CN112939034B - Method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate - Google Patents
Method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate Download PDFInfo
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 357
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 239000000047 product Substances 0.000 claims abstract description 45
- 238000001816 cooling Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 239000012043 crude product Substances 0.000 claims abstract description 24
- 238000004806 packaging method and process Methods 0.000 claims abstract description 21
- 239000007788 liquid Substances 0.000 claims abstract description 20
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- 238000009993 causticizing Methods 0.000 claims abstract description 17
- 208000005156 Dehydration Diseases 0.000 claims abstract description 15
- 230000018044 dehydration Effects 0.000 claims abstract description 15
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 15
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000011031 large-scale manufacturing process Methods 0.000 claims abstract description 6
- 239000000243 solution Substances 0.000 claims description 32
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004090 dissolution Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000011261 inert gas Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 230000005347 demagnetization Effects 0.000 claims description 8
- 238000011010 flushing procedure Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 6
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 6
- 239000000920 calcium hydroxide Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910021645 metal ion Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000010413 mother solution Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 3
- 229940039790 sodium oxalate Drugs 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- 239000013078 crystal Substances 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003763 carbonization Methods 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000010406 cathode material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 238000003908 quality control method Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 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
- C01D15/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- 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
Abstract
The invention provides a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate, which comprises the following steps: step 1, carrying out a causticizing reaction, and carrying out solid-liquid separation after the causticizing reaction to obtain a lithium hydroxide primary liquid; step 2, impurity removal and purification; step 3, evaporating and concentrating for one time; step 4, cooling and crystallizing for the first time to obtain a lithium hydroxide crude product; step 5, redissolving and filtering; step 6, secondary evaporation concentration; step 7, recrystallizing; step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer; step 9, demagnetizing; step 10, secondary dehydration, namely using a disc dryer to dehydrate crystal water of the demagnetized product; step 11, crushing, namely crushing dehydrated lithium hydroxide particles to obtain battery-grade anhydrous lithium hydroxide; and 12, packaging. The invention can solve the problems that the dehydration consistency is poor, continuous large-scale production cannot be realized, and dehydrated anhydrous products are easy to carbonize, absorb moisture and agglomerate in the prior art.
Description
Technical Field
The invention relates to the technical field of lithium hydroxide preparation, in particular to a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate.
Background
With the increase of global climate change, governments of various countries are increasingly paying attention to the use and development of new energy sources. The national country is a large-quantity country with the automobile conservation, and a development strategy of going from the large country to the strong country is put forward in 2014. The new energy automobile industry development planning (2021-2035) of the new energy automobile in 2020 clearly proposes that the strategy of developing the pure electric automobile is unchanged, and the ambitious goal that the sales amount of the new energy automobile is 20% of the total sales amount of the new automobile is realized in 2025. The popularization of new energy automobiles is not free from the rapid development of lithium ion battery technology, and the ternary layered composite anode material becomes a material with great development prospect due to the good electrochemical performance.
Battery grade lithium hydroxide is the primary lithium source used in the ternary cathode materials described above. The lithium hydroxide used in the current cathode material factory is basically lithium hydroxide hydrate containing crystal water, and the lithium hydroxide content accounts for only 57.09 percent. The cathode material factory needs 7-8 hours to dehydrate in the processing process, the energy consumption of the process is increased, carbonization easily occurs in the dehydration process, the quality control of the product is not facilitated, and bottlenecks are easily formed in part of production links. Therefore, the use of the battery-grade anhydrous lithium hydroxide is more beneficial to quality control in the production process of the anode material, and improves the production efficiency. However, the current production of battery-grade anhydrous lithium hydroxide has the following technical problems: the dehydration consistency is poor, continuous large-scale production cannot be realized, and in addition, the dehydrated anhydrous product has strong moisture absorption, and the carbonization moisture absorption and agglomeration of the product are easy to cause.
Disclosure of Invention
In view of the above, the invention provides a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate, which aims to solve the problems that the dehydration consistency is poor, continuous large-scale production cannot be realized, and dehydrated anhydrous products are easy to carbonize, absorb moisture and agglomerate in the prior art.
The technical scheme of the invention is as follows:
a method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the following steps:
step 1, causticizing reaction, namely, according to lithium carbonate: calcium hydroxide: carrying out causticization reaction on the lithium carbonate which is industrial grade lithium carbonate according to the proportion of (105-115) to (1900-2100), and carrying out solid-liquid separation after the causticization reaction to obtain lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding a precipitator into the lithium hydroxide primary liquid to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for the first time, and cooling by using cooling circulating water to obtain a lithium hydroxide crude product;
step 5, re-dissolving and filtering, namely adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolution temperature is 60 ℃, and performing precise filtration after dissolution;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, and cooling by using cooling circulating water to obtain lithium hydroxide mother liquor and lithium hydroxide refined product;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, carrying out hydrothermal heat supply, and carrying out feeding at the temperature of 80 ℃ and the feeding frequency of 8HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating crystal water of the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere, wherein the heating temperature is 200-250 ℃ and the feeding frequency is 5HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment.
The method for preparing the battery-grade anhydrous lithium hydroxide from the industrial-grade lithium carbonate has the following beneficial effects:
(1) The industrial grade lithium carbonate is selected as a raw material, and the causticization process route is used, so that the high standard and high quality of chemical components of the product are ensured through twice crystallization, and the preparation of the battery grade anhydrous lithium hydroxide by taking the industrial grade lithium carbonate as the raw material is realized;
(2) Through a secondary drying and dehydration process: the free water in the product is removed by the first drying, and after the demagnetization, the product is dried for the second time, so that the crystal water in the product is removed, and the problem of poor dehydration consistency is solved;
(3) The disc dryer is adopted as drying and dewatering equipment, so that continuous large-scale production is realized, the production efficiency is improved, the operation cost is reduced, the product carbonization can be prevented by the protection of inert gas atmosphere in the secondary crystallization water removal stage, and the inert gas can be recycled;
(4) The problems of moisture absorption and agglomeration of the product are solved by adopting automatic nitrogen flushing packaging.
In addition, the method for preparing the battery-grade anhydrous lithium hydroxide from the industrial-grade lithium carbonate provided by the invention has the following technical characteristics:
in the step 1, the reaction temperature of the causticization reaction is 85-90 ℃ and the reaction time is 4 hours.
In the step 1, solid-liquid separation is performed by adopting a plate-frame filter pressing separation mode after the causticization reaction.
In step 2, the precipitant is one or more of oxalic acid, sodium oxalate, lithium carbonate and lithium phosphate.
Further, step 4 specifically includes:
and cooling and crystallizing at one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product.
Further, in step 5, the ratio of the lithium hydroxide crude product to pure water is: pure water=1:4.7.
Further, the step 7 specifically includes:
recrystallizing, cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain lithium hydroxide mother liquor and lithium hydroxide refined products;
in step 11, the dehydrated lithium hydroxide particles in step 10 are crushed to a D50 particle size of 10-15 μm.
Further, in step 12, the weight of each pack of the battery grade anhydrous lithium hydroxide was 10kg.
Detailed Description
The invention will be described more fully hereinafter with reference to the accompanying examples in order to facilitate an understanding of the invention, however, the invention may be embodied in many different forms and is not limited to the examples described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
Example 1:
a method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the following steps:
step 1, carrying out a causticizing reaction by weighing 500g of industrial grade lithium carbonate, 525g of calcium hydroxide and 9.5kg of water, wherein the reaction temperature of the causticizing reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticizing reaction, and carrying out plate-frame filter pressing separation to obtain a lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding a precipitator sodium oxalate into the lithium hydroxide primary liquid to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product;
and 5, re-dissolving and filtering, namely re-dissolving the lithium hydroxide crude product by adding pure water, wherein the dissolution temperature is 60 ℃, and performing precise filtering after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is the lithium hydroxide crude product: pure water = 1:4.7;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, namely cooling by using cooling circulating water to enable the temperature of the solution to be reduced to 40 ℃ for 4 hours, so as to obtain lithium hydroxide mother liquor and lithium hydroxide refined products;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, carrying out hydrothermal heat supply, and carrying out feeding at the temperature of 80 ℃ and the feeding frequency of 8HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating crystal water of the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere, wherein the heating temperature is 200-230 ℃ and the feeding frequency is 5HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 until the particle size of D50 is 10-15 mu m, so as to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10kg.
Example 2:
a method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the following steps:
step 1, carrying out a causticizing reaction by weighing 500g of industrial grade lithium carbonate, 560g of calcium hydroxide and 10kg of water, wherein the reaction temperature of the causticizing reaction is 86-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticizing reaction, and carrying out plate-frame filter pressing separation to obtain a lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding precipitator oxalic acid into the lithium hydroxide primary liquid to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product;
and 5, re-dissolving and filtering, namely re-dissolving the lithium hydroxide crude product by adding pure water, wherein the dissolution temperature is 60 ℃, and performing precise filtering after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is the lithium hydroxide crude product: pure water = 1:4.7;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, namely cooling by using cooling circulating water to enable the temperature of the solution to be reduced to 40 ℃ for 4 hours, so as to obtain lithium hydroxide mother liquor and lithium hydroxide refined products;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, carrying out hydrothermal heat supply, and carrying out feeding at the temperature of 80 ℃ and the feeding frequency of 8HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating crystal water of the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere, wherein the heating temperature is 220-250 ℃ and the feeding frequency is 5HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 until the particle size of D50 is 10-15 mu m, so as to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10kg.
Example 3:
a method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the following steps:
step 1, carrying out a causticizing reaction by weighing 500g of industrial grade lithium carbonate, 575g of calcium hydroxide and 10.5kg of water, wherein the reaction temperature of the causticizing reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticizing reaction, and carrying out plate-frame filter pressing separation to obtain a lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding a precipitant lithium carbonate into the lithium hydroxide primary solution to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product;
and 5, re-dissolving and filtering, namely re-dissolving the lithium hydroxide crude product by adding pure water, wherein the dissolution temperature is 60 ℃, and performing precise filtering after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is the lithium hydroxide crude product: pure water = 1:4.7;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, namely cooling by using cooling circulating water to enable the temperature of the solution to be reduced to 40 ℃ for 4 hours, so as to obtain lithium hydroxide mother liquor and lithium hydroxide refined products;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, carrying out hydrothermal heat supply, and carrying out feeding at the temperature of 80 ℃ and the feeding frequency of 8HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating crystal water of the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere, wherein the heating temperature is 210-240 ℃ and the feeding frequency is 5HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 until the particle size of D50 is 10-15 mu m, so as to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10kg.
Example 4:
a method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the following steps:
step 1, carrying out a causticizing reaction by weighing 500g of industrial grade lithium carbonate, 530g of calcium hydroxide and 9.5kg of water, wherein the reaction temperature of the causticizing reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticizing reaction, and carrying out plate-frame filter pressing separation to obtain a lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding a precipitant lithium phosphate into the lithium hydroxide primary solution to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product;
and 5, re-dissolving and filtering, namely re-dissolving the lithium hydroxide crude product by adding pure water, wherein the dissolution temperature is 60 ℃, and performing precise filtering after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is the lithium hydroxide crude product: pure water = 1:4.7;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, namely cooling by using cooling circulating water to enable the temperature of the solution to be reduced to 40 ℃ for 4 hours, so as to obtain lithium hydroxide mother liquor and lithium hydroxide refined products;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, carrying out hydrothermal heat supply, and carrying out feeding at the temperature of 80 ℃ and the feeding frequency of 8HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating crystal water of the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere, wherein the heating temperature is 200-240 ℃ and the feeding frequency is 5HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 until the particle size of D50 is 10-15 mu m, so as to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10kg.
In summary, the method for preparing the battery-grade anhydrous lithium hydroxide from the industrial-grade lithium carbonate has the following beneficial effects:
(1) The industrial grade lithium carbonate is selected as a raw material, and the causticization process route is used, so that the high standard and high quality of chemical components of the product are ensured through twice crystallization, and the preparation of the battery grade anhydrous lithium hydroxide by taking the industrial grade lithium carbonate as the raw material is realized;
(2) Through a secondary drying and dehydration process: the free water in the product is removed by the first drying, and after the demagnetization, the product is dried for the second time, so that the crystal water in the product is removed, and the problem of poor dehydration consistency is solved;
(3) The disc dryer is adopted as drying and dewatering equipment, so that continuous large-scale production is realized, the production efficiency is improved, the operation cost is reduced, the product carbonization can be prevented by the protection of inert gas atmosphere in the secondary crystallization water removal stage, and the inert gas can be recycled;
(4) The problems of moisture absorption and agglomeration of the product are solved by adopting automatic nitrogen flushing packaging.
The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (5)
1. A method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate, comprising the steps of:
step 1, causticizing reaction, namely, according to lithium carbonate: calcium hydroxide: carrying out causticization reaction on the lithium carbonate which is industrial grade lithium carbonate according to the proportion of (105-115) to (1900-2100), and carrying out solid-liquid separation after the causticization reaction to obtain lithium hydroxide primary liquid;
step 2, removing impurities and purifying, namely adding a precipitator into the lithium hydroxide primary liquid to remove metal ion impurities in the solution;
step 3, primary evaporation concentration, namely evaporating concentration is carried out on the lithium hydroxide primary solution by using an MVR evaporator, and the concentration ratio is 5:1;
step 4, cooling and crystallizing for the first time, and cooling by using cooling circulating water to obtain a lithium hydroxide crude product;
step 5, re-dissolving and filtering, namely adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolution temperature is 60 ℃, and performing precise filtration after dissolution;
step 6, secondary evaporation concentration, namely mixing the heavy solution and the mother solution according to a ratio of 1:1, and then performing evaporation concentration by using an MVR evaporator, wherein the concentration ratio is 1.5:1;
step 7, recrystallizing, and cooling by using cooling circulating water to obtain lithium hydroxide mother liquor and lithium hydroxide refined product;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8Hz;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the product after the demagnetization by using a disc dryer, heating by using steam, and protecting by using inert gas atmosphere at the heating temperature of 200-250 ℃ and the feeding frequency of 5Hz so as to realize continuous large-scale production;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain battery-grade anhydrous lithium hydroxide;
step 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen flushing packaging equipment;
in the step 1, the reaction temperature of the causticization reaction is 85-90 ℃ and the reaction time is 4 hours;
in the step 1, after causticizing reaction, solid-liquid separation is carried out by adopting a plate-frame filter pressing separation mode;
in the step 2, the precipitant is one or more of oxalic acid, sodium oxalate, lithium carbonate and lithium phosphate;
the step 4 specifically comprises the following steps: and cooling and crystallizing at one time, and cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain a lithium hydroxide crude product.
2. The method for preparing battery grade anhydrous lithium hydroxide from industrial grade lithium carbonate according to claim 1, wherein in step 5, the ratio of crude lithium hydroxide to pure water is: pure water=1:4.7.
3. The method for preparing battery grade anhydrous lithium hydroxide according to claim 1, wherein step 7 specifically comprises: and (3) recrystallizing, cooling by using cooling circulating water, and cooling the solution to 40 ℃ for 4 hours to obtain lithium hydroxide mother liquor and lithium hydroxide refined products.
4. The method for preparing battery grade anhydrous lithium hydroxide according to claim 1, wherein in step 11, the dehydrated lithium hydroxide particles of step 10 are crushed to a D50 particle size of 10-15 μm.
5. The method for preparing battery grade anhydrous lithium hydroxide according to claim 1, wherein the weight of each package of battery grade anhydrous lithium hydroxide in step 12 is 10kg.
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