first spray-drying after also comprising the gained washing of precipitate, then the product after the spray-drying is carried out sintering, described spray-dired condition comprises that inlet temperature can be 140～180 ℃, atomizing pressure can be 20～40 MPas, the flow of material can be 2～5 l/hs, and described material is that sediment concentration is the sediment of 10～30 grams per liters and the mixed solution of water.
According to preparation method provided by the invention, wherein, the condition of described sintering comprises that temperature can be 450～800 ℃, and preferred 450～600 ℃, the time of sintering can be 1～10 hour, is preferably 3～5 hours.
The composite oxide material pattern of conventional coprecipitation preparation is bulk or graininess more, and be sphere or subsphaeroidal according to the cerium zirconium aluminum based multiple oxide material pattern that method provided by the invention is prepared, thereby the specific area of the fresh sample of gained cerium zirconium aluminum based multiple oxide material is obviously higher.
The cerium zirconium aluminum based multiple oxide material of the present invention's preparation can be as auxiliary agent or the carrier of three-effect catalyst for purifying tail gas of car.
Further specify cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof below by embodiment.
Embodiment 1
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Form component Al according to cerium zirconium aluminum based multiple oxide material in the table 1
2O
3, CeO
2, ZrO
2, La
2O
3, Y
2O
3Content, calculate Y
2O
3Weight with the precursor boehmite (alumina content 57 % by weight, Shandong Aluminum Plant) of each oxide, cerous nitrate, zirconium nitrate, lanthanum nitrate.The red fuming nitric acid (RFNA) of 65 % by weight is dropped to the Y of above-mentioned amount of calculation
2O
3In until fully dissolving obtain the nitrate solution of yttrium.With the nitrate solution of yttrium obtained above and the boehmite of amount of calculation, cerous nitrate, zirconium nitrate, lanthanum nitrate joins in 1000 milliliters of there-necked flasks, and use dissolved in distilled water, being made into the metal ion total concentration is the precursor mixed solution of 0.2mol/L, in there-necked flask, use spray gun (Foochow wealth machinery Co., Ltd when then under 1200 rev/mins rotating speed, stirring this precursor mixed solution, two-position self-priming adjustable double lance tube) spraying concentration is the ammoniacal liquor of 20 % by weight, jet velocity is 30mL/ minute, it is vaporific spraying into drop, and the injection terminal point is that the pH value of precipitation reaction mixed liquor is about 9.Continuation was stirred 10 minutes after reaction was finished, and then descended still aging 5 hours 25 ℃ of room temperatures.Ageing is removed supernatant liquor after finishing, and is about 7 with deionized water washing sediment to pH value.Sediment adds deionized water and is made into mixed solution, and weight of precipitate concentration is 15g/L, and mechanical agitation got a uniform mixture in 1 hour.
Be that 140 ℃, compressed air atomizing pressure are that 20MPa, mass flow are to carry out spray-drying under the condition of 5L/h with this homogeneous mixture solotion in inlet temperature, obtain dry gel particle.Gel particle 550 ℃ of roastings 4 hours in heat-treatment furnace obtain faint yellow cerium zirconium aluminum based multiple oxide spherical powder.
Comparative Examples 1
Method according to embodiment 1 prepares cerium zirconium aluminum based multiple oxide material, and different is not contain Y in the raw material
2O
3, do not contain yttrium nitrate in the precursor mixed solution.
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Form component Al according to cerium zirconium aluminum based multiple oxide material in the table 1
2O
3, CeO
2, ZrO
2, La
2O
3And Eu
2O
3Content, calculate Eu
2O
3Weight with the precursor boehmite (alumina content 57 % by weight, Shandong Aluminum Plant) of each oxide, cerous nitrate, zirconium nitrate, lanthanum nitrate.The red fuming nitric acid (RFNA) of 65 % by weight is dropped to the Eu of above-mentioned amount of calculation
2O
3In until fully dissolving obtain the nitrate solution of europium.With the nitrate solution of europium obtained above and the boehmite of amount of calculation, cerous nitrate, zirconium nitrate, lanthanum nitrate joins in 1000 milliliters of there-necked flasks, and use dissolved in distilled water, being made into the metal ion total concentration is the precursor mixed solution of 0.2mol/L, in there-necked flask, use spray gun (Foochow wealth machinery Co., Ltd when then under 1200 rev/mins rotating speed, stirring this precursor mixed solution, two-position self-priming adjustable double lance tube) spraying concentration is the ammoniacal liquor of 25 % by weight, jet velocity is 80mL/ minute, it is vaporific spraying into drop, and the injection terminal point is that the pH value of precipitation reaction mixed liquor is 14.Continuation was stirred 10 minutes after reaction was finished, and then descended still aging 15 hours at 30 ℃.Ageing is removed supernatant liquor after finishing, and is about 8 with deionized water washing sediment to pH value.Sediment adds deionized water and is made into mixed solution, and weight of precipitate concentration is 30g/L, and mechanical agitation got a uniform mixture in 1 hour.
Be that 180 ℃, compressed air atomizing pressure are that 40MPa, mass flow are to carry out spray-drying under the condition of 2L/h with this homogeneous mixture solotion in inlet temperature, obtain dry gel particle.Gel particle 550 ℃ of roastings 4 hours in heat-treatment furnace obtain the spherical powder of faint yellow cerium zirconium aluminum based multiple oxide.
Embodiment 3
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Form component Al according to cerium zirconium aluminum based multiple oxide material in the table 1
2O
3, CeO
2, ZrO
2, La
2O
3, Gd
2O
3Content, calculate Gd
2O
3Weight with the precursor boehmite (alumina content 57 % by weight, Shandong Aluminum Plant) of each oxide, cerous nitrate, zirconium nitrate, lanthanum nitrate.The red fuming nitric acid (RFNA) of 65 % by weight is dropped to the Gd of above-mentioned amount of calculation
2O
3In until fully dissolving obtain the nitrate solution of gadolinium.With the nitrate solution of gadolinium obtained above and the boehmite of amount of calculation, cerous nitrate, zirconium nitrate, lanthanum nitrate joins in 1000 milliliters of there-necked flasks, and use dissolved in distilled water, being made into the metal ion total concentration is the precursor mixed solution of 0.2mol/L, in there-necked flask, use spray gun (Foochow wealth machinery Co., Ltd when then under 1200 rev/mins rotating speed, stirring this precursor mixed solution, two-position self-priming adjustable double lance tube) spraying concentration is the ammoniacal liquor of 25 % by weight, jet velocity is 60mL/ minute, it is vaporific spraying into drop, and the injection terminal point is that the pH value of precipitation reaction mixed liquor is about 11.Continuation was stirred 10 minutes after reaction was finished, and then descended still aging 15 hours 25 ℃ of room temperatures.Ageing is removed supernatant liquor after finishing, and is about 7 with deionized water washing sediment to pH value.Sediment adds deionized water and is made into mixed solution, and weight of precipitate concentration is 10g/L, and mechanical agitation got a uniform mixture in 1 hour.
Be that 160 ℃, compressed air atomizing pressure are that 30MPa, mass flow are to carry out spray-drying under the condition of 3L/h with this homogeneous mixture solotion in inlet temperature, obtain dry gel particle.Gel particle 550 ℃ of roastings 4 hours in heat-treatment furnace obtain faint yellow cerium zirconium aluminum based multiple oxide spherical powder.
Comparative Examples 2
Method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that the composition of adjusting raw material makes Gd in the gained cerium zirconium aluminum based multiple oxide material
2O
3Content be 20 % by weight.
Comparative Examples 3
Method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that the composition of adjusting raw material makes La in the gained cerium zirconium aluminum based multiple oxide material
2O
3Content be 10 % by weight.
Embodiment 4
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that the composition of raw material and content calculate according to table 1.
Embodiment 5
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 4 prepares cerium zirconium aluminum based multiple oxide material, and different is Tb
4O
7Sm with 2.5 % by weight
2O
3Tb with 2.5 % by weight
4O
7Replace.
Embodiment 6
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 4 prepares cerium zirconium aluminum based multiple oxide material, and different is Tb
4O
7Sm with 5 % by weight
2O
3Replace.
Embodiment 7
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that lance ejection speed is 20mL/ minute.
Embodiment 8
Preparation method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is, uses the dropping method instead precipitating reagent is added drop-wise in the precursor mixed solution, and the speed of dropping is 60mL/ minute.
Embodiment 9
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that the composition of raw material and content calculate according to table 1.
The present embodiment is used for illustrating cerium zirconium aluminum based multiple oxide material of the present invention and preparation method thereof.
Preparation method according to embodiment 3 prepares cerium zirconium aluminum based multiple oxide material, and different is that the composition of raw material and content calculate according to table 1.
Performance test
Specific area test: with specific surface area measuring instrument (BeiFen Instrument Techogy Co., Ltd., BeiJing City, the ST-08 type) the employing method of comparison is carried out the specific area test to the cerium zirconium aluminum based multiple oxide material of each embodiment 1-10 and Comparative Examples 1-3 preparation, and test result is as shown in table 2.
The ageing resistace test:
The cerium zirconium aluminum based multiple oxide material of embodiment 1-10 and Comparative Examples 1-3 preparation was calcined respectively 10 hours and 5 hours at 1000 ℃ and 1100 ℃ respectively separately, obtained the aged samples of cerium zirconium aluminum based multiple oxide material.Then test according to the method described above the specific area of each sample.
XRD (X-ray diffraction) test: with x-ray powder diffraction instrument (Rigaku company, the D/MAX2200PC type) cerium zirconium aluminum based multiple oxide material of each embodiment and Comparative Examples preparation and above-mentioned material are carried out XRD at 1000 ℃ and 1100 ℃ after calcining respectively 10 hours and 5 hours and test, wherein embodiment 1,2,3,4,5 and the test result of Comparative Examples 1 distinguish as Figure 1-3.Wherein embodiment 1,2,3,4,5 and the test result of Comparative Examples 1 respectively shown in Fig. 1～3.
Table 1
Table 2
The cerium zirconium aluminum based multiple oxide material of the present invention preparation, 1000 ℃ of roastings after 10 hours in atmospheric environment, the XRD test result shows, and zirconium and stabilizer element solid solution are not isolated cenotype in cerium oxide, and aluminium oxide is also without obvious phase transformation.1100 ℃ of roastings are after 5 hours, except a small amount of LaAlO occurring in atmospheric environment
3Outside the cenotype, cerium zirconium sosoloid is the variation on the recurring structure not.Show the cerium zirconium aluminum based multiple oxide material that the present invention prepares, lanthana at high temperature generates stable phase LaAlO as the stabilizing agent of aluminium oxide
3, suppresses aluminium oxide and change mutually to α, thereby the effect of stabilization ratio surface area is played in the rapid reduction of rejection ratio surface area.Cerium zirconium sosoloid is not isolated cenotype yet under 1100 ℃ of high temperature, have good structural stability, and this is a stable necessary condition of storage oxygen.
In addition, the cerium zirconium aluminum based multiple oxide material of the present invention's preparation also has higher storage oxygen performance.
Claims (7)
1. cerium zirconium aluminum based multiple oxide material, it is characterized in that, take the composite oxide material total amount as benchmark, this composite oxide material is comprised of the aluminium oxide of 30 ~ 50 % by weight, the cerium oxide of 30 ~ 50 % by weight, the zirconia of 10 ~ 25 % by weight, the lanthana of 2 ~ 4.5 % by weight and the stabilization aid of 2 ~ 10 % by weight, and described stabilization aid is Tb
4O
7Or Tb
4O
7With one or more the mixture in the oxide of Y, Eu, Gd and Sm.
2. cerium zirconium aluminum based multiple oxide material according to claim 1, wherein, described cerium zirconium aluminum based multiple oxide material is spheric granules, particle diameter is 0.6 ~ 9 micron.
3. the preparation method of the described cerium zirconium aluminum based multiple oxide material of claim 1, it is characterized in that, the method comprises the cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the precursor mixed solution of lanthana precursor and stabilization aid precursor contacts with precipitating reagent, to carry out sintering after the gained washing of precipitate drying, described cerium oxide precursor, the zirconia precursor, the aluminium oxide precursor, the consumption of lanthana precursor and stabilization aid precursor makes the gained cerium zirconium aluminum based multiple oxide material by the aluminium oxide of 30 ~ 50 % by weight, the cerium oxide of 30 ~ 50 % by weight, the zirconia of 10 ~ 25 % by weight, the stabilization aid of the lanthana of 2 ~ 4.5 % by weight and 2 ~ 10 % by weight forms, and described stabilization aid is Tb
4O
7Or Tb
4O
7With one or more the mixture in the oxide of Y, Eu, Gd and Sm.
4. preparation method according to claim 3, wherein, the method of described contact comprises precipitant solution is injected in the described precursor mixed solution with vaporific under stirring condition, and the amount that sprays into makes that the pH value of gained solution is 9 ~ 14 after the contact, and the speed that sprays into is 30 ~ 80 ml/min.
5. preparation method according to claim 4, wherein, the method also comprises carried out ageing 5 ~ 15 hours with gained solution after the contact.
6. preparation method according to claim 3, wherein, the method is carried out first spray-drying after also comprising the gained washing of precipitate, then the product after the spray-drying is carried out sintering, described spray-dired condition comprises that inlet temperature is 140 ~ 180 ℃, atomizing pressure is 20 ~ 40 MPas, and the flow of material is 2 ~ 5 l/hs, and described material is that sediment concentration is the sediment of 10 ~ 30 grams per liters and the mixed solution of water.
7. according to claim 3 or 6 described preparation methods, wherein, described precipitating reagent is one or more in ammoniacal liquor, carbonic hydroammonium and the ammonium carbonate, the total concentration of metal ion is 0.1 ~ 0.2 mol/L in the described precursor mixed solution, the condition of described sintering comprises that temperature is 450 ~ 800 ℃, and the time of sintering is 1 ~ 10 hour.
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| EP2731709B1 (en) * | 2011-07-14 | 2020-01-22 | Treibacher Industrie AG | Ceria zirconia alumina composition with enhanced thermal stability |
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| CN102716733B (en) * | 2012-05-08 | 2016-01-20 | 赣州博晶科技有限公司 | A kind of preparation method of high performance cerium zirconium aluminum oxygen-storage material |
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| CN102962047B (en) * | 2012-11-12 | 2014-10-08 | 上海华明高纳稀土新材料有限公司 | Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof |
| CN103861577A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特汽车净化器有限公司 | Preparation method of oxygen storage material |
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| CN103861654A (en) * | 2012-12-14 | 2014-06-18 | 上海郎特汽车净化器有限公司 | An oxygen storage material |
| CN103349978A (en) * | 2013-06-25 | 2013-10-16 | 上海华明高纳稀土新材料有限公司 | Cerium-zirconium-aluminium-based composite oxide catalytic material and preparation method thereof |
| EP3045226B1 (en) * | 2015-01-19 | 2024-08-21 | Umicore AG & Co. KG | Double layer three-way catalytic converter with improved ageing resistance |
| EP3752463A4 (en) * | 2018-02-15 | 2021-11-17 | Sumitomo Chemical Company Limited | Inorganic oxide |
| KR20210005550A (en) * | 2018-02-15 | 2021-01-14 | 스미또모 가가꾸 가부시끼가이샤 | Inorganic oxide |
| 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 |
| CN110586145B (en) * | 2019-09-04 | 2022-07-26 | 昆明贵金属研究所 | Cerium-zirconium-aluminum composite material with high thermal stability, preparation method and application thereof |
| CN112275286A (en) * | 2020-09-14 | 2021-01-29 | 无锡威孚环保催化剂有限公司 | Ir-Rh iridium-rhodium bimetallic catalyst and preparation method thereof |
| CN114551910B (en) * | 2022-02-25 | 2023-09-22 | 内蒙古科技大学 | Composite rare earth oxide and preparation method and application thereof |
| CN115254129B (en) * | 2022-06-24 | 2023-08-22 | 江阴华音陶瓷机电科技有限公司 | Honeycomb body for purifying automobile exhaust and preparation method thereof |
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