CN101274782A - Method and apparatus for preparing high-intensity cobaltic-cobaltous oxide power - Google Patents
Method and apparatus for preparing high-intensity cobaltic-cobaltous oxide power Download PDFInfo
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- CN101274782A CN101274782A CNA2007100346156A CN200710034615A CN101274782A CN 101274782 A CN101274782 A CN 101274782A CN A2007100346156 A CNA2007100346156 A CN A2007100346156A CN 200710034615 A CN200710034615 A CN 200710034615A CN 101274782 A CN101274782 A CN 101274782A
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Abstract
The invention provides a method for preparing Co3O4 (tricobalt tetreoxide) powder with high density and equipment thereof. Anhydrous CoCl2 is taken as raw material, the granularity of which is 100 to 400 meshes, and added into a reaction furnace to be fully mixed with oxidizing gas that contains water vapour at a motion state under 500 to 1000 DEG C for reaction so as to generate the Co3O4 powder. The equipment comprises a furnace body, the upper part of which is a drum body provided with a feeding tube and a discharging tube of airflow and products; the lower part of the furnace body is a conical tube, the bottom end of which is provided with a slag discharging tube, and the conical surface of the lower end of the conical tube is connected with a warm-air tube. The technique process of the method and the equipment of the invention are simple, the process system of the invention is convenient for controlling and regulating, reaction products only contain two phases of gas and solid, which are easy to be separated, then treatment procedures are carried out, namely, separation of the gas and the solid, washing, drying and classification of the powder, recovery of HCl gas, etc. are connected with the prior art, therefore, the quality of the products is high and no pollution is caused in the production process.
Description
Technical field
The present invention relates to prepare the method and apparatus of high-intensity cobaltic-cobaltous oxide power, its raw material is a cobalt chloride.
Background technology
Tricobalt tetroxide is to make anode material for lithium-ion batteries LiCoO
2Raw material.At present, the method for industrial production tricobalt tetroxide mainly is wet-precipitated-calcination method, and this method has 2 kinds of concrete technologies.One adds in the cobalt salt solution for being precipitation agent with the ammonium hydrogencarbonate, generates the cobaltous dihydroxycarbonate precipitation, after filtration, washing and the drying, calcines under 800 ℃ of left and right sides high temperature, obtains the tricobalt tetroxide product.It two is that to adopt NaOH be neutralizing agent, and under conditions such as controlled temperature, pH value, hydrolytic precipitation goes out Co (OH) from cobalt salt solution
2, under 800 ℃ of left and right sides high temperature, calcine again, obtain the tricobalt tetroxide product.The advantage of wet-precipitated one calcination method is that the technology starting point is low, is easy to realize and grasp; But the shortcoming that exists is that technical process is longer, and production efficiency is low, exists nitrogen-containing wastewater to pollute, and the product pattern is the porous coacervate, and tap density is low, has dephasigns such as cobaltous oxide, and homogeneity is poor, and performance can not finely satisfy LiCoO
2Production requirement.
Grace gram company etc. adopts solution atomization-roasting method to produce tricobalt tetroxide.Concrete technology is, with CoCl
2That the aqueous solution adopts is centrifugal, high pressure or method atomizing such as ultrasonic, spray in the high-temperature roasting stove, under 800 ℃ of left and right sides high temperature, droplet is converted into cobaltosic oxide powder through serial physics, chemical processes such as thermal dehydration, crystallization, pyrohydrolysis, oxidation, collision reunion and sintering.The advantage of this method is to produce high-intensity cobaltic-cobaltous oxide power, but have that the atomizing stoving oven is bulky, material requires deficiencies such as high, that energy consumption is high, gather dust and exhaust treatment system complexity, investment be big.
200410023350.6) and " Reaktionsofen for preparing high-quality tricobalt tetroxide " (application number: in the patent application 200420036289.4) at " novel method for preparing high-quality tricobalt tetroxide " (application number:, having proposed a kind of is raw material with the cobalt salt that contains crystal water, it is contained in container, place the push boat type tunnel furnace to heat, make the method for cobaltosic oxide powder.The problem that this method exists is, material remains static, if the bed of material is too thin, then production efficiency is very low; And the bed of material is blocked up, and then because the bed of material is heated irregularly, crystal water is separated out generations such as making furnace charge fusion, crust in a large number during heating, causes problems such as reaction conditions is inhomogeneous, homogeneity of product is poor, particle is thick.Thereby its operation control difficulty is bigger on industrial production.
Summary of the invention
The objective of the invention is, the poor product quality that exists in the prior art at the preparation tricobalt tetroxide, existence are polluted, deficiencies such as investment is big, performance difficulty, propose a kind of method and apparatus for preparing high-density cobaltosic oxide.
Its scheme is, with the Powdered anhydrous CoCl of 100 orders～400 purposes
2Be raw material, it is added in the Reaktionsofen that under 500～1000 ℃ of temperature, be the oxidizing gas thorough mixing of kinestate and moisture vapor, reaction generates cobaltosic oxide powder, its reaction formula is:
3CoCl
2(s)+3H
2O
(g)+1/2O
2(g)＝Co
3O
4(s)+6HCl
(g)。
Described Reaktionsofen comprises a body of heater for the formula Reaktionsofen that floats, and its top is cylindrical shell, is provided with feed-pipe and vapor pipe; Its underpart is taper, and the bottom is provided with slag-drip opening, and the conical surface of cone lower end is provided with inlet mouth.
The inventive method technological process and equipment are simple, process system is convenient to grasp regulation and control, reaction product has only gas-solid two-phase and separate easily, its postprocessing working procedures, the recovery etc. that is washing, drying, classification and the HCl gas of gas solid separation, powder is easy to be connected with existing process means, the quality product height, production process is pollution-free.
Description of drawings
Fig. 1 is a principle flow chart of the present invention;
Fig. 2 is the showy formula Reaktionsofen synoptic diagram of the present invention;
Fig. 3 detects photo for sample SEM of the present invention;
Fig. 4 is a sample XRD detected result of the present invention.
Embodiment
Below the technical scheme of being invented is described in detail.
As shown in Figure 1, CoCl of the present invention
2Raw material is to adopt cell-grade CoCl
26H
2O, after heating, vacuum dehydration under 250 ℃ of temperature, through pulverizing preparation, its granularity is at 100～400 orders again.The reactant gases oxygen level is 21～50%, generally gets final product with air, or allocate oxygen in air; Institute's water content in the reactant gases, adopt volume pump that water is delivered to spraying gun, spraying into the high temperature gas flow gasification after the water atomization adds, therefore, in the high temperature oxidation gas, water content is controlled, general by stoichiometric 100～120% addings, the too high tail gas dew point that then causes raises, and causes dust collecting system at high temperature to move, and the cloth bag material of gathering dust is selected difficulty.
The structure of showy formula Reaktionsofen as shown in Figure 2.The top of its shell is cylindrical shell 1, and the top is provided with filling tube 2 and air-flow and product vent pipe 3; The bottom is a tapered tube 4, and bottom 5 is provided with scum pipe 6 (bleed valve is equipped with in its outlet), is connected to heating duct 7 on the conical surface of tapered tube 4 lower ends, and heating duct 7 is preferably pressed tangential way and inserted, and gas is sent into cyclone mode, can strengthen and the mixing and reaction effect of raw material.Stove is made into electricity (outward) heating-type, and the outside of body of heater shell is thermal insulation layer and electrical heating element 8.Feeder 9 adopts dosing equipment.The stove material is used Haynes HR-160 or Haynes HR-120 or Haynes 230 nickel-base alloys, and high temperature and resisting corrosion of chlorine ion performance are good.For temperature requirement that satisfies reaction and the work-ing life of taking into account the body of heater material, the operating temperature of stove is preferably 600～900 ℃.
During operation, anhydrous CoCl
2Send in the stove by filling tube 2 by feeder 9, the high temperature oxidation stability gas of moisture vapor is sent into by heating duct 7, raw material powder is reverse mode with waft form of spreading and air flow line and adds, powder is suspended state under the effect of air-flow, with gas thorough mixing and reaction, the decline process of fines in cylindrical shell 1 promptly reacted and finished.The part macrobead enters in the tapered tube 4, because the cross section of tapered tube 4 from top to bottom diminishes gradually, gas velocity then from top to bottom increases gradually, can make varigrained macrobead be suspended state and gas thorough mixing and reaction in tapered tube 4.Reaction product is discharged by air-flow and product vent pipe 3, enters postprocessing working procedures.
The equipment of the inventive method also can adopt fluidized roaster or rotary type stoving oven, as long as material is in flow or stirs state, realizes good contact the with oxidizing aqueous property air-flow, thereby makes it to mix and rapid reaction.
The tricobalt tetroxide that generates carries out gas solid separation in dust collecting system, adopt whirlwind and bag filter to collect, and through washing, drying, comminution by gas stream and classification, obtains the tricobalt tetroxide product.Contained HCl gas in the tail gas adopts graphite absorption tower water to absorb, and is converted into 36% hydrochloric acid and recycles.Cool off the device of the part of gathering dust, when being higher than 250 ℃, with Hastelly C-22 or Hastelly G-30, this material adaptive temperature is not too high, the acidic oxidation gas of chloride ion-containing.After being lower than 250 ℃, available 304L or 316L stainless steel, liner Teflon or silicon rubber, the cloth bag that gathers dust is made of the glasscloth that applies tetrafluoroethylene.The later pipeline of the cloth bag that gathers dust adopts polypropylene tube.Graphite absorption tower selection standard equipment.The induced draft fan plastic fan.
Deionized water wash is adopted in washing, the steel basin pulp, and the pressure filter press filtration is washed till no chlorion and detects (adopting silver nitrate aqueous solution to detect), and the dry DoubletaperedVacuumdrier that adopts is pulverized with classification and is adopted the jet mill grinding machine.
The production process of the inventive method is a successive, when blow-on, adopt coal gas, liquefied gas or Sweet natural gas, with burner in the stove internal combustion, furnace temperature is promoted to temperature rating, keeps constant temperature by electrically heated, thereafter, reaction process institute heat requirement is brought into the oxidizing gas heating of moisture vapor by high-temperature heat-exchanging.
Adopt the method and apparatus invented, being characterized as of the cobaltosic oxide powder of preparation, powder particle degree of crystallinity height is polyhedron shape, no dephasign, tap density is greater than 2.5g/cm
3, granularity shown in the XRD detected result of the SEM of Fig. 3 and Fig. 4, is specially adapted to make anode material for lithium-ion batteries LiCoO between 1～20 micron
2Raw material.
Claims (6)
1. the preparation method of a high-intensity cobaltic-cobaltous oxide power is characterized in that, is the anhydrous CoCl of 100～400 purposes with granularity
2Be raw material, it is added in the Reaktionsofen that under 500～1000 ℃ of temperature, be the oxidizing gas thorough mixing of kinestate and moisture vapor, reaction generates cobaltosic oxide powder, its reaction formula is:
3CoCl
2(s)+3H
2O
(g)+1/2O
2(g)＝Co
3O
4(s)+6HCl
(g)。
2. preparation method according to claim 1 is characterized in that, the oxygen level of described oxidizing gas is 21～50%.
3. preparation method according to claim 2 is characterized in that, described oxidizing gas is an oxygen.
4. preparation method according to claim 1 and 2 is characterized in that, in the described oxidizing gas, moisture content adds by stoichiometric 100～120%.
5. an equipment for preparing high-intensity cobaltic-cobaltous oxide power is characterized in that, comprises a body of heater, and its top is cylindrical shell, is provided with feed-pipe and air-flow and product vent pipe; Its underpart is a tapered tube, and the bottom is provided with scum pipe, is connected to heating duct on the conical surface of tapered tube lower end.
6. equipment according to claim 5 is characterized in that, described heating duct is pressed on the conical surface of tangential way access tapered tube lower end.
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| CN2007100346156A CN101274782B (en) | 2007-03-26 | 2007-03-26 | Method and apparatus for preparing high-intensity cobaltic-cobaltous oxide power |
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| CN2007100346156A CN101274782B (en) | 2007-03-26 | 2007-03-26 | Method and apparatus for preparing high-intensity cobaltic-cobaltous oxide power |
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| CN101274782A true CN101274782A (en) | 2008-10-01 |
| CN101274782B CN101274782B (en) | 2010-10-06 |
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ID=39994698
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437326A (en) * | 2011-09-13 | 2012-05-02 | 天津巴莫科技股份有限公司 | Method for preparing large-grain-size lithium cobaltate as cathode material for lithium-ion secondary battery |
| CN106197025A (en) * | 2016-08-23 | 2016-12-07 | 兰州金川新材料科技股份有限公司 | A kind of spray pyrolysis stove preparing pure phase Cobalto-cobaltic oxide |
| US20180076454A1 (en) * | 2016-09-13 | 2018-03-15 | Samsung Sdi Co., Ltd. | Cobalt oxide for lithium secondary battery, preparing method thereof, lithium cobalt oxide formed from the cobalt oxide, and lithium secondary battery having positive electrode including the lithium cobalt oxide |
| CN109502553A (en) * | 2019-01-19 | 2019-03-22 | 广西晶联光电材料有限责任公司 | A kind of device and method preparing metal-oxide powder |
| CN110526303A (en) * | 2019-08-14 | 2019-12-03 | 成都益志科技有限责任公司 | A kind of system and its production technology using spray roasting production cobaltosic oxide |
| CN113697864A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Preparation method of cobaltosic oxide |
| CN113697841A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by low-temperature decomposition method |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100398454C (en) * | 2004-06-28 | 2008-07-02 | 南通奥克赛德新材料有限公司 | New process for preparing high quality Co3O4 |
| CN2756616Y (en) * | 2004-06-28 | 2006-02-08 | 湖南瑞翔新材料有限公司 | Reaction furnace for preparing high quality Co3O4 tricobalt tetroxide |
-
2007
- 2007-03-26 CN CN2007100346156A patent/CN101274782B/en not_active Expired - Fee Related
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102437326B (en) * | 2011-09-13 | 2014-02-26 | 天津巴莫科技股份有限公司 | Method for preparing large-grain-size lithium cobaltate as cathode material for lithium-ion secondary battery |
| CN102437326A (en) * | 2011-09-13 | 2012-05-02 | 天津巴莫科技股份有限公司 | Method for preparing large-grain-size lithium cobaltate as cathode material for lithium-ion secondary battery |
| CN106197025B (en) * | 2016-08-23 | 2018-07-10 | 兰州金川新材料科技股份有限公司 | A kind of spray pyrolysis stove for preparing pure phase cobaltosic oxide |
| CN106197025A (en) * | 2016-08-23 | 2016-12-07 | 兰州金川新材料科技股份有限公司 | A kind of spray pyrolysis stove preparing pure phase Cobalto-cobaltic oxide |
| CN107814417B (en) * | 2016-09-13 | 2020-03-03 | 三星Sdi株式会社 | Cobalt oxide for lithium secondary battery, method for preparing same, lithium cobalt oxide, and lithium secondary battery |
| CN107814417A (en) * | 2016-09-13 | 2018-03-20 | 三星Sdi株式会社 | For the cobalt/cobalt oxide of lithium secondary battery, its preparation method, lithium and cobalt oxides and lithium secondary battery |
| US20180076454A1 (en) * | 2016-09-13 | 2018-03-15 | Samsung Sdi Co., Ltd. | Cobalt oxide for lithium secondary battery, preparing method thereof, lithium cobalt oxide formed from the cobalt oxide, and lithium secondary battery having positive electrode including the lithium cobalt oxide |
| US10892484B2 (en) | 2016-09-13 | 2021-01-12 | Samsung Sdi Co., Ltd. | Cobalt oxide for lithium secondary battery, preparing method thereof, lithium cobalt oxide formed from the cobalt oxide, and lithium secondary battery having positive electrode including the lithium cobalt oxide |
| US11482704B2 (en) | 2016-09-13 | 2022-10-25 | Samsung Sdi Co., Ltd. | Lithium cobalt oxide for a lithium secondary battery and lithium secondary battery comprising positive electrode including the same |
| CN109502553A (en) * | 2019-01-19 | 2019-03-22 | 广西晶联光电材料有限责任公司 | A kind of device and method preparing metal-oxide powder |
| CN109502553B (en) * | 2019-01-19 | 2023-08-22 | 广西晶联光电材料有限责任公司 | Device and method for preparing metal oxide powder |
| CN110526303A (en) * | 2019-08-14 | 2019-12-03 | 成都益志科技有限责任公司 | A kind of system and its production technology using spray roasting production cobaltosic oxide |
| CN113697864A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Preparation method of cobaltosic oxide |
| CN113697841A (en) * | 2020-05-21 | 2021-11-26 | 江西理工大学 | Method for preparing rare earth oxide by low-temperature decomposition method |
| CN113697841B (en) * | 2020-05-21 | 2023-06-02 | 江西理工大学 | Method for preparing rare earth oxide by low-temperature decomposition method |
| CN113697864B (en) * | 2020-05-21 | 2023-08-15 | 江西理工大学 | Preparation method of cobaltosic oxide |
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|---|---|
| CN101274782B (en) | 2010-10-06 |
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