CN109279664A - A kind of water-saving preparation method of tertiary cathode material hydroxide precursor and water-saving preparation system - Google Patents
A kind of water-saving preparation method of tertiary cathode material hydroxide precursor and water-saving preparation system Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 40
- 239000002243 precursor Substances 0.000 title claims abstract description 30
- 239000010406 cathode material Substances 0.000 title claims abstract description 25
- 239000002351 wastewater Substances 0.000 claims abstract description 144
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000005406 washing Methods 0.000 claims abstract description 33
- 238000000975 co-precipitation Methods 0.000 claims abstract description 32
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 14
- 238000004140 cleaning Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 52
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 47
- 238000003860 storage Methods 0.000 claims description 44
- 239000012452 mother liquor Substances 0.000 claims description 33
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 26
- 235000011152 sodium sulphate Nutrition 0.000 claims description 26
- 229910021529 ammonia Inorganic materials 0.000 claims description 25
- 238000001914 filtration Methods 0.000 claims description 14
- 239000003518 caustics Substances 0.000 claims description 10
- 229910001385 heavy metal Inorganic materials 0.000 claims description 8
- 230000009615 deamination Effects 0.000 claims description 6
- 238000006481 deamination reaction Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 230000008901 benefit Effects 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 238000010612 desalination reaction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims 1
- 238000000034 method Methods 0.000 description 16
- 238000005516 engineering process Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 239000012535 impurity Substances 0.000 description 6
- 239000011734 sodium Substances 0.000 description 6
- 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 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000007790 solid phase Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 229910019421 CoxAly Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000009938 salting Methods 0.000 description 1
- NIWMEUWZZDPUEQ-UHFFFAOYSA-M sodium;azane;hydroxide Chemical compound N.[OH-].[Na+] NIWMEUWZZDPUEQ-UHFFFAOYSA-M 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
-
- 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
- C01P2006/40—Electric properties
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a kind of water-saving preparation methods of tertiary cathode material hydroxide precursor, the following steps are included: preparing ternary hydroxide using coprecipitation reaction, ternary hydroxide is using alkali cleaning, washing, drying to obtain tertiary cathode material hydroxide precursor；Wherein, the washing includes first wash, second wash and third wash, and the second wash waste water, which returns, is used for first wash water, and the third wash waste water returns to coprecipitation reaction and is used to prepare reaction raw materials solution.The present invention also provides a kind of water-saving preparation systems of tertiary cathode material hydroxide precursor corresponding with above-mentioned water-saving preparation method.The step that washing water may be implemented in the present invention recycles, and can reduce by 35% or more wastewater treatment capacity, and then saves 1/3 or more cost for wastewater treatment, and the production cost of tertiary cathode material hydroxide precursor is lower.
Description
Technical field
The invention belongs to battery material field more particularly to a kind of preparation sides of tertiary cathode material hydroxide precursor
Method and preparation system.
Background technique
The continuous deterioration and the progress of high-energy power battery technology of natural ecological environment have expedited the emergence of the fast of electric car
Speed development, the core of electric car is then lithium electricity positive electrode.Existing market prospect lithium electricity tertiary cathode material the most good
Core be nickel system ternary precursor (Ni1-x-yCoxMny(OH)2Or Ni1-x-yCoxAly(OH)2), production is widely used and ball
The almost the same ammonia alkali of the synthesis technology of shape nickel hydroxide cooperates the continuous coprecipitation of wet process, this method using nickel sulfate (cobalt,
Manganese), ammonium hydroxide, sodium hydroxide as a raw material for production.Production process consumes great lot of water resources, and the waste water main component of generation is sulfuric acid
Sodium (80-100g/L), sodium hydroxide about (2g/L), ammonia nitrogen (3000-8000mg/L) and heavy metal (about 30mg/L), i.e.,
Na2SO4-NaOH-NH3The comprehensive waste water of heavy metal, if this kind of waste water has great danger without being effectively treated, to ecological environment
Evil.
Currently, being mostly to be routed directly to the processing of waste water workshop without reuse for this kind of wastewater treatment method, prevailing technology is
Stripping ammonia still process removal of ammonia and nitrogen-physical filtering removing heavy metal-evaporative crystallization removing sodium sulphate-evaporation technology condensation film is handled
Pure water reuse.This method can be properly arrived at the target of wastewater treatment, but since waste water main component concentration is low, cause to handle
High process cost, the ammonium hydroxide and sodium sulphate product economy benefit of unit Sewage treatment are low.Most ternary precursor manufacturing enterprises
15-40 tons of ton product wastewater discharge, be " qualified discharge " or " reuse after comprehensive decontamination " cost in 60 yuan/ton of waste water
More than, this means that one ton of nickel system ternary precursor material of every production, and cost of water treatment is at 900 yuan or more, this is to correlation
Manufacturing enterprise brings great environmental burden, seriously affects the development of New-energy electric vehicle industry.
In view of the problems of ternary precursor production wastewater treatment process, it is necessary to analyse in depth nickel system hydroxide
The production technology of object material is adjusted control from efficient utilize of the technical process angle to water resource.Existing coprecipitation reaction
Underflow afterwards, which enters in washing press or plate and frame filter press, to be separated by solid-liquid separation, and after mother liquor separation, is directly added into a certain concentration
Lye carry out alkali cleaning, pure water is added after alkali cleaning and is washed, stops washing after washing to specified pH value.Due to ternary precursor
Material is high to the content requirement of impurity sulfate radical and sodium, therefore washing process needs to consume a large amount of water resource, and generates big
The waste water of amount can save cost for wastewater treatment if can recycle to the Sewage treatment generated in washing process to a certain extent.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, one kind is provided
The water-saving preparation method of tertiary cathode material hydroxide precursor and water-saving preparation system, the preparation method and preparation system can
To realize that the step of washing water recycles, waste water yield is reduced, resource is more saved.In order to solve the above technical problems, this
Invent the technical solution proposed are as follows:
A kind of water-saving preparation method of tertiary cathode material hydroxide precursor, comprising the following steps: utilize co-precipitation
Reaction prepares ternary hydroxide, and ternary hydroxide is using alkali cleaning (being washed with sodium hydroxide), washing, drying to obtain three
First positive electrode hydroxide precursor；Wherein, it is described washing include first wash, second wash and third wash, described two
Section washes (waste water generated during second wash), which returns, is used for first wash water, the third wash waste water (three
The waste water that generates in section washing process) it returns to coprecipitation reaction and is used to prepare reaction raw materials solution (such as ternary metal salting liquid).
In the present invention, the waste water of generation is sodium sulphate-compound waste water of ammonia-sodium hydroxide.Reaction raw materials solution water and first wash
It is supplemented when inadequate with the water consumption of water using pure water.
In above-mentioned preparation method, it is preferred that prepare the underflow mother liquor generated in ternary hydroxide using coprecipitation reaction
(i.e. by the filtered liquid phase of underflow) includes the component of following concentration: sodium sulphate 80-160g/L, ammonia 5000-10000mg/L, institute
The pH for stating underflow mother liquor is 11-12.
In above-mentioned preparation method, it is preferred that the alkali-wash waste water generated in alkaline cleaning procedure includes the component of following concentration: sulfuric acid
Sodium 20-60g/L, NaOH 0.5-5g/L, ammonia 2000-5000mg/L.
In above-mentioned preparation method, it is preferred that the concentration of sodium sulphate is 10-50g/L in first wash waste water, and ammonia density is
The pH control of 50-3000mg/L, first wash waste water are 10-13；The concentration of sodium sulphate is 300- in second wash waste water
The pH control of 5000mg/L, ammonia density 20-50mg/L, second wash waste water are 9.5-10；Sodium sulphate in third wash waste water
Concentration be 15-300mg/L, ammonia density 10-30mg/L, third wash waste water pH control be 8-9.5.It is furthermore preferred that one
The concentration of sodium sulphate is 10-40g/L in section washes, and the pH control of ammonia density 50-2500mg/L, first wash waste water are
10-12.6。
In the present invention, in order to balance washing effect and comprehensive benefit, in order to guarantee the trouble-free operation of washing system, to underflow
Mother liquor, alkali-wash waste water, one section, two sections, the sodium sulphate in third wash waste water, ammonia and pH value have specific requirement, need it
Control preferably could provide concrete operations index in above-mentioned restriction for continuous washes sort operation and limit, and be conducive to reality
Implement on border.Also, underflow mother liquor, alkali-wash waste water, one section, two sections, between the relevant parameter in third wash waste water be that there are phases
Relationship is mutually influenced, cooperates between only each parameter, can be only achieved water-saving, high-efficient washing effect, a certain parameter drift-out
Limit value, entire washing process may need to redesign, it is difficult to reach water-saving, efficient purpose.
In above-mentioned preparation method, it is preferred that the tertiary cathode material hydroxide precursor is ternary nickel cobalt manganese hydrogen-oxygen
Compound presoma or ternary nickel cobalt aluminium hydroxide presoma.
In above-mentioned preparation method, it is preferred that the coprecipitation reaction prepares the overflow mother liquor generated in ternary hydroxide
The first wash waste water generated in the process with alkali-wash waste water, the first wash generated in underflow mother liquor, alkaline cleaning procedure accumulates height
It is handled after concentration waste water using deamination, the processing of removing heavy metal, removing sodium sulphate is handled, condensing hot air furnace handles to obtain ammonia
Water, sodium sulphate and pure water.
As a general technical idea, the present invention also provides a kind of the water-saving of tertiary cathode material hydroxide precursor
Preparation system, including coprecipitation reaction device, the feeding inlet of the coprecipitation reaction device are connected with for installing coprecipitation reaction original
The flow container processed of material, the underflow outlet of the coprecipitation reaction device are connected with filtration system, caustic washing system, water wash system in turn and do
Drying system, the water wash system include first wash system, second wash system and third wash system, the third wash system
It unites and is equipped with first delivery pipeline system for being used to for third wash waste water being delivered to flow container processed between flow container processed, described two sections
One is equipped between washing system and first wash system for second wash waste water to be delivered to the second defeated of first wash system
Send pipe-line system.
In above-mentioned preparation system, it is preferred that the preparation system further includes at high-concentration waste water storage tank and high-concentration waste water
Reason system, the high-concentration waste water storage tank are connected with each other with high concentration wastewater treatment system by third delivery pipeline system, institute
State the overflow port of coprecipitation reaction device by one for overflow mother liquor is delivered to the overflow mother liquor pipe of high-concentration waste water storage tank with
The connection of high-concentration waste water storage tank is used to generate filtration system between the filtration system and high-concentration waste water storage tank equipped with one
Underflow mother liquor is delivered to the underflow mother liquor pipe of high-concentration waste water storage tank, is equipped between the caustic washing system and high-concentration waste water storage tank
One for the alkali-wash waste water that caustic washing system generates to be delivered to the alkali-wash waste water pipe of high-concentration waste water storage tank, the first wash system
One is equipped between system and high-concentration waste water storage tank for the first wash waste water that first wash system generates to be delivered to high concentration
The first wash waste pipe of wastewater storage tank；The high concentration wastewater treatment system includes sequentially connected deamination system, heavy metal
Separate neutralized system, evaporative crystallization desalination system and condensation water recovery system.
In above-mentioned preparation system, it is preferred that third wash wastewater storage tank is equipped in first delivery pipeline system, it is described
Second wash wastewater storage tank is equipped in second delivery pipeline system.
In above-mentioned preparation system, it is preferred that the first delivery pipeline system, the second delivery pipeline system and third transfer pipeline
Circulating pump is equipped in system.
Studies have shown that since tertiary cathode material hydroxide precursor is to the content requirement pole of impurity sulfate radical and sodium
Height, therefore washing process needs to consume a large amount of water resource, and generates a large amount of waste water, in these waste water main component concentration with
Wash time extends and gradually reduces.Tertiary cathode material hydroxide precursor synthesizes different processes to the requirement with water water quality
There is larger difference, in contrast, the requirement of first wash process water is minimum, and reaction raw materials solution water requires secondly, two sections are washed
Wash, third wash water requirement highest more demanding with water.It therefore, can be by washers for the specific material system of the application
The washes of sequence different phase is back to use in synthesis technology according to wastewater characteristics and different processes with water feature, can certain journey
The usage amount for reducing washing water on degree, reduces the discharge amount of waste water, saves cost for wastewater treatment.
Compared with the prior art, the advantages of the present invention are as follows:
1, using the water-saving preparation method of tertiary cathode material hydroxide precursor of the invention and water-saving preparation system,
The indexs such as the hydroxide materials apparent form of synthesis, impurity content, chemical property are equal compared to using pure water synthetic system
There is no significant change.
2, using the water-saving preparation method of tertiary cathode material hydroxide precursor of the invention and water-saving preparation system
The step that washing water may be implemented recycles, and can reduce by 35% or more wastewater treatment capacity, and then saves 1/3 or more waste water
The production cost of processing cost, tertiary cathode material hydroxide precursor is lower.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the structural schematic diagram of the water-saving preparation system of the present invention.
Marginal data:
1, coprecipitation reaction device；2, flow container processed；3, filtration system；4, caustic washing system；5, water wash system；51, first wash
System；52, second wash system；53, third wash system；6, drying system；7, the first delivery pipeline system；71, it washes for three sections
Wash wastewater storage tank；8, the second delivery pipeline system；81, second wash wastewater storage tank；9, high-concentration waste water storage tank；10, high concentration
Waste water treatment system；101, deamination system；102, heavy metal separates neutralized system；103, evaporative crystallization desalination system；104, cold
Condensed water recovering system；11, third delivery pipeline system；12, overflow mother liquor pipe；13, underflow mother liquor pipe；14, alkali-wash waste water pipe；
15, first wash waste pipe；16, alkali liquor pipe；17, pure water pipe.
Specific embodiment
To facilitate the understanding of the present invention, the present invention is made below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but the protection scope of the present invention is not limited to the following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter and the normally understood meaning of those skilled in the art
It is identical.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of water-saving preparation method of tertiary cathode material hydroxide precursor, comprising the following steps: utilize co-precipitation
Reaction prepares ternary hydroxide, and ternary hydroxide is using alkali cleaning (being washed with sodium hydroxide), first wash, second wash
With third wash, drying to obtain tertiary cathode material hydroxide precursor；Wherein, the waste water generated during second wash
It returns and is used for first wash water, it is molten that the waste water return coprecipitation reaction generated during third wash is used to prepare reaction raw materials
Liquid.
As shown in Figure 1, the water-saving preparation system of the tertiary cathode material hydroxide precursor of the present embodiment, including it is coprecipitated
Shallow lake reactor 1, the feeding inlet of coprecipitation reaction device 1 are connected with the flow container processed 2 for installing coprecipitation reaction raw material, and co-precipitation is anti-
The underflow outlet of device 1 is answered to be connected with filtration system 3 (plate compression or secondary filter processing), caustic washing system 4, water wash system in turn
5 with drying system 6, water wash system 5 include first wash system 51, second wash system 52 and third wash system 53, and three sections
One is equipped between washing system 53 and flow container processed 2 for third wash waste water to be delivered to the first transfer pipeline system of flow container 2 processed
System 7 is equipped with one for second wash waste water to be delivered to first wash between second wash system 52 and first wash system 51
Second delivery pipeline system 8 of system 51.
In the present embodiment, preparation system further includes high-concentration waste water storage tank 9 and high concentration wastewater treatment system 10, high concentration
Wastewater storage tank 9 and high concentration wastewater treatment system 10 are connected with each other by third delivery pipeline system 11, coprecipitation reaction device 1
Overflow port is by one for overflow mother liquor to be delivered to the overflow mother liquor pipe 12 and high-concentration waste water storage tank of high-concentration waste water storage tank 9
9 connections are equipped with one for the underflow mother liquor that filtration system 3 generates to be delivered between filtration system 3 and high-concentration waste water storage tank 9
The underflow mother liquor pipe 13 of high-concentration waste water storage tank 9 is equipped with one and is used for alkali cleaning between caustic washing system 4 and high-concentration waste water storage tank 9
The alkali-wash waste water that system 4 generates is delivered to the alkali-wash waste water pipe 14 of high-concentration waste water storage tank 9, first wash system 51 and high concentration
One is equipped between wastewater storage tank 9 for the first wash waste water that first wash system 51 generates to be delivered to high-concentration waste water storage tank
9 first wash waste pipe 15；High concentration wastewater treatment system 10 includes sequentially connected deamination system 101, heavy metal separation
Neutralized system 102, evaporative crystallization desalination system 103 and condensation water recovery system 104.
In the present embodiment, third wash wastewater storage tank 71, the second delivery pipeline system are equipped in the first delivery pipeline system 7
Second wash wastewater storage tank 81 is equipped in 8.
The water-saving preparation method in the present embodiment is described in detail below with reference to the water-saving preparation system in the present embodiment:
(1) ternary hydroxide is prepared using coprecipitation reaction device 1, material liquid is provided by flow container 2 processed, coprecipitation reaction device
Filtration system 3, liquid phase, that is, underflow mother liquor of the discharge of filtration system 3 are sent into 1 underflow, and underflow mother liquor passes through underflow mother liquor pipe 13
It send to high concentration wastewater storage tank 9, the overflow mother liquor of coprecipitation reaction device 1 is sent by overflow mother liquor pipe 12 to high concentration wastewater storage tank
9；
(2) solid phase that filtration system 3 is discharged passes through caustic washing system 4, (passes through alkali liquor pipe 16 using 4% NaOH solution
Addition) solid phase is washed, scrub raffinate is sent by alkali-wash waste water pipe 14 to high concentration wastewater storage tank 9；
(3) solid phase Jing Guo alkali cleaning is passed sequentially through into first wash system 51, second wash system 52 and third wash system
System 53, wherein the washes that first wash system 51 generates is sent by first wash waste pipe 15 to high concentration wastewater storage tank
9, the generation washes of second wash system 52 is sent to first wash system 51 by the second delivery pipeline system 8 and is washed for one section
It washs and uses water, third wash system 53 generates washes and sent to flow container 2 processed by the first delivery pipeline system 7 for preparation raw material
Liquid；
(4) solid phase after third wash handles through drying system 6 and obtains the tertiary cathode material in the present embodiment
Hydroxide precursor；Waste water in high-concentration waste water storage tank 9 is sent to high concentration wastewater treatment system 10 and recycles ammonium hydroxide, sodium sulphate
With condensed water.
In the above process, second wash water and third wash water are supplemented by pure water pipe 17, first wash with water not
It is supplemented when enough also by pure water pipe 17.
In the present embodiment, main component is as follows in underflow mother liquor: sodium sulphate 120g/L, NaOH 5g/L, ammonia 9000mg/L,
Solid content 200mg/L, pH=11.3；Alkali-wash waste water, first wash waste water, second wash waste water, third wash waste water, this quadravalence
The wash water of section is divided with pH value, and the cut-off pH value that alkali-wash waste water is collected is 12.7, the cut-off pH of first wash wastewater collection
Value is 10, and the cut-off pH value of second wash wastewater collection is 9.5, the later waste water of pH value 9.5 as third wash waste water, this
When, the main component in first wash waste water is as follows: sodium sulphate 25g/L, NaOH 0.08g/L, ammonia 6000mg/L, second wash
Main component in waste water is as follows: sodium sulphate 600mg/L, NaOH 0.002g/L, ammonia 30mg/L, the master in third wash waste water
Want ingredient as follows: sodium sulphate 300mg/L, NaOH 0.0001g/L, ammonia 16mg/L.
The nickel-cobalt-manganese ternary presoma synthesized using the preparation method in the present embodiment with preparation system is as lithium electricity ternary
The raw material of positive electrode, the indexs such as surface topography, specific surface area, electrochemistry, impurity content are all satisfied user's requirement, production
Positive electrode properties meet power battery requirement.
Embodiment 2:
The preparation method of the present embodiment is identical as preparation system and embodiment 1.The difference is that control underflow mother liquor
Contents of Main Components is different, alkali-wash waste water, first wash waste water, second wash waste water, third wash waste water cut-off pH value not
Together.
Specifically, underflow mother liquor main component is as follows: Na in the present embodiment2SO4100g/L, NaOH 4g/L, ammonia
8000mg/L, solid content 200mg/L, pH=11.5；Alkali-wash waste water, first wash waste water, second wash waste water, third wash are useless
The wash water of water, this four stage is divided with pH value, and the cut-off pH value that alkali-wash waste water is collected is 12.6, first wash wastewater collection
Cut-off pH value be 9.7, the cut-off pH value of second wash wastewater collection is 9.2, and the later waste water of pH value 9.2 is as third wash
Waste water, at this point, the main component in first wash waste water is as follows: sodium sulphate 20g/L, NaOH 0.06g/L, ammonia 4500mg/L,
Main component in second wash waste water is as follows: sodium sulphate 500mg/L, NaOH 0.001g/L, ammonia 28mg/L, and third wash is useless
Main component in water is as follows: sodium sulphate 300mg/L, NaOH 0.0001g/L, ammonia 16mg/L.
The nickel-cobalt-manganese ternary presoma synthesized using the preparation method in the present embodiment with preparation system is as lithium electricity ternary
The raw material of positive electrode, the indexs such as surface topography, specific surface area, electrochemistry, impurity content are all satisfied user's requirement, production
Positive electrode properties meet power battery requirement.
Comparative example:
The preparation method of this comparative example is identical as preparation system and embodiment 1.The difference is that underflow mother liquor, alkali cleaning give up
Water and subsequent all wash waters are all mixed into waste water treatment system and carry out stripping ammonia still process, in sulfuric acid and pH value and MVR removing
Sodium sulphate processing.For producing the production scale of 10000 tons of ternary nickel cobalt manganese presomas per year, waste water day discharge amount is 1600m3,
The processing cost of every cube of waste water is 76 yuan, and waste water day processing cost is 121600 yuan, and year processing cost is 36,480,000 yuan.
And the water-saving preparation method and preparation system in embodiment 1 are used, wastewater discharge 1024m3/ day, at waste water
It is essentially identical to manage cost, waste water day processing cost is 77824 yuan, and year processing cost is 2334.7 ten thousand yuan.Using the section of embodiment 1
Water preparation method and preparation system, wastewater treatment capacity can reduce 36%, and year saves 13,130,000 yuan of processing cost or more, economic benefit
It is very considerable.And wastewater treatment capacity is only reduced using the water-saving preparation method and preparation system of embodiment 1, before the ternary of preparation
Body physical property, chemical property and impurity content is driven not to be affected.
Claims (10)
1. a kind of water-saving preparation method of tertiary cathode material hydroxide precursor, which comprises the following steps: benefit
Ternary hydroxide is prepared with coprecipitation reaction, ternary hydroxide is using alkali cleaning, washing, drying to obtain tertiary cathode material
Expect hydroxide precursor；Wherein, the washing includes first wash, second wash and third wash, and the second wash is useless
Water, which returns, is used for first wash water, and the third wash waste water returns to coprecipitation reaction and is used to prepare reaction raw materials solution.
2. preparation method according to claim 1, which is characterized in that prepared in ternary hydroxide using coprecipitation reaction
The underflow mother liquor of generation includes the component of following concentration: sodium sulphate 80-160g/L, ammonia 5000-10000mg/L, the underflow are female
The pH of liquid is 11-12.
3. preparation method according to claim 1, which is characterized in that the alkali-wash waste water generated in alkaline cleaning procedure includes following
The component of concentration: sodium sulphate 20-60g/L, NaOH 0.5-5g/L, ammonia 2000-5000mg/L.
4. preparation method according to claim 1, which is characterized in that the concentration of sodium sulphate is 10- in first wash waste water
The pH control of 50g/L, ammonia density 50-3000mg/L, first wash waste water are 10-13；Sodium sulphate in second wash waste water
Concentration is 300-5000mg/L, and the pH control of ammonia density 20-50mg/L, second wash waste water are 9.5-10；Third wash is useless
The concentration of sodium sulphate is 15-300mg/L in water, and the pH control of ammonia density 10-30mg/L, third wash waste water are 8-9.5.
5. the preparation method according to claim 4, which is characterized in that the concentration of sodium sulphate is 10- in first wash waste water
The pH control of 40g/L, ammonia density 50-2500mg/L, first wash waste water are 10-12.6.
6. preparation method according to any one of claims 1-5, which is characterized in that the tertiary cathode material hydroxide
Object presoma is ternary nickel cobalt manganese hydroxide precursor or ternary nickel cobalt aluminium hydroxide presoma.
7. preparation method according to any one of claims 1-5, which is characterized in that the coprecipitation reaction prepares ternary
Production during the overflow mother liquor generated in hydroxide and the alkali-wash waste water generated in underflow mother liquor, alkaline cleaning procedure, first wash
Raw first wash waste water is handled using deamination after accumulating high-concentration waste water, the processing of removing heavy metal, is removed at sodium sulphate
Reason, condensing hot air furnace handle to obtain ammonium hydroxide, sodium sulphate and pure water.
8. a kind of water-saving preparation system of tertiary cathode material hydroxide precursor, which is characterized in that including coprecipitation reaction
Device (1), the feeding inlet of the coprecipitation reaction device (1) is connected with the flow container processed (2) for installing coprecipitation reaction raw material, described
The underflow outlet of coprecipitation reaction device (1) is connected with filtration system (3), caustic washing system (4), water wash system (5) and drying in turn
System (6), the water wash system (5) include first wash system (51), second wash system (52) and third wash system
(53), one is equipped between the third wash system (53) and flow container processed (2) for third wash waste water to be delivered to flow container processed
(2) the first delivery pipeline system (7) is equipped with one and is used between the second wash system (52) and first wash system (51)
Second wash waste water is delivered to the second delivery pipeline system (8) of first wash system (51).
9. preparation system according to claim 8, which is characterized in that the preparation system further includes high-concentration waste water storage tank
(9) pass through with high concentration wastewater treatment system (10), the high-concentration waste water storage tank (9) with high concentration wastewater treatment system (10)
Third delivery pipeline system (11) is connected with each other, and the overflow port of the coprecipitation reaction device (1) is used for by one by overflow mother liquor
The overflow mother liquor pipe (12) for being delivered to high-concentration waste water storage tank (9) is connect with high-concentration waste water storage tank (9), the filtration system
(3) one is equipped between high-concentration waste water storage tank (9) for the underflow mother liquor that filtration system (3) generate to be delivered to high-concentration waste
The underflow mother liquor pipe (13) of water storage tank (9), being used between the caustic washing system (4) and high-concentration waste water storage tank (9) equipped with one will
The alkali-wash waste water that caustic washing system (4) generates is delivered to the alkali-wash waste water pipe (14) of high-concentration waste water storage tank (9), the first wash
The first wash waste water for generating first wash system (51) is equipped between system (51) and high-concentration waste water storage tank (9)
It is delivered to the first wash waste pipe (15) of high-concentration waste water storage tank (9)；The high concentration wastewater treatment system (10) include according to
Deamination system (101), heavy metal separation neutralized system (102), evaporative crystallization desalination system (103) and the condensed water of secondary connection return
Receipts system (104).
10. preparation system according to claim 8 or claim 9, which is characterized in that set in first delivery pipeline system (7)
Have third wash wastewater storage tank (71), is equipped with second wash wastewater storage tank (81) in second delivery pipeline system (8).
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| CN112441624A (en) * | 2019-08-30 | 2021-03-05 | 荆门市格林美新材料有限公司 | Preparation method of nickel-cobalt-aluminum precursor with high tap density and low impurity content |
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