CN1288091C - Process for preparing cobalto cobaltic oxide - Google Patents
Process for preparing cobalto cobaltic oxide Download PDFInfo
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- CN1288091C CN1288091C CNB2004100187230A CN200410018723A CN1288091C CN 1288091 C CN1288091 C CN 1288091C CN B2004100187230 A CNB2004100187230 A CN B2004100187230A CN 200410018723 A CN200410018723 A CN 200410018723A CN 1288091 C CN1288091 C CN 1288091C
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- cobalt
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- tricobalt tetroxide
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- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The present invention relates to a process for preparing cobaltosic oxid, which comprises the steps that cobaltiferous salts and oxides or hydroxides comprising cobalt chloride, cobalt sulfate, cobalt carbonate, cobalt acetate, citric acid cobalt and the like and various cobaltous organic acid, cobaltous oxide, cobaltous hydroxide and cobalt hydroxide are reduced into metal cobalt powder by hydrogen, hydrogen and nitrogen or carbon monoxide; the metal cobalt powder is continuously oxygenized into the product of cobaltosic oxid again through air or oxygen. The method has the characteristics of integration of the reduction process and the oxidation process, complete avoidance of the troublesome processes of filtration, washing, drying and the like produced by the liquid phase precipitation method, continuous completion by operation in the dry method, labor saving, time saving and money saving.
Description
Technical field
The invention belongs to, particularly a kind of manufacture method of tricobalt tetroxide.
Background technology
The manufacture method of tricobalt tetroxide has many kinds, for example the patent No. is the Japanese Patent of JP10324523, its method of producing tricobalt tetroxide is to make cobalt saline solution generate hydroxide cobalt suspensoid with the excess base aqueous solution, again with blow oxygen-containing gas or add hydrogen peroxide oxidation wherein cobalt be the trivalent cobalt, form cobaltous hydroxide, make tricobalt tetroxide again, this method process is tediously long, washing and filtering very difficult (because of cobaltous hydroxide is carefully to lack gelatinous precipitate) and products therefrom particle diameter are very thin, can not be used for specific purposes.For example application number is the Chinese patent of 0211970 (2002.04.22) again, its production method is to precipitate with the complex-precipitation agent when the PH4.0-5.5 with cobalt salt solution, refilter washing and drying calcining 5-25h classification and obtain tricobalt tetroxide again, this method is filtered, washing is still bothersome, and the calcining 25h time is long, and calcining temperature can reach 1000 ℃ of energy consumption height, and tricobalt tetroxide can be decomposed into cobaltous oxide, and visible calcination condition is insincere.Again for example, application number is that 3148092.6 Chinese patent (2004.01.28 is open) is with generating the cobaltous dihydroxycarbonate sedimentation and filtration, use hydrogen peroxide treatment again after washing, the drying, and it is dry to refilter washing, and obviously flow process is oversize, uneconomical.The common drawback of above method is a sedimentation and filtration, washing, and baking step is many, and the time is long, cleans to be difficult for, and expends a large amount of deionized waters, and the cost height is difficult to form scale operation.Again for example " mineral compound synthesizes the available oxygen cobaltous oxide of introducing in the handbook, cobaltous oxide, cobaltous carbonate, cobalt salts such as Xiao Suangu, directly roasting and make tricobalt tetroxide in air, save trouble though do simply like this, products obtained therefrom can not satisfy the needs of specific end use on size distribution and tap density.
Flourish along with emerging high energy green battery industry, to the manufacturing raw material of such battery no matter quantitatively or qualitative requirement all more and more higher.The battery raw material of producing with general manufacture method can not meet the demands, and we study and have invented the art of this patent for this reason.
Summary of the invention
Technical problem to be solved by this invention is: the manufacture method that a kind of tricobalt tetroxide is provided.
Technical scheme of the present invention is:
A kind of manufacture method of tricobalt tetroxide, it is characterized in that: salt, oxide compound or the oxyhydroxide that will contain cobalt is reduced to metal cobalt powder with the mixed gas or the carbon monoxide of hydrogen, hydrogen and nitrogen, is tricobalt tetroxide with metal cobalt powder blowing air or dioxygen oxidation once continuously again.
The salt of described cobalt, oxide compound or oxyhydroxide are following a kind of: cobalt chloride, rose vitriol, cobaltous carbonate, cobaltous acetate, citric acid cobalt, cobaltous oxide, hydroxide cobalt, cobaltous hydroxide.
Reduction adopts intermittent type continuous production stoving oven salable, vacuum-pumping, controlled atmosphere to carry out.
With metal cobalt powder blowing air or dioxygen oxidation in stoving oven is tricobalt tetroxide.
The intermittent type continuous production stoving oven of salable, vacuum-pumping, controlled atmosphere vacuumizes earlier and afterwards fills with nitrogen, is warming up to 350-600 ℃ and feeds hydrogen or carbon monoxide 2-2.5h, and making wherein, cobalt compound is reduced to cobalt powder; Open hermatic door, make air admission wherein; Or bubbling air, cobalt powder began oxidation and produced heat temperature of reaction is remained between 400-600 ℃ this moment, and oxidizing reaction is carried through to the end automatically like this; Reaction stirred makes its oxidation abundant frequently in oxidising process is carried out, and the 2-3h afterreaction is finished and can be come out of the stove.
Effect of the present invention is: the characteristics of this method are for integrating reduction process and oxidising process, have avoided the filtration that produces with liquid-phase precipitation method fully, and loaded down with trivial details process such as washing and drying is that the dry method operation is accomplished without any letup fully.Time saving and energy saving saving money.Once can obtain the required particle size range of specific end use after gained tricobalt tetroxide product is classified, loose density, tap density and chemical ingredients meet the demands fully.This method is the raw material of the cobaltous oxide used of the another kind of green high-capacity battery of coproduction simultaneously nickel-hydrogen secondary cell also, make the best use of everything, flow process is reasonable, technology is simple, cost is lower, raw material sources are extensive, and some present method of lay special stress on do not have the discharging of slag and effluent and poisonous fume, realized that zero of Chemical Manufacture pollutes.
Embodiment
The concrete implementation step of the present invention is: the compound (salt, oxide compound, oxyhydroxide) of cobalt is placed special process furnace, fill with nitrogen after vacuumizing, be warming up to 350-600 ℃ and feed hydrogen or carbon monoxide 2-2.5h, making wherein, cobalt compound is reduced to cobalt powder.Open hermatic door, make air admission wherein.Or bubbling air, cobalt powder began oxidation and produced heat temperature of reaction is remained between 400-600 ℃ this moment, and oxidizing reaction is carried through to the end automatically like this.Reaction stirred or automatically stir and make its oxidation abundant frequently in oxidising process is carried out.The 2-3h afterreaction is finished and can be come out of the stove.
Embodiment 1
Take by weighing the 2.0kg cobaltous oxide and place stoving oven, stoving oven is obturaged, be evacuated to below the 0.06MP, take out once again with vacuum pump with lid.Feeding nitrogen to stove exit aperture water seal has denumerable bubble to emerge.Be warming up to 480 ℃.Feed hydrogen, its flow velocity is 100-120ml/min.For keeping malleation, hydrogen outlet has the about 150mm height of water column.Behind 2-2.5h, stop to feed hydrogen.Logical nitrogen is driven hydrogen out of, opens hermatic door, makes air admission, and this moment, oxidizing reaction began, and stirred once after a while, behind 2-3h.Reaction is finished.Coming out of the stove is chilled to room temperature, uses the grading machine classification, gets tricobalt tetroxide 1.94kg, and gets fine powder 0.12kg.Amount to productive rate more than 95%.The gained fine powder is used to produce cobaltous oxide.Meet fully after tested and produce the lithium cell requirement.
Embodiment 2
Take by weighing 2.0kg hydroxide cobalt and place stoving oven, with lid stove is obturaged, be evacuated to below the 0.06MP, take out once again, logical nitrogen is to there being nitrogen bubble to emerge.Be warming up to 450 ℃.Feed hydrogen, its flow velocity is 80-100ml/min.The about 150mm height of hydrogen outlet water column.Behind ventilation 2-3h, stop to feed hydrogen, logical nitrogen is driven hydrogen out of, opens hermatic door.Make air admission.Behind the 2-3h, promptly come out of the stove.Get tricobalt tetroxide 1.60kg after the classification, and get fine powder 0.07kg, same test meets and produces the lithium cell requirement.
Embodiment 3
Take by weighing the 50.0g cobaltous carbonate and place stoving oven, stoving oven is obturaged, be evacuated to below the 0.06MP, take out once again with vacuum pump with lid.Feeding nitrogen to stove exit aperture water seal has denumerable bubble to emerge.Be warming up to 500 ℃.Feed hydrogen, its flow velocity is 80-100ml/min.Hydrogen outlet has the about 150mm height of water column.Behind 2-3h, stop to feed hydrogen.Logical nitrogen is driven hydrogen out of, opens hermatic door, makes air admission, promptly comes out of the stove behind the 2-3h, gets tricobalt tetroxide 30.5g after the classification, and gets fine powder 1.94g.After tested, meet the requirement of production lithium cell.
Embodiment 4
Take by weighing the 50.0g cobaltous carbonate and place stoving oven, stoving oven is obturaged, be evacuated to below the 0.06MP, take out once again with vacuum pump with lid.Logical nitrogen is to there being bubble to emerge.Be warming up to 500 ℃.Feed hydrogen, its flow velocity is 80-100ml/min.Hydrogen outlet has the about 150mm height of water column.Behind 2-3h, stop to feed hydrogen.Logical nitrogen is driven hydrogen out of, opens hermatic door, makes air admission, promptly comes out of the stove behind the 2-3h, gets tricobalt tetroxide 14.9g after the classification, and gets fine powder 0.7g.After tested, meet the requirement of production lithium cell.
Claims (5)
1, a kind of manufacture method of tricobalt tetroxide, it is characterized in that: salt, oxide compound or the oxyhydroxide that will contain cobalt is reduced to metal cobalt powder with the mixed gas or the carbon monoxide of hydrogen, hydrogen and nitrogen, is tricobalt tetroxide to metal cobalt powder blowing air or dioxygen oxidation once continuously again.
2, according to the manufacture method of the described tricobalt tetroxide of claim 1, it is characterized in that: the salt of described cobalt, oxide compound or oxyhydroxide are following a kind of: cobalt chloride, rose vitriol, cobaltous carbonate, cobaltous acetate, citric acid cobalt, cobaltous oxide, hydroxide cobalt, cobaltous hydroxide.
3, the manufacture method of tricobalt tetroxide according to claim 1 is characterized in that: reduction adopts intermittent type continuous production stoving oven salable, vacuum-pumping, controlled atmosphere to carry out.
4, the manufacture method of tricobalt tetroxide according to claim 3 is characterized in that: with metal cobalt powder blowing air or dioxygen oxidation in stoving oven is tricobalt tetroxide.
5, the manufacture method of tricobalt tetroxide according to claim 4, it is characterized in that: in the intermittent type continuous production stoving oven of salable, vacuum-pumping, controlled atmosphere, vacuumize earlier and afterwards fill with nitrogen, be warming up to 350-600 ℃ and feed hydrogen or carbon monoxide 2-2.5h, make wherein the salt that contains cobalt, oxide compound or oxyhydroxide be reduced to cobalt powder; Open hermatic door, make air admission wherein; Or bubbling air, cobalt powder began oxidation and produced heat temperature of reaction is remained between 400-600 ℃ this moment, and oxidizing reaction is carried through to the end automatically like this; Reaction stirred makes its oxidation abundant frequently in oxidising process is carried out, and the 2-3h afterreaction is finished and can be come out of the stove.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2004100187230A CN1288091C (en) | 2004-03-10 | 2004-03-10 | Process for preparing cobalto cobaltic oxide |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2004100187230A CN1288091C (en) | 2004-03-10 | 2004-03-10 | Process for preparing cobalto cobaltic oxide |
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| CN1666958A CN1666958A (en) | 2005-09-14 |
| CN1288091C true CN1288091C (en) | 2006-12-06 |
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| CNB2004100187230A Expired - Fee Related CN1288091C (en) | 2004-03-10 | 2004-03-10 | Process for preparing cobalto cobaltic oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106966439A (en) * | 2017-03-15 | 2017-07-21 | 四川大学 | A kind of preparation method of battery electrode cobaltosic oxide nano line |
| CN108033494B (en) * | 2017-12-08 | 2019-11-22 | 蒋央芳 | A kind of preparation method of nanometer of ball-type cobaltosic oxide |
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