CN1105682C - Process for Preparing nm-class cobalt oxide - Google Patents
Process for Preparing nm-class cobalt oxide Download PDFInfo
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- CN1105682C CN1105682C CN99114908A CN99114908A CN1105682C CN 1105682 C CN1105682 C CN 1105682C CN 99114908 A CN99114908 A CN 99114908A CN 99114908 A CN99114908 A CN 99114908A CN 1105682 C CN1105682 C CN 1105682C
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- cobalt
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- cobaltous carbonate
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- cobalt oxide
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Abstract
The present invention relates to a nanometer cobalt oxide manufacture method characterized in that nitric acid or sulphuric acid is adopted to dissolve metal cobalt, hydrocarbonate is used for reacting to generate cobalt carbonate under the existence of surface active agents, and nanometer level cobalt oxide powder is manufactured through the processes of filtration, washing, calcination, etc. The particle diameter is from 5mm to 60mm, and the powder has the characteristics of high purity, low impurity content, sphericity, high specific surface area, etc., meets the requirements of electronic level powder materials and can be widely applied to electric, chemical and alloy material fields.
Description
The present invention relates to a kind of industrial process of nanometer grade cobalt oxide, belong to the manufacturing field of inorganic materials.
The manufacture method of nano_scale particle is a lot, and at present report has a solid phase method, vapor phase process and liquid phase method three major types, but, on the basis of above-mentioned three class methods, derive many new technologies along with the continuous development of science and technology and demand to different physics, chemical property particulate.
Liquid-phase precipitation method is precipitation agent to be joined in the metal salt solution after the reaction precipitation is heat-treated.Chinese patent CN1173855A is entitled as " cobalt oxide (II) that contains the cobalt metal, its manufacture method and application thereof " and has disclosed and contain the cobalt cobalt metal oxide, and its particle diameter is about 0.5 μ m, is mainly used in the electrode materials in the electrochemical secondary cell; The electronic-grade cobalt oxide has been reported in Chinese science and technology achievement storehouse, and this product is mainly used in the painted and semi-conductor of television picture tube glass bulb and other special glasss, pottery etc., but can not suitability for industrialized production, also is difficult to produce the nanometer grade cobalt oxide product.Chemical precipitation method has advantage simple to operate, but introduces impurity easily, is difficult to make the uniform nanometer particle of particle diameter.
The objective of the invention is to provide a kind of manufacture method of nanometer cobalt oxide at the deficiencies in the prior art, be characterized in adopting nitric acid or sulfuric acid dissolution cobalt metal, and in the presence of tensio-active agent, generate the cobaltous carbonate slip with the bicarbonate solution precipitation, after filtration, operation such as washing, roasting produces the nanometer grade cobalt oxide powder, its grain diameter is 5～60nm, and size distribution is inhomogeneous.
Purpose of the present invention is realized by following technical measures
The manufacture method of nanometer cobalt oxide:
1. the preparation of cobalt salt solution
Adopt nitric acid or sulfuric acid dissolution cobalt metal, generate Xiao Suangu or cobalt sulfate solution, cobalt contents is 50～300 grams per liters in the solution, and free acid is controlled at below 20 grams per liters.
2. the preparation of bicarbonate solution
Supercarbonate is dissolved in the deionized water, and is mixed with 5～40% the aqueous solution.
3. the preparation of cobaltous carbonate
The Xiao Suangu of preparation or cobalt sulfate solution and tensio-active agent added have in the reactor of agitator and thermometer, the consumption of tensio-active agent be in Xiao Suangu or the cobalt sulfate solution cobalt contents 0.01～10%, under agitation add the bicarbonate solution reaction and generate the cobaltous carbonate slip in 40～100 ℃ of temperature.
4. the filtration of cobaltous carbonate slip, washing
With slurry filtration, and with boiling water or hot wash to the filtrate alkalimetal ion or ammonium ion content less than 50ppm.
5. the roasting of cobaltous carbonate
The cobaltous carbonate that washing is good is inserted in the stoving oven, and in 300～550 ℃ of temperature, roasting 5～25 hours obtains the nanometer grade cobalt oxide powder, and grain diameter is 5～60nm.
Tensio-active agent is fatty acid loss water sorbit ester class (a Tween series), alkylphenol polyoxyethylene class (OP series) or arlacels (Span series) nonionogenic tenside and alkyl trimethyl ammonium salt, alkyl dimethyl ammonium salt or alkyl dimethyl benzyl ammonium salt cats product are at least a.
Chemical precipitation agent supercarbonate among the present invention is sodium bicarbonate or saleratus or bicarbonate of ammonia, and this all is to well known to a person skilled in the art knowledge.
The nano oxidized cobalt dust that the present invention makes, grain diameter is 5～60nm, thing is α-Co mutually
3O
4, cobalt contents is 70～73%, specific surface area reaches 40 meters
2/ gram, the purity height, foreign matter content is few, has characteristics such as spherical and high-specific surface area, meets the requirement of electronic-grade powder body material.Be mainly used in metal oxide arrester, pressure-sensitive and thermistor, stealth material, fields such as Wimet and coating.
The present invention has following advantage:
1. in the presence of tensio-active agent, adopt the size of chemical precipitation method control cobalt carbonate particle particle diameter, be easy to make nanometer grade cobalt oxide.This method is simple, is easy to apply.
2. the nanometer cobalt oxide grain graininess is even, and particle diameter is 5～60nm, the purity height, and foreign matter content is few, has the characteristics of spherical and high-specific surface area, meets the requirement of electronic-grade powder body material; Purposes is wide, and remarkable economic efficiency and social benefit are arranged.
Embodiment
The present invention is described further below by embodiment; be necessary to be pointed out that at this following examples only are used for the present invention is further specified; can not be interpreted as limiting the scope of the invention, the person skilled in art can foregoing according to the present invention to the present invention as some nonessential improvement and adjustment.
1. cobalt metal is dissolved in the industrial nitric acid solution, makes that cobalt contents is 110 grams per liters in the solution, free acid content is less than 10 grams per liters; Bicarbonate of ammonia is dissolved in the deionized water, concentration 10%.Get 250 liters of above-mentioned cobalt nitrate solutions, 0.1 liter of Tween-20, adding has in the reactor of agitator and thermometer, under agitation in 80 ℃ of temperature, the ammonium bicarbonate soln of preparation is added reaction kettle for reaction, when the pH value is 6.5 in the reaction soln, stop to add ammonium bicarbonate soln.Continue to stir after 20 minutes, with sedimentary cobaltous carbonate slurry filtration, and with the deionized water wash of boil (heat) to the filtrate ammonium ion content less than 50ppm.The cobaltous carbonate that washing is good is inserted in the stoving oven, in 300 ℃ of roastings of temperature 15 hours, obtains nano oxidized cobalt dust.Its grain diameter is 20～60nm, and thing is α-Co mutually
3O
4, cobalt contents is 72%.
2. cobalt metal is dissolved in the industrial nitric acid solution, makes that cobalt contents is 100 grams per liters in the solution, free acid content is less than 10 grams per liters; Bicarbonate of ammonia is dissolved in the deionized water, and concentration is 20%, Triton X-100 is dissolved in the deionized water again, and concentration is 15%.Get 250 liters of above-mentioned cobalt nitrate solutions, 1 liter of Triton X-100 adds in the equipment identical with enforcement 1, under agitation in 90 ℃ of temperature, ammonium bicarbonate soln is added reaction kettle for reaction.When the pH value is 6.5 in the reaction soln, stop to add ammonium bicarbonate soln, continue to stir after 20 minutes, with sedimentary cobaltous carbonate slurry filtration, and with the deionized water wash of boil (heat) to the filtrate ammonium ion content less than 50ppm.The cobaltous carbonate that washing is good is inserted in the stoving oven, and in 400 ℃ of temperature, roasting 12 hours obtains the nanometer grade cobalt oxide powder.Its grain diameter is 5～60nm, and thing is α-Co mutually
3O
4, cobalt contents is 72.5%.
3. the electrolytic metal cobalt is dissolved in the industrial nitric acid solution, cobalt contents is 170 grams per liters, and free acid content is less than 10 grams per liters; Sodium bicarbonate is dissolved in the deionized water, and concentration is 10%; Cetyl trimethylammonium bromide is dissolved in the deionized water, and concentration is 2%.Get 250 liters of above-mentioned cobalt nitrate solutions, 5 liters of cetyl trimethylammonium bromides add in the equipment identical with enforcement 1, under agitation in 90 ℃ of temperature, sodium hydrogen carbonate solution are added reaction kettle for reaction.When pH value in the reaction soln is about 6.5, stop to add sodium hydrogen carbonate solution, continue to stir after 20 minutes, method filtration, washing, the roasting of pressing embodiment 2 obtain the nanometer grade cobalt oxide powder.Its grain diameter is that 5～60nm thing is α-Co mutually
3O
4, cobalt contents is 72.3%.
4. the electrolytic metal cobalt is dissolved in the industrial sulphuric acid, cobalt contents is 100 grams per liters, and free acid content is less than 10 grams per liters; Saleratus is dissolved in the deionized water, and concentration is 20%, hexadecyldimethyl benzyl ammonium ammonium chloride is dissolved in the deionized water concentration 2% again.Get 250 liters of above-mentioned cobalt sulfate solutions, 10 liters of hexadecyldimethyl benzyl ammonium ammonium chloride solutions add in the equipment identical with embodiment 1, under agitation in 80 ℃ of temperature, potassium bicarbonate solution are added reaction kettle for reaction.When pH value in the reaction soln is about 6.5, stop to add potassium bicarbonate solution, continue to stir after 20 minutes, method filtration, washing, the roasting of pressing embodiment 2 obtain the nanometer grade cobalt oxide powder.Its grain graininess is 5～60nm, and thing is α-Co mutually
3O
4, cobalt contents is 71.5%.
Claims (2)
1. the manufacture method of a nanometer cobalt oxide is characterized in that:
(1) preparation of cobalt salt solution
Adopt nitric acid or sulfuric acid dissolution cobalt metal, generate Xiao Suangu or cobalt sulfate solution, cobalt contents is 50～300 grams per liters in the solution, and free acid is controlled at below 20 grams per liters,
(2) preparation of bicarbonate solution
Supercarbonate is mixed with 5～40% the aqueous solution,
(3) preparation of cobaltous carbonate
The Xiao Suangu or the cobalt sulfate solution adding of preparation are had in the reactor of agitator and thermometer, under agitation add the bicarbonate solution reaction and generate the cobaltous carbonate slip in 40～100 ℃ of temperature,
(4) cobaltous carbonate slurry filtration, washing
With the cobaltous carbonate slurry filtration, and with boiling water or hot wash,
(5) roasting of cobaltous carbonate
The cobaltous carbonate that washing is good is inserted in the stoving oven, and in 300～550 ℃ of temperature, roasting 5～25 hours obtains the nanometer grade cobalt oxide powder, and its grain diameter is 5～60nm,
Wherein, when the preparation of cobaltous carbonate, introduce tensio-active agent in the aqueous solution of Xiao Suangu or rose vitriol, consumption be in the solution cobalt contents 0.01%～10%.
2. according to the manufacture method of the described nanometer cobalt oxide of claim 1, it is characterized in that tensio-active agent is the fatty acid loss water sorbit ester class, alkylphenol polyoxyethylene class or arlacels nonionogenic tenside and alkyl trimethyl ammonium salt, alkyl dimethyl ammonium salt or alkyl dimethyl benzyl ammonium salt cats product at least a.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114908A CN1105682C (en) | 1999-06-02 | 1999-06-02 | Process for Preparing nm-class cobalt oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99114908A CN1105682C (en) | 1999-06-02 | 1999-06-02 | Process for Preparing nm-class cobalt oxide |
Publications (2)
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|---|---|
| CN1276345A CN1276345A (en) | 2000-12-13 |
| CN1105682C true CN1105682C (en) | 2003-04-16 |
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| CN99114908A Expired - Fee Related CN1105682C (en) | 1999-06-02 | 1999-06-02 | Process for Preparing nm-class cobalt oxide |
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Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1373083A (en) | 2001-03-07 | 2002-10-09 | 鞍山钢铁学院 | Process for preparing size-controllable nano-powder |
| KR100867281B1 (en) * | 2001-10-12 | 2008-11-06 | 재단법인서울대학교산학협력재단 | Synthesis of Monodisperse and Highly-Crystalline Nanoparticles of Metals, Alloys, Metal Oxides, and Multi-metallic Oxides without a Size-selection Process |
| CN1313380C (en) * | 2005-08-05 | 2007-05-02 | 北京化工大学 | Mesoporous structure Co3O4 nanocrystalline preparation method |
| CN1995482B (en) * | 2006-09-25 | 2010-05-12 | 厦门大学 | Nano cobalt monoxide crystal plane controllable growth method |
| CN1931727B (en) * | 2006-09-29 | 2010-09-08 | 自贡金丰新材料科技有限公司 | Production process of subnanometer level cobalt oxide |
| CN100425538C (en) * | 2006-10-31 | 2008-10-15 | 山东师范大学 | Synthesis method of cobaltous oxide nano-tube |
| CN101376529B (en) * | 2008-09-24 | 2010-10-13 | 周红阳 | Method for producing spherical cobaltous carbonate |
| CN112794369B (en) * | 2021-01-12 | 2023-03-10 | 广东邦普循环科技有限公司 | Preparation method and application of nano lithium cobalt oxide positive electrode material |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO58658A2 (en) * | 1972-02-05 | 1975-06-30 | Chimica Sinteza Oradea Intrepr | PROCEDURE FOR OBTAINING COBALY OXIDE FROM USED CATALYZERS |
| US4389339A (en) * | 1979-10-22 | 1983-06-21 | Allied Corporation | Process for making a cobalt oxide catalyst |
| JPH0896323A (en) * | 1994-09-22 | 1996-04-12 | Tdk Corp | Production of thin film magnetic head |
-
1999
- 1999-06-02 CN CN99114908A patent/CN1105682C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RO58658A2 (en) * | 1972-02-05 | 1975-06-30 | Chimica Sinteza Oradea Intrepr | PROCEDURE FOR OBTAINING COBALY OXIDE FROM USED CATALYZERS |
| US4389339A (en) * | 1979-10-22 | 1983-06-21 | Allied Corporation | Process for making a cobalt oxide catalyst |
| JPH0896323A (en) * | 1994-09-22 | 1996-04-12 | Tdk Corp | Production of thin film magnetic head |
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