CN112591772A - Process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores - Google Patents
Process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores Download PDFInfo
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- CN112591772A CN112591772A CN202011543676.7A CN202011543676A CN112591772A CN 112591772 A CN112591772 A CN 112591772A CN 202011543676 A CN202011543676 A CN 202011543676A CN 112591772 A CN112591772 A CN 112591772A
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- lithium hydroxide
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- spodumene
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- 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 title claims abstract description 28
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 27
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 title claims abstract description 26
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 title claims abstract description 26
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 24
- 238000002156 mixing Methods 0.000 title claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 108
- 238000001816 cooling Methods 0.000 claims abstract description 28
- 239000002002 slurry Substances 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 22
- 238000002386 leaching Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 238000001704 evaporation Methods 0.000 claims abstract description 11
- 238000007710 freezing Methods 0.000 claims abstract description 11
- 230000008014 freezing Effects 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 5
- 238000009993 causticizing Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 22
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 20
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 16
- 239000000292 calcium oxide Substances 0.000 claims description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 16
- 239000012452 mother liquor Substances 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 15
- 239000012065 filter cake Substances 0.000 claims description 11
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 10
- 229910001424 calcium ion Inorganic materials 0.000 claims description 10
- 230000008020 evaporation Effects 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000007259 addition reaction Methods 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000004806 packaging method and process Methods 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 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 6
- 239000000203 mixture Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 230000003139 buffering effect Effects 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- 239000012043 crude product Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 3
- 239000008237 rinsing water Substances 0.000 claims description 3
- 238000012216 screening Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000008399 tap water Substances 0.000 claims description 3
- 235000020679 tap water Nutrition 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Chemical compound [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 abstract description 7
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052744 lithium Inorganic materials 0.000 abstract description 5
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 2
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 229910001947 lithium oxide Inorganic materials 0.000 abstract 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000004075 alteration Effects 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical group Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/08—Carbonates; Bicarbonates
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to the technical field of lithium hydroxide production, in particular to a process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores, which comprises the following steps: sequentially calcining spodumene, cooling, finely grinding, adding acid for reaction, cooling, mixing slurry, leaching, squeezing and separating by a filter press, adding salt lake ore, purifying, filtering, causticizing, freezing and separating sodium sulfate, evaporating, recrystallizing at low temperature, drying and the like. The invention relates to a process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ore, which takes the mixed spodumene and salt lake ore as raw materials, wherein the salt lake ore Li2SO4·H2The O content reaches 80.1-92.1%, the average content is 85.1%, spodumene and salt lake ore are mixed to produce the lithium hydroxide monohydrate, the dilemma that the lithium ore resource is insufficient is solved, the risk of resisting the resource insufficiency of a production line is increased, and the problem of producing hydrogen from the salt lake ore resource is solvedThe quality of lithium oxide is low.
Description
Technical Field
The invention relates to the technical field of lithium hydroxide production, in particular to a process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores.
Background
The lithium hydroxide is widely applied to industries such as chemical raw materials, metallurgy, battery industry, ceramics, national defense, atomic energy, aerospace and the like, is used as an alkaline storage battery additive in the battery industry, can prolong the service life of the alkaline storage battery additive and increase the storage capacity of the alkaline storage battery additive. The main method for producing lithium hydroxide monohydrate at present is to use spodumene as a raw material and obtain the lithium hydroxide monohydrate through the process steps of high-temperature calcination transformation, cooling, ball milling, acidification roasting, cooling, size mixing, leaching, squeezing separation, sodium sulfate freezing separation, evaporation, low-temperature recrystallization and the like.
However, spodumene is insufficient in resources, and a new mineral source needs to be searched to meet the production requirement. Salt lake ore Li2SO4·H2The content of O is 80.1-92.1%, the average content is 85.1%, in the prior art, lithium products produced by salt lake ores are only industrial grade generally, and the economic restriction factors for producing battery grade products from the path are more.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ore.
The purpose of the invention is realized by the following technical scheme:
a process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores comprises the following steps:
s1, sequentially calcining spodumene, cooling, finely grinding, carrying out acid addition reaction and cooling, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry with the solid content of 10-70%;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, adding calcium oxide to adjust the pH value to be 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into the filtered clear liquid, and controlling the mixed material Li2The concentration of O is 30-48 g/L, the mixed liquid is purified by lithium hydroxide mother liquor or calcium oxide, the pH value is adjusted to 9-12, and impurities of iron, manganese, aluminum and calcium in the filtered clear liquid are removed;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
s4, filtering the solution causticized in the step S3 to obtain a causticized liquid and causticized filter residues, wherein the equivalent content of lithium hydroxide Li2O in the causticized liquid is controlled to be 30-75 g/L, and the causticized liquid is filtered by a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating to 200-800 ℃, filtering the lithium hydroxide solution through a precision filter to remove a part of calcium ions, then carrying out evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, carrying out evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating to 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
Further, in step S1, during calcination, the calcination temperature is 950 to 1200 ℃, the particle size of the fine powder is required to be 200 meshes, acid is added for reaction, sulfuric acid with a concentration of 98% is added, and the acid-to-material ratio is 2 to 4: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
Further, in step S2, the calcium carbonate slurry is mixed with calcium carbonate and water to form a slurry with a solid content of 10% to 55%; after filtering by the filter press, rinsing the filter cake by using tap water or process water, then purging the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning the obtained rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
Further, in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
Further, in step S4, the causticized filter residue is added with water to be prepared into slurry with the solid content of 10-70%, and then the process returns to the step S2 for purification.
The invention has the following advantages:
1. the process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ore takes the mixed spodumene and salt lake ore as raw materials, wherein the salt lake ore Li2SO4·H2The content of O is 80.1-92.1%, and the average content is 85.1%. According to the process, spodumene and salt lake ore are mixed to produce the lithium hydroxide monohydrate, so that the dilemma of insufficient lithium ore resources is solved, the risk of resisting resource shortage of a production line is increased, and the problem of low quality of lithium hydroxide produced from the salt lake ore resources is solved.
2. The improvement of the process can precipitate most of impurity ions such as Fe, Cu, Zn, Al and the like in the leaching stage, and filter the leached filter residue as a filter cake.
3. The lithium hydroxide mother liquor is used for purification, so that the introduction of calcium ions can be greatly reduced, the content of the calcium ions in the product is reduced, the quality of the lithium hydroxide product is improved, meanwhile, calcium oxide is properly used as a purifying agent, calcium salt can be used as a filter cake in a filter pressing step, the impurity removal effect of purification is improved, and part of impurities are removed.
4. The lithium hydroxide mother liquor is used for causticizing instead of liquid caustic soda, so that the using amount of the liquid caustic soda can be reduced, the generation cost is saved, the external moisture is reduced, the circulation of water in a system is greatly reduced, and the operation cost is saved.
5. The adjusted leaching process can reduce the use amount of calcium carbonate, thereby reducing the generation amount of carbon dioxide, enabling the leaching reaction to become mild, and avoiding the potential safety hazards such as overflowing caused by a large amount of bubbles.
6. The main component of the salt lake ore is lithium sulfate which can be directly purified and causticized, thereby reducing the introduction of calcium ions in the leaching link, reducing the content of the calcium ions in the product and improving the grade of the product; and meanwhile, the mother liquor containing the chloride ions is carbonized and precipitated to obtain industrial-grade lithium carbonate, the added value of the product is increased, and the mother liquor containing the chloride ions obtained by lithium precipitation is used for producing lithium chloride.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings, but the scope of the invention is not limited to the following.
As shown in fig. 1, a process for producing lithium hydroxide monohydrate from a mixture of spodumene and salt lake ore, comprising the steps of:
s1, sequentially calcining spodumene, cooling, finely grinding, carrying out acid addition reaction and cooling, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry with the solid content of 10-70%;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, adding calcium oxide to adjust the pH value to be 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into the filtered clear liquid, and controlling the mixed material Li2The concentration of O is 30-48 g/L, the mixed liquid is purified by lithium hydroxide mother liquor or calcium oxide, the pH value is adjusted to 9-12, and impurities of iron, manganese, aluminum and calcium in the filtered clear liquid are removed;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
s4, filtering the solution causticized in the step S3 to obtain a causticized liquid and causticized filter residues, wherein the equivalent content of lithium hydroxide Li2O in the causticized liquid is controlled to be 30-75 g/L, and the causticized liquid is filtered by a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating to 200-800 ℃, filtering the lithium hydroxide solution through a precision filter to remove a part of calcium ions, then carrying out evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, carrying out evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating to 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
Further, in step S1, during calcination, the calcination temperature is 950 to 1200 ℃, the particle size of the fine powder is required to be 200 meshes, acid is added for reaction, sulfuric acid with a concentration of 98% is added, and the acid-to-material ratio is 2 to 4: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
Further, in step S2, the calcium carbonate slurry is mixed with calcium carbonate and water to form a slurry with a solid content of 10% to 55%; after filtering by the filter press, rinsing the filter cake by using tap water or process water, then purging the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning the obtained rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
Further, in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
Further, in step S4, the causticized filter residue is added with water to be prepared into slurry with the solid content of 10-70%, and then the process returns to the step S2 for purification.
The invention improves the traditional method for preparing lithium hydroxide by adopting spodumene, and the process for preparing the lithium hydroxide monohydrate by mixing the spodumene and the salt lake ore takes the mixed spodumene and the salt lake ore as raw materials, wherein the salt lake ore Li is2SO4·H2The content of O is 80.1-92.1%, and the average content is 85.1%. According to the process, spodumene and salt lake ore are mixed to produce the lithium hydroxide monohydrate, so that the dilemma of insufficient lithium ore resources is solved, the risk of resisting resource shortage of a production line is increased, and the problem of low quality of lithium hydroxide produced from the salt lake ore resources is solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A process for producing lithium hydroxide monohydrate by mixing spodumene and salt lake ores is characterized by comprising the following steps: the method comprises the following steps:
s1, sequentially calcining spodumene, cooling, finely grinding, carrying out acid addition reaction and cooling, cooling a product of the acid addition reaction to be less than or equal to 90 ℃, and then mixing the product with water to obtain slurry with the solid content of 10-70%;
s2, adding calcium carbonate slurry into the slurry obtained in the step S1, stirring and leaching, adjusting the temperature in a leaching tank to be less than or equal to 60 ℃ and the pH value to be 5.5-6, adding calcium oxide to adjust the pH value to be 8-9 after leaching for 20 minutes, then filtering by using a filter press, adding salt lake ore into the filtered clear liquid, and controlling the mixed material Li2The concentration of O is 30-48 g/L, the mixed liquid is purified by lithium hydroxide mother liquor or calcium oxide, the pH value is adjusted to 9-12, and impurities of iron, manganese, aluminum and calcium in the filtered clear liquid are removed;
s3, filtering the clear filtrate obtained in the step S2 again to obtain purified liquid and purified filter residues, causticizing the purified liquid by using 50% alkaline solution or crude product mother liquor, wherein the pH value of the causticized solution is 11-14, and the temperature is normal temperature;
S4filtering the solution causticized in the step S3 to obtain causticized liquid and causticized filter residue, wherein lithium hydroxide Li in the causticized liquid2Controlling the equivalent content of O to be 30-75 g/L, and filtering the causticized liquid through a precision filter to remove part of calcium ions;
s5, freezing and separating the filtered causticized liquid into sodium sulfate decahydrate and lithium hydroxide solution in a freezing workshop, wherein the freezing temperature is-5 to-20 ℃;
s6, purifying sodium sulfate decahydrate through evaporation concentration, heating to take out crystal water to obtain anhydrous sodium sulfate, heating to 200-800 ℃, filtering the lithium hydroxide solution through a precision filter to remove a part of calcium ions, then carrying out evaporation concentration, crystallizing, centrifuging, re-melting, filtering through the precision filter, carrying out evaporation concentration after filtering, cooling, crystallizing and separating to obtain lithium hydroxide crystals, heating through a disc dryer to obtain lithium hydroxide monohydrate, and heating to 50-150 ℃;
s7, conveying the lithium hydroxide monohydrate obtained by heating the disc dryer to a vibrating screen through an air conveying device for particle screening, conveying the screened material to a vacuum feeding system for buffering, intermittently feeding the material to a weighing system through a spiral feeder, and then discharging the material to a pre-mixer;
s8, conveying the materials from the pre-mixer to a raw material distribution system, conveying one path of the materials to a vacuum feeding system, stacking the materials after passing through an automatic packaging system, and entering a finished product warehouse; and the other path is sent to a vacuum feeding system, is stacked through an airflow crushing system and an automatic packaging system and enters a finished product warehouse, and the finished product controls the magnetic substance not to exceed 30 PPb.
2. The process for producing lithium hydroxide monohydrate from a mixture of spodumene and salt lake ore according to claim 1, wherein: in step S1, during calcination, the calcination temperature is 950 to 1200 ℃, the particle size of the fine grinding is required to be 200 meshes, acid is added for reaction, sulfuric acid with a concentration of 98% is added, and the acid-to-material ratio is 2 to 4: 1, adding acid for reaction, and cooling to below 60 ℃; and during cooling, the cooling is carried out in a water cooling mode.
3. The process for producing lithium hydroxide monohydrate from a mixture of spodumene and salt lake ore according to claim 1, wherein: in step S2, the calcium carbonate slurry is prepared into slurry by calcium carbonate and water, and the solid content is 10-55%; after filtering by the filter press, rinsing the filter cake by using tap water or process water, then purging the filter cake by using compressed air to ensure that the water content of the filter cake is less than or equal to 20%, and returning the obtained rinsing water to be used for size mixing in the step S1; during purification, if lithium hydroxide mother liquor is added, the concentration of the lithium hydroxide mother liquor is 10-50%, and if calcium oxide is added, the calcium oxide is powder with the mass fraction of more than 75% or calcium oxide slurry with the solid content of 10-55%.
4. The process for producing lithium hydroxide monohydrate from a mixture of spodumene and salt lake ore according to claim 1, wherein: in the step S3, adding water into the purified filter residue to prepare slurry with the solid content of 10-70%, and returning to the step S1; the alkaline solution is sodium hydroxide solution, lithium hydroxide solution or the mixed solution of the sodium hydroxide solution and the lithium hydroxide solution.
5. The process for producing lithium hydroxide monohydrate from a mixture of spodumene and salt lake ore according to claim 1, wherein: in step S4, adding water into the causticized filter residue to prepare slurry with the solid content of 10-70%, and then returning to the step S2 for purification.
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