CN117865190A - Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method - Google Patents
Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method Download PDFInfo
- Publication number
- CN117865190A CN117865190A CN202311844913.7A CN202311844913A CN117865190A CN 117865190 A CN117865190 A CN 117865190A CN 202311844913 A CN202311844913 A CN 202311844913A CN 117865190 A CN117865190 A CN 117865190A
- Authority
- CN
- China
- Prior art keywords
- lithium
- brine
- reaction
- stirring
- potassium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 133
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 133
- 238000000034 method Methods 0.000 title claims abstract description 62
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 title claims abstract description 30
- 229910052808 lithium carbonate Inorganic materials 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- 239000012267 brine Substances 0.000 claims abstract description 134
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 134
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 73
- 238000006243 chemical reaction Methods 0.000 claims abstract description 59
- 238000003756 stirring Methods 0.000 claims abstract description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 33
- 238000001914 filtration Methods 0.000 claims abstract description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims abstract description 32
- 238000001556 precipitation Methods 0.000 claims abstract description 26
- 238000002386 leaching Methods 0.000 claims abstract description 21
- 239000002893 slag Substances 0.000 claims abstract description 21
- 229940037003 alum Drugs 0.000 claims abstract description 20
- KLZUFWVZNOTSEM-UHFFFAOYSA-K Aluminium flouride Chemical group F[Al](F)F KLZUFWVZNOTSEM-UHFFFAOYSA-K 0.000 claims abstract description 17
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims abstract description 16
- 239000003513 alkali Substances 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 9
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims abstract description 7
- 235000011941 Tilia x europaea Nutrition 0.000 claims abstract description 7
- 239000004571 lime Substances 0.000 claims abstract description 7
- IRPGOXJVTQTAAN-UHFFFAOYSA-N 2,2,3,3,3-pentafluoropropanal Chemical compound FC(F)(F)C(F)(F)C=O IRPGOXJVTQTAAN-UHFFFAOYSA-N 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- RGKMZNDDOBAZGW-UHFFFAOYSA-N aluminum calcium Chemical compound [Al].[Ca] RGKMZNDDOBAZGW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 3
- 239000012535 impurity Substances 0.000 claims description 49
- 239000011575 calcium Substances 0.000 claims description 38
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 34
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 229910052629 lepidolite Inorganic materials 0.000 claims description 25
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052791 calcium Inorganic materials 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 15
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 15
- 235000011151 potassium sulphates Nutrition 0.000 claims description 15
- 239000001488 sodium phosphate Substances 0.000 claims description 14
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 14
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 14
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 8
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 claims description 7
- 229910001634 calcium fluoride Inorganic materials 0.000 claims description 7
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- 235000011009 potassium phosphates Nutrition 0.000 claims description 6
- HEHRHMRHPUNLIR-UHFFFAOYSA-N aluminum;hydroxy-[hydroxy(oxo)silyl]oxy-oxosilane;lithium Chemical compound [Li].[Al].O[Si](=O)O[Si](O)=O.O[Si](=O)O[Si](O)=O HEHRHMRHPUNLIR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052670 petalite Inorganic materials 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- 235000010333 potassium nitrate Nutrition 0.000 claims description 4
- 239000004323 potassium nitrate Substances 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 239000005696 Diammonium phosphate Substances 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- 239000001506 calcium phosphate Substances 0.000 claims description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 claims description 2
- 235000011010 calcium phosphates Nutrition 0.000 claims description 2
- -1 celadon Chemical compound 0.000 claims description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 2
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 2
- 229940094522 laponite Drugs 0.000 claims description 2
- XCOBTUNSZUJCDH-UHFFFAOYSA-B lithium magnesium sodium silicate Chemical compound [Li+].[Li+].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3.O1[Si](O2)([O-])O[Si]3([O-])O[Si]1([O-])O[Si]2([O-])O3 XCOBTUNSZUJCDH-UHFFFAOYSA-B 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 235000011008 sodium phosphates Nutrition 0.000 claims description 2
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims 1
- 230000008025 crystallization Effects 0.000 claims 1
- 238000000605 extraction Methods 0.000 abstract description 14
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000003723 Smelting Methods 0.000 abstract description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 56
- 239000011777 magnesium Substances 0.000 description 36
- 239000011572 manganese Substances 0.000 description 30
- 229910052742 iron Inorganic materials 0.000 description 25
- 235000017550 sodium carbonate Nutrition 0.000 description 25
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 229910018068 Li 2 O Inorganic materials 0.000 description 18
- 229910052749 magnesium Inorganic materials 0.000 description 18
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 15
- 229910052731 fluorine Inorganic materials 0.000 description 15
- 239000011737 fluorine Substances 0.000 description 15
- 239000000126 substance Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 239000000292 calcium oxide Substances 0.000 description 12
- 235000012255 calcium oxide Nutrition 0.000 description 12
- 229910052748 manganese Inorganic materials 0.000 description 12
- 230000001105 regulatory effect Effects 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 239000011734 sodium Substances 0.000 description 12
- 238000005406 washing Methods 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 6
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000007654 immersion Methods 0.000 description 6
- 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 description 6
- 239000010413 mother solution Substances 0.000 description 6
- 238000005057 refrigeration Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 235000010755 mineral Nutrition 0.000 description 3
- 239000011707 mineral Substances 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910007857 Li-Al Inorganic materials 0.000 description 1
- 229910008447 Li—Al Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004673 fluoride salts Chemical class 0.000 description 1
- 150000002221 fluorine Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910000271 hectorite Inorganic materials 0.000 description 1
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a process for preparing lithium carbonate by extracting lithium from lithium ore by wet method, which relates to the technical field of wet smelting and comprises the following steps: adding lithium ore, sulfuric acid and fluoride into a reaction kettle, heating, stirring for reaction, and filtering to obtain silica slag and brine; adding alkali to regulate pH of brine, adding potassium salt, stirring for reaction, cooling, and filtering to obtain alum and alum-removed brine; adding phosphate and alkali into the alum-removed brine, stirring for reaction, and filtering to obtain aluminum fluoride residues and primary purified brine; lime is added into the primary purified brine, and the aluminum-calcium slag and the secondary purified brine are obtained through stirring reaction; adding sodium carbonate into the secondary purified brine, and stirring for reaction to obtain magnesium-calcium slag and tertiary purified brine; concentrating the purified brine for three times, and adding saturated sodium carbonate solution for lithium precipitation reaction to obtain lithium carbonate. The invention adopts the intensified leaching means to realize the normal pressure low temperature wet method lithium extraction, has high lithium recovery rate and low energy consumption, and can recycle aluminum fluoride slag and alum generated in the process of preparing lithium carbonate.
Description
Technical Field
The invention relates to the technical field of wet smelting, in particular to a process for preparing lithium carbonate by extracting lithium from lithium ore by a wet method.
Background
Lithium is known as "new energy metal", and metal and compound thereof are indispensable raw materials for the development of new energy industry. Currently, lithium resources with industrial exploitation can be classified into a halogen water type and an ore type, wherein the halogen water type lithium ore accounts for about 64%, and the ore type lithium ore accounts for about 36%. Although the total amount of brine lithium resources is dominant, and the cost of extracting the brine lithium is lower than that of extracting the lithium from the ores, the brine lithium is limited by an extraction technology and a mining environment, so that the expansion of the production of extracting the brine lithium is slow. Future global ore lithium extraction and brine lithium extraction are developed for a long time. Therefore, research into the process of extracting lithium carbonate from lithium ore is also of great importance.
There are about 145 kinds of lithium-containing minerals which have been found in nature, but the main industrial exploitation values are spodumene, petalite, lepidolite, petalite, and phospholitite. Common methods for extracting lithium from ores mainly comprise a sulfuric acid method, a sulfate method, a lime sintering method, a chloridizing roasting method, a soda ash autoclaving method and the like, wherein the sulfuric acid method for producing lithium carbonate has the advantages of strong adaptability to raw materials, simplicity in operation, high recovery rate and the like. However, other metals in the ore can react with acid in the process of extracting lithium by an acid method so as to enter the solution, and the problems of high technical difficulty, high cost and the like exist in the classification recycling of the impurities.
The invention patent CN103145158B discloses that the lithium carbonate is prepared by sulfating roasting, caustic soda flake purification and carbonization precipitation; the process adopts concentrated sulfuric acid for roasting, the reaction temperature is 200-300 ℃, the energy consumption is reduced compared with the traditional salt method, but the acid consumption is large, the tail gas is difficult to treat, and the atmospheric pollution exists; the impurity removing process adopts caustic soda flakes to remove impurities, and forms Li-Al layered double hydroxide (LDH, liAl) 2 (OH) 7 ·2H 2 O) so that a large amount of lithium enters the impurity removal slag, resulting in lithium loss. The literature 'process for selectively leaching lithium by fluoroacidolysis lepidolite' adopts a hydrochloric acid system, realizes low-temperature leaching of lithium by introducing fluoride, has leaching temperature of less than 100 ℃, and reduces the impurity concentration in brine by introducing a cryolite process for removing impurities; however, the hydrochloric acid is easy to volatilize, the equipment corrosiveness is high, the system introduces fluoride ions, the impurity removal is not thorough, the consumption of precipitant is high, and the like, and the direct acquisition is difficultHigh purity lithium carbonate product.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a process for preparing lithium carbonate by extracting lithium from lithium ore by a wet method, wherein potassium salt and fluorine salt are added into the lithium ore to cooperate with sulfuric acid to strengthen leaching for extracting lithium, so that the lithium is extracted by the wet method at normal pressure and low temperature, the lithium recovery rate is high, and the energy consumption is low.
The invention provides a process for preparing lithium carbonate by extracting lithium from lithium ore by a wet method, which comprises the following steps:
s1, acid leaching under normal pressure: adding lithium ore, sulfuric acid and fluoride into a reaction kettle, heating, stirring for reaction, and filtering to obtain silica slag and brine;
s2, cooling and alum precipitation: adding alkali to regulate pH of brine, adding potassium salt, stirring for reaction, cooling, and filtering to obtain alum and alum-removed brine;
s3, removing impurities once: adding phosphate and alkali into the alum-removed brine, stirring for reaction, and filtering to obtain aluminum fluoride residues and primary purified brine;
s4, secondary impurity removal: lime is added into the primary purified brine, and the aluminum-calcium slag and the secondary purified brine are obtained through stirring reaction;
s5, removing impurities for three times: adding sodium carbonate into the secondary purified brine, and stirring for reaction to obtain magnesium-calcium slag and tertiary purified brine;
s6, concentrating and precipitating lithium: concentrating the purified brine for three times, and adding saturated sodium carbonate solution for lithium precipitation reaction to obtain lithium carbonate.
Further, in S1, the lithium ore is one or more selected from lepidolite, petalite, lithium porcelain stone, and laponite;
the mass percentage concentration of the sulfuric acid is 5% -50%; the solid-liquid ratio in the reaction kettle is 0.5-4: 1, a step of;
the fluoride is selected from one or more of sodium fluoride, calcium fluoride, potassium fluoride, aluminum fluoride, hydrogen fluoride and fluosilicic acid; the addition amount of the fluoride is 0.1 to 1 time of the total aluminum molar amount in the lithium ore;
the temperature of the stirring reaction is 30-100 ℃, the stirring speed is 100-600 r/min, and the reaction time is 2-12 h.
Further, in S1, potassium salt is added into the reaction kettle at the same time;
the potassium salt is one or more of potassium sulfate, potassium chloride, potassium nitrate and potassium phosphate;
the addition amount of the potassium salt is 0-10% of the weight of the lithium ore.
Further, in S2, adding alkali to adjust the pH of the brine to 0-2; the alkali is selected from potassium hydroxide or/and sodium hydroxide;
the potassium salt is selected from one or more of potassium sulfate, potassium chloride, potassium nitrate and potassium phosphate; adding potassium salt to regulate the molar ratio of potassium to aluminum in the brine to be 0.5-1.1: 1.
further, in S2, stirring and reacting for 20-120 min at 40-70 ℃, then cooling to 0-10 ℃ and crystallizing for 20-80 min.
Further, in S3, the phosphate is one or more selected from sodium phosphate, potassium phosphate, ammonium phosphate, diammonium phosphate, and calcium phosphate; the dosage of the phosphate is 0.8 to 1.2 times of the molar weight of aluminum in the alum-removed brine;
the alkali is sodium hydroxide, and the pH end point of the system is adjusted to 3.0-4.5 by adding alkali.
Further, in S3, the temperature of the stirring reaction is 20-90 ℃ and the reaction time is 0.5-3 h;
the obtained aluminum fluoride slag is returned to the lithium ore acid leaching step in S1.
Further, in S4, the lime is added in an amount of 30-100 kg/m based on the volume of the once purified brine 3 ；
The temperature of the stirring reaction is 50-80 ℃, the reaction time is 0.5-3 h, and the stirring speed is 100-600 r/min.
Further, in S5, the adding amount of the sodium carbonate is 1.0 to 1.2 times of the molar amount of the calcium in the secondary purified brine; the concentration of the sodium carbonate solution is 200 g/L-300 g/L;
the stirring reaction time is 0.5-3 h, and the reaction temperature is 10-50 ℃.
Further, in S6, the sodium carbonate is added in a solution form, and the adding amount of the sodium carbonate is 1.0-1.5 times of the molar amount of lithium in the tertiary purified brine by the volume of the tertiary purified brine; the concentration of the sodium carbonate solution is 200 g/L-300 g/L;
the temperature of the lithium precipitation reaction is 80-100 ℃ and the aging time is 1-5 h.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, on the basis of the traditional sulfuric acid method for extracting lithium, potassium salt and fluoride salt are added to cooperatively strengthen the lithium extraction process, the potassium salt promotes substitution (electrical property) of lithium ions in mica minerals, and fluoride is utilized to complex with aluminum to promote mineral structure damage. The whole leaching process has mild conditions and low energy consumption, and has good adaptability to low-grade ores such as lepidolite, petalite, hectorite, phospholithange and the like, and the lithium leaching rate is more than 95 percent.
2. According to the invention, the alkali alum such as potassium, rubidium, cesium and the like is obtained by cooling and separating alum, so that impurity elements such as potassium, rubidium, cesium, aluminum and the like in brine are recycled, the recycling degree of lithium ores is improved, the resource waste is avoided, and the load and the slag amount of the subsequent impurity removing process are effectively reduced.
3. According to the invention, phosphate is adopted to cooperate with lime to remove impurities such as iron, aluminum, fluorine and the like in the fluorine chemical lithium extraction water leaching solution in the lithium ore, the technical problems of high impurity content, large lithium loss in the impurity removal process and the like of the low Wen Suanfa lithium extraction leaching solution are systematically solved, and the aluminum fluoride residues obtained by impurity removal can be reused in the leaching process.
The invention adopts the intensified leaching means to realize the normal pressure low temperature wet method lithium extraction, and has the advantages of high lithium recovery rate, low energy consumption and the like. In addition, aluminum fluoride residues and alum generated in the process of preparing lithium carbonate can be recycled, so that the problems of fluorine pollution, valuable resource waste of aluminum, rubidium, cesium and the like in the ores and the like generated by a traditional sulfuric acid roasting method of lithium ores are solved, and the method accords with the concept of developing green economy in China.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
As shown in fig. 1, fig. 1 is a process flow chart of the present invention.
The technical scheme of the invention is described in detail through specific embodiments.
Example 1
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
The process flow for preparing lithium carbonate by extracting lithium from lepidolite is shown in figure 1, and the specific operation is as follows:
taking 1.2kg of the lithium ore, 40g of calcium fluoride and 30g of potassium sulfate, sequentially adding into 2.2L of 25% sulfuric acid by mass fraction, heating to 95 ℃ in a water bath, stirring at a speed of 300r/min, and reacting for 6h. After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～18.38g/L，Li 2 O～16.3g/L，Al 3+ ～34.1g/L，Fe 2+ ～1.3g/L，Ca 2+ ～0.48g/L，Mg 2+ ～0.35g/L，Mn 2+ ～0.41g/L，F - About 9.2g/L. The lithium lepidolite leaching rate was 98.8% based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 2.0 by adopting potassium hydroxide, adding 80g of potassium sulfate, stirring at the temperature of 60 ℃ for reacting for 20min, placing in refrigeration equipment, regulating the temperature to 5 ℃, slowly stirring, and reacting for 30min to obtain alum and 1.9L of alum removal brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～8.4g/L，Li 2 O～17.15g/L，Al 3+ ～13.07g/L，Fe 3+ ～1.37g/L，Ca 2+ ～0.51g/L，Mg 2+ ～0.38g/L，Mn 2+ ～0.44g/L，F - ～9.6g/L。
Adding 95g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. Disposable impurity-removing brineThe main component of (C) is K + ～8.3g/L，Li 2 O～16.98g/L，Al 3+ ～0.42g/L，Fe 3+ ～ND，Ca 2+ ～0.37g/L，Mg 2+ ～0.34g/L，Mn 2+ ～0.40g/L，F - ～0.35g/L。
Adding 100g of quicklime into the primary impurity-removed brine, reacting for 1.5 hours at 60 ℃, and filtering after the reaction to obtain secondary impurity-removed brine. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～8.3g/L，Ca 2+ About 2.0g/L. And (3) carrying out three-time impurity removal on the secondary impurity-removed brine by adopting 200g/L sodium carbonate solution, wherein the adding amount of the sodium carbonate solution is 55mL, reacting for 0.5h, and filtering to obtain purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 4.6% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.2 times of lithium ion molar quantity of sodium carbonate by adopting an inverse method, performing precipitation reaction at the temperature of 90 ℃, aging for 2 hours, washing twice by adopting deionized water at the temperature of 90 ℃, and drying to obtain 64.42g of lithium carbonate product. The primary lithium precipitation rate is 81.2%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.64％，K～0.76％，Na～0.19％，Ca～0.0069％，Mg～0.0019％，Fe～0.0014％，Al～0.0049％，Mn～0.012％。
The lithium yield of the whole process is more than 88 percent without counting the lithium in the lithium precipitation mother solution.
Example 2
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
The process flow for preparing lithium carbonate by extracting lithium from lepidolite is shown in figure 1, and the specific operation is as follows:
taking 1.2kg of the lithium ore, 35g of calcium fluoride and 25g of potassium sulfate, sequentially adding into 2.2L of 25% sulfuric acid with mass fraction, heating to 95 ℃ in a water bath, stirring at 300r/min, and reacting for 6h. After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～13.51g/L，Li 2 O～16.2g/L，Al 3+ ～33.9g/L，Fe 2+ ～1.3g/L，Ca 2+ ～0.45g/L，Mg 2+ ～0.37g/L，Mn 2+ ～0.40g/L，F - About 8.7g/L. The lithium lepidolite leaching rate was 98.1% based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 1.5 by adopting potassium hydroxide, adding 90g of potassium sulfate, stirring at the temperature of 60 ℃ for reacting for 20min, placing in refrigeration equipment, regulating the temperature to 3 ℃, slowly stirring, and reacting for 40min to obtain alum and 1.9L of alum removal brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～7.9g/L，Li 2 O～17.10g/L，Al 3+ ～10.0g/L，Fe 3+ ～1.33g/L，Ca 2+ ～0.48g/L，Mg 2+ ～0.40g/L，Mn 2+ ～0.43g/L，F - ～9.1g/L。
Adding 85g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. The main component of the primary impurity-removing brine is K + ～7.8g/L，Li 2 O～16.99g/L，Al 3+ ～0.31g/L，Fe 3+ ～ND，Ca 2+ ～0.38g/L，Mg 2+ ～0.33g/L，Mn 2+ ～0.39g/L，F - ～0.30g/L。
Adding 90g of quicklime into the primary impurity-removed brine, reacting for 1.5 hours at 60 ℃, and filtering after the reaction to obtain secondary impurity-removed brine. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～7.9g/L，Ca 2+ 1.9g/L. Adopting 200g/L sodium carbonate solution to remove impurities from secondary impurity-removed brine for three times, wherein the adding amount of the sodium carbonate solution is 50mL, reacting for 0.5h, and filteringObtaining purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 4.4% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.1 times of lithium ion molar quantity of sodium carbonate by adopting an inverse method, performing precipitation reaction at the temperature of 90 ℃, aging for 2 hours, washing twice by adopting deionized water at the temperature of 90 ℃, and drying to obtain 63.37g of lithium carbonate product. The primary lithium precipitation rate is 80.8%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.61％，K～0.74％，Na～0.21％，Ca～0.007％，Mg～0.002％，Fe～0.002％，Al～0.005％，Mn～0.009％。
The lithium yield of the whole process is more than 88 percent without counting the lithium in the lithium precipitation mother solution.
Example 3
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
Taking 1.2kg of the lithium ore, 30g of calcium fluoride and 20g of potassium sulfate, sequentially adding into 2.2L of 25% sulfuric acid by mass fraction, heating to 90 ℃ in a water bath, stirring at the speed of 250r/min, and reacting for 4h. After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～11.14g/L，Li 2 O～15.96g/L，Al 3+ ～32.7g/L，Fe 2+ ～1.2g/L，Ca 2+ ～0.43g/L，Mg 2+ ～0.39g/L，Mn 2+ ～0.41g/L，F - About 7.4g/L. The lithium lepidolite leaching rate was 96.7% based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 1.0 by adopting potassium hydroxide, adding 100g of potassium sulfate, stirring at the temperature of 60 ℃ for reaction for 25min, and then coolingIn freezing equipment, regulating the temperature to 2 ℃, slowly stirring, and reacting for 40min to obtain alum and 1.9L of alum-removed brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～7.3g/L，Li 2 O～16.80g/L，Al 3+ ～9.1g/L，Fe 3+ ～1.32g/L，Ca 2+ ～0.49g/L，Mg 2+ ～0.47g/L，Mn 2+ ～0.45g/L，F - ～7.8g/L。
Adding 80g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. The main component of the primary impurity-removing brine is K + ～7.1g/L，Li 2 O～16.71g/L，Al 3+ ～0.29g/L，Fe 3+ ～ND，Ca 2+ ～0.35g/L，Mg 2+ ～0.36g/L，Mn 2+ ～0.38g/L，F - ～0.27g/L。
Adding 85g of quicklime into the primary impurity-removed brine, reacting for 1.5 hours at 60 ℃, and filtering after the reaction to obtain secondary impurity-removed brine. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～7.1g/L，Ca 2+ 1.9g/L. And (3) carrying out three-time impurity removal on the secondary impurity-removed brine by adopting 200g/L sodium carbonate solution, wherein the adding amount of the sodium carbonate solution is 50mL, reacting for 0.5h, and filtering to obtain purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 4.9% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.05 times of lithium ion molar quantity into the solution to obtain sodium carbonate, performing precipitation reaction at 90 ℃ for 2 hours, washing twice by adopting deionized water at 90 ℃ after ageing, and drying to obtain 61.13g of lithium carbonate product. The primary lithium precipitation rate is 78.94%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.73％，K～0.64％，Na～0.18％，Ca～0.006％，Mg～0.001％，Fe～0.003％，Al～0.006％，Mn～0.007％。
The lithium yield of the whole process is more than 88 percent without counting the lithium in the lithium precipitation mother solution.
Example 4
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
Taking 1.2kg of the lithium ore, 25g of calcium fluoride and 15g of potassium sulfate, sequentially adding into 2.2L of 25% sulfuric acid by mass fraction, heating to 85 ℃ in a water bath, stirring at a speed of 200r/min, and reacting for 2h. After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～9.72g/L，Li 2 O～15.49g/L，Al 3+ ～31.9g/L，Fe 2+ ～1.18g/L，Ca 2+ ～0.40/L，Mg 2+ ～0.37g/L，Mn 2+ ～0.39g/L，F - 6.1g/L. The lithium lepidolite leaching rate was 93.9% based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 2.0 by adopting potassium hydroxide, adding 110g of potassium sulfate, stirring at the temperature of 60 ℃ for reaction for 25min, placing in refrigeration equipment, regulating the temperature to 5 ℃, slowly stirring, and reacting for 40min to obtain alum and 1.9L of alum removal brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～8.2g/L，Li 2 O～15.90g/L，Al 3+ ～7.9g/L，Fe 3+ ～1.22g/L，Ca 2+ ～0.42g/L，Mg 2+ ～0.39g/L，Mn 2+ ～0.42g/L，F - ～6.4g/L。
Adding 75g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. The main component of the primary impurity-removing brine is K + ～8.1g/L，Li 2 O～15.79g/L，Al 3+ ～0.28g/L，Fe 3+ ～ND，Ca 2+ ～0.32g/L，Mg 2+ ～0.34g/L，Mn 2+ ～0.35g/L，F - ～0.21g/L。
Adding 80g of quicklime into the primary impurity-removed brine, reacting for 1.5 hours at 60 ℃, and filtering after the reaction to obtain secondary impurity-removed brine. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～7.9g/L，Ca 2+ About 2.0g/L. And (3) carrying out three-time impurity removal on the secondary impurity-removed brine by adopting 200g/L sodium carbonate solution, wherein the adding amount of the sodium carbonate solution is 55mL, reacting for 0.5h, and filtering to obtain purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 5.3% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.2 times of lithium ion molar quantity into the solution to obtain sodium carbonate, performing precipitation reaction at 90 ℃ for 2 hours, washing twice by adopting deionized water at 90 ℃ after ageing, and drying to obtain 58.68g of lithium carbonate product. The primary lithium precipitation rate is 81.04%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.53％，K～0.69％，Na～0.20％，Ca～0.007％，Mg～0.002％，Fe～0.004％，Al～0.005％，Mn～0.005％。
The lithium yield of the whole process is more than 88 percent without counting the lithium in the lithium precipitation mother solution.
Example 5
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
Taking 1.2kg of the lithium ore, 70g of aluminum fluoride slag, 10g of calcium fluoride and 30g of potassium sulfate, sequentially adding into 2.2L of sulfuric acid with mass fraction of 30%, heating to 95 ℃ in a water bath, and reacting for 6h at stirring speed of 300 r/min.After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～18.4g/L，Li 2 O～16.4g/L，Al 3+ ～39.2g/L，Fe 2+ ～1.3g/L，Ca 2+ ～0.48g/L，Mg 2+ ～0.35g/L，Mn 2+ ～0.45g/L，F - About 10.3g/L. The lithium lepidolite leaching rate is 99.4 percent based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 2.0 by adopting potassium hydroxide, adding 100g of potassium sulfate, stirring at the temperature of 60 ℃ for reacting for 20min, placing in refrigeration equipment, regulating the temperature to 5 ℃, slowly stirring, and reacting for 30min to obtain alum and 1.9L of alum removal brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～8.5g/L，Li 2 O～17.23g/L，Al 3+ ～13.04g/L，Fe 3+ ～1.38g/L，Ca 2+ ～0.52g/L，Mg 2+ ～0.41g/L，Mn 2+ ～0.49g/L，F - ～10.57g/L。
Adding 95g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. The main component of the primary impurity-removing brine is K + ～8.4g/L，Li 2 O～17.09g/L，Al 3+ ～0.41g/L，Fe 3+ ～ND，Ca 2+ ～0.33g/L，Mg 2+ ～0.35g/L，Mn 2+ ～0.40g/L，F - ～0.31g/L。
Adding 100g of quicklime into the primary impurity-removed brine, reacting for 1.5 hours at 60 ℃, and filtering after the reaction to obtain secondary impurity-removed brine. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～8.3g/L，Ca 2+ About 2.0g/L. And (3) carrying out three-time impurity removal on the secondary impurity-removed brine by adopting 200g/L sodium carbonate solution, wherein the adding amount of the sodium carbonate solution is 55mL, reacting for 0.5h, and filtering to obtain purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 4.8% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.2 times of lithium ion molar quantity of sodium carbonate by adopting an inverse method, performing precipitation reaction at the temperature of 90 ℃, aging for 2 hours, washing twice by adopting deionized water at the temperature of 90 ℃, and drying to obtain 65.17g of lithium carbonate product. The primary lithium precipitation rate is 81.3%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.68％，K～0.74％，Na～0.20％，Ca～0.0067％，Mg～0.0018％，Fe～0.0016％，Al～0.0048％，Mn～0.014％。
The lithium yield of the whole process is more than 88 percent without counting the lithium in the lithium precipitation mother solution.
Comparative example 1
The lithium-containing ore is lepidolite, and the chemical formula is K { Li 2-x Al 1+x [Al 2x Si 4-2x O 10 ](OH,F) 2 And (x=0 to 0.5), the main chemical components are: li (Li) 2 O～3.3％，Na 2 O～2.1％，Al 2 O 3 ～21.8％，SiO 2 ～48.44％，Fe 2 O 3 ～0.18％，K 2 O～6.7％，CaO～0.8％，MgO～0.23％。
1.2kg of the lithium ore is taken and added into 2.2L of sulfuric acid with mass fraction of 30%, the mixture is heated to 95 ℃ in a water bath, the stirring speed is 300r/min, and the reaction is carried out for 6 hours. After the reaction is finished, filtering and washing to obtain brine with a volume of 2.4L and a component of K + ～4.8g/L，Li 2 O～12.3g/L，Al 3+ ～30.7g/L，Fe 2+ ～0.9g/L，Ca 2+ ～0.3g/L，Mg 2+ ～0.2g/L，Mn 2+ ～0.2g/L，F - About 1.5g/L. The lithium lepidolite leaching rate is 74.45 percent based on the liquid.
Taking 2.0L of lepidolite acidized lithium extraction brine, regulating the pH value to 2.0 by adopting potassium hydroxide, adding 100g of potassium sulfate, stirring at the temperature of 60 ℃ for reacting for 20min, placing in refrigeration equipment, regulating the temperature to 5 ℃, slowly stirring, and reacting for 30min to obtain alum and 1.9L of alum removal brine. The lithium is basically not lost in the process, and the main component of the alum-removed brine is K + ～6.4g/L，Li 2 O～12.4g/L，Al 3+ ～3.8g/L，Fe 3+ ～0.95g/L，Ca 2+ ～0.31g/L，Mg 2+ ～0.25g/L，Mn 2+ ～0.24g/L，F - ～1.7g/L。
Adding 35g of sodium phosphate into the alum-removed brine, after the sodium phosphate is fully dissolved, adjusting the pH end point of the water immersion liquid to 4.5 by using caustic soda flakes, reacting at 85 ℃ for 1.0h, standing and filtering to obtain primary impurity-removed brine and aluminum fluoride residues. The main component of the primary impurity-removing brine is K + ～6.3g/L，Li 2 O～12.32g/L，Al 3+ ～0.11g/L，Fe 3+ ～ND，Ca 2+ ～0.13g/L，Mg 2+ ～0.15g/L，Mn 2+ ～0.20g/L，F - ～0.12g/L。
70g of quicklime is added into the primary impurity-removed brine, the reaction is carried out for 1.5 hours at 60 ℃, and the secondary impurity-removed brine is obtained after the filtration after the reaction. At this time, impurities such as aluminum, iron, magnesium, manganese, fluorine and the like in the brine are completely removed, and the residue is mainly K + ～6.3g/L，Ca 2+ About 2.0g/L. And (3) carrying out three-time impurity removal on the secondary impurity-removed brine by adopting 200g/L sodium carbonate solution, wherein the adding amount of the sodium carbonate solution is 55mL, reacting for 0.5h, and filtering to obtain purified brine and magnesium-calcium slag. Through detection, the impurities such as aluminum, iron, fluorine, manganese and the like in the purified brine are all lower than 5mg/L, and the impurity content of calcium, magnesium and the like is lower than 15mg/L. The lithium loss rate of the impurity removal in this example was 5.5% based on the liquid.
Taking purified brine 1.9L, evaporating and concentrating to Li 2 O-25 g/L. Preparing saturated sodium carbonate solution, adding 1.2 times of lithium ion molar quantity of sodium carbonate by adopting an inverse method, performing precipitation reaction at the temperature of 90 ℃, aging for 2 hours, washing twice by adopting deionized water at the temperature of 90 ℃, and drying to obtain 48.22g of lithium carbonate product. The primary lithium precipitation rate is 81.1%, and the lithium carbonate comprises the following components: li (Li) 2 O 3 ～98.63％，K～0.71％，Na～0.22％，Ca～0.007％，Mg～0.002％，Fe～0.001％，Al～0.0045％，Mn～0.018％。
The lithium yield of the whole process is less than 75% without counting the lithium in the lithium precipitation mother solution.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.
Claims (10)
1. The process for preparing lithium carbonate by extracting lithium from lithium ore through wet method is characterized by comprising the following steps:
s1, acid leaching under normal pressure: adding lithium ore, sulfuric acid and fluoride into a reaction kettle, heating, stirring for reaction, and filtering to obtain silica slag and brine;
s2, cooling and alum precipitation: adding alkali to regulate pH of brine, adding potassium salt, stirring for reaction, cooling, and filtering to obtain alum and alum-removed brine;
s3, removing impurities once: adding phosphate and alkali into the alum-removed brine, stirring for reaction, and filtering to obtain aluminum fluoride residues and primary purified brine;
s4, secondary impurity removal: lime is added into the primary purified brine, and the aluminum-calcium slag and the secondary purified brine are obtained through stirring reaction;
s5, removing impurities for three times: adding sodium carbonate into the secondary purified brine, and stirring for reaction to obtain magnesium-calcium slag and tertiary purified brine;
s6, concentrating and precipitating lithium: concentrating the purified brine for three times, and adding saturated sodium carbonate solution for lithium precipitation reaction to obtain lithium carbonate.
2. The process according to claim 1, wherein in S1, the lithium ore is selected from one or more of lepidolite, petalite, celadon, laponite;
the mass percentage concentration of the sulfuric acid is 5% -50%; the solid-liquid ratio in the reaction kettle is 0.5-4: 1, a step of;
the fluoride is selected from one or more of sodium fluoride, calcium fluoride, potassium fluoride, aluminum fluoride, hydrogen fluoride and fluosilicic acid; the addition amount of the fluoride is 0.1 to 1 time of the total aluminum molar amount in the lithium ore;
the temperature of the stirring reaction is 30-100 ℃, the stirring speed is 100-600 r/min, and the reaction time is 2-12 h.
3. The process of claim 1, wherein in S1, further comprising simultaneously adding a potassium salt to the reaction vessel;
the potassium salt is one or more of potassium sulfate, potassium chloride, potassium nitrate and potassium phosphate;
the addition amount of the potassium salt is 0-10% of the weight of the lithium ore.
4. The process according to claim 1, wherein in S2, the pH of the brine is adjusted to 0-2 by adding alkali; the alkali is selected from potassium hydroxide or/and sodium hydroxide;
the potassium salt is selected from one or more of potassium sulfate, potassium chloride, potassium nitrate and potassium phosphate; adding potassium salt to regulate the molar ratio of potassium to aluminum in the brine to be 0.5-1.1: 1.
5. the process according to claim 1, wherein in S2, the reaction is carried out under stirring at 40 to 70 ℃ for 20 to 120min, and then the temperature is reduced to 0 to 10 ℃ for cooling crystallization for 20 to 80min.
6. The process according to claim 1, wherein in S3, the phosphate is selected from one or more of sodium phosphate, potassium phosphate, ammonium phosphate, diammonium phosphate, calcium phosphate; the dosage of the phosphate is 0.8 to 1.2 times of the molar weight of aluminum in the alum-removed brine;
the alkali is sodium hydroxide, and the pH end point of the system is adjusted to 3.0-4.5 by adding alkali.
7. The process according to claim 1, wherein in S3, the temperature of the stirring reaction is 20-90 ℃ and the reaction time is 0.5-3 h;
the obtained aluminum fluoride slag is returned to the lithium ore acid leaching step in S1.
8. The process according to claim 1, wherein in S4, the lime is added in an amount of 30 to 100kg/m based on the volume of one purified brine 3 ；
The temperature of the stirring reaction is 50-80 ℃, the reaction time is 0.5-3 h, and the stirring speed is 100-600 r/min.
9. The process according to claim 1, wherein in S5, the sodium carbonate is added in an amount of 1.0 to 1.2 times the molar amount of calcium in the secondary purified brine; the concentration of the sodium carbonate solution is 200 g/L-300 g/L;
the stirring reaction time is 0.5-3 h, and the reaction temperature is 10-50 ℃.
10. The process according to claim 1, wherein in S6, the sodium carbonate is added in the form of a solution, the addition amount of the sodium carbonate being 1.0 to 1.5 times the molar amount of lithium in the tertiary purified brine, based on the volume of the tertiary purified brine; the concentration of the sodium carbonate solution is 200 g/L-300 g/L;
the temperature of the lithium precipitation reaction is 80-100 ℃ and the aging time is 1-5 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311844913.7A CN117865190A (en) | 2023-12-29 | 2023-12-29 | Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311844913.7A CN117865190A (en) | 2023-12-29 | 2023-12-29 | Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117865190A true CN117865190A (en) | 2024-04-12 |
Family
ID=90587563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311844913.7A Pending CN117865190A (en) | 2023-12-29 | 2023-12-29 | Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117865190A (en) |
-
2023
- 2023-12-29 CN CN202311844913.7A patent/CN117865190A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113684369B (en) | Method for treating waste industrial lithium-containing aluminum electrolyte | |
| CN106319218B (en) | Method for recovering rare earth, aluminum and silicon from rare earth-containing aluminum-silicon waste | |
| CN109777960B (en) | Method for separating and recovering lithium and aluminum from fly ash | |
| CN101885496B (en) | Process for extracting lithium from lithionite by fluorine chemistry | |
| CN105039699A (en) | Method for treatment and resource utilization of alkali metal slag extracted through lepidolite solid fluorine reconstruction | |
| CN114875250B (en) | Method for purifying lithium from lithium-containing clay | |
| CN115216645B (en) | Method for extracting lithium from electrolytic aluminum waste residue by mixed salt calcination | |
| CN112624161B (en) | Method for preparing lithium carbonate by extracting lithium from mechanically activated lepidolite | |
| CN108178171A (en) | A kind of method that lithium carbonate is produced from lepidolite | |
| CN108118143B (en) | Method for preparing lithium carbonate by extracting lithium from lepidolite through two-stage chlorination roasting-alkali liquor leaching method | |
| CN109913652A (en) | The integrated conduct method of waste refractory materials in a kind of tertiary cathode material preparation process | |
| CN116497235A (en) | Method for extracting lithium from low-lithium clay | |
| CN116716480A (en) | Method for recycling multiple metals in red mud by high-acid leaching crystallization precipitation method | |
| CN108063295B (en) | Method for extracting lithium from slag generated by pyrogenic recovery of lithium battery | |
| CN116005006A (en) | Method for extracting lithium from electrolytic aluminum waste residues and application thereof | |
| CN115505740A (en) | Resource method for treating red mud by adopting nitrate wastewater | |
| CN117865190A (en) | Process for preparing lithium carbonate by extracting lithium from lithium ore through wet method | |
| CN112645363A (en) | Method for preparing battery-grade lithium carbonate by taking lepidolite as raw material | |
| CN114684835B (en) | Method for preparing aluminum fluoride product by combined treatment of aluminum industry solid waste | |
| CN111041249B (en) | Method for treating magnesium and/or calcium-containing waste liquid in rare earth smelting separation process | |
| CN115216630B (en) | Recycling treatment method of waste lithium-containing aluminum electrolyte | |
| CN117658182B (en) | Efficient recycling method of aluminum electrolyte waste | |
| CN117070772A (en) | Method for comprehensively extracting lithium, aluminum and phosphorus resources from phospholithiumstone | |
| CN116497236A (en) | Method for extracting lithium from phospholith-aluminum stone raw material | |
| CN116397109A (en) | Method for recovering lithium from acid process intermediate alumina and lithium-containing solution |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |