CN102962047B - Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof - Google Patents
Aluminum-cerium-zirconium based composite oxide catalytic material and preparation method thereof Download PDFInfo
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- CN102962047B CN102962047B CN201210450711.XA CN201210450711A CN102962047B CN 102962047 B CN102962047 B CN 102962047B CN 201210450711 A CN201210450711 A CN 201210450711A CN 102962047 B CN102962047 B CN 102962047B
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- -1 Aluminum-cerium-zirconium Chemical compound 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 230000003197 catalytic effect Effects 0.000 title abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 12
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910004625 Ce—Zr Inorganic materials 0.000 claims description 18
- 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 claims description 18
- 239000004411 aluminium Substances 0.000 claims description 17
- 229910052782 aluminium Inorganic materials 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 17
- 238000006555 catalytic reaction Methods 0.000 claims description 17
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 16
- 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 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 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 claims description 9
- 150000002910 rare earth metals Chemical class 0.000 claims description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 6
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 6
- 239000002002 slurry Substances 0.000 claims description 6
- 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 claims description 4
- 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 claims description 4
- 229910001960 metal nitrate Inorganic materials 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 4
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 3
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 238000010009 beating Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910000420 cerium oxide Inorganic materials 0.000 abstract description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 12
- 238000007084 catalytic combustion reaction Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000746 purification Methods 0.000 abstract description 5
- 238000003860 storage Methods 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000008030 elimination Effects 0.000 abstract description 3
- 238000003379 elimination reaction Methods 0.000 abstract description 3
- 239000003345 natural gas Substances 0.000 abstract description 3
- 239000002912 waste gas Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 239000012266 salt solution Substances 0.000 abstract description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 4
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000010815 organic waste Substances 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
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 65
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 9
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- 239000013049 sediment Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 238000009413 insulation Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000003381 stabilizer Substances 0.000 description 5
- 239000012071 phase Substances 0.000 description 4
- 239000011232 storage material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000004094 surface-active agent Substances 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
- PZZOEXPDTYIBPI-UHFFFAOYSA-N 2-[[2-(4-hydroxyphenyl)ethylamino]methyl]-3,4-dihydro-2H-naphthalen-1-one Chemical compound C1=CC(O)=CC=C1CCNCC1C(=O)C2=CC=CC=C2CC1 PZZOEXPDTYIBPI-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Abstract
The invention provides an aluminum-cerium-zirconium based composite oxide catalytic material and a preparation method thereof. The aluminum-cerium-zirconium based composite oxide catalytic material comprises the following components in percentage by weight: 15-30% of cerium oxide, 5-20% of zirconium oxide, 50-75% of aluminum oxide, and 0-5% of other rear earth oxides except from cerium. Compared with the prior art, the aluminum-cerium-zirconium based composite oxide catalytic material and the preparation method thereof have the advantages that aluminum hydroxide is formed by carrying out a hydrolytic treatment on aluminum oxide, and the aluminum hydroxide is hydro-thermally synthesized with the mixed metal salt solution coagent to form the aluminum-cerium-zirconium based composite oxide catalytic material. On one hand, a mutual effect between the aluminum oxide and the aluminum-cerium-zirconium based composite oxide is strengthened; on the other hand, uniformity between the aluminum oxide and the aluminum-cerium-zirconium based composite oxide is sufficiently ensured to achieve the characteristics of a large specific surface, good high-temperature ageing resistance, high oxygen storage and discharge capability and the like. The aluminum-cerium-zirconium based composite oxide catalytic material is suitable for vehicle tail gas purification, organic waste gas elimination and waste gas purifications or catalytic combustions such as natural gas catalytic combustion.
Description
Technical field
The present invention relates to a kind of catalysis material and preparation method thereof, particularly a kind of aluminium Ce-Zr based composite oxide catalysis material that is applicable to the waste gas purifications such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion or catalytic combustion and preparation method thereof.
Background technology
Reducing automobile exhaust pollution, environment protection quality, realize ecological environment and social sustainable development, is one of important topic of China environmental protection in the current and following long duration.
Pollute for reducing, must break through from improving gasoline quality, improve engine combustion state and increasing exhaust purification catalytic efficiency three aspects:.Up to the present be, that effective way reduces HC in tail gas, CO and NO by three-way catalytic apparatus exactly with cleaning catalyst for tail gases of automobiles
xthe content of three kinds of toxic gases.
Three-way catalyst is mainly by the noble metal active component that plays catalytic action, contains CeO
2catalyst aid (hydrogen-storing material) and for supporting the carrier composition of active component.And dispersion and stable play a key effect of suitable purifying vehicle exhaust storage oxygen coating material to noble metal, store up the oxygen storage capacity that oxygen coating material can improve catalyst under hot conditions simultaneously, expand its air-fuel ratio operation window, catalyst activity under very harsh operating condition is had clear improvement.
The rare earth oxygen storage material containing cerium of current commercial use and the γ-Al with high-specific surface area and stronger thermal ageing resistant capacity
2o
3prepare respectively.
Due to CeO
2heat endurance poor, limited its use.Therefore while, at high temperature use, must suppress CeO
2sintering.When by CeO
2in cerium ion while replacing with other cationic moiety, can produce fault of construction, obviously improve its high high-temp stability.
Zr0
2add Ce0 to
2in, can form Ce0
2-Zr0
2solid solution and improve Ce0
2body phase behaviour, be beneficial to migration and the diffusion of body phase oxygen atom, body phase reaction process is become vivaciously, can improve Ce0
2oxygen storage capacity and high-temperature stability.Meanwhile, the rare earths such as Pr, Nd, Y, Nb, La and Ba and alkaline earth element add the high-temperature aging resisting that can further strengthen hydrogen-storing material, improve its oxygen storage capacity.Hydrogen-storing material is the dispersion of stabilizing active component effectively, therefore there is large specific area, larger pore volume and suitable pore-size distribution, and the cerium zirconium based oxygen storage material with good high-temperature aging resisting performance, excellent low-temperature catalyzed performance becomes the critical material of new three-way catalyst.
γ-Al
2o
3heat endurance, specific area, pore volume, pore-size distribution, surface acidity and NO adsorption capacity affect to a great extent the catalytic performance of catalyst.Improve γ-Al
2o
3high high-temp stability and surface property significant to improving activity and service life of catalyst.Research shows.Can improve the high high-temp stability of aluminium oxide by adding rare earth, alkaline earth element etc., suppress aluminium oxide by the γ transformation of α phase in opposite directions.Industrial now widely used be the aluminium oxide that by rare earth element or transition metal, boehmite is carried out having through roasting preparation after surface modification stronger thermal ageing resistant capacity.
With rare earth material and the mutual modifications of aluminium oxide such as cerium zirconium based solid solutions, prepare Ce-Zr-Al based composite, making its common advantage that has hydrogen-storing material and aluminium oxide concurrently, improve the high temperature ageing resistance of hydrogen-storing material and aluminium oxide, is the key technology of catalyst coatings of new generation.
The Chinese patent patent No. is that 200510020615.1 patent of invention discloses a kind of Ce-Zr-Al based oxygen stored material and preparation method thereof, its basic composition is by cerium oxide, zirconia, aluminium oxide and stabilizing agent, and stabilizing agent is selected from least one of lanthana, yittrium oxide and alkaline earth oxide; Its preparation technology is that (1) prepares nitrate mixed solution and alkaline precipitating agent by given material composition component; (2) the two kinds of solution preparing conductance are entered in reaction vessel to precipitate, after precipitation finishes, be not less than 2h 90-100 DEG C of ageing; (3) the reaction feed liquid after ageing is carried out Separation of Solid and Liquid, and isolated solid phase precipitation thing washs, is then made into slurries with surfactant and water; (4) slurries are by evaporation drying, then roasting obtains Ce-Zr-Al based oxygen stored material.
The specific surface agent of the hydrogen-storing material of preparing with said method reaches as high as 110m after 1000 DEG C of roasting 5h
2more than/g, at least can reach 38m
2more than/g; But the method is taking aluminum nitrate as raw material, cost is higher, and the hydrogen-storing material aperture high temperature ageing resistace less, hydrogen-storing material of simultaneously preparing is poor.
Chinese patent patent publication No. is that the patent of invention of CN101940921A discloses a kind of bilayer structured oxygen storage material and preparation method thereof, by cerium zirconium sosoloid and Large ratio surface γ-Al
2o
3be composited, its preparation method is: (1) gets lanthanum nitrate hexahydrate, cerous nitrate solution, yttrium nitrate and zirconium nitrate solution, inserts in container, to add ammoniacal liquor to precipitate to be precipitated thing; (2) in the sediment of step (1), add the industrial hydrogen peroxide of cerium oxide quality, obtain cerium zirconium precursor compound; (3) by presoma and γ-Al
2o
3mass ratio 1:1 mixes, stirring obtains mixture; (4) by the mixture in step (3) through washing, filter, adding after surfactant, then drying, roasting, air-flow crushing, obtain double-deck powder hydrogen-storing material.
Said method is with cerium zirconium precursor body and γ-Al
2o
3mechanical mixture, this just caused the mixing uniformity of aluminium oxide and cerium zirconium compound oxide and the caking property of aluminium oxide and cerium zirconium compound oxide poor, affect catalytic performance and the high-temperature thermal stability agent of hydrogen-storing material.
The Chinese patent patent No. is that 98108256.4 patent of invention discloses a kind of method that has the hydrogen-storing material of high thermal stability and prepare this material, cerium oxide and at least one stabilizing agent high degree of dispersion that is selected from praseodymium oxide, lanthana, yittrium oxide and neodymia, on the specific surface of the high surface area carriers such as aluminium oxide, zirconia, titanium oxide, silica or other oxides, and then are obtained through roasting; Its preparation method be the precursor of described stabilizing agent dissolving and cerium oxide be added to a kind of preprepared, constantly in the water dispersion of the selected carrier mass that stirring, then by adding alkali, slowly improve the pH value of dispersion to 8-10, thereby stabilizing agent and cerium oxide are deposited on carrier mass.
Said method does not carry out surface treatment to carrier, and granular size, the pattern etc. of carrier all affect the cohesive force of coated uniformity and coat and carrier, affects catalytic activity and the high high-temp stability of hydrogen-storing material.
To sum up, the existing research for Ce-Zr-Al based rare earth oxygen storage material is less, and adhesion and high temperature ageing resistance between cerium zirconium and aluminium oxide exist larger contradiction, and the high temperature ageing resistance of material is poor.
Therefore, need especially a kind of aluminium Ce-Zr based composite oxide catalysis material and preparation method thereof, to solve the above-mentioned existing problem existing.
Summary of the invention
The object of the present invention is to provide a kind of aluminium Ce-Zr based composite oxide catalysis material and preparation method thereof, to overcome the deficiencies in the prior art.
The invention provides a kind of aluminium Ce-Zr based composite oxide catalysis material, the composite oxides that formed by cerium oxide, zirconia, aluminium oxide and other rare earth oxides except cerium, its percentage by weight is as follows:
Cerium oxide: 15-30%;
Zirconia: 5-20%;
Aluminium oxide: 50-75%;
Other rare earth oxides: 0-5% except cerium.
Described other rare earth oxides except cerium are selected from one or more the combination in lanthana, yittrium oxide, praseodymium oxide and neodymia;
The preparation method of aluminium Ce-Zr based composite oxide catalysis material provided by the invention, comprises the steps:
Boehmite is hydrolyzed with water making beating at 80 ~ 100 DEG C, obtains slurries A
Cerous nitrate, other rare earth soluble-salts and zirconium nitrate except cerium is water-soluble, obtain hybrid metal nitrate solution B;
Then slurries A and hybrid metal nitrate solution B are mixed, it is 9-10 that the ammoniacal liquor that is 10～20% by weight concentration regulates pH value;
Add Ce
3+be oxidized to Ce
4+required stoichiometric hydrogen peroxide, continues insulated and stirred 2～4h;
Then cooling, suction filtration, washing, to neutral, is dried 4 ~ 12h at 70 ~ 120 DEG C, and roasting 3-6h at 550-750 DEG C, obtains described aluminium Ce-Zr based composite oxide catalysis material.
Described boehmite is that pore volume is the boehmite of 0.3-0.7g/ml.
Described other rare earth solubility nitrate except cerium are selected from the one or more combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate, neodymium nitrate, or nitric acid reacts the corresponding nitrate solution of generation with lanthana, yittrium oxide, praseodymium oxide and neodymia.
In described mixed metal salt salpeter solution, the ratio of each nitrate is:
Cerous nitrate 15-30%;
Zirconium nitrate 5-20%;
Other rare earth solubility nitrate 0-5% except cerium.
Aluminium Ce-Zr based composite oxide catalysis material of the present invention and preparation method thereof, compared with prior art, by processing that aluminium oxide is hydrolyzed, forms aluminium hydroxide, then with mixed salt solution coagent Hydrothermal Synthesis.Interaction between oxidation reinforced aluminium and Ce-Zr based composite oxide on the one hand; Ensure fully on the other hand the homogeneity between aluminium oxide and Ce-Zr based composite oxide, have that specific area is large, high temperature ageing resistance is good and store oxygen ability high, be applicable to waste gas purification or the catalytic combustions such as purifying vehicle exhaust, organic exhaust gas elimination and natural gas catalytic combustion.
Brief description of the drawings
Fig. 1 is the XRD schematic diagram that embodiments of the invention 1 are prepared aluminium Ce-Zr based composite oxide catalysis material.
Detailed description of the invention
In embodiment, if no special instructions, component is weight percent concentration.
Embodiment 1
Be that 70% boehmite 85.7kg joins in 200kg pure water by alumina content, in 80 DEG C of aqueous solution, stir 4h; Then under heat-retaining condition, 64.9kg cerous nitrate, 29.8kg zirconium nitrate, 13.5kg lanthanum nitrate are dissolved with 500kg pure water, join in above-mentioned solution; Slowly add 10% ammoniacal liquor, the pH that controls terminal is 9, adds 30% hydrogen peroxide 11.8kg, insulation 4h.Then sediment is extremely neutral through suction filtration, washing, dry 12h at 70 DEG C, 550 DEG C of roasting 6h, obtain described aluminium Ce-Zr based composite oxide catalysis material.
Consisting of of this material, cerium oxide 24%, zirconia 11%, lanthana 5%, aluminium oxide 60%.The fresh specific area of this material is 151m
2/ g, the specific area that this material is obtained after 1000 DEG C of roasting 4h is 108m
2/ g.
Embodiment 2
Be that 70% boehmite 85.7kg joins in 200kg pure water by alumina content, in 100 DEG C of aqueous solution, stir 4h; 64.9kg cerous nitrate, 29.8kg zirconium nitrate, 13.5kg lanthanum nitrate are dissolved with 500kg pure water, join in above-mentioned solution; Slowly add 10% ammoniacal liquor, the pH that controls terminal is 10, adds 30% hydrogen peroxide 11.8kg, insulation 2h; Then sediment is extremely neutral through suction filtration, washing, dry 4h at 120 DEG C, 550 DEG C of roasting 5h, obtain described aluminium Ce-Zr based composite oxide catalysis material.
Consisting of of this material, cerium oxide 24%, zirconia 11%, lanthana 5%, aluminium oxide 60%.The fresh specific area of this material is 182m
2/ g, the specific area that this material is obtained after 1000 DEG C of roasting 4h is 132m
2/ g.
Embodiment 3
Be that 70% boehmite 107kg joins in 200kg pure water by alumina content, in 80 DEG C of aqueous solution, stir 3h; 40.5kg cerous nitrate, 13.5kg zirconium nitrate are dissolved with 500kg pure water, join in above-mentioned solution; Slowly add 15% ammoniacal liquor, the pH that controls terminal is 9.5, adds 30% hydrogen peroxide 11.8kg, insulation 2h; Then sediment is extremely neutral through suction filtration, washing, dry 8h at 100 DEG C, 750 DEG C of roasting 3h, obtain described aluminium Ce-Zr based composite oxide catalysis material.
Consisting of of this material, cerium oxide 15%, zirconia 5%, aluminium oxide 75%.The fresh specific area of this material is 195m
2/ g, the specific area that this material is obtained after 1000 DEG C of roasting 4h is 151m
2/ g.
Embodiment 4
Be that 70% boehmite 71.5kg joins in 200kg pure water by alumina content, in 90 DEG C of aqueous solution, stir 2h; 81kg cerous nitrate, 52.6kg zirconium nitrate are dissolved with 500kg pure water, join in above-mentioned solution; Slowly add 10% ammoniacal liquor, the pH that controls terminal is 9.5, adds 30% hydrogen peroxide 11.8kg, insulation 1h.Then sediment is extremely neutral through suction filtration, washing, dry 10h at 80 DEG C, 700 DEG C of roasting 4h, obtain described aluminium Ce-Zr based composite oxide catalysis material.
Consisting of of this material, cerium oxide 30%, zirconia 20%, aluminium oxide 50%.The fresh specific area of this material is 162m
2/ g, the specific area that this material is obtained after 1000 DEG C of roasting 4h is 154m
2/ g.
Embodiment 5
Be that 70% boehmite 95.7kg joins in 200kg pure water by alumina content, in 90 DEG C of aqueous solution, stir 2h; By 54kg cerous nitrate, 26.3kg zirconium nitrate, 2.7kg yttrium nitrate, 1.5kg praseodymium nitrate, 4.5kg neodymium nitrate dissolves with 500kg pure water, joins in above-mentioned solution; Slowly add 20% ammoniacal liquor, the pH that controls terminal is 9.5, adds 30% hydrogen peroxide 9.5kg, insulation 2h.Then sediment is extremely neutral through suction filtration, washing, dry 7h at 120 DEG C, 650 DEG C of roasting 4h, obtain described aluminium Ce-Zr based composite oxide catalysis material.
Consisting of of this material, cerium oxide 20%, zirconia 10%, yittrium oxide 1%, praseodymium oxide 0.5%, neodymia 1.5%, aluminium oxide 67%.The fresh specific area of this material is 193m
2/ g, the specific area that this material is obtained after 1000 DEG C of roasting 4h is 145m
2/ g.
More than show and described general principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications; these changes and improvements all fall in the claimed scope of the invention, and the claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (2)
1. the method for preparing aluminium Ce-Zr based composite oxide catalysis material, is characterized in that, comprises the steps:
Boehmite is hydrolyzed with water making beating at 80～100 DEG C, obtains slurries A;
Cerous nitrate, other rare earth soluble-salts and zirconium nitrate except cerium is water-soluble, obtain hybrid metal nitrate solution B;
Then slurries A and hybrid metal nitrate solution B are mixed, regulating pH value with ammoniacal liquor is 9-10;
Add Ce
3+be oxidized to Ce
4+required stoichiometric hydrogen peroxide, continues insulated and stirred 2～4h;
Then cooling, suction filtration, washing, to neutral, is dried 4～12h at 70～120 DEG C, and roasting 3-6h at 550-750 DEG C, obtains described aluminium Ce-Zr based composite oxide catalysis material; The percentage by weight of component is as follows:
Described other rare earth oxides except cerium are selected from one or more the combination in lanthana, yittrium oxide, praseodymium oxide and neodymia, and described boehmite is that pore volume is the boehmite of 0.3-0.7ml/g.
2. method according to claim 1, it is characterized in that, described other rare earth solubility nitrate except cerium are selected from the one or more combination in lanthanum nitrate, yttrium nitrate, praseodymium nitrate, neodymium nitrate, or nitric acid reacts the corresponding nitrate solution of generation with lanthana, yittrium oxide, praseodymium oxide and neodymia.
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| CN103831100B (en) * | 2014-03-05 | 2016-03-23 | 浙江达峰汽车技术有限公司 | A kind of high bond strength POC coating |
| CN104445317B (en) * | 2014-11-12 | 2016-09-14 | 中国海洋石油总公司 | A kind of preparation method of modified boehmite |
| CN104984747B (en) * | 2015-06-19 | 2019-07-23 | 中煤科工集团重庆研究院有限公司 | Alumina composite oxide and preparation method thereof |
| KR102538140B1 (en) * | 2016-12-23 | 2023-05-31 | 로디아 오퍼레이션스 | Aging resistant mixed oxides made from cerium, zirconium, aluminum and lanthanum for automotive catalytic converters |
| CN110586145B (en) * | 2019-09-04 | 2022-07-26 | 昆明贵金属研究所 | A kind of cerium-zirconium-aluminum composite material with high thermal stability, preparation method and application thereof |
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