CN106745100B - The preparation system and preparation method of battery-level lithium carbonate - Google Patents
The preparation system and preparation method of battery-level lithium carbonate Download PDFInfo
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- CN106745100B CN106745100B CN201611205229.4A CN201611205229A CN106745100B CN 106745100 B CN106745100 B CN 106745100B CN 201611205229 A CN201611205229 A CN 201611205229A CN 106745100 B CN106745100 B CN 106745100B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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Abstract
The invention provides a kind of preparation system of battery-level lithium carbonate, preparation system includes hydriding reactor, trash separator, filter and decomposer；Agitating shaft and stirrer paddle, and the guide shell that upper and lower side is open are provided with the kettle of hydriding reactor, is additionally provided with multiple feed pipes and the first CO2Access tube and overfall, the hydriding reactor is used for thick level lithium carbonate slurry and carbon dioxide reaction obtains primary hydride；Trash separator is connected with the overfall, and the hydride that cleans is obtained for removing the impurity in primary hydride；Filter is connected with the outlet of trash separator, obtains filtered fluid for filtering and impurity removing hydride, decomposer is connected with the leakage fluid dram of filter, for thermally decomposing the lithium carbonate after filtered fluid is decomposed.The preparation system can realize the consecutive production to battery-level lithium carbonate, shorten production procedure, reduce energy expenditure.Present invention also offers the preparation method of battery-level lithium carbonate.
Description
Technical field
The present invention relates to technical field of chemical, and in particular to a kind of preparation system of battery-level lithium carbonate and preparation side
Method.
Background technology
Lithium carbonate is widely used, and it is indispensable in industrial circles such as battery, lubricant, ceramics, glass, smeltings
Raw material.Recently as the upsurge of global new energy development, application of the lithium carbonate in lithium battery is more and more of interest by everybody.
More is industrial level lithium carbonate in the market, and its practical value is not so good as battery-level lithium carbonate.Lithium carbonate moves as lithium ion
The core material of power battery, solid foundation can be provided for lithium-ion-power cell by preparing the battery-level lithium carbonate of high-purity.
The hydrogenation mode of production lithium carbonate at present, typically carries out hydrogenation treatment using reactor agitating mode, if reaction
Kettle capacity is excessive, and inventory is excessive, then can cause to stir it is uneven, therefore, because the limitation of agitating mode so that majority reaction
Kettle can only be designed as 1-5m3Struck capacity, in industrial big production, the limitation of reaction vessel, cause in industrial production carbon
, it is necessary to spend more duplication of labour times and energy consumption during sour lithium, the production in enormous quantities of lithium carbonate can be met；Meanwhile hydrogen
Change typically reacted under 0.2~0.6mpa states, reactor need seal and it is pressure-resistant, per kettle reaction will boost, release, cause
Carbon dioxide wastes, low production efficiency.
The content of the invention
In view of this, the invention provides a kind of preparation system of battery-level lithium carbonate, the production of lithium carbonate can be improved
Capacity, energy expenditure is reduced, improve production efficiency.
In a first aspect, the invention provides a kind of preparation system of battery-level lithium carbonate, the preparation system includes hydrogenation
Kettle, trash separator, filter and decomposer；
The hydriding reactor includes kettle and the agitating shaft and stirrer paddle that are arranged in kettle, the agitating shaft and agitating paddle
The open guide shell of upper and lower side is provided with around leaf, the guide shell is fixed on the inwall of the kettle by support；The kettle
Multiple feed pipes and the first CO are provided with body2The water conservancy diversion is stretched into access tube, the lower end of the feed pipe from guide shell upper end
At stirrer paddle in cylinder；The top and bottom of the kettle are respectively equipped with overfall and discharge gate；Thick level lithium carbonate slurry, two
Carbonoxide is respectively via the feed pipe, CO2Access tube enters in the kettle obtains primary hydride so that hydrogenation occurs；
The trash separator is provided with precipitation and complexation agent access tube, inlet tube, outlet, the inlet tube and the overfall phase
Connect so that the primary hydride enters in the trash separator, there is the 2nd CO in the inlet tube also branch2Access tube, it is described to remove
The impurity that miscellaneous device is used to remove in the primary hydride obtains the hydride that cleans；
Filter, it is connected with the outlet of the trash separator, there is the 3rd CO in the entrance also branch of the filter2It is passed through
Pipe, the insoluble matter that the filter is used to filter off in the removal of impurities hydride obtain filtered fluid；
Decomposer, it is connected with the leakage fluid dram of the filter, the decomposer is divided for thermally decomposing the filtered fluid
Lithium carbonate after solution.
Preferably, the guide shell has inside and outside two layers of cylinder, forms a cavity between inside and outside two layers of cylinder, and described first
CO2Access tube is connected with the cavity of the guide shell, is offered in the internal layer cylinder side wall close to the stirrer paddle more
Individual CO2Import.First CO2Access tube C1 is with being provided with multiple CO2The guide shell cavity of import is connected, and can increase CO2With thick level
The contact area of lithium carbonate slurry, improve reaction efficiency.
Preferably, the feed pipe includes the first pipeline section and the second pipeline section, and first pipeline section is located at the guide shell
On the opening of upper end, inwall of second pipeline section along the guide shell is stretched at the stirrer paddle, first pipeline section
And second connected with flange between pipeline section.
Preferably, the guide shell is tubular, and the guide shell has the upper end being oppositely arranged open and lower end is open, institute
It is open close to the stirrer paddle, the open size in the upper end size open more than the lower end to state lower end.
Preferably, the guide shell is in closing in type, and the end face diameter of the shell portion of the guide shell extended from up to down is terraced
Degree reduces.
Preferably, it is additionally provided with channel-section steel on the kettle cover of the kettle, stirring frame is installed from bottom up on the channel-section steel
And drive mechanism, the drive mechanism are connected with the agitating shaft stretched into kettle, the drive mechanism is used to drive the stirring
Axle rotates.
Guide shell is installed additional in the hydriding reactor in the present invention, the material material entered in kettle can be pressed into bottom, so
Bottom material outside guide shell by reaching kettle top afterwards, so circulation；Footpath can be formed in guide shell into the material in kettle
To with axial flowing, realize the uniform mixing of material, can also accelerate thick level lithium carbonate slurry and CO2Between collision, improve anti-
Answer speed.In addition, the special construction of the feed pipe is advantageous to the installation and cleaning of the guide shell.
Preferably, online calcium ion detector is provided with the trash separator, for detecting the Ca contents in trash separator；Institute
State primary hydride into the trash separator inlet pipeline on be additionally provided with Flow Meter Based.The trash separator is flowed into by calculating
In primary hydrogenation flow quantity and Ca contents, added to control to the amount of the precipitation and complexation agent in trash separator.
Preferably, the outlet of the trash separator is arranged on the bottom of the trash separator, and the outlet is provided with first
Online pH instrument, the outlet is divided into line pipeline and reflux line after by the described first online pH instrument, described in line
In line valve and return valve, the first online pH instrument and in line valve, return valve are respectively equipped with pipeline and reflux line
Door, and the 2nd CO2The valve of air inlet pipe mutually interlocks, and controls the removal of impurities hydride pH in the outlet to maintain 8.5-9.0；
The return valve is used to open when the removal of impurities hydride pH in the outlet is more than 8.5-9.0, makes part removal of impurities hydrogenation
Liquid is back in the trash separator.
Preferably, the entrance of the filter is provided with gas-liquid mixed shower nozzle, and the gas-liquid mixed shower nozzle is used for described remove
Miscellaneous hydride and CO2It is mixed to get mixed material.
It is further preferred that the gas-liquid mixed shower nozzle is venturi mixer.It so may be such that CO2Air-flow and it is mingled with not
The mixed effect of the removal of impurities hydride slurry of molten thing is preferable.
Preferably, the first CO2Access tube, the 2nd CO2Air inlet pipe and the 3rd CO2Air inlet pipe with a CO2Supply source phase
Connection.
Preferably, multiple screen pipes are provided with the filter, the screen pipe is used under 0.1-0.3mPa pressure
To being connected with CO2Removal of impurities hydride filtered.
Preferably, the decomposer is additionally provided with a CO2Outlet, the CO2Outlet and the CO2Supply source is connected.
The CO2Outlet is used for caused CO in the decomposer2It can be back in the equipment such as hydriding reactor, trash separator.
Preferably, the preparation system also includes the second filter, the deslagging of second filter and the decomposer
Mouth is connected, and second filter is used to isolate the lithium carbonate after the decomposition.
The preparation system for the battery-level lithium carbonate that first aspect present invention provides, the preparation system include hydrogenation
Kettle, trash separator, filter and decomposer, it is closely connected between each equipment of the preparation system, it is possible to achieve to LITHIUM BATTERY
The consecutive production of lithium carbonate.Wherein, the guide shell in the hydriding reactor can realize the high-speed stirred to material, obtain primary
Hydride；The trash separator can remove the Ca impurity in primary hydride, and regulate and control to be passed through the CO in trash separator2, make primary
Unhydrided lithium carbonate further hydrogenates in hydride, obtains the hydride that cleans；The filter can filter off the removal of impurities hydrogen
Change the insoluble matter in liquid, and the CO made in filter process2Obtained with the further hydrogenation of lithium carbonate in removal of impurities hydride
Filtered fluid；The decomposer can carry out the filtered fluid to thermally decompose to yield lithium carbonate.
Second aspect, the invention provides a kind of preparation method of battery-level lithium carbonate, comprise the following steps：
(1) thick level lithium carbonate slurry is placed in hydriding reactor, and is passed through carbon dioxide, be stirred in the hydriding reactor
5-8h is reacted, obtains primary hydride, wherein, Li stable contents are in 7.5-8g/L in the primary hydride；
(2) the primary hydride is entered into trash separator via the overfall of the hydriding reactor, added into the trash separator
Enter precipitation and complexation agent, be passed through CO2, the contamination precipitation in the primary hydride is got off or is existed with complex form, obtain
Clean hydride, and the Ca impurity contents in the removal of impurities hydride are within 1mg/L；
(3) the removal of impurities hydride enters filter via the outlet of the trash separator, is passed through into the filter
CO2, the removal of impurities hydride is cut insoluble matter under 0.1-0.3mPa pressure and obtain filtered fluid, the pH of the filtered fluid
For 7.0-8.0；
(4) filtered fluid is thermally decomposed in decomposer, the lithium carbonate after being decomposed.
Above-mentioned hydriding reactor, trash separator, filter and decomposer are setting in the preparation system of first aspect present invention
It is standby.
Preferably, when the pH value of the removal of impurities hydride flowed out from the trash separator is more than 8.5-9.0, trash separator stream is reduced
The flow of the removal of impurities hydride gone out, part removal of impurities hydride is set to be back to the trash separator, while adjustment is passed into the removal of impurities
CO in device and filter2Flow, make the pH of the filtered fluid of the filter discharge stable in 7.0-8.0.
Preferably, the thick level lithium carbonate slurry is the mixture of industrial level lithium carbonate and water, and the thick level lithium carbonate is starched
The liquid-solid ratio of material is (20-25):1.
Preferably, the slurry flow that the thick level lithium carbonate slurry enters in the hydriding reactor via the feed pipe is 2-
3 cubes ms/h.
Preferably, in the hydriding reactor, the mole of the carbon dioxide exceedes carbonic acid in the thick level lithium carbonate slurry
The 5-10% of lithium.
Preferably, the precipitation and complexation agent includes disodium edta (i.e. EDETATE SODIUM), ethylenediamine tetra-acetic acid, fluorine
Change the one or more in sodium, oxalic acid, thioacetamide and 8- hydroxyl viper woodss.
Preferably, online calcium ion detector is provided with the trash separator, for detecting the Ca contents in trash separator.
Preferably, enter in the primary hydride on the inlet pipeline of the trash separator and be additionally provided with Flow Meter Based, lead to
Primary hydrogenation flow quantity and the Ca contents for calculating and flowing into the trash separator are crossed, to control the amount of the precipitation and complexation agent of addition,
So that the Ca impurity contents in the removal of impurities hydride are in below 1mg/L.
It is further preferred that the precipitation and complexation agent is 1.1-1.5 times of Ca quality in the trash separator.
The preparation method for the battery-level lithium carbonate that second aspect of the present invention provides, its technological design is reasonable, successively by just
Level hydrogenation, removal of impurities, filtering, thermal decomposition, and regulate and control CO in removal of impurities, filtering2Dosage, to the utilization rate of thick level lithium carbonate raw material
Height, hydrogenation is more complete, and the production procedure of the preparation method is short, reduces the energy loss in production, realizes to battery-level lithium carbonate
Continuous production.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification
, or can be known by the implementation of the embodiment of the present invention.
Brief description of the drawings
Fig. 1 is the structural representation of the preparation system of battery-level lithium carbonate in the embodiment of the present invention；
Fig. 2 is the structural representation of the stirrer paddle of hydriding reactor in the embodiment of the present invention.
Embodiment
Below in conjunction with the accompanying drawing in embodiment of the present invention, the technical scheme in embodiment of the present invention is carried out clear
Chu, it is fully described by.
Each label is as follows in the application：
Hydriding reactor 100：Kettle 1, agitating shaft 2, stirrer paddle 3, guide shell 4, the support 5 of guide shell, feed pipe 6, overflow
Mouthful N1, discharge gate N2, chuck 8, channel-section steel 9 stir frame 10, drive mechanism 11, condensation water inlet N3, condensation-water drain N4, auxiliary
Expect discharge gate N5, the first CO2Access tube C1, CO2Import 7；
Trash separator 200：Precipitation and complexation agent access tube 21, inlet tube 22, outlet 23, the 2nd CO2Access tube C2, vertical pipe
Road 231, reflux line 232, in line valve V2, return valve V3, delivery pump P1；Online calcium ion detector T1, online temperature
Instrument T2, the first online pH instrument T3；
Filter 300：Gas-liquid mixed shower nozzle 31, screen pipe 32, the leakage fluid dram N6 of filter；3rd CO2Air inlet pipe C3, the
Two online pH instrument T4；
Decomposer 400：Slag-drip opening N7, CO2Outlet C4.
Referring to Fig. 1, Fig. 1 is a kind of structure of the preparation system for battery-level lithium carbonate that the preferred embodiment of the present invention provides
Schematic diagram.The preparation system includes hydriding reactor 100, trash separator 200, filter 300 and decomposer 400.
The hydriding reactor 100 includes kettle 1 and the agitating shaft 2 and stirrer paddle 3 that are arranged in kettle 1, the agitating paddle
Leaf 3 sets the bottom of the agitating shaft 1, and the open guide shell 4 of upper and lower side is provided with around the agitating shaft 2 and stirrer paddle 3,
The guide shell 4 is fixed on the inwall of the kettle 1 by support 5.In the application, the agitating shaft 2 is set along the vertical direction,
The guide shell 4 is coaxially disposed with the agitating shaft 2, stirrer paddle 3；The upper end of the guide shell 4, lower end opening communicate.It is aobvious
So, the maximum cross section external diameter of the guide shell 4 is less than the cross sectional inner diameter of the kettle 1.So design is to ensure
There is clearance space between kettle 1 and guide shell 4.
Multiple feed pipes 6 are provided with the kettle 1, described lead is stretched into the lower end of the feed pipe 6 from the upper end of guide shell 4
The inner chamber of flow cartridge 4.Wherein, the feed pipe 6 includes the first pipeline section 61 and the second pipeline section 62, and first pipeline section 61 is positioned at described
On the upper end opening of guide shell 4, inwall of second pipeline section 62 along the guide shell 4 is stretched at the stirrer paddle 3,
Connected between the pipeline section 62 of first pipeline section 61 and second with flange 63.In the application, the lower end insertion stirring of the feed pipe 6
At blade 3, into guide shell 4 before connected with flange 63；The pipeline section 62 of first pipeline section 61 and second can be dismantled, so favourable
In the installation and cleaning of guide shell 4.
Preferably, second pipeline section 62 is in broken line type, and second pipeline section 62 includes the first sub- pipeline section and the second son pipe
Section, the first sub- pipeline section parallel to vertical direction, the second sub- pipeline section parallel to the inwall of guide shell 4, and with it is described
First sub- pipeline section forms a knuckle.It is further preferred that the size of the knuckle is 120-160 °.
The first CO is additionally provided with the kettle 12Access tube C1.The guide shell 4 two layers of cylinder with inside and outside, inside and outside two
A cavity, the first CO are formed between layer cylinder2Access tube C1 is connected with the cavity of the guide shell 4, close to described
Multiple CO are offered in the internal layer cylinder side wall of the guide shell 4 of stirrer paddle2Import 7.In the application, the first CO2Access tube C1 with
Provided with multiple CO2The guide shell cavity of import is connected, and can increase CO2With the contact area of thick level lithium carbonate slurry, improve anti-
Answer efficiency.
The top and bottom of the kettle 1 are respectively equipped with overfall N1 and discharge gate N2.Thick level lithium carbonate slurry is via institute
State feed pipe 6 to enter in the kettle, carbon dioxide is via the CO2Access tube C1, CO2Import 7 enters in the kettle 1.Slightly
Hydrogenation occurs in the hydriding reactor 100 and obtains primary hydride for level lithium carbonate slurry and carbon dioxide.
In the embodiment of the application one, the guide shell 4 is welded by least one support 5 and the inwall of kettle 1.The branch
Frame 5 is arranged on the upper and lower ends of the guide shell 4, and the setting direction of the support 5 is perpendicular to vertical direction.
In the embodiment of the application one, the guide shell 4 is tubular, and there is the guide shell 4 upper end being oppositely arranged to open
Mouth and lower end opening, the lower end is open to be more than lower end opening close to the stirrer paddle 3, the size of the upper end opening
Size.
On installing additional in the kettle 1 greatly under guide shell 4, guide shell 4 is the top material come in from feed pipe 6 under
Pressure type stirring press-in bottom, then bottom material outside guide shell 4 by reaching kettle top, so circulation；Into the material in kettle
Radial and axial flowing is formed in guide shell 4, material can be well mixed, can also accelerate to collide between particle spheroid, favorably
In the close spheric granules of formation.
It is further preferred that the guide shell 4 is in closing in type, the end of the shell portion of the guide shell 4 extended from up to down
Face diameter gradient reduces.In another preferred embodiment of the application, the guide shell 4 is taper.
It is further preferred that diameter D open with the upper end diameter d of lower end opening ratio is in 0.1-0.6.
More preferably 0.1-0.45.
Preferably, the height of the guide shell 4 is the 0.3-0.6 of the straight section of kettle 1.Wherein, the straight section of kettle 1 is
Refer to the kettle part in addition to autoclave body bottom.
Fig. 2 is referred to, Fig. 2 is the structural representation of stirrer paddle in hydriding reactor.The edge of the stirrer paddle 3 is in arc
Shape, the stirrer paddle 3 be not perpendicular with the agitating shaft 2.The angle of the stirrer paddle 3 and the agitating shaft 2 is 30-
60°.Stirring resistance can be so reduced, improves speed of agitator, power consumption is reduced, is easy to form the material to stir.
In the embodiment of the application one, the blade of stirrer paddle 3 is in downwards 45 degree of angles.The stirrer paddle 3 is 3 groups.In other implementations
In mode, stirrer paddle can also be 1,2,4,5 or 6.
The kettle 1 includes kettle cover and kettle body, and the kettle cover and kettle body are connected by flange.
It is additionally provided with channel-section steel 9 on the kettle cover of the kettle 1, the stirring He of frame 10 is installed from bottom up on the channel-section steel 9
Drive mechanism 11, for supporting the stirring frame 10 and drive mechanism 11.The drive mechanism 11, which is connected with, to be stretched into kettle 1
Agitating shaft 2, the drive mechanism 11 is used to drive the rotation of the agitating shaft 2.The stirring frame 10 has double layer supporting points.
The drive mechanism 11 includes the reductor that motor connects with motor lower end.The speed reducing ratio of the reductor is relatively low, the channel-section steel
With the stirring frame of double layer supporting points, the hydriding reactor is contributed to keep higher stability while high mixing speed is realized.
Axle mouth on the kettle cover around the agitating shaft 2 is provided with multiple charging aperture (not shown), multiple feed pipes 6
Upper end pass multiple charging apertures respectively.
The bottom of the kettle 1 is provided with discharge gate N2, is mainly used in discharging in kettle in the case of in each production cycle terminating
Material.The top of the kettle 1 is provided with overfall N1, goes out primary hydride for overflow, the raw material as follow-up trash separator.
The periphery of kettle 1 is also enclosed provided with chuck 8, and condensation water inlet N3, condensation-water drain are provided with the chuck 8
N4.It is further preferred that the condensation water inlet N3 is located at the bottom of the chuck 8, the condensation-water drain N4 is positioned at described
The top of chuck 8.
It is further preferred that the overfall N1 and condensation-water drain N4 is separately positioned on the top of kettle 1
Not homonymy.
Preferably, the bottom of the kettle 1 is ball crown type, and the bottom of the kettle 1 is provided with kettle end socket, the kettle envelope
Head is provided with the discharge gate N2, and auxiliary material discharge gate N5.The auxiliary material discharge gate N5 is used for the discharge gate in autoclave body bottom
N2 occurs discharging material etc. in kettle under abnormal conditions.
The bottom of the chuck 8 is provided with jacket head, and the jacket head is provided with the condensation water inlet N3.
In the application, guide shell 4 is installed in the kettle of the hydriding reactor 100 additional, can be the material material pressure entered in kettle
Enter bottom, then bottom material reaches kettle top by the outside of guide shell 4, so circulation；It can led into the material in kettle
Radial and axial flowing is formed in flow cartridge 4, the uniform mixing of material is realized, can also accelerate thick level lithium carbonate slurry and CO2Between
Collision, improve reaction rate.In addition, the special construction of the feed pipe is advantageous to the installation and cleaning of the guide shell.
Further, the preparation system be provided be used for monitor hydrogenation temperature in the kettle online thermometer T2, it is described
(dotted line in Fig. 1, which represents, has connection for line thermometer T2 and the condensed water switching signal interlocking that is passed through in the chuck of hydriding reactor 100
Lock acts on).
In an embodiment of the present invention, the online thermometer T2 may also be arranged in the trash separator 200, by institute
The primary hydride for stating generation in hydriding reactor 100 is constantly overflowed in the trash separator 200, is arranged in the trash separator 200
The temperature that also reflects in the hydriding reactor 100 of thermometer.
In another embodiment of the present invention, the hydriding reactor 100 is provided with the online temperature of monitoring hydrogenation temperature in the kettle
Instrument T2.
Preferably, the temperature control in hydriding reactor 100 is below 30 DEG C.More preferably 10-30 DEG C.
When the temperature in the hydriding reactor 100 is higher than 30 DEG C, condensation taps is opened, and according in hydriding reactor 100
Temperature height adjusts the aperture of condensation taps to control condensate flow in chuck 8.The aperture for condensing taps can be by
Condensation penstock V4 on the inlet pipeline of condensed water is adjusted.
Trash separator 200 is provided with precipitation and complexation agent access tube 21, inlet tube 22, outlet 23, the inlet tube 22 and institute
State overfall N1 to be connected so that the primary hydride enters in the trash separator 200, the inlet tube 22 also branch has the
Two CO2Access tube, the impurity that the trash separator 200 is used to remove in the primary hydride obtain the hydride that cleans.
Online calcium ion detector T1 is provided with the trash separator 200, for detecting the Ca in trash separator 2002+Content.
The primary hydride, which enters on the inlet tube 22 of the trash separator 200, is additionally provided with Flow Meter Based V1.Flowed into by calculating
Primary hydrogenation flow quantity and Ca in the trash separator 2002+Content, added to control to the precipitation and complexation in trash separator 200
The amount of agent.
Agitator is provided with the trash separator 200, in order to which the material stirring in trash separator is uniform.
The outlet 23 of the trash separator 200 is arranged on the bottom of the trash separator 200, and the outlet 23 is provided with the
One online pH instrument T3, the outlet 23 are divided into line pipeline 231 and return duct after by the described first online pH instrument T3
Road 232, is respectively equipped with line valve V2 and return valve V3 on the in line pipeline 231 and reflux line 232, described first
Line pH instrument T3 and in line valve V2, return valve V3, and the 2nd CO2Air inlet pipe C2 valve mutually interlocks, and controls the outlet
Removal of impurities hydride pH in pipe 23 maintains 8.5-9.0；The return valve V3 is used to work as the removal of impurities hydrogen in the outlet 23
Opened when changing liquid pH more than 8.5-9.0, part removal of impurities hydride is back in the trash separator 200.
Further, the outlet 23 of the trash separator 200 is provided with a delivery pump P1, for by the trash separator 200
Interior removal of impurities hydride is delivered to filter 300 or is partly refluxed to trash separator 200.The delivery pump P1 positioned at described first
Before line pH instrument T3.That is, described removal of impurities hydride first passes through the delivery pump P1, then by the described first online pH instrument T3.
Filter 300, it is connected with the outlet 23 of the trash separator 200, so that the removal of impurities hydride enters the mistake
In filter 300, there is the 3rd CO in the entrance also branch of the filter 3002Access tube, the filter 300 are used to filter off institute
The insoluble matter stated in removal of impurities hydride obtains filtered fluid.
Multiple screen pipes 32 are provided with the filter 300, the screen pipe 32 is used under 0.1-0.3mPa pressure
To being connected with CO2Removal of impurities hydride filtered.
The entrance of the filter 300 is provided with gas-liquid mixed shower nozzle 31, and the gas-liquid mixed shower nozzle 31 is used for described remove
Miscellaneous hydride and CO2It is mixed to get mixed material.
It is further preferred that the gas-liquid mixed shower nozzle 31 is venturi mixer.It so may be such that CO2Air-flow and it is mingled with
The mixed effect of the removal of impurities hydride slurry of insoluble matter is preferable.
The second online pH instrument T4 is provided with the leakage fluid dram N6 of the filter 300, for detecting from the row of filter 300
The pH value of the filtered fluid gone out.
In the application, the first CO2Access tube C1, the 2nd CO2Air inlet pipe C2 and the 3rd CO2Set respectively on air inlet pipe C3
Put multiple CO2Intake valve.As another embodiment of the present invention, the hydriding reactor 100, trash separator 200, filter
The first CO in 3002Access tube C1, the 2nd CO2Air inlet pipe C2 and the 3rd CO2Air inlet pipe C3 can also by a total valve (such as
Three-way valve) dispatched to realize.
Preferably, the first CO2Access tube C1, the 2nd CO2Air inlet pipe C2 and the 3rd CO2Air inlet pipe C3 with a CO2For
It is connected to source.The CO2Supply source can be CO2Gas reservoir or liquefied CO2Storage tank.
It is further preferred that the first CO2The liquefied CO of access tube C1 and one2Storage tank is connected, and supplies the hydriding reactor
100 liquefied CO2.The liquefied CO2Become CO during entering in the kettle2Gas.The liquefied CO2
Become CO2It can be absorbed heat in the gasification of gas, the temperature in the hydriding reactor 100 can be reduced, promote lithium carbonate and CO2Between
The progress of hydrogenation.
Decomposer 400, it is connected with the leakage fluid dram N6 of the filter 300, the decomposer 400 is used to thermally decompose the mistake
Filtrate decomposed after lithium carbonate.
In the application, the decomposer 400 is mainly used in entering the filtered fluid (lithium bicarbonate) of the filter 300 discharge
Row heating so that it, which is decomposed, becomes lithium carbonate, while the CO generated2Hydriding reactor 100, trash separator 200, filter can be back to
In 300, to be recycled.
The decomposer 400 is additionally provided with a CO2Outlet C4, the CO2The outlet C4 and CO2Supply source is connected.
The CO2Outlet C4 is used for caused CO in the decomposer 4002Hydriding reactor 100, trash separator 200 etc. can be back to set
In standby.
The preparation system also includes the second filter 300, the row of second filter 300 and the decomposer 400
Cinder notch N7 is connected, and second filter 300 is used to isolate the lithium carbonate after the decomposition.
The embodiments of the invention provide the preparation system of battery-level lithium carbonate, the preparation system includes hydriding reactor 100, removed
Miscellaneous device 200, filter 300 and decomposer 400, it is closely connected between each equipment of the preparation system, it is possible to achieve to electricity
The consecutive production of pond level lithium carbonate.Wherein, the guide shell in the hydriding reactor 100 can realize the high-speed stirred to material,
Obtain primary hydride；The trash separator 200 can remove the Ca impurity in primary hydride, and regulate and control to be passed through trash separator 200
Interior CO2, unhydrided lithium carbonate in primary hydride is further hydrogenated, obtain the hydride that cleans；The filter 300 can
To filter off the insoluble matter in the removal of impurities hydride, and the CO made in filter process2Enter with the lithium carbonate in removal of impurities hydride
One step hydrogenation obtains filtered fluid；The decomposer 400 can carry out the filtered fluid to thermally decompose to yield lithium carbonate.
The embodiment of the present invention additionally provides a kind of preparation method of battery-level lithium carbonate, comprises the following steps：
(1) thick level lithium carbonate slurry is placed in hydriding reactor 100, and is passed through carbon dioxide, entered in the hydriding reactor 100
Row stirring reaction 5-8h, obtains primary hydride, wherein, Li stable contents are in 7.5-8g/L in the primary hydride；
(2) the primary hydride is entered into trash separator 200 via the overfall N1 of the hydriding reactor 100, removed to described
Precipitation and complexation agent is added in miscellaneous device 200, is passed through CO2, the contamination precipitation in the primary hydride is got off or with complex compound shape
Formula exist, obtain clean hydride, it is described removal of impurities hydride in Ca impurity contents within 1mg/L；
(3) the removal of impurities hydride enters filter 300 via the outlet 23 of the trash separator 200, to the filtering
CO is passed through in device 3002, the removal of impurities hydride is cut insoluble matter under 0.1-0.3mPa pressure and obtain filtered fluid, institute
The pH for stating filtered fluid is 7.0-8.0；
(4) filtered fluid is thermally decomposed in decomposer 400, the lithium carbonate after being decomposed.
Above-mentioned hydriding reactor 100, trash separator 200, filter 300 and decomposer 400 are the system of first aspect present invention
Equipment in standby system.
Preferably, the thick level lithium carbonate slurry is the mixture of industrial level lithium carbonate and water.The industrial level lithium carbonate
Refer to that product purity is relatively low, impurity content does not reach the lithium carbonate of LITHIUM BATTERY standard.
Preferably, in the thick level lithium carbonate slurry, the liquid-solid ratio of industrial level lithium carbonate and water is (20-25):1Kg/L.
Preferably, the slurry flow that the thick level lithium carbonate slurry enters in the hydriding reactor 100 via the feed pipe
For 2-3 cubes m/h.
Preferably, in the hydriding reactor 100, the mole of the carbon dioxide exceedes carbon in the thick level lithium carbonate slurry
The 5-10% of sour lithium.
In the application, the precipitation and complexation agent include disodium edta (i.e. EDETATE SODIUM), ethylenediamine tetra-acetic acid,
One or more in sodium fluoride, oxalic acid, thioacetamide and 8- hydroxyl viper woodss, but not limited to this.
Online calcium ion detector T1 is provided with the trash separator 200, for detecting the Ca in trash separator 2002+Content.
Preferably, enter in the primary hydride on the inlet tube 22 of the trash separator 200 and be additionally provided with flow rate calculation
Instrument V1, by calculating primary the hydrogenation flow quantity and Ca that flow into the trash separator 2002+Content, to control the precipitation of addition
The amount of complexing agent so that the Ca in the removal of impurities hydride2+Impurity content is in below 1mg/L.
It is further preferred that the precipitation and complexation agent is Ca in the trash separator 2002+1.1-1.5 times of quality.
Agitator is provided with the trash separator 200.It so may be such that primary hydride and precipitation and complexation agent, CO2Deng between
Reaction it is more abundant.
The outlet 23 of the trash separator 200 is provided with the first online pH instrument T3, and the outlet 23 is by described the
After one online pH instrument T3, it is divided into line pipeline 231 and reflux line 232, on the in line pipeline 231 and reflux line 232
In line valve V2 and return valve V3, the first online pH instrument T3 and in line valve V2, return valve V3 are respectively equipped with, and
2nd CO2Air inlet pipe C2 valve mutually interlocks, and controls the removal of impurities hydride pH in the outlet 23 to maintain 8.5-9.0；Institute
State return valve V3 to be used to open when the removal of impurities hydride pH in the outlet 23 is more than 8.5-9.0, part is cleaned
Hydride is back in the trash separator 200.
When the pH value of the removal of impurities hydride is more than 8.5-9.0, the return valve V3 is opened, returns part hydride
It flow in the trash separator 200, reduces the flow of the in line pipeline 231.Now and pass through CO2Intake valve control, which is passed into, to remove
CO in miscellaneous device 200 and filter 3002Amount, the pH stable for the filtered fluid that filter 300 discharges is set so may be used in 7.0-8.0
Ensure that the lithium carbonate in raw material hydrogenates completely.Simultaneously with the continuation of technique, the removal of impurities hydride pH of the outlet of trash separator 200
8.5-9.0 can be maintained.
In the application, if the in line valve V2 of trash separator 200 described in Close All, preparation LITHIUM BATTERY carbonic acid can be made
The continuity of lithium is affected.Hydride pH in the application in the outlet 23 of the trash separator 200 is more than 8.5-9.0
When, in line valve V2 and return valve V3 are opened simultaneously, are reduced the flow of the in line pipeline 231, still can be met battery
The preparation demand of level lithium carbonate, while also it is connected with high pressure CO in subsequent filter 3002, it is possible to achieve to carbon in removal of impurities hydride
Sour lithium enters level deep hydrogenation.But if not reacting complete into the lithium carbonate in the removal of impurities hydride of filter 300, and
And the flow of the hydride that cleans when entering filter 300 is again very big, cannot so ensure total overall reaction in the filter, most
The purity of battery-level lithium carbonate can be influenceed eventually.
The second online pH instrument T4 is provided with the leakage fluid dram N6 of the filter 300, for detecting from the row of filter 300
The pH value of the filtered fluid gone out.
Multiple screen pipes 32 are provided with the filter 300, are being passed through CO2In the case of, the removal of impurities hydride exists
Filtered under 0.1-0.3mPa pressure by the screen pipe 32.The removal of impurities hydride flowed into the filter 300, in filter
In 300, its a small amount of lithium carbonate side contained and CO2Reaction becomes lithium bicarbonate, while being filtered, reduces insoluble lithium carbonate by mistake
The risk filtered.
Some undissolved solids (including some insoluble and water lithium carbonates) in trash separator 200 be present, in Ca2+With sinking
During the complexing agent reaction of shallow lake, the insoluble solids thing can play a part of heavy core agent, accelerate the precipitation of the fine particles such as CaF, Ke Yiti
The filter efficiency of high subsequent filter 300；Filtering is played with another after removal of impurities process by preliminary hydrogenation simultaneously, production can be shortened
Flow, reduce the energy loss in production.
0.1~0.3mpa pressure is carried in the filter 300, it is ensured that lithium carbonate and CO2Further reaction, ensure
Lithium carbonate hydrogenates completely；Into the filter 300 mixed slurry through the screen pipe 32 filtering after, filtered fluid is expelled to
In decomposer 400, solid is stayed in filter 300；Filtered fluid decomposes in subsequent decomposition device 400 and obtains lithium carbonate and CO2, mistake
The CO for the unnecessary dissolving being mingled with filtrate2Also isolated in subsequent decomposition device 400, and return to hydriding reactor 100 and trash separator 200
Etc. being recycled in equipment.Decompose the obtained lithium carbonate later stage and pass through filtering, washing, battery-level lithium carbonate product can be obtained,
Washing obtains mother liquor and wash water can be used for preparing thick level lithium carbonate slurry, and realization recycles, and whole process produces without waste water, green
Colour circle is protected.
The preparation method of battery-level lithium carbonate provided in an embodiment of the present invention, its technological design is reasonable, successively by primary
Hydrogenation, removal of impurities, filtering, thermal decomposition, and regulate and control CO in removal of impurities, filtering2Dosage, to the utilization rate of thick level lithium carbonate raw material
Height, hydrogenation is more complete, and the production procedure of the preparation method is short, reduces the energy loss in production, realizes to battery-level lithium carbonate
Continuous production.
Described above is the preferred embodiment of the present invention, but therefore can not be interpreted as to the scope of the claims of the present invention
Limitation.It should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention, also
Some improvements and modifications can be made, these improvements and modifications are also considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation system of battery-level lithium carbonate, it is characterised in that the preparation system includes hydriding reactor, trash separator, mistake
Filter and decomposer；The hydriding reactor includes jacketed still body and the agitating shaft and stirrer paddle that are arranged in kettle, described
The open guide shell of upper and lower side is provided with around agitating shaft and stirrer paddle, the guide shell is fixed on the kettle by support
Inwall；Multiple feed pipes and the first CO are provided with the kettle2Access tube, the lower end of the feed pipe is from guide shell upper end
Stretch at the stirrer paddle in the guide shell；The top and bottom of the kettle are respectively equipped with overfall and discharge gate；Thick level
Lithium carbonate slurry, carbon dioxide are respectively via the feed pipe, CO2Access tube enters in the kettle to be obtained so that hydrogenation occurs
To primary hydride, the kettle includes kettle cover and kettle body, and the kettle cover and kettle body are connected by flange；
The trash separator is provided with precipitation and complexation agent access tube, inlet tube, outlet, and the inlet tube is connected with the overfall
So that the primary hydride enters in the trash separator, there is the 2nd CO in the inlet tube also branch2Access tube, the trash separator
The hydride that cleans is obtained for removing the impurity in the primary hydride；
Filter, it is connected with the outlet of the trash separator, there is the 3rd CO in the entrance also branch of the filter2Access tube, institute
State the insoluble matter that filter is used to filter off in the removal of impurities hydride and obtain filtered fluid；
Decomposer, it is connected with the leakage fluid dram of the filter, the decomposer is used to thermally decomposing after the filtered fluid obtains decomposition
Lithium carbonate.
2. preparation system as claimed in claim 1, it is characterised in that the feed pipe includes the first pipeline section and the second pipeline section,
First pipeline section is located on the upper end opening of the guide shell, and inwall of second pipeline section along the guide shell stretches into
At the stirrer paddle, connected between first pipeline section and the second pipeline section with flange.
3. preparation system as claimed in claim 1, it is characterised in that the guide shell is tubular, and the guide shell has phase
And lower end open to the upper end of setting is open, and the lower end is open big close to the stirrer paddle, the open size in the upper end
In the size that the lower end is open.
4. preparation system as claimed in claim 1, it is characterised in that the guide shell two layers of cylinder with inside and outside, inside and outside two
A cavity, the first CO are formed between layer cylinder2Access tube is connected with the cavity of the guide shell, close to the stirring
Multiple CO are offered in the internal layer cylinder side wall of blade2Import.
5. preparation system as claimed in claim 1, it is characterised in that online calcium ion detector is provided with the trash separator,
For detecting the Ca contents in trash separator；Enter in the primary hydride on the inlet pipeline of the trash separator and be additionally provided with flow
Calculating instrument.
6. preparation system as claimed in claim 1, it is characterised in that the outlet of the trash separator is arranged on the trash separator
Bottom, the outlet is provided with the first online pH instrument, and the outlet is divided into after by the described first online pH instrument
In line pipeline and reflux line, are respectively equipped with line valve and return valve on the in line pipeline and reflux line, and described
One online pH instrument and in line valve, return valve, and the 2nd CO2The valve of air inlet pipe mutually interlocks, and controls in the outlet
Removal of impurities hydride pH maintain 8.5-9.0；The removal of impurities hydride pH that the return valve is used to work as in the outlet exceedes
Opened during 8.5-9.0, part removal of impurities hydride is back in the trash separator.
7. preparation system as claimed in claim 1, it is characterised in that the entrance of the filter is sprayed provided with gas-liquid mixed
Head, the gas-liquid mixed shower nozzle are used for the removal of impurities hydride and CO2It is mixed to get mixed material.
8. preparation system as claimed in claim 1, it is characterised in that be provided with multiple screen pipes, the mistake in the filter
Chimney filter is used under 0.1-0.3MPa pressure to being connected with CO2Removal of impurities hydride filtered.
9. a kind of preparation method of battery-level lithium carbonate, it is characterised in that comprise the following steps：
(1) thick level lithium carbonate slurry is placed in hydriding reactor, and is passed through carbon dioxide, reaction is stirred in the hydriding reactor
5-8h, primary hydride is obtained, wherein, Li stable contents are in 7.5-8g/L in the primary hydride；
(2) the primary hydride is entered into trash separator via the overfall of the hydriding reactor, it is heavy to be added into the trash separator
Shallow lake complexing agent, it is passed through CO2, the contamination precipitation in the primary hydride is got off or is existed with complex form, cleaned
Hydride, it is described removal of impurities hydride in Ca impurity contents within 1mg/L；
(3) the removal of impurities hydride enters filter via the outlet of the trash separator, and CO is passed through into the filter2, make
The removal of impurities hydride is cut insoluble matter under 0.1-0.3MPa pressure and obtains filtered fluid, and the pH of the filtered fluid is
7.0-8.0；
(4) filtered fluid is thermally decomposed in decomposer, the lithium carbonate after being decomposed.
10. preparation method as claimed in claim 9, it is characterised in that when the removal of impurities hydride flowed out from the trash separator
When pH value is more than 8.5-9.0, the flow of the removal of impurities hydride of trash separator outflow is reduced, is back to part removal of impurities hydride described
Trash separator, while adjustment is passed into the CO in the trash separator and filter2Flow, make the filtered fluid of the filter discharge
PH is stable in 7.0-8.0.
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| CN107308898B (en) * | 2017-07-28 | 2023-09-15 | 格林美（江苏）钴业股份有限公司 | Rapid synthesis device for ternary lithium battery anode material precursor |
| CN109534370B (en) * | 2018-10-25 | 2023-08-18 | 四川能投鼎盛锂业有限公司 | Battery grade lithium carbonate crude product stirring and washing device |
| CN110894078B (en) * | 2019-12-26 | 2023-09-26 | 合肥天晟锂业科技有限公司 | Method and device for purifying battery-grade lithium carbonate |
| CN114774714B (en) * | 2022-06-22 | 2022-09-23 | 广东芳源新材料集团股份有限公司 | Device for separating lithium and ternary metal ions M from lithium solution |
| CN115536045B (en) * | 2022-11-01 | 2023-04-25 | 甘肃睿思科新材料有限公司 | Method for efficiently and continuously preparing ultrapure lithium carbonate with uniform granularity |
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| CN102531002B (en) * | 2011-12-23 | 2013-08-14 | 四川天齐锂业股份有限公司 | Method for purifying lithium carbonate |
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