CN1631771A - Preparation method of metal complex oxide - Google Patents
Preparation method of metal complex oxide Download PDFInfo
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- CN1631771A CN1631771A CN 200310119459 CN200310119459A CN1631771A CN 1631771 A CN1631771 A CN 1631771A CN 200310119459 CN200310119459 CN 200310119459 CN 200310119459 A CN200310119459 A CN 200310119459A CN 1631771 A CN1631771 A CN 1631771A
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Abstract
The invention relates to a metal complex oxide powder specifically to the preparation method of this metal complex oxide. Dissolve mixingly two or more metal oxide each in acid or directly add soluble metal-salt into water till the metal-salt in the system saturated. Add to system alcoholic dissolvent till the volume ratio of alcohol to water is 1 : 0.2-0.4; add to system the precipitant so to completely precipitate the metal ion and peptizate the metal deposit by adding inorganic acid and inorganic base; after the solution is totally peptizated put the reaction container in high temperature furnace at temperature between 400 to 600 deg. C to pyrolyze, when the predecessor block self ignites the pyrolyzation is done and the binary or multi-nary metal complex oxide powder is obtained; the precipitant is organic amine or ammonia liquor. The invention is of simple process, short composite cycle, and stable reaction system. The complex oxide powder has advantages such as large specific area, pure phase, particle diameter uniformly arranged.
Description
Technical field
The present invention relates to the composite oxide of metal powder, is a kind of preparation method of composite oxide of metal specifically.
Background technology
Complex rare-earth oxidate containing valuable metal is a kind of material with extensive use, as electrode materials, oxygen permeable film, sensor material etc.Different preparation methods has a significant impact the material character of oxide compound, and the character of material has particular requirement to different purposes; The composite oxide catalysts that has high-specific surface area as preparation is the key that improves its catalytic activity; Prepare ceramic powder high-purity, ultra-fine, narrow size distribution and be the key of preparation high-performance ceramic etc.
Solid reaction process is used in the preparation of traditional complex rare-earth oxidate containing valuable metal powder always, and this method is simple to operate, and the element system that is suitable for is very wide, still is widely adopted so far; But because heterogeneous solid state reaction needs high-temperature roasting repeatedly, with process of lapping, the powder phase composite of gained is inhomogeneous, and specific surface area is little; High in addition maturing temperature may cause the loss of some volatile raw material.In order to overcome above shortcoming, people develop various wet chemical methods, can be at synthetic high-purity, the superfine oxide powder of low temperature; As sol-gel method, complexometry, hydrothermal synthesis method, combustion method etc.
Sol-gel (sol-gel) method is a kind of method that preparation high quality complex rare-earth oxidate containing valuable metal powder often adopts.This method realized the uniform mixing of reactant molecule level and successfully eliminated the resistance of the diffusion of reaction, can be synthetic high-purity at low temperature, and the superfine powder of homogeneous grain diameter; But since common sol-gel method need to adopt the metal alkoxide that costs an arm and a leg is raw material, cost height so not only, and the system of the element that is suitable for is less; Because reaction system is strict to the pH value of whole colloidal sol and gelation process, technological process is difficult to be controlled in addition.Citric acid complex method has overcome some shortcomings of common sol-gel method, and wider as the system of the element that is suitable for, the cost of raw material is lower, system can be in big pH value scope stable existence etc.; But also there is a stubborn problem in this method, the colloid that promptly makes is at the pyrolysated preliminary stage, owing to making colloid increase rapidly, the generation of the decomposition of the nitrate in the system and water vapor is easy to overflow container, thereby in the process of preparation, need about 100 ℃, carry out long pre-treatment, make the carrying out of slow decomposition of nitrate, therefore, the output cycle is long; And this method the surface-area of powder less relatively.
Summary of the invention
The object of the present invention is to provide and a kind ofly can synthesize the method that has high-specific surface area, pure phase, has the serial high-test metal composite oxide powder of homogeneous size distribution, the particularly method of complex rare-earth oxidate containing valuable metal powder at low temperatures.
For achieving the above object, the technical solution used in the present invention is:
Under agitation condition, be dissolved in two or more metal oxide in the acid respectively or directly adopt soluble metallic salt to add in the aqueous solution, make that metal-salt is in saturated mode in the system, in reaction system, add alcoholic solvent, make that the volume ratio of alcohol and water is 1: 0.2～0.4 in the reaction system; In reaction system, add precipitation agent metal ion is precipitated fully, add mineral acid or mineral alkali again the precipitated metal thing is carried out peptization; Behind the complete peptization of solution, reactor is placed 400～600 ℃ High Temperature Furnaces Heating Apparatus, carry out thermolysis, when presoma generation spontaneous combustion, thermolysis finishes, and promptly gets the above composite oxide of metal powder of binary or binary; Wherein precipitation agent is organic amine material and/or ammoniacal liquor.
Described organic amine material is triammonium citrate, amine acetate and/or oxamide, and the mole number that requires the NH4+ in the precipitation agent and the ratio of metal ion total mole number are more preferably greater than 3; Composite oxide powder has A
1-xA
# xB
1-yB
# yO
3 ± δStructure, wherein A is La, Pr or Ce, A
#Be Sr or Ca, B is Mn, Co or Ni, B
#Be Fe, Al, Cu or Mg, x=0～1, y=0～1, δ=0.01～0.15; Described alcohol is C
2～C
4Unit and/or polyvalent alcohol, as ethanol, ethylene glycol and/or glycerol; Soluble metal salt is nitrate, acetate, oxalate or the Citrate trianion of metal; The mineral acid that uses in the peptization course is nitric acid, the PH of the hierarchy of control≤2; The mineral alkali that uses in the peptization course is ammoniacal liquor, the PH of the hierarchy of control 〉=8; When the mineral acid that adopts in the reaction system is nitric acid and/or metal soluble salt when being nitrate, NO
- 3With NH
+ 4Mol ratio be 1: 0.8～1.2; A kind of when the rare earth oxide when having at least in the metal oxide, wherein rare earth element accounts for 10～90% of metallic element integral molar quantity.
The present invention has following advantage:
1. technology is simple, synthesis cycle short.The synthesizing rare-earth composite oxides wet chemical method that the present invention developed has overcome the shortcoming of synthetic method in the past, synthesize at low temperatures have high-specific surface area, the serial high quality complex rare-earth oxidate containing valuable metal powder of pure phase, homogeneous size distribution, because whole reaction system has very strong pH value self-regulated ability, complexing agent has fabulous dispersiveness and stable in pure water solvent, need not be in the long dehydration of the low temperature under 100 ℃, simplify technological process, and shortened synthesis cycle simultaneously.
2. reaction system is stable.The present invention adopts peptisation, and selected precipitation agent is a weak acid and weak base salt, has the ability of very strong regulation system pH value, can guarantee system pH value stable in the evaporative process of heating moisture; Precipitation agent is again a complexing agent in the present invention, and metal ion is had stronger complexing action, improves complexing agent dispersive ability in solvent by adding alcohols material simultaneously, guarantees that system is more stable.
3. product specific surface area height.Spontaneous combustion and slight blast after system is heated to certain temperature, can take place owing to have organism, nitrate ion, the amine radical ion of certain proportion content in the system in the present invention, and this is the process of accelerated reaction not only, and improves the specific surface area of powder greatly.
Description of drawings
Fig. 1 is La
0.8Sr
0.2MnO
3 ± δPowder (embodiment 1) X-ray diffractogram;
Fig. 2 is LaNi
0.6Fe
0.4O
3 ± δPowder (embodiment 2) X-ray diffractogram.
Embodiment
Embodiment 1
Adopt alcohol-water to make solvent, triammonium citrate is made precipitation agent, synthetic La
0.8Sr
0.2MnO
3 ± δOxide powder:
Take by weighing La respectively
2O
3: 8.7g, Sr (NO
3)
2: 2.8g, Mn (NO
3)
2(50wt% solution): 23.8g is at La
2O
3The middle secondary deionized water that adds 20ml adds an amount of 66～68%HNO again
3, make solid La
2O
3Powder fully dissolves.The secondary deionized water preparation Sr (NO that adds 5ml
3)
2Solution; The solution of three metal ion species is mixed, stirs evenly.With the triammonium citrate of 20ml ethanol and 8.8 grams, introduce simultaneously in the mixing solutions of metal ion, fully stir.Use an amount of 66～68%HNO
3System is carried out peptization, and the PH of system is transferred 1～2; Under 600 ℃ of High Temperature Furnaces Heating Apparatuss, the heating mixed solution system is to the presoma spontaneous combustion with mixed system, and thermolysis finishes.The powder that is obtained be black and particle diameter little, quality is fluffy, even, becomes single uhligite phase (as shown in Figure 1).
Adopt ethylene glycol-water as solvent, amine acetate is made precipitation agent, synthetic LaNi
0.6Fe
0.4O
3 ± δOxide powder:
Take by weighing La respectively
2O
3: 8.2g, Ni (NO
3)
2.6H
2O:8.7g, Fe (NO
3)
3.9H
2O:8.1g is at La
2O
3The middle secondary deionized water that adds 20ml adds an amount of 66～68%HNO again
3, make solid La
2O
3Powder fully dissolves.The secondary deionized water preparation Ni (NO that adds 10ml
3)
2Solution.The secondary deionized water preparation Fe (NO that adds 10ml
3)
3Solution.The solution of three metal ion species is mixed, stirs evenly.With 15ml ethylene glycol and 20 gram amine acetates, introduce simultaneously in the mixing solutions of metal ion, fully stir.Use an amount of 66～68%HNO
3System is carried out peptization, and the PH of system is transferred 1～2.Under 600 ℃ of High Temperature Furnaces Heating Apparatuss, the heating mixed solution system is to the presoma spontaneous combustion with mixed system, and thermolysis finishes.The powder that is obtained be beige and particle diameter little, quality is fluffy, even, becomes single uhligite phase (as shown in Figure 2).
Embodiment 3
Adopt glycerol-water as solvent, triammonium citrate is made precipitation agent, synthetic Pr
0.7Sr
0.3CoO
3 ± δOxide powder:
Take by weighing Pr respectively
6O
11: 7.84g, Sr (NO
3)
2: 4.17g, Co (NO
3)
26H
2O:19.13g is at Pr
6O
11The middle secondary deionized water that adds 40ml adds an amount of 66～68%HNO again
3, make solid Pr
6O
11Powder fully dissolves.The secondary deionized water preparation Sr (NO that adds 50ml
3)
2And Co (NO
3)
2Mixing solutions.The solution of three metal ion species is mixed, stirs evenly.With the triammonium citrate of 100ml glycerol and 50 grams, introduce simultaneously in the mixing solutions of metal ion, fully stir.Use an amount of 66～68%HNO
3System is carried out peptization, and the PH of system is transferred 1～2.Under 600 ℃ of High Temperature Furnaces Heating Apparatuss, the heating mixed solution system is to the presoma spontaneous combustion with mixed system, and thermolysis finishes.The powder gray and the particle diameter that are obtained are little, and quality is fluffy, even.
Embodiment 4
Adopt alcohol-water to make solvent, triammonium citrate is made precipitation agent, synthetic La
0.8Ca
0.2Co
0.6Fe
0.4O
3 ± δOxide powder:
Take by weighing La respectively
2O
3: 13.04g, CaO:1.12g, Co (NO
3)
26H
2O:18.66g, Fe (NO
3)
3.9H
2O:16.16g is at La
2O
3The middle secondary deionized water that adds 20ml adds an amount of 66～68%HNO again
3, make solid La
2O
3Powder fully dissolves.In CaO, add the secondary deionized water of 5ml, add an amount of 66～68%HNO again
3, solid CaO powder is fully dissolved.The secondary deionized water preparation Co (NO that adds 35ml
3)
2And Fe (NO
3)
3Mixing solutions.The solution of three metal ion species is mixed, stirs evenly.With the triammonium citrate of 40ml ethanol and 35 grams, introduce simultaneously in the mixing solutions of metal ion, fully stir.Use an amount of 66～68%HNO
3System is carried out peptization, and the PH of system is transferred 1～2.Under 600 ℃ of High Temperature Furnaces Heating Apparatuss, the heating mixed solution system is to the presoma spontaneous combustion with mixed system, and thermolysis finishes.The diameter of particle that is obtained is little, and quality is fluffy, even.
Embodiment 5
Adopt alcohol-water to make solvent, oxamide is made precipitation agent, synthetic La
0.8Sr
0.2MnO
3 ± δOxide powder:
Take by weighing La respectively
2O
3: 8.7g, Sr (NO
3)
2: 2.8g, Mn (CH
3CH
2O
2)
2: 13.08g, at La
2O
3The middle secondary deionized water that adds 20ml adds an amount of 66～68%HNO again
3, make solid La
2O
3Powder fully dissolves.The secondary deionized water preparation Sr (NO that adds 35ml
3)
2And Mn (CH
3CH
2O
2)
2Mixing solutions.The solution of three metal ion species is mixed, stirs evenly.With 20ml ethanol and 28 gram oxamides, introduce simultaneously in the mixing solutions of metal ion, fully stir.Use an amount of 66～68%HNO
3System is carried out peptization, and the PH of system is transferred 1～2.Under 600 ℃ of High Temperature Furnaces Heating Apparatuss, the heating mixed solution system is to the presoma spontaneous combustion with mixed system, and thermolysis finishes.The powder that is obtained be black and particle diameter little, quality is fluffy, even.
Claims (10)
1. the preparation method of a composite oxide of metal is characterized in that:
Under agitation condition, be dissolved in two or more metal oxide in the acid respectively or directly adopt soluble metallic salt to add in the aqueous solution, make that metal-salt is in saturated mode in the system, in reaction system, add alcoholic solvent, make that the volume ratio of alcohol and water is 1: 0.2～0.4 in the reaction system; In reaction system, add precipitation agent metal ion is precipitated fully, add mineral acid or mineral alkali again the precipitated metal thing is carried out peptization; Behind the complete peptization of solution, reactor is placed 400～600 ℃ High Temperature Furnaces Heating Apparatus, carry out thermolysis, when presoma generation spontaneous combustion, thermolysis finishes, and promptly gets the above composite oxide of metal powder of binary or binary; Wherein precipitation agent is organic amine material and/or ammoniacal liquor.
2. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: described organic amine material is triammonium citrate, amine acetate and/or oxamide.
3. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: the ratio of the mole number of the NH4+ in the precipitation agent and metal ion total mole number is greater than 3.
4. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: composite oxide powder has A
1-xA
# xB
1-yB
# yO
3 ± δStructure, wherein A is La, Pr or Ce, A
#Be Ar or Ca, B is Mn, Co or Ni, B
#Be Fe, Al, Cu or Mg, x=0～1, y=0～1, δ=0.01～0.15.
5. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: described alcohol is C
2～C
4Unit and/or polyvalent alcohol.
6. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: described alcohol is ethanol, ethylene glycol and/or glycerol.
7. press the preparation method of the described composite oxide of metal of claim 1,, it is characterized in that: it is characterized in that: soluble metal salt is nitrate, acetate, oxalate or the Citrate trianion of metal.
8. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: the mineral acid that uses in the peptization course is nitric acid, the PH of the hierarchy of control≤2; The mineral alkali that uses in the peptization course is ammoniacal liquor, the PH of the hierarchy of control 〉=8.
9. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: when the mineral acid that adopts in the reaction system is nitric acid and/or metal soluble salt when being nitrate, NO
- 3With NH
+ 4Mol ratio be 1: 0.8～1.2.
10. by the preparation method of the described composite oxide of metal of claim 1, it is characterized in that: a kind of during for rare earth oxide when having at least in the metal oxide, wherein rare earth element accounts for 10～90% of metallic element integral molar quantity.
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|---|---|---|---|
| CNB2003101194595A CN1312027C (en) | 2003-12-24 | 2003-12-24 | Preparation method of metal complex oxide |
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|---|---|---|---|
| CNB2003101194595A CN1312027C (en) | 2003-12-24 | 2003-12-24 | Preparation method of metal complex oxide |
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|---|---|
| CN1631771A true CN1631771A (en) | 2005-06-29 |
| CN1312027C CN1312027C (en) | 2007-04-25 |
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727950A (en) * | 2016-03-17 | 2016-07-06 | 西安凯立新材料股份有限公司 | Catalyst for carbon monoxide oxidation and preparation method of catalyst for carbon monoxide oxidation |
| CN107188242A (en) * | 2017-06-01 | 2017-09-22 | 范佳晨 | Co0.4Fe0.6LaO3The preparation method of nano particle |
| CN107855074A (en) * | 2017-11-28 | 2018-03-30 | 桂林电子科技大学 | A kind of particle diameter thinning method that metal oxide materials are prepared using nitrate as raw material |
| CN110237658A (en) * | 2019-06-17 | 2019-09-17 | 中国矿业大学 | Oxygen generation system based on high temperature oxygen permeation membrane |
| CN111484329A (en) * | 2020-05-20 | 2020-08-04 | 中国科学院重庆绿色智能技术研究院 | Liquid phase synthesis L axSr1-xCoO3-Method for preparing composite oxide |
| CN111621807A (en) * | 2020-05-28 | 2020-09-04 | 华中科技大学 | Electrode material of quasi-symmetrical solid oxide electrolytic cell and preparation method and application thereof |
Family Cites Families (3)
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| CN1107661C (en) * | 1999-12-16 | 2003-05-07 | 上海师范大学 | Preparation method of composite Bi-Pb-Sr-Ca-Cu oxide powder |
| CN1305957A (en) * | 2001-02-07 | 2001-08-01 | 钟兴文 | Process for preparing powdered mixture of indium oxide and tin oxide |
| CN1412117A (en) * | 2001-10-15 | 2003-04-23 | 正隆股份有限公司 | Method for preparing indium tin oxide powder by aqueous solution method |
-
2003
- 2003-12-24 CN CNB2003101194595A patent/CN1312027C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105727950A (en) * | 2016-03-17 | 2016-07-06 | 西安凯立新材料股份有限公司 | Catalyst for carbon monoxide oxidation and preparation method of catalyst for carbon monoxide oxidation |
| CN105727950B (en) * | 2016-03-17 | 2018-09-21 | 西安凯立新材料股份有限公司 | A kind of Oxidation of Carbon Monoxide catalyst and preparation method thereof |
| CN107188242A (en) * | 2017-06-01 | 2017-09-22 | 范佳晨 | Co0.4Fe0.6LaO3The preparation method of nano particle |
| CN107855074A (en) * | 2017-11-28 | 2018-03-30 | 桂林电子科技大学 | A kind of particle diameter thinning method that metal oxide materials are prepared using nitrate as raw material |
| CN110237658A (en) * | 2019-06-17 | 2019-09-17 | 中国矿业大学 | Oxygen generation system based on high temperature oxygen permeation membrane |
| CN111484329A (en) * | 2020-05-20 | 2020-08-04 | 中国科学院重庆绿色智能技术研究院 | Liquid phase synthesis L axSr1-xCoO3-Method for preparing composite oxide |
| CN111621807A (en) * | 2020-05-28 | 2020-09-04 | 华中科技大学 | Electrode material of quasi-symmetrical solid oxide electrolytic cell and preparation method and application thereof |
| CN111621807B (en) * | 2020-05-28 | 2022-04-29 | 华中科技大学 | Electrode material of quasi-symmetrical solid oxide electrolytic cell and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1312027C (en) | 2007-04-25 |
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