CN113620321A - Method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation - Google Patents
Method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation Download PDFInfo
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- CN113620321A CN113620321A CN202111063462.4A CN202111063462A CN113620321A CN 113620321 A CN113620321 A CN 113620321A CN 202111063462 A CN202111063462 A CN 202111063462A CN 113620321 A CN113620321 A CN 113620321A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 92
- 238000001556 precipitation Methods 0.000 title claims abstract description 56
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 44
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000007788 liquid Substances 0.000 title claims abstract description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000000926 separation method Methods 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 19
- 150000003839 salts Chemical class 0.000 claims abstract description 19
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 229910052742 iron Inorganic materials 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 239000011734 sodium Substances 0.000 claims abstract description 13
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 12
- 238000001704 evaporation Methods 0.000 claims abstract description 7
- 230000008020 evaporation Effects 0.000 claims abstract description 7
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 7
- 239000012452 mother liquor Substances 0.000 claims description 98
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 40
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 238000006386 neutralization reaction Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- -1 aluminum ions Chemical class 0.000 claims description 12
- 239000011777 magnesium Substances 0.000 claims description 12
- 229910052749 magnesium Inorganic materials 0.000 claims description 12
- UOVHNSMBKKMHHP-UHFFFAOYSA-L potassium;sodium;sulfate Chemical compound [Na+].[K+].[O-]S([O-])(=O)=O UOVHNSMBKKMHHP-UHFFFAOYSA-L 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 9
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 9
- 235000011152 sodium sulphate Nutrition 0.000 claims description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001416 lithium ion Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 229910052629 lepidolite Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 5
- 238000005086 pumping Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052700 potassium Inorganic materials 0.000 abstract description 8
- 239000011591 potassium Substances 0.000 abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 7
- 239000011575 calcium Substances 0.000 abstract description 7
- 229910052791 calcium Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010413 mother solution Substances 0.000 abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 14
- 238000001514 detection method Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 4
- 229910052939 potassium sulfate Inorganic materials 0.000 description 4
- 235000011151 potassium sulphates Nutrition 0.000 description 4
- 239000000203 mixture Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- LPUQAYUQRXPFSQ-DFWYDOINSA-M monosodium L-glutamate Chemical compound [Na+].[O-]C(=O)[C@@H](N)CCC(O)=O LPUQAYUQRXPFSQ-DFWYDOINSA-M 0.000 description 1
- 235000013923 monosodium glutamate Nutrition 0.000 description 1
- 239000004223 monosodium glutamate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The invention discloses a method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation, which comprises the following steps: 1) adding sulfuric acid to adjust the pH value; 2) adding caustic soda flakes, and filtering with a plate frame to remove impurities; 3) MVR evaporation concentration and centrifugal separation; 4) settling and centrifugal separation; 5) filtering by a plate frame; 6) secondary lithium precipitation; 7) and returning the mother solution after secondary lithium precipitation to the step 1) for secondary lithium precipitation circularly. The invention can prepare the industrial special grade lithium carbonate product with white color and main content of more than 99.35 percent from the lithium liquid with low content after the primary lithium precipitation, and the contents of impurities such as iron, calcium, potassium, sodium, sulfate radical and the like of the product all meet the requirements of industrial special grade; the sodium carbonate and potassium carbonate mixed salt obtained in the secondary lithium precipitation process can be recycled, so that the production cost is saved.
Description
Technical Field
The invention relates to the technical field of lithium carbonate purification, in particular to a method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation.
Background
Lepidolite is an important mineral resource and contains abundant rare metal materials, lithium, sodium, potassium, rubidium, cesium, aluminum and the like. Lithium and its salts are the basic materials of new energy of lithium battery, and are praised by scientists as "industrial monosodium glutamate, energy star", which are the best materials for producing lithium ion battery, and are important metals for developing new energy and new materials.
The process for preparing lithium carbonate by lepidolite comprises a lime method, a sulfate method, a chlorination method and the like, wherein in the process for preparing lithium carbonate by adopting the sulfate method, a mother solution after lithium precipitation is obtained by centrifugal separation after a primary lithium precipitation reaction, the mother solution after lithium precipitation also contains part of lithium ions, and in order to improve the recovery rate of lithium, the mother solution after lithium precipitation needs to be subjected to a secondary lithium precipitation reaction to recover residual lithium ions, so that the resource waste is avoided. The existing secondary lithium precipitation process comprises the following steps: 1) adding sulfuric acid to adjust the pH value; 2) MVR evaporation concentration, centrifugal filtration; 3) and (5) secondary lithium precipitation reaction. However, the lithium solution after the primary lithium deposition has the problems of low lithium content, high content of impurities such as sodium, potassium, calcium, magnesium, iron and the like, and the secondary recovery of lithium carbonate can cause low purity and high content of impurities of lithium carbonate.
Disclosure of Invention
In order to solve the problems that most of lithium carbonate prepared by the existing secondary lithium precipitation process is reddish in color and impurities such as iron, calcium, potassium, sodium, sulfate radicals and the like cannot meet the industrial grade requirement through detection, the invention improves the existing process, and provides a method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation.
In order to achieve the purpose, the invention provides the following technical scheme:
a method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation is characterized by comprising the following steps:
(1) adding sulfuric acid into the mother liquor after the primary lithium precipitation to adjust the pH value to 5.5-6.5, and removing carbonate in the mother liquor to obtain a lithium precipitation neutralization mother liquor;
(2) adding caustic soda flakes into the precipitated lithium neutralization mother liquor, adjusting the pH value to 11-12, reacting the caustic soda flakes with a small amount of iron, magnesium and aluminum ions in the precipitated lithium neutralization mother liquor, conveying the mother liquor to a first plate-and-frame filter for filtering after the reaction is finished, and removing the iron, magnesium and aluminum ions in the mother liquor to obtain the impurity-removed mother liquor;
(3) pumping the mother liquor after impurity removal into a sodium sulfate MVR high-efficiency evaporator for concentration, performing centrifugal separation after concentration to obtain sodium potassium sulfate mixed salt and a lithium sulfate mother liquor I, and controlling Li in the lithium sulfate mother liquor I2The concentration of O is 15-20 g/L;
(4) conveying the lithium sulfate mother liquor I to a sodium separation mother liquor tank for sedimentation, and then carrying out centrifugal separation to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor II;
(5) conveying the lithium sulfate mother liquor II to a second plate-and-frame filter for filtering to obtain solid residues and clean lithium sulfate mother liquor III;
(6) adding a saturated sodium carbonate solution into the lithium sulfate mother liquor III, carrying out secondary lithium precipitation reaction at the temperature of 80-95 ℃ for 3-5 hours, and filtering and separating by using a centrifuge after the reaction is finished to obtain mother liquor after lithium precipitation and wet lithium carbonate;
(7) stirring and washing wet lithium carbonate with pure water for 2 times, drying and crushing to obtain industrial special-grade lithium carbonate;
(8) and (4) centrifugally separating the mother liquor obtained after lithium precipitation in the step (6) to repeat the steps (1) to (7).
Preferably, the settling time in the step (4) is set to be 3-5 h.
Preferably, the molar mass ratio of the lithium ions in the lithium sulfate solution in the step (6) to the carbonate ions in the sodium carbonate solution is controlled to be 1: 4.2-4.5.
Preferably, the agitation washing in the step (7) is that pure water is added according to the solid-to-liquid ratio of 1: 3-5, and the agitation washing is carried out for 30-60 min at the temperature of over 90 ℃.
Preferably, the condensed water obtained by condensing the water vapor generated by the evaporation and concentration in the step (3) through a condenser is recycled.
Preferably, the sodium sulfate and potassium sulfate mixed salt obtained through centrifugal separation in the step (3) and the step (4) is collected by a storage tank and can be used as a sulfate auxiliary material in the process of preparing lithium carbonate by the lepidolite sulfate roasting method.
Compared with the prior art, the invention has the beneficial effects that: 1) residual iron, magnesium and aluminum ions in the mother liquor can be removed by adding caustic soda flakes into the lithium precipitation neutralization mother liquor, and the content of the iron ions reaches the industrial grade requirement; 2) through twice centrifugal separation and twice plate-frame filtration, most of calcium, potassium, sodium, sulfate radical and other impurities in the mother liquor can be removed through lithium precipitation neutralization, so that the calcium, potassium, sodium, sulfate radical and other impurities in the mother liquor can meet the industrial special-grade requirements, and 3) an industrial special-grade lithium carbonate product which is white in color and has the main content of 99.35% can be prepared through the twice lithium precipitation reaction; 4) the sodium carbonate and potassium carbonate mixed salt obtained by centrifugal separation and plate-frame filtration can be recycled, and the production cost is saved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation comprises the following steps:
(1) adding sulfuric acid into the mother liquor after the primary lithium precipitation to adjust the pH value to 5.5, and removing carbonate in the mother liquor to obtain a lithium precipitation neutralization mother liquor;
(2) adding caustic soda flakes into the precipitated lithium neutralization mother liquor, adjusting the pH value to 11-12, reacting the caustic soda flakes with a small amount of iron, magnesium and aluminum ions in the precipitated lithium neutralization mother liquor for 30min, conveying the mother liquor to a first plate-and-frame filter for filtering after the reaction is finished, and removing the iron, magnesium and aluminum ions in the mother liquor to obtain the mother liquor after impurity removal;
(3) pumping the mother liquor after impurity removal into a sodium sulfate MVR high-efficiency evaporator for concentration, performing centrifugal separation after concentration to obtain sodium potassium sulfate mixed salt and a lithium sulfate mother liquor I, and controlling Li in the lithium sulfate mother liquor I2The concentration of O is 15 g/L;
(4) conveying the lithium sulfate mother liquor I to a sodium separation mother liquor tank for sedimentation for 3 hours, and then carrying out centrifugal separation to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor II;
(5) conveying the lithium sulfate mother liquor II to a second plate-and-frame filter for filtering to obtain solid residues and clean lithium sulfate mother liquor III;
(6) adding a saturated sodium carbonate solution into the lithium sulfate mother liquor III, controlling the molar mass ratio of lithium ions in the lithium sulfate solution to carbonate ions in the sodium carbonate solution to be 1: 4.2, carrying out secondary lithium precipitation reaction at the temperature of 80 ℃ for 3 hours, and filtering and separating by using a centrifuge after the reaction is finished to obtain mother liquor after lithium precipitation and wet lithium carbonate;
(7) stirring and washing wet lithium carbonate with pure water for 2 times, wherein the stirring and washing is to add pure water according to a solid-to-liquid ratio of 1:3, stirring and washing for 30min at the temperature of more than 90 ℃, drying and crushing after stirring and washing for 2 times to obtain industrial special-grade lithium carbonate;
(8) and (4) centrifugally separating the mother liquor obtained after lithium precipitation in the step (6) to repeat the steps (1) to (7).
Preferably, the condensed water obtained by condensing the water vapor generated by evaporation and concentration in the step (3) by a condenser is recycled.
Preferably, the sodium sulfate and potassium sulfate mixed salt obtained through centrifugal separation in the step (3) and the step (4) is collected by a storage tank and can be used as a sulfate auxiliary material in the process of preparing lithium carbonate by the lepidolite sulfate roasting method.
Example two
A method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation comprises the following steps:
(1) adding sulfuric acid into the mother liquor after the primary lithium precipitation to adjust the pH value to 6, and removing carbonate in the mother liquor to obtain a lithium precipitation neutralization mother liquor;
(2) adding caustic soda flakes into the precipitated lithium neutralization mother liquor, adjusting the pH value to 11-12, reacting the caustic soda flakes with a small amount of iron, magnesium and aluminum ions in the precipitated lithium neutralization mother liquor for 45min, conveying the mother liquor to a first plate-and-frame filter for filtering after the reaction is finished, and removing the iron, magnesium and aluminum ions in the mother liquor to obtain the mother liquor after impurity removal;
(3) pumping the mother liquor after impurity removal into a sodium sulfate MVR high-efficiency evaporator for concentration, performing centrifugal separation after concentration to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor I, and controlling the lithium sulfate mother liquorLi in liquid one2The concentration of O is 18 g/L;
(4) conveying the lithium sulfate mother liquor I to a sodium separation mother liquor tank for sedimentation for 4 hours, and then carrying out centrifugal separation to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor II;
(5) conveying the lithium sulfate mother liquor II to a second plate-and-frame filter for filtering to obtain solid residues and clean lithium sulfate mother liquor III;
(6) adding a saturated sodium carbonate solution into the lithium sulfate mother liquor III, controlling the molar mass ratio of lithium ions in the lithium sulfate solution to carbonate ions in the sodium carbonate solution to be 1: 4.3, carrying out secondary lithium precipitation reaction at the temperature of 90 ℃ for 4 hours, and filtering and separating by using a centrifuge after the reaction is finished to obtain mother liquor after lithium precipitation and wet lithium carbonate;
(7) stirring and washing wet lithium carbonate with pure water for 2 times, wherein the stirring and washing is to add pure water according to a solid-to-liquid ratio of 1:4, stirring and washing for 45min at the temperature of more than 90 ℃, drying and crushing after stirring and washing for 2 times to obtain industrial special-grade lithium carbonate;
(8) and (4) centrifugally separating the mother liquor obtained after lithium precipitation in the step (6) to repeat the steps (1) to (7).
Preferably, the condensed water obtained by condensing the water vapor generated by evaporation and concentration in the step (3) by a condenser is recycled.
Preferably, the sodium sulfate and potassium sulfate mixed salt obtained through centrifugal separation in the step (3) and the step (4) is collected by a storage tank and can be used as a sulfate auxiliary material in the process of preparing lithium carbonate by the lepidolite sulfate roasting method.
Example three:
a method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation comprises the following steps:
(1) adding sulfuric acid into the mother liquor after the primary lithium precipitation to adjust the pH value to 6.5, and removing carbonate in the mother liquor to obtain a lithium precipitation neutralization mother liquor;
(2) adding caustic soda flakes into the precipitated lithium neutralization mother liquor, adjusting the pH value to 11-12, reacting the caustic soda flakes with a small amount of iron, magnesium and aluminum ions in the precipitated lithium neutralization mother liquor for 60min, conveying the mother liquor to a first plate-and-frame filter for filtering after the reaction is finished, and removing the iron, magnesium and aluminum ions in the mother liquor to obtain the mother liquor after impurity removal;
(3) pumping the mother liquor after impurity removal into a sodium sulfate MVR high-efficiency evaporator for concentration, performing centrifugal separation after concentration to obtain sodium potassium sulfate mixed salt and a lithium sulfate mother liquor I, and controlling Li in the lithium sulfate mother liquor I2The concentration of O is 20 g/L;
(4) conveying the lithium sulfate mother liquor I to a sodium separation mother liquor tank for sedimentation for 5 hours, and then carrying out centrifugal separation to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor II;
(5) conveying the lithium sulfate mother liquor II to a second plate-and-frame filter for filtering to obtain solid residues and clean lithium sulfate mother liquor III;
(6) adding a saturated sodium carbonate solution into the lithium sulfate mother liquor III, controlling the molar mass ratio of lithium ions in the lithium sulfate solution to carbonate ions in the sodium carbonate solution to be 1: 4.5, carrying out secondary lithium precipitation reaction at the temperature of 95 ℃ for 5 hours, and filtering and separating by using a centrifuge after the reaction is finished to obtain mother liquor after lithium precipitation and wet lithium carbonate;
(7) stirring and washing wet lithium carbonate with pure water for 2 times, wherein the stirring and washing is to add pure water according to a solid-to-liquid ratio of 1: 5 and stir and wash the mixture for 60min at the temperature of more than 90 ℃, and after stirring and washing for 2 times, drying and crushing the mixture to obtain industrial special-grade lithium carbonate;
(8) and (4) centrifugally separating the mother liquor obtained after lithium precipitation in the step (6) to repeat the steps (1) to (7).
Preferably, the condensed water obtained by condensing the water vapor generated by evaporation and concentration in the step (3) by a condenser is recycled.
Preferably, the sodium sulfate and potassium sulfate mixed salt obtained through centrifugal separation in the step (3) and the step (4) is collected by a storage tank and can be used as a sulfate auxiliary material in the process of preparing lithium carbonate by the lepidolite sulfate roasting method.
The following are data detection comparisons:
the first table shows the quality detection data of the secondary lithium deposition product prepared by the prior process in month 4 in 2020 and in month 5 in 2020, and the second table shows the quality detection data of the secondary lithium deposition product prepared by the embodiment of the invention in month 12 in 2020 and in month 1 in 2021.
Watch 1
Watch two
As can be seen from the detection data in the first and second tables, the main content of lithium carbonate in the secondary lithium deposition product is increased by 0.95% -1.07%, the color is changed from reddish to white, and impurities such as iron, calcium, potassium, sodium, sulfate radicals and the like are changed from the condition that the impurities do not meet the industrial requirements to the condition that the impurities such as iron, calcium, potassium, sodium, sulfate radicals and the like meet the industrial special requirements.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. A method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation is characterized by comprising the following steps:
(1) adding sulfuric acid into the mother liquor after the primary lithium precipitation to adjust the pH value to 5.5-6.5, and removing carbonate in the mother liquor to obtain a lithium precipitation neutralization mother liquor;
(2) adding caustic soda flakes into the precipitated lithium neutralization mother liquor, adjusting the pH value to 11-12, reacting the caustic soda flakes with a small amount of iron, magnesium and aluminum ions in the precipitated lithium neutralization mother liquor, conveying the mother liquor to a first plate-and-frame filter for filtering after the reaction is finished, and removing the iron, magnesium and aluminum ions in the mother liquor to obtain the impurity-removed mother liquor;
(3) pumping the mother liquor after impurity removal into a sodium sulfate MVR high-efficiency evaporator for concentration, performing centrifugal separation after concentration to obtain sodium potassium sulfate mixed salt and a lithium sulfate mother liquor I, and controlling Li in the lithium sulfate mother liquor I2The concentration of O is 15-20 g/L;
(4) conveying the lithium sulfate mother liquor I to a sodium separation mother liquor tank for sedimentation, and then carrying out centrifugal separation to obtain sodium potassium sulfate mixed salt and lithium sulfate mother liquor II;
(5) conveying the lithium sulfate mother liquor II to a second plate-and-frame filter for filtering to obtain solid residues and clean lithium sulfate mother liquor III;
(6) adding a saturated sodium carbonate solution into the lithium sulfate mother liquor III, carrying out secondary lithium precipitation reaction at the temperature of 80-95 ℃ for 3-5 hours, and filtering and separating by using a centrifuge after the reaction is finished to obtain mother liquor after lithium precipitation and wet lithium carbonate;
(7) stirring and washing wet lithium carbonate with pure water for 2 times, drying and crushing to obtain industrial special-grade lithium carbonate;
(8) and (4) centrifugally separating the mother liquor obtained after lithium precipitation in the step (6) to repeat the steps (1) to (7).
2. The method for preparing industrial special grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation according to claim 1, wherein the method comprises the following steps: and (4) setting the settling time to be 3-5 h.
3. The method for preparing industrial special grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation according to claim 1, wherein the method comprises the following steps: and (3) controlling the molar mass ratio of the lithium ions in the lithium sulfate solution in the step (6) to the carbonate ions in the sodium carbonate solution to be 1: 4.2-4.5.
4. The method for preparing industrial special grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation according to claim 1, wherein the method comprises the following steps: the step (7) of agitation washing is to add pure water according to the solid-to-liquid ratio of 1: 3-5 and to agitate and wash for 30-60 min at the temperature of more than 90 ℃.
5. The method for preparing industrial special grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation according to claim 1, wherein the method comprises the following steps: and (4) condensing the water vapor generated by evaporation and concentration in the step (3) by using a condenser to obtain condensed water which is recycled.
6. The method for preparing industrial special grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation according to claim 1, wherein the method comprises the following steps: and (4) collecting the sodium potassium sulfate mixed salt obtained by centrifugal separation in the steps (3) and (4) by using a storage tank, and using the sodium potassium sulfate mixed salt as a sulfate auxiliary material in the process of preparing lithium carbonate by using a lepidolite sulfate roasting method.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202111063462.4A CN113620321A (en) | 2021-09-10 | 2021-09-10 | Method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111063462.4A CN113620321A (en) | 2021-09-10 | 2021-09-10 | Method for preparing industrial special-grade lithium carbonate from low-concentration lithium liquid after primary lithium precipitation |
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787784A (en) * | 2015-03-18 | 2015-07-22 | 江西赣锋锂业股份有限公司 | Method for preparing lithium salt through recycling lithium fluoride-containing waste material material |
| CN108002411A (en) * | 2017-12-12 | 2018-05-08 | 福州大学 | A kind of method that defluorinate lepidolite multistage pressure tank dissolution carries lithium |
| CN109437255A (en) * | 2018-11-25 | 2019-03-08 | 长沙市原鹏化工科技有限公司 | A method of extracting lithium salts from lithium ore |
| CN110104815A (en) * | 2019-05-28 | 2019-08-09 | 南京南环水务科技有限公司 | A kind of method and system from mine water recycling potassium |
| CN110550643A (en) * | 2019-09-30 | 2019-12-10 | 山东瑞福锂业有限公司 | process for recovering and preparing battery-grade lithium salt from sodium-separating mother liquor |
| CA3109244A1 (en) * | 2018-08-09 | 2020-02-13 | DAI, Ailin | Method for greatly reducing sulphate content in various levels of lithium carbonate in spodumene sulfuric acid method |
| CN110923452A (en) * | 2019-11-11 | 2020-03-27 | 中南大学 | Process for recovering potassium and sodium salts from lithium-precipitated liquid of lepidolite by using ethanol |
| CN112142080A (en) * | 2020-09-28 | 2020-12-29 | 江西永兴特钢新能源科技有限公司 | Method for preparing battery-grade lithium carbonate by freezing, circulating and recycling lithium precipitation concentrated mother solution |
-
2021
- 2021-09-10 CN CN202111063462.4A patent/CN113620321A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104787784A (en) * | 2015-03-18 | 2015-07-22 | 江西赣锋锂业股份有限公司 | Method for preparing lithium salt through recycling lithium fluoride-containing waste material material |
| CN108002411A (en) * | 2017-12-12 | 2018-05-08 | 福州大学 | A kind of method that defluorinate lepidolite multistage pressure tank dissolution carries lithium |
| CA3109244A1 (en) * | 2018-08-09 | 2020-02-13 | DAI, Ailin | Method for greatly reducing sulphate content in various levels of lithium carbonate in spodumene sulfuric acid method |
| CN109437255A (en) * | 2018-11-25 | 2019-03-08 | 长沙市原鹏化工科技有限公司 | A method of extracting lithium salts from lithium ore |
| CN110104815A (en) * | 2019-05-28 | 2019-08-09 | 南京南环水务科技有限公司 | A kind of method and system from mine water recycling potassium |
| CN110550643A (en) * | 2019-09-30 | 2019-12-10 | 山东瑞福锂业有限公司 | process for recovering and preparing battery-grade lithium salt from sodium-separating mother liquor |
| CN110923452A (en) * | 2019-11-11 | 2020-03-27 | 中南大学 | Process for recovering potassium and sodium salts from lithium-precipitated liquid of lepidolite by using ethanol |
| CN112142080A (en) * | 2020-09-28 | 2020-12-29 | 江西永兴特钢新能源科技有限公司 | Method for preparing battery-grade lithium carbonate by freezing, circulating and recycling lithium precipitation concentrated mother solution |
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