CN113750946B - Reaction for preparing battery anode material precursor and purification system and process thereof - Google Patents
Reaction for preparing battery anode material precursor and purification system and process thereof Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 158
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000002243 precursor Substances 0.000 title claims abstract description 32
- 238000000746 purification Methods 0.000 title claims abstract description 30
- 230000008569 process Effects 0.000 title claims abstract description 23
- 239000010405 anode material Substances 0.000 title claims description 17
- 239000012528 membrane Substances 0.000 claims abstract description 136
- 239000007788 liquid Substances 0.000 claims abstract description 119
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 91
- 238000005406 washing Methods 0.000 claims abstract description 89
- 238000004140 cleaning Methods 0.000 claims abstract description 52
- 238000000926 separation method Methods 0.000 claims abstract description 41
- 239000002994 raw material Substances 0.000 claims abstract description 39
- 239000012452 mother liquor Substances 0.000 claims abstract description 37
- 239000002699 waste material Substances 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000003860 storage Methods 0.000 claims abstract description 12
- 239000007774 positive electrode material Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 35
- 239000002351 wastewater Substances 0.000 claims description 28
- 230000001276 controlling effect Effects 0.000 claims description 22
- 150000003839 salts Chemical class 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 16
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000008139 complexing agent Substances 0.000 claims description 13
- 239000000047 product Substances 0.000 claims description 13
- 239000011343 solid material Substances 0.000 claims description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 10
- 239000012065 filter cake Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- 239000010406 cathode material Substances 0.000 claims description 9
- 238000007599 discharging Methods 0.000 claims description 9
- 230000004907 flux Effects 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 8
- 239000012141 concentrate Substances 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- 229910021529 ammonia Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 5
- 238000001728 nano-filtration Methods 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 238000001223 reverse osmosis Methods 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- -1 liOH Chemical compound 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000001502 supplementing effect Effects 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 239000001099 ammonium carbonate Substances 0.000 claims description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 2
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 10
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 6
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000712 assembly Effects 0.000 abstract description 2
- 238000000429 assembly Methods 0.000 abstract description 2
- 230000010354 integration Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 description 17
- 230000000694 effects Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000012716 precipitator Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0053—Details of the reactor
- B01J19/0066—Stirrers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
- B01J19/1893—Membrane reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention particularly relates to a reaction and purification system and process suitable for preparing a precursor of a positive electrode material of a lithium/sodium ion battery. The integrated reaction kettle comprises a reaction kettle and at least one group of built-in dynamic disc membrane assemblies, wherein the top of the reaction kettle is provided with at least one raw material feed port communicated with the raw material tank, a cleaning liquid inlet communicated with the cleaning device, and the bottom of the reaction kettle is provided with at least one discharge port communicated with the qualified material storage tank; the dynamic disc membrane assembly is provided with a plurality of hollow membranes and hollow rotating shafts which sequentially penetrate through and are communicated with the membranes and are rotatably connected to the reaction kettle, and the hollow rotating shafts are communicated with the mother liquor discharge tank and the washing water waste liquid circulating device, so that the integration of the reaction, dynamic separation and washing process can be realized.
Description
Technical Field
The invention particularly relates to a reaction and purification system and process suitable for preparing a precursor of a positive electrode material of a lithium/sodium ion battery.
Background
The lithium ion battery has the advantages of high working voltage, long cycle life, light weight, less self-discharge, no memory effect, high cost performance and the like, and is widely applied to the fields of consumer electronic products, new energy automobiles and the like. Compared with a lithium ion battery, the energy density and the voltage of the sodium ion battery are relatively low, the lithium ion battery can be used for the situation that the volume and the portability are not high, and the advantages of high sodium content and low cost can be fully exerted, so that the lithium ion battery becomes a research hot spot and is hopeful to become an inexpensive way for replacing the lithium ion battery. Wherein the positive electrode material is one of the core parts of the lithium/sodium ion battery, and determines the performance of the lithium/sodium ion battery. The positive electrode materials of the lithium/sodium ion battery comprise lithium cobalt oxide/sodium, lithium manganese oxide/sodium, binary materials, ternary materials and the like, and precursors of the positive electrode materials can be generally prepared by utilizing corresponding metal salt solutions and alkali solutions to crystallize through coprecipitation reaction, and then filtering, separating, washing, purifying, drying and the like.
In the existing preparation process, when a continuous method is adopted, the nucleation rate in a reaction kettle is difficult to control, and most of crystal nuclei are likely to be generated due to improper operation or untimely reasons, so that the average particle size of a final product is too small, the particle size distribution is too wide, and clear mother liquor with a large number of crystal nuclei and fine crystal grains needs to be discharged from the reaction kettle in the actual operation process; when the batch process or the semi-continuous semi-indirect process is adopted, along with the progress of the reaction, the solid content in the reaction kettle is continuously increased, the number of crystal nuclei in the reaction kettle is also continuously increased, and in order to fully utilize the volume of the reaction kettle and prevent the explosion of the reaction kettle from nucleation, the clear mother solution containing the crystal nuclei is also required to be separated from the reaction kettle. In the actual production process, a solid lifting device is arranged outside the reaction kettle body to separate clear mother solution, and the separated solid particles return to the reaction kettle to continue growing. Common extractors include settling tanks and thickeners, where the settling tank cannot concentrate the slurry to a higher solids content, typically not more than 20%; the thickener realizes solid-liquid separation of slurry in a filter rod filtering mode, and the filter cake is easy to form and the growth morphology of particles is influenced although the filtering area and the efficiency are higher. The external solid lifting device separation increases the complexity and investment cost of the process flow and operation. In the conventional in-vitro separation process, crystals generated by coprecipitation in a reaction kettle are treated by separation and washing equipment which are arranged independently, and the washing process is usually filter cake filtration washing (such as a centrifuge and a plate frame), and the material washing is insufficient and uneven due to the thickness of a filter cake layer, the directional flow direction of washing water and dead angles formed by the equipment, so that the requirement of impurity removal can be met only through dilution effect of a large amount of water consumption.
Disclosure of Invention
The invention aims at overcoming the defects in the prior art, and provides a reaction for preparing a precursor of a battery anode material, a purification system and a purification process thereof, so as to integrate the reaction, dynamic separation and water washing processes.
The invention aims at providing a reaction and purification system for preparing a battery anode material precursor, which adopts the following technical scheme:
the reaction and purification system for preparing the battery anode material precursor comprises a raw material tank, a cleaning device, a mother liquor discharge tank, a qualified material storage tank, a washing water waste liquid circulating device and an integrated reaction kettle, wherein the integrated reaction kettle comprises the reaction kettle and at least one group of built-in dynamic disc membrane components, the top of the reaction kettle is provided with at least one raw material feed port communicated with the raw material tank, a cleaning liquid inlet communicated with the cleaning device, and the bottom of the reaction kettle is provided with at least one discharge port communicated with the qualified material storage tank; the dynamic disc membrane assembly comprises a plurality of hollow membranes which are arranged at intervals and can enable liquid to penetrate through the surface and penetrate into the inner cavity, and hollow rotating shafts which are sequentially connected with the membranes in a penetrating mode and can be driven by the driving device to rotate and are connected to the reaction kettle, the membranes are communicated with the hollow rotating shafts, and the hollow rotating shafts are communicated with the mother liquor discharge tank and the washing water waste liquid circulating device.
Preferably, the reaction kettle is internally provided with a liquid distributor parallel to the hollow rotating shaft, and the liquid distributor is communicated with the raw material feed port and the cleaning liquid inlet.
Preferably, the raw material feed port and the cleaning liquid inlet are shared.
Preferably, the plurality of raw material feed inlets and the plurality of cleaning liquid inlets are symmetrically distributed.
Preferably, turbulence members for enhancing turbulence of the slurry are arranged between the plurality of diaphragms.
Preferably, the membrane is of a hollow disc-shaped structure, the surface of the membrane is provided with a filter hole communicated with the inner cavity of the membrane, and the diameter of the filter hole is 10 nm-50 mu m and/or; the membrane is of a circular structure, and the diameter of the membrane is 50-5000mm.
Preferably, the hollow rotating shaft is a hollow column with an outer diameter of 10-500mm and a wall thickness of 2-25 mm.
Preferably, the cleaning device comprises an alkali liquid tank, a washing water supply tank, a cleaning liquid tank and a backflushing tank, wherein the alkali liquid tank, the washing water supply tank and the cleaning liquid tank share a cleaning liquid inlet and are communicated with the liquid distributor, the backflushing tank is communicated with the hollow rotating shaft, the backflushing tank backflushes the membrane by utilizing a backflushing air source, and the cleaning liquid tank is used for cleaning the membrane; the washing water waste liquid circulation device comprises a waste water tank and a membrane separation unit, wherein the membrane separation unit for purifying waste water is arranged on a pipeline of the waste water tank communicated with the washing water supply tank, and clear liquid generated by the membrane separation unit is returned to the washing water supply tank and is used as washing water supplementing water for recycling
Preferably, the membrane separation unit adopts a nanofiltration membrane and/or a reverse osmosis membrane.
Preferably, the device also comprises a gas outlet arranged at the top of the reaction kettle, a drain hole arranged at the bottom of the reaction kettle and used for discharging residual mother liquor and cleaning waste liquid, a buffer tank and a clear liquid viewing mirror which are connected in series between the hollow rotating shaft and the mother liquor discharge tank.
The second purpose of the invention is to provide a process based on the reaction and purification system for preparing the precursor of the battery anode material, which adopts the following technical scheme:
a process based on the reaction for preparing the battery positive electrode material precursor and a purification system thereof comprises the following steps:
step one, respectively preparing a metal salt mixed solution, a precipitant solution and a complexing agent solution with corresponding concentrations in a raw material tank according to the proportion of positive electrode material elements;
step two, conveying the prepared metal salt mixed solution, the precipitant solution and the complexing agent solution into an integrated reaction kettle;
step three, regulating the flux of clear liquid in the reaction kettle by controlling the pressure difference and the rotating speed of the dynamic disc membrane assembly; in the reaction process, feeding and reaction are synchronously carried out, the temperature and the pH value suitable for the reaction in the reaction kettle are maintained, and part of mother liquor is separated and filtered through a dynamic disc membrane assembly in the reaction process;
stopping feeding when the solid materials generated by the reaction in the reaction kettle meet the physicochemical properties of the product; the physicochemical properties of the product in the technical scheme comprise the particle size, tap density and specific surface area of the reaction product, and the physicochemical properties adopted by different reaction materials can be different.
And fifthly, starting the cleaning device to perform a water cleaning process, and collecting the waste water and the waste liquid into a waste water tank through a hollow rotating shaft after the waste water and the waste liquid are separated through the dynamic disc membrane assembly.
And step six, after the solid materials reach the standard through water washing, unloading the solid materials to a qualified material storage tank, and carrying out subsequent treatment procedures.
Preferably, the pressure difference of the dynamic disc membrane component is between 0.5 and 5bar, and the rotating speed of the membrane component is between 0 and 1500r/min.
Preferably, the following process steps are further included between the fourth step and the fifth step: and controlling the rotating speed of the dynamic disc membrane assembly to concentrate the slurry, forming a filter cake on the surface of the membrane of the dynamic disc membrane assembly by the solid material, and discharging residual mother liquor in the reaction kettle through a drain hole at the bottom of the reaction kettle.
Preferably, the fifth step further comprises the following process steps: separating the washing water waste liquid in the waste water tank through a membrane separation unit, and refluxing the obtained clear liquid to a washing water supply tank for recycling, wherein the obtained concentrated liquid and the discharged mother liquid enter a recovery system together, the membrane separation unit adopts a nanofiltration membrane and/or a reverse osmosis membrane, and the recovery rate of the membrane separation clear liquid of the membrane separation unit is not lower than 70%.
Preferably, in the water washing process, naOH solution with the concentration of 0.1-1.0 mol/L and the temperature of 0-95 ℃ is adopted for alkali washing, and pure water with the temperature of 0-95 ℃ is used for water washing until the impurity ion content in the material reaches the standard, and the water washing is stopped.
Preferably, the total metal ion concentration in the prepared metal salt mixed solution is 1.0-5.0 mol/L; the concentration of the prepared precipitant solution is 1.0-9.0 mol/L; the concentration of the prepared complexing agent solution is 1.0-10.0 mol/L.
Preferably, the ratio of the feed rate of the metal salt mixed solution to the feed rate of the precipitant solution to the feed rate of the complexing agent solution is (4-6): 1-2): 1.
Preferably, the temperature in the reaction kettle is 20-95 ℃, the pH value is 10-13, the ammonia concentration is 5-12 g/L, and the solid content is 100-1000 g/L.
Preferably, the metal salt mixed solution is prepared from one or more soluble salts of nickel salt, cobalt salt, manganese salt, aluminum salt and copper salt, wherein the soluble salts are one or more of sulfate, nitrate, chloride salt and acetate; the precipitant solution is at least one of NaOH, KOH, liOH, sodium carbonate and sodium bicarbonate; the complexing agent solution is at least one of ammonia water, ammonium bicarbonate, ammonium sulfate and citric acid EDTA.
The invention adopts the technical proposal at least has the following beneficial effects that 1) through the internal dynamic disc membrane component in the reaction kettle, the stirring effect can be realized through the membrane rotation, the cross flow effect can be formed, the coupling between the dynamic separation in the reaction kettle and the reaction process can be realized, the continuous operation requirement of feeding the reaction and discharging the mother liquor can be met, the reaction efficiency is improved, and the defects of the external separation in the aspects of complexity of the process flow, high energy consumption, poor uniformity of particle growth morphology and the like can be avoided; 2) The raw material feed port and the cleaning liquid feed port are shared, so that the conversion of a water washing process can be realized, in the water washing process, the granular products are uniformly dispersed in the reaction kettle under the cross flow effect, the filter cake-free water washing is realized, the water washing is more sufficient, the water washing efficiency is higher, the product quality is improved, the water washing waste liquid can be recycled through treatment, and the water consumption is greatly reduced; 3) The dynamic disc membrane component is utilized for separation, washing and filtration, so that the energy consumption can be obviously reduced, and the purposes of energy conservation and environmental protection are achieved.
Drawings
For a clearer description of the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings described below are only some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of a reaction and purification system for preparing a precursor of a battery anode material according to an embodiment of the present invention;
FIG. 2 is a process flow diagram of an embodiment of the present invention.
Reference numerals: the device comprises a motor 11, a reaction kettle 12, a membrane 13, a hollow rotating shaft 14, a turbulence piece 15, a liquid distributor 16, a clear liquid view mirror 17, a buffer tank 18, a raw material liquid inlet 21, a cleaning liquid inlet 22, a heat source 23, a gas outlet 24, a backflushing tank inlet 25, a mother liquid discharge tank inlet 26, a discharge outlet 27 and a discharge outlet 28.
Detailed Description
In order to make the technical features, objects and effects of the present invention more clearly understood, the following detailed description of the embodiments of the present invention will be given with reference to the accompanying drawings.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1
Please refer to fig. 1, which is a schematic structural diagram of a reaction and purification system for preparing a precursor of a battery anode material, and the reaction and purification system comprises a raw material tank, a cleaning device, a mother liquor discharge tank, a qualified material storage tank, a washing water waste liquid circulation device and an integrated reaction kettle, wherein all the devices are communicated through pipelines. The number of the raw material tanks is reasonably increased, decreased and distributed according to the types of actual reaction raw materials.
The integrated reaction kettle comprises a reaction kettle 12 and at least one group of built-in dynamic disc membrane components, wherein the top of the reaction kettle 12 is provided with a raw material feed port 21 communicated with a raw material tank, a cleaning liquid inlet 22 communicated with a cleaning device and a gas discharge port 24, and the raw material feed port 21 and the cleaning liquid inlet 22 are preferably shared; the bottom of the reaction kettle 12 is provided with a discharge port 27 communicated with a qualified material storage tank and a discharge port 28 for discharging residual mother liquor and cleaning waste liquid. The reaction vessel 12 may be heated by an external heat source 23 to maintain the temperature required for the reaction inside the reaction vessel.
The dynamic disc membrane assembly comprises a plurality of hollow membranes 13 and a hollow rotating shaft 14 which sequentially penetrates through and is connected with the membranes, each membrane 13 is communicated with the hollow rotating shaft 14, one end of the hollow rotating shaft 14 penetrating through the kettle wall of the reaction kettle 12 is driven by a motor 11, the other end of the hollow rotating shaft is a mother liquor clear liquid discharge port, and the mother liquor clear liquid discharge port is sequentially communicated with a buffer tank 18 and a clear liquid viewing mirror 17 and then is respectively communicated with a mother liquor discharge tank inlet 26 and a washing water waste liquid circulating device. In some embodiments, the hollow shaft 14 is mechanically sealed to the reactor housing and is driven by a shaft or belt or gear.
The integrated reaction kettle in the embodiment can realize the integration of the reaction, dynamic separation and washing processes through the cross flow effect formed by the rotation of a plurality of diaphragms, and the specific principle is described as follows: the raw material solution input into the reaction kettle through the raw material tank reacts in the reaction kettle, and under the turbulent flow effect of the dynamic disc membrane component, part of mother liquor clear liquid after the reaction is permeated and converged into the inner cavity of the hollow rotating shaft 14 through the surface filtering holes of the membrane 13, so that the mother liquor is discharged to the mother liquor discharge tank through the buffer tank 18 to be collected, and solid particles generated by the reaction are trapped on the surface of the membrane, so that the coupling of the reaction process and the separation process is realized, and the continuous operation requirement of mother liquor discharge while raw material reaction is simultaneously carried out is met; the water washing process is the same as the principle, the material generated by the reaction is dynamically washed by using the water washing, and the water washing waste liquid is recycled after being treated by a water washing waste liquid recycling device.
In some preferred embodiments, the volume of the reactor 12 is 5-20 m 3 The method comprises the steps of carrying out a first treatment on the surface of the The membrane 13 of the dynamic disc membrane assembly is of a hollow disc structure, the surface of the membrane is provided with a filter hole communicated with the inner cavity of the membrane, and the diameter of the filter hole is 10 nm-50 mu m; the membrane is of a circular structure, and the diameter of the membrane is 50-5000mm; the preferred diaphragms are uniformly distributed axially along the hollow shaft 14; and the hollow rotating shaft 14 is of a hollow columnar structure with the outer diameter of 10-500mm and the wall thickness of 2-25 mm.
In another preferred embodiment, the reaction kettle 12 is internally provided with a liquid distributor 16 parallel to the hollow rotating shaft 14, and the liquid distributor 16 is communicated with a raw material feeding port 21. In this embodiment, the raw material solution fed into the reaction vessel 12 via the liquid distributor 16 is uniformly distributed in the reaction vessel 12, which is advantageous in improving the reaction efficiency and the uniformity of the product. In order to further improve the reaction efficiency and the uniformity of the products, the raw material feed inlets 21 are symmetrically distributed; correspondingly, the cleaning liquid inlets 22 are also symmetrically distributed.
In a further preferred embodiment, the device further comprises a plurality of turbulence members 15 arranged between the membranes, specifically, the turbulence members 15 are arranged in parallel along the hollow rotating shaft 14, and have comb teeth inserted into the gaps between the membranes 13. The turbulence piece 15 in the embodiment strengthens the turbulence of the solution in the reaction kettle, is matched with the rotary diaphragm 13, ensures that the particles are uniformly suspended in the reaction mixture in the reaction and separation processes, realizes uniform growth of the particles, has easily controlled granularity and uniform morphology, and realizes separation without filter cakes; meanwhile, the turbulence piece 15 is matched with the rotary membrane 13, so that the washing process is more complete, the product quality is excellent, and the filter cake-free washing is realized.
In a further preferred embodiment, the dynamic disc membrane assemblies in the reaction kettle 12 can be arranged in 2 groups or more than 2 groups, so that the mixed liquid in the reaction kettle can be disturbed, separated and washed more fully and efficiently. In this embodiment, the hollow shafts are parallel to each other, and the dynamic disc diaphragms of different groups are overlapped in a crossing manner, and each mother liquor outlet is communicated with the buffer tank 18.
In order to recycle the washing water waste liquid, reduce the water consumption of washing water and improve the flux of the dynamic disc membrane assembly, the cleaning device comprises an alkali liquid tank, a washing water supply tank, a cleaning liquid tank and a backflushing tank, wherein the alkali liquid tank, the washing water supply tank and the cleaning liquid tank share a cleaning liquid inlet 22 and are communicated with the liquid distributor 16 through the cleaning liquid inlet 22; the backflushing tank is communicated with the hollow rotating shaft 14, backflushing is carried out on the membrane 13 by utilizing a backflushing air source, the cleaning liquid tank is used for cleaning the membrane 13, and the cleaning waste liquid is discharged from the exhaust port 28. The washing water waste liquid circulating device comprises a waste water tank and a membrane separation unit, wherein the membrane separation unit for purifying waste water is arranged on a pipeline of the waste water tank communicated with the washing water supply tank. Specifically, the membrane separation unit adopts nanofiltration membrane and/or reverse osmosis membrane, and the recovery rate of the membrane separation clear liquid of the membrane separation unit is not lower than 70%. The clear liquid generated by the membrane separation unit is returned to the washing water supply tank and is recycled as washing water supplementing water; the concentrated solution generated by the membrane separation unit and the reaction mother solution are recycled together. In the water washing process, alkali liquor and washing water are sequentially utilized to carry out in-situ washing on the materials generated by the reaction, and washing water waste liquid is collected into a waste water tank and pumped into a membrane separation unit for treatment and recycling.
When the clear liquid discharge efficiency of the dynamic disc membrane assembly is reduced, an air source is output through a backflushing tank to push clear liquid or washing water waste liquid in a buffer tank 18 to flow back, and the clear liquid or washing water waste liquid is impacted into an upper filtering hole of the membrane 13 from the inner side of the membrane to perform a backflushing process, so that the membrane 13 is maintained to operate at high flux, and the separation and washing efficiency is improved; when the clear liquid flux cannot be effectively recovered after a plurality of backwashing processes, the membrane 13 is required to be cleaned by introducing cleaning liquid through the cleaning liquid tank, the cleaning waste liquid is discharged out of the system through the drain port 28, and the cleaning liquid is washed by using the washing water in the washing water supply tank after the cleaning is finished, so that the pollution of residual cleaning liquid to products is avoided. Because of the recycling of the waste water of the washing water, the water supply tank of the washing water only needs to be supplemented with a small amount of fresh pure water.
Referring to fig. 2 in combination, the present invention also provides a process based on the reaction and purification system for preparing the precursor of the battery cathode material.
Example 1:
the method comprises the following specific process steps:
step 1, in the raw material tank 1, according to Ni: co: the molar ratio of Mn is 5:2:3, preparing a nickel cobalt manganese sulfate mixed aqueous solution with the total metal ion concentration of 2.0mol/L, preparing an NaOH solution with the concentration of 8mol/L serving as a precipitant in a raw material tank 2, and preparing an ammonia water solution with the concentration of 5.5mol/L serving as a complexing agent in the raw material tank 3;
step 2, 2.0mol/L nickel cobalt manganese sulfate mixed water solution, 8mol/L NaOH solution and 5.5mol/L ammonia water solution are added into the mixture in parallel flow to the volume of 6.0m by a metering pump 3 In the integrated reaction kettle, the liquid distributor in the reaction kettle is uniformly distributed in the reaction system, the flow of the metal salt mixed solution is controlled to be 400L/h, and OH is controlled - The molar ratio/(Ni+Co+Mn) was 2;
step 3, controlling the pressure difference of the membranes of the dynamic disc membrane assembly in the reaction kettle to be 0.2Mpa through an automatic control valve of the mother liquor discharge flow, keeping the clear liquid flux of the mother liquor consistent with the total feeding flow, controlling the stirring rotating speed of the dynamic disc membrane assembly to be 350r/min, controlling the temperature of the reaction kettle to be 60 ℃, controlling the ammonia concentration to be 8.0g/L and controlling the pH value to be 11.0;
the principle is explained as follows: the reacted mother liquor clear liquid is permeated from the surface of the membrane to the central rotating shaft under the drive of pressure, is discharged to the mother liquor tank through the buffer tank, solid particles generated by the reaction are trapped on the surface of the membrane, are uniformly suspended and distributed in the reaction kettle under the combined action of the rotation of the membrane and the turbulence piece, cross flow is formed between slurry and the membrane, the solid particles generated by the reaction are prevented from being deposited on the surface of the membrane, the surface of the membrane is always smooth and no filter cake is generated, the stable high clear liquid flux of the membrane is ensured, the raw materials are fed simultaneously, and the mother liquor is discharged simultaneously.
Step 4, stopping feeding when the solid content of solid particles in the reaction kettle reaches 400g/L and the particle size of the product meets the requirement, controlling the rotating speed of the dynamic disc membrane assembly to concentrate slurry, forming a filter cake on the surface of the membrane by the solid materials generated by the reaction, opening a drain valve at the bottom of the reaction kettle, and draining residual mother liquor in the reaction kettle;
step 5, switching to a water washing process, firstly, performing alkali washing by using normal-temperature sodium hydroxide solution with the concentration of 0.6mol/L, then performing water washing by using pure water with the temperature of 75 ℃, collecting waste water and waste water in a wastewater tank, entering a membrane separation unit for treatment by a booster pump, refluxing the separated clear liquid to a water supply tank, and allowing the concentrated liquid to enter a subsequent recovery process, wherein when Na in the materials is contained + Stopping washing with water to less than or equal to 120ppm, and discharging to a qualified material storage tank;
and 6, dehydrating the water-washed qualified material, drying at 120 ℃ and screening by a screen, and then preserving.
The drying temperature is selected to be 100-150 DEG C
The battery anode material precursor Ni prepared through the steps 0.5 Co 0.2 Mn 0.3 (OH) 2 Wherein d 10 ＝7.54um，d 50 ＝10.02um，d 90 =13.21 um, tap density=2.36 g/cm 3 Specific surface area=5.91 m 2 And/g, is sphere-like.
Example 2:
the specific process steps differing from example 1 are:
step 1, in the raw material tank 1, according to Ni: co: molar ratio of Mn 8:1:1, preparing a nickel cobalt manganese sulfate mixed aqueous solution with the total metal ion concentration of 2.0mol/L, preparing a NaOH solution with the concentration of 6mol/L serving as a precipitator in a raw material tank 2, and preparing an ammonia water solution with the concentration of 10mol/L serving as a complexing agent in a raw material tank 3;
step 2, 2.0mol/L nickel cobalt manganese sulfate mixed water solution, 6mol/L NaOH solution and 10mol/L ammonia water solution are added into the mixture with a metering pump to be 6.0m in volume 3 In the integrated reaction kettle, the mixed solution of metal salt is uniformly distributed in a reaction system through a liquid distributor in the reaction kettle, and the flow of the mixed solution of metal salt is controlled to be 500L/h and OH is controlled during the period - The molar ratio/(Ni+Co+Mn) was 1.9;
step 3, controlling the pressure difference of the membranes of the dynamic disc membrane assembly in the reaction kettle to be 0.25Mpa through an automatic control valve of the mother liquor discharge flow, keeping the clear liquid flux of the mother liquor consistent with the total feeding flow, controlling the stirring rotating speed of the dynamic disc membrane assembly to be 600r/min, controlling the temperature of the reaction kettle to be 55 ℃, controlling the ammonia concentration to be 9.0g/L and controlling the pH value to be 11.3;
step 4, stopping feeding when the solid content of solid particles in the reaction kettle is about 480g/L and the particle size of the product meets the requirement, controlling the rotating speed of the dynamic disc membrane assembly to concentrate slurry, forming a filter cake on the surface of the membrane by the solid materials generated by the reaction, opening a drain valve at the bottom of the reaction kettle, and draining residual mother liquor in the reaction kettle;
step 5, switching to a water washing process, firstly, performing alkali washing by using normal-temperature sodium hydroxide solution with the concentration of 0.6mol/L, then performing water washing by using pure water with the temperature of 75 ℃, collecting waste water and waste water in a wastewater tank, entering a membrane separation unit for treatment by a booster pump, refluxing the separated clear liquid to a water supply tank, and allowing the concentrated liquid to enter a subsequent recovery process, wherein when Na in the materials is contained + Stopping washing with water to less than or equal to 120ppm, and discharging to a qualified material storage tank;
and 6, dehydrating the water-washed qualified material, drying at 120 ℃ and screening by a screen, and then preserving.
The battery anode material precursor Ni prepared through the steps 0.8 Co 0.1 Mn 0.1 (OH) 2 Wherein d 10 ＝6.88um，d 50 ＝9.05um，d 90 12.30um, tap density 2.28g/cm 3 Specific surface area=6.15 m 2 And/g, is sphere-like.
Embodiment 3:
the specific process steps differing from example 1 are:
step 1, the mole ratio of Ni, co, cu and Al in the raw material tank 1 is 8.3:0.8:0.6:0.3, preparing nickel cobalt copper aluminum sulfate mixed water solution with the total metal ion concentration of 2.0mol/L, preparing NaOH solution with the concentration of 2mol/L in a raw material tank 2 as a precipitator, and preparing ammonia water solution with the concentration of 5mol/L in the raw material tank 3 as a complexing agent;
step 2, 2.0mol/L of nickel cobalt copper aluminum sulfate mixed aqueous solution, 2mol/L of NaOH solution and 5mol/L of ammonia water solution are added into the mixture in parallel flow to the volume of 6.0m by using a metering pump 3 In the integrated reaction kettle, the liquid distributor in the reaction kettle is uniformly distributed in the reaction system, the flow of the metal salt mixed solution is controlled to be 500L/h, and OH is controlled - The molar ratio/(Ni+Co+Cu+Al) was 1.9;
step 3, controlling the pressure difference of the membranes of the dynamic disc membrane assembly in the reaction kettle to be 0.25Mpa through an automatic control valve of the mother liquor discharge flow, keeping the clear liquid flux of the mother liquor consistent with the total feeding flow, controlling the stirring rotating speed of the dynamic disc membrane assembly to be 600r/min, controlling the temperature of the reaction kettle to be 55 ℃, controlling the ammonia concentration to be 9.0g/L and controlling the pH value to be 11.5;
step 4, stopping feeding when the solid content of solid particles in the reaction kettle is 550g/L and the particle size of the product meets the requirement, controlling the rotating speed of the dynamic disc membrane assembly to concentrate slurry, forming a filter cake on the surface of the membrane by the solid materials generated by the reaction, opening a drain valve at the bottom of the reaction kettle, and draining residual mother liquor in the reaction kettle;
step 5, switching to a water washing process, firstly, performing alkali washing by using normal-temperature sodium hydroxide solution with the concentration of 0.6mol/L, then performing water washing by using pure water with the temperature of 75 ℃, collecting washing water waste liquid into a wastewater tank, entering a membrane separation unit for treatment by using a booster pump, and refluxing the separated clear liquid to a washing water supply tank, and concentratingThe liquid enters the subsequent recovery procedure, when Na in the material + Stopping washing with water to less than or equal to 120ppm, and discharging to a qualified material storage tank;
and 6, dehydrating the water-washed qualified material, drying at 120 ℃ and screening by a screen, and then preserving.
The battery anode material precursor Ni prepared through the steps 0.83 Co 0.08 Cu 0.06 Al 0.03 (OH) 2 Wherein d 10 ＝7.88um，d 50 ＝9.85um，d 90 =13.30 um, tap density=2.35 g/cm 3 Specific surface area=5.85 m 2 And/g, is sphere-like.
The foregoing examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of the invention should be assessed as that of the appended claims.
It should be understood by those skilled in the art that while the present invention has been described in terms of several embodiments, not every embodiment contains only one independent technical solution. The description is given for clearness of understanding only, and those skilled in the art will understand the description as a whole and will recognize that the technical solutions described in the various embodiments may be combined with one another to understand the scope of the present invention.
Claims (17)
1. A reaction and purification system for preparing a battery anode material precursor is characterized by comprising a raw material tank, a cleaning device, a mother liquor discharge tank, a qualified material storage tank, a washing water waste liquid circulating device and an integrated reaction kettle,
the integrated reaction kettle comprises a reaction kettle and at least one group of built-in dynamic disc membrane components,
one side of the reaction kettle is provided with at least one raw material feeding port communicated with a raw material tank, a cleaning liquid inlet communicated with a cleaning device, and the bottom of the reaction kettle is provided with at least one discharge port communicated with a qualified material storage tank;
the dynamic disc membrane assembly comprises a plurality of hollow membranes which are arranged at intervals and can enable liquid to penetrate through the surface and penetrate into the inner cavity, and hollow rotating shafts which are sequentially connected with the membranes in a penetrating way and can be driven by the driving device to rotate and be connected to the reaction kettle, the surface of each membrane is provided with a filtering hole communicated with the inner cavity of the membrane, the inner cavity of the membrane is communicated with the hollow rotating shafts, the hollow rotating shafts are communicated with the mother liquor discharge tank and the washing water waste liquid circulating device, and the hollow rotating shafts are mechanically sealed with the reaction kettle shell and are driven by a connecting shaft or a belt or a gear;
the cleaning device comprises an alkali liquid tank, a washing water supply tank, a cleaning liquid tank and a backflushing tank, wherein the alkali liquid tank, the washing water supply tank and the cleaning liquid tank share the cleaning liquid inlet, the backflushing tank is communicated with the hollow rotating shaft, the membrane is backflushed by utilizing a backflushing air source, and the cleaning liquid tank is used for cleaning the membrane; the washing water waste liquid circulation device comprises a waste water tank and a membrane separation unit, wherein a membrane separation unit for purifying waste water is arranged on a pipeline of the waste water tank, which is communicated with the washing water supply tank, and clear liquid generated by the membrane separation unit is returned to the washing water supply tank to be recycled as washing water supplementing water.
2. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 1, wherein a liquid distributor parallel to a hollow rotating shaft is arranged in the reaction kettle, the liquid distributor is communicated with the raw material feed inlet, and the liquid distributor is communicated with the cleaning liquid inlet.
3. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 2, wherein the raw material inlets and the cleaning liquid inlets are symmetrically distributed.
4. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 1, wherein turbulence members for reinforcing turbulence of slurry are provided between adjacent ones of the membranes.
5. The reaction and purification system for preparing the battery anode material precursor according to claim 1, wherein the membrane is of a hollow disc-shaped structure, the surface of the membrane is provided with a filter hole communicated with an inner cavity of the membrane, and the diameter of the filter hole is 10 nm-50 μm; and/or;
the membrane is of a circular structure, and the diameter of the membrane is 50-5000mm.
6. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 1, wherein the hollow rotating shaft has a hollow columnar structure with an outer diameter of 10-500mm and a wall thickness of 2-25 mm.
7. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 1, wherein the membrane separation unit adopts a nanofiltration membrane and/or a reverse osmosis membrane.
8. The reaction and purification system for preparing a precursor of a battery cathode material according to claim 1, further comprising a gas discharge port provided at the top of the reaction vessel, a drain port provided at the bottom of the reaction vessel for discharging residual mother liquor and washing waste liquid, and a buffer tank and a clear liquid viewing mirror connected in series to a pipeline between the hollow rotating shaft and the mother liquor discharge tank.
9. Process based on a reaction for the preparation of a precursor of a battery positive electrode material and its purification system according to any of claims 1-8, characterized in that it comprises the following steps:
step one, respectively preparing a metal salt mixed solution, a precipitant solution and a complexing agent solution with corresponding concentrations in a raw material tank according to the proportion of positive electrode material elements;
step two, conveying the prepared metal salt mixed solution, the precipitant solution and the complexing agent solution into an integrated reaction kettle;
step three, regulating the flux of clear liquid in the reaction kettle by controlling the pressure difference and the rotating speed of the dynamic disc membrane assembly; in the reaction process, feeding and reaction are synchronously carried out, the temperature and the pH value suitable for the reaction in the reaction kettle are maintained, and part of mother liquor is separated and filtered through a dynamic disc membrane assembly in the reaction process;
stopping feeding when the solid materials generated by the reaction in the reaction kettle meet the physicochemical properties of the product;
step five, starting a cleaning device to perform a water cleaning process, and collecting the waste water and the waste water into a waste water tank through a hollow rotating shaft after the waste water and the waste water are separated through a dynamic disc membrane assembly;
and step six, after the solid materials reach the standard through water washing, unloading the solid materials to a qualified material storage tank, and carrying out subsequent treatment procedures.
10. The process of preparing a precursor of a battery anode material and a purification system thereof according to claim 9, wherein the dynamic disc membrane module has a pressure difference of 0.5-5.0 bar and a membrane module rotating speed of 0-1500 r/min.
11. The process of a reaction and purification system for the preparation of a precursor of a battery positive electrode material according to claim 9, further comprising the following process steps between the fourth step and the fifth step: and controlling the rotating speed of the dynamic disc membrane assembly to concentrate the slurry, forming a filter cake on the surface of the membrane of the dynamic disc membrane assembly by the solid material, and discharging residual mother liquor in the reaction kettle through a drain hole at the bottom of the reaction kettle.
12. The process of a reaction and purification system for preparing a precursor of a battery cathode material according to claim 9, further comprising the following process steps:
separating the washing water waste liquid in the waste water tank through a membrane separation unit, refluxing the obtained clear liquid to a washing water supply tank for recycling, and enabling the obtained concentrated liquid and the discharged mother liquid to enter a recovery system together, wherein the membrane separation unit adopts a nanofiltration membrane and/or a reverse osmosis membrane, and the recovery rate of the membrane separation clear liquid of the membrane separation unit is not lower than 70%.
13. The process of the reaction and purification system for preparing the battery anode material precursor according to claim 9, wherein in the water washing process, naOH solution with the concentration of 0.1-1.0 mol/L and the temperature of 0-95 ℃ is firstly adopted for alkali washing, and pure water with the temperature of 0-95 ℃ is used for water washing until the impurity ion content in the material reaches the standard, and the water washing is stopped.
14. The process for preparing a precursor of a battery anode material and a purification system thereof according to claim 9, wherein the total metal ion concentration in the prepared metal salt mixed solution is 1.0-5.0 mol/L; the concentration of the prepared precipitant solution is 1.0-9.0 mol/L; the concentration of the prepared complexing agent solution is 1.0-10.0 mol/L.
15. The process of claim 9, wherein the ratio of the metal salt mixed solution feed rate to the precipitant solution feed rate to the complexing agent solution feed rate is (4-6): 1-2): 1.
16. The process for preparing a precursor of a battery anode material and a purification system thereof according to claim 9, wherein the reaction temperature in the integrated reaction kettle is 20-95 ℃, the pH value is 10-13, the ammonia concentration is 5-12 g/L, and the solid content is 100-1000 g/L.
17. The process of a reaction for preparing a precursor of a battery cathode material and a purification system thereof according to claim 9, wherein the metal salt mixed solution is prepared from one or more soluble salts of nickel salt, cobalt salt, manganese salt, aluminum salt and copper salt, and the soluble salts are one or more of sulfate, nitrate, chloride salt and acetate;
the precipitant solution is at least one of NaOH, KOH, liOH, sodium carbonate and sodium bicarbonate;
the complexing agent solution is at least one of ammonia water, ammonium bicarbonate and ammonium sulfate.
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