CN115571926B - Method for removing carbonate radical from lithium precipitation mother liquor - Google Patents
Method for removing carbonate radical from lithium precipitation mother liquor Download PDFInfo
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- CN115571926B CN115571926B CN202211218282.3A CN202211218282A CN115571926B CN 115571926 B CN115571926 B CN 115571926B CN 202211218282 A CN202211218282 A CN 202211218282A CN 115571926 B CN115571926 B CN 115571926B
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- precipitation mother
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 140
- 238000001556 precipitation Methods 0.000 title claims abstract description 126
- 239000012452 mother liquor Substances 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 46
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 92
- 239000002893 slag Substances 0.000 claims abstract description 59
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 55
- 239000002351 wastewater Substances 0.000 claims abstract description 53
- 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 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000010413 mother solution Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000706 filtrate Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 25
- 229910052782 aluminium Inorganic materials 0.000 claims description 25
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 25
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 25
- 229910001437 manganese ion Inorganic materials 0.000 claims description 25
- 229910001453 nickel ion Inorganic materials 0.000 claims description 25
- 239000007788 liquid Substances 0.000 claims description 22
- 238000004537 pulping Methods 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- -1 aluminum ions Chemical class 0.000 claims description 13
- 238000001704 evaporation Methods 0.000 claims description 9
- 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
- 230000008020 evaporation Effects 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 3
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 13
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 12
- 238000003825 pressing Methods 0.000 description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 229910001416 lithium ion Inorganic materials 0.000 description 10
- 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
- 238000005303 weighing Methods 0.000 description 7
- 229910000019 calcium carbonate Inorganic materials 0.000 description 6
- 230000008021 deposition Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 239000007774 positive electrode material 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
- 238000001914 filtration Methods 0.000 description 4
- 238000004519 manufacturing process Methods 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
- 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
- 239000010405 anode material Substances 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
- 238000005253 cladding Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011085 pressure filtration Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 238000010438 heat treatment 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
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 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
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 solution, which comprises the steps of mixing the lithium precipitation mother solution with nickel cobalt manganese wastewater, then carrying out a reaction, and removing carbonate from the lithium precipitation mother solution to prepare nickel cobalt manganese carbonate slag. The invention does not need to adjust the pH value in the process of removing carbonate in the lithium precipitation mother liquor, avoids the use of acid liquor or alkali liquor, can greatly reduce the carbonate content in the lithium precipitation mother liquor, and realizes the efficient, simple and low-cost removal of the carbonate in the lithium precipitation mother liquor. And nickel cobalt manganese carbonate slag is prepared while carbonate is removed, and can be used for preparing ternary cathode materials, so that the effect of recovering nickel cobalt manganese from nickel cobalt 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
Along 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 of lithium batteries is increasing sharply. The lithium carbonate is an important component of a lithium battery, and is generally precipitated by adopting excessive sodium carbonate in industry, solid lithium carbonate and precipitated lithium mother solution are obtained after solid-liquid separation, and due to the problem of lithium precipitation efficiency, more lithium ions are contained in the precipitated lithium mother solution, and if the part of precipitated lithium mother solution is directly discharged, a large amount of lithium is lost. Therefore, the lithium deposition mother liquor is evaporated and concentrated to deposit lithium again, and the carbonate radical needs to be removed before the lithium deposition mother liquor enters an evaporation system, and at present, the industrial process firstly uses sulfuric acid to remove the carbonate radical in the lithium deposition mother liquor, and then uses liquid alkali to adjust the value of the lithium deposition mother liquor to be neutral and then enters the evaporation and concentration system.
For example, CN113912090a discloses a method for recovering high-purity lithium carbonate by causticizing a lithium precipitation mother liquor and freezing and removing mirabilite, wherein a certain amount of calcium oxide is added into the lithium precipitation mother liquor for causticizing and stirring, the pH of the solution is regulated to be 12-14, the reaction is carried out for 2.0-8.5 hours, the temperature is 30-60 ℃, calcium carbonate precipitation and causticizing liquid are obtained after filtration, and carbonate radical in the lithium precipitation mother liquor is removed. For example, CN112158865a discloses a method for recycling lithium element in a lithium precipitation mother liquor, wherein the method for removing lithium carbonate is to add hydrochloric acid into the lithium precipitation mother liquor, control the pH value of the mother liquor to be in the range of 4-7, add chloride ion of hydrochloric acid with a molar amount 1.5-3.0 times of that of carbonate ion in the solution, mix the lithium precipitation mother liquor and hydrochloric acid, then sequentially stir in a buffer tank, heat while stirring, so that carbon dioxide generated in the solution is discharged, and remove carbonate. For example, CN105347364a discloses a method for closed-loop recovery of lithium precipitation mother liquor in lithium carbonate production, wherein the method for removing carbonate is as follows: hydrochloric acid is added into the lithium precipitation mother solution, the pH value of the mother solution is controlled within the range of 3.5-6.5, the molar quantity of chloride ions added into the hydrochloric acid is 1.1-3.0 times of the molar quantity of carbonate ions in the solution, and carbon dioxide generated in the solution is discharged out of the system as soon as possible through stirring, heating, natural evaporation and vacuumizing modes, so that the purpose of removing carbonate radicals is achieved.
However, the method for removing the carbonate is complicated, and the pH value of the mother solution needs to be adjusted by adding the pH regulator, which takes a long time and is not beneficial to expanding production.
Based on the above, in order to avoid the use of acid liquor and alkali liquor, a method for removing carbonate from the lithium precipitation mother liquor with high efficiency and green color needs to be invented.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a method for removing carbonate from a lithium precipitation mother solution.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for removing carbonate from a lithium precipitation mother liquor, the method comprising the steps of: mixing the lithium precipitation mother liquor and nickel cobalt manganese wastewater, and then carrying out a reaction, and removing carbonate in the lithium precipitation mother liquor to prepare nickel cobalt manganese carbonate slag.
According to the method, the carbonate in the lithium precipitation mother liquor is removed by utilizing the nickel-cobalt-manganese wastewater, on one hand, the pH value of the lithium precipitation mother liquor is not required to be adjusted in the removal process of the carbonate, the use of acid liquor and alkali liquor is avoided, and on the other hand, the nickel-cobalt-manganese carbonate slag is generated while the carbonate in the lithium precipitation mother liquor is removed, so that the method can be used for preparing ternary cathode materials.
In the invention, the carbonate in the lithium precipitation mother solution cannot be well removed by using the aluminum salt or the calcium oxide alone, and more aluminum ions and calcium ions are introduced after the carbonate is removed, so that the primary filtrate of the lithium precipitation mother solution after the carbonate is removed can be recycled after the 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.
In the present invention, the preparation method of the ternary positive electrode material is not limited, and illustratively, the preparation method of the ternary positive electrode material includes: and mixing nickel cobalt manganese carbonate slag and a lithium source, and sintering to prepare the ternary positive electrode material, wherein the lithium source comprises, but is not limited to, lithium carbonate, lithium hydroxide or lithium acetate.
In the invention, the lithium precipitation mother solution refers to mother solution discharged in the lithium carbonate production process, and the main ions in the lithium precipitation mother solution are Li + The main impurity is CO 3 2- 。
In the invention, the nickel-cobalt-manganese wastewater refers to wastewater generated after lithium and nickel-cobalt-manganese are recovered from a ternary retired lithium battery, and the 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 carbonate content in the lithium precipitation mother liquor is (0.7-1.5): 1, for example "0.7-1.5" may be 0.7, 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4 or 1.5, 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 carbonate content in the lithium precipitation mother liquor is less than 0.7, the carbonate in the lithium precipitation mother liquor cannot be effectively removed, and when the 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 proper, 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 ℃, e.g. 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the reaction time is 1-5 hours, for example 1, 2, 3, 4 or 5 hours.
Preferably, after the reaction, the liquid and the solid in the reaction system are separated for the first time, so as to obtain primary filtrate and nickel cobalt manganese carbonate slag.
The present invention is not limited to a primary separation process, which illustratively includes, but is 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 residual lithium ions and carbonate in the nickel cobalt manganese carbonate slag.
Preferably, the pulping water is washed and then subjected to secondary separation to obtain secondary filtrate and nickel cobalt manganese carbonate washing slag.
The present invention is not limited to a secondary separation process, which illustratively includes, but is not limited to, pressure filtration or suction filtration.
Preferably, the secondary filtrate is returned to the lithium precipitation mother liquor for reuse.
The secondary filtrate contains lithium ions and carbonate, and the secondary filtrate is returned to the lithium precipitation mother liquor for recycling, so that the loss of lithium can be effectively avoided.
Preferably, the secondary filtrate is concentrated by evaporation before being returned to the lithium precipitation mother liquor.
Preferably, the pulping water washing comprises: and 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 water is 1 (3-5), for example, "3-5" may be 3, 4 or 5.
In the invention, the solid-to-liquid ratio refers to the ratio of the mass of nickel cobalt manganese carbonate slag to the mass of water.
As a preferable technical scheme of the method, the lithium precipitation mother liquor and aluminum salt are pre-reacted in advance before the lithium precipitation mother liquor and nickel cobalt manganese wastewater are mixed for reaction.
In the invention, if the lithium precipitation mother liquor and the aluminum salt are not subjected to pre-reaction, 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 subjected to pre-reaction, and then aluminum salt is added for reaction, part of nickel cobalt manganese carbonate slag is dissolved to generate aluminum hydroxide, and the recovery of nickel ions, cobalt ions and manganese ions in the nickel cobalt manganese wastewater is also not facilitated.
In the invention, the lithium precipitation mother solution and 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 used as doping elements or cladding elements on the other handThe element is doped in nickel cobalt manganese carbonate slag or coated on the surface of the nickel cobalt manganese carbonate slag, so that the electrochemical performance of the prepared anode 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 carbonization and lithium precipitation after being recycled.
Preferably, the aluminum salt includes at least one of aluminum sulfate and aluminum chloride.
Preferably, the molar ratio of aluminum ions in the aluminum salt to carbonate in the lithium precipitation mother liquor is (0.05-0.15): 1, e.g. "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 large or too small, the electrochemical performance of the prepared positive electrode material is affected, and the performance of the prepared positive electrode material can be optimized only when the addition amount of the aluminum salt is moderate.
Preferably, the temperature of the pre-reaction is 50-150 ℃, e.g. 50 ℃, 60 ℃, 70 ℃, 80 ℃, 90 ℃, 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃ or 150 ℃.
Preferably, the pre-reaction time is 0.5-3h, for example 0.5h, 1h, 2h, 2.5h or 3h.
Compared with the prior art, the invention has the following beneficial effects:
(1) The invention does not need to adjust the pH value in the process of removing carbonate in the lithium precipitation mother liquor, avoids the use of acid liquor or alkali liquor, can greatly reduce the carbonate in the lithium precipitation mother liquor, and thereby realizes the efficient, simple and low-cost removal of the carbonate in the lithium precipitation mother liquor.
(2) The method for removing carbonate radical in the invention prepares nickel cobalt manganese carbonate slag while removing carbonate radical, and the nickel cobalt manganese carbonate slag can be used for preparing ternary cathode materials, thereby achieving the effect of recovering nickel cobalt manganese from nickel cobalt manganese wastewater.
(3) Further, in the invention, the carbonate is removed from the lithium precipitation mother liquor in advanceThe lithium precipitation mother solution and aluminum salt are subjected to pre-reaction, aluminum ions in the aluminum salt have the function of removing carbonate on one hand, and on the other hand, the aluminum ions can be used as doping elements or cladding elements to be doped in nickel cobalt manganese carbonate slag or clad on the surface of the nickel cobalt manganese carbonate slag, so that the electrochemical performance of the prepared anode 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 carbonization and lithium precipitation after being recycled.
Drawings
FIG. 1 is a flow chart of removing carbonate from a lithium precipitation mother liquor in an embodiment of the invention.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
In one embodiment, the invention provides a method for removing carbonate from lithium precipitation mother liquor, wherein a flow chart is shown in fig. 1, and the method comprises the following steps: and (3) reacting the lithium-precipitation mother liquor with nickel-cobalt-manganese wastewater, performing primary separation after the reaction to obtain nickel-cobalt-manganese carbonate slag and primary filtrate, performing pulping water washing on the nickel-cobalt-manganese carbonate slag, performing secondary separation on the obtained nickel-cobalt-manganese carbonate slurry in a filter pressing mode to obtain nickel-cobalt-manganese carbonate slag washing and secondary filtrate, evaporating and concentrating the secondary filtrate, and returning the secondary filtrate to the original lithium-precipitation mother liquor, and removing carbonate again.
Example 1
The embodiment provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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: placing 2L of lithium precipitation mother liquor and 4.4L of nickel cobalt manganese wastewater into a reaction tank, and reacting for 2 hours at 80 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through filter pressing to obtain nickel cobalt manganese carbonate slag and primary filtrate with the carbonate content of 0.09g/L, wherein the primary filtrate is 6.3L;
s4: and (3) pulping nickel cobalt manganese carbonate slag, washing with water, and press-filtering to remove lithium ions entrained in the nickel cobalt manganese carbonate slag, wherein the obtained secondary filtrate is evaporated and concentrated and returned to the lithium precipitation mother liquor to continuously remove carbonate, and the solid-liquid ratio of the nickel cobalt manganese carbonate slag to water in the pulping water washing process is 1:3.
In the embodiment, 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 1.02:1.
Example 2
The embodiment provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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: placing 2L of lithium precipitation mother liquor and 8.5L of nickel cobalt manganese wastewater into a reaction tank, and reacting for 3 hours at 120 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through filter pressing to obtain nickel cobalt manganese carbonate slag and primary filtrate with the carbonate content of 0.04g/L, wherein the primary filtrate contains 10.3L;
s4: and (3) pulping nickel cobalt manganese carbonate slag, washing with water, and press-filtering to remove lithium ions entrained in the nickel cobalt manganese carbonate slag, wherein the obtained secondary filtrate is evaporated and concentrated and returned to the lithium precipitation mother liquor to continuously remove carbonate, and the solid-liquid ratio of the nickel cobalt manganese carbonate slag to water in the pulping water washing process is 1:3.
In the embodiment, 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 1.2:1.
Example 3
The embodiment provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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 filter pressing to obtain primary filtrate 5.3L of aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag and 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, and carrying out filter pressing, so as to wash away lithium ions entrained in the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-liquid ratio of the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag to water in the pulping and washing process is 1:3.
In the embodiment, the mole 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 0.89:1, and the mole ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is calculated to be 0.11:1.
Example 4
The embodiment provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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, pre-reacting for 2 hours at the temperature of 120 ℃, then adding 5L of nickel cobalt manganese wastewater, and reacting for 2 hours at the temperature of 130 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through filter pressing to obtain primary filtrate 6.9L of aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag and 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, and carrying out filter pressing, so as to wash away lithium ions entrained in the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-liquid ratio of the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag to water in the pulping and washing process is 1:3.
In the embodiment, 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 1.1:1, and the molar ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is calculated to be 0.09:1.
Example 5
The embodiment provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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, pre-reacting for 2 hours at the temperature of 120 ℃, then adding 4.8L of nickel cobalt manganese wastewater, and reacting 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 filter pressing to obtain primary filtrate 5.3L of aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag and 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, and carrying out filter pressing, so as to wash away lithium ions entrained in the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag, evaporating and concentrating the obtained secondary filtrate, returning to the lithium precipitation mother liquor, and continuously removing carbonate, wherein the solid-liquid ratio of the aluminum-doped or aluminum-coated nickel cobalt manganese carbonate slag to water in the pulping and washing process is 1:3.
In the embodiment, the mole 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 0.89:1, and the mole ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is calculated to be 0.12:1.
Example 6
The difference from example 1 is only that the amount of 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 1.4:1, and the volume of the primary filtrate is 7.9L.
Comparative example 1
The comparative example provides a method for removing carbonate from lithium precipitation mother liquor, which comprises the following steps:
s1: weighing 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 2 hours at 80 ℃;
s3: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through filter pressing to obtain solid slag and primary filtrate with the carbonate content of 0.08g/L, wherein the primary filtrate contains 6.9L;
s4: and (3) pulping the solid slag, washing the solid slag with water, and press-filtering to remove lithium ions entrained in the solid slag, wherein the obtained secondary filtrate is evaporated and concentrated and returned to the lithium precipitation mother liquor to continuously remove carbonate, and the solid-liquid ratio of the solid slag to water in the pulping water washing process is 1:3.
In the embodiment, 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 1.1:1, and the molar ratio of aluminum ions to carbonate in the lithium precipitation mother liquor is calculated to be 0.09:1.
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 radical in the lithium precipitation mother liquor is 29.8g/L;
s2: the pH value of the solution is regulated to be 12.2, and the reaction is carried out for 2 hours at the temperature of 80 ℃;
s2: cooling the reacted solution to 25 ℃, and carrying out primary separation on the reacted liquid and solid through filter pressing to obtain 1.9L of calcium carbonate slag and filtrate with the carbonate content of 3.6 g/L;
s4: and (3) pulping the calcium carbonate slag, washing the calcium carbonate slag with water, and carrying out filter pressing to remove lithium ions entrained in the calcium carbonate slag, wherein the obtained secondary filtrate is evaporated and concentrated and returned to the lithium precipitation mother liquor to continuously remove carbonate, and the solid-liquid ratio of the calcium carbonate slag to water in the pulping water washing process is 1:3.
And (3) performance detection:
detecting the carbonate content in the primary filtrate by adopting a double-indicator neutralization method; the content of metal ions in the primary filtrate is detected by adopting an atomic absorption spectrometry.
The contents of ions in the primary filtrate after removal of 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 CO in the lithium precipitation mother solution is 3 2- Content of (C) and CO in the primary filtrate after removal of carbonate 3 2- The difference of the content of (2) and CO in the lithium precipitation mother solution 3 2- Is a ratio of the contents of (3).
Analysis:
table 1 is a statistical table of the content of each ion in the primary filtrate after the carbonic acid is removed in examples 1 to 6 and comparative examples 1 to 2, and as can be seen from examples 1 to 6, the content of carbonate in the lithium precipitation mother liquor can be obviously reduced by using the nickel cobalt manganese wastewater to react with the lithium precipitation mother liquor or firstly using aluminum salt and the lithium precipitation mother liquor to react with the nickel cobalt manganese wastewater after pre-reaction, and when the mole 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 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, carbonate in the lithium precipitation mother liquor can be removed well, but more nickel ions, manganese ions and cobalt ions are introduced into primary filtrate.
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 the aluminum ions and the nickel ions, the manganese ions and the cobalt ions, and the aluminum ions also affect the formation of nickel cobalt manganese carbonate slag.
As can be seen from the data of comparative example 2, carbonate in the lithium precipitation mother liquor cannot be removed well by simply using calcium oxide, and relatively more calcium ions remain in the obtained primary filtrate.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (10)
1. A method for removing carbonate from lithium precipitation mother liquor, which is characterized by comprising the following steps:
mixing the lithium precipitation mother liquor and nickel cobalt manganese wastewater, and then carrying out a reaction, and removing carbonate in the lithium precipitation mother liquor to prepare nickel cobalt manganese carbonate slag;
pre-reacting the lithium precipitation mother liquor and aluminum salt in advance before mixing and reacting the lithium precipitation mother liquor and nickel cobalt manganese wastewater;
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;
the temperature of the reaction is 50-150 ℃; the reaction time is 1-5h;
the aluminum salt comprises at least one of aluminum sulfate and aluminum chloride;
the molar ratio of aluminum ions in the aluminum salt to carbonate in the lithium precipitation mother solution is (0.05-0.15): 1;
the temperature of the pre-reaction is 50-150 ℃; the pre-reaction time is 0.5-3h.
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 (0.8-1.4): 1.
3. The method according to claim 1, wherein after the reaction, liquid and solid in the reaction system are separated once to obtain primary filtrate and nickel cobalt manganese carbonate slag.
4. A method according to claim 3, characterized in that the nickel cobalt manganese carbonate slag is subjected to pulping water washing.
5. The method according to claim 4, wherein the pulping water is washed and then subjected to secondary separation to obtain secondary filtrate and nickel cobalt manganese carbonate washing slag.
6. The method of claim 5, wherein the secondary filtrate is returned to the lithium precipitation mother liquor for reuse.
7. The method of claim 6, wherein the secondary filtrate is concentrated by evaporation before being returned to the lithium precipitation mother liquor.
8. The method of claim 4, wherein the pulping water wash comprises: and mixing the nickel cobalt manganese carbonate slag with water to form nickel cobalt manganese carbonate slurry.
9. The method of claim 8, wherein the solid to liquid ratio of nickel cobalt manganese carbonate slag to water is 1 (3-5).
10. The method according to claim 1, wherein the molar ratio of aluminum ions in the aluminum salt to carbonate in the lithium precipitation mother liquor is (0.08-0.12): 1.
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