CN108970602B - Oxygen storage material and preparation method and application thereof - Google Patents
Oxygen storage material and preparation method and application thereof Download PDFInfo
- Publication number
- CN108970602B CN108970602B CN201810864524.3A CN201810864524A CN108970602B CN 108970602 B CN108970602 B CN 108970602B CN 201810864524 A CN201810864524 A CN 201810864524A CN 108970602 B CN108970602 B CN 108970602B
- Authority
- CN
- China
- Prior art keywords
- oxygen storage
- ions
- storage material
- solution
- producing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 83
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000001301 oxygen Substances 0.000 title claims abstract description 81
- 239000011232 storage material Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- -1 cerium ions Chemical class 0.000 claims abstract description 85
- 239000000243 solution Substances 0.000 claims abstract description 35
- 239000012266 salt solution Substances 0.000 claims abstract description 25
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 23
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 23
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 23
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 22
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 22
- 150000001413 amino acids Chemical class 0.000 claims abstract description 17
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000002485 combustion reaction Methods 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 230000002269 spontaneous effect Effects 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 230000003301 hydrolyzing effect Effects 0.000 claims abstract description 3
- 238000013268 sustained release Methods 0.000 claims abstract description 3
- 239000012730 sustained-release form Substances 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 20
- 235000001014 amino acid Nutrition 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 16
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 14
- 229910002651 NO3 Inorganic materials 0.000 claims description 12
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 12
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 10
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 claims description 4
- 235000004279 alanine Nutrition 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 3
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 claims description 3
- 239000004472 Lysine Substances 0.000 claims description 3
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000003860 storage Methods 0.000 abstract description 13
- 230000032683 aging Effects 0.000 abstract description 10
- 239000011858 nanopowder Substances 0.000 abstract description 3
- 239000011882 ultra-fine particle Substances 0.000 abstract 1
- JLDSOYXADOWAKB-UHFFFAOYSA-N aluminium nitrate Chemical compound [Al+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O JLDSOYXADOWAKB-UHFFFAOYSA-N 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical class [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical class [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 6
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical class [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 230000007062 hydrolysis Effects 0.000 description 5
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 238000006068 polycondensation reaction Methods 0.000 description 5
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Inorganic materials [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 5
- LBVWQMVSUSYKGQ-UHFFFAOYSA-J zirconium(4+) tetranitrite Chemical compound [Zr+4].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O LBVWQMVSUSYKGQ-UHFFFAOYSA-J 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(III) nitrate Inorganic materials [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 150000000703 Cerium Chemical class 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000010436 fluorite Substances 0.000 description 2
- 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 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 150000001213 Praseodymium Chemical class 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003325 scandium Chemical class 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003754 zirconium Chemical class 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Images
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
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/613—10-100 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
- B01D2258/012—Diesel engines and lean burn gasoline engines
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application relates to a preparation method of an oxygen storage material, which comprises the following steps: reacting a salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions with amino acid in an organic solvent to obtain sol; mixing the sol and the sustained-release solution, and hydrolyzing and polycondensing to obtain gel; and heating the gel to a spontaneous combustion temperature, and collecting the combusted powder to obtain the oxygen storage material. The method can prepare ultrafine particle size nano powder, increase the specific surface area of the oxygen storage material and improve the high-temperature stability of the oxygen storage material, so that the prepared oxygen storage material has excellent high-temperature aging resistance and oxygen storage performance.
Description
Technical Field
The invention relates to the field of automobile exhaust purification treatment, in particular to an oxygen storage material and a preparation method and application thereof.
Background
The three-way catalyst is one of the most effective methods for treating the automobile exhaust pollution. The oxygen storage material is an important component of the three-way catalyst and is a main influence factor of the activity, the high-temperature stability and the dosage of the noble metal of the catalyst. The oxygen storage material overcomes the fluctuation caused by the air-fuel ratio during tail gas purification to a certain extent by adjusting the oxygen content in the tail gas, plays a role in buffering, can enlarge an operation window and improve the tail gas purification rate.
The traditional oxygen storage material is mainly a cerium-zirconium solid solution, which can maintain good oxygen storage performance at high temperature, but has poor thermal stability and low specific surface area, and tetragonal phase zirconium dioxide is easy to dissociate at high temperature, so that a single cubic phase is converted into multiphase coexistence. With the increasingly strict emission standards of automobiles and the development of automobile engines to lean-burn engines, the development of rare earth oxygen storage materials with large specific surface area, large oxygen storage amount and good high-temperature stability is a new development direction of three-way catalysts.
There is a prior art disclosing an oxygen storage material consisting of cerium oxide, zirconium oxide, lanthanum oxide and yttrium oxide. The oxygen storage material has good high-temperature aging resistance, but the oxygen storage performance is poor.
Therefore, it is a hot spot of research to find an oxygen storage material having excellent high temperature aging resistance and oxygen storage performance.
Disclosure of Invention
Based on this, there is a need for an oxygen storage material having excellent high-temperature aging resistance and oxygen storage properties.
In addition, the application also provides a preparation method and application of the oxygen storage material.
A method for preparing an oxygen storage material, comprising the steps of:
reacting a salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions with amino acid in an organic solvent to obtain sol, wherein the molar ratio of the total amount of the cerium ions, the zirconium ions, the praseodymium ions, the aluminum ions and the scandium ions in the salt solution to the amino acid is 1 (2-5);
mixing the solvent and the sustained-release solution, and performing hydrolysis and polycondensation to obtain gel;
and heating the gel to a spontaneous combustion temperature, and collecting the combusted powder to obtain the oxygen storage material.
In one embodiment, the molar ratio of the cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions is (4-6): (0.2-0.4): (0.5-1): 0.1-0.5).
In one embodiment, the salt solution is a nitrate solution, an acetate solution, or a carbonate solution.
In one embodiment, the amino acid is glycine, alanine, or lysine.
In one embodiment, the organic solvent is a mixed solution of benzene and ethanol, and the molar ratio of the benzene to the ethanol in the mixed solution is 1 (2-3).
In one embodiment, the reaction temperature of the reaction in the organic solvent is 70-70 ℃, the reaction time is 4-6 hours, and the pH value of the reaction system is 5-6.
In one embodiment, the slow release solution is a combination of hydrochloric acid and hexamethylenetetramine, a combination of potassium hydrogen phthalate and sodium hydroxide or a combination of potassium dihydrogen phosphate and sodium hydroxide.
In one embodiment, the spontaneous combustion temperature is 200 ℃ to 300 ℃.
An oxygen storage material produced by the method for producing an oxygen storage material according to any one of the above.
An application of the oxygen storage material in a three-way catalyst.
According to the preparation method of the oxygen storage material, the salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions reacts with amino acid, and by controlling the molar ratio of the total amount of the cerium ions, the zirconium ions, the praseodymium ions, the aluminum ions and the scandium ions in the salt solution to the amino acid, on one hand, the cerium ions, the zirconium ions, the praseodymium ions, the aluminum ions and the scandium ions are uniformly dispersed on the molecular level through a sol-gel process, on the other hand, the gel is spontaneously combusted, so that the superfine particle size nano-powder can be prepared, the specific surface area of the oxygen storage material is increased, the high temperature stability of the oxygen storage material is improved, and the prepared oxygen storage material has excellent high temperature aging resistance and oxygen storage performance.
Drawings
Fig. 1 is an XRD pattern of the oxygen storage material prepared in example 1;
fig. 2 is an SEM image of the oxygen storage material prepared in example 1.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The method for producing an oxygen storage material according to an embodiment includes the following steps S110 to S140:
s110, providing a salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions.
In this embodiment, the molar ratio of cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions in the salt solution is (4-6): 0.2-0.4: (0.5-1): 0.1-0.5.
Further, the molar ratio of cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions in the salt solution is 5:4:0.3:0.6: 0.1.
Further, the salt solution is a nitrate solution, an acetate solution or a carbonate solution.
It is to be understood that the salt solution is not limited to the ones described above, and in other embodiments, the salt solution may also be other salt solutions that may be removed by spontaneous combustion.
In the present embodiment, the salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions, and scandium ions is prepared by the following method:
cerium salt, zirconium salt, praseodymium salt, aluminum salt and scandium salt are mixed to prepare an aqueous solution.
Wherein the cerium salt is Ce (NO)3)3·6H2O, Zr (NO) as zirconium salt3)4·5H2O, Pr (NO) as praseodymium salt3)3The aluminum salt is Al (NO)3)3·9H2Sc (NO) as scandium salt3)3·6H2O。
The particle size of the prepared oxygen storage material can be controlled by adjusting the molar ratio of cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions in the solution, and the high-temperature stability of the oxygen storage material is improved.
S120, reacting the salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions with amino acid in an organic solvent to obtain sol.
Wherein the molar ratio of the total amount of cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions in the salt solution to the amino acid is 1 (2-5).
Further, the amino acid is glycine, alanine or lysine.
It can be understood that a part of amino acids participate in the reaction to form sol, so as to realize uniform dispersion of cerium, zirconium, praseodymium, aluminum and scandium, and a part of amino acids are used as a combustion agent, so that the subsequently formed gel is spontaneously combusted, and the particle size of the oxygen storage material is finer.
In the present embodiment, the organic solvent is a mixed solution of benzene and ethanol, and is used to promote the reaction.
Furthermore, the molar ratio of benzene to ethanol in the organic solvent is 1 (2-3).
Further, the reaction temperature of the step S120 is 70-70 ℃, the reaction time is 4-6 hours, and the pH value of the reaction system is 5-6.
The pH value of the reaction system is controlled to be 5-6, so that the reaction can be promoted.
The pH of the system is adjusted by using an acid corresponding to the salt solution. For example, if the salt solution is a nitrate solution, nitric acid is used to adjust the pH of the system; if the salt solution is an acetate solution, acetic acid is adopted to adjust the pH of the system.
And S130, mixing the sol and the slow-release solution, and hydrolyzing and polycondensing to obtain gel.
Wherein the slow release solution is a combination of hydrochloric acid and hexamethylenetetramine, a combination of potassium hydrogen phthalate and sodium hydroxide or a combination of potassium dihydrogen phosphate and sodium hydroxide.
Further, when the slow release solution is a combination of hydrochloric acid and hexamethylenetetramine, the preparation method comprises the following steps: diluting 40g of hexamethylenetetramine and 10ml of concentrated hydrochloric acid into 100ml of water; when the slow release solution is the combination of potassium hydrogen phthalate and sodium hydroxide, the preparation method comprises the following steps: diluting 25ml of 0.2mol/L potassium hydrogen phthalate and 17.5ml of 0.1mol/L sodium hydroxide into 100ml of water; when the slow release solution is the combination of potassium dihydrogen phosphate and sodium hydroxide, the preparation method comprises the following steps: 25ml of 0.2mol/L potassium dihydrogen phosphate are diluted with 23.6ml of 0.1mol/L sodium hydroxide into 100ml of water.
The sol and the slow-release solution are mixed, so that the hydrolysis and polycondensation of the sol can be promoted to form gel, and the uniform mixing of cerium, zirconium, praseodymium, aluminum and scandium on the molecular level is realized, so that the particle size distribution of the prepared oxygen storage material is uniform.
S140, heating the gel to a spontaneous combustion temperature, and collecting the combusted powder to obtain the oxygen storage material.
In the present embodiment, the spontaneous combustion temperature is 200 to 300 ℃.
The gel undergoes spontaneous combustion, and the particle size of the oxygen storage material can be made finer.
Further, the method also comprises the following steps after collecting the powder after combustion:
the powder after burning is ground and sieved, so that the oxygen storage material has finer grain diameter and more uniform distribution, and the performance of the oxygen storage material is more excellent.
According to the preparation method of the oxygen storage material, a salt solution containing cerium, zirconium, praseodymium, aluminum and scandium in a certain proportion reacts with amino acid, and by controlling the molar ratio of cerium, zirconium, praseodymium, aluminum, scandium and amino acid in the salt solution, on one hand, cerium, zirconium, praseodymium, aluminum and scandium are uniformly dispersed on the molecular level through a sol-gel process, on the other hand, gel can be spontaneously combusted, superfine particle size nano-powder can be prepared, the specific surface area of the oxygen storage material is increased, the high-temperature stability of the oxygen storage material is improved, and therefore the prepared oxygen storage material has excellent high-temperature aging resistance and oxygen storage performance.
In addition, the preparation method of the oxygen storage material does not need the steps of washing, filtering, drying and the like, and has short process flow.
The oxygen storage material prepared by the method has superfine and controllable particle size, is a single fluorite cubic phase structure, and has excellent ageing resistance and oxygen storage capacity.
The oxygen storage material is used for the three-way catalyst, so that the light-off temperature of the three-way catalyst in the catalytic conversion process of tail gas can be obviously reduced, the consumption of noble metal is reduced, and the cost is reduced.
The following are specific examples.
Example 1
(1) Separately weighing Ce (NO)3)3·6H2O、Zr(NO3)4·5H2O、Pr(NO3)3、Al(NO3)3·9H2O、Sc(NO3)3·6H221.7g (0.05mol), 17.2g (0.04mol), 0.97g (0.003mol), 2.25g (0.006mol) and 0.337g (0.001mol) of O to prepare an aqueous solution.
(2) Adding the prepared nitrate solution and 22.5g (0.3mol) of glycine into a mixed organic solvent system of benzene and ethanol (the molar ratio is 1:2), controlling the reaction temperature to be 70 ℃, adding nitric acid, controlling the pH of the solution to be 5, and reacting for 4 hours to obtain the sol.
(3) Adding the sol into a slow-release solution formed by hydrochloric acid and hexamethylenetetramine, wherein the preparation method comprises the steps of diluting 40g of hexamethylenetetramine and 10mL of concentrated hydrochloric acid to 100mL of water, and quickly converting the solution into gel through hydrolysis and polycondensation.
(4) Heating the gel to 200 ℃, carrying out spontaneous combustion after evaporation concentration, collecting the burned powder, grinding and screening to obtain 1.4g of nano oxygen storage material powder with excellent performance.
The oxygen storage material prepared in example 1 was found to have a D50 of 210nm and a D90 of 260 nm.
The XRD pattern and SEM pattern of the oxygen storage material prepared in example 1 are shown in fig. 1 and 2, respectively, and the results of comparing the specific surface area before and after aging and the oxygen storage amount are shown in table 1 when the oxygen storage material prepared in example 1 is subjected to aging treatment at 1200 ℃.
TABLE 1
Example 2
(1) Separately weighing Ce (NO)3)3·6H2O、Zr(NO3)4·5H2O、Pr(NO3)3、Al(NO3)3·9H2O、Sc(NO3)3·6H221.7g, 17.2g, 0.97g, 2.25g and 0.337g of O to prepare an aqueous solution.
(2) Adding the prepared nitrate solution and 26.7g (0.3mol) of alanine into a mixed organic solvent system of benzene and ethanol (the molar ratio is 1:2), controlling the reaction temperature to be 70 ℃, adding nitric acid, controlling the pH of the solution to be 5.5, and reacting for 6 hours to obtain the sol.
(3) Adding the sol into a slow release solution formed by potassium hydrogen phthalate and sodium hydroxide, wherein the preparation method comprises the steps of diluting 25mL of 0.2mol/L potassium hydrogen phthalate and 17.5mL of 0.1mol/L sodium hydroxide to 100mL of water, and quickly converting the water into gel through hydrolysis and polycondensation.
(4) Heating the gel to 250 ℃, carrying out spontaneous combustion after evaporation concentration, collecting the burned powder, grinding and screening to obtain 1.4g of nano oxygen storage material powder with excellent performance.
The oxygen storage material prepared in example 2 was found to have a D50 of 220nm and a D90 of 270 nm.
Comparative example 1
(1) Separately weighing Ce (NO)3)3·6H2O、Zr(NO3)4·5H2O、Pr(NO3)3、Al(NO3)3·9H2O、Sc(NO3)3·6H221.7g (0.05mol), 17.2g (0.04mol), 0.97g (0.003mol), 2.25g (0.006mol) and 0.337g (0.001mol) of O to prepare an aqueous solution.
(2) Adding the prepared nitrate solution and 7.5g (0.1mol) of glycine into a mixed organic solvent system of benzene and ethanol (the molar ratio is 1:2), controlling the reaction temperature to be 70 ℃, adding nitric acid, controlling the pH of the solution to be 5, and reacting for 4 hours to obtain the sol.
(3) Adding the sol into a slow-release solution formed by hydrochloric acid and hexamethylenetetramine, wherein the preparation method comprises the steps of diluting 40g of hexamethylenetetramine and 10mL of concentrated hydrochloric acid to 100mL of water, and quickly converting the solution into gel through hydrolysis and polycondensation.
(4) And roasting the gel at 600 ℃, collecting roasted powder, grinding and screening to obtain 1.4g of oxygen storage material powder.
It was found that D50 was 720nm and D90 was 960nm in the oxygen storage material prepared in comparative example 1.
Comparative example 2
Comparative example 2 is substantially the same as example 1 except that the preparation method of comparative example 2 is a coprecipitation method, i.e., 21.7g (0.05mol) of Ce (NO)3)3·6H2O、17.2g(0.04mol)Zr(NO3)4·5H2O、0.97g(0.003mol)Pr(NO3)3、2.25g(0.006mol)Al(NO3)3·9H2O and 0.337g (0.001mol) Sc (NO)3)3·6H2And O is prepared into an aqueous solution, ammonia water is added to obtain an oxygen storage material precursor, and then the oxygen storage material precursor is washed, dried and roasted to obtain oxygen storage material powder.
Through detection, the particle size of the oxygen storage material prepared in the comparative example 2 is generally 1-10 μm, and the oxygen storage performance is low.
Example 3
Example 3 is essentially the same as example 1, except that the raw materials in example 3 are added in the following amounts:
43.4g(0.1mol)Ce(NO3)3·6H2O、30.1g(0.07mol)Zr(NO3)4·5H2O、1.63g(0.005mol)Pr(NO3)3、7.5g(0.02mol)Al(NO3)3·9H2O、1.69g(0.005mol)Sc(NO3)3·6H2o, 45g (0.6mol) glycine.
The results show that example 3 cannot form a solid solution and also does not form a fluorite cubic phase structure, the particle size of the powder is about 20 to 50 μm, the high temperature stability is poor, and the specific surface area after aging is only 5m2About/g, the oxygen storage performance is also seriously reduced, and the oxygen storage amount is about 100 mu mol/g.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. The preparation method of the oxygen storage material is characterized by comprising the following steps of:
reacting a salt solution containing cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions with amino acid in an organic solvent to obtain sol, wherein the molar ratio of the total amount of the cerium ions, the zirconium ions, the praseodymium ions, the aluminum ions and the scandium ions in the salt solution to the amino acid is 1 (2-5);
mixing the sol and the sustained-release solution, and hydrolyzing and polycondensing to obtain gel;
heating the gel to a spontaneous combustion temperature, and collecting the combusted powder to obtain an oxygen storage material;
the molar ratio of cerium ions, zirconium ions, praseodymium ions, aluminum ions and scandium ions in the salt solution is (4-6): 0.2-0.4): 0.5-1): 0.1-0.5;
the organic solvent is a mixed solution of benzene and ethanol, and the molar ratio of the benzene to the ethanol in the mixed solution is 1 (2-3);
the reaction temperature of the reaction in the organic solvent is 70-80 ℃, the reaction time is 4-6 hours, and the pH value of the reaction system is 5-6;
the slow release solution is a combination of hydrochloric acid and hexamethylenetetramine, a combination of potassium hydrogen phthalate and sodium hydroxide or a combination of potassium dihydrogen phosphate and sodium hydroxide.
2. The method for producing an oxygen storage material according to claim 1, wherein the molar ratio of benzene to ethanol in the mixed solution is 1: 2.
3. The method for producing an oxygen storage material according to claim 1 or 2, wherein the salt solution is a nitrate solution, an acetate solution, or a carbonate solution.
4. The method for producing an oxygen storage material according to claim 1, wherein the amino acid is glycine, alanine, or lysine.
5. The method for producing an oxygen storage material according to claim 1, wherein the amino acid is glycine.
6. The method for producing an oxygen storage material as claimed in claim 1, wherein the slow-release solution is a combination of hydrochloric acid and hexamethylenetetramine.
7. The method for preparing an oxygen storage material according to claim 1, wherein the spontaneous combustion temperature is 200 ℃ to 300 ℃.
8. An oxygen storage material produced by the method for producing an oxygen storage material according to any one of claims 1 to 7.
9. Use of the oxygen storage material of claim 8 in a three-way catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864524.3A CN108970602B (en) | 2018-08-01 | 2018-08-01 | Oxygen storage material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810864524.3A CN108970602B (en) | 2018-08-01 | 2018-08-01 | Oxygen storage material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108970602A CN108970602A (en) | 2018-12-11 |
| CN108970602B true CN108970602B (en) | 2021-05-28 |
Family
ID=64550836
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810864524.3A Active CN108970602B (en) | 2018-08-01 | 2018-08-01 | Oxygen storage material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108970602B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895743A (en) * | 2006-06-09 | 2007-01-17 | 中国科学院山西煤炭化学研究所 | Nano-desulfurizing agent for gas, its preparation and use |
| CN101269830A (en) * | 2008-05-13 | 2008-09-24 | 福建师范大学 | Method for producing nano-scale rare earth doping composite oxides sosoloid with low-temperature carbothermic method |
| CN102416315A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Magnesium-containing rare earth oxygen storage material and preparation method thereof |
| CN102716733A (en) * | 2012-05-08 | 2012-10-10 | 赣州博晶科技有限公司 | Preparation method of high performance cerium zirconium aluminum oxygen-storage material |
| CN104689827A (en) * | 2015-02-12 | 2015-06-10 | 柳州豪祥特科技有限公司 | Method for preparing automobile exhaust gas purification catalyst |
-
2018
- 2018-08-01 CN CN201810864524.3A patent/CN108970602B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1895743A (en) * | 2006-06-09 | 2007-01-17 | 中国科学院山西煤炭化学研究所 | Nano-desulfurizing agent for gas, its preparation and use |
| CN101269830A (en) * | 2008-05-13 | 2008-09-24 | 福建师范大学 | Method for producing nano-scale rare earth doping composite oxides sosoloid with low-temperature carbothermic method |
| CN102416315A (en) * | 2010-09-28 | 2012-04-18 | 北京有色金属研究总院 | Magnesium-containing rare earth oxygen storage material and preparation method thereof |
| CN102716733A (en) * | 2012-05-08 | 2012-10-10 | 赣州博晶科技有限公司 | Preparation method of high performance cerium zirconium aluminum oxygen-storage material |
| CN104689827A (en) * | 2015-02-12 | 2015-06-10 | 柳州豪祥特科技有限公司 | Method for preparing automobile exhaust gas purification catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 蔓延低温燃烧一溶胶凝胶合成Ce0.8Sm0.2O1.9及烧结性能;燕萍等;《化工学报》;20110131;第62卷(第1期);参见第1.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108970602A (en) | 2018-12-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8026193B2 (en) | Metal oxide particle, production process thereof and exhaust gas purifying catalyst | |
| EP1921044B1 (en) | Zirconia-ceria-yttria-based mixed oxide and process for producing the same | |
| US7989387B2 (en) | Process for producing metal oxide particle and exhaust gas purifying catalyst | |
| JP5361855B2 (en) | Palladium-rhodium single layer catalyst | |
| JP3664182B2 (en) | High heat-resistant exhaust gas purification catalyst and production method thereof | |
| JP4179299B2 (en) | Catalyst carrier powder and exhaust gas purification catalyst | |
| JP3861303B2 (en) | Exhaust gas purification catalyst | |
| US20070197373A1 (en) | Zirconia core particles coated with ceria particles, production process thereof and exhaust gas purifying catalyst | |
| JP5526502B2 (en) | Exhaust gas purification catalyst and method for producing the same | |
| JP4257684B2 (en) | Cerium oxide washcoat | |
| CN106732521B (en) | Preparation method of high-performance cerium-zirconium solid solution material | |
| JP2013129554A (en) | Composite oxide, method for producing the same, and catalyst for exhaust gas purification | |
| CN108187665B (en) | Denitration catalyst and preparation method thereof | |
| CN107405570B (en) | For BaAl2O4Formation of NO with improved stabilityxTrapping catalyst support materials | |
| JP2578219B2 (en) | Method for producing exhaust gas purifying catalyst | |
| JP5168527B2 (en) | Oxide powder and production method thereof | |
| JP4928931B2 (en) | Ceria-zirconia composite oxide and method for producing the same | |
| CN108970602B (en) | Oxygen storage material and preparation method and application thereof | |
| JP4697503B2 (en) | Composite oxide powder, method for producing the same and catalyst | |
| JP2006043683A (en) | Catalyst carrier and its manufacturing method and catalyst for cleaning exhaust gas | |
| JP5202034B2 (en) | Method for producing exhaust gas purification catalyst | |
| CN116618037A (en) | Cerium-zirconium composite oxide with doped grain boundary and surface, and preparation method and application thereof | |
| JPH09175822A (en) | Heat-resistant oxide | |
| JP4586293B2 (en) | NOx occlusion agent, NOx occlusion reduction type catalyst and method for producing the same | |
| EP0970747A2 (en) | Process for producing titanium-aluminum composite oxides and process for producing a catalyst containing same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |