CN117802320A - Method for extracting lithium from clay-type lithium ore - Google Patents
Method for extracting lithium from clay-type lithium ore Download PDFInfo
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- CN117802320A CN117802320A CN202311802748.9A CN202311802748A CN117802320A CN 117802320 A CN117802320 A CN 117802320A CN 202311802748 A CN202311802748 A CN 202311802748A CN 117802320 A CN117802320 A CN 117802320A
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- lithium
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- iron
- clay
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 186
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 186
- 238000000034 method Methods 0.000 title claims abstract description 65
- 239000011734 sodium Substances 0.000 claims abstract description 134
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 57
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 56
- 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 55
- 229910052934 alunite Inorganic materials 0.000 claims abstract description 41
- 239000010424 alunite Substances 0.000 claims abstract description 41
- KPZTWMNLAFDTGF-UHFFFAOYSA-D trialuminum;potassium;hexahydroxide;disulfate Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Al+3].[Al+3].[Al+3].[K+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KPZTWMNLAFDTGF-UHFFFAOYSA-D 0.000 claims abstract description 39
- 239000002244 precipitate Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 123
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 88
- 239000000706 filtrate Substances 0.000 claims description 63
- 238000002386 leaching Methods 0.000 claims description 63
- 238000001914 filtration Methods 0.000 claims description 62
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 60
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 42
- 239000002253 acid Substances 0.000 claims description 40
- 239000007787 solid Substances 0.000 claims description 31
- 239000000843 powder Substances 0.000 claims description 29
- HLQCPNUQRKCTJD-UHFFFAOYSA-N [Na].[Fe].[V] Chemical compound [Na].[Fe].[V] HLQCPNUQRKCTJD-UHFFFAOYSA-N 0.000 claims description 21
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 21
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 21
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 18
- 239000004927 clay Substances 0.000 claims description 17
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 17
- 235000011152 sodium sulphate Nutrition 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 12
- 239000007800 oxidant agent Substances 0.000 claims description 9
- 239000000292 calcium oxide Substances 0.000 claims description 8
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- VKJKEPKFPUWCAS-UHFFFAOYSA-M potassium chlorate Chemical compound [K+].[O-]Cl(=O)=O VKJKEPKFPUWCAS-UHFFFAOYSA-M 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 2
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 154
- 230000007062 hydrolysis Effects 0.000 abstract description 51
- 235000021110 pickles Nutrition 0.000 abstract description 51
- 229910052742 iron Inorganic materials 0.000 abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 27
- 238000001556 precipitation Methods 0.000 abstract description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 abstract description 12
- 229940037003 alum Drugs 0.000 abstract description 10
- 238000001704 evaporation Methods 0.000 abstract description 10
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 235000011127 sodium aluminium sulphate Nutrition 0.000 abstract description 6
- 238000005554 pickling Methods 0.000 abstract description 5
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 230000008020 evaporation Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 92
- 229910052500 inorganic mineral Inorganic materials 0.000 description 27
- 239000011707 mineral Substances 0.000 description 27
- 238000012360 testing method Methods 0.000 description 25
- 239000000725 suspension Substances 0.000 description 22
- 230000001276 controlling effect Effects 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 230000003301 hydrolyzing effect Effects 0.000 description 15
- 239000000084 colloidal system Substances 0.000 description 14
- 239000003002 pH adjusting agent Substances 0.000 description 13
- 238000005406 washing Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 11
- 239000003513 alkali Substances 0.000 description 10
- 230000003647 oxidation Effects 0.000 description 10
- 238000007254 oxidation reaction Methods 0.000 description 10
- 239000002893 slag Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 9
- 238000000498 ball milling Methods 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 239000002245 particle Substances 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000010703 silicon Substances 0.000 description 9
- 229910052710 silicon Inorganic materials 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 235000019698 starch Nutrition 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 5
- 150000007514 bases Chemical class 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- -1 iron ions Chemical class 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229960004887 ferric hydroxide Drugs 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- 229910052935 jarosite Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011435 rock Substances 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 230000005653 Brownian motion process Effects 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 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 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
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 239000001120 potassium sulphate Substances 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting lithium from clay-type lithium ores, which comprises the steps of adding Na into pickle liquor 2 SO 4 To provide the sodium source required to produce the sodium alum and sodium alunite, respectively, by controlling the pH, sodium alum and sodium alunite precipitate are formed. Compared with the traditional method, the method has the advantages that the obtained precipitate has higher crystallinity and better filterability, the purpose of removing iron and aluminum in the pickle liquor is achieved, lithium loss can not be caused in the precipitation process, the concentration of the lithium-rich solution is improved, and the energy consumption is reduced. The sodium-iron-yellow alum and sodium alunite which are generated at the same time can generate Fe through hydrolysis 2 O 3 、Al 2 O 3 And Na (Na) 2 SO 4 Solution, na 2 SO 4 The solution can be used as a sodium source for the next batch of pickling liquid after evaporation and crystallization, thereby improving the comprehensive utilization of the whole process.
Description
Technical Field
The invention relates to the technical field of lithium extraction from lithium ores, in particular to a method for extracting lithium from clay-type lithium ores.
Background
Lithium is an important strategic metal for energy sources, and is widely applied to the fields of new energy sources, nuclear energy, medical treatment, ceramics and the like at present, and is known as white petroleum. Based on the importance of lithium, the development of lithium in the future will also be of great interest. Current lithium resources can be divided into three types, one being hard rock, such as spodumene, lepidolite, petalite and phospholitite; the other is a salt lake brine lithium resource; the last one is clay-type lithium ore. The lithium resources developed and utilized at present are mainly hard rock type and salt lake brine type lithium resources. However, with the increasing demand for lithium resources, the development and utilization of clay-type lithium resources have been attracting attention.
At present, the method for treating clay-type lithium ores mainly comprises an auxiliary agent roasting method, an alkaline method and an acid method. The auxiliary agent roasting method has high lithium extraction energy consumption, and impurities can be introduced, so that the subsequent impurity removal cost is increased; the alkaline method has high requirements on equipment required for extracting lithium. Compared with the auxiliary agent roasting and alkaline methods, the acid method can effectively extract lithium from clay lithium ore under relatively simple and mild conditions. However, in the leaching of clay lithium ores using acidsIn the process of lithium extraction, the acid consumption is huge, and Fe in clay lithium ore is leached out 3+ And Al 3+ And is correspondingly leached. Therefore, it is often necessary to remove Fe from the clay lithium ore pickle liquor 3+ And Al 3+ . The conventional removal method is to use a large amount of alkali solution (such as NaOH solution) to adjust the pH to make Fe 3+ And Al 3+ Respectively forming amorphous Fe (OH) 3 And Al (OH) 3 And (5) precipitation. However, when Fe in pickle liquor 3+ And Al 3+ At higher concentrations, a simple adjustment of the pH of the pickling solution causes a very high nucleation rate, which leads to the formation of fine and light Fe (OH) 3 And Al (OH) 3 And (5) colloid. These fine colloidal particles can be suspended in a solution for a long time due to brownian motion, and are difficult to separate by gravity settling. Moreover, since the particles are too fine, the filtration takes a long time and consumes a lot of energy, which is not industrially valuable. More importantly, the resulting colloidal particles will absorb a significant amount of lithium, resulting in a significant amount of lithium loss, and this absorbed lithium cannot be washed away by deionized water, indicating that lithium loss is not caused by entrainment but by the unique adsorption of lithium by the colloid. Aiming at the unique adsorption characteristic of the colloid particles on lithium, researchers innovatively utilize the generated colloid to fully adsorb lithium, and then bake the obtained adsorption slag to ensure Fe (OH) 3 And Al (OH) 3 Conversion of colloid into water-insoluble Fe 2 O 3 And Al 2 O 3 Then water leaching is carried out to realize lithium and Fe 3+ 、Al 3+ Is separated from the other components. However, due to the Fe (OH) formed 3 And Al (OH) 3 The colloid is fine and light, and the solid-liquid separation process performed after lithium is fully absorbed takes a long time and consumes a large amount of energy, and the subsequent secondary roasting process also consumes energy, which is unfavorable for industrial production.
Accordingly, there is a need to provide a method for removing Fe from a pickling solution while ensuring excellent filtering performance and minimal lithium loss 3+ And Al 3+ And finally, concentrating and carbonizing the pickle liquor to prepare the battery grade lithium carbonate with the yield and purity meeting the requirements.
Disclosure of Invention
The present invention aims to solve one of the technical problems in the related art at least to some extent. To this end, the invention provides a method for extracting lithium from clay-type lithium ores by forming sodium-iron-yellow alum and sodium-alunite precipitates in the pickle liquor to remove Fe in the pickle liquor 3+ And Al 3+ . Compared with the traditional method for forming Fe (OH) 3 And Al (OH) 3 Colloidal precipitation to remove Fe 3+ And Al 3+ According to the method, the precipitate particle size of the sodium-iron-yellow alum and sodium alunite is larger, the filterability is better, and the lithium loss in the pickle liquor is avoided. Meanwhile, the sodium-iron-yellow alum and sodium alunite precipitate formed by the invention are hydrolyzed to form Fe respectively 2 O 3 And Al 2 O 3 Precipitation, and filtrate after hydrolysis is Na 2 SO 4 Solution, na after evaporation and crystallization 2 SO 4 Can be used as a sodium source required for forming the sodium-iron-yellow alum and sodium alunite precipitate, and realizes the comprehensive utilization of clay-type lithium ores.
To this end, the first aspect of the present invention provides a method for extracting lithium from clay-type lithium ores, comprising:
(1) Mixing clay type lithium ores with an acidic solution to obtain leaching liquid and leaching residues;
(2) Adding an oxidant into the leaching solution to obtain a mixed solution;
(3) Adding sodium sulfate solution into the mixed solution, regulating the pH value of the system to be 1.5-3.0 and not 3.0, and obtaining iron-removing filtrate and sodium-iron-vanadium filter residues when the pH value of the system is not changed;
(4) Adding sodium sulfate solution into the iron-removing filtrate, adjusting the pH value of the system to be 3.0-4.5 and not 3.0 and 4.5, and obtaining lithium-rich filtrate and sodium alunite filter residues after the pH value of the system is not changed.
Preferably, in the step (3), the pH value of the system is adjusted to be 1.5-2.5.
Preferably, in the step (4), the pH value of the system is adjusted to 3.5-4.0.
In the prior art, alkaline liquor is used for regulating the pH value of pickle liquor (generally 3-7) to generate amorphous Fe (OH) 3 And Al (OH) 3 Colloidal precipitation to remove Fe from leachate 3+ And Al 3+ However, the two colloids have small particle size and difficult filtration, and the adsorptivity of the colloids can cause a great deal of loss of lithium, and the subsequent roasting and water leaching steps have high energy consumption, so that the method is not beneficial to industrial production. In order to solve the defects in the prior art, na is added into the pickle liquor 2 SO 4 To provide the sodium source required for the formation of the sodium alum and sodium alunite, the sodium alum and sodium alunite precipitate is formed in two steps by controlling the pH. Compared with the traditional method, the method has the advantages that the obtained precipitate has higher crystallinity and better filterability, the purpose of removing iron and aluminum in the pickle liquor is achieved, a great deal of lithium loss can not be caused in the precipitation process, the concentration of the lithium-rich solution is improved, and meanwhile, the energy consumption is reduced because secondary roasting is not needed.
According to an embodiment of the present invention, the acidic solution in step (1) includes at least one selected from the group consisting of sulfuric acid solution, hydrochloric acid solution, nitric acid solution and phosphoric acid solution. Thus, lithium, iron and aluminum in the clay-type lithium ore are leached to obtain leaching liquid.
According to an embodiment of the invention, the liquid-solid ratio of the acidic solution to the clay-type lithium ore is 1-5mL/g. Thereby fully leaching lithium, iron and aluminum in the clay-type lithium ore.
According to an embodiment of the invention, the acid leaching time in the step (1) is 1h-4h, and the acid leaching temperature is 30-90 ℃. Thereby fully leaching lithium, iron and aluminum in the clay-type lithium ore.
According to an embodiment of the present invention, the oxidizing agent in step (2) includes at least one selected from hydrogen peroxide, potassium chlorate, sodium chlorate and potassium permanganate. Thereby Fe in the leaching solution 2+ Oxidation to Fe 3+ 。
According to an embodiment of the present invention, step (3) further includes: the pH value of the system is regulated by a first alkaline compound, wherein the first alkaline compound comprises at least one selected from calcium carbonate, calcium oxide, sodium hydroxide and ammonia water.
According to an embodiment of the invention, step (3) is performed at 80-100 ℃.
According to an embodiment of the present invention, step (4) further includes: the system pH is adjusted by a second basic compound comprising at least one selected from the group consisting of calcium carbonate, calcium oxide, sodium hydroxide and aqueous ammonia.
According to an embodiment of the invention, step (4) is performed at 80-100 ℃.
According to an embodiment of the invention, the method further comprises:
(5) And removing impurities, concentrating and carbonizing the lithium-rich filtrate to obtain lithium carbonate. Thereby obtaining battery grade lithium carbonate.
According to an embodiment of the invention, the method further comprises: and (3) carrying out hydrolysis reaction on the sodium-iron-vanadium filter residue obtained in the step (3), and filtering to obtain sodium sulfate filtrate and ferric oxide precipitate.
According to an embodiment of the invention, the method further comprises: and (3) carrying out hydrolysis reaction on the sodium alunite filter residue obtained in the step (4), and filtering to obtain sodium sulfate filtrate and alumina precipitate.
According to an embodiment of the invention, the method further comprises: crushing and roasting the clay-type lithium ore in the step (1) to obtain a roasting sample, and mixing the roasting sample with an acidic solution to obtain leaching liquid and leaching residues. Thereby destroying the crystal structure of the clay-type lithium ore through pretreatment.
According to the embodiment of the invention, clay-type lithium ore powder in the step (1) is crushed to 80-325 meshes;
according to the embodiment of the invention, the roasting temperature is 700-900 ℃ and the roasting time is 1-4 h.
Compared with the prior art, the invention has the beneficial effects that:
(1) Traditional method for removing Fe in pickle liquor 3+ And Al 3+ By adjusting the pH using sodium hydroxide solution to form amorphous Fe (OH) 3 And Al (OH) 3 The two kinds of colloid precipitates are small in particle size, are difficult to filter and settle, have adsorption performance, easily cause huge loss of lithium, and do not have industrial advantages. In contrast, the sodium-iron-yellow alum and sodium alunite precipitate formed by the invention has large particle size, strong crystallinity, good filterability, no adsorption performance and no generation ofThe great loss of lithium formation has industrial advantages;
(2) The sodium sulfate can be used for removing Fe from the pickle liquor next time 3+ And Al 3+ The required sodium source improves the comprehensive utilization rate of clay type lithium ores;
(3) The lithium-rich solution obtained by the method for extracting lithium from the clay-type lithium ore provided by the invention has few impurities and high lithium concentration, and can be obtained through carbonization and other steps.
Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
fig. 1 shows a flow chart of the process steps of the clay-type lithium ore extraction method in example 1 of the present invention.
Detailed Description
Embodiments of the present invention are described in detail below. The following examples are illustrative only and are not to be construed as limiting the invention.
It should be noted that the terms "first," "second," and "second" are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or implying a number of technical features being indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. Further, in the description of the present invention, unless otherwise indicated, the meaning of "a plurality" is two or more.
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In order that the invention may be more readily understood, certain technical and scientific terms are defined below. Unless clearly defined otherwise herein in this document, all other technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
In this document, the terms "comprise" or "include" are used in an open-ended fashion, i.e., to include what is indicated by the present invention, but not to exclude other aspects.
In this document, the terms "optionally," "optional," or "optionally" generally refer to the subsequently described event or condition may, but need not, occur, and the description includes instances in which the event or condition occurs, as well as instances in which the event or condition does not.
According to an embodiment of the invention, the invention provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps:
(1) Mixing clay type lithium ores with an acidic solution to obtain leaching liquid and leaching residues;
according to a specific embodiment of the invention, the acidic solution can be sulfuric acid solution, hydrochloric acid solution, nitric acid solution and phosphoric acid solution, the liquid-solid ratio of the acidic solution to clay-type lithium ore is 1-5mL/g, the acid leaching time is 1-4 h, and the acid leaching temperature is 30-90 ℃, so that lithium, iron and aluminum in the clay-type lithium ore are fully leached, and a leaching solution is obtained. Wherein the acid solution is preferably sulfuric acid solution, the concentration can be 35wt%, the acid leaching temperature is preferably 80 ℃, the acid leaching time is preferably 2h, and the liquid-solid ratio of the sulfuric acid solution to the clay-type lithium ore is preferably 5mL/g.
According to a specific embodiment of the present invention, clay-type lithium ores may also be subjected to pretreatment, such as crushing and roasting, to obtain a roasted sample, and then mixed with an acidic solution. Specifically, clay-type lithium ore may be crushed to 80-325 mesh, preferably 100 mesh, and calcined at 700-900 deg.c for 1-4 h, preferably 800 deg.c for 1h, to destroy the crystal structure of the clay-type lithium ore.
(2) Adding an oxidant into the leaching solution to obtain a mixed solution;
According to specific embodiments of the present invention, the oxidizing agent may be selected from hydrogen peroxide, sodium chlorate, potassium chlorate, and potassium permanganate, but is not limited to the above. Fe in the leaching solution can be added into the leaching solution by adding an oxidant 2+ Oxidation to Fe 3+ . Specifically, when the oxidizing agent is hydrogen peroxide, it oxidizes Fe 2+ The ionic equation of (2) is: 2Fe 2+ +H 2 O 2 +2H + ＝2Fe 3+ +2H 2 O. The oxidant can be added into the leaching solution by adding Fe into the leaching solution 2+ The concentration was tested and found to be in combination with the ionic equation.
(3) Adding sodium sulfate solution into the mixed solution, regulating the pH value of the system to be 1.5-3.0 and not 3.0, preferably 1.5-2.5, and obtaining iron removal filtrate and sodium iron vitriol filter residues after the pH value of the system is not changed;
according to a specific embodiment of the present invention, the pH of the system may be adjusted by a first basic compound, which may be selected from calcium carbonate, calcium oxide, sodium hydroxide and ammonia, preferably a weak basic compound, to avoid that the strong basic compound induces fine and amorphous particles, thereby affecting the filtration performance. Meanwhile, the pH value of the system cannot be 3.0, and when the pH value of the system is 3.0, iron ions in the solution can form ferric hydroxide colloid, so that a great amount of lithium is lost.
According to a specific embodiment of the invention, the mixed solution obtained in the step (2) can be added into a reaction container, after a certain amount of sodium sulfate solution is added, an oil bath is heated to a set temperature, timing is started, a pH meter is continuously used for monitoring the pH of the system in the reaction process, and alkali liquor is needed to stabilize the pH of the system due to sulfuric acid generated in the reaction process. When the pH value of the system is not changed any more, the reaction is finished, the reaction time is recorded, and the filter liquor is filtered after the reaction time is cooled to room temperature, so that iron-removing filtrate and sodium-iron-vanadium filter residues are obtained.
According to a specific embodiment of the invention, the reaction equation of the iron deposition by the sodium-iron-vanadium method is 3Fe 2 (SO 4 ) 3 +Na 2 SO 4 +12H 2 O→2NaFe 3 (SO 4 ) 2 (OH) 6 ↓+6H 2 SO 4 Based on the stoichiometric ratio of this equation, the molar ratio of sodium to iron forming sodium-iron-alum is 1:3, indicating that 1 mole of sodium can precipitate 3 moles of iron, when Na 2 SO 4 The addition amount of (2) is theoretical, so that at least theoretical amount of Na is added into the leaching solution before the reaction 2 SO 4 . Since sulfuric acid is generated during the reaction, alkali liquor is required to neutralize the excess sulfuric acid. The alkali solution can be NaOH solution, caCO 3 Suspensions, ammonia or calcium oxide suspensions, preferably CaCO 3 The suspension reacts with sulfuric acid to generate calcium sulfate, which provides a template for the formation of sodium-ferric-aluminum sulfate on the surface of the suspension, so that the removal rate of iron ions is promoted, and the concentration of alkali liquor is 15wt%. The pH of the system needs to be adjusted to 1.5-3.0 and not 3.0, preferably 1.5-2.5, more preferably 2.0 during the reaction. The temperature required for the reaction is 80-100 ℃, including but not limited to, a point value of any one of 80 ℃, 85 ℃, 90 ℃, 95 ℃, 100 ℃ or a range value between any two, preferably 90 ℃. The reaction time is 2h-6h, including but not limited to any one of 2h, 4h and 6h, or any range between the two, preferably 4h, and the reaction time can also be determined according to the change of the pH of the system, and the reaction can be ended when the pH is no longer lower than 2.
According to a specific embodiment of the invention, the obtained yellow sodium iron alum filter residue can be subjected to hydrolysis reaction and filtered to obtain Fe 2 O 3 Precipitation and Na 2 SO 4 Solution of Na 2 SO 4 The solution is evaporated and crystallized, and the sodium source required for removing iron and aluminum in the next pickling solution is used. Specifically, the hydrolysis equation of the sodium-iron-yellow alum is: 2NaFe 3 (SO 4 ) 2 (OH) 6 +6NaOH+3nH 2 O＝3Fe 2 O 3 ·nH 2 O+4Na 2 SO 4 +3H 2 O. The temperature required for hydrolysis is 40℃to 100℃including, but not limited to, 40℃45℃50℃55℃60℃65℃70℃75℃80℃85℃90℃95℃100℃or a range of values between any two, preferably 95 ℃. The hydrolysis time is 5min-30min, including but not limited to a point value of any one of 5min, 10min, 15min, 20min, 25min, 30min or a range value between any two, preferably 25min. The hydrolysis pH is set to 8-14, including but not limited to a point value of any one of pH 8, 9, 10, 11, 12, 13, 14 or a range between any two, preferably pH 12. The liquid-solid ratio of the hydrolysis is 1-5mL/g, preferably 5mL/g.
According to a specific embodiment of the invention, in this step, in addition to the sodium sulphate solution, potassium sulphate or ammonium sulphate solution may be added, producing jarosite and potassium alunite, jarosite and ammonium alunite, respectively. However, sodium sulfate has a relatively low price in view of raw material costs, and thus sodium sulfate is preferable.
(4) Adding sodium sulfate solution into the iron-removing filtrate, adjusting the pH value of the system to be 3.0-4.5 and not 3.0 and 4.5, preferably 3.5-4.0, and obtaining lithium-rich filtrate and sodium alunite filter residues when the pH value of the system is not changed.
According to a specific embodiment of the present invention, the system pH may be adjusted by a second basic compound selected from the group consisting of calcium carbonate, calcium oxide, sodium hydroxide and ammonia. Meanwhile, the pH value of the system cannot be 3.0 and 4.5. When the pH value of the system is 4.5, aluminum ions in the solution can form aluminum hydroxide colloid, so that a great amount of lithium is lost, and when the pH value of the system is 3.0, the reaction is unfavorable to the direction of generating sodium alunite, so that the removal rate of aluminum is reduced.
According to a specific embodiment of the invention, the iron-removing filtrate obtained in the step (3) is added into a reaction vessel, a certain amount of sodium sulfate solution is added, then the oil bath is heated to a set temperature, timing is started, a pH meter is continuously used for monitoring the pH of the system in the reaction process, sulfuric acid is generated in the reaction process, and alkali liquor is used for stabilizing the pH of the system to a certain value. When the pH value of the system is not changed any more, the reaction is finished, the reaction time is recorded, and the lithium-rich solution and sodium alunite filter residue are obtained after the reaction time is cooled to room temperature and filtered.
According to a specific embodiment of the invention, the reaction equation for sodium alunite aluminum precipitation is 3Al 2 (SO 4 ) 3 +Na 2 SO 4 +12H 2 O→2NaAl 3 (SO 4 ) 2 (OH) 6 ↓+6H 2 SO 4 Similar to the reaction principle of iron deposition of sodium-iron-vanadium, the theoretical amount of Na is added into the iron-removing filtrate before the reaction 2 SO 4 . Sulfuric acid is produced during the reaction, so that alkali lye is required to neutralize the excess sulfuric acid. The alkali solution can be NaOH solution, caCO 3 Suspensions, ammonia or calcium oxide suspensions, preferably CaCO 3 The concentration of the alkali liquor in the suspension is 15wt%. The pH of the system during the reaction is adjusted to 3.0 to 4.5, preferably 3.5 to 4.0, more preferably 3.5. The temperature required for the reaction is preferably 90 ℃. The reaction time is 1h-6h, including but not limited to any one of 1h, 2h, 3h, 4h, 5h and 6h, or any range between the two, preferably 4h, and the reaction time can also be determined according to the change of the pH of the system, and the reaction can be ended when the pH is no longer lower than 3.5.
According to a specific embodiment of the invention, the obtained sodium alunite filter residue can also be subjected to hydrolysis reaction, and filtered to obtain Al 2 O 3 Precipitation and Na 2 SO 4 Solution of Na 2 SO 4 The solution is evaporated and crystallized, and the sodium source required for removing iron and aluminum in the next pickling solution is used. Specifically, the hydrolysis equation of sodium alunite is: 2NaAl 3 (SO 4 ) 2 (OH) 6 +6NaOH+3nH 2 O＝3Al 2 O 3 ·nH 2 O+4Na 2 SO 4 +3H 2 O. The temperature required for hydrolysis can be selected to be 95 ℃. The time required for hydrolysis is 10min-60min, including but not limited to any one of 10min, 20min, 30min, 40min, 50min, 60min or a range between any two, preferably 40min. The hydrolysis pH is set to 8-14, including but not limited to a point value of any one of pH 8, 9, 10, 11, 12, 13, 14 or a range between any two, preferably pH 13. The liquid-solid ratio of the hydrolysis is 1-5mL/g, preferably 5mL/g.
(5) And removing impurities, concentrating and carbonizing the lithium-rich filtrate to obtain lithium carbonate.
According to a specific embodiment of the present invention, the impurity removal can be performed by multistage resin, mainly removing Ca 2+ 、Mg 2+ Equal divalentAnd (3) carrying out cation, and then dropwise adding a saturated sodium carbonate solution to carry out lithium precipitation, wherein the temperature of the lithium precipitation can be 90 ℃. Filtering after the reaction is finished, and washing with hot water to obtain the battery grade lithium carbonate.
The scheme of the present invention will be explained below with reference to examples. It will be appreciated by those skilled in the art that the following examples are illustrative of the present invention and should not be construed as limiting the scope of the invention. The examples are not to be construed as limiting the specific techniques or conditions described in the literature in this field or as per the specifications of the product. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, the flow of which is shown in fig. 1, and the method comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 80 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 1.5. When the temperature was raised to 80 ℃, the timing was started, and after 2 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: to remove ironAdding theoretical amount of Na into the filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 3.0. When the temperature was increased to 90 ℃, the time was started, and after 1 hour of reaction, the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the yellow sodium iron vitriol filter residue obtained in the step S5 at 40 ℃ with hydrolysis pH of 8.0 for 5min, with hydrolysis liquid-solid ratio of 1mL/g, and filtering after the reaction is finished to obtain Fe with the pH regulator of NaOH 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH value of 8.0 for 10min, the hydrolysis liquid-solid ratio of 1mL/g, and the selected pH regulator of NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 2
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
S1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration according toOxidation of Fe with hydrogen 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 100 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 3.0. When the temperature was raised to 100 ℃, the time was started, and after 6 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 4.5. When the temperature was increased to 90 ℃, the time was started, and after 6 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 100deg.C for 30min at 14 pH, with 5mL/g liquid-solid ratio, and filtering after the reaction to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH of 14, the hydrolysis time of 60min, the hydrolysis liquid-solid ratio of 5mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 3
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
S3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 2.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the system pH at 3.5. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
S8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 95 ℃ for 25min at a hydrolysis pH of 12, wherein the hydrolysis liquid-solid ratio is 5mL/g, and the selected pH regulator isNaOH, filtering after the reaction is finished to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH value of 13, the hydrolysis time of 40min, the hydrolysis liquid-solid ratio of 5mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 4
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
S4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 2.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension is a pH regulator to maintain the pH of the system at3.5. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the yellow sodium iron vitriol filter residue obtained in the step S5 at 90 ℃ for 20min at 11 pH, with 4mL/g liquid-solid ratio, and filtering after the reaction to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH of 12, the hydrolysis time of 30min, the hydrolysis liquid-solid ratio of 4mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 5
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 2.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the system pH at 3.5. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 100deg.C for 30min at 14 pH, with 5mL/g liquid-solid ratio, and filtering after the reaction to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH of 14, the hydrolysis time of 60min, the hydrolysis liquid-solid ratio of 5mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 6
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 2.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 3.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 95 ℃ for 25min at a hydrolysis pH of 12, wherein the hydrolysis liquid-solid ratio is 5mL/g, the selected pH regulator is NaOH, and filtering after the reaction is finished to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Filtering the sodium alunite residue obtained in the step S6Hydrolyzing at 95deg.C, pH of 13, hydrolysis time of 40min, hydrolysis liquid-solid ratio of 5mL/g, and pH regulator of NaOH, filtering after reaction to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Example 7
The embodiment provides a method for extracting lithium from clay-type lithium ores and preparing battery-grade lithium carbonate, which comprises the following steps:
S1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 2.0. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 Controlling the reaction temperature to 90 ℃ and CaCO 3 The suspension was a pH adjuster to maintain the pH of the system at 4.5. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 95 ℃ for 25min at a hydrolysis pH of 12, wherein the hydrolysis liquid-solid ratio is 5mL/g, the selected pH regulator is NaOH, and filtering after the reaction is finished to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH value of 13, the hydrolysis time of 40min, the hydrolysis liquid-solid ratio of 5mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Comparative example 1
The embodiment provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
S4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a theoretical amount of Na to the pickle liquor of hydrogen peroxide oxidation 2 SO 4 Controlling the reaction temperature to 90 ℃ and adjusting the pH by taking NaOH solution as pHThe pH of the system was maintained at 2.0 by the conditioning agent. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium-iron-vanadium filter residue and iron-removing filtrate, and testing Fe in the iron-removing filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s6: adding a theoretical amount of Na to the iron-removing filtrate 2 SO 4 The reaction temperature is controlled to 90 ℃, and NaOH solution is used as a pH regulator to maintain the pH of the system to be 3.5. When the temperature was increased to 90 ℃, the time was started, and after 4 hours the reaction was ended. Filtering to obtain sodium alunite filter residue and lithium-rich solution, and testing Fe in the lithium-rich filtrate 3+ ，Al 3+ ，Na + And Li (lithium) + Concentration;
s7: removing impurities from the lithium-rich filtrate through multistage resin, then dropwise adding saturated sodium carbonate solution to precipitate lithium at 90 ℃, filtering after the reaction is finished, and washing with hot water at 90 ℃ to obtain lithium carbonate;
s8: hydrolyzing the sodium-iron-vanadium filter residue obtained in the step S5 at 95 ℃ for 25min at a hydrolysis pH of 12, wherein the hydrolysis liquid-solid ratio is 5mL/g, the selected pH regulator is NaOH, and filtering after the reaction is finished to obtain Fe 2 O 3 Starch and Na 2 SO 4 A solution. Hydrolyzing the sodium alunite filter residue obtained in the step S6 at 95 ℃, the hydrolysis pH value of 13, the hydrolysis time of 40min, the hydrolysis liquid-solid ratio of 5mL/g, the selected pH regulator being NaOH, filtering after the reaction is finished to obtain Al 2 O 3 Precipitation and Na 2 SO 4 A solution. Na (Na) 2 SO 4 Evaporating and crystallizing the solution, and recovering the solution to remove iron and sodium source required by aluminum from the pickle liquor.
Comparative example 2
The embodiment provides a method for extracting lithium from clay-type lithium ores, which comprises the following steps:
s1: crushing and ball milling clay type lithium ores to 100 meshes to obtain mineral powder;
s2: weighing 500g of mineral powder, roasting for 1h at 800 ℃ to destroy the crystal structure of the mineral powder, and obtaining a roasting sample after roasting;
s3: fully mixing the roasting sample with 35wt% sulfuric acid solution, performing an acid leaching experiment at the acid leaching temperature of 80 ℃ for 2 hours, and filtering after the reaction is finished, wherein the liquid-solid ratio is 5mL/g, so as to obtain acid leaching liquid and silicon slag;
s4: testing Fe in pickle liquor 2+ Concentration of Fe oxidized according to hydrogen peroxide 2+ Adding hydrogen peroxide to the pickle liquor at room temperature to add Fe 2+ Fully oxidized to Fe 3+ ；
S5: adding a sodium hydroxide solution with the concentration of 20wt% into the pickle liquor oxidized by hydrogen peroxide to adjust the pH to 3.2-3.5, filtering and separating, and washing with pure water to obtain ferric hydroxide precipitate and iron removal filtrate;
S6: continuously adding a sodium hydroxide solution with the concentration of 20wt% into the iron-removing filtrate to adjust the pH value to 5-7, filtering and separating, and washing with pure water to obtain lithium-rich aluminum hydroxide precipitate and sodium sulfate solution;
s7: drying the lithium-rich aluminum hydroxide precipitate, roasting in a muffle furnace at 600-900 ℃ for 20-60 min to obtain the lithium-rich aluminum oxide precipitate, mixing and stirring the lithium-rich aluminum oxide precipitate and pure water according to the mass ratio of 1:1.5-3.1, filtering and separating, and washing with pure water to obtain the aluminum oxide precipitate and lithium-rich solution.
The total removal rate of iron and aluminum, the total loss rate of lithium, the hydrolysis rate of iron and the hydrolysis rate of aluminum in examples 1 to 7 and comparative examples 1 to 2 were calculated, and the results are shown in Table 1. Wherein the total removal rate of iron and aluminum and the total loss rate of lithium are determined by the acid leaching solution and Fe in the lithium-rich solution 3+ 、Al 3+ And Li (lithium) + The concentration is calculated, the hydrolysis rate of iron is calculated by the mass before and after the hydrolysis of the sodium-iron alum, and the hydrolysis rate of aluminum is calculated by the mass before and after the hydrolysis of sodium-alunite.
Table 1 comparison of total removal rate of iron and aluminum, total loss rate of lithium, hydrolysis rate of iron and aluminum in each of examples and comparative examples
In conclusion, compared with the traditional method for adjusting the pH value of the pickle liquor by using alkali liquor, amorphous Fe (OH) is generated 3 And Al (OH) 3 The colloid precipitation to remove iron and aluminium is carried out by adding Na into pickle liquor 2 SO 4 To provide the sodium source required to produce the sodium alum and sodium alunite, respectively, by controlling the pH, sodium alum and sodium alunite precipitate are formed. The precipitate obtained by the method has higher crystallinity and better filterability, not only achieves the purpose of removing iron and aluminum in the pickle liquor, but also does not cause lithium loss in the precipitation process, improves the concentration of lithium-rich solution, and simultaneously reduces energy consumption because secondary roasting is not needed.
In comparative example 1, naOH solution was used as a pH adjustor, compared with CaCO 3 The suspension, naOH solution is more alkaline and reacts rapidly, resulting in insufficient reaction, thereby reducing the removal rate of iron and aluminum. However, at the optimum reaction temperature and pH, the reaction products remain sodium-iron-yellow alum and sodium alunite, resulting in little lithium loss.
In comparative example 2, since the pH was adjusted to 3.2 to 3.5 directly using NaOH solution, iron hydroxide colloid was formed and lithium loss was caused; and then adding NaOH solution into the iron-removing filtrate to adjust the pH to 5-7, thus obtaining lithium-rich aluminum hydroxide colloid precipitate, and roasting and leaching the precipitate, thus correspondingly increasing energy consumption.
In the description of the present specification, a description referring to terms "one embodiment," "some embodiments," "examples," "specific examples," or "some examples," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (10)
1. The method for extracting lithium from clay-type lithium ores is characterized by comprising the following steps:
(1) Mixing clay type lithium ores with an acidic solution to obtain leaching liquid and leaching residues;
(2) Adding an oxidant into the leaching solution to obtain a mixed solution;
(3) Adding sodium sulfate solution into the mixed solution, regulating the pH value of the system to be 1.5-3.0 and not 3.0, and obtaining iron-removing filtrate and sodium-iron-vanadium filter residues when the pH value of the system is not changed;
(4) Adding sodium sulfate solution into the iron-removing filtrate, adjusting the pH value of the system to be 3.0-4.5 and not 3.0 and 4.5, and obtaining lithium-rich filtrate and sodium alunite filter residues after the pH value of the system is not changed.
2. The method of claim 1, wherein the acidic solution in step (1) comprises at least one selected from the group consisting of sulfuric acid, hydrochloric acid, nitric acid, and phosphoric acid;
optionally, the liquid-solid ratio of the acidic solution to the clay-type lithium ore is 1-5mL/g;
optionally, the acid leaching time in the step (1) is 1h to 4h, and the acid leaching temperature is 30 ℃ to 90 ℃.
3. The method of claim 1, wherein the oxidizing agent in step (2) comprises at least one selected from the group consisting of hydrogen peroxide, sodium chlorate, potassium chlorate, and potassium permanganate.
4. The method of claim 1, wherein step (3) further comprises: adjusting the pH value of the system through a first alkaline compound, wherein the first alkaline compound comprises at least one selected from calcium carbonate, calcium oxide, sodium hydroxide and ammonia water;
Optionally, in the step (3), the pH value of the system is adjusted to be 1.5-2.5;
optionally, step (3) is performed at 80 ℃ to 100 ℃.
5. The method of claim 1, wherein step (4) further comprises: adjusting the pH value of the system by a second alkaline compound, wherein the second alkaline compound comprises at least one selected from calcium carbonate, calcium oxide, sodium hydroxide and ammonia water;
optionally, in the step (4), adjusting the pH value of the system to 3.5-4.0;
optionally, step (4) is performed at 80 ℃ to 100 ℃.
6. The method according to claim 1, wherein the method further comprises:
(5) And removing impurities, concentrating and carbonizing the lithium-rich filtrate to obtain lithium carbonate.
7. The method according to claim 1, wherein the method further comprises: and (3) carrying out hydrolysis reaction on the sodium-iron-vanadium filter residue obtained in the step (3), and filtering to obtain sodium sulfate filtrate and ferric oxide precipitate.
8. The method according to claim 1, wherein the method further comprises: and (3) carrying out hydrolysis reaction on the sodium alunite filter residue obtained in the step (4), and filtering to obtain sodium sulfate filtrate and alumina precipitate.
9. The method according to claim 1, wherein the method further comprises: crushing and roasting the clay-type lithium ore in the step (1) to obtain a roasting sample, and mixing the roasting sample with an acidic solution to obtain leaching liquid and leaching residues.
10. The method according to claim 9, wherein clay-type lithium ore powder in the step (1) is crushed to 80-325 mesh;
optionally, the roasting temperature is 700-900 ℃ and the roasting time is 1-4 h.
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