CN112939034A - 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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- CN112939034A CN112939034A CN202110295000.9A CN202110295000A CN112939034A CN 112939034 A CN112939034 A CN 112939034A CN 202110295000 A CN202110295000 A CN 202110295000A CN 112939034 A CN112939034 A CN 112939034A
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 379
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 39
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000001816 cooling Methods 0.000 claims abstract description 48
- 239000000047 product Substances 0.000 claims abstract description 47
- 238000006243 chemical reaction Methods 0.000 claims abstract description 34
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 239000012043 crude product Substances 0.000 claims abstract description 25
- 230000008020 evaporation Effects 0.000 claims abstract description 25
- 238000004806 packaging method and process Methods 0.000 claims abstract description 19
- 208000005156 Dehydration Diseases 0.000 claims abstract description 17
- 230000018044 dehydration Effects 0.000 claims abstract description 17
- 238000006297 dehydration reaction Methods 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 15
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 13
- 239000012535 impurity Substances 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- 238000002425 crystallisation Methods 0.000 claims description 8
- 230000008025 crystallization Effects 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
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 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
- 239000012716 precipitator Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000498 cooling water Substances 0.000 claims description 4
- 238000011049 filling Methods 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 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 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
- 230000005389 magnetism Effects 0.000 description 2
- 239000007774 positive electrode material Substances 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
- 239000010406 cathode material Substances 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 causticization reaction, and carrying out solid-liquid separation after the causticization reaction to obtain a lithium hydroxide primary solution; step 2, removing impurities and purifying; step 3, evaporating and concentrating for the first time; step 4, cooling and crystallizing for the first time to obtain a lithium hydroxide crude product; step 5, re-dissolving and filtering; step 6, secondary evaporation and concentration; step 7, recrystallizing; step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc type dryer; step 9, demagnetizing; step 10, secondary dehydration, namely dehydrating the crystal water of the demagnetized product by using a disc dryer; step 11, crushing, namely crushing the dehydrated lithium hydroxide particles to obtain battery-grade anhydrous lithium hydroxide; and step 12, packaging. The invention can solve the problems that the prior art has poor dehydration consistency, can not realize continuous large-scale production, and the dehydrated anhydrous product is easy to carbonize, absorb moisture, agglomerate and agglomerate.
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 global climate change aggravation, governments of various countries pay more and more attention to the use and development of new energy. China holds a large number of countries as automobiles, and development strategies for advancing from the large automobile countries to the strong automobile countries are provided in 2014. New energy automobile industry development planning (2021-2035) coming in 2020 definitely proposes that strategies for developing pure electric automobiles are unchanged, and a great target that the new energy automobile sales volume accounts for 20% of the total new automobile sales volume is realized by 2025. The popularization of new energy automobiles cannot be separated from the rapid development of the lithium ion battery technology, and the ternary layered composite positive electrode material becomes a material with great development prospect due to good electrochemical performance.
Battery grade lithium hydroxide is the primary lithium source used for the above-described ternary positive electrode materials. Lithium hydroxide used by the existing anode material factory is basically lithium hydroxide hydrate containing one crystal water, and the content of the lithium hydroxide is only 57.09%. In the processing process of the anode material factory, the time of 7-8 hours is needed to be spent for dehydration treatment, the energy consumption is increased in the process, carbonization is easy to occur in the dehydration process, the product quality control is not facilitated, and bottlenecks are easy to form in part of production links. Therefore, the use of the battery-grade anhydrous lithium hydroxide is more beneficial to the quality control in the production process of the cathode 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, so that the product is easy to carbonize, absorb moisture and agglomerate.
Disclosure of Invention
In view of the above situation, the invention provides a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate, so as to solve the problems that the dehydration consistency is poor, continuous large-scale production cannot be realized, and an anhydrous product after dehydration is easy to carbonize, absorb moisture, agglomerate 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 comprises the following steps:
step 1, carrying out causticization reaction according to the proportion of lithium carbonate: calcium hydroxide: carrying out causticization reaction on water in a ratio of (105-115) to (1900-2100), wherein lithium carbonate is industrial-grade lithium carbonate, and carrying out solid-liquid separation after the causticization reaction to obtain a lithium hydroxide primary solution;
step 2, removing impurities and purifying, namely adding a precipitator into the primary lithium hydroxide solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization is carried out, and cooling circulating water is used for cooling to obtain a lithium hydroxide crude product;
step 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and carrying out precise filtration after dissolution;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 200-250 ℃, and the feeding frequency is 5 HZ;
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 filling packaging equipment.
The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate provided by the invention has the following beneficial effects:
(1) industrial-grade lithium carbonate is selected as a raw material, a causticization process route is used, and high-standard high-quality chemical components of the product are ensured through twice crystallization, so that the preparation of battery-grade anhydrous lithium hydroxide by using the industrial-grade lithium carbonate as the raw material is realized;
(2) through a secondary drying dehydration process: the product is dried for the first time to remove free water in the product, and after the magnetism is removed, the product is dried for the second time to remove crystal water in the product, so that the problem of poor dehydration consistency is solved;
(3) the disc type dryer is used as drying and dehydrating equipment, so that continuous large-scale production is realized, the production efficiency is improved, the operation cost is reduced, the product can be prevented from being carbonized through the protection of the inert gas atmosphere in the secondary crystal water removal stage, and the inert gas can be recycled;
(4) the automatic nitrogen filling package is adopted, and the problems of carbonization, moisture absorption, agglomeration and caking of the product are solved.
In addition, the method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate provided by the invention also has the following technical characteristics:
further, in the step 1, the reaction temperature of the causticization reaction is 85-90 ℃, and the reaction time is 4 hours.
Further, in the step 1, after the causticization reaction, solid-liquid separation is carried out by adopting a plate-and-frame filter-pressing separation mode.
Further, 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 (3) cooling and crystallizing for the first time, cooling by using circulating cooling water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and thus a lithium hydroxide crude product is obtained.
Further, in step 5, the ratio of the lithium hydroxide crude product to the pure water is the lithium hydroxide crude product: pure water 1: 4.7.
Further, step 7 specifically includes:
recrystallizing, cooling by using circulating cooling water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and lithium hydroxide mother liquor and lithium hydroxide refined product are obtained;
further, in step 11, the lithium hydroxide particles dehydrated in step 10 are pulverized to D50 with a particle size of 10-15 μm.
Further, in step 12, each package of the grade anhydrous lithium hydroxide weighs 10 kg.
Detailed Description
The present invention will now be described more fully hereinafter with reference to various embodiments for the purpose of facilitating an understanding of the invention, but the invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth 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 in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" 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 comprises the following steps:
step 1, carrying out causticization reaction, namely weighing 500g of industrial-grade lithium carbonate, 525g of calcium hydroxide and 9.5kg of water to carry out causticization reaction, wherein the reaction temperature of the causticization reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticization reaction, and carrying out plate-and-frame filter pressing separation to obtain primary lithium hydroxide solution;
step 2, removing impurities and purifying, namely adding a precipitator sodium oxalate into the primary lithium hydroxide solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization, cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and a lithium hydroxide crude product is obtained;
and 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and performing precise filtration after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is that of the lithium hydroxide crude product: pure water is 1: 4.7;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and lithium hydroxide mother liquor and lithium hydroxide refined products are obtained;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 200-230 ℃, and the feeding frequency is 5 HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain D50 with the particle size of 10-15 microns to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen-filled packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10 kg.
Example 2:
a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate comprises the following steps:
step 1, carrying out causticization reaction, namely weighing 500g of industrial-grade lithium carbonate, 560g of calcium hydroxide and 10kg of water to carry out causticization reaction, wherein the reaction temperature of the causticization reaction is 86-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticization reaction, and carrying out plate-and-frame filter pressing separation to obtain a lithium hydroxide primary solution;
step 2, removing impurities and purifying, namely adding a precipitator oxalic acid into the lithium hydroxide primary solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization, cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and a lithium hydroxide crude product is obtained;
and 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and performing precise filtration after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is that of the lithium hydroxide crude product: pure water is 1: 4.7;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and lithium hydroxide mother liquor and lithium hydroxide refined products are obtained;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 220-;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain D50 with the particle size of 10-15 microns to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen-filled packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10 kg.
Example 3:
a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate comprises the following steps:
step 1, carrying out causticization reaction, namely weighing 500g of industrial-grade lithium carbonate, 575g of calcium hydroxide and 10.5kg of water to carry out causticization reaction, wherein the reaction temperature of the causticization reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticization reaction, and carrying out plate-and-frame filter pressing separation to obtain primary lithium hydroxide solution;
step 2, removing impurities and purifying, namely adding precipitator lithium carbonate into the primary lithium hydroxide solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization, cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and a lithium hydroxide crude product is obtained;
and 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and performing precise filtration after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is that of the lithium hydroxide crude product: pure water is 1: 4.7;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and lithium hydroxide mother liquor and lithium hydroxide refined products are obtained;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 210-;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain D50 with the particle size of 10-15 microns to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen-filled packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10 kg.
Example 4:
a method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate comprises the following steps:
step 1, carrying out causticization reaction, namely weighing 500g of industrial-grade lithium carbonate, 530g of calcium hydroxide and 9.5kg of water to carry out causticization reaction, wherein the reaction temperature of the causticization reaction is 85-90 ℃, the reaction time is 4 hours, carrying out solid-liquid separation after the causticization reaction, and carrying out plate-and-frame filter pressing separation to obtain primary lithium hydroxide solution;
step 2, removing impurities and purifying, namely adding precipitator lithium phosphate into the primary lithium hydroxide solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization, cooling by using cooling circulating water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and a lithium hydroxide crude product is obtained;
and 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and performing precise filtration after dissolution, wherein the ratio of the lithium hydroxide crude product to the pure water is that of the lithium hydroxide crude product: pure water is 1: 4.7;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and lithium hydroxide mother liquor and lithium hydroxide refined products are obtained;
step 8, primary drying, namely removing free water in the lithium hydroxide refined product by using a disc type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 200-240 ℃, and the feeding frequency is 5 HZ;
step 11, crushing, namely crushing the lithium hydroxide particles dehydrated in the step 10 to obtain D50 with the particle size of 10-15 microns to obtain battery-grade anhydrous lithium hydroxide;
and 12, packaging, namely packaging the battery-grade anhydrous lithium hydroxide by using automatic nitrogen-filled packaging equipment, wherein the weight of each package of battery-grade anhydrous lithium hydroxide is 10 kg.
In conclusion, the method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate provided by the invention has the following beneficial effects:
(1) industrial-grade lithium carbonate is selected as a raw material, a causticization process route is used, and high-standard high-quality chemical components of the product are ensured through twice crystallization, so that the preparation of battery-grade anhydrous lithium hydroxide by using the industrial-grade lithium carbonate as the raw material is realized;
(2) through a secondary drying dehydration process: the product is dried for the first time to remove free water in the product, and after the magnetism is removed, the product is dried for the second time to remove crystal water in the product, so that the problem of poor dehydration consistency is solved;
(3) the disc type dryer is used as drying and dehydrating equipment, so that continuous large-scale production is realized, the production efficiency is improved, the operation cost is reduced, the product can be prevented from being carbonized through the protection of the inert gas atmosphere in the secondary crystal water removal stage, and the inert gas can be recycled;
(4) the automatic nitrogen filling package is adopted, and the problems of carbonization, moisture absorption, agglomeration and caking of the product are solved.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (9)
1. A method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate is characterized by comprising the following steps:
step 1, carrying out causticization reaction according to the proportion of lithium carbonate: calcium hydroxide: carrying out causticization reaction on water in a ratio of (105-115) to (1900-2100), wherein lithium carbonate is industrial-grade lithium carbonate, and carrying out solid-liquid separation after the causticization reaction to obtain a lithium hydroxide primary solution;
step 2, removing impurities and purifying, namely adding a precipitator into the primary lithium hydroxide solution to remove metal ion impurities in the solution;
step 3, carrying out primary evaporation concentration, and carrying out evaporation concentration on the lithium hydroxide primary solution by using an MVR (mechanical vapor recompression) evaporator, wherein the concentration ratio is 5: 1;
step 4, primary cooling crystallization is carried out, and cooling circulating water is used for cooling to obtain a lithium hydroxide crude product;
step 5, re-dissolving and filtering, adding pure water to re-dissolve the lithium hydroxide crude product, wherein the dissolving temperature is 60 ℃, and carrying out precise filtration after dissolution;
step 6, secondary evaporation concentration, mixing the heavy solution and the mother liquor according to a ratio of 1:1, and then carrying out 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 type dryer, and carrying out hydrothermal heat supply at the temperature of 80 ℃ and the feeding frequency of 8 HZ;
step 9, demagnetizing, namely removing metal magnetic substances in the product by adopting an electromagnetic iron remover;
step 10, secondary dehydration, namely dehydrating the demagnetized product by using a disc dryer, supplying heat by using steam, and simultaneously protecting by using an inert gas atmosphere, wherein the heating temperature is 200-250 ℃, and the feeding frequency is 5 HZ;
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 filling packaging equipment.
2. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in the step 1, the reaction temperature of the causticization reaction is 85-90 ℃ and the reaction time is 4 hours.
3. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in the step 1, after the causticization reaction, solid-liquid separation is performed by adopting a plate-and-frame filter pressing separation mode.
4. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in the step 2, the precipitant is one or more of oxalic acid, sodium oxalate, lithium carbonate and lithium phosphate.
5. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein the step 4 specifically comprises:
and (3) cooling and crystallizing for the first time, cooling by using circulating cooling water to reduce the temperature of the solution to 40 ℃, wherein the cooling time is 4 hours, and thus a lithium hydroxide crude product is obtained.
6. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in the step 5, the ratio of the crude lithium hydroxide to the pure water is the crude lithium hydroxide: pure water 1: 4.7.
7. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein the step 7 specifically comprises:
and (4) recrystallizing, and cooling by using circulating cooling water to reduce the temperature of the solution to 40 ℃ for 4 hours to obtain lithium hydroxide mother liquor and lithium hydroxide refined product.
8. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in step 11, the lithium hydroxide particles dehydrated in step 10 are crushed to D50 with the particle size of 10-15 μm.
9. The method for preparing battery-grade anhydrous lithium hydroxide from industrial-grade lithium carbonate according to claim 1, wherein in the step 12, each package of battery-grade anhydrous lithium hydroxide weighs 10 kg.
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