CN106395916A - Preparation method for ultrapure ultrafine cobalt carbonate - Google Patents
Preparation method for ultrapure ultrafine cobalt carbonate Download PDFInfo
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Abstract
The invention provides a preparation method for ultrapure ultrafine cobalt carbonate. The preparation method comprises the following steps: (1) adding a base reaction solution into a reaction vessel, adding a carbonate solution or bicarbonate solution and a cobalt salt solution into the base reaction solution, and carrying out a reaction under stirring so as to obtain slurry containing cobalt carbonate, wherein a mol ratio of carbonate or bicarbonate to cobalt ions in the cobalt salt is (3.0-6.0): 1, the pH value of a reaction system is 6.8 to 8.2, reaction temperature is 25 to 80 DEG C and reaction time is 0.5 to 3 h; (2) subjecting the slurry containing cobalt carbonate to solid-liquid separation so as to obtain a filter cake, conveying the filter cake to a slurrying tank for slurrying so as to obtain a slurried material, conveying the slurried material to a washing tank for washing at a constant temperature and carrying out solid-liquid separation after completion of washing so as to obtain a cobalt carbonate precipitate; and (3) drying, crushing and sieving the cobalt carbonate precipitate so as to obtain ultrapure ultrafine cobalt carbonate. The preparation method provided by the invention is low in cost, simple in process flow and easy to operate.
Description
Technical field
The invention belongs to metal particle preparing technical field, the preparation side of more particularly, to a kind of ultrapure ultra-fine cobalt carbonate
Method.
Background technology
As preparing one of presoma of cobalt powder, its physical and chemical performance directly influences the application of cobalt powder to cobalt carbonate.
For obtaining cobalt powder of good performance, typically there is strict restriction to the content of impurity in cobalt carbonate, such as LITHIUM BATTERY
The requirement to impurity content for the cobalt carbonate is：Cl content is less than 0.01%, Na content and is less than 0.01%, Ca content
It is less than 0.01%, Fe content less than 0.01%, Mg content and be less than 0.005%.But due to cobalt carbonate particle particle diameter
Little, specific surface area is big, sad filter after synthesis, difficult washing, difficult be dried so that the ultrapure property of cobalt carbonate and
Ultra-fine property is often difficult to take into account.As added cobaltous chloride amount 4-6 in the invention of Publication No. CN103922426A
Cobalt deposition with ammonium bicarbonate again, washs after ageing 12h, Cl only can guarantee that less than 500ppm；As Publication No.
The cobalt carbonate that D50 is 5 μm about is prepared in the invention of CN102115214A, but with the addition of many in the method
Plant surfactant, chelating agent, in product, impurity is difficult to process, subsequent treatment cost is inevitable very high；Open
Number for CN102910686A invention in, using low temperature (0-30 DEG C) synthetic method, be prepared for D50 be 1.6-2.4 μm
Cobalt carbonate, but for D50 during microporous filter in the method<1.5 the interception result of μm granule is limited, product
Yield is relatively low, and is difficult to effectively remove Cl ion by way of drip washing in micropore.
Therefore, how to produce ultrapure and ultra-fine cobalt carbonate becomes the emphasis of this area research.
Content of the invention
For solving the above problems, the invention provides a kind of preparation method of ultrapure ultra-fine cobalt carbonate, this preparation
Method process is simple, prepared cobalt carbonate particle diameter is less, and purity is higher simultaneously, solves production ultrapure ultra-fine
A difficult problem for cobalt carbonate.
Heretofore described ultrapure ultra-fine cobalt carbonate refers to D50 particle diameter and is 0.5-3.0 μm, and Cl content is less than etc.
Cobalt carbonate in 100ppm.
The invention provides a kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprise the following steps：
(1) add reaction bottom liquid in a kettle., by carbonate solution or bicarbonate solution and cobalt salt solution
It is added in the liquid of described reaction bottom, reacted under agitation, described carbonate or described bicarbonate
Mol ratio with cobalt ion in described cobalt salt is 3.0-6.0:1, the pH of reaction system is 6.8-8.2, reaction temperature
For 25-80 DEG C, the response time is 0.5-3h, obtains the slurry containing cobalt carbonate；
(2) the described slurry containing cobalt carbonate is carried out obtaining filter cake after solid-liquid separation, described filter cake is carried out
Pulp obtains the material after pulp, and the material after described pulp is carried out constant temperature washing, and washing is carried out after terminating
Solid-liquid separation, obtains cobalt carbonate precipitation；
(3) described cobalt carbonate precipitation is dried, crushes and sieves, obtain ultrapure ultra-fine cobalt carbonate.
Preferably, the liquid of reaction bottom described in step (1) is pure water, carbonate solution or bicarbonate solution.
It is highly preferred that in step (1) when described reaction bottom liquid is carbonate solution or bicarbonate solution,
In the liquid of described reaction bottom, the concentration of carbonate or bicarbonate is more than 0g/L less than 50g/L.
It is highly preferred that described carbonate is ammonium carbonate, described bicarbonate is ammonium hydrogen carbonate.
Preferably, cobalt salt described in step (1) is at least one in cobaltous chloride, cobaltous sulfate and cobalt nitrate.
Preferably, described carbonate is ammonium carbonate, and described bicarbonate is ammonium hydrogen carbonate.
The present invention, is decreased in raw material as precipitant using the ammonium carbonate without metallic element or ammonium hydrogen carbonate
The impurity element such as metal cation introduction volume, reduce the follow-up removal of impurities cost for cobalt carbonate.
Preferably, in step (1), by described carbonate solution or described bicarbonate solution and described cobalt salt
Solution cocurrent is added in the liquid of described reaction bottom.
It is highly preferred that in step (1), when cocurrent adds, described cobalt salt flow is 200L/h-1000L/h.
The present invention can adjust reaction pH according to reaction practical situation by changing the flow of carbonate or bicarbonate.
The present invention by the way of cocurrent adding material during carbonate synthesis cobalt, by adjusting described carbonate solution or institute
State the flow of bicarbonate solution to adjust pH value during charging, can avoid just flowing method and counter-current charging
During being widely varied and local excessive concentration phenomenon of pH value, contribute to the stable and continuous of product quality
Metaplasia is produced.
Preferably, carbonate described in step (1) or described bicarbonate and the rubbing of cobalt ion in described cobalt salt
That ratio is 3.5-6.0:1.
Preferably, mixing speed described in step (1) is 130-600rpm.Under this mixing speed, permissible
Obtain the less cobalt carbonate of particle diameter.
It is highly preferred that mixing speed described in step (1) is 200-500rpm.
The pH of the reaction system in step (1) is 6.8-8.2, can prepare particle diameter in the range of this pH
Less cobalt carbonate, can reduce production cost simultaneously.
Preferably, the pH of reaction system described in step (1) is 7.0-8.2.
Preferably, reaction temperature described in step (1) is 35-65 DEG C.
In the method for the invention, by controlling described carbonate or described bicarbonate and cobalt in described cobalt salt
The mol ratio of ion and the pH adjusting reaction system, and then control the hypersaturated state of reaction system, lead to carbon
The explosive nucleation of sour cobalt, in certain reaction temperature and reaction time range, obtains that particle diameter is little, compare table
Area is big and the cobalt carbonate particle of good dispersion, and reaction fully, is subsequently not required to carry out ageing process, in shortening
While technological process, reduction processing cost, the performance of product is also better controled over.
Preferably, in step (2), divided using at least one solid-liquid in filter press and microfilter
Carry out described solid-liquid separation from equipment.
It is highly preferred that when carrying out solid-liquid separation using described filter press, pressure is 18-22MPa.
It is highly preferred that when carrying out solid-liquid separation using described microfilter, pressure is 0.1-0.25MPa.
The mother solution obtaining after solid-liquid separation can enter recovery system and be reused, and the filter cake obtaining is starched
Change washing.
Solid-liquid separating equipment used herein is filter press or microfilter or two kinds of washing facilitys
Combination, obtain filter cake after solid-liquid separation, filter cake need not be washed, direct discharging carries out follow-up
Pulping and washing operates.
It is highly preferred that in step (2), the described slurry containing cobalt carbonate is carried out solid using filter press
Liquid separates and obtains filter cake.During using filter press, pressure is bigger, can improve solid-liquid separation speed, that is,
Improve production efficiency.
Preferably, in step (2), the described slurry containing cobalt carbonate is carried out obtaining filter cake after solid-liquid separation,
By described filter cake discharging to funneling blanking groove, then with carrying out pulp, pulp in pure water rinsing to slurrying tank
Afterwards, obtain the material after pulp, the material after described pulp is delivered to by pump to wash and starch in groove, carries out constant temperature
Washing, washing carries out solid-liquid separation after terminating, and obtains cobalt carbonate precipitation.
It is highly preferred that described slurry time is 20min-40min, by sludging process, filter cake is uniformly dispersed,
Contribute to being fed directly to wash and starch groove by pump by material being washed, meanwhile, be conducive to follow-up remove impurity washing
Operation.
It is highly preferred that in step (2), the temperature of described washing is 25-85 DEG C.
It is further preferred that in step (2), the temperature of described washing is 40-85 DEG C.
It is highly preferred that in step (2), the time of described washing is 0.4-10h.
It is highly preferred that being stirred during described constant temperature washing, described mixing speed is 30-200rpm.
Preferably, the number of times of described constant temperature washing is 1-4 time.Every time after constant temperature washing, solid-liquid will be carried out and divide
From, then carry out second washing or enter subsequent technique.
Described washing temperature, the washing water yield, washing time and washing times are according in material in washing process
Cl-、NO3 -、SO4 2-Determine Deng impurity content.
Preferably, at the end of washing for the first time, with Cl-As a example, in material, Cl content should be not higher than 0.6%,
If Cl-Content is higher then to be increased the water yield, extends wash time；At the end of second is washed, Cl in material-Content
0.05% should be not higher than, if content is higher than 0.05%, increases leaching requirement, extend wash time；If second
Washing terminates rear Cl-Content is higher than 0.1%, then carry out third time and wash, until Cl in material-Content is less than
0.05%, enter next operation.
Preferably, the present invention can also be according to Cl in slurry-Content adjusts washing process temperature, if Cl-Content
Higher than control standard, then raise wash temperature, Cl-Content is relatively low, then suitably turn down wash temperature.By control
Washing process temperature processed, in the case of can maintaining identical slurry amount to a certain extent, strengthens washing
Effect, and then save slurry amount.
After the mode of washing of prior art is mainly solid-liquid separation, directly the filter cake being filtrated to get or filtering residue are entered
Row simply drip washing, or by after filter cake or filtering residue pulp, then carry out solid-liquid separation, obtains after filter cake again
Washing filter cake.Then judge the impurity content in filter cake by detecting the impurity content in filtrate, these are washed
The mode washed, because mode of washing is single, wash conditions are fixed, is all difficult to remove the impurity in product completely.
Product particle skewness can be caused, concordance is poor, is unfavorable for stablizing of product quality simultaneously.
With in prior art pass through detect filtrate in impurity (as Cl-) content and wash time, the washing water yield
Fixing mode is different.The present invention is advantageously according to the Cl in material after washing-Content situation control washing temperature,
The washing factor such as the water yield and washing time, under preferred wash temperature, under the washing water yield, under wash time
And more preferable clean result under washing times, can be obtained, and therefore, the preferred washing side that the present invention provides
Method is more beneficial for saving industrial water and production time, meanwhile, can reach more preferable impurity-eliminating effect, finally
Significantly reduce the impurity content in material.
The present invention passes through the impurity content that solid-liquid separation and washing operation can significantly decrease in cobalt carbonate, with
When solid-liquid separation and pulping and washing operation serialization degree high, reduce capacity consumption, enhance clean result,
Be conducive to large-scale production.
Preferably, in step (3), the method for described drying is centrifugal spray drying, expansion drying or air blast
It is dried.
Preferably, in step (3), the condition of described centrifugal spray drying is：Inlet temperature is 160-250 DEG C,
Discharging opening temperature is 70-105 DEG C
It is highly preferred that the condition of described centrifugal spray drying is：Inlet temperature is 180-220 DEG C, discharging opening
Temperature is 80-100 DEG C.
Preferably, in step (3), described expansion drying condition is：Inlet temperature is 170-230 DEG C,
Discharging opening temperature is 90-120 DEG C.
It is highly preferred that in step (3), described expansion drying condition is：Inlet temperature is 180-220 DEG C,
Discharging opening temperature is 100-110 DEG C.
During using described centrifugal spray drying or described expansion drying method, the dry materials time is less than 5min,
Compared to the drying mode of prior art, substantially reduce drying time, reduce dry run to properties of product
Impact.
Preferably, the condition of described forced air drying is：Baking temperature is 75-140 DEG C, and drying time is 6-12h.
More preferably baking temperature is 80-120 DEG C.
Preferably, in step (3), described broken method is at least during airflow crash and turbine crush
Kind.
Preferably, in step (3), sieved using 200 eye mesh screens.
Preferably, the D50 particle diameter of described ultrapure ultra-fine cobalt carbonate is 0.5-3.0 μm, and apparent density is
0.2-0.5g/cm3, specific surface area is 40-150m2/g.
Preferably, in described ultrapure ultra-fine cobalt carbonate Cl content be less than or equal to 100ppm, Ca, Na, Mg,
Fe constituent content is less than or equal to 20ppm, and Cu, Zn, Al constituent content is less than or equal to 10ppm.
By the preparation method of the ultrapure ultra-fine cobalt carbonate of the present invention, prepared cobalt carbonate particle diameter is little, and purity is high,
Wherein Cl content is less than or equal to 100ppm, and Ca, Na, Mg, Fe constituent content is less than or equal to 20ppm,
Cu, Zn, Al constituent content is less than or equal to 10ppm, and this is other inaccessiable effects of prior art institute.
The synthesis of ultra-fine grain needs to carry out under solution supersaturated condition, in supersaturated solution, precipitant
Addition can lead to cobalt carbonate explosivity nucleation, the cobalt carbonate particle of formation is little, specific surface area big it is difficult to enter
Row solid-liquid separation and remove impurity.The present invention, after precipitation terminates, the slurry containing cobalt carbonate is passed through solid-liquid
So that mother solution removes completely after separating, decrease impurities left.Carry out high intensity afterwards at a certain temperature
Pulping and washing, promote to adsorb the foreign ion desorption on cobalt carbonate particle surface, then through solid-liquid separation,
Remove partial impurities again.After solid-liquid separation and pulping and washing terminate, drying under appropraite condition for the material,
Crush and obtain the cobalt carbonate particle that particle diameter is little, purity is high.
For industrial at present, cobalt carbonate particle is difficult to realize ultrapure Yu ultra-fine problem simultaneously, and the present invention adopts
Be raw material with cobalt salt, carbonate or bicarbonate are precipitant, certain raw material and precipitant mol ratio, pH,
In temperature range, synthesize the slurry containing cobalt carbonate.Then the described slurry containing cobalt carbonate is divided through solid-liquid
From and pulping and washing after, be dried, crush, sieve, finally give that impurity content is low, particle diameter is little, ratio
The big cobaltous carbonate powder of surface area.Compare other preparation methoies, the present invention does not draw during preparing cobalt carbonate
Enter any other additive, low production cost, flow process is simple, and elementary metal impurities and the moon in products obtained therefrom
Ionic impurity content is all very low, successfully solves the difficult problem producing ultrapure ultra-fine cobalt carbonate.
The preparation method of the ultrapure ultra-fine cobalt carbonate that the present invention provides, has the advantages that：
During the present invention prepares cobalt carbonate and be not introduced into any other additive, low production cost, flow process letter
Single, and in products obtained therefrom, elementary metal impurities and anionic impurity content are all very low, successfully solve production super
A difficult problem for pure ultra-fine cobalt carbonate.
Brief description
Fig. 1 is the schematic flow sheet of ultrapure ultra-fine cobalt carbonate preparation method in one embodiment of the invention；
Fig. 2 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 1 preparation；
Fig. 3 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 2 preparation；
Fig. 4 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 3 preparation.
Specific embodiment
Described below is the preferred embodiment of the present invention it is noted that common skill for the art
For art personnel, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, this
A little improvements and modifications are also considered as protection scope of the present invention.
Refer to Fig. 1, Fig. 1 is that the flow process of ultrapure ultra-fine cobalt carbonate preparation method in one embodiment of the invention is illustrated
Figure, comprises the following steps：
S01, in a kettle. addition reaction bottom liquid, by carbonate solution or bicarbonate solution and cobalt salt solution
Be added in reaction bottom liquid, reacted under agitation, carbonate or bicarbonate and cobalt in cobalt salt from
The mol ratio of son is 3.0-6.0:1, the pH of reaction system is 6.8-8.2, and reaction temperature is 25-80 DEG C, reaction
Time is 0.5-3h, obtains the slurry containing cobalt carbonate；
S02, the slurry containing cobalt carbonate is carried out obtaining filter cake after solid-liquid separation, filter cake is carried out pulp and obtains
Material after pulp, the material after pulp is carried out constant temperature washing, and washing carries out solid-liquid separation after terminating, obtains
To cobalt carbonate precipitation；
S03, cobalt carbonate precipitation is dried, broken and sieve, obtain ultrapure ultra-fine cobalt carbonate.
The D50 particle diameter of described ultrapure ultra-fine cobalt carbonate is 0.5-3.0 μm, and apparent density is 0.2-0.5g/cm3,
Specific surface area is 40-150m2/g.
In described ultrapure ultra-fine cobalt carbonate, Cl content is less than or equal to 100ppm, Ca, Na, Mg and Fe element
Content is less than or equal to 20ppm, and Cu, Zn and Al constituent content is less than or equal to 10ppm.
Do not add in preparation process of the present invention that other any additives, supplementary product onsumption be few, low cost, flow process
Simple to operation, easy industrialization large-scale production, gained cobalt carbonate particle is little, purity is high.
Embodiment 1
A kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprises the following steps：
(1) in synthesis reaction vessel, add the ammonium bicarbonate soln (reaction bottom liquid) that concentration is 40g/L to stirring
Mix at oar, raise temperature of reaction kettle to after 35 DEG C, start stirring paddle, control rotating speed is 250rpm, simultaneously simultaneously
Stream adds cobalt chloride solution and ammonium bicarbonate soln, and the wherein flow of cobalt chloride solution is 400L/h, by carbon
Sour hydrogen ammonium Flow-rate adjustment pH, controls reaction pH between 6.8-7.8, reaction temperature is 35 DEG C.Reaction 2h
Stop charging afterwards, obtain the slurry containing cobalt carbonate；In ammonium hydrogen carbonate and cobaltous chloride, the mol ratio of cobalt ion is
4.5:1；
(2) slurry containing cobalt carbonate is delivered to filter press and carries out solid-liquid separation, pressure is 22Mpa,
Obtain mother solution and filter cake, mother solution enters recovery system, filter cake discharging to funneling blanking groove, then use pure water
Filter cake is rinsed to the slurrying tank with stirring slurry, after pulp 20min, obtains the material after pulp, by pulp
Material afterwards is delivered to by pump and carries out constant temperature washing in groove with washing and starching of stirring slurry, starts stirring, stirring speed
Spend for 30rpm, keep wash temperature to be 50 DEG C, wash 1h.After washing terminates, repeat above-mentioned solid-liquid
Separate and pulping and washing 1 time, material is pressed dry through filter press after terminating by washing, obtain cobalt carbonate precipitation；
(3) cobalt carbonate precipitation is transferred to baking oven, at 80 DEG C, 10h is dried.After drying, material is through air-flow
Ultrapure ultra-fine cobalt carbonate is obtained after broken, screening.
The D50 particle diameter of the ultrapure ultra-fine cobalt carbonate that embodiment 1 is obtained is 1.53 μm, and apparent density is
0.36g/cm3, specific surface area is 110m2/g；In ultrapure ultra-fine cobalt carbonate, Ca, Na, Fe, Mg content is less than
15ppm, Cl content is less than 60ppm, and impurity content is referring specifically to table 1.From table 1 it follows that this reality
Apply the prepared ultrapure ultra-fine cobalt carbonate impurity content of example 1 little, purity height.
Impurity content in the ultrapure ultra-fine cobalt carbonate that table 1 embodiment 1 is obtained
| Ni | Cu | Fe | Ca | Mg | Mn | Zn | Pb |
| 0.0007% | 0.0001% | 0.0008% | 0.0011% | 0.0008% | 0.0002% | 0.0001% | 0.0002% |
| Cd | Na | Al | Si | Cr | S | As | Cl |
| 0.0001% | 0.0015% | 0.0001% | 0.0005% | 0.0005% | 0.0020% | 0.0001% | 0.0052% |
Fig. 2 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 1 preparation；Can from Fig. 2
Go out, the ultrapure ultra-fine cobalt carbonate particle diameter that embodiment 1 is obtained is less, uniform particle sizes are distributed.
Embodiment 2
A kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprises the following steps：
(1) pure water (reaction bottom liquid) is added to stirring paddle, to raise temperature of reaction kettle in synthesis reaction vessel
To after 50 DEG C, start stirring paddle, control rotating speed is 500rpm, cocurrent adds cobalt chloride solution and carbonic acid simultaneously
The flow of ammonium salt solution, wherein cobalt chloride solution is 300L/h, by ammonium carbonate Flow-rate adjustment pH, controls reaction
Between 7.3-8.2, reaction temperature is 50 DEG C to pH.Stop charging after reaction 1h, obtain containing cobalt carbonate
Slurry；In ammonium carbonate and cobaltous chloride, the mol ratio of cobalt ion is 6.0:1；
(2) slurry containing cobalt carbonate is delivered to microfilter and carries out solid-liquid separation, pressure is 0.2Mpa,
Obtain mother solution and filter cake, mother solution enters recovery system, filter cake discharging to funneling blanking groove, then use pure water
Filter cake is rinsed to the slurrying tank with stirring slurry, after pulp 40min, obtains the material after pulp, by pulp
Material afterwards is delivered to by pump and carries out constant temperature washing in groove with washing and starching of stirring slurry, starts stirring, stirring speed
Spend for 200rpm, keep wash temperature to be 40 DEG C, wash 2h.After washing terminates, repeat above-mentioned solid-liquid
Separate and pulping and washing 3 times, washing terminates rear material and press dry through microfilter, obtain cobalt carbonate precipitation；
(3) cobalt carbonate precipitation is dried using flash dryer.Inlet temperature is 215 DEG C, discharging
Mouth temperature is 85 DEG C, and after being dried, material obtains ultrapure ultra-fine cobalt carbonate after airflow crash, screening.
The D50 particle diameter of the ultrapure ultra-fine cobalt carbonate that embodiment 2 is obtained is 0.86 μm, and apparent density is
0.23g/cm3, specific surface area is 145m2/g；In ultrapure ultra-fine cobalt carbonate, Ca, Na, Fe, Mg content is less than
17ppm, Cl content is less than 75ppm, and impurity content is referring specifically to table 2.From Table 2, it can be seen that this reality
Apply the prepared ultrapure ultra-fine cobalt carbonate impurity content of example 2 little, purity height.
Impurity content in the ultrapure ultra-fine cobalt carbonate that table 2 embodiment 2 is obtained
| Ni | Cu | Fe | Ca | Mg | Mn | Zn | Pb |
| 0.0006% | 0.0001% | 0.0004% | 0.0012% | 0.0006% | 0.0002% | 0.0001% | 0.0001% |
| Cd | Na | Al | Si | Cr | S | As | Cl |
| 0.0001% | 0.0016% | 0.0001% | 0.0005% | 0.0005% | 0.0015% | 0.0001% | 0.0070% |
Fig. 3 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 2 preparation；Can from Fig. 3
Go out, the ultrapure ultra-fine cobalt carbonate particle diameter that embodiment 2 is obtained is less, uniform particle sizes are distributed.
Embodiment 3
A kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprises the following steps：
(1) pure water and concentration, is added to be ammonium bicarbonate soln (pure water and the carbon of 20g/L in synthesis reaction vessel
The volume ratio of sour hydrogen ammonium salt solution is 2:1) to stirring paddle, raise temperature of reaction kettle to after 25 DEG C, start stirring
Oar, control rotating speed is 200rpm, and cocurrent adds cobalt sulfate solution and sal volatile, wherein cobaltous sulfate simultaneously
The flow of solution be 700L/h, by ammonium carbonate Flow-rate adjustment react pH, control reaction pH 7.0-8.2 it
Between, reaction temperature is 25 DEG C.Stop charging after reaction 3h, obtain the slurry containing cobalt carbonate；Ammonium carbonate and
In cobaltous sulfate, the mol ratio of cobalt ion is 5.0:1；
(2) slurry containing cobalt carbonate is delivered to filter press and carries out solid-liquid separation, pressure is 19Mpa,
Obtain mother solution and filter cake, mother solution enters recovery system, filter cake discharging to funneling blanking groove, then use pure water
Filter cake is rinsed to the slurrying tank with stirring slurry, after pulp 30min, obtains the material after pulp, by pulp
Material afterwards is delivered to by pump and carries out constant temperature washing in groove with washing and starching of stirring slurry, starts stirring, stirring speed
Spend for 100rpm, keep wash temperature to be 85 DEG C, wash 0.4h.After washing terminates, repeat above-mentioned solid
Liquid separates and pulping and washing 2 times, and material is pressed dry after terminating by washing through microfilter, obtains cobalt carbonate and sinks
Form sediment；
(3) cobalt carbonate precipitation is dried using centrifugal atomizer, inlet temperature is 220 DEG C, discharging
Mouth temperature is 85 DEG C.After drying, material obtains ultrapure ultra-fine cobalt carbonate after turbine crushes, sieves.
The D50 particle diameter of the ultrapure ultra-fine cobalt carbonate that embodiment 3 is obtained is 2.82 μm, and apparent density is
0.46g/cm3, specific surface area is 58m2/g；In ultrapure ultra-fine cobalt carbonate, Ca, Na, Fe, Mg content is less than
20ppm, Cl content is less than 90ppm, and impurity content is referring specifically to table 3.From table 3 it is observed that this reality
Apply the prepared ultrapure ultra-fine cobalt carbonate impurity content of example 3 little, purity height.
Impurity content in the ultrapure ultra-fine cobalt carbonate that table 3 embodiment 3 is obtained
| Ni | Cu | Fe | Ca | Mg | Mn | Zn | Pb |
| 0.0007% | 0.0002% | 0.0006% | 0.0015% | 0.0005% | 0.0002% | 0.0001% | 0.0001% |
| Cd | Na | Al | Si | Cr | S | As | Cl |
| 0.0002% | 0.0013% | 0.0001% | 0.0007% | 0.0004% | 0.0018% | 0.0001% | 0.0085% |
Fig. 4 is scanning electron microscope (SEM) figure of the cobalt carbonate of the embodiment of the present invention 3 preparation；Can from Fig. 4
To find out, the ultrapure ultra-fine cobalt carbonate particle diameter that embodiment 3 is obtained is less, and uniform particle sizes are distributed.
Embodiment 4
A kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprises the following steps：
(1) pure water (reaction bottom liquid) is added to stirring paddle, to raise temperature of reaction kettle in synthesis reaction vessel
To after 80 DEG C, start stirring paddle, control rotating speed is 150rpm, cocurrent adds cobalt nitrate solution and carbonic acid simultaneously
The flow of hydrogen ammonium salt solution, wherein cobalt nitrate solution is 200L/h, by ammonium hydrogen carbonate Flow-rate adjustment pH, controls
PH is between 7.2-8.2 for reaction, and reaction temperature is 80 DEG C.Stop charging after reaction 3h, obtain containing carbonic acid
The slurry of cobalt；In ammonium hydrogen carbonate and cobalt nitrate, the mol ratio of cobalt ion is 3.0:1；
(2) slurry containing cobalt carbonate is delivered to microfilter and carries out solid-liquid separation, pressure is 0.2Mpa,
Obtain mother solution and filter cake, mother solution enters recovery system, filter cake discharging to funneling blanking groove, then use pure water
Filter cake is rinsed to the slurrying tank with stirring slurry, after pulp 20min, obtains the material after pulp, by pulp
Material afterwards is delivered to by pump and carries out constant temperature washing in groove with washing and starching of stirring slurry, starts stirring, stirring speed
Spend for 30rpm, keep wash temperature to be 25 DEG C, wash 5h.After washing terminates, repeat above-mentioned solid-liquid
Separate and pulping and washing 2 times, washing terminates rear material and press dry through filter press, obtain cobalt carbonate precipitation；
(3) cobalt carbonate precipitation is transferred to baking oven, at 120 DEG C, 4h is dried.After drying, material is through air-flow
Ultrapure ultra-fine cobalt carbonate is obtained after broken, screening.
The D50 particle diameter of the ultrapure ultra-fine cobalt carbonate that embodiment 4 is obtained is 1.94 μm, and apparent density is
0.40g/cm3, specific surface area is 84m2/g；In ultrapure ultra-fine cobalt carbonate, Ca, Na, Fe, Mg content is less than
16ppm, Cl content is less than 110ppm, and impurity content is referring specifically to table 4.As can be seen from Table 4, originally
The ultrapure ultra-fine cobalt carbonate impurity content that embodiment 4 is obtained is little, and purity is high.
Impurity content in the ultrapure ultra-fine cobalt carbonate that table 4 embodiment 4 is obtained
| Ni | Cu | Fe | Ca | Mg | Mn | Zn | Pb |
| 0.0003% | 0.0001% | 0.0004% | 0.0015% | 0.0002% | 0.0001% | 0.0001% | 0.0001% |
| Cd | Na | Al | Si | Cr | S | As | Cl |
| 0.0001% | 0.0012% | 0.0001% | 0.0004% | 0.0003% | 0.0015% | 0.0001% | 0.00105% |
Embodiment 5
A kind of preparation method of ultrapure ultra-fine cobalt carbonate, comprises the following steps：
(1) pure water (reaction bottom liquid) is added to stirring paddle, to raise temperature of reaction kettle in synthesis reaction vessel
To after 65 DEG C, start stirring paddle, control rotating speed is 600rpm, cocurrent adds cobalt chloride solution and carbonic acid simultaneously
The flow of ammonium salt solution, wherein cobalt chloride solution is 600L/h, by ammonium carbonate Flow-rate adjustment pH, controls reaction
Between 7.4-8.2, reaction temperature is 65 DEG C to pH.Stop charging after reaction 0.5h, obtain containing cobalt carbonate
Slurry；In ammonium carbonate and cobaltous chloride, the mol ratio of cobalt ion is 3.5:1；
(2) slurry containing cobalt carbonate is delivered to filter press and carries out solid-liquid separation, pressure is 18Mpa,
Obtain mother solution and filter cake, mother solution enters recovery system, filter cake discharging to funneling blanking groove, then use pure water
Filter cake is rinsed to the slurrying tank with stirring slurry, after pulp 20min, obtains the material after pulp, by pulp
Material afterwards is delivered to by pump and carries out constant temperature washing in groove with washing and starching of stirring slurry, starts stirring, stirring speed
Spend for 30rpm, keep wash temperature to be 60 DEG C, wash 1h.After washing terminates, repeat above-mentioned solid-liquid
Separate and pulping and washing 1 time, washing terminates rear material and press dry through filter press, obtain cobalt carbonate precipitation；
(3) cobalt carbonate precipitation is dried using centrifugal atomizer, inlet temperature is 200 DEG C, discharging
Mouth temperature is 95 DEG C.After drying, material obtains ultrapure ultra-fine cobalt carbonate after airflow crash, screening.
The D50 particle diameter of the ultrapure ultra-fine cobalt carbonate that embodiment 5 is obtained is 0.55 μm, and apparent density is
0.30g/cm3, specific surface area is 128m2/g；In ultrapure ultra-fine cobalt carbonate, Ca, Na, Fe, Mg content is less than
18ppm, Cl content is less than 100ppm, and impurity content is referring specifically to table 5.As can be seen from Table 5, originally
The ultrapure ultra-fine cobalt carbonate impurity content that embodiment 5 is obtained is little, and purity is high.
Impurity content in the ultrapure ultra-fine cobalt carbonate that table 5 embodiment 5 is obtained
| Ni | Cu | Fe | Ca | Mg | Mn | Zn | Pb |
| 0.0005% | 0.0001% | 0.0008% | 0.0015% | 0.0006% | 0.0002% | 0.0001% | 0.0001% |
| Cd | Na | Al | Si | Cr | S | As | Cl |
| 0.0001% | 0.0016% | 0.0001% | 0.0005% | 0.0005% | 0.0016% | 0.0001% | 0.0094% |
To sum up, no any additive in preparation process of the present invention, preparation cost is low, flow process is simple to operation,
Easily industrialization large-scale production, gained cobalt carbonate particle is little, purity is high, solves prior art scale system
The difficult problem existing during standby ultrapure ultra-fine cobalt carbonate.
The above is the preferred embodiment of the present invention it is noted that common skill for the art
For art personnel, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, this
A little improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of ultrapure ultra-fine cobalt carbonate is it is characterised in that comprise the following steps：
(1) add reaction bottom liquid in a kettle., by carbonate solution or bicarbonate solution and cobalt salt solution
It is added in the liquid of described reaction bottom, reacted under agitation, described carbonate or described bicarbonate
Mol ratio with cobalt ion in described cobalt salt is 3.0-6.0:1, the pH of reaction system is 6.8-8.2, reaction temperature
For 25-80 DEG C, the response time is 0.5-3h, obtains the slurry containing cobalt carbonate；
(2) the described slurry containing cobalt carbonate is carried out obtaining filter cake after solid-liquid separation, described filter cake is carried out
Pulp obtains the material after pulp, and the material after described pulp is carried out constant temperature washing, and washing is carried out after terminating
Solid-liquid separation, obtains cobalt carbonate precipitation；
(3) described cobalt carbonate precipitation is dried, crushes and sieves, obtain ultrapure ultra-fine cobalt carbonate.
2. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (1)
Described in carbonate or described bicarbonate be 3.5-6.0 with the mol ratio of cobalt ion in described cobalt salt:1.
3. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (1)
Described in reaction system pH be 7.0-8.2.
4. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (1)
Described in reaction temperature be 35-65 DEG C.
5. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (1)
Described in mixing speed be 130-600rpm.
6. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (1)
Described in cobalt salt be cobaltous chloride, at least one in cobaltous sulfate and cobalt nitrate；Described carbonate is ammonium carbonate,
Described bicarbonate is ammonium hydrogen carbonate.
7. as claimed in claim 1 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (2)
In, described solid-liquid is carried out using at least one solid-liquid separating equipment in filter press and microfilter and divides
From.
8. the ultrapure ultra-fine cobalt carbonate as described in any one of claim 1-7 preparation method it is characterised in that
In step (2), the described slurry containing cobalt carbonate is carried out obtaining filter cake after solid-liquid separation, by described filter cake
Discharging, to funneling blanking groove, then with carrying out pulp in pure water rinsing to slurrying tank, after pulp, is starched
Material after change, the material after described pulp is delivered to by pump to wash and starch carries out constant temperature washing in groove, washing
Carry out solid-liquid separation after end, obtain cobalt carbonate precipitation.
9. as claimed in claim 8 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step (2)
In, the time of described washing is 0.4-10h.
10. as claimed in claim 8 the preparation method of ultrapure ultra-fine cobalt carbonate it is characterised in that step
(2), in, the temperature of described washing is 25-85 DEG C.
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| CN106927488A (en) * | 2017-05-03 | 2017-07-07 | 中南大学 | A kind of preparation method of cobalt carbonate |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200309A (en) * | 2007-12-11 | 2008-06-18 | 周红阳 | Method for producing cobaltous oxide |
| CN102910686A (en) * | 2011-08-04 | 2013-02-06 | 深圳市格林美高新技术股份有限公司 | Cobalt carbonate preparation method and superfine cobalt powder preparation method |
| CN103771545A (en) * | 2012-10-17 | 2014-05-07 | 宇辰新能源材料科技无锡有限公司 | Preparation method of high-purity superfine spherical cobalt carbonate |
| CN104418388A (en) * | 2013-08-26 | 2015-03-18 | 荆门市格林美新材料有限公司 | Process and device for continuous production of superfine cobalt carbonate powder |
| CN104556248A (en) * | 2013-10-12 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Method for continuously producing large-particle spherical cobalt carbonate |
-
2015
- 2015-07-31 CN CN201510466195.3A patent/CN106395916A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101200309A (en) * | 2007-12-11 | 2008-06-18 | 周红阳 | Method for producing cobaltous oxide |
| CN102910686A (en) * | 2011-08-04 | 2013-02-06 | 深圳市格林美高新技术股份有限公司 | Cobalt carbonate preparation method and superfine cobalt powder preparation method |
| CN103771545A (en) * | 2012-10-17 | 2014-05-07 | 宇辰新能源材料科技无锡有限公司 | Preparation method of high-purity superfine spherical cobalt carbonate |
| CN104418388A (en) * | 2013-08-26 | 2015-03-18 | 荆门市格林美新材料有限公司 | Process and device for continuous production of superfine cobalt carbonate powder |
| CN104556248A (en) * | 2013-10-12 | 2015-04-29 | 中国电子科技集团公司第十八研究所 | Method for continuously producing large-particle spherical cobalt carbonate |
Cited By (22)
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| CN114455641A (en) * | 2020-11-10 | 2022-05-10 | 荆门市格林美新材料有限公司 | Preparation method of cobalt carbonate with low chlorine content |
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