CN109465003A - A kind of rare earth element composite oxides and its preparation method and application - Google Patents
A kind of rare earth element composite oxides and its preparation method and application Download PDFInfo
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- CN109465003A CN109465003A CN201811173983.3A CN201811173983A CN109465003A CN 109465003 A CN109465003 A CN 109465003A CN 201811173983 A CN201811173983 A CN 201811173983A CN 109465003 A CN109465003 A CN 109465003A
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 35
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002738 chelating agent Substances 0.000 claims abstract description 14
- 230000001376 precipitating effect Effects 0.000 claims abstract description 12
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 11
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 230000009467 reduction Effects 0.000 claims abstract description 7
- 238000010992 reflux Methods 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 230000033228 biological regulation Effects 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 3
- 239000010703 silicon Substances 0.000 claims abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 36
- 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 26
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 13
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 13
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 13
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229910002651 NO3 Inorganic materials 0.000 claims description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 9
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 7
- 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 7
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 5
- 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 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical class OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 4
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000003945 anionic surfactant Substances 0.000 claims description 3
- RUDFQVOCFDJEEF-UHFFFAOYSA-N oxygen(2-);yttrium(3+) Chemical class [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- URDCARMUOSMFFI-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(2-hydroxyethyl)amino]acetic acid Chemical compound OCCN(CC(O)=O)CCN(CC(O)=O)CC(O)=O URDCARMUOSMFFI-UHFFFAOYSA-N 0.000 claims description 2
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical class OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- -1 oxide Chemical compound 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 12
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical group [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 239000000908 ammonium hydroxide Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 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 2
- 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 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 239000005639 Lauric acid Substances 0.000 description 2
- KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- UJVRJBAUJYZFIX-UHFFFAOYSA-N nitric acid;oxozirconium Chemical compound [Zr]=O.O[N+]([O-])=O.O[N+]([O-])=O UJVRJBAUJYZFIX-UHFFFAOYSA-N 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003679 aging effect Effects 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229960003237 betaine Drugs 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- HQPMKSGTIOYHJT-UHFFFAOYSA-N ethane-1,2-diol;propane-1,2-diol Chemical compound OCCO.CC(O)CO HQPMKSGTIOYHJT-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920001993 poloxamer 188 Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 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 1
- 230000001603 reducing effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009283 thermal hydrolysis Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
-
- B01J35/613—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The present invention relates to a kind of rare earth element composite oxides and its preparation method and application.The preparation method includes: that (1) dissolves rare earth element, silicon source respectively, chelating agent is separately added into the solution containing cerium, zirconium rare earth element, then each solution is mixed, obtains the presoma system containing chelating agent, regulation system pH to 1.3-2.0；(2) under stirring condition, system is heated to reflux, obtains colloidal sol；Cooling, the colloidal sol is mixed with the alkaline precipitating agent containing surfactant, the presoma precipitated；(3) presoma of precipitating is placed in autoclave and carries out hydro-thermal reaction, the product after reaction obtains rare earth element composite oxides by dry, calcining.After gained compound is calcined 4 hours at 1000 DEG C and 1100 DEG C, it is respectively provided at least 60m2/ g and at least 40m2The specific surface area of/g；Its highest reduction temperature is no more than 480 DEG C.Meanwhile the compound granularity is small, water absorption rate is low, is conducive to subsequent application performance.
Description
Technical field
The present invention relates to a kind of rare earth element composite oxides and its preparation method and application, belong to inorganic non-metallic green wood
Expect technical field.
Background technique
The composite oxides of cerium zirconium and other rare earth elements are mainly used in moving source catalytic field, such as gasoline engine, bavin
Oil machine vent gas treatment catalysis system.High temperature ageing and reproducibility are most important to the catalytic performance of composite oxides.Aluminium adds
Enter can be improved the high temperature ageing performance of composite oxides, cerium zirconium aluminium and other rare earth elements form solid solution to greatest extent,
More lattice defects can be manufactured, the synergistic effect between each metallic element could play to the greatest extent, to promote solid solution
Ageing properties and reducing property.
Currently, cerium zirconium and the preparation method of other rare earth element composite oxides mainly have coprecipitation, co-precipitation-hydro-thermal
Method etc..However, do not interact each other since the presoma before precipitating mainly exists in the form of dissociated ion,
After alkaline precipitating agent is added, since ion has different solubility product constants, easily there is precipitating and unevenly and after calcining be dissolved
The situation of cation distribution unevenness in body lattice, seriously affects the high-temperature stability and reproducibility of composite oxides.
Summary of the invention
In order to solve the above technical problem, the present invention provides a kind of new methods to adjust pH and water by the way that chelating agent is added
The method of heat is prepared to obtain the solid solution of favorable dispersibility, so that obtaining has excellent hot ageing stability, the cerium of reproducibility, zirconium
And the composite oxides of other rare earth elements.
The technical solution adopted by the present invention is as follows.
A kind of preparation method of rare earth element composite oxides, comprising:
(1) rare earth element, silicon source are dissolved respectively, is separately added into chelating agent into the solution containing cerium, zirconium, then by each solution
Mixing, obtains the presoma system containing chelating agent, regulation system pH to 1.3-2.0；
(2) under stirring condition, system is heated to reflux (i.e. hydro-thermal hydrolysis), obtains colloidal sol；It is cooling, the colloidal sol with contain
The alkaline precipitating agent of surfactant mixes, the presoma precipitated；
(3) presoma of precipitating is placed in autoclave and carries out hydro-thermal reaction, the product after reaction passes through drying, forges
It burns, obtains rare earth element composite oxides.
Further, in step (1), the rare earth element further includes one or more of praseodymium, neodymium, samarium, lanthanum, yttrium etc.；
The rare earth element is used in the form of its nitrate, acetate, chloride, sulfate, oxide etc.；Preferably, cerium, zirconium with
Based on its nitrate, oxide, it is also possible to acetate, chloride, further preferred four valence states nitrate, oxide.
Further, in step (1), source of aluminium is based on the nitrate of aluminium, it is also possible to chloride, sulfate.
Further, in step (1), the chelating agent is selected from NTA series, and EDTA series, DTPA is serial, Gu amine,
HEDTA series, preferably NTA series and EDTA series.The additional amount of the chelating agent is the 1/4-1/ of the respective mole of cerium and zirconium
3。
Further, in step (1), preferably pH to 1.4-1.6.
Further, as another preferred embodiment of the present invention, in step (1), the presoma system includes
The component of following parts by weight: 20-80 parts of cerium oxide, 15-70 parts of zirconium oxides, 5-50 parts of aluminium oxide, 3-5 parts of lanthana or oxidation
Praseodymium or neodymia, 5-15 part yttrium oxide；
Or, the presoma system includes the component of following parts by weight: 35-45 parts of cerium oxide, 35-50 parts of zirconium oxides, 5-
15 parts of aluminium oxide, 3-5 parts of lanthana, 5-10 parts of yttrium oxides, praseodymium oxide or neodymia；It is further preferred that the presoma
System includes the component of following parts by weight: 40 parts of cerium oxide, 40-45 parts of zirconium oxides, 5-10 parts of aluminium oxide, 4-5 parts of lanthana,
5-6 parts of yttrium oxides, praseodymium oxide or neodymia.
Further, in step (1), the partial size of particle is 300-500nm in the presoma system.
Further, described to be heated to reflux the time as 3-4h in step (2).
Further, described to be cooled to 40-50 DEG C in step (2).
Further, in step (2), the surfactant is selected from anionic surfactant, amphoteric ion surface is lived
Property agent or nonionic surfactant；Wherein, the anionic surfactant such as higher fatty acids or salt, hydrosulphate, sulphur
Acidulants；The zwitterionic surfactant such as amino acid pattern, betaine type；The nonionic surfactant such as ester acid is sweet
Grease, polyol type, polyoxyethylene-type, Pluronic F68 etc..Preferably, the surfactant plus
Enter the 50-70% that amount is forerunner's weight.
Further, in step (2), the alkaline precipitating agent is selected from ammonium hydroxide, amine, urea etc..The alkaline precipitating agent
Additional amount be advisable with opposite presoma excessive 10%.
Further, in step (3), the presoma is warming up to 170-190 DEG C in 2-3 hours, keeps the temperature 8-10h；Instead
Product after answering is washed, dry, 5h is calcined in an inert atmosphere in 750-800 DEG C of temperature, then at 500-600 DEG C of air atmosphere
Lower calcining 4h.
The present invention also provides a kind of rare earth element composite oxides prepared by the above method based on cerium, zirconium, storages
Oxygen amount is in 500 μm of olO2/ g to 1200 μm of olO2Between/g.The rare earth element composite oxides have the property that
4h is calcined at (1) 1000 DEG C, BET specific surface is at least 60m2The hole /g, BJH hold 0.60ml/g to 0.85ml/g it
Between, diplopore distribution, based on mesoporous, distribution 2-5nm, 10-50nm is presented in aperture；
4h is calcined at (2) 1100 DEG C, BET specific surface is at least 40m2/g；The hole BJH hold 0.20ml/g to 0.50ml/g it
Between, diplopore distribution, based on mesoporous, distribution 2-3nm, 30-100nm is presented in aperture；
(3) oxygen storage capacity is in 500 μm of olO2/ g to 1200 μm of olO2Between/g；
(4) it is less than or equal to 480 DEG C by the highest reduction temperature of temperature programmed reduction (H2-TPR) measurement.
The present invention also provides application of the above-mentioned rare earth element composite oxides in moving source catalytic field.
Chelating agent is added in existing presoma in the present invention, forms chelate with metal ion, changes the molten of metal ion
Spend product constant；And control system obtains the molten of cerium, zirconium, aluminium and other rare earth elements in the pH value and hydrothermal condition of moment
Colloid system, the composite oxides obtained based on this system have good high-temperature stability and reproducibility；Meanwhile gained is compound
The granularity of object oxide is small, and water absorption rate is low, is conducive to the subsequent application performance of composite oxides.
Specific embodiment
The following examples are used to illustrate the present invention, but are not intended to limit the scope of the present invention..
Embodiment 1 it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, yttrium oxide composition
The present embodiment provides it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, yttrium oxide composition, the combination
Object presses oxide weight percentage composition are as follows: 40%, 45%, 5%, 4%, 6%.
Specific preparation process is as follows:
(1) in first beaker, the corresponding ammonium ceric nitrate of 196g cerium oxide is dissolved in 500ml deionized water, is added
54.4gNTA chelating agent stirs 1h；
In second beaker, the corresponding zirconyl nitrate of 220.5g zirconium oxide is dissolved in 700ml deionized water, is added
85.4gNTA stirs 1h；
By the corresponding aluminum nitrate of 24.5g aluminium oxide, the corresponding lanthanum nitrate of 19.6g lanthana, 29.4g in third beaker
The corresponding yttrium nitrate of yttrium oxide is dissolved in 500ml deionized water, is stirred to clarify.
Solution in three beakers is added into the 4th beaker, liquor capacity is settled to 3500ml, then 40
PH is adjusted to 1.4-1.6 with ammonium hydroxide under the conditions of DEG C, solution is clarified at this time.
(2) solution is transferred in three-necked flask, is heated to reflux 4h, solution is collosol state at this time, is cooled to 40-50 and takes the photograph
Family name's degree.By 1600mL, the ammonium hydroxide of 10mol/l is introduced in 10L stainless steel autoclave, while 245g lauric acid is dissolved in ammonia
In water, and it is settled to 3500mL.
(3) under stiring, the presoma of collosol state is introduced in autoclave, the time controls in 30min or so.
Under stirring, obtained precipitating 50L water is beaten washing three times, then dried, in 750 DEG C of inert atmospheres by 170 DEG C of hydro-thermal 8h
5h is calcined, 5h is calcined in 500 DEG C of air atmospheres, obtains final composite oxides.
Embodiment 2 it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, yttrium oxide composition
The present embodiment provides it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, yttrium oxide composition, the combination
Object presses oxide weight percentage composition are as follows: 40%, 40%, 10%, 5%, 5%.
Specific preparation process is as follows:
In first beaker, the corresponding ammonium ceric nitrate of 196g cerium oxide is dissolved in 500ml deionized water, is added
54.4gNTA chelating agent stirs 1h；
In second beaker, the corresponding zirconyl nitrate of 196g zirconium oxide is dissolved in 700ml deionized water, is added
75.9gNTA stirs 1h；
By the corresponding aluminum nitrate of 49g aluminium oxide, the corresponding lanthanum nitrate of 24.5g lanthana, 24.5g oxygen in third beaker
Change the corresponding yttrium nitrate of yttrium to be dissolved in 500ml deionized water, stir to clarify.
Solution in three beakers is added into the 4th beaker, liquor capacity is settled to 3500ml, then 40
PH is adjusted to 1.4-1.6 with ammonium hydroxide under the conditions of DEG C, solution is clarified at this time.
Solution is transferred in three-necked flask, 4h is heated to reflux, solution is collosol state at this time, is cooled to 40 DEG C -50 DEG C.
By 1650mL, the ammonium hydroxide of 10mol/l is introduced in 10L stainless steel autoclave, while 245g lauric acid being dissolved in ammonium hydroxide,
And it is settled to 3500mL.
Under stiring, the presoma of collosol state is introduced in autoclave, the time controls in 30min or so.It stirs
It mixes down, 170 DEG C of hydro-thermal 8h, obtained precipitating 50L water is beaten washing three times, then dries, is forged in 750 DEG C of inert atmospheres
5h is burnt, 5h is calcined in 500 DEG C of air atmospheres, obtains final composite oxides.
Embodiment 3 it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, praseodymium oxide composition
The present embodiment provides it is a kind of based on cerium oxide, zirconium oxide, aluminium oxide, lanthana, praseodymium oxide composition, the combination
Object presses oxide weight percentage composition are as follows: 40%, 45%, 5%, 4%, 6%.
With embodiment 1, difference is specific implementation method, and what is be added in third beaker is that 29.4g praseodymium oxide is corresponding
Praseodymium nitrate, the ammonium hydroxide volume being added in autoclave are 1544ml.
Compliance test result
Compound obtained by above-described embodiment 1-3 is tested for the property, the results are shown in Table 1.
Wherein, highest reduction temperature passes through temperature programmed reduction (H2- TPR) measurement；Oxygen storage capacity is then according to hydrogen gas consumption
It is calculated.
Table 1
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Cause
This, these modifications or improvements, fall within the scope of the claimed invention without departing from theon the basis of the spirit of the present invention.
Claims (10)
1. a kind of preparation method of rare earth element composite oxides characterized by comprising
(1) rare earth element, silicon source are dissolved respectively, chelating agent is separately added into the solution containing cerium, zirconium rare earth element, then will be each
Solution mixing, obtains the presoma system containing chelating agent, regulation system pH to 1.3-2.0；
(2) under stirring condition, system is heated to reflux, obtains colloidal sol；It is cooling, the colloidal sol and the alkalinity containing surfactant
Precipitant mix, the presoma precipitated；
(3) presoma of precipitating being placed in autoclave and carries out hydro-thermal reaction, the product after reaction passes through dry, calcining,
Obtain rare earth element composite oxides.
2. the preparation method of rare earth element composite oxides according to claim 1, which is characterized in that in step (1), institute
Stating rare earth element further includes one or more of praseodymium, neodymium, samarium, lanthanum, yttrium；
And/or
The rare earth element is used with its nitrate, acetate, chloride, sulfate, oxide form；Preferably, cerium, zirconium
It is used in the form of its nitrate, oxide, acetate, chloride, further preferred four valence states nitrate, oxide.
3. the preparation method of rare earth element composite oxides according to claim 1 or 2, which is characterized in that step (1)
In, the chelating agent is selected from NTA series, and EDTA series, DTPA series, Gu amine, HEDTA is serial, preferably NTA series, EDTA
Series；
And/or
The additional amount of the chelating agent is the 1/4-1/3 of cerium, the respective mole of zirconium.
4. the preparation method of rare earth element composite oxides according to claim 1 to 3, which is characterized in that step
(1) in, the system pH to 1.4-1.6 is adjusted.
5. the preparation method of rare earth element composite oxides according to claim 1 to 3, which is characterized in that step
(1) in, the presoma system includes the component of following parts by weight: 20-80 parts of cerium oxide, 15-70 parts of zirconium oxides, 5-50 parts of oxygen
Change aluminium, 3-5 parts of lanthana or praseodymium oxide or neodymia, 5-15 part yttrium oxide；
Or, the presoma system includes the component of following parts by weight: 35-45 parts of cerium oxide, 35-50 parts of zirconium oxides, 5-15 parts
Aluminium oxide, 3-5 parts of lanthana, 5-10 parts of yttrium oxides, praseodymium oxide or neodymia.
6. the preparation method of -5 any rare earth element composite oxides according to claim 1, which is characterized in that step
(1) in, the partial size of particle is 300-500nm in the presoma system.
7. the preparation method of -6 any rare earth element composite oxides according to claim 1, which is characterized in that step
(2) described to be heated to reflux the time as 3-4h in；
And/or the surfactant is selected from anionic surfactant, zwitterionic surfactant or non-ionic surface and lives
Property agent.
8. the preparation method of -7 any rare earth element composite oxides according to claim 1, which is characterized in that step
(3) in, the presoma was warming up to 170-190 DEG C in 2-3 hours；Product after reaction is washed, dry, in 750-800
DEG C temperature is calcined in an inert atmosphere, is calcined under 500-600 DEG C of air atmosphere.
9. a kind of rare earth element composite oxides, which is characterized in that based on cerium, zirconium, and there is following performance:
4h is calcined at (1) 1000 DEG C, BET specific surface is at least 60m2The hole /g, BJH holds in 0.60ml/g between 0.85ml/g, hole
Diplopore distribution, based on mesoporous, distribution 2-5nm, 10-50nm is presented in diameter；
4h is calcined at (2) 1100 DEG C, BET specific surface is at least 40m2/g；The hole BJH holds in 0.20ml/g between 0.50ml/g, hole
Diplopore distribution, based on mesoporous, distribution 2-3nm, 30-100nm is presented in diameter；
(3) oxygen storage capacity is in 500 μm of olO2/ g to 1200 μm of olO2Between/g；
(4) it is less than or equal to 480 DEG C by the highest reduction temperature that temperature programmed reduction measures.
10. application of the rare earth element composite oxides as claimed in claim 9 in moving source catalytic field.
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