CN115571926A - Method for removing carbonate from lithium precipitation mother liquor - Google Patents
Method for removing carbonate from lithium precipitation mother liquor Download PDFInfo
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- CN115571926A CN115571926A CN202211218282.3A CN202211218282A CN115571926A CN 115571926 A CN115571926 A CN 115571926A CN 202211218282 A CN202211218282 A CN 202211218282A CN 115571926 A CN115571926 A CN 115571926A
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- cobalt
- carbonate
- nickel
- mother liquor
- manganese
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 142
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 142
- 239000012452 mother liquor Substances 0.000 title claims abstract description 127
- 238000001556 precipitation Methods 0.000 title claims abstract description 122
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 title claims abstract description 96
- 238000000034 method Methods 0.000 title claims abstract description 50
- 239000002893 slag Substances 0.000 claims abstract description 56
- 239000002351 wastewater Substances 0.000 claims abstract description 52
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- DDXROPFGVVLFNZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) tricarbonate Chemical compound [Mn+2].[Co+2].C([O-])([O-])=O.[Ni+2].C([O-])([O-])=O.C([O-])([O-])=O DDXROPFGVVLFNZ-UHFFFAOYSA-H 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000010941 cobalt Substances 0.000 claims abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 4
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 4
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 4
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 4
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 4
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims abstract description 4
- 239000000706 filtrate Substances 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000005406 washing Methods 0.000 claims description 26
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 24
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 24
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 24
- 229910001437 manganese ion Inorganic materials 0.000 claims description 24
- 229910001453 nickel ion Inorganic materials 0.000 claims description 24
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- 238000004537 pulping Methods 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 21
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 18
- 239000007787 solid Substances 0.000 claims description 14
- -1 aluminum ions Chemical class 0.000 claims description 10
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 10
- 239000011572 manganese Substances 0.000 abstract description 6
- 239000003513 alkali Substances 0.000 abstract description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 4
- 229910017052 cobalt Inorganic materials 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052748 manganese Inorganic materials 0.000 abstract description 4
- 229910052759 nickel Inorganic materials 0.000 abstract description 4
- 238000011085 pressure filtration Methods 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- 238000001704 evaporation Methods 0.000 description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 230000008021 deposition Effects 0.000 description 9
- 229910052808 lithium carbonate Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000010413 mother solution Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 238000009993 causticizing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000010446 mirabilite Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Removal Of Specific Substances (AREA)
Abstract
The invention provides a method for removing carbonate from a lithium precipitation mother liquor, which comprises the steps of mixing the lithium precipitation mother liquor and nickel cobalt manganese wastewater, reacting, removing carbonate in the lithium precipitation mother liquor, and preparing to obtain nickel cobalt manganese carbonate slag. According to the invention, the pH value is not required to be adjusted in the process of removing carbonate in the lithium precipitation mother liquor, so that the use of acid liquor or alkali liquor is avoided, and the carbonate content in the lithium precipitation mother liquor can be greatly reduced, thereby realizing the removal of carbonate in the lithium precipitation mother liquor with high efficiency, simplicity and low cost. And the nickel, cobalt and manganese carbonate slag is prepared while the carbonate radical is removed, and can be used for preparing the ternary cathode material, so that the effect of recovering nickel, cobalt and manganese from the nickel, cobalt and manganese wastewater is achieved.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and relates to a method for removing carbonate from lithium precipitation mother liquor.
Background
With the increasing shortage of traditional energy sources such as petroleum, the development of new energy sources is more and more emphasized, and particularly, the demand for lithium batteries is rapidly increasing. Lithium carbonate is an important component of a lithium battery, lithium is generally precipitated by excess sodium carbonate in industry, solid lithium carbonate and lithium precipitation mother liquor are obtained after solid-liquid separation, the lithium precipitation mother liquor also contains more lithium ions due to the problem of lithium precipitation efficiency, and if the lithium precipitation mother liquor is directly discharged, a large amount of lithium loss is caused. Therefore, the lithium deposition mother liquor is generally evaporated and concentrated to deposit lithium again, the lithium deposition mother liquor needs to remove carbonate before entering an evaporation system, at present, the lithium deposition mother liquor is industrially treated by sulfuric acid to remove carbonate in the lithium deposition mother liquor, and then the lithium deposition mother liquor is adjusted to be neutral by liquid alkali and enters the evaporation and concentration system.
For example, CN113912090a discloses a method for recovering high-purity lithium carbonate by removing mirabilite through causticizing and freezing lithium precipitation mother liquor, wherein a certain amount of calcium oxide is added into the lithium precipitation mother liquor for causticizing and stirring, the pH =12-14 of the solution is adjusted, the reaction lasts for 2.0-8.5h, the temperature is 30-60 ℃, calcium carbonate precipitate and causticizing liquor are obtained after filtering, and carbonate in the lithium precipitation mother liquor is removed. For example, CN112158865a discloses a method for recycling lithium element in lithium precipitation mother liquor, wherein the lithium carbonate is removed by adding hydrochloric acid into the lithium precipitation mother liquor, controlling the pH of the mother liquor within the range of 4 to 7, adding hydrochloric acid with the molar weight of chloride ions being 1.5 to 3.0 times of the molar weight of carbonate ions in the solution, mixing the lithium precipitation mother liquor and hydrochloric acid, then sequentially stirring through a buffer tank, heating while stirring, discharging carbon dioxide generated in the solution, and removing carbonate. For example, CN105347364a discloses a method for closed-loop recovery of lithium deposition mother liquor in lithium carbonate production, wherein the carbonate removal method comprises the following steps: adding hydrochloric acid into the lithium precipitation mother liquor, controlling the pH value of the mother liquor within the range of 3.5-6.5, controlling the molar weight of chloride ions added with the hydrochloric acid to be 1.1-3.0 times of the molar weight of carbonate ions in the solution, and discharging carbon dioxide generated in the solution out of the system as soon as possible by stirring, heating, natural evaporation and vacuumizing to achieve the aim of removing the carbonate.
However, the above methods for removing carbonate are complicated, and the pH of the mother liquor needs to be adjusted by adding a pH adjusting agent, which takes a long time and is not suitable for mass production.
Therefore, in order to avoid the use of acid liquor and alkali liquor, the invention needs to invent a method for removing carbonate from lithium precipitation mother liquor with high efficiency and green performance.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a method for removing carbonate in a lithium precipitation mother liquor.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a method for removing carbonate from a lithium precipitation mother liquor, which comprises the following steps: and mixing the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater, reacting, and removing carbonate in the lithium precipitation mother liquor to prepare the nickel-cobalt-manganese carbonate slag.
According to the invention, carbonate in the lithium precipitation mother liquor is removed by using the nickel cobalt manganese wastewater, on one hand, the pH value of the lithium precipitation mother liquor does not need to be adjusted in the removal process of the carbonate, so that the use of acid liquor and alkali liquor is avoided, and on the other hand, carbonate in the lithium precipitation mother liquor is removed while carbonate residues are generated, so that the method can be used for preparing a ternary cathode material.
In the invention, carbonate in the lithium precipitation mother liquor cannot be well removed by singly using aluminum salt or calcium oxide, and more aluminum ions and calcium ions are introduced after the carbonate is removed, so that the primary filtrate after the carbonate is removed from the lithium precipitation mother liquor can be recycled after impurity ions are further removed.
In the invention, the equation of the reaction of the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater is as follows:
xNi 2+ +yCo 2+ +(1-x-y)Mn 2+ +CO 3 2- ＝Ni x Co y Mn 1-x-y CO 3 and ↓, wherein, 1 > x > 0,1 > y > 0,1 > 1-x-y > 0, e.g., x is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, e.g., y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, e.g., 1-x-y is 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9.
In the present invention, a method for preparing a ternary cathode material is not limited, and for example, the method for preparing a ternary cathode material includes: and mixing the nickel-cobalt-manganese carbonate slag and a lithium source, and sintering to prepare the ternary cathode material, wherein the lithium source comprises but is not limited to lithium carbonate, lithium hydroxide or lithium acetate.
In the invention, the lithium deposition mother liquor refers to mother liquor discharged in the lithium carbonate production process, and main ions in the lithium deposition mother liquor are Li + The main impurity is CO 3 2- 。
In the invention, the nickel-cobalt-manganese wastewater is wastewater generated after lithium and nickel-cobalt-manganese are recovered from a ternary retired lithium battery, and main ions in the nickel-cobalt-manganese wastewater are nickel ions, cobalt ions and manganese ions.
Preferably, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is (0.7-1.5): 1, for example, "0.7-1.5" can be 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5, and is preferably (0.8-1.4): 1. When the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is less than 0.7, carbonate in the lithium precipitation mother liquor cannot be effectively removed, and when the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater is appropriate to the content of carbonate in the lithium precipitation mother liquor, the effect of better removing carbonate in the lithium precipitation mother liquor can be achieved, and the introduction of redundant impurity ions is avoided.
Preferably, the temperature of the reaction is 50-150 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the reaction time is 1-5h, such as 1h, 2h, 3h, 4h or 5h.
Preferably, after the reaction, the liquid and the solid in the reaction system are subjected to primary separation to obtain primary filtrate and the nickel cobalt manganese carbonate slag.
The method of primary separation is not limited in the present invention, and exemplary methods of primary separation include, but are not limited to, pressure filtration or suction filtration.
Preferably, the nickel-cobalt-manganese carbonate slag is subjected to pulping water washing, and the purpose of the pulping water washing is to wash away residual lithium ions and carbonate in the nickel-cobalt-manganese carbonate slag.
Preferably, the pulping water is washed for secondary separation to obtain secondary filtrate and the nickel cobalt manganese carbonate washing slag.
The method of the secondary separation is not limited in the present invention, and exemplary methods of the secondary separation include, but are not limited to, pressure filtration or suction filtration.
Preferably, the secondary filtrate is returned to the lithium precipitation mother liquor again for reuse.
Lithium ions and carbonate are contained in the secondary filtrate, and the secondary filtrate is returned to the lithium precipitation mother liquor again for reuse, so that the loss of lithium can be effectively avoided.
Preferably, the secondary filtrate is evaporated and concentrated before returning to the lithium precipitation mother liquor.
Preferably, the pulping water wash comprises: and mixing the nickel, cobalt and manganese carbonate slag with water to form nickel, cobalt and manganese carbonate slurry.
Preferably, the solid-to-liquid ratio of the nickel-cobalt-manganese carbonate slag to the water is 1 (3-5), for example, 3-5 can be 3, 4 or 5.
In the invention, the solid-to-liquid ratio refers to the ratio of the mass of the nickel-cobalt-manganese carbonate slag to the mass of water.
As a preferable technical scheme of the method, the lithium precipitation mother liquor and the aluminum salt are pre-reacted before the mixed reaction of the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater.
In the invention, if the lithium precipitation mother liquor and the aluminum salt are not pre-reacted, and the lithium precipitation mother liquor, the aluminum salt and the nickel-cobalt-manganese wastewater are directly mixed at the same time, more aluminum hydroxide can be preferentially generated, and the recovery of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater is influenced; if the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater are pre-reacted and then the aluminum salt is added for reaction, part of the nickel-cobalt-manganese carbonate slag is dissolved to generate aluminum hydroxide, which is also not beneficial to the recovery of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater.
In the invention, the lithium precipitation mother liquor and the aluminum salt are pre-reacted in advance, and aluminum ions in the aluminum salt have the function of removing carbonate on one hand and can be doped in the nickel-cobalt-manganese carbonate slag or coated on the surface of the nickel-cobalt-manganese carbonate slag as a doping element or a coating element on the other hand, thereby improving the electrochemical performance of the prepared cathode material. In addition, CO generated in the reaction process of lithium precipitation mother liquor and aluminum salt 2 Can be recycled, and can be used in the process of lithium precipitation by carbonization after being recycled.
Preferably, the aluminum salt includes at least one of aluminum sulfate and aluminum chloride.
Preferably, the molar ratio of the aluminum ions in the aluminum salt to the carbonate in the lithium precipitation mother liquor is (0.05-0.15): 1, for example, "0.05-0.15" may be 0.05, 0.06, 0.07, 0.08, 0.09, 0.10, 0.11, 0.12, 0.13, 0.14 or 0.15, preferably (0.08-0.12): 1.
In the invention, when the addition amount of the aluminum salt is too much or too little, the electrochemical performance of the prepared cathode material is influenced, and the performance of the prepared cathode material can be optimized only when the addition amount of the aluminum salt is moderate.
Preferably, the pre-reaction temperature is 50-150 ℃, such as 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the pre-reaction time is 0.5 to 3h, such as 0.5h, 1h, 2h, 2.5h or 3h.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the pH value is not required to be adjusted in the process of removing carbonate in the lithium precipitation mother liquor, so that the use of acid liquor or alkali liquor is avoided, and the carbonate in the lithium precipitation mother liquor can be greatly reduced, thereby realizing the removal of the carbonate in the lithium precipitation mother liquor with high efficiency, simplicity and low cost.
(2) The method for removing carbonate in the invention can remove carbonate radical and prepare the nickel cobalt manganese carbonate slag, the nickel cobalt manganese carbonate slag can be used for preparing the ternary cathode material, and the effect of recovering nickel, cobalt and manganese from the nickel, cobalt and manganese wastewater is achieved.
(3) Further, in the invention, the lithium precipitation mother liquor and the aluminum salt are pre-reacted in advance in the process of removing carbonate in the lithium precipitation mother liquor, and aluminum ions in the aluminum salt have the function of removing the carbonate on one hand and can be doped in the nickel-cobalt-manganese carbonate slag or coated on the surface of the nickel-cobalt-manganese carbonate slag as a doping element or a coating element on the other hand, so that the electrochemical performance of the prepared cathode material is improved. In addition, CO generated in the reaction process of lithium precipitation mother liquor and aluminum salt 2 Can be recycled, and can be used in the process of lithium precipitation by carbonization after being recycled.
Drawings
FIG. 1 is a flow chart of removing carbonate from lithium precipitation mother liquor in the embodiment of the present invention.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The invention provides a method for removing carbonate from lithium precipitation mother liquor, a flow chart is shown in figure 1, and the method comprises the following steps: reacting the lithium precipitation mother liquor with the nickel-cobalt-manganese wastewater, performing primary separation after reaction to obtain nickel-cobalt-manganese carbonate slag and primary filtrate, performing pulping and washing on the nickel-cobalt-manganese carbonate slag, performing secondary separation on the obtained nickel-cobalt-manganese carbonate pulp in a filter pressing mode to obtain nickel-cobalt-manganese carbonate washing slag and secondary filtrate, and performing evaporation concentration on the secondary filtrate to return to the original lithium precipitation mother liquor for removing carbonate again.
Example 1
The embodiment provides a method for removing carbonate from a lithium precipitation mother solution, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 4.4L of nickel cobalt manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 29.8g/L, the content of nickel ions in the nickel cobalt manganese wastewater is 4.48g/L, the content of cobalt ions is 4.50g/L, and the content of manganese ions is 4.20g/L;
s2: putting 2L of lithium precipitation mother liquor and 4.4L of nickel-cobalt-manganese wastewater into a reaction tank, and reacting for 2h at 80 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 6.3L of primary filtrate containing 0.09g/L of carbonate and nickel-cobalt-manganese carbonate slag;
s4: and (3) washing the nickel-cobalt-manganese carbonate slag with pulping water and performing pressure filtration to wash away lithium ions carried in the nickel-cobalt-manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated secondary filtrate to the lithium precipitation mother liquor to continuously remove carbonate, wherein the solid-to-liquid ratio of the nickel-cobalt-manganese carbonate slag to water in the pulping water washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 1.02.
Example 2
The embodiment provides a method for removing carbonate from a lithium precipitation mother solution, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 8.5L of nickel-cobalt-manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 25.6g/L, the content of nickel ions in the nickel-cobalt-manganese wastewater is 2.83g/L, the content of cobalt ions is 1.42g/L, and the content of manganese ions is 2.65g/L;
s2: putting 2L of lithium precipitation mother liquor and 8.5L of nickel-cobalt-manganese wastewater into a reaction tank, and reacting for 3h at 120 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 10.3L of primary filtrate containing 0.04g/L of carbonate and nickel-cobalt-manganese carbonate slag;
s4: and (3) washing the nickel-cobalt-manganese carbonate slag with pulping water and performing pressure filtration to wash away lithium ions carried in the nickel-cobalt-manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated secondary filtrate to the lithium precipitation mother liquor to continuously remove carbonate, wherein the solid-to-liquid ratio of the nickel-cobalt-manganese carbonate slag to water in the pulping water washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 1.2.
Example 3
The embodiment provides a method for removing carbonate from a lithium precipitation mother solution, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 3.4L of nickel cobalt manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 26.8g/L, the content of nickel ions in the nickel cobalt manganese wastewater is 6.84g/L, the content of cobalt ions is 2.75g/L, and the content of manganese ions is 3.84g/L;
s2: adding 2L of lithium precipitation mother liquor and 16.8g of aluminum sulfate into a reaction tank, pre-reacting for 1h at the temperature of 80 ℃, then adding 3.4L of nickel-cobalt-manganese wastewater, and reacting for 2h at the temperature of 80 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 5.3L of aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag and primary filtrate with the carbonate content of 0.09 g/L;
s4: and (3) pulping and washing the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag with water, performing pressure filtration, washing away lithium ions carried in the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated secondary filtrate to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-to-liquid ratio of the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag to the water in the pulping and washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 0.89, and the molar ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is calculated to be 0.11.
Example 4
The embodiment provides a method for removing carbonate from a lithium precipitation mother solution, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 5L of nickel cobalt manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 31.3g/L, the content of nickel ions in the nickel cobalt manganese wastewater is 6.12g/L, the content of cobalt ions is 3.69g/L, and the content of manganese ions is 3.44g/L;
s2: adding 2L of lithium precipitation mother liquor and 16g of aluminum sulfate into a reaction tank, carrying out pre-reaction for 2h at the temperature of 120 ℃, then adding 5L of nickel-cobalt-manganese wastewater, and carrying out reaction for 2h at the temperature of 130 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 6.9L of aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag and primary filtrate with carbonate content of 0.06 g/L;
s4: and (3) pulping and washing the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag with water, performing pressure filtration, washing away lithium ions carried in the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated secondary filtrate to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-to-liquid ratio of the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag to the water in the pulping and washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 1.1, and the molar ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is 0.09.
Example 5
The embodiment provides a method for removing carbonate from a lithium precipitation mother solution, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 3.4L of nickel cobalt manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 26.8g/L, the content of nickel ions in the nickel cobalt manganese wastewater is 6.84g/L, the content of cobalt ions is 2.75g/L, and the content of manganese ions is 3.84g/L;
s2: adding 2L of lithium precipitation mother liquor and 14.5g of aluminum sulfate of aluminum chloride into a reaction tank, carrying out pre-reaction for 2 hours at the temperature of 120 ℃, then adding 4.8L of nickel-cobalt-manganese wastewater, and carrying out reaction for 4 hours at the temperature of 100 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 5.3L of aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag and primary filtrate with the carbonate content of 0.08 g/L;
s4: and (3) pulping and washing the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag with water, performing pressure filtration, washing away lithium ions carried in the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated secondary filtrate to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-to-liquid ratio of the aluminum-doped or aluminum-coated nickel-cobalt-manganese carbonate slag to the water in the pulping and washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 0.89.
Example 6
The difference from the example 1 is only that the usage amount of the nickel cobalt manganese wastewater is 6L, in this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel cobalt manganese wastewater to the carbonate content in the lithium precipitation mother liquor is calculated to be 1.4.
Comparative example 1
The comparative example provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: measuring 2L of lithium precipitation mother liquor and 5L of nickel cobalt manganese wastewater, wherein the content of carbonate in the lithium precipitation mother liquor is 31.3g/L, the content of nickel ions in the nickel cobalt manganese wastewater is 6.12g/L, the content of cobalt ions is 3.69g/L, and the content of manganese ions is 3.44g/L;
s2: adding 2L of lithium precipitation mother liquor, 16g of aluminum sulfate and 5L of nickel-cobalt-manganese wastewater into a reaction tank, and reacting for 2h at 80 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 6.9L of primary filtrate with the solid slag and carbonate content of 0.08 g/L;
s4: and (3) washing the solid slag with pulping water and performing filter pressing, washing lithium ions carried in the solid slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated and concentrated secondary filtrate to the lithium precipitation mother liquor to continuously remove carbonate, wherein the solid-liquid ratio of the solid slag to water in the pulping water washing process is 1:3.
In this example, the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is calculated to be 1.1, and the molar ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is 0.09.
Comparative example 2
The method for removing carbonate from the lithium precipitation mother liquor in the comparative example comprises the following steps:
s1: weighing 2L of lithium precipitation mother liquor and 55.6g of calcium oxide, wherein the content of carbonate in the lithium precipitation mother liquor is 29.8g/L;
s2: adjusting the pH value of the solution to 12.2, and reacting at the temperature of 80 ℃ for 2h;
s2: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through pressure filtration to obtain 1.9L of filtrate with the contents of calcium carbonate slag and carbonate being 3.6 g/L;
s4: and (3) washing the calcium carbonate slag with pulping water and performing filter pressing, washing away lithium ions carried in the calcium carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning the evaporated and concentrated secondary filtrate to the lithium precipitation mother liquor to continuously remove carbonate, wherein the solid-to-liquid ratio of the calcium carbonate slag to water in the pulping water washing process is 1:3.
And (3) performance detection:
detecting the content of carbonate in the primary filtrate by adopting a double-indicator neutralization method; and detecting the content of the metal ions in the primary filtrate by adopting an atomic absorption spectrometry.
The contents of each ion in the primary filtrate after removing carbonate from the lithium deposition mother liquor in examples 1 to 6 and comparative examples 1 to 2 are shown in table 1.
TABLE 1
Wherein, CO 3 2- The removal rate of the catalyst is CO in the lithium precipitation mother liquor 3 2- Content of (D) and CO in the primary filtrate after removal of carbonate 3 2- The difference of the contents of the lithium and CO in the lithium precipitation mother liquor 3 2- The ratio of the contents of (a) to (b).
And (3) analysis:
table 1 is a statistical table of the content of each ion in the primary filtrate after removing carbonic acid in examples 1 to 6 and comparative examples 1 to 2 of the present invention, and it can be seen from examples 1 to 6 that the content of carbonate in the lithium precipitation mother liquor can be significantly reduced by using the nickel-cobalt-manganese wastewater to react with the lithium precipitation mother liquor or by using the aluminum salt and the lithium precipitation mother liquor to pre-react and then react with the nickel-cobalt-manganese wastewater, and when the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the content of carbonate in the lithium precipitation mother liquor is moderate, the removal effect of carbonate can be ensured, and the introduction of excessive impurity ions can be avoided; when the total content of nickel ions, manganese ions and cobalt ions in the nickel-cobalt-manganese wastewater is relatively high, more nickel ions, manganese ions and cobalt ions are introduced into the primary filtrate, although carbonate in the lithium precipitation mother liquor can be removed well.
As can be seen from the data of comparative example 1, if the lithium precipitation mother liquor, the aluminum salt and the nickel cobalt manganese wastewater are mixed together, although carbonate in the lithium precipitation mother liquor can be removed, relatively more impurity ions remain in the primary filtrate due to the interaction between aluminum ions and nickel ions, manganese ions and cobalt ions, and the aluminum ions also affect the formation of the nickel cobalt manganese carbonate slag.
It can be seen from the data of comparative example 2 that carbonate in the lithium precipitation mother liquor can not be removed well by using calcium oxide alone, and relatively more calcium ions can remain in the obtained primary filtrate.
The applicant states that the present invention is illustrated by the above examples to show the detailed method of the present invention, but the present invention is not limited to the above detailed method, that is, it does not mean that the present invention must rely on the above detailed method to be carried out. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. The method for removing carbonate from lithium precipitation mother liquor is characterized by comprising the following steps:
and mixing the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater, reacting, and removing carbonate in the lithium precipitation mother liquor to prepare the nickel-cobalt-manganese carbonate slag.
2. The method according to claim 1, wherein the molar ratio of the total content of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese wastewater to the carbonate content in the lithium precipitation mother liquor is (0.7-1.5): 1, preferably (0.8-1.4): 1.
3. The process according to claim 1 or 2, characterized in that the temperature of the reaction is 50-150 ℃;
preferably, the reaction time is 1-5h.
4. The method according to any one of claims 1 to 3, characterized in that after the reaction, liquid and solid in the reaction system are subjected to primary separation to obtain primary filtrate and the cobalt nickel manganese carbonate slag;
preferably, the nickel, cobalt and manganese carbonate slag is subjected to pulping and water washing.
5. The method according to claim 4, characterized in that the pulping water is washed for secondary separation to obtain secondary filtrate and cobalt nickel manganese carbonate washing slag;
preferably, the secondary filtrate is returned to the lithium precipitation mother liquor again for reuse;
preferably, the secondary filtrate is evaporated and concentrated before returning to the lithium precipitation mother liquor.
6. The method according to claim 4 or 5, characterized in that the pulping water wash comprises: mixing the nickel cobalt manganese carbonate slag with water to form nickel cobalt manganese carbonate slurry;
preferably, the solid-to-liquid ratio of the nickel-cobalt-manganese carbonate slag to the water is 1 (3-5).
7. The method of any one of claims 1 to 6, wherein the lithium precipitation mother liquor and the aluminum salt are pre-reacted before the mixed reaction of the lithium precipitation mother liquor and the nickel-cobalt-manganese wastewater.
8. The method of claim 7, wherein the aluminum salt comprises at least one of aluminum sulfate and aluminum chloride.
9. The method according to claim 7 or 8, wherein the molar ratio of the aluminum ions in the aluminum salt to the carbonate in the lithium precipitation mother liquor is (0.05-0.15): 1, preferably (0.08-0.12): 1.
10. The process according to any one of claims 7 to 9, wherein the pre-reaction temperature is 50 to 150 ℃;
preferably, the pre-reaction time is 0.5 to 3 hours.
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