CN111592017A - Method for preparing battery-grade lithium chloride by pressing and soaking spodumene - Google Patents
Method for preparing battery-grade lithium chloride by pressing and soaking spodumene Download PDFInfo
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- CN111592017A CN111592017A CN202010274783.8A CN202010274783A CN111592017A CN 111592017 A CN111592017 A CN 111592017A CN 202010274783 A CN202010274783 A CN 202010274783A CN 111592017 A CN111592017 A CN 111592017A
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- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 title claims abstract description 174
- 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 59
- 238000000034 method Methods 0.000 title claims abstract description 53
- 229910052642 spodumene Inorganic materials 0.000 title claims abstract description 52
- 238000003825 pressing Methods 0.000 title claims description 14
- 238000002791 soaking Methods 0.000 title description 3
- 239000011734 sodium Substances 0.000 claims abstract description 34
- 238000001914 filtration Methods 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 23
- 239000003463 adsorbent Substances 0.000 claims abstract description 20
- 230000008020 evaporation Effects 0.000 claims abstract description 20
- 239000011575 calcium Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 18
- 238000002386 leaching Methods 0.000 claims abstract description 17
- 239000001110 calcium chloride Substances 0.000 claims abstract description 16
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 16
- 150000002500 ions Chemical class 0.000 claims abstract description 16
- 238000000926 separation method Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 230000020477 pH reduction Effects 0.000 claims abstract description 8
- 235000017550 sodium carbonate Nutrition 0.000 claims abstract description 8
- 229910052644 β-spodumene Inorganic materials 0.000 claims abstract description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 5
- 230000009466 transformation Effects 0.000 claims abstract description 4
- 238000011085 pressure filtration Methods 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 36
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- 239000007788 liquid Substances 0.000 claims description 28
- 229910001415 sodium ion Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 19
- 229910001868 water Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000013078 crystal Substances 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 8
- 238000007789 sealing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 230000000694 effects Effects 0.000 claims description 6
- 239000012530 fluid Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 230000007797 corrosion Effects 0.000 claims description 3
- 238000005260 corrosion Methods 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910019898 NaxMnO2 Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- 159000000000 sodium salts Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 67
- 230000008569 process Effects 0.000 abstract description 9
- 239000002994 raw material Substances 0.000 abstract description 7
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 abstract description 5
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 235000011148 calcium chloride Nutrition 0.000 abstract 1
- 239000012045 crude solution Substances 0.000 abstract 1
- 238000003837 high-temperature calcination Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 229910052744 lithium Inorganic materials 0.000 description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 description 6
- 235000019738 Limestone Nutrition 0.000 description 5
- 239000006028 limestone Substances 0.000 description 5
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 238000007710 freezing Methods 0.000 description 4
- 230000008014 freezing Effects 0.000 description 4
- 239000013067 intermediate product Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000920 calcium hydroxide Substances 0.000 description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 3
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000002642 lithium compounds Chemical class 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910010092 LiAlO2 Inorganic materials 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910052629 lepidolite Inorganic materials 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
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000001238 wet grinding Methods 0.000 description 1
- 229910001845 yogo sapphire 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
- C01D15/04—Halides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
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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 discloses a method for preparing battery-grade lithium chloride by spodumene pressure leaching, which takes spodumene as a raw material and comprises the following preparation steps: carrying out pressure leaching reaction on beta spodumene subjected to high-temperature calcination and transformation, a CaCl2 solution and a small amount of Ca (OH)2 solution at high temperature and high pressure, carrying out flash evaporation and pressure filtration to obtain a LiCl crude solution, carrying out Na2CO3 calcium removal and filtration to obtain a LiCl solution, carrying out acidification stripping, evaporative concentration, cooling sodium precipitation, sodium removal by an ion adsorbent, carrying out evaporative crystallization, separation and drying to finally obtain battery-grade lithium chloride; the method has the advantages of simple process, low impurity content, low energy consumption, low cost and stable product quality, and particularly, the method for removing sodium is simple and effective.
Description
Technical Field
The invention relates to the technical field of chemical production of battery-grade lithium chloride, in particular to a method for preparing battery-grade lithium chloride by spodumene pressure leaching.
Background
Lithium chloride is a white, regular crystal with a NaCl type of face-centered lattice. It has strong hygroscopicity, is very easy to dissolve in water, and can be dissolved in organic solvents such as methanol, ethanol, pyridine, etc. Lithium chloride has a wide range of applications, and is mainly used for flux and flux for electrolytically producing lithium metal and aluminum, and moisture absorbent in non-freezing air conditioners. Lithium chloride is a raw material for preparing metal lithium, and the electrolytic production of the metal lithium is the field with the largest lithium chloride consumption. Lithium metal and its alloys and compounds have wide applications in many fields such as atomic energy industry, metallurgical industry, batteries, glass, chemical industry, aerospace industry, etc. Due to the rapid development of lithium batteries and the biopharmaceutical industry in recent years, the demand of high-purity lithium metal and lithium compounds is greatly increased, lithium chloride is used as a main raw material of the lithium metal, and the quality of the lithium chloride has a fundamental influence on the quality of the lithium metal.
The raw materials for preparing the lithium chloride are the same as other lithium and lithium compound raw materials, and are mainly obtained from spodumene, lepidolite, salt lake brine containing lithium ions, underground brine and seawater. The preparation is mainly prepared by extracting lithium from spodumene in China. Spodumene is a lithium-containing mineral with Li as the main component2O、SiO2、Al2O3The content of Li2O in the spodumene concentrate is about 6.3-7.5%, and the method for extracting lithium from spodumene mainly comprises a sulfuric acid acidification roasting method, a limestone sintering method, a soda ash pressure cooking method and the like, wherein the sulfuric acid roasting method comprises the steps of mixing β spodumene subjected to high-temperature transformation with a certain proportion of sulfuric acid at 250-300 ℃ for roasting, leaching an acidification roasting material by using water, and simultaneously adding Ca0 or CaCO3Neutralization is carried out to obtain Li2SO4A solution; mixing Li2SO4Solution with CaCl2The crude LiCl liquid can be obtained by reaction, and then LiCl product can be obtained by removing impurities. The sulfuric acid roasting method is a main method for extracting lithium at home and abroad at present, the development is mature, and the industrial application is the most extensive. The limestone sintering method comprises the steps of mixing spodumene and limestone according to a certain weight ratio, mixing, grinding and blending, sintering at 1000-1200 ℃ to produce lithium aluminate and calcium silicate, carrying out wet grinding and crushing, leaching lithium aluminate with washing liquor, carrying out sedimentation and filtration, evaporating and concentrating leaching liquor, and adding soda to generate lithium carbonate; lithium chloride can be prepared by adding hydrochloric acid into lithium carbonate for acidification. The limestone sintering method has the advantages of cheap and easily obtained auxiliary materials and simple process; the defects are that the concentration of the leaching solution is low, the evaporation energy consumption is large, and the recovery rate of lithium is low. Soda ash is pressed and boiled by using excessive Na2CO3β spodumene is treated by the solution under a certain pressure, lithium in the spodumene is replaced by lithium carbonate crystal, and then lithium chloride is prepared by acidifying lithium carbonate with hydrochloric acid.
The method for preparing LiCl by sulfuric acid acidification roasting method, limestone sintering method, soda ash pressure boiling method and the like generally comprises the steps of firstly extracting lithium to prepare Li2SO4、Li2CO3、LiAlO2After the intermediate product is converted again to LiCl, it cannot be directly converted from spodumeneLiCl is generated. In the conversion process, new impurities are easily introduced, impurity removal is difficult, a plurality of working procedures are added, and the preparation method is complex. And the product usually has more impurities, cannot meet the standard of battery-grade lithium chloride and needs to be further refined.
Disclosure of Invention
The invention aims to provide a method for preparing battery-grade lithium chloride by pressing and soaking spodumene, aiming at the defects and shortcomings of the prior art, the spodumene is not required to be roasted at high temperature, no intermediate product is generated, partial raw materials can be recycled, and the method has the advantages of simple process, less energy consumption, low cost and the like.
In order to achieve the purpose, the invention adopts the technical scheme that: it comprises the following steps:
s1, high-temperature transformation: roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
s2, pressure leaching, namely, the transformed β spodumene and CaCl2Solution and a small amount of Ca (OH)2Mixing, sealing in a high-pressure reaction kettle, heating and stirring;
s3, flash evaporation: decompressing the high-temperature high-pressure immersion fluid into a flash tank, and carrying out gas-liquid separation after the fluid is vaporized; wherein the water vapor can be liquefied to obtain condensed water, and the condensed water can be recovered for washing, filtering and CaCl preparation2Recycling the solution;
s4, filter pressing: carrying out pressure filtration on the liquid component obtained by flash evaporation to obtain filter pressing residue and LiCl crude liquid;
s5, washing: washing the filter-pressing residue with condensed water, and filtering to obtain spodumene slag and washing water part for preparing CaCl2A solution;
S6、NaCO3calcium removal: adding soda ash into the LiCl crude liquid, and mixing uniformly to generate CaCO3After precipitation, calcium impurities are removed by filtration, and Mg and Fe impurities in the solution are removed;
s7, acidification and stripping: adjusting the pH value of the solution to be 2-3 by using excessive hydrochloric acid, acidifying the solution, and removing generated CO2 by using a steam stripping method; the CO2 generated by the reaction is collected by adopting a stripping method, so that the corrosion of equipment can be reduced, and the overlarge pressure intensity of the equipment caused by the gas entering the equipment is prevented;
s8, evaporation and concentration: carrying out triple effect evaporation and concentration on the treated solution until the mass percentage concentration of LiCl is 35-45%;
s9, cooling and sodium precipitation: cooling the concentrated solution to normal temperature to separate out partial NaCl crystal; filtering and separating to remove sodium chloride solids to obtain a lithium chloride solution with low sodium content;
s10, removing sodium by using a sodium ion adsorbent: removing sodium by adopting an ion sieve type sodium ion adsorbent;
s11, evaporative crystallization: evaporating and crystallizing the LiCl solution after impurity removal;
s12, separation and drying: and filtering and separating the crystals by adopting a centrifugal machine, drying by using a disc type dryer, and packaging to finally obtain the battery-grade lithium chloride product.
Further, in step S2, the heating temperature is controlled between 160-200 ℃, the pressure is set at 1.2-1.8 MPa, the stirring speed is 300-.
Further, in step S6, Na produced by adding soda ash to the crude LiCl liquid2CO3Adjusting the pH value of the solution to 9-10, and removing Ca in the solution after impurity removal2+The content is lower than 0.0001%;
further, CaCO generated in step S63Can be recovered and then acidified by hydrochloric acid to prepare CaCl2The solution is used in the step 1 and recycled;
further, the preparation method of the sodium ion adsorbent in step S10 is: mixing sodium salt and manganese-containing substance, and calcining to obtain precursor NaxMnO2Mixing the precursor with hydrochloric acid at a mixing ratio of n (Na)xMnO2): and (n) (HCl) ((1: 0.1-0.01)), and then washing, filtering and drying the product to finally obtain the ion sieve type sodium ion adsorbent.
Compared with other lithium chloride product preparation methods, the method has the following characteristics:
1. spodumene reacts with calcium chloride solutions mainly as follows:
CaO+H2O→Ca(OH)2
adding the sintered β spodumene, water, calcium chloride solution and a small amount of calcium hydroxide into a high-pressure reaction kettle according to the reaction equation2About 5 to 10% excess, Ca (OH)2The addition amount is about 1-2% of the content of spodumene, and water is added to adjust the solid-to-liquid ratio to be 1: 3-1: 4; adding a small amount of Ca (OH)2The conversion rate of LiCl can be improved; the reaction of spodumene with calcium chloride solution is reversible and, due to the effect of the homoionic effect, the solution contains small amounts of Ca (OH)2Can lead CaCl in the solution2The content is reduced, the reaction direction is favorably moved to the direction of generating LiCl, and the generation rate of lithium chloride is improved.
2. The solution acidification stripping reaction equation is as follows:
adding excessive hydrochloric acid to adjust the pH of the solution to 2-3 to remove excessive CO3 2-Ions, absorbing CO formed by stripping2The condensed liquid is absorbed and purified and then is discharged to the atmosphere, so that the corrosion of acid gas to equipment can be reduced, and CO is prevented2High pressure is caused when the waste water enters the equipment, so that the production safety is influenced.
3. Because the properties of sodium ions and lithium ions in the lithium chloride solution are similar, sodium chloride is the impurity which is most difficult to remove in the middle and later stages of the lithium chloride production and preparation process; common removal methods include solution extraction, ion exchange, salting out, and the like; however, most of these methods require the introduction of new impurities, and the post-treatment is complicated. The invention mainly adopts two methods of cooling sodium separation and ion adsorbent adsorption to remove sodium chloride under the combined action:
(1) the method comprises the following steps of removing NaCl by using a normal-temperature sodium separation method by utilizing the homoionic effect and the change of the solubility of a lithium chloride system and a sodium chloride system along with the temperature, wherein the sodium ion content of a lithium chloride solution subjected to normal-temperature sodium separation is lower than 1 g/l;
(2) the ion sieve type sodium ion adsorbent is used for removing impurities, the removal rate of the ion sieve type sodium ion adsorbent in the invention to sodium ions is more than 98%, and can reach 99% at a higher rate, the ion sieve type sodium ion adsorbent is suitable for removing sodium from a high-concentration lithium chloride solution, and the used ion sieve type sodium ion adsorbent residue can be regenerated after being mixed with hydrochloric acid and can be reused.
The two methods have simple process, no new impurity is introduced, and the impurity removal effect is good; the content of sodium impurities in the lithium chloride obtained by removing impurities by the two methods is lower than 0.0015 percent, and the requirement of the content of the sodium impurities in the battery-grade lithium chloride is met.
4. Using CaCl2、Ca(OH)2The raw materials have low price and wide source, and the condensed water and CaCO generated in the preparation process3And intermediate products such as the ion sieve type sodium ion adsorbent and the like can be recycled and reused, so that the material is saved, the cyclic utilization of resources is realized, and the cost is greatly reduced.
5. The method is different from the traditional method for preparing lithium chloride by spodumene, does not need to prepare intermediate products such as lithium sulfate, lithium carbonate, lithium aluminate and the like firstly and then react with hydrochloric acid to generate lithium chloride, and directly uses spodumene and CaCl2Lithium chloride solution is obtained by a one-step method of solution pressure leaching reaction; the prepared battery-grade lithium chloride has the components with the mass percentage concentration (LiCl) of more than or equal to 99.50 percent, Na of less than or equal to 0.0015 percent, K of less than or equal to 0.05 percent, Fe of less than or equal to 0.0003 percent, Ca of less than or equal to 0.0025 percent, Ba of less than or equal to 0.01 percent and SO of less than or equal to 0.05 percent4 2-Less than or equal to 0.002 percent, less than or equal to 0.0005 percent of Mg, less than or equal to 0.0005 percent of Cu, less than or equal to 0.003 percent of hydrochloric acid insoluble substances, and more than or equal to 85 percent of whiteness, thereby meeting the standard of battery-grade anhydrous lithium chloride.
After the scheme is adopted, the invention has the beneficial effects that: the method for preparing battery-grade lithium chloride by spodumene pressure leaching has the advantages of simple process, simple and effective method for removing sodium, low impurity content, low energy consumption, low cost and stable product quality.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a process flow diagram for the preparation of battery grade lithium chloride by the spodumene pressure leach process of the present invention.
Detailed Description
The invention will be further described with reference to the accompanying drawings.
Example 1: referring to fig. 1, it comprises the following steps:
1. roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
2. 400g of water, 100g of transformed β spodumene fine powder, 1g of Ca (OH)265g of 35% CaCl2Pouring the solution into a high-pressure reaction kettle, sealing and heating, wherein T is 200 ℃, P is 1.45MPa, the rotating speed n is 350r/min, and the reaction time is 60 min;
3. quickly decompressing and flashing, taking out and filtering to obtain filter pressing residue and LiCl crude liquid;
4. adding Na into the LiCl crude liquid2CO3Adjusting the pH value of the solution to 9-10, and filtering to remove generated CaCO3Precipitating;
5. adding excessive hydrochloric acid, adjusting the pH value of the solution to be 2-3, and removing generated CO after acidification2A gas;
6. heating the solution for triple-effect evaporation and concentration, and evaporating until the concentration of LiCl is 40 percent of concentrated solution;
7. cooling the LiCl solution to-5 ℃, freezing and crystallizing, and filtering to remove precipitated NaCl crystals;
8. removing sodium by using an ion sieve type sodium ion adsorbent;
9. and (3) carrying out solid-liquid separation after evaporation and crystallization, and drying to obtain 15.6g of battery-grade lithium chloride finished product, which is marked as product 1.
Example 2: referring to fig. 1, it comprises the following steps:
1. roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
2. 400g of water, 100g of transformed β spodumene fine powder, 1.5g of Ca (OH)270g of 35% CaCl2Pouring the solution into a high-pressure reaction kettle, sealing and heating, wherein T is 200 ℃, P is 1.45MPa, the rotating speed n is 300r/min, and the reaction time is 40 min;
3. quickly decompressing and flashing, taking out and filtering to obtain filter pressing residue and LiCl crude liquid;
4. adding Na into the LiCl crude liquid2CO3Adjusting the pH value of the solution to 9-10, and filtering to remove generated CaCO3Precipitating;
5. adding excessive hydrochloric acid, adjusting the pH value of the solution to be 2-3, and continuously stirring to remove generated CO2A gas;
6. heating the solution to 120 ℃ for continuous evaporation until concentrated solution with LiCl concentration of 35% is obtained;
7. cooling the LiCl solution to-5 ℃, and filtering to remove NaCl crystals while the solution is cold;
8. removing sodium by using an ion sieve type sodium ion adsorbent;
9. and (3) carrying out solid-liquid separation after evaporation and crystallization, drying and collecting 16.3g of battery-grade lithium chloride finished product, wherein the green label is product 2.
Example 3: referring to fig. 1, it comprises the following steps:
1. roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
2. taking 800g of water, 200g of transformed β type spodumene fine powder, 2g of Ca (OH)2130g of 35% CaCl2Pouring the solution into a high-pressure reaction kettle, sealing and heating, wherein T is 180 ℃, P is 1.5MPa, the rotating speed n is 350r/min, and the reaction time is 120 min;
3. quickly decompressing and flashing, taking out and filtering to obtain filter pressing residue and LiCl crude liquid;
4. adding Na into the LiCl crude liquid2CO3Adjusting the pH value of the solution to 9-10, and filtering to remove generated CaCO3Precipitating;
5. adding excessive hydrochloric acid to adjust the pH of the solution to 2 to c3, continuously stirring to remove the generated CO2A gas;
6. heating the solution for triple-effect evaporation and concentration, and evaporating until the concentration of LiCl is 40 percent of concentrated solution;
7. cooling the LiCl solution to-5 ℃, freezing and crystallizing, and filtering to remove precipitated NaCl crystals;
8. removing sodium by using an ion sieve type sodium ion adsorbent;
9. and (3) carrying out solid-liquid separation after evaporation and crystallization, and drying to obtain 28.7g of battery-grade lithium chloride finished product which is marked as product 3.
Example 4: referring to fig. 1, it comprises the following steps:
1. roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
2. taking 700g of water, 200g of transformed β type spodumene fine powder, 3g of Ca (OH)2150g of 30% CaCl2Pouring the solution into a high-pressure reaction kettle, sealing and heating, wherein T is 200 ℃, P is 1.5MPa, the rotating speed n is 350r/min, and the reaction time is 45 min;
3. quickly decompressing and flashing, taking out and filtering to obtain filter pressing residue and LiCl crude liquid;
4. adding Na into the LiCl crude liquid2CO3Adjusting the pH value of the solution to 9-10, and filtering to remove generated CaCO3Precipitating;
5. adding excessive hydrochloric acid, adjusting the pH value of the solution to be 2-3, acidifying, and removing CO2A gas;
6. heating the solution for triple-effect evaporation and concentration, and concentrating to obtain a concentrated solution with the LiCl concentration of 40%;
7. cooling the LiCl solution to-10 ℃, and filtering to remove NaCl crystals while the solution is cold;
8. removing sodium by using an ion sieve type sodium ion adsorbent;
9. and (4) carrying out solid-liquid separation after evaporation and crystallization, drying and collecting 30.6g of battery-grade lithium chloride finished product, wherein the label is product 4.
Example 5: referring to fig. 1, it comprises the following steps:
1. roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
2. taking 700g of water, 200g of transformed β type spodumene fine powder, 2g of Ca (OH)2140g of 35% CaCl2Pouring the solution into a high-pressure reaction kettle, sealing and heating, wherein T is 200 ℃, P is 1.5MPa, the rotating speed n is 300r/min, and the reaction time is 30 min;
3. quickly decompressing and flashing, taking out and filtering to obtain filter pressing residue and LiCl crude liquid;
4. adding Na into the LiCl crude liquid2CO3Adjusting the pH value of the solution to 9-10, and filtering to remove generated CaCO3Precipitating;
5. adding excessive hydrochloric acid, adjusting the pH value of the solution to be 2-3, and continuously stirring to remove generated CO2A gas;
6. heating the solution for triple-effect evaporation and concentration, and evaporating until the concentration of LiCl is 40 percent of concentrated solution;
7. cooling the LiCl solution to-5 ℃, freezing and crystallizing, and filtering to remove precipitated NaCl crystals;
8. removing sodium by using a self-made ion sieve type sodium ion adsorbent;
9. and (3) carrying out solid-liquid separation after evaporation and crystallization, and drying to obtain 30.3g of battery-grade lithium chloride finished product, which is marked as product 5.
In examples 1 to 5, the concentrations of the components were all mass percent concentrations.
The results of analyzing the components of the products 1 to 5 obtained in the above examples 1 to 5 are shown in the following table:
the detection data show that the prepared sample meets the standard of battery-grade anhydrous lithium chloride, the battery-grade lithium chloride is prepared by adopting a spodumene pressure leaching method, the process is simple, particularly, the method for removing sodium is simple and effective, the impurity content is low, the energy consumption is low, the cost is low, and the product quality is stable.
The above description is only for the purpose of illustrating the technical solutions of the present invention and not for the purpose of limiting the same, and other modifications or equivalent substitutions made by those skilled in the art to the technical solutions of the present invention should be covered within the scope of the claims of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (5)
1. A method for preparing battery-grade lithium chloride by spodumene pressure leaching is characterized by comprising the following steps of S1, high-temperature transformation: roasting spodumene at the high temperature of 1000-1100 ℃ to convert the spodumene into active beta-type spodumene from alpha type;
s2, pressure leaching, namely, the transformed β spodumene and CaCl2Solution and a small amount of Ca (OH)2Mixing, sealing in a high-pressure reaction kettle, heating and stirring;
s3, flash evaporation: decompressing the high-temperature high-pressure immersion fluid into a flash tank, and carrying out gas-liquid separation after the fluid is vaporized; wherein the water vapor can be liquefied to obtain condensed water, and the condensed water can be recovered for washing, filtering and CaCl preparation2Recycling the solution;
s4, filter pressing: carrying out pressure filtration on the liquid component obtained by flash evaporation to obtain filter pressing residue and LiCl crude liquid;
s5, washing: washing the filter-pressing residue with condensed water, and filtering to obtain spodumene slag and washing water part for preparing CaCl2A solution;
S6、 NaCO3calcium removal: adding soda ash into the LiCl crude liquid, and mixing uniformly to generate CaCO3After precipitation, calcium impurities are removed by filtration, and Mg and Fe impurities in the solution are removed;
s7, acidification and stripping: adjusting the pH = 2-3 of the solution by using excessive hydrochloric acid, acidifying the solution, and removing generated CO2 by using a steam stripping method; the CO2 generated by the reaction is collected by adopting a stripping method, so that the corrosion of equipment can be reduced, and the overlarge pressure intensity of the equipment caused by the gas entering the equipment is prevented;
s8, evaporation and concentration: carrying out triple effect evaporation and concentration on the treated solution until the mass percentage concentration of LiCl is 35-45%;
s9, cooling and sodium precipitation: cooling the concentrated solution to normal temperature to separate out partial NaCl crystal; filtering and separating to remove sodium chloride solids to obtain a lithium chloride solution with low sodium content;
s10, removing sodium by using a sodium ion adsorbent: removing sodium by adopting an ion sieve type sodium ion adsorbent;
s11, evaporative crystallization: evaporating and crystallizing the LiCl solution after impurity removal;
s12, separation and drying: and filtering and separating the crystals by adopting a centrifugal machine, drying by using a disc type dryer, and packaging to finally obtain the battery-grade lithium chloride product.
2. The method of claim 1, wherein in step S2, the heating temperature is controlled to be 160-200 ℃, the pressure is set to be 1.2-1.8 MPa, the stirring speed is 300-500r/min, and the pressure leaching time is about 0.5-3 h.
3. The process for preparing battery-grade lithium chloride by spodumene pressure leaching according to claim 1, wherein in step S6, Na generated after soda ash is added to the LiCl crude liquid2CO3Adjusting the pH of the solution to be 9-10, and removing Ca in the solution after impurity removal2+The content is less than 0.0001%.
4. The method for preparing battery-grade lithium chloride by spodumene pressure leaching according to claim 1, wherein CaCO generated in step S63Can be recovered and then acidified by hydrochloric acid to prepare CaCl2The solution is used in step 1 and recycled.
5. The method for preparing battery-grade lithium chloride by spodumene pressure leaching according to claim 1, wherein the preparation method of the sodium ion adsorbent in the step S10 is as follows: mixing sodium salt and manganese-containing substance, and calcining to obtain precursor NaxMnO2Mixing the precursor with hydrochloric acid at a mixing ratio of n (Na)xMnO2): n (HCl) = (1: 0.1-0.01), and then washing, filtering and drying are carried out to finally obtain the ion sieve type sodium ion adsorbent.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
| CN116040659A (en) * | 2023-01-17 | 2023-05-02 | 天齐锂业(射洪)有限公司 | Preparation method of battery-grade anhydrous lithium chloride |
| GB2623593A (en) * | 2022-10-21 | 2024-04-24 | Res By British Lithium Limited | Impurity removal and leaching of lithium material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833830A (en) * | 2016-04-19 | 2016-08-10 | 天齐锂业股份有限公司 | Ion sieve type sodium ion adsorbent and method for removing impurity sodium in lithium chloride |
| CN107089674A (en) * | 2017-07-03 | 2017-08-25 | 福州大学 | A kind of spodumene sodium sulphate pressure leaching puies forward lithium technique |
| CN107934998A (en) * | 2017-11-13 | 2018-04-20 | 江西赣锋锂业股份有限公司 | A kind of method that spodumene leachate prepares LITHIUM BATTERY lithium chloride |
| CN110117020A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院过程工程研究所 | A method of it is handled using mineral element phase transfer containing lithium minerals |
-
2020
- 2020-04-09 CN CN202010274783.8A patent/CN111592017A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105833830A (en) * | 2016-04-19 | 2016-08-10 | 天齐锂业股份有限公司 | Ion sieve type sodium ion adsorbent and method for removing impurity sodium in lithium chloride |
| CN107089674A (en) * | 2017-07-03 | 2017-08-25 | 福州大学 | A kind of spodumene sodium sulphate pressure leaching puies forward lithium technique |
| CN107934998A (en) * | 2017-11-13 | 2018-04-20 | 江西赣锋锂业股份有限公司 | A kind of method that spodumene leachate prepares LITHIUM BATTERY lithium chloride |
| CN110117020A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院过程工程研究所 | A method of it is handled using mineral element phase transfer containing lithium minerals |
Non-Patent Citations (2)
| Title |
|---|
| 朱朝梁等: "离子筛型钠吸附剂的制备和吸附性能研究", 《盐业与化工》 * |
| 王彦飞等: "去除氯化锂中氯化钠的研究进展", 《无机盐工业》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114890441A (en) * | 2022-05-16 | 2022-08-12 | 昆明理工大学 | Method for recovering lithium chloride and cobalt oxide from waste lithium cobaltate battery positive plate |
| CN114890441B (en) * | 2022-05-16 | 2023-05-23 | 昆明理工大学 | Method for recycling lithium chloride and cobalt oxide from waste lithium cobalt oxide battery positive plate |
| GB2623593A (en) * | 2022-10-21 | 2024-04-24 | Res By British Lithium Limited | Impurity removal and leaching of lithium material |
| WO2024084229A1 (en) * | 2022-10-21 | 2024-04-25 | Research By British Lithium Ltd | Impurity removal and leaching of lithium material |
| CN116040659A (en) * | 2023-01-17 | 2023-05-02 | 天齐锂业(射洪)有限公司 | Preparation method of battery-grade anhydrous lithium chloride |
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