CN103342394A - Method for continuously preparing cobalt hydroxide with high bulk density - Google Patents
Method for continuously preparing cobalt hydroxide with high bulk density Download PDFInfo
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- CN103342394A CN103342394A CN2013102905899A CN201310290589A CN103342394A CN 103342394 A CN103342394 A CN 103342394A CN 2013102905899 A CN2013102905899 A CN 2013102905899A CN 201310290589 A CN201310290589 A CN 201310290589A CN 103342394 A CN103342394 A CN 103342394A
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Abstract
The invention discloses a method for continuously preparing cobalt hydroxide with high bulk density. The current cobalt hydroxide preparation methods include an alkali solution sedimentation method, a sedimentation conversion method and the like which have the following three difficulties: cobalt hydroxide sedimentation particles are smaller, difficult to filter and wash, and the recovery rate of materials is low; the materials are low in quality and high in impurity content; the high energy consumption is caused by intermittent production. The technical scheme is as follows: the method is characterized by comprising the following steps of: with cobalt-contained ore material as the raw material, leaching the cobalt-contained ore material, and then, purifying the cobalt-contained ore material to obtain a cobalt chloride solution; with NaOH as a base solution, merging NaOH, cobalt chloride and a complexing agent solution, adding the mixed solution into a reaction kettle, rapidly controlling the pH value at 8-12, the temperature at 30-90 DEG C and the stirring speed at 200-1000rpm in the flow merging process, and opening an overflow valve of the reaction kettle to begin to carry out continuous production after the reaction is carried out for 6-40h. The method is simple in process, capable of realizing continuous production, convenient in operation and beneficial to the industrial production; a product is excellent and is shaped like a porous sphere, and the particle size of the product is distributed normally.
Description
Technical field
The present invention relates to a kind of serialization and prepare high pine than the method for cobaltous hydroxide.
Background technology
Cobaltous hydroxide is a kind of important industrial raw material, in the Chemical Manufacture for the manufacture of cobalt salt, cobalt-containing catalyst and the agent of electrolytic process production decomposing hydrogen dioxide solution, coatings industry is as paint drier, glass is warded off industry as tinting material etc., at battery industry for the manufacture of MH-Ni, lithium ion battery.Along with the fast development of China's economic society, the parent that green energy resource is subjected to people relies, and battery industry grows continuously and fast, and the Application Areas of cobaltous hydroxide is constantly expanded in addition, and the demand in market is also increasing.
The method of at present existing cobaltous hydroxide preparation has the alkali lye precipitator method, precipitation transformation method etc.There are three difficult problems aborning in current technology: (1) cobaltous hydroxide deposit seeds is less, sad filter, and difficult washing, material recovery rate is low; (2) materials quality is poor, the foreign matter content height; (3) batch production, the energy consumption height.
The patent of invention CN1359353 of OMG Kokkola Chemicals OY and domestic patent CN101570348A need add ammonia alkali such as ammoniacal liquor, foreign matter content height in the product, and also waste water is difficult for handling.
The patent of invention CN1190947 of H.C. Starck GmbH ﹠ Co. KG discloses the employing precipitation transformation method and has prepared big particle diameter cobaltous hydroxide, at first with cobalt salt and carbonate or supercarbonate formation cobaltous dihydroxycarbonate, after the washing drying cobaltous dihydroxycarbonate is pulled an oar, mix with NaOH solution then, washing back product needs vacuum dehydrating at lower temperature.This method production process is long, and the drying conditions harshness is unfavorable for suitability for industrialized production.
Summary of the invention
At defective and the technical difficulty that above-mentioned technology exists, the invention provides a kind of serialization and prepare high pine than the method for cobaltous hydroxide, its technology is simple, and serialization production is easy to operate, and product fine is conducive to suitability for industrialized production.
For this reason, the present invention adopts following technical scheme: a kind of serialization prepares high pine than the method for cobaltous hydroxide, and its step is as follows: it is raw material that employing contains the cobalt ore material, purifies through leaching, and obtains 30～200g/L cobalt chloride solution; Preparation 50～400g/L NaOH solution and 0.01～100g/L enveloping agent solution; Be end liquid with NaOH, NaOH, cobalt chloride and enveloping agent solution and stream are added reactor, rapidly pH value is controlled 8～12 in the co-current process, temperature control is at 30～90 ℃, and stirring velocity is at 200～1000rpm, behind reaction 6～40h, open the surplus valve of reactor, beginning serialization production; The reaction material that overflows adds an amount of antioxidant, and ageing 2～4h namely gets cobaltous hydroxide after filtration, washing, the drying.
The cobalt chloride that the present invention produces, its quality standard is: Co:30～200g/L, Cu＜0.001g/L, Mg＜0.001g/L, Fe＜0.001g/L, Ni＜0.001g/L, Ca＜0.001g/L, Mn＜0.001g/L, Zn＜0.001g/L, Na＜0.001g/L, Cd＜0.001g/L, Cr＜0.001g/L, Pb＜0.001g/L, Al＜0.001g/L.
The cobaltous hydroxide excellent product quality that the present invention produces, pattern is porous spherical, and granularity is normal distribution, D50:8～20 μ m, Na＜0.004%, Cl
-＜0.025%, AD (pine ratio): 1.0～2.0g/cm
3
Further, the control of DCS distributed control system is adopted in the control of temperature of reaction, pH value, cocurrent adding material speed and stirring velocity, and is easy to operate.
Further, described complexing agent is preferably one or more mixture of Polyvinylpyrolidone (PVP) (PVP), polyvinyl alcohol (PVA), disodium ethylene diamine tetraacetate (EDTA), polyoxyethylene glycol (PEG), Seignette salt (rocchelle's salt).
Further, when cocurrent adding material, enveloping agent solution can add separately, also may be combined in cobalt chloride or the NaOH solution to add.
Further, described antioxidant is preferably one or more mixture of xitix, glucose, Tenox PG, hydroxyl hydramine.
Further, described filtration, washing process adopt whizzer.
Technology of the present invention is simple, and serialization production, easy to operate is conducive to suitability for industrialized production; Product fine, pattern is porous spherical, and granularity is normal distribution.
Description of drawings
Fig. 1 is the cobaltous hydroxide SEM figure of the embodiment of the invention 1 preparation.
Fig. 2 is the cobaltous hydroxide SEM figure of the embodiment of the invention 2 preparations.
Embodiment
The invention will be further described below in conjunction with specification drawings and specific embodiments.
Embodiment 1
Be end liquid with NaOH, with 60g/L NaOH, 100g/L cobalt chloride, 12g/L polyvinyl alcohol solution, and stream adds reactor, rapidly the pH value is controlled 10.0 in the process, temperature control is at 30～90 ℃, and stirring velocity 200～1000rpm is behind reaction 6～40h, open surplus valve, beginning serialization production.The reaction material that overflows adds an amount of glucose, ageing 2～4h.Can obtain cobaltous hydroxide after washing after filtration,, the drying.
Embodiment 2
Be end liquid with NaOH, 250g/L NaOH is mixed with the 25g/L disodium ethylene diamine tetra-acetic acid solution, and add reactor with 150g/L cobalt chloride and stream, rapidly the pH value is controlled 10.5 in the process, temperature control is at 30～90 ℃, and stirring velocity 200～1000rpm is behind reaction 6～40h, open surplus valve, beginning serialization production.The reaction material that overflows adds an amount of xitix, ageing 2～4h.Can obtain cobaltous hydroxide after washing after filtration,, the drying.
Claims (6)
1. a serialization prepares high pine than the method for cobaltous hydroxide, and its step is as follows: it is raw material that employing contains the cobalt ore material, purifies through leaching, and obtains 30～200g/L cobalt chloride solution; Preparation 50～400g/L NaOH solution and 0.01～100g/L enveloping agent solution; Be end liquid with NaOH, NaOH, cobalt chloride and enveloping agent solution and stream are added reactor, rapidly pH value is controlled 8～12 in the co-current process, temperature control is at 30～90 ℃, and stirring velocity is at 200～1000rpm, behind reaction 6～40h, open the surplus valve of reactor, beginning serialization production; The reaction material that overflows adds an amount of antioxidant, and ageing 2～4h namely gets cobaltous hydroxide after filtration, washing, the drying.
2. serialization according to claim 1 prepares high pine than the method for cobaltous hydroxide, it is characterized in that the control of DCS distributed control system is adopted in the control of temperature of reaction, pH value, cocurrent adding material speed and stirring velocity.
3. serialization according to claim 1 and 2 prepares high pine than the method for cobaltous hydroxide, it is characterized in that described complexing agent is one or more mixture of Polyvinylpyrolidone (PVP), polyvinyl alcohol, disodium ethylene diamine tetraacetate, polyoxyethylene glycol, Seignette salt.
4. serialization according to claim 1 and 2 prepares high pine than the method for cobaltous hydroxide, it is characterized in that, when cocurrent adding material, enveloping agent solution adopts to add separately or be blended in cobalt chloride or the NaOH solution and adds.
5. serialization according to claim 1 and 2 prepares high pine than the method for cobaltous hydroxide, it is characterized in that, described antioxidant is one or more mixture of xitix, glucose, Tenox PG, hydroxyl hydramine.
6. serialization according to claim 1 and 2 prepares high pine than the method for cobaltous hydroxide, it is characterized in that described filtration and washing process adopt whizzer.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104445442A (en) * | 2014-12-09 | 2015-03-25 | 英德佳纳金属科技有限公司 | Cobalt hydroxide with low chlorine/sulfur and large particle size and preparation method thereof |
| CN104716303A (en) * | 2015-04-01 | 2015-06-17 | 浙江华友钴业股份有限公司 | Preparation method of spherical hydroxyl cobaltous oxide-cobaltosic oxide composite material |
| CN105304897A (en) * | 2014-11-29 | 2016-02-03 | 董亚伦 | Preparation method for large particle cobalt hydroxide battery material |
| CN105329954A (en) * | 2014-08-11 | 2016-02-17 | 荆门市格林美新材料有限公司 | Large-particle size cobalt hydroxide and preparation method thereof |
| CN105439212A (en) * | 2014-09-30 | 2016-03-30 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN106006760A (en) * | 2016-05-27 | 2016-10-12 | 湖南海纳新材料有限公司 | Method for preventing amorphous cobaltous hydroxide from being oxidized in purification process |
| CN106077692A (en) * | 2016-05-30 | 2016-11-09 | 湖州师范学院 | A kind of preparation method of metallic cobalt microsphere |
| CN106077691A (en) * | 2016-05-30 | 2016-11-09 | 湖州师范学院 | A kind of metallic cobalt microsphere |
| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN114380338A (en) * | 2022-01-25 | 2022-04-22 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, products and applications thereof |
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| CN101955234A (en) * | 2009-07-15 | 2011-01-26 | 海南金亿新材料股份有限公司 | Method for preparing high purity nano cobalt hydroxide |
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| CN101955234A (en) * | 2009-07-15 | 2011-01-26 | 海南金亿新材料股份有限公司 | Method for preparing high purity nano cobalt hydroxide |
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105329954A (en) * | 2014-08-11 | 2016-02-17 | 荆门市格林美新材料有限公司 | Large-particle size cobalt hydroxide and preparation method thereof |
| CN105329954B (en) * | 2014-08-11 | 2017-09-19 | 荆门市格林美新材料有限公司 | Big particle diameter cobalt hydroxide and preparation method thereof |
| CN105439212A (en) * | 2014-09-30 | 2016-03-30 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN105439212B (en) * | 2014-09-30 | 2017-05-17 | 荆门市格林美新材料有限公司 | Preparation method for cell grade cobalt hydroxide |
| CN105304897A (en) * | 2014-11-29 | 2016-02-03 | 董亚伦 | Preparation method for large particle cobalt hydroxide battery material |
| CN105304897B (en) * | 2014-11-29 | 2017-09-15 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of bulky grain cobalt hydroxide battery material |
| CN104445442A (en) * | 2014-12-09 | 2015-03-25 | 英德佳纳金属科技有限公司 | Cobalt hydroxide with low chlorine/sulfur and large particle size and preparation method thereof |
| CN104445442B (en) * | 2014-12-09 | 2016-05-11 | 英德佳纳金属科技有限公司 | A kind of low chlorine/sulphur, large particle diameter cobalt hydroxide and preparation method thereof |
| CN104716303A (en) * | 2015-04-01 | 2015-06-17 | 浙江华友钴业股份有限公司 | Preparation method of spherical hydroxyl cobaltous oxide-cobaltosic oxide composite material |
| CN104716303B (en) * | 2015-04-01 | 2017-03-29 | 浙江华友钴业股份有限公司 | The preparation method of spherical hydroxy cobalt oxide cobaltosic oxide composite material |
| CN106006760A (en) * | 2016-05-27 | 2016-10-12 | 湖南海纳新材料有限公司 | Method for preventing amorphous cobaltous hydroxide from being oxidized in purification process |
| CN106077691A (en) * | 2016-05-30 | 2016-11-09 | 湖州师范学院 | A kind of metallic cobalt microsphere |
| CN106077692A (en) * | 2016-05-30 | 2016-11-09 | 湖州师范学院 | A kind of preparation method of metallic cobalt microsphere |
| CN111533179A (en) * | 2020-05-16 | 2020-08-14 | 赣州腾远钴业新材料股份有限公司 | Preparation method for continuously preparing large-particle-size beta-type cobalt sulfide crystals |
| CN114380338A (en) * | 2022-01-25 | 2022-04-22 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, products and applications thereof |
| CN114380338B (en) * | 2022-01-25 | 2023-11-03 | 重庆邮电大学 | Preparation method of magnetic cobalt oxide mesoporous nanospheres, product and application thereof |
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