CN115536046A - Method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution - Google Patents
Method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution Download PDFInfo
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 203
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 196
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 195
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 152
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 152
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 134
- 238000006243 chemical reaction Methods 0.000 claims abstract description 101
- 239000012452 mother liquor Substances 0.000 claims abstract description 80
- 238000001556 precipitation Methods 0.000 claims abstract description 59
- 238000009993 causticizing Methods 0.000 claims abstract description 34
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 23
- 238000002425 crystallisation Methods 0.000 claims abstract description 22
- 230000008025 crystallization Effects 0.000 claims abstract description 22
- 238000001914 filtration Methods 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 18
- 239000007787 solid Substances 0.000 claims abstract description 18
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 16
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 238000005261 decarburization Methods 0.000 claims abstract description 11
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 10
- 239000010413 mother solution Substances 0.000 claims abstract description 6
- 239000007791 liquid phase Substances 0.000 claims abstract description 4
- 238000000197 pyrolysis Methods 0.000 claims description 51
- 238000003763 carbonization Methods 0.000 claims description 38
- 239000002002 slurry Substances 0.000 claims description 35
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 238000004537 pulping Methods 0.000 claims description 22
- 230000035484 reaction time Effects 0.000 claims description 22
- 238000001704 evaporation Methods 0.000 claims description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 17
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 239000011575 calcium Substances 0.000 claims description 7
- 238000005262 decarbonization Methods 0.000 claims description 7
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000001376 precipitating effect Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 230000000694 effects Effects 0.000 description 12
- 238000004064 recycling Methods 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002893 slag Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 239000011593 sulfur Substances 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
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
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- 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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- 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)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution, which comprises the following steps: and (3) precipitating lithium: after the lithium-containing solution reacts with water-soluble carbonate, filtering the reaction solution to obtain crude lithium carbonate solid and a lithium precipitation mother solution; causticizing: after the crude lithium carbonate and calcium hydroxide react in a liquid phase, removing impurities from the reaction liquid, and carrying out evaporative crystallization to obtain a lithium hydroxide solid; and (3) utilizing lithium precipitation mother liquor: and adding acid into the lithium precipitation mother liquor for decarburization, and combining the decarburized lithium precipitation mother liquor with the lithium-containing solution for reuse. The lithium carbonate and lithium hydroxide co-production device can co-produce two products of lithium carbonate and lithium hydroxide from a lithium-containing solution, flexibly allocate the output of the two products according to market price fluctuation, and maximize benefits.
Description
Technical Field
The invention relates to the technical field of lithium salt preparation, in particular to a method for co-producing lithium carbonate and lithium hydroxide by using lithium-containing solution.
Background
Lithium carbonate and lithium hydroxide are used as important compounds of lithium salt, wherein battery-grade lithium carbonate is widely used for preparing lithium iron phosphate anode materials, and battery-grade lithium hydroxide is applied to preparation of nickel cobalt lithium manganate ternary materials. Due to the fact that the lithium iron phosphate and the ternary precursor have good and bad performances and the market share is changed continuously, the prices of corresponding raw materials, namely battery-grade lithium carbonate and battery-grade lithium hydroxide, fluctuate along with the raw materials. Therefore, the invention provides a process capable of co-producing battery-grade lithium carbonate and battery-grade lithium hydroxide and flexibly adjusting the capacity of lithium carbonate and lithium hydroxide according to market demands, and the process has great market value.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for coproducing lithium carbonate and lithium hydroxide by using a lithium-containing solution, and solves the problem that the capacity of lithium carbonate and lithium hydroxide cannot be flexibly adjusted by using the conventional method for coproducing lithium carbonate and lithium hydroxide.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for co-producing lithium carbonate and lithium hydroxide with a lithium-containing solution, comprising the following steps:
and (3) precipitating lithium: after reacting a lithium-containing solution with water-soluble carbonate, filtering a reaction solution to obtain a crude lithium carbonate solid and a lithium precipitation mother solution;
causticizing: after partial crude lithium carbonate and calcium hydroxide react in a liquid phase, evaporating and crystallizing reaction liquid to obtain lithium hydroxide solid;
and (3) utilizing lithium precipitation mother liquor: and adding acid into the lithium precipitation mother liquor for decarburization, and combining the decarburized lithium precipitation mother liquor with the lithium-containing solution for reuse.
In alternative embodiments, the lithium-containing solution has a lithium content of 20 to 25g/L;
preferably, when the lithium content in the lithium-containing solution is lower than 20g/L, the lithium-containing solution is evaporated and concentrated to the lithium content of 20-25g/L.
In an alternative embodiment, in the lithium precipitation step, the water-soluble carbonate is sodium carbonate or potassium carbonate;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.8:1;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.6:1;
preferably, the water-soluble carbonate is added in the form of a solution in the lithium precipitation step;
preferably, the mass fraction of sodium carbonate in the sodium carbonate solution is 20-30%;
preferably, the lithium precipitation step is carried out for 30-120min at 60-90 ℃;
preferably, the reaction temperature of the lithium precipitation step is 80-90 ℃, and the reaction time is 90-120min;
preferably, the lithium precipitation step is used for stirring the reaction liquid at the stirring speed of 400-600rpm;
preferably, the lithium content in the lithium precipitation mother liquor is lower than 3g/L.
In an alternative embodiment, in the causticizing step, the molar ratio of calcium hydroxide to lithium carbonate in the crude lithium carbonate is 1.0 to 1.5;
preferably, in the causticizing step, the molar ratio of calcium hydroxide to lithium carbonate is 1.1-1.2;
preferably, in the causticizing step, the reaction temperature is 50-80 ℃, and the reaction time is 30-120min;
preferably, in the causticizing step, the reaction temperature is 60-80 ℃, and the reaction time is 60-90min;
preferably, in the causticizing step, the reaction solution is stirred at the stirring speed of 400-600rpm;
preferably, in the causticizing step, before the evaporation and crystallization, the calcium in the reaction liquid is removed by using resin.
In an optional embodiment, the causticizing reaction is carried out after the coarse lithium carbonate and pure water are subjected to first pulping;
preferably, the mass ratio of the crude lithium carbonate to the pure water is 1:3-5, performing first pulping;
preferably, in the causticizing step, calcium hydroxide is mixed with crude lithium carbonate in the form of a calcium hydroxide solution;
preferably, before the causticizing step, washing crude lithium carbonate by pure water;
preferably, in the step of washing the crude lithium carbonate with pure water, the mass ratio of pure water to crude lithium carbonate is 5 to 10.
In an alternative embodiment, in the lithium precipitation mother liquor utilization step, acid is added to the lithium precipitation mother liquor until no bubble is generated in the solution:
preferably, the acid in the lithium precipitation mother liquor utilization step is sulfuric acid;
preferably, the lithium-containing solution is evaporated and concentrated to obtain a byproduct sodium sulfate decahydrate;
preferably, the reaction temperature of the decarbonization step is 60-70 ℃;
preferably, the lithium precipitation mother liquor after decarburization
The content is less than 0.5g/L.
In an alternative embodiment, a part of the crude lithium carbonate solid enters a causticizing step, and the other part of the crude lithium carbonate solid is purified, and the purifying step includes second pulping, carbonization and high-temperature pyrolysis to obtain purified lithium carbonate.
In an alternative embodiment, a second slurry is obtained after the second pulping is finished, and the mass concentration of lithium in the second slurry is 6.5-9.5g/L;
preferably, the crystallization mother liquor obtained after the evaporation crystallization is transferred to a second slurry for reuse;
preferably, the mass concentration of lithium in the second slurry is 8-9g/L g/L.
In an alternative embodiment, the carbonization is by introducing CO into the second slurry 2 Obtaining a lithium bicarbonate solution;
preferably, CO is introduced in the carbonization step 2 The pressure of (A) is 0.2-0.3Mpa;
preferably, the CO released by the decarbonation step 2 Introducing into the second slurry;
preferably, the reaction temperature of the carbonization step is 15-40 ℃, and the reaction time is 30-120min;
preferably, the reaction temperature of the carbonization step is 25-30 ℃, and the reaction time is 60-90min;
preferably, the carbonization step stirs the reaction solution at a stirring speed of 400-600rpm;
preferably, the carbonization step is followed by filtration of the reaction to obtain a lithium bicarbonate solution.
In an optional embodiment, the high-temperature pyrolysis is to heat the lithium bicarbonate solution to 70-95 ℃, react for 30-120min, and filter to obtain purified lithium carbonate;
preferably, in the high-temperature pyrolysis step, the temperature is 85-95 ℃, and the reaction time is 60-90min;
preferably, in the high-temperature pyrolysis step, the reaction solution is stirred at the stirring speed of 400-600rpm;
preferably, in the high-temperature pyrolysis step, purified lithium carbonate and a high-temperature pyrolysis mother liquor are obtained through filtration, and the high-temperature pyrolysis mother liquor is transferred to the second slurry for reuse;
preferably, in the high-temperature pyrolysis step, washing the solid obtained by filtering with water to remove impurities to obtain purified lithium carbonate;
preferably, the CO released in the high temperature pyrolysis step 2 Collecting and introducing the second slurry for reuse.
The invention has the following beneficial effects:
the lithium carbonate and lithium hydroxide co-production device can co-produce two products of lithium carbonate and lithium hydroxide from a lithium-containing solution, can flexibly allocate the yields of the two products according to market price fluctuation, and achieves benefit maximization.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart of the present application.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The embodiment provides a method for co-producing lithium carbonate and lithium hydroxide by using a lithium-containing solution, which comprises the following steps:
and (3) lithium deposition: after reacting a lithium-containing solution with water-soluble carbonate, filtering a reaction solution to obtain a crude lithium carbonate solid and a lithium precipitation mother solution;
causticizing: after part of the crude lithium carbonate reacts with calcium hydroxide in a liquid phase, evaporating and crystallizing the reaction liquid to obtain lithium hydroxide solid;
and (3) utilizing lithium precipitation mother liquor: and adding acid into the lithium precipitation mother liquor for decarbonization, and combining the decarbonized lithium precipitation mother liquor with the lithium-containing solution for reuse.
The method and the device adopt a high-temperature lithium precipitation method and a causticization method to co-produce two products, namely lithium carbonate and lithium hydroxide, and can be used for producing battery-grade lithium carbonate and battery-grade lithium hydroxide, wherein the distribution of coarse lithium carbonate can be flexibly allocated according to the fluctuation of the market prices of lithium carbonate and lithium hydroxide, so that the benefit maximization is realized; CO which can also be produced by the decarbonation reaction 2 The mass of the supplementary crude lithium carbonate required by the carbonization reaction is calculated according to the output, the lithium content in the crystallization mother liquor and the high-temperature pyrolysis mother liquor, and the cost is minimized.
The lithium precipitation is to drop excessive sodium carbonate solution into the concentrated mother liquor, white precipitate is continuously generated in the solution, namely lithium carbonate is generated, coarse lithium carbonate is obtained by filtration, and the high-temperature lithium precipitation method has the advantages of high conversion rate, high reaction speed and the like, and the reaction formula is as follows:
lithium hydroxide is prepared by causticizing lithium carbonate and calcium hydroxide solution at high temperature, filtering to obtain lithium hydroxide solution, and removing impurities before evaporating and crystallizing the reaction solution, wherein the reaction formula is as follows:
Ca(OH) 2 +Li 2 CO 3 →LiOH+CaCO 3 ↓
in other embodiments herein, the lithium-containing solution has a lithium content of 20 to 25g/L;
preferably, when the lithium content in the lithium-containing solution is lower than 20g/L, the lithium-containing solution is evaporated and concentrated to the lithium content of 20-25g/L.
The lithium-containing solution in the present application may be obtained by recovering lithium in a battery material, or may be obtained by extracting lithium from a lithium-containing ore such as spodumene.
The lithium content in the solution is relatively high, which is beneficial to the precipitation of the subsequent lithium carbonate; the lithium content is too high, the energy consumption of concentration is high, and the solubility of impurities in the solution is also high, so that the impurity content in the coarse lithium carbonate is relatively high, and the subsequent purification of the coarse lithium carbonate is not facilitated.
When lithium content was low in the solution after lithium-containing solution and the mother liquor that sinks lithium were merged, carried out the heavy lithium again after evaporating concentration to the solution, carried out the decarbonization to the mother liquor that sinks lithium in this application, can avoid sinking lithium mother liquor and carrying out the jam equipment when evaporating concentration after lithium-containing solution merges.
In other embodiments of the present application, in the step of precipitating lithium, the water-soluble carbonate is sodium carbonate or potassium carbonate, and potassium sulfate or sodium sulfate can be collected correspondingly;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.8:1;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.6:1, fully converting lithium into lithium carbonate;
preferably, in the step of precipitating lithium, water-soluble carbonate is added in the form of solution, so that the reaction rate of precipitating lithium is improved, the solution can be dropwise added into the lithium-containing solution, and the lithium carbonate crystal grains are prevented from being generated too fast, so that impurities enter lithium carbonate crystal lattices, and the product purity is improved conveniently;
preferably, the mass fraction of sodium carbonate in the sodium carbonate solution is 20-30%, which is beneficial to the subsequent precipitation of lithium carbonate;
preferably, the lithium precipitation step is carried out for 30-120min at 60-90 ℃;
preferably, the reaction temperature in the lithium precipitation step is 80-90 ℃, and the reaction time is 90-120min;
preferably, the lithium precipitation step is used for stirring the reaction liquid at the stirring speed of 400-600rpm;
preferably, the lithium content in the lithium precipitation mother liquor is lower than 3g/L.
In other embodiments herein, the causticizing step is carried out in a molar ratio of calcium hydroxide to lithium carbonate in the crude lithium carbonate of 1.0 to 1.5, with an excess of calcium hydroxide, such that lithium carbonate can be sufficiently converted to lithium hydroxide;
preferably, in the causticizing step, the molar ratio of calcium hydroxide to lithium carbonate is 1.1-1.2;
preferably, in the causticizing step, the reaction temperature is 50-80 ℃, and the reaction time is 30-120min;
preferably, in the causticizing step, the reaction temperature is 60-80 ℃, and the reaction time is 60-90min;
preferably, in the causticizing step, the reaction solution is stirred at the stirring speed of 400-600rpm;
preferably, in the causticizing step, before the evaporation and crystallization, the calcium in the reaction liquid is removed by using resin.
The method comprises the steps of reacting high-purity lithium carbonate with a calcium hydroxide aqueous solution, separating and removing impurities to obtain a high-purity lithium hydroxide solution, and evaporating and crystallizing to obtain a battery-grade lithium hydroxide solid.
In other embodiments of the present application, the causticizing reaction is performed after the first slurry preparation is performed on the coarse lithium carbonate and the pure water;
preferably, the mass ratio of the crude lithium carbonate to the pure water is 1:3-5, performing first pulping;
preferably, in the causticizing step, calcium hydroxide is mixed with crude lithium carbonate in the form of a calcium hydroxide solution;
preferably, before the causticizing step, washing crude lithium carbonate by using pure water;
preferably, in the step of washing the crude lithium carbonate with pure water, the mass ratio of pure water to crude lithium carbonate is 5 to 10.
After the content of impurities such as Na, S and the like in part of the crude lithium carbonate is reduced by washing, pure water is used for pulping, and causticization reaction is carried out on the crude lithium carbonate and a calcium hydroxide solution at high temperature, so that the content of the impurities in the product is reduced. The crude lithium carbonate reacts with the calcium hydroxide solution, and the homogeneous reaction is favorable for improving the reaction rate.
In other embodiments of the present application, in the lithium deposition mother liquor utilization step, acid is added to the lithium deposition mother liquor until no bubble is generated in the solution:
preferably, the acid in the lithium precipitation mother liquor utilization step is sulfuric acid, which is beneficial to obtaining a byproduct, namely sodium sulfate decahydrate;
preferably, the lithium-containing solution is evaporated and concentrated to obtain a byproduct sodium sulfate decahydrate;
preferably, the reaction temperature of the decarburization step is 60-70 ℃, which is beneficial to accelerating the decarburization speed of the solution;
preferably, the lithium precipitation mother liquor after decarburization
The content is less than 0.5g/L. The lithium deposition mother liquor contains a large amount of lithium deposition mother liquor due to the excessive sodium carbonate solution in the lithium deposition reaction
Dilute acid is added to remove the CO to generate a large amount of CO 2 The reaction formula is as follows:
the present application also applies to CO of the decarbonation reaction 2 The mass of the supplementary crude lithium carbonate required by the carbonization reaction is calculated according to the output, the lithium content in the crystallization mother liquor and the high-temperature pyrolysis mother liquor, and the cost is minimized.
In other embodiments of the present application, a portion of the crude lithium carbonate solids is subjected to a causticizing step, and another portion is subjected to purification, wherein the purification step includes a second pulping step, carbonization, and high temperature pyrolysis to obtain purified lithium carbonate.
The existing production methods of battery-grade lithium carbonate mainly comprise a high-temperature lithium precipitation method, a carbonization decomposition method and the like. The high-temperature lithium precipitation method has the advantages of high conversion rate, high reaction speed and the like, but the total mass fraction of sodium and sulfur in the product is higher than 1 percent, so that the problem of overhigh content of sodium impurities in the product exists; the carbonization decomposition method can decompose the lithium bicarbonate in a heating mode to generate the battery-grade lithium carbonate, the total mass fraction of the sodium and the sulfur of the product is lower than 0.2 percent, and the method has the advantages of simple operation and high product purity. The application creatively combines the lithium carbonate and the lithium carbonate to obtain the high-purity lithium carbonate.
In other embodiments of the present application, a second slurry is obtained after the second pulping is finished, and the mass concentration of lithium in the second slurry is 6.5-9.5g/L;
preferably, the crystallization mother liquor obtained after the evaporation crystallization is transferred to the second slurry for reuse;
preferably, the mass concentration of lithium in the second slurry is 8-9g/L g/L.
In other embodiments of the present application, the carbonizing is by introducing CO into the second slurry 2 Obtaining a lithium bicarbonate solution;
preferably, CO is introduced in the carbonization step 2 The pressure of (A) is 0.2-0.3Mpa;
preferably, the CO released by the decarbonation step 2 Introducing into the second slurry;
preferably, the reaction temperature of the carbonization step is 15-40 ℃, and the reaction time is 30-120min;
preferably, the reaction temperature of the carbonization step is 25-30 ℃, and the reaction time is 60-90min;
preferably, the carbonization step stirs the reaction solution at a stirring speed of 400-600rpm;
preferably, the carbonization step is followed by filtration of the reaction to obtain a lithium bicarbonate solution.
Mixing part of crude lithium carbonate with crystallization mother liquor and high-temperature pyrolysis mother liquor to prepare pulp, and continuously introducing excessive CO 2 Obtaining a lithium bicarbonate solution and insoluble impurities, wherein the insoluble impurities are mainly compounds containing Ca, mg and Si, and the reaction formula is as follows:
Li 2 CO 3 +CO 2 +H 2 O→2LiHCO 3
in other embodiments of the present application, the high-temperature pyrolysis is to heat the lithium bicarbonate solution to 70-95 ℃, react for 30-120min, and filter to obtain purified lithium carbonate;
preferably, in the high-temperature pyrolysis step, the temperature is 85-95 ℃, and the reaction time is 60-90min;
preferably, in the high-temperature pyrolysis step, the reaction solution is stirred at the stirring speed of 400-600rpm;
preferably, in the high-temperature pyrolysis step, purified lithium carbonate and a high-temperature pyrolysis mother liquor are obtained through filtration, and the high-temperature pyrolysis mother liquor is transferred to the second slurry for reuse;
preferably, in the high-temperature pyrolysis step, washing the solid obtained by filtering with water to remove impurities to obtain purified lithium carbonate;
preferably, the CO released in the high temperature pyrolysis step 2 Collecting and introducing the second slurry for reuse.
Heating and decomposing the filtered and impurity-removed lithium bicarbonate solution to obtain high-purity lithium carbonate, pyrolysis mother liquor and CO 2 Recycling of pyrolysis mother liquor and pulping with crude lithium carbonate, CO 2 Recycling the mixture to the front end carbonization reaction, wherein the reaction formula is as follows:
the application discloses a method for co-producing lithium carbonate and lithium hydroxide by using lithium-containing solutionThe process flow chart is shown in figure 1, firstly, lithium-containing solution is evaporated and concentrated to obtain high-lithium concentrated mother liquor, a certain amount of sodium carbonate solution is added into the concentrated mother liquor to carry out high-temperature lithium precipitation reaction, crude lithium carbonate precipitation and lithium precipitation mother liquor are obtained by filtration, and the lithium precipitation mother liquor is subjected to acid decarbonization to obtain a large amount of CO 2 Gas and lithium-containing mother liquor, in which CO 2 The method is used for subsequent carbonization reaction to realize recycling of carbon resources, the lithium-containing mother liquor enters an evaporation system again for concentration to realize closed-loop recycling of lithium resources, and a byproduct sodium sulfate decahydrate is obtained at the same time; one part of coarse lithium carbonate obtained by high-temperature lithium deposition is subjected to causticization reaction to prepare battery-grade lithium hydroxide, the other part of coarse lithium carbonate is subjected to carbonization and high-temperature pyrolysis reaction to prepare battery-grade lithium carbonate, and meanwhile, the crystallization mother liquor and the high-temperature pyrolysis mother liquor of the lithium hydroxide solution are returned to be used for coarse lithium carbonate pulping, so that the use amount of pure water is saved, and the recycling of lithium resources is realized.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment of the invention provides a method for coproducing lithium carbonate and lithium hydroxide by using lithium-containing solution, and particularly provides a method for coproducing battery-grade lithium carbonate and battery-grade lithium hydroxide by using lithium-containing solution, which comprises the following steps:
(1) Taking a certain amount of concentrated lithium-containing mother liquor, wherein the lithium content is 21.3g/L, dropwise adding a 30wt% sodium carbonate solution into the lithium-containing mother liquor, and the molar ratio of the sodium carbonate dosage to the Li content in the solution is 0.6:1, stirring and reacting at 85 ℃ and 400rpm for 120min, filtering to obtain crude lithium carbonate solid, carrying out decarburization reaction on lithium precipitation mother liquor, and then carrying out decarburization reaction on the lithium precipitation mother liquor
The content is 15g/L;
(2) Slowly dripping concentrated sulfuric acid into the lithium precipitation mother liquor at 65 ℃ until no bubble is generated in the solution, and collecting CO in the reaction process 2 Purifying and purifying the solution for subsequent carbonization reaction, returning the lithium-containing mother liquor to an evaporation system again to obtain a byproduct sodium sulfate decahydrate, wherein the sodium sulfate decahydrate is in the lithium-containing mother liquor
The content is 0.3g/L;
(3) Taking part of the crude lithium carbonate according to the proportion of 1:10, washing with pure water, wherein the crude lithium carbonate after washing and impurity removal is according to the mass ratio of 1:3, pure water pulping, adding a calcium hydroxide solution with the theoretical amount of 1.2 times into the crude lithium carbonate slurry, stirring and reacting at 70 ℃ and 400rpm for 60min, filtering to obtain a lithium hydroxide solution, removing calcium from the lithium hydroxide solution by using resin, evaporating and crystallizing to obtain a battery-grade lithium hydroxide product, and recycling a crystallization mother liquor for the raw material pulping of the carbonization reaction;
(4) Mixing part of crude lithium carbonate with crystallization mother liquor and high-temperature pyrolysis mother liquor to prepare slurry, wherein the theoretical mass concentration of lithium in the slurry is 8.5g/L, and continuously introducing 0.3Mpa of CO from decarburization and high-temperature pyrolysis reaction into the slurry 2 Stirring and reacting at 25 ℃ and 400rpm for 60min, and filtering to remove insoluble impurities such as Ca, mg, si and the like to obtain a clarified lithium bicarbonate solution;
(5) Heating the obtained clarified lithium bicarbonate solution to 90 ℃, stirring and reacting for 90min at 400rpm, filtering to obtain high-purity lithium carbonate precipitate, washing and drying to obtain a battery-grade lithium carbonate product, and collecting CO generated in the reaction process 2 And recycling the gas to the carbonization reaction, collecting the filtered high-temperature pyrolysis mother liquor for pulping the carbonization reaction raw material, wherein the lithium content in the high-temperature pyrolysis mother liquor is lower than 3g/L.
Wherein, the sodium carbonate high-temperature lithium deposition reaction in the step (1):
wherein: c. C 1 Is the mass concentration of Li in the lithium-containing solution, c 2 The mass concentration of Li in the filtrate after the high-temperature lithium precipitation reaction; v 1 Volume of lithium-containing solution, V 2 The volume of the filtrate after the high-temperature lithium precipitation reaction.
Carbonization and high-temperature pyrolysis reaction in the steps (4) and (5):
wherein: c. C 3 Is the mass concentration of Li in the crude lithium carbonate slurry, c 4 The mass concentration of Li in the filtrate after the high-temperature pyrolysis reaction; v 3 Volume of crude lithium carbonate slurry, V 4 The volume of the filtrate after pyrolysis reaction.
Causticizing reaction in the step (3):
wherein: c. C 5 The mass concentration of Li in the slurry of the coarse lithium carbonate after being slurried by pure water, c 6 The mass concentration of Li in the filtrate after the causticization reaction; v 5 Volume of pure water slurry for crude lithium carbonate, V 6 The filtrate volume after the causticization reaction.
The lithium recovery rate of the whole process is as follows:
wherein: the washing water is completely recycled to an evaporation system, and the lithium loss is not counted; c. C 1 Is the mass concentration of Li in the lithium-containing solution, c 7 Is the mass concentration of Li in the crystallization mother liquor, c 8 The mass concentration of Li in the high-temperature pyrolysis mother liquor; v 1 Volume of lithium-containing solution, V 7 Volume of mother liquor for crystallization, V 8 Volume of high temperature pyrolysis mother liquor; omega 1 The mass ratio of lithium in the calcium carbonate slag after the causticization reaction is omega 2 The mass ratio of lithium in insoluble impurity slag after carbonization reaction is adopted; m is a unit of 1 M is the mass of calcium carbonate slag after causticization 2 The mass of insoluble impurities after the carbonization reaction.
The recycling efficiency of the carbon in the whole process is as follows:
wherein: for the sake of convenience of calculation, it is assumed here that all reaction solutions have a volume of 1L, i.e.m 1 CO generated for decarbonization of 1L solution 2 Mass, m 2 CO generated by high-temperature thermal decomposition reaction of 1L solution 2 Mass, m 3 CO required for 1L solution carbonization 2 And (4) quality.
Examples 2 to 6
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the reaction temperature of the sodium carbonate high-temperature lithium precipitation in the step (1) is 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃.
And (3) effect comparison:
| examples | 1 | 2 | 3 | 4 | 5 | 6 |
| Conversion of crude lithium carbonate% | 86.5％ | 43.3％ | 62.1％ | 74.5％ | 81.6％ | 86.3％ |
Examples 7 to 9
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with lithium-containing solution, which only differs from example 1 in that: the reaction time of the high-temperature lithium deposition in the step (1) is 30min, 60min and 90min, and the reaction time is not further prolonged in consideration of the production efficiency.
And (3) effect comparison:
| examples | 1 | 7 | 8 | 9 |
| Conversion of crude lithium carbonate% | 86.5％ | 69.3％ | 74.8％ | 83.8％ |
Examples 10 to 12
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the molar ratio of the sodium carbonate consumption in the step (1) to the Li content in the solution is 0.5: 1. 0.7:1 and 0.8:1.
and (3) effect comparison:
examples 13 to 15
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: and (4) carrying out carbonization reaction for 30min, 90min and 120min.
And (3) effect comparison:
| examples | 1 | 13 | 14 | 15 |
| Conversion of Battery grade lithium carbonate% | 67.3％ | 35.8％ | 68.2％ | 67.5％ |
Examples 16 to 18
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the carbonization reaction temperature in the step (4) is 40 ℃, 30 ℃ and 20 ℃.
And (3) effect comparison:
| examples | 1 | 16 | 17 | 18 |
| Conversion rate of battery grade lithium carbonate% | 67.3％ | 45.7％ | 64.7％ | 66.5％ |
Examples 19 to 21
This example presents a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the theoretical mass concentration of lithium in the slurry in the step (4) is 7.5g/L, 6.5g/L and 9.5g/L.
And (3) effect comparison:
| examples | 1 | 19 | 20 | 21 |
| Conversion of Battery grade lithium carbonate% | 67.3％ | 60.0％ | 53.8％ | 71.4％ |
Examples 22 to 25
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with lithium-containing solution, which only differs from example 1 in that: the high-temperature pyrolysis reaction time in the step (5) is 60min, 70min, 80min and 95min.
And (3) effect comparison:
| examples | 1 | 22 | 23 | 24 | 25 |
| Conversion of Battery grade lithium carbonate% | 67.3％ | 63.6％ | 63.9％ | 66.2％ | 67.9％ |
Examples 26 to 28
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the causticization reaction time in the step (3) is 30min, 90min and 120min.
And (3) effect comparison:
| examples | 1 | 26 | 27 | 28 |
| Conversion of Battery grade lithium hydroxide% | 81.3％ | 72.6％ | 83.0％ | 82.6％ |
Examples 29 to 32
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with lithium-containing solution, which only differs from example 1 in that: the causticization reaction temperature in the step (3) is 50 ℃, 60 ℃, 80 ℃ and 90 ℃.
And (3) effect comparison:
| examples | 1 | 29 | 30 | 31 | 32 |
| Conversion of Battery grade lithium hydroxide% | 81.3％ | 72.5％ | 79.6％ | 82.4％ | 82.2％ |
Examples 33 to 34
This example provides a method for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, which differs from example 1 only in that: the addition amount of the calcium hydroxide in the step (3) is 1 time and 1.1 time of the theoretical amount.
And (3) effect comparison:
| examples | 1 | 33 | 34 |
| Conversion of Battery grade lithium hydroxide% | 81.3％ | 66.1％ | 75.5％ |
Comparative example 1
The present comparative example provides a process for co-producing battery grade lithium carbonate and battery grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: and (4) directly discharging the crystallization mother liquor in the step (3) without returning to pulping.
Comparative example 2
This comparative example provides a process for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: and (5) directly discharging the high-temperature pyrolysis mother liquor without returning to pulping.
Comparative example 3
This comparative example provides a process for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: and (4) directly discharging the crystallization mother liquor in the step (3) and the high-temperature pyrolysis mother liquor in the step (5) without returning to pulping.
And (3) effect comparison:
| full process lithium recovery rate | |
| Example 1 | 91.2％ |
| Comparative example 1 | 75.7％ |
| Comparative example 2 | 63.2％ |
| Comparative example 3 | 52.6％ |
Comparative example 4:
the present comparative example provides a process for co-producing battery grade lithium carbonate and battery grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: CO produced by the carbonation reaction in step (2) 2 Not collected, and directly discharged.
Comparative example 5:
this comparative example provides a process for co-producing cell-grade lithium carbonate and cell-grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: CO generated by the high-temperature pyrolysis reaction in the step (5) 2 Not collected, and directly discharged.
Comparative example 6:
the present comparative example provides a process for co-producing battery grade lithium carbonate and battery grade lithium hydroxide with a lithium-containing solution, differing from example 1 only in that: CO generated by the carbonization reaction in the step (2) and the high-temperature pyrolysis reaction in the step (5) 2 Are not collected and are directly discharged.
And (3) effect comparison:
| full-flow carbon recycling efficiency | |
| Example 1 | 90.3％ |
| Comparative example 4 | 49.9％ |
| Comparative example 5 | 40.4％ |
| Comparative example 6 | 0％ |
(1) The technology can realize the co-production of two products, namely battery-grade lithium carbonate and battery-grade lithium hydroxide, from the lithium-containing solution, and can flexibly allocate the yields of the two products according to the fluctuation of market prices, thereby realizing the maximization of benefits; the quality of the crude lithium carbonate required by pulping can be determined according to the yields of the crystallization mother liquor and the high-temperature pyrolysis mother liquor in the process, the consumption of pure water required by pulping is reduced, and the cost minimization is realized.
(2) The invention utilizes the lithium-containing crystallization mother liquor, the high-temperature pyrolysis mother liquor and the crude lithium carbonate to prepare the slurry, reduces the consumption of pure water, realizes the recycling of lithium resources and greatly improves the lithium recovery rate of the whole process.
(3) The process collects CO generated in decarburization reaction and high-temperature pyrolysis reaction 2 The method is used for carbonization reaction, avoids waste gas emission, realizes recycling of carbon resources and greatly saves production cost.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for co-producing lithium carbonate and lithium hydroxide by lithium-containing solution is characterized by comprising the following steps:
and (3) lithium deposition: after reacting a lithium-containing solution with water-soluble carbonate, filtering a reaction solution to obtain a crude lithium carbonate solid and a lithium precipitation mother solution;
causticizing: after partial crude lithium carbonate and calcium hydroxide react in a liquid phase, evaporating and crystallizing reaction liquid to obtain lithium hydroxide solid;
and (3) utilizing lithium precipitation mother liquor: and adding acid into the lithium precipitation mother liquor for decarbonization, and combining the decarbonized lithium precipitation mother liquor with the lithium-containing solution for reuse.
2. The method for co-producing lithium carbonate and lithium hydroxide with a lithium-containing solution according to claim 1, wherein the lithium content in the lithium-containing solution is 20 to 25g/L;
preferably, when the lithium content in the lithium-containing solution is lower than 20g/L, the lithium-containing solution is evaporated and concentrated to the lithium content of 20-25g/L.
3. The method for co-producing lithium carbonate and lithium hydroxide with a lithium-containing solution according to claim 1, wherein the water-soluble carbonate in the lithium precipitation step is sodium carbonate or potassium carbonate;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.8:1;
preferably, the molar ratio of the water-soluble carbonate to the Li content in the lithium-containing solution is 0.5-0.6:1;
preferably, the water-soluble carbonate is added in the form of a solution in the lithium precipitation step;
preferably, the mass fraction of sodium carbonate in the sodium carbonate solution is 20-30%;
preferably, the lithium precipitation step is carried out for 30-120min at 60-90 ℃;
preferably, the reaction temperature in the lithium precipitation step is 80-90 ℃, and the reaction time is 90-120min;
preferably, the lithium precipitation step is used for stirring the reaction liquid at the stirring speed of 400-600rpm;
preferably, the lithium content in the lithium precipitation mother liquor is lower than 3g/L.
4. The method for co-producing lithium carbonate and lithium hydroxide with lithium-containing solution according to claim 1, wherein in the causticizing step, the molar ratio of calcium hydroxide to lithium carbonate in crude lithium carbonate is 1.0-1.5;
preferably, in the causticizing step, the molar ratio of calcium hydroxide to lithium carbonate is 1.1-1.2;
preferably, in the causticizing step, the reaction temperature is 50-80 ℃, and the reaction time is 30-120min;
preferably, in the causticizing step, the reaction temperature is 60-80 ℃, and the reaction time is 60-90min;
preferably, in the causticizing step, stirring the reaction solution at the stirring speed of 400-600rpm;
preferably, in the causticizing step, before the evaporation and crystallization, the calcium in the reaction liquid is removed by using resin.
5. The method for coproducing lithium carbonate and lithium hydroxide from a lithium-containing solution according to claim 1, wherein the causticization reaction is performed after the first pulping of crude lithium carbonate and pure water;
preferably, the mass ratio of the crude lithium carbonate to the pure water is 1:3-5, performing first pulping;
preferably, in the causticizing step, calcium hydroxide is mixed with crude lithium carbonate in the form of a calcium hydroxide solution;
preferably, before the causticizing step, washing crude lithium carbonate by pure water;
preferably, in the step of washing the crude lithium carbonate with pure water, the mass ratio of pure water to crude lithium carbonate is 5 to 10.
6. The method for co-producing lithium carbonate and lithium hydroxide with the lithium-containing solution as claimed in claim 1, wherein in the step of utilizing the lithium precipitation mother solution, acid is added into the lithium precipitation mother solution until no bubbles are generated in the solution:
preferably, the acid in the lithium precipitation mother liquor utilization step is sulfuric acid;
preferably, the lithium-containing solution is evaporated and concentrated to obtain a byproduct sodium sulfate decahydrate;
preferably, the reaction temperature of the decarbonization step is 60-70 ℃;
preferably, CO in the lithium precipitation mother liquor after decarburization 3 2- The content is less than 0.5g/L.
7. The method for coproducing lithium carbonate and lithium hydroxide with lithium-containing solution according to claim 1, wherein a part of the crude lithium carbonate solid is subjected to a causticization step, and the other part of the crude lithium carbonate solid is subjected to purification, and the purification step comprises second pulping, carbonization and high-temperature pyrolysis to obtain purified lithium carbonate.
8. The method for coproducing lithium carbonate and lithium hydroxide with lithium-containing solution according to claim 7, wherein a second slurry is obtained after the second pulping is finished, and the mass concentration of lithium in the second slurry is 6.5-9.5g/L;
preferably, the crystallization mother liquor obtained after the evaporation crystallization is transferred to the second slurry for reuse;
preferably, the mass concentration of lithium in the second slurry is 8-9g/L.
9. The method of claim 7, wherein the carbonizing comprises introducing CO into the second slurry 2 Obtaining a lithium bicarbonate solution;
preferably, CO is introduced in the carbonization step 2 The pressure of (A) is 0.2-0.3Mpa;
preferably, the CO released by the decarbonation step 2 Introducing into the second slurry;
preferably, the reaction temperature of the carbonization step is 15-40 ℃, and the reaction time is 30-120min;
preferably, the reaction temperature of the carbonization step is 25-30 ℃, and the reaction time is 60-90min;
preferably, the carbonization step stirs the reaction solution at a stirring speed of 400-600rpm;
preferably, the carbonization step is followed by filtration of the reaction to obtain a lithium bicarbonate solution.
10. The method for co-producing lithium carbonate and lithium hydroxide with lithium-containing solution according to claim 7, characterized in that the high-temperature pyrolysis is to heat the lithium bicarbonate solution to 70-95 ℃ for 30-120min, and to obtain purified lithium carbonate by filtration;
preferably, in the high-temperature pyrolysis step, the temperature is 85-95 ℃, and the reaction time is 60-90min;
preferably, in the high-temperature pyrolysis step, the reaction solution is stirred at the stirring speed of 400-600rpm;
preferably, in the high-temperature pyrolysis step, purified lithium carbonate and a high-temperature pyrolysis mother liquor are obtained through filtration, and the high-temperature pyrolysis mother liquor is transferred to the second slurry for reuse;
preferably, in the high-temperature pyrolysis step, washing the solid obtained by filtering with water to remove impurities to obtain purified lithium carbonate;
preferably, the CO released in the high temperature pyrolysis step 2 Collecting and introducing into the second slurry for reuse.
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