CN103191712A - Cerium oxide and zirconium oxide based composite rare earth oxide with favorable ageing resistance and high reduction activity and preparation method of cerium oxide and zirconium oxide based composite rare earth oxide - Google Patents
Cerium oxide and zirconium oxide based composite rare earth oxide with favorable ageing resistance and high reduction activity and preparation method of cerium oxide and zirconium oxide based composite rare earth oxide Download PDFInfo
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- CN103191712A CN103191712A CN2013101169597A CN201310116959A CN103191712A CN 103191712 A CN103191712 A CN 103191712A CN 2013101169597 A CN2013101169597 A CN 2013101169597A CN 201310116959 A CN201310116959 A CN 201310116959A CN 103191712 A CN103191712 A CN 103191712A
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- earth oxide
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- 229910001404 rare earth metal oxide Inorganic materials 0.000 title claims abstract description 82
- 239000002131 composite material Substances 0.000 title claims abstract description 79
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 76
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title claims abstract description 49
- 230000032683 aging Effects 0.000 title claims abstract description 17
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 title abstract 5
- 229910001928 zirconium oxide Inorganic materials 0.000 title abstract 5
- 230000010757 Reduction Activity Effects 0.000 title abstract 2
- 230000002349 favourable effect Effects 0.000 title abstract 2
- 239000000243 solution Substances 0.000 claims abstract description 76
- 238000001354 calcination Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 26
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000004202 carbamide Substances 0.000 claims abstract description 17
- 239000002243 precursor Substances 0.000 claims abstract description 17
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 17
- -1 rare earth metal salt Chemical class 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 142
- 239000012190 activator Substances 0.000 claims description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 21
- 239000001301 oxygen Substances 0.000 claims description 21
- 229910052760 oxygen Inorganic materials 0.000 claims description 21
- 229910052726 zirconium Inorganic materials 0.000 claims description 21
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 20
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 claims description 17
- 239000011148 porous material Substances 0.000 claims description 17
- 229910021653 sulphate ion Inorganic materials 0.000 claims description 16
- IJZKJRUCRGJGKO-UHFFFAOYSA-N oxalic acid;zirconium Chemical compound [Zr].OC(=O)C(O)=O IJZKJRUCRGJGKO-UHFFFAOYSA-N 0.000 claims description 15
- 238000005303 weighing Methods 0.000 claims description 15
- 239000013049 sediment Substances 0.000 claims description 14
- 238000003860 storage Methods 0.000 claims description 14
- 150000000703 Cerium Chemical class 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 9
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 9
- 238000010298 pulverizing process Methods 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 6
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- 238000000498 ball milling Methods 0.000 claims description 4
- 238000003801 milling Methods 0.000 claims description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
- 235000011151 potassium sulphates Nutrition 0.000 claims description 4
- 239000006104 solid solution Substances 0.000 claims description 4
- 150000003754 zirconium Chemical class 0.000 claims description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910000311 lanthanide oxide Inorganic materials 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 3
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical class [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 abstract 3
- XMHIUKTWLZUKEX-UHFFFAOYSA-N hexacosanoic acid Chemical compound CCCCCCCCCCCCCCCCCCCCCCCCCC(O)=O XMHIUKTWLZUKEX-UHFFFAOYSA-N 0.000 abstract 2
- QRTRRDMHGTZPBF-UHFFFAOYSA-L oxygen(2-);zirconium(4+);sulfate Chemical compound [O-2].[Zr+4].[O-]S([O-])(=O)=O QRTRRDMHGTZPBF-UHFFFAOYSA-L 0.000 abstract 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000002585 base Substances 0.000 description 53
- 229910052684 Cerium Inorganic materials 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 15
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 14
- 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 14
- 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
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 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 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 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
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000001603 reducing effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 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 3
- 230000003679 aging effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 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 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- XEEVLJKYYUVTRC-UHFFFAOYSA-N oxomalonic acid Chemical compound OC(=O)C(=O)C(O)=O XEEVLJKYYUVTRC-UHFFFAOYSA-N 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
- 239000000843 powder Substances 0.000 description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical group [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007423 decrease Effects 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
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Chemical class 0.000 description 1
- 239000002184 metal Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B01J35/40—
-
- B01J35/613—
-
- B01J35/635—
-
- B01J35/66—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/30—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6
- C01F17/32—Compounds containing rare earth metals and at least one element other than a rare earth metal, oxygen or hydrogen, e.g. La4S3Br6 oxide or hydroxide being the only anion, e.g. NaCeO2 or MgxCayEuO
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G25/00—Compounds of zirconium
- C01G25/06—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/90—Other properties not specified above
Abstract
The invention discloses a preparation method of a cerium oxide and zirconium oxide based composite rare earth oxide. The method comprises the following steps of: (1) weighting zircon salt with a certain mass and preparing a zircon salt solution; (2) mixing urea and sulfuric acid or sulfate to prepare an activating agent solution; (3) heating the zircon salt solution under the room temperature, meanwhile, slowly and dropwise adding the activating agent solution, controlling the temperature rise speed to ensure that the temperature is raised to 60 DEG C after the addition of the activating agent solution is finished, continuing to raising the temperature to 90-95 DEG C, and keeping the temperature for 20-100min to form a basic zirconium sulfate composite salt precursor solution; (4) preparing soluble cerate and rare earth metal salt, adding the soluble cerate and the rare earth metal salt into the basic zirconium sulfate composite salt precursor solution, and settling by using a soluble hydroxide or an aqueous solution of ammonia; and (5) filtering and cleaning precipitates, and then, calcining the precipitates to obtain the cerium oxide and zirconium oxide based composite rare earth oxide. The cerium oxide and zirconium oxide based composite rare earth oxide prepared by using the method provided by the invention has favorable ageing resistance and high reduction activity.
Description
Technical field
The present invention relates to a kind of cerium oxide zirconia base composite rare-earth oxide and preparation method thereof, especially a kind of cerium oxide zirconia base composite rare-earth oxide with good resistance ageing properties, high reducing activity and preparation method thereof.
Background technology
Because automobile, motorcycle and the tractor particularly exhaust emissions of motor vehicle such as automobile have become the main source of atmospheric pollution in big and medium-sized cities, the world, and controller motor-car pollution emission, effective measures are the outer automobile exhaust purifiers of fitting machine.As the active carbon layer of automobile exhaust purifier carrier, cerium pick composite has become the automobile catalyst indispensable material.Cerium pick composite has good oxygen storage capacity and high-temperature hydrothermal stability, can effectively widen the air-fuel ratio window of auto-exhaust catalyst, improves performance and the service life of catalyst.Particularly cerium pick can be improved the availability of precious metal catalyst dispersion of nano-particles degree and noble metal, reduces noble metal dosage, thereby reduces the Preparation of catalysts cost.Cerium pick composite oxides both can effectively reduce the atmosphere pollution that motor vehicle exhaust emission causes, and can promote the industry of pick chemicals and ZrO again
2Product will promote also that to the development of deep processing field the rare-earth products structural adjustment transforms to high value added product.
Cerium zirconium compound catalyze material has high stable, high reducing power and the high characteristics of storing the oxygen ability, makes three-way catalyst that very high low-temperature catalyzed conversion capability be arranged.Its excellent properties derives from the special electronic structure of rare earth in characteristic.Cerium has the valence state changeability, excess of oxygen can be stored under the oxygen enrichment state and be converted into quadrivalent cerium, promotes the reduction of waste gas to purify.When oxygen deprivation, can transfer oxygen evolution to trivalent cerium, promote the oxidation, purification of waste gas.And ZrO
2Can improve the high-temperature stability of material, keep the material higher specific surface area.CeO
2And ZrO
2Can be compound in very big ratio range, form stable cerium zirconium sosoloid, have the not available characteristic advantage of single Ce, Zr.In addition, in cerium oxide, mix ZrO
2To stablize cube fluorite structure of cerium oxide, can improve the high-temperature stability of catalyst, reduce Ce
4+Activation energy and the initial reduction temperature of body mutually, make the oxygen storage capacity (OSC) of cerium zirconia material in bigger temperature range, high conversion rate be arranged.
The interpolation of different proportion rare earth element has stoped the growth of cerium zirconium crystal grain, has suppressed the high temperature sintering phenomenon of catalyst and the effect that causes catalyst activity to reduce significantly thereof, has improved the high high-temp stability of catalyst.For the combustion conditions that satisfies Automobile Complex and the discharge standard of increasingly stringent, auto-exhaust catalyst generally uses under high-speed and high temperature (reaching sometimes more than 1000 ℃) condition, and its installation site is more and more near engine, and serviceability temperature is more and more higher.The cerium Zr catalyst of conventional method preparation at high temperature can keep storing up preferably the oxygen performance, can satisfy high-performing car tail gas clean-up three-way catalyst to the requirement of hydrogen-storing material storage oxygen performance and high-temperature stability thereof, but cerium zirconium sosoloid is structure thermally-stabilised relatively poor at high temperature, and specific area is less than normal.As report prepared cerium zirconium hydrogen-storing material behind 1000 ℃ of roasting 4hr, 200 ℃ of following oxygen storage capacities still can reach more than the 300 μ mol/g, but specific area is less than 10g/m
2Three-way catalyst must have stronger durability under high-speed, the conventional cerium zirconia material cubic phase ZrO that dissociates under higher temperature
2, make single cube to change heterogeneous coexistence mutually into, be separated and the instability of texture property can cause the serious decline of catalyst performance.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art part and provide a kind of total pore to hold big, fresh specific area height, specific area Heat stability is good at high temperature, have the cerium oxide zirconia base composite rare-earth oxide of good resistance ageing properties and high reducing activity; Simultaneously, the present invention also provides the preparation method of described cerium oxide zirconia base composite rare-earth oxide.
For achieving the above object, the technical scheme that the present invention takes is: a kind of preparation method of cerium oxide zirconia base composite rare-earth oxide may further comprise the steps:
(1) preparation solubility zirconates: take by weighing the certain mass zirconates, zirconates is water-soluble, be mixed with zirconium salt solution;
(2) preparation activator solution: urea and sulfuric acid or sulfate are hybridly prepared into activator solution, the mass ratio of zirconates is 1:99～2:98 in wherein said urea and the step (1), and the mass ratio of zirconates is 1:3～3:5 in described sulfate radical and the step (1);
(3) under the room temperature zirconium salt solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 90～95 ℃, insulation 20～100min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) preparation solubility cerium salt and rare earth metal salt, and in the zirconium basic sulphate complex salt precursor solution with described solubility cerium salt and rare earth metal salt adding step (3) gained, precipitate with solubility hydroxide or ammonia spirit then, sediment got;
(5) with step (4) gained sediment filtration washing, calcining gets cerium oxide zirconia base composite rare-earth oxide then.
The present application people is through research widely, and found through experiments, by the activator solution in the configuration step (2), described activator solution is slowly joined in the soluble zirconium salting liquid, constantly heat up in the process that drips, when temperature rose to 60 ℃, the urea in the activator decomposed, sulfate ion and pick ion react simultaneously, control hydrolysis of urea by the control programming rate and become NH
3And CO
2Speed, the NH of generation
3And CO
2Play the effect of pore-creating and dispersion, make and improved its reactivity by the zirconium basic sulphate complex salt presoma that finally can form the short texture porous; In described zirconium basic sulphate complex salt presoma, add cerium salt and rare earth metal salt solutions, add alkali reaction then and generate cerium pick class rare-earth hydroxide, thereby form good cerium pick solid solution, improved ageing resistance and the reproducibility of products obtained therefrom.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, the zirconates in the described step (1) is at least a in zirconium oxychloride, zirconyl nitrate and the oxalic acid zirconium.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, the sulfate in the described step (2) is at least a in sodium sulphate, potassium sulfate, the ammonium sulfate.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, the solubility cerium salt in the described step (4) and rare earth metal salt are at least a in nitrate and the chlorate.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, the calcining heat in the described step (5) is 400～900 ℃, and calcination time is 1～5h.Calcination atmosphere can be set in the atmosphere or oxidizing atmosphere.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, described method is further comprising the steps of:
(6) the cerium oxide zirconia base composite rare-earth oxide after will calcining is pulverized, and at least a in hammer pulverizing, planetary mills pulverizing, ball milling, the airflow milling adopted in described pulverizing.According to different purposes, can select one or more methods and usefulness in hammer pulverizing, planetary mills pulverizing, ball milling, the airflow milling.
As the preparation method's of cerium oxide zirconia base composite rare-earth oxide of the present invention preferred embodiment, the addition of described zirconates, cerium salt and rare earth metal salt is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 20～75wt%, CeO
2: the composition proportion of 15～75wt%, rare earth oxide: 1～30wt% takes by weighing.The addition of zirconates, cerium salt and rare earth metal salt in the described method is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 20～75wt%, CeO
2: the composition proportion of 15～75wt% recently takes by weighing according to the needed stoichiometry of various oxides.
The invention also discloses a kind of employing cerium oxide zirconia base composite rare-earth oxide of preparing of method as mentioned above, described cerium oxide zirconia base composite rare-earth oxide contain following component by mass percent: ZrO
2: 20～75wt%, CeO
2: 15～75wt%, rare earth oxide: 1～30wt%;
The granularity of described cerium oxide zirconia base composite rare-earth oxide is 5～20nm, wherein ZrO
2, CeO
2Exist with the form of rare earth oxide with solid solution.
As the preferred embodiment of cerium oxide zirconia base composite rare-earth oxide of the present invention, described rare earth oxide is at least a in lanthanide oxide, scandium oxide and the yittrium oxide.
The cerium oxide zirconia base composite rare-earth oxide that adopts the method for the invention to prepare, its total pore volume is no less than 0.55ml/g, has 10～100nm pore volume and is not less than 0.25ml/g, has 100nm～10 μ m pore volume and is not higher than 0.2ml/g; Fresh specific area 〉=70m
2/ g, aging specific area is not less than 50m behind 1000 ℃ of heat treatment 3h
2/ g is not less than 20m at 1100 ℃ of heat treatment 3h or aging specific area
2/ g; Fresh oxygen storage capacity 〉=250 μ mol/g, aging oxygen storage capacity 〉=200 μ mol/g behind 1000 ℃ of heat treatment 3h.
The preparation method of cerium oxide zirconia base composite rare-earth oxide of the present invention, selection by activator solution and the control of programming rate when adding activator, can form the zirconium basic sulphate salt precursor body of porosity and looseness, improve its reactivity, then by adding cerium salt and metal salt solution, add alkali reaction and generate cerium pick class rare-earth hydroxide, thereby form good cerium pick solid solution, improved ageing resistance and the reproducibility of products obtained therefrom.The cerium oxide zirconia base composite rare-earth oxide that adopts the method for the invention to prepare, total pore holds big, and fresh specific area height has good reactivity, specific area Heat stability is good at high temperature has good ageing resistace and high reducing activity.
The specific embodiment
For the purpose, technical solutions and advantages of the present invention better are described, the invention will be further described below in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of cerium oxide zirconia base composite rare-earth oxide said method comprising the steps of:
(1) preparation solubility zirconates: take by weighing the certain mass zirconium oxychloride, zirconium oxychloride is water-soluble, be mixed with the zirconyl chloride solution of 25wt%;
(2) preparation activator solution: urea and sulfuric acid are hybridly prepared into the activator solution of 10wt%, and the mass ratio of the middle zirconium oxychloride of wherein said urea and step (1) is 1:99, and the mass ratio of the middle zirconium oxychloride of described sulfate radical and step (1) is 3:5;
(3) under the room temperature zirconyl chloride solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 90 ℃, insulation 100min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) cerous nitrate solution of preparation 20wt% and the lanthanum nitrate hexahydrate of 20wt%, and in the zirconium basic sulphate complex salt precursor solution with described cerous nitrate solution and lanthanum nitrate hexahydrate adding step (3) gained, ammoniacal liquor 500g with 25wt% precipitates then, gets sediment;
(5) with step (4) gained sediment filtration washing, calcining then, calcining heat is 400 ℃, calcination time is 5h, cerium oxide zirconia base composite rare-earth oxide after the calcining is adopted ball mill grinding, and getting granularity is the cerium oxide zirconia base composite rare-earth oxide of 20nm.
In the present embodiment, the addition of described zirconium oxychloride, cerous nitrate and lanthanum nitrate is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 20wt%, CeO
2: the composition proportion of 75wt%, lanthana: 5wt% takes by weighing.
Embodiment 2
A kind of preparation method of cerium oxide zirconia base composite rare-earth oxide said method comprising the steps of:
(1) preparation solubility zirconates: take by weighing the certain mass zirconyl nitrate, zirconyl nitrate is water-soluble, be mixed with the zirconyl nitrate solution of 20wt%;
(2) preparation activator solution: urea and sodium sulphate are hybridly prepared into the activator solution of 15wt%, and the mass ratio of the middle zirconyl nitrate of wherein said urea and step (1) is 2:98, and the mass ratio of the middle zirconyl nitrate of described sulfate radical and step (1) is 1:3;
(3) under the room temperature zirconyl nitrate solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 92 ℃, insulation 60min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) preparation 20wt% solution of cerium chloride by oxidation and 25wt% praseodymium nitrate solution, and in the zirconium basic sulphate complex salt precursor solution with described solution of cerium chloride by oxidation and praseodymium nitrate solution adding step (3) gained, sodium hydroxide solution 550g with 20wt% precipitates then, gets sediment;
(5) with step (4) gained sediment filtration washing, calcining then, calcining heat is 900 ℃, calcination time is 1h, adopt airflow milling to pulverize the cerium oxide zirconia base composite rare-earth oxide after the calcining, getting granularity is the cerium oxide zirconia base composite rare-earth oxide of 15nm.
In the present embodiment, the addition of described zirconyl nitrate, cerium chloride and praseodymium nitrate is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 75wt%, CeO
2: the composition proportion of 15wt%, praseodymium oxide: 10wt% takes by weighing.
Embodiment 3
A kind of preparation method of cerium oxide zirconia base composite rare-earth oxide said method comprising the steps of:
(1) preparation solubility zirconates: take by weighing certain mass oxalic acid zirconium, the oxalic acid zirconium is water-soluble, be mixed with the oxalic acid zirconium solution of 25wt%;
(2) preparation activator solution: urea and potassium sulfate are hybridly prepared into the activator solution of 10wt%, and the mass ratio of wherein said urea and step (1) mesoxalic acid zirconium is 1.5:98.5, and the mass ratio of described sulfate radical and step (1) mesoxalic acid zirconium is 2:5;
(3) under the room temperature oxalic acid zirconium solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 95 ℃, insulation 20min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) preparation 25wt% cerous nitrate and the mixed solution of cerium chloride, the scandium nitrate solution of 20wt%, and the mixed solution of described cerous nitrate and cerium chloride, scandium nitrate solution added in the zirconium basic sulphate complex salt precursor solution of step (3) gained, potassium hydroxide solution 600g with 15wt% precipitates then, get sediment, wherein in the mixed solution of cerous nitrate and cerium chloride, the mass ratio of cerous nitrate and cerium chloride is 1:1;
(5) with step (4) gained sediment filtration washing, calcining then, calcining heat is 800 ℃, calcination time is 4h, adopt the method for ball milling and planetary mills and usefulness to pulverize the cerium oxide zirconia base composite rare-earth oxide after the calcining, getting granularity is the cerium oxide zirconia base composite rare-earth oxide of 5nm.
In the present embodiment, the addition of described oxalic acid zirconium, cerous nitrate, cerium chloride and scandium nitrate is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 75wt%, CeO
2: the composition proportion of 20wt%, scandium oxide: 5wt% takes by weighing.
Embodiment 4
A kind of preparation method of cerium oxide zirconia base composite rare-earth oxide said method comprising the steps of:
(1) preparation solubility zirconates: take by weighing certain mass zirconyl nitrate and oxalic acid zirconium, zirconyl nitrate and oxalic acid zirconium is water-soluble, be mixed with the zirconyl nitrate of 25wt% and the mixed solution of oxalic acid zirconium, wherein, the mass ratio of zirconyl nitrate and oxalic acid zirconium is 2:1;
(2) preparation activator solution: the activator solution that urea and ammonium sulfate is hybridly prepared into 12wt%, the mass ratio of zirconyl nitrate and oxalic acid zirconium total amount is 1:99 in wherein said urea and the step (1), and the mass ratio of zirconyl nitrate and oxalic acid zirconium total amount is 1:2 in described sulfate radical and the step (1);
(3) under the room temperature zirconyl nitrate in the step (1) and oxalic acid zirconium mixed solution are heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 93 ℃, insulation 80min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) mixed solution of preparation 20wt% cerous nitrate solution, 25wt% lanthanum nitrate and praseodymium nitrate, and the mixed solution of described cerous nitrate solution, lanthanum nitrate and praseodymium nitrate is added in the zirconium basic sulphate complex salt precursor solution of step (3) gained, NaOH 600g solution with 20wt% precipitates then, get sediment, wherein in the mixed solution of lanthanum nitrate and praseodymium nitrate, the mass ratio of lanthanum nitrate and praseodymium nitrate is 3:1;
(5) with step (4) gained sediment filtration washing, calcining then, calcining heat is 600 ℃, calcination time is 3h, adopt hammer to pulverize the cerium oxide zirconia base composite rare-earth oxide after the calcining, getting granularity is the cerium oxide zirconia base composite rare-earth oxide of 18nm.
In the present embodiment, the addition of described zirconyl nitrate, oxalic acid zirconium, cerous nitrate, lanthanum nitrate, praseodymium nitrate is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 30wt%, CeO
2: the composition proportion of 40wt%, lanthana and praseodymium oxide: 30wt% takes by weighing.
Embodiment 5
A kind of preparation method of cerium oxide zirconia base composite rare-earth oxide said method comprising the steps of:
(1) preparation solubility zirconates: take by weighing the certain mass zirconium nitrate, zirconium nitrate is water-soluble, be mixed with the zirconium nitrate solution of 25wt%;
(2) preparation activator solution: urea and potassium sulfate are hybridly prepared into the 10wt% activator solution, and the mass ratio of zirconium nitrate is 2:98 in wherein said urea and the step (1), and the mass ratio of zirconium nitrate is 9:20 in described sulfate radical and the step (1);
(3) under the room temperature zirconium nitrate solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 95 ℃, insulation 40min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) cerous nitrate solution of preparation 25wt% and the yttrium nitrate solution of 20wt%, and in the zirconium basic sulphate complex salt precursor solution with described cerous nitrate solution and yttrium nitrate solution adding step (3) gained, precipitate with 25wt% potassium hydroxide solution 500g then, get sediment;
(5) with step (4) gained sediment filtration washing, calcining then, calcining heat is 500 ℃, calcination time is 2, cerium oxide zirconia base composite rare-earth oxide planetary mills after the calcining is pulverized, and getting granularity is the cerium oxide zirconia base composite rare-earth oxide of 10nm.
In the present embodiment, the addition of described zirconium nitrate, cerous nitrate and yttrium nitrate is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 50wt%, CeO
2: the composition proportion of 49wt%, yittrium oxide: 1wt% takes by weighing.
Embodiment 6
Adopt the method for the invention to prepare the mensuration of the physical property of gained cerium oxide zirconia base composite rare-earth oxide
(1) total pore volume
Method of testing: cerium oxide zirconia base composite rare-earth oxide to be measured is placed at 120 ℃ of dry 2h is dried to room temperature in the drying basin, put into the pore-size distribution determinator and measure, measurement range is 0.001～10 μ m.
Adopt said method respectively total pore volume of the cerium oxide zirconia base composite rare-earth oxide of embodiment 1-5 gained to be measured, the results are shown in Table shown in 1.
The total pore volume result of table 1
| Group | Total pore volume | 10～100nm pore volume | 100nm～10um pore volume |
| Embodiment 1 | 0.65ml/g | 0.46ml/g | 0.18ml/g |
| Embodiment 2 | 0.61ml/g | 0.50ml/g | 0.17ml/g |
| Embodiment 3 | 0.62ml/g | 0.44ml/g | 0.18ml/g |
| Embodiment 4 | 0.59ml/g | 0.32ml/g | 0.18ml/g |
| Embodiment 5 | 0.64ml/g | 0.37ml/g | 0.19ml/g |
As seen from Table 1, adopt total pore volume of the cerium oxide zirconia base composite rare-earth oxide of the method for the invention gained to be no less than 0.55ml/g, have 10～100nm pore volume and be not less than 0.25ml/g, have 100nm～10 μ m pore volume and be not higher than 0.2ml/g.
(2) specific area
Method of testing: utilize and measure based on the specific area instrument of liquid nitrogen absorption method.
Adopt said method respectively the specific area of the cerium oxide zirconia base composite rare-earth oxide of embodiment 1-5 gained to be measured, the results are shown in Table shown in 2.
Table 2 specific area result
| Group | Fresh S BET(m 2/g) | Aging S BET 1000℃/3hr(m 2/g) | Aging S BET 1100℃/3hr(m 2/g) |
| Embodiment 1 | 76 | 52 | 21 |
| Embodiment 2 | 72 | 50 | 25 |
| Embodiment 3 | 75 | 56 | 22 |
| Embodiment 4 | 74 | 55 | 23 |
| Embodiment 5 | 75 | 51 | 20 |
As seen from Table 2, adopt the fresh specific area 〉=70m of the cerium oxide zirconia base composite rare-earth oxide of the method for the invention gained
2/ g, aging specific area 〉=50m behind 1000 ℃ of heat treatment 3hr
2/ g, aging specific area 〉=20m behind 1100 ℃ of heat treatment 3hr
2/ g.
(3) oxygen storage capacity
Method of testing: measure H2-TPR according to programmed temperature method.
Get 0.3g cerium oxide zirconia base composite rare-earth oxide powder and be heated to 600 ℃ and in high purity oxygen gas, keep 60min to carry out abundant oxidation.Firing rate with 10 ℃/min in the 5%H2/Ar air-flow is heated to 600 ℃ with cerium oxide zirconia base composite rare-earth oxide powder from 120 ℃, the hydrogen of Xiao Haoing QMS continuous measurement during this period, from the hydrogen consumption curve that obtains and the burst size of area estimation oxygen, be oxygen storage capacity OSC at last.
Adopt said method respectively the oxygen storage capacity of the cerium oxide zirconia base composite rare-earth oxide of embodiment 1-5 gained to be measured, the results are shown in Table shown in 3.
Table 3 oxygen storage capacity result
| Group | Fresh OSC (μ mol/g) | Aging OSC 1000℃/3hr(μmol/g) |
| Embodiment 1 | 255 | 225 |
| Embodiment 2 | 257 | 219 |
| Embodiment 3 | 253 | 220 |
| Embodiment 4 | 250 | 217 |
| Embodiment 5 | 251 | 200 |
As seen from Table 3, adopt the fresh oxygen storage capacity 〉=250 μ mol/g of the cerium oxide zirconia base composite rare-earth oxide of the method for the invention gained, aging oxygen storage capacity 〉=200 μ mol/g behind 1000 ℃ of heat treatment 3hr.
Last institute should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention but not limiting the scope of the invention; although with reference to preferred embodiment the present invention has been done detailed description; those of ordinary skill in the art is to be understood that; can make amendment or be equal to replacement technical scheme of the present invention, and not break away from essence and the scope of technical solution of the present invention.
Claims (10)
1. the preparation method of a cerium oxide zirconia base composite rare-earth oxide is characterized in that, may further comprise the steps:
(1) preparation solubility zirconates: take by weighing the certain mass zirconates, zirconates is water-soluble, be mixed with zirconium salt solution;
(2) preparation activator solution: urea and sulfuric acid or sulfate are hybridly prepared into activator solution, the mass ratio of zirconates is 1:99～2:98 in wherein said urea and the step (1), and the mass ratio of zirconates is 1:3～3:5 in described sulfate radical and the step (1);
(3) under the room temperature zirconium salt solution in the step (1) is heated, slowly drip the activator solution in the step (2) simultaneously, the control programming rate, temperature rose to 60 ℃ when activator solution was dropwised, continue then to heat up, be warming up to 90～95 ℃, insulation 20～100min, formation zirconium basic sulphate complex salt precursor solution from 60 ℃ in the 30min;
(4) preparation solubility cerium salt and rare earth metal salt, and in the zirconium basic sulphate complex salt precursor solution with described solubility cerium salt and rare earth metal salt adding step (3) gained, precipitate with solubility hydroxide or ammonia spirit then, sediment got;
(5) with step (4) gained sediment filtration washing, calcining gets cerium oxide zirconia base composite rare-earth oxide then.
2. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, the zirconates in the described step (1) is at least a in zirconium oxychloride, zirconyl nitrate and the oxalic acid zirconium.
3. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, the sulfate in the described step (2) is at least a in sodium sulphate, potassium sulfate, the ammonium sulfate.
4. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, the solubility cerium salt in the described step (4) and rare earth metal salt are at least a in nitrate and the chlorate.
5. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, the calcining heat in the described step (5) is 400～900 ℃, and calcination time is 1～5h.
6. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, described method is further comprising the steps of:
(6) the cerium oxide zirconia base composite rare-earth oxide after will calcining is pulverized, and at least a in hammer pulverizing, planetary mills pulverizing, ball milling, the airflow milling adopted in described pulverizing.
7. the preparation method of cerium oxide zirconia base composite rare-earth oxide as claimed in claim 1 is characterized in that, the addition of described zirconates, cerium salt and rare earth metal salt is according to containing ZrO in the gained cerium oxide zirconia base composite rare-earth oxide
2: 20～75wt%, CeO
2: the composition proportion of 15～75wt%, rare earth oxide: 1～30wt% takes by weighing.
8. an employing is characterized in that as the cerium oxide zirconia base composite rare-earth oxide that method as described in claim 1 or 7 prepares, described cerium oxide zirconia base composite rare-earth oxide contain following component by mass percent: ZrO
2: 20～75wt%, CeO
2: 15～75wt%, rare earth oxide: 1～30wt%;
The granularity of described cerium oxide zirconia base composite rare-earth oxide is 5～20nm, wherein ZrO
2, CeO
2Exist with the form of rare earth oxide with solid solution.
9. cerium oxide zirconia base composite rare-earth oxide as claimed in claim 8 is characterized in that, described rare earth oxide is at least a in lanthanide oxide, scandium oxide and the yittrium oxide.
10. cerium oxide zirconia base composite rare-earth oxide as claimed in claim 8, it is characterized in that, total pore volume of described cerium oxide zirconia base composite rare-earth oxide is no less than 0.55ml/g, have 10～100nm pore volume and be not less than 0.25ml/g, have 100nm～10 μ m pore volume and be not higher than 0.2ml/g; Fresh specific area 〉=70m
2/ g, aging specific area is not less than 50m behind 1000 ℃ of heat treatment 3h
2/ g is not less than 20m at 1100 ℃ of heat treatment 3h or aging specific area
2/ g; Fresh oxygen storage capacity 〉=250 μ mol/g, aging oxygen storage capacity 〉=200 μ mol/g behind 1000 ℃ of heat treatment 3h.
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| Publication number | Publication date |
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| CN103191712B (en) | 2014-12-31 |
| WO2014161204A1 (en) | 2014-10-09 |
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