CN114471521A - Preparation method of cerium oxide-based composite oxide material - Google Patents
Preparation method of cerium oxide-based composite oxide material Download PDFInfo
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- CN114471521A CN114471521A CN202111523922.7A CN202111523922A CN114471521A CN 114471521 A CN114471521 A CN 114471521A CN 202111523922 A CN202111523922 A CN 202111523922A CN 114471521 A CN114471521 A CN 114471521A
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- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 36
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 63
- 238000005530 etching Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 35
- 239000000243 solution Substances 0.000 claims description 28
- 150000000703 Cerium Chemical class 0.000 claims description 25
- 150000003754 zirconium Chemical class 0.000 claims description 25
- 238000001556 precipitation Methods 0.000 claims description 23
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- -1 cerium ion Chemical class 0.000 claims description 19
- 238000001914 filtration Methods 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 239000000706 filtrate Substances 0.000 claims description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000012716 precipitator Substances 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 8
- 230000002378 acidificating effect Effects 0.000 claims description 8
- 239000012065 filter cake Substances 0.000 claims description 8
- 229910017604 nitric acid Inorganic materials 0.000 claims description 8
- 238000000975 co-precipitation Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
- 150000001768 cations Chemical class 0.000 claims description 6
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 229910052727 yttrium Inorganic materials 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001450 anions Chemical class 0.000 claims description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 4
- 239000000920 calcium hydroxide Substances 0.000 claims description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 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 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 2
- 229910052691 Erbium Inorganic materials 0.000 claims description 2
- 229910052693 Europium Inorganic materials 0.000 claims description 2
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 2
- 229910052689 Holmium Inorganic materials 0.000 claims description 2
- 229910052765 Lutetium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052771 Terbium Inorganic materials 0.000 claims description 2
- 229910052775 Thulium Inorganic materials 0.000 claims description 2
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 2
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 2
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 2
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 2
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001428 transition metal ion Inorganic materials 0.000 claims description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 8
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 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 13
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 9
- 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 7
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 238000004438 BET method Methods 0.000 description 4
- 239000012190 activator Substances 0.000 description 4
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- WMOHXRDWCVHXGS-UHFFFAOYSA-N [La].[Ce] Chemical compound [La].[Ce] WMOHXRDWCVHXGS-UHFFFAOYSA-N 0.000 description 3
- LENJPRSQISBMDN-UHFFFAOYSA-N [Y].[Ce] Chemical compound [Y].[Ce] LENJPRSQISBMDN-UHFFFAOYSA-N 0.000 description 3
- FZMFJORHWIAQFU-UHFFFAOYSA-N [Y].[Zr].[Ce] Chemical compound [Y].[Zr].[Ce] FZMFJORHWIAQFU-UHFFFAOYSA-N 0.000 description 3
- WLLURKMCNUGIRG-UHFFFAOYSA-N alumane;cerium Chemical compound [AlH3].[Ce] WLLURKMCNUGIRG-UHFFFAOYSA-N 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- RCFVMJKOEJFGTM-UHFFFAOYSA-N cerium zirconium Chemical compound [Zr].[Ce] RCFVMJKOEJFGTM-UHFFFAOYSA-N 0.000 description 2
- 239000011258 core-shell material Substances 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000002910 rare earth metals Chemical class 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910004664 Cerium(III) chloride Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
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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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of catalyst materials, and relates to a preparation method of a cerium oxide-based composite oxide material. The preparation method comprises the following steps: (1) precipitating; (2) pre-treating; (3) etching; (4) and (5) post-treatment. The preparation method of the cerium oxide-based composite oxide material has the advantages of simple process flow, low cost, no need of an organic template agent and suitability for large-scale industrial production and preparation of the cerium oxide-based composite oxide material with large specific surface area.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, and relates to a preparation method of a cerium oxide-based composite oxide material.
Background
Cerium (Ce) is a rare earth element with a relatively abundant abundance, and has two variable valence states of +3/+ 4. The cerium oxide-based composite oxide material generally has excellent oxygen storage and storage capacity and catalytic capacity, and is widely applied to the fields of industrial catalysis, pollutant adsorption, industrial waste gas treatment, motor vehicle tail gas purification and the like as a catalyst or a catalyst carrier.
The cerium oxide-based composite oxide material is required to have a sufficiently large specific surface area as a catalyst or a catalyst carrier, however, the cerium oxide-based composite oxide material obtained by the conventional method has a small specific surface area and cannot meet the use requirement, and oxide particles with a special morphology or a porous structure are required to be obtained by a specific preparation process so as to obtain a larger specific surface area.
For example, patent document CN112275274A discloses a method for preparing a mesoporous cerium oxide catalyst for imine synthesis, which comprises mixing a raw material such as cerium nitrate in n-butanol to obtain a sol using P123 as a template, and performing multi-step treatment to obtain a cerium oxide catalyst with a large specific surface area.
For example, patent document CN111939894A discloses a core-shell structured cerium-zirconium-based composite oxide and a preparation method thereof, which prepares the cerium-zirconium solid solution composite oxide oxygen storage material with a core-shell structure and a large specific surface area by processes such as fractional precipitation, surface treatment with a modifier and the like.
However, in the current various processes for preparing the cerium oxide-based composite oxide material with large specific surface area, a large amount of organic surfactant, modifier, high molecular polymer and the like are needed and removed by a high-temperature burning method. Such methods have two major drawbacks: firstly, the template agent is often carbonized in the high-temperature firing process, remains in the oxide to block pore channels, and reduces the specific surface area of the oxide; secondly, the organic template agent is converted into gases such as carbon dioxide and the like after being burned at high temperature and dissipated, and the gases cannot be recycled, so that the production cost is increased, and the carbon neutralization advocated by the nation is also not easy to be practiced.
Disclosure of Invention
The invention aims to provide a preparation method of a cerium oxide-based composite oxide material, which is used for preparing the cerium oxide-based composite oxide material with large specific surface area, has simple process flow, low cost and no need of an organic template agent and is suitable for large-scale industrial production.
To achieve the object, in a basic embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, the method comprising the steps of:
(1) and (3) precipitation: adding a precipitator into a solution containing cerium salt, optional zirconium salt and an inorganic template agent for precipitation, wherein the obtained precipitate is a first intermediate;
(2) pretreatment: burning, cooling and crushing the first intermediate obtained in the step (1) to obtain a second intermediate;
(3) etching: dispersing the second intermediate obtained in the step (2) in a solvent, adding an etching agent for etching, filtering and washing a mixed solution after etching, and obtaining a filter cake which is a third intermediate;
(4) and (3) post-treatment: and (4) burning, cooling and crushing the third intermediate obtained in the step (3) to obtain the cerium oxide-based composite oxide material.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (1),
the cation in the cerium salt is selected from + 3-valent or + 4-valent cerium ion or a mixture of the two, and the anion is selected from one or more of nitrate, sulfate, chloride and acetate (preferably, the cerium salt is selected from cerium (III) chloride and/or cerium (III) nitrate);
the zirconium salt is selected from one or more of zirconyl nitrate, zirconyl sulfate, zirconyl chloride and zirconium acetate (preferably, the zirconium salt is selected from zirconyl nitrate and/or zirconyl chloride);
the cation of the inorganic template is selected from one or more of rare earth ions except cerium or non-rare earth metal ions, and the anion is selected from one or more of nitrate, sulfate, chloride and acetate;
the rare earth ions except cerium are selected from one or more of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium ions (preferably, the rare earth ions except cerium are lanthanum or yttrium ions);
the non-rare earth metal ions are selected from one or more of transition metal ions, alkaline earth metal ions and aluminum ions;
the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, bicarbonate, carbonate, oxalic acid and oxalate (preferably ammonia water or ammonium bicarbonate).
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (1),
calculated by the mole number of the metal ions, the cerium salt accounts for 10 to 95 percent of the total mole amount of the cerium salt, the optional zirconium salt and the inorganic template agent; the ratio of the zirconium salt to the total molar weight of the cerium salt, the optional zirconium salt and the inorganic template agent is 0-70%; the inorganic template agent accounts for 5 to 90 percent of the total molar weight of the cerium salt, the optional zirconium salt and the inorganic template agent;
calculated by the mole number of the metal ions, the ratio of the mole number of the precipitator to the total mole number of the cerium salt, the optional zirconium salt and the inorganic template agent is 1-10.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (1),
the temperature of the precipitation reaction is 20-80 ℃;
the precipitation is coprecipitation, namely adding a precipitant solution into a solution containing cerium salt, optional zirconium salt and an inorganic template agent under the condition of continuous stirring for coprecipitation, and filtering and washing to obtain a first intermediate;
or the precipitation is gradient precipitation, namely adding partial precipitator solution into partial solution containing cerium salt, optional zirconium salt and inorganic template agent for precipitation (stirring for 0.5-2 hours) under the condition of continuous stirring, then adding partial solution containing cerium salt, optional zirconium salt and inorganic template agent, adding partial precipitator solution into the solution for precipitation (stirring for 0.5-2 hours), repeating the operations for precipitation for multiple times until all the solution containing cerium salt, optional zirconium salt and inorganic template agent and all the precipitator solution are added, filtering and washing to obtain a first intermediate (preferably, the cerium salt adding amount accounts for 10-90% of the total cerium salt using amount, the zirconium salt adding amount accounts for 10-90% of the total zirconium salt using amount, the inorganic template agent adding amount accounts for 10-90% of the total inorganic template agent using amount, and the precipitator adding amount accounts for 10-90% of the total precipitating agent using amount -90%).
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (2), the burning temperature is 100-900 ℃, the heating rate is 1-10 ℃/min, and the time is 0.5-10 h.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (3),
the solvent is selected from one or more of water, methanol and ethanol;
the etching agent is an acidic substance or an alkaline substance, the acidic substance is selected from one or more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the alkaline substance is selected from one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (3),
when the etching agent is an acidic substance, an activating agent is added into the solvent, and the composition of the activating agent is the same as that of the inorganic template;
when the etching agent is alkaline substance, no activating agent is added in the solvent;
the etching temperature is 20-80 ℃;
when the etching agent is an acidic substance, the pH value of the etching operation solution is 0-5;
when the etching agent is alkaline substance, the pH value of the etching operation solution is 10-14.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (3), after the addition of the etching agent is stopped, if the cation concentration of the inorganic templating agent in the mixed solution system remains stable (for 0.5-2 hours), the etching reaction is terminated; and otherwise, continuously adding an etching agent for etching, and filtering and washing the mixed solution after etching to obtain a filter cake, namely the third intermediate.
In a preferred embodiment, the present invention provides a method for producing a cerium oxide-based composite oxide material, wherein in step (3), the filtrate containing the inorganic template obtained after the etching operation is returned to step (1) for recycling and/or to step (3) for addition to the solvent after the pH is adjusted to 3 to 7.
In a preferred embodiment, the present invention provides a method for preparing a cerium oxide-based composite oxide material, wherein in step (4), the burning temperature is 300-.
The preparation method of the cerium oxide-based composite oxide material has the beneficial effects that the preparation method of the cerium oxide-based composite oxide material has simple process flow and low cost, does not need an organic template agent, and is suitable for preparing the cerium oxide-based composite oxide material with large specific surface area in large-scale industrial production.
According to the preparation method, rare earth or non-rare earth metal elements are used as recyclable inorganic template agents, and the cerium oxide-based composite oxide material with large specific surface area is prepared by an acid etching or alkali etching method, so that the problem that the organic template agents are carbonized and block pore channels in the firing process is solved; the inorganic template agent can be recycled, so that the production cost is reduced, and the problem of carbon emission in the firing process is greatly reduced.
Drawings
Fig. 1 is a flowchart illustrating a method for preparing a cerium oxide-based composite oxide material according to the present invention, which is exemplified in each example of the embodiment.
Detailed Description
The following examples further illustrate specific embodiments of the present invention.
Example 1: preparation and detection of cerium oxide-based composite oxide Material
The preparation method of the cerium-lanthanum composite oxide with the large specific surface area by adopting a coprecipitation method comprises the following specific steps:
(1) under the condition of 20 ℃ and continuous stirring, 144mL of 5mol/L ammonia water is added into 1L of aqueous solution containing 0.1mol of cerium chloride and 0.08mol of inorganic template lanthanum chloride, the total amount of the ammonia water is 0.72mol, and the intermediate A is obtained after filtration and washing.
(2) And (3) burning the intermediate A at 300 ℃ for 4 hours at the heating rate of 2 ℃/min, and cooling and crushing to obtain an intermediate C.
(3) At 20 ℃, dispersing the intermediate C in 1L of aqueous solution containing 0.5mol/L of activator lanthanum chloride, gradually adding 1mol/L of hydrochloric acid and maintaining the pH of the solution between 2.5 and 4.5. If the concentration of lanthanum ions in the mixed solution system is kept unchanged for 2 hours after the hydrochloric acid is stopped being added, the etching operation is finished; otherwise, hydrochloric acid is continuously added for etching. And filtering and washing the etched mixed solution to obtain a filter cake, namely the intermediate D. Part of the obtained filtrate is returned to the step (1) after the pH value is adjusted to be 4-5, and the filtrate is used as a new inorganic template agent for recycling; and (4) returning the rest filtrate to the step (3) to be used as a new activating agent for recycling.
(4) And (3) burning the intermediate D at 300 ℃ for 4 hours at the heating rate of 1 ℃/min, and cooling and crushing to obtain the cerium-lanthanum composite oxide with the large specific surface.
(5) The specific surface area of the cerium-lanthanum composite oxide obtained in step (4) was measured by the BET method using a NOVA2000e specific surface Analyzer of Congta, USA, and was 150m2/g。
Example 2: preparation and detection of cerium oxide-based composite oxide material
The preparation method of the cerium-yttrium composite oxide with the large specific surface area by adopting a gradient precipitation method comprises the following specific steps:
(1) under the condition of 80 ℃ and continuous stirring, the first round of precipitation operation is carried out, 0.21L of 1mol/L ammonium bicarbonate is added into 0.4L of aqueous solution containing 0.04mol of cerium nitrate and 0.03mol of inorganic template yttrium nitrate, and the mixture is stirred for 1 hour; secondly, carrying out precipitation operation, namely adding 0.3L of aqueous solution containing 0.03mol of cerium nitrate and 0.03mol of inorganic template yttrium nitrate into the mixed solution, then adding 0.18L of 1mol/L ammonium bicarbonate, and stirring for 1 hour; and thirdly, performing precipitation operation, namely adding 0.3L of aqueous solution containing 0.03mol of cerium nitrate and 0.02mol of inorganic template yttrium nitrate into the mixed solution, then adding 0.33L of 1mol/L ammonium bicarbonate, and stirring for 1 hour. And the total dosage of cerium nitrate is 0.1mol, the total dosage of yttrium nitrate is 0.08mol, and the total dosage of ammonium bicarbonate is 0.72mol, and an intermediate B is obtained after filtration and washing.
(2) And (3) burning the intermediate B at 100 ℃ for 4 hours at the heating rate of 10 ℃/min, and cooling and crushing to obtain an intermediate C.
(3) Dispersing the intermediate C in 1L of aqueous solution containing 0.5mol/L of activator yttrium nitrate at 80 ℃, gradually adding 1mol/L of nitric acid and maintaining the pH of the solution between 0 and 2. If the concentration of yttrium ions in the mixed solution system is kept unchanged for 1 hour after the addition of the nitric acid is stopped, ending the etching operation; otherwise, continuously adding nitric acid for etching. And filtering and washing the etched mixed solution to obtain a filter cake, namely the intermediate D. Part of the obtained filtrate is returned to the step (1) after the pH value is adjusted to be 4-4.5, and the filtrate is used as a new inorganic template agent for recycling; and (4) returning the rest filtrate to the step (3) to be used as a new activating agent for recycling.
(4) And (3) burning the intermediate D at 1000 ℃ for 4 hours at the heating rate of 5 ℃/min, and cooling and crushing to obtain the cerium-yttrium composite oxide with the large specific surface.
(5) The specific surface area of the cerium-yttrium composite oxide obtained in step (4) was measured by the BET method using a NOVA2000e specific surface Analyzer of Congta, USA, and was 40m2/g。
Example 3: preparation and detection of cerium oxide-based composite oxide Material
The preparation method of the cerium-zirconium-yttrium composite oxide with the large specific surface area by adopting a coprecipitation method comprises the following specific steps:
(1) under the condition of stirring continuously at 50 ℃, 144mL of 5mol/L ammonia water is added into 1L of aqueous solution containing 0.06mol of cerium nitrate, 0.04mol of zirconyl nitrate and 0.08mol of inorganic template yttrium nitrate, the total dosage of the ammonia water is 0.72mol, and the intermediate A is obtained after filtration and washing.
(2) And (3) burning the intermediate A at 900 ℃ for 1 hour, wherein the heating rate is 10 ℃/min, and cooling and crushing to obtain an intermediate C.
(3) Dispersing the intermediate C in 1L of aqueous solution containing 0.5mol/L of activator yttrium nitrate at 80 ℃, gradually adding 1mol/L of nitric acid and maintaining the pH of the solution between 0 and 2. If the concentration of yttrium ions in the mixed solution system is kept unchanged for 1 hour after the addition of the nitric acid is stopped, ending the etching operation; otherwise, continuously adding nitric acid for etching. And filtering and washing the etched mixed solution to obtain a filter cake, namely the intermediate D. Part of the obtained filtrate is returned to the step (1) after the pH value is adjusted to be 4-5, and the filtrate is used as a new inorganic template agent for recycling; and (4) returning the rest filtrate to the step (3) to be used as a new activating agent for recycling.
(4) And (3) burning the intermediate D at 1000 ℃ for 10 hours, wherein the heating rate is 2 ℃/min, and cooling and crushing to obtain the cerium-zirconium-yttrium composite oxide with the large specific surface.
(5) The specific surface area of the cerium-zirconium-yttrium composite oxide obtained in step (4) was measured by the BET method using a NOVA2000e specific surface Analyzer of Congta, USA, and was 100m2/g。
Example 4: preparation and detection of cerium oxide-based composite oxide Material
The preparation method of the cerium-aluminum composite oxide with the large specific surface area by adopting a coprecipitation method comprises the following specific steps:
(1) under the condition of 20 ℃ and continuous stirring, 144mL of 5mol/L ammonia water is added into 1L of aqueous solution containing 0.1mol of cerium chloride and 0.08mol of inorganic template agent aluminum chloride, the total using amount of the ammonia water is 0.72mol, and the intermediate A is obtained after filtration and washing.
(2) And (3) burning the intermediate A at 300 ℃ for 4 hours at the heating rate of 2 ℃/min, and cooling and crushing to obtain an intermediate C.
(3) At 80 ℃, the intermediate C is dispersed in 1L pure water without activator, 5mol/L sodium hydroxide is gradually added and the pH of the solution is maintained between 13 and 14. If the concentration of the metaaluminate ions in the mixed solution system is kept unchanged for 2 hours after the sodium hydroxide addition is stopped, the etching operation is finished; otherwise, continuing to add the sodium hydroxide for etching. And filtering and washing the etched mixed solution to obtain a filter cake, namely the intermediate D. And (3) adjusting the pH value of the obtained filtrate to 3-3.5, returning the filtrate to the step (1), and recycling the filtrate as a new inorganic template.
(4) And (3) burning the intermediate D at 300 ℃ for 4 hours at the heating rate of 10 ℃/min, and cooling and crushing to obtain the cerium-aluminum composite oxide with the large specific surface.
(5) Measuring the product of step (4) by BET method using NOVA2000e specific surface analyzer of Corta, USATo a specific surface area of 140m of a cerium-aluminum composite oxide2/g。
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is intended to include such modifications and variations. The foregoing examples or embodiments are merely illustrative of the present invention, which may be embodied in other specific forms or in other specific forms without departing from the spirit or essential characteristics thereof. The described embodiments are, therefore, to be considered in all respects as illustrative and not restrictive. The scope of the invention should be indicated by the appended claims, and any changes that are equivalent to the intent and scope of the claims should be construed to be included therein.
Claims (10)
1. A preparation method of a cerium oxide-based composite oxide material is characterized by comprising the following steps:
(1) and (3) precipitation: adding a precipitator into a solution containing cerium salt, optional zirconium salt and an inorganic template agent for precipitation, wherein the obtained precipitate is a first intermediate;
(2) pretreatment: burning, cooling and crushing the first intermediate obtained in the step (1) to obtain a second intermediate;
(3) etching: dispersing the second intermediate obtained in the step (2) in a solvent, adding an etching agent for etching, filtering and washing a mixed solution after etching, and obtaining a filter cake which is a third intermediate;
(4) and (3) post-treatment: and (4) burning, cooling and crushing the third intermediate obtained in the step (3) to obtain the cerium oxide-based composite oxide material.
2. The production method according to claim 1, characterized in that: in the step (1), the step (c),
the cation in the cerium salt is selected from + 3-valent or + 4-valent cerium ion or a mixture of the two, and the anion is selected from one or more of nitrate, sulfate, chloride and acetate;
the zirconium salt is selected from one or more of zirconyl nitrate, zirconyl sulfate, zirconyl chloride and zirconium acetate;
the cation of the inorganic template is selected from one or more of rare earth ions except cerium or non-rare earth metal ions, and the anion is selected from one or more of nitrate, sulfate, chloride and acetate;
the rare earth ions except cerium are selected from one or more of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium ions;
the non-rare earth metal ions are selected from one or more of transition metal ions, alkaline earth metal ions and aluminum ions;
the precipitant is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, ammonia water, bicarbonate, carbonate, oxalic acid and oxalate.
3. The method of claim 1, wherein: in the step (1), the step (c),
calculated by the mole number of the metal ions, the cerium salt accounts for 10 to 95 percent of the total mole amount of the cerium salt, the optional zirconium salt and the inorganic template agent; the zirconium salt accounts for 0 to 70 percent of the total molar weight of the cerium salt, the optional zirconium salt and the inorganic template agent; the inorganic template agent accounts for 5 to 90 percent of the total molar weight of the cerium salt, the optional zirconium salt and the inorganic template agent;
calculated by the mole number of the metal ions, the ratio of the mole number of the precipitator to the total mole number of the cerium salt, the optional zirconium salt and the inorganic template agent is 1-10.
4. The method of claim 1, wherein: in the step (1), the step (c),
the temperature of the precipitation reaction is 20-80 ℃;
the precipitation is coprecipitation, namely adding a precipitant solution into a solution containing cerium salt, optional zirconium salt and an inorganic template agent under the condition of continuous stirring for coprecipitation, and filtering and washing to obtain a first intermediate;
or the precipitation is gradient precipitation, namely adding partial precipitator solution into partial solution containing cerium salt, optional zirconium salt and inorganic template agent for precipitation under the condition of continuous stirring, then adding partial solution containing cerium salt, optional zirconium salt and inorganic template agent, adding partial precipitator solution into the solution for precipitation, repeating the operations for multiple times of precipitation until all solution containing cerium salt, optional zirconium salt and inorganic template agent and all precipitator solution are added, and filtering and washing to obtain the first intermediate.
5. The method of claim 1, wherein: in the step (2), the burning temperature is 100-.
6. The method of claim 1, wherein: in the step (3), the step (c),
the solvent is selected from one or more of water, methanol and ethanol;
the etching agent is an acidic substance or a basic substance, the acidic substance is selected from one or a combination of more of hydrochloric acid, sulfuric acid, nitric acid and acetic acid, and the basic substance is selected from one or a combination of more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and ammonia water.
7. The method of claim 6, wherein: in the step (3), the step (c),
when the etching agent is an acidic substance, an activating agent is added into the solvent, and the composition of the activating agent is the same as that of the inorganic template;
when the etching agent is alkaline substances, no activating agent is added into the solvent;
the etching temperature is 20-80 ℃;
when the etching agent is an acidic substance, the pH value of the etching operation solution is 0-5;
when the etching agent is alkaline substance, the pH value of the etching operation solution is 10-14.
8. The method of claim 1, wherein: in the step (3), after the addition of the etching agent is stopped, if the concentration of the inorganic template agent cations in the mixed solution system is kept stable, the etching reaction is finished; and otherwise, continuously adding an etching agent for etching, and filtering and washing the mixed solution after etching to obtain a filter cake, namely the third intermediate.
9. The method of claim 1, wherein: in the step (3), the pH of the filtrate containing the inorganic template agent obtained after the etching operation is adjusted to 3-7, and then the filtrate is returned to the step (1) for recycling and/or returned to the step (3) to be added into the solvent.
10. The method of claim 1, wherein: in the step (4), the burning temperature is 300-.
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