CN115747520B - Method for extracting lithium from lithium-containing ore - Google Patents
Method for extracting lithium from lithium-containing ore Download PDFInfo
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- CN115747520B CN115747520B CN202211449279.2A CN202211449279A CN115747520B CN 115747520 B CN115747520 B CN 115747520B CN 202211449279 A CN202211449279 A CN 202211449279A CN 115747520 B CN115747520 B CN 115747520B
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- ion exchange
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 193
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 193
- 238000000034 method Methods 0.000 title claims abstract description 79
- 238000001728 nano-filtration Methods 0.000 claims abstract description 60
- 238000001914 filtration Methods 0.000 claims abstract description 46
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000012530 fluid Substances 0.000 claims abstract description 33
- 238000005342 ion exchange Methods 0.000 claims abstract description 27
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 239000013522 chelant Substances 0.000 claims abstract description 13
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 12
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000003456 ion exchange resin Substances 0.000 claims abstract description 10
- 229920003303 ion-exchange polymer Polymers 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims description 38
- 230000020477 pH reduction Effects 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000001471 micro-filtration Methods 0.000 claims description 11
- 238000000108 ultra-filtration Methods 0.000 claims description 11
- 230000033558 biomineral tissue development Effects 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- 230000008020 evaporation Effects 0.000 claims description 9
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 6
- 239000011734 sodium Substances 0.000 abstract description 19
- 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 abstract description 18
- 229910052708 sodium Inorganic materials 0.000 abstract description 18
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 44
- 150000002500 ions Chemical class 0.000 description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 125000004429 atom Chemical group 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 229910001385 heavy metal Inorganic materials 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000002386 leaching Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229910052629 lepidolite Inorganic materials 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000001276 controlling effect Effects 0.000 description 5
- 229910052701 rubidium Inorganic materials 0.000 description 5
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229910052792 caesium Inorganic materials 0.000 description 4
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 229910052749 magnesium Inorganic materials 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003929 acidic solution Substances 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 3
- 229910000502 Li-aluminosilicate Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 239000003729 cation exchange resin Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- 229910052808 lithium carbonate Inorganic materials 0.000 description 2
- 229910003002 lithium salt Inorganic materials 0.000 description 2
- 159000000002 lithium salts Chemical class 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 229910020489 SiO3 Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- VHUJINUACVEASK-UHFFFAOYSA-J aluminum;cesium;disulfate;dodecahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.O.O.[Al+3].[Cs+].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VHUJINUACVEASK-UHFFFAOYSA-J 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 125000006297 carbonyl amino group Chemical group [H]N([*:2])C([*:1])=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910000174 eucryptite Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 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
- 239000011521 glass Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000004137 mechanical activation Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229910052670 petalite Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002918 waste heat Substances 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
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- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a method for extracting lithium from lithium-containing ores, which comprises the following steps: (1) Acidizing the lithium-containing ore to obtain lithium-containing acidizing fluid; (2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment comprises chelate resin taking N as a coordination atom; (3) And removing sodium from the lithium-containing concentrated solution to obtain a lithium chloride product. The method is suitable for extracting lithium from various aluminosilicate lithium-containing ores and aluminosilicate lithium-containing ores, the yield of lithium is high, the purity of the obtained lithium chloride product is high, the method does not need high-temperature roasting, the energy consumption and pollution in the roasting process are reduced, and the environment-friendly high-efficiency production of extracting lithium from ores is realized.
Description
Technical Field
The invention relates to the technical field of ore lithium extraction, in particular to a method for extracting lithium from lithium-containing ore.
Background
Lithium is an important strategic resource substance and is an indispensable important raw material for modern high-tech products. The existing methods for extracting lithium from ores mainly comprise a lime sintering method, a sulfate method, a chloridizing roasting method and an alkali autoclaving method. However, the above method has low lithium extraction efficiency.
The prior art discloses a method for extracting lithium salt from lepidolite, which comprises the following steps: mixing lepidolite mineral aggregate with CaO and Ca (CH 3COO)2), ball milling, calcining in a plasma generator, reacting the calcined material with dilute sulfuric acid solution and ammonia sulfate under a pressurized state, controlling the acid leaching temperature to be 85-100 ℃, obtaining a solid-liquid mixture, cooling, freezing, separating potassium, rubidium and cesium alum, filtering, adding alkali, removing impurities, precipitating lithium and preparing lithium salt.
Another prior art discloses a method for extracting lithium and removing aluminum by treating lepidolite with sulfuric acid, wherein the recovery method comprises the steps of lepidolite mechanical activation, sulfuric acid 200-300 ℃ segmented continuous leaching treatment of valuable metal elements, medium-temperature sintering, tail gas recovery, normal-temperature water leaching and sulfate extraction, and the like. In the method, the sectional continuous leaching of sulfuric acid at 200-300 ℃ is difficult to control and has safety problems in operation due to higher temperature.
Still another prior art discloses a method and system for recovering lithium, rubidium and/or cesium from lepidolite ore, the method converts lithium, rubidium and cesium from poorly soluble aluminosilicates into soluble sulfates by ball milling and roasting lepidolite, leaches lithium, rubidium and cesium from the roasted material into solution by acid leaching, removes impurities such as iron, aluminum, manganese and magnesium by extraction, prepares lithium carbonate by precipitation with sodium carbonate, and concentrates the mother liquor left after preparing lithium carbonate with sulfuric acid after neutralization to recover sulfates, recovers sulfates to return to the ingredients, and finally recovers lithium, rubidium and cesium in the mother liquor by extraction. However, this method involves the problem of high environmental pollution and high energy consumption caused by high-temperature roasting.
It can be seen that the existing methods for extracting lithium from ores all require roasting at high temperature and then leaching crystallization, and have the defects of high energy consumption and complex process.
Therefore, the method for extracting lithium from the lithium-containing ore without roasting treatment is developed, the purposes of energy conservation, environmental protection and high efficiency lithium extraction are achieved, and the method has important significance.
Disclosure of Invention
In view of the problems existing in the prior art, the invention provides a method for extracting lithium from lithium-containing ores, which is characterized in that after various aluminosilicate-type lithium-containing ores and iron aluminate-type lithium-containing ores are acidized, the method is used for extracting lithium by adopting a membrane method, high-temperature roasting is not needed for the content ores, the environmental pollution is reduced, the lithium yield is high, the purity of the obtained lithium chloride product is high, and the method has a large-scale popularization and application prospect.
To achieve the purpose, the invention adopts the following technical scheme:
The invention provides a method for extracting lithium from lithium-containing ores, which comprises the following steps:
(1) Acidizing the lithium-containing ore to obtain lithium-containing acidizing fluid;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment comprises chelate resin taking N as a coordination atom;
(3) And removing sodium from the lithium-containing concentrated solution to obtain a lithium chloride product.
Compared with the prior art, the invention has at least the following beneficial effects:
compared with the method for extracting lithium by high-temperature roasting, the method provided by the invention reduces environmental pollution and lithium loss, realizes high-efficiency direct lithium extraction on various lithium-containing ores, ensures that the lithium yield can reach more than 88%, ensures that the purity of the obtained lithium chloride product is high, and reduces the concentration of heavy metal ions to 1ppb.
Drawings
FIG. 1 is a flow chart of a method for extracting lithium from a lithium-containing ore provided by the present invention;
Fig. 2 is a flow chart of another method for extracting lithium from lithium-containing ores provided by the present invention.
Detailed Description
The technical scheme of the invention is further described below by the specific embodiments with reference to the accompanying drawings.
The invention provides a method for extracting lithium from lithium-containing ores, the process flow chart of which is shown in figure 1, and the method comprises the following steps:
(1) Acidizing the lithium-containing ore to obtain lithium-containing acidizing fluid;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment comprises chelate resin taking N as a coordination atom;
(3) And removing sodium from the lithium-containing concentrated solution to obtain a lithium chloride product.
According to the method for extracting lithium from the lithium-containing ore, disclosed by the invention, the lithium-containing ore is subjected to acidification treatment, so that main components in the lithium-containing ore are dissolved in an acidizing fluid in an ionic form, then the lithium-containing acidizing fluid is subjected to primary filtration treatment in sequence to remove insoluble particles in the lithium-containing acidizing fluid, produced water is subjected to nanofiltration treatment to remove bivalent and multivalent ions in the lithium-containing acidizing fluid, produced water is subjected to ion exchange treatment to further remove residual heavy metal ions and silicon ions in the produced water, and a lithium-containing concentrated solution only containing sodium ions and lithium ions is obtained; and (3) carrying out sodium removal treatment on the lithium-containing concentrated solution to obtain a lithium chloride product. The ion exchange resin used in the ion exchange treatment comprises chelate resin taking N as a coordination atom, wherein the N atom contains lone pair electrons and has small atom volume, strong bonding capability with metal ions, and the N atom serving as a ligand atom has the characteristic of Lewis base, so that the lone pair electrons can be combined with empty orbitals provided by metal with Lewis acid characteristic, and coordination and selective adsorption can be easily carried out on Cu 2+、Ag+、Hg2+、Pt2+、Au+、Cd2+、Pd2+、Hg2+ and the like. According to the method disclosed by the invention, high-temperature roasting treatment is not required for the lithium-containing ore, so that the pollution to the environment is reduced, the efficient extraction of lithium from various aluminosilicate-containing ores and iron-aluminate-containing lithium ores is realized, the heavy metal ions are effectively separated and removed in the lithium extraction process, and the obtained lithium chloride product has high purity and is convenient for subsequent direct utilization.
Preferably, the lithium-containing ore of step (1) comprises lithium aluminosilicate ore or lithium iron aluminate tailings.
The lithium-containing ore comprises aluminosilicate lithium ore or iron aluminate lithium-containing tailings, the aluminosilicate is an inorganic substance, the molecular formula is xAl 2O3·ySiO2, a part of SiO 4 2- tetrahedron in the silicate is formed by substitution of AlO 4 2- tetrahedron, glass crystals formed by the aluminosilicate and metal ions are insoluble matters, slag is discharged in the processes of acidification and coarse filtration, the nanofiltration treatment is realized by AI 3+,AlO2 -,AlO3 3-SiO3 2-,SiO2 plasma substances formed by dissolution in leaching liquid in the process of hydrochloric acid acidification, the nanofiltration membrane has higher interception rate on anions formed by Al in an acidic environment, the silicon ions are basically not intercepted, and the interception rate is high when the PH of the alkaline environment is more than 7, but insoluble matters such as silicate double salts which are easy to form and take aluminum hydroxide as a complex block nanofiltration membranes and pipeline equipment, so that the process cannot be carried out.
Preferably, as shown in fig. 2, the lithium-containing ore of step (1) is crushed prior to the acidification treatment.
The particle diameter of the crushed lithium-containing ore is preferably not more than 8mm, and may be, for example, equal to or less than the above-mentioned value, but is not limited to the above-mentioned value, and other values not mentioned in the above-mentioned value range are equally applicable.
The particle size of the lithium-containing ore after the crushing treatment is preferably less than or equal to 8mm, the contact area of the lithium-containing ore and the acid liquor is increased, the acidification reaction is facilitated, and the acidification time is reduced. The main component LiAlSi2O6、LiAlPO4FOH、LiAlSi4O10、LiAlSiO4、Na0.3(MgLi)Si4O10(OH)2 in the lithium-containing ore reacts with the acid solution to form a solution containing lithium, sodium, calcium, magnesium, iron and anionic groups, and other insoluble substances exist in a solid or colloid form, so that the subsequent separation is facilitated.
Preferably, the acid solution used for the acidification treatment comprises hydrochloric acid.
The temperature of the acidification reaction is preferably 45 to 60 ℃, and may be, for example, 45 ℃, 47 ℃, 50 ℃, 55 ℃, 58 ℃, 60 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The temperature of the acidification reaction is preferably 45-60 ℃, when the temperature of the acidification reaction is low, the acidification of the lithium-containing ore is incomplete, the yield of lithium is reduced, and when the temperature of the acidification reaction is high, more energy is required to be consumed, and the lithium extraction cost of the lithium-containing ore is increased.
The time of the acidification reaction in the invention refers to the time required by the lithium content in the leaching solution of the lithium-containing ore added into the acidification reactor in the hydrochloric acid acidification environment in unit time to be more than or equal to 90 percent of the lithium content of the ore. The time of the acidification reaction is related to the type and design of the acidification equipment, and continuous reaction and discharge can be achieved through the combination of process equipment.
Preferably, the pH of the lithium-containing acidizing fluid is less than or equal to 1.6, and can be 1.6, 1.5, 1, 0.9, 0.8, 0.5, 0.3 or 0.1, for example.
The pH value of the lithium-containing acidizing fluid is preferably less than or equal to 1.6, so that the excessive hydrochloric acid in the acidizing treatment is ensured, and the acidizing reaction is facilitated.
Preferably, the primary filtration treatment in the step (2) comprises that the lithium-containing acidified solution is filtered through a microfiltration membrane and an ultrafiltration membrane in sequence.
In the invention, after the primary filtration treatment is carried out firstly by removing large-particle insoluble impurities in the lithium-containing acidizing fluid through a microfiltration membrane, the large-particle insoluble impurities and microorganisms are continuously removed by pumping the lithium-containing acidizing fluid into an ultrafiltration membrane through a lift pump.
The pore size of the microfiltration membrane is preferably 0.1 to 10. Mu.m, and may be, for example, 0.1. Mu.m, 1. Mu.m, 3. Mu.m, 5. Mu.m, 8. Mu.m, or 10. Mu.m, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned numerical range are equally applicable.
The operation pressure of the filtration of the lithium-containing acidified solution with the microfiltration membrane is preferably 0.2 to 0.7MPa, and may be, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa or 0.7MPa, etc., but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are equally applicable.
The pore diameter of the ultrafiltration membrane is preferably 2 to 10nm, and may be, for example, 2nm, 3nm, 5nm, 7nm, 9nm, or 10nm, etc., but is not limited to the values recited, and other values not recited in the numerical range are equally applicable.
The operation pressure of the lithium-containing acidified solution by ultrafiltration membrane filtration is preferably 0.2 to 0.7MPa, and may be, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa or 0.7MPa, etc., but is not limited to the values listed, and other values not listed in the range are equally applicable.
The contamination index SDI of the lithium-containing acidic solution after the primary filtration treatment is preferably 5 or less, for example, 5, 4.5, 4,3, 2, 1 or 0.5, etc., but the present invention is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
The mineralization degree of the lithium-containing acidic solution after the primary filtration treatment is preferably 20 to 50g/L, and may be, for example, 20g/L, 25g/L, 30g/L, 36g/L, 40g/L, 50g/L, or the like, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned value range are equally applicable.
The pH of the lithium-containing acidified solution after the primary filtration treatment is preferably adjusted to 2.5 to 3.5, and then nanofiltration treatment is performed, for example, 2.5, 2.7, 2.9, 3, 3.2 or 3.5, but the present invention is not limited to the above-mentioned values, and other values not mentioned in the above-mentioned value range are applicable.
The pH value of the lithium-containing acidizing fluid after the primary filtration treatment is regulated to be 2.5-3.5 by adding 32% NaOH, the nanofiltration treatment is carried out, and divalent cations such as calcium, magnesium, aluminum, iron and the like and cations such as aluminate and sulfate radical and the like are removed by sieving of a nanofiltration membrane and interception under the effect of the daonam.
The temperature of the lithium-containing acidic solution after the primary filtration treatment is preferably controlled to 25 to 28 ℃, and may be, for example, 25 ℃, 25.5 ℃, 26 ℃, 26.3 ℃, 27 ℃, 28 ℃, or the like, but is not limited to the above-mentioned values, and other values not shown in the above-mentioned range are equally applicable.
The nanofiltration membrane used in the nanofiltration treatment in the step (2) preferably has a pore size of 0.5 to 2nm, and may be, for example, 0.5nm, 0.7nm, 1nm, 1.2nm, 1.5nm or 2nm, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The invention carries out nanofiltration treatment on the lithium-containing acidized solution after the primary filtration treatment, and utilizes the screening effect and the southward effect of the nanofiltration membrane to selectively permeate monovalent ions such as lithium, sodium, chlorine and the like through the nanofiltration membrane to intercept metal cations such as calcium, magnesium, iron, aluminum and the like and anions such as acid radicals and the like with the divalent or more, wherein the concentration of aluminum ions can reach below 2mg/L, but the nanofiltration treatment can not intercept and remove silicon in the lithium-containing acidized solution. In order to remove heavy metal ions and anions with more than two valences more efficiently, multistage nanofiltration treatment can be adopted, and the retention rate of nanofiltration membranes adopted in the second stage and above nanofiltration treatment is gradually increased.
Preferably, the nanofiltration membrane comprises an acid-resistant nanofiltration membrane.
The nanofiltration treatment is preferably carried out at an operating pressure of 3 to 4MPa, and may be carried out at 3MPa, 3.2MPa, 3.5MPa, 3.7MPa, 3.9MPa, 4MPa, or the like, for example, but the present invention is not limited to the values recited, and other values not recited in the range are equally applicable.
Preferably, the pH of the water produced after the nanofiltration treatment is adjusted to 8.5 to 9.5, and insoluble substances such as silicates are removed by a filter, and then the water is subjected to an ion exchange treatment, for example, 8.5, 8.8, 9, 9.1, 9.4, or 9.5, but the water is not limited to the above-mentioned values, and other non-mentioned values within the above-mentioned range are applicable.
The pH value of the produced water after nanofiltration treatment is preferably regulated to 8.5-9.5, which is favorable for filtering and separating solid-containing silicate insoluble substances, and then ion exchange treatment is carried out, under the pH value condition, the high-efficiency adsorption removal of the heavy metal ions in the lithium-containing solution after nanofiltration treatment by the chelate resin with N as a coordination atom can be realized, the concentration of the heavy metal ions can be lower than 0.01mg/L, and meanwhile, the concentration of the silicon ions can be removed and can be lower than 0.01 mg/L. When the pH is low, the resin is transformed and heavy metal ions cannot be removed; when the pH value is too high, metal ions in the solution are not in the form of ions, which is unfavorable for ion chelation of the coordination group, so that the effluent index exceeds the standard.
Preferably, the chelate resin with N as the coordinating atom in the step (2) comprises a chelate resin with N as the coordinating group, -NH 2、-NH、≡N、-C-NH、-C-N、-C-N-OH、-CONHNH2、-CONH2, -N or nitrogen-containing heterocyclic compound resin, such as-NH 2 and-NH, a combination of N and-C-NH, a combination of C-N and-CONHNH 2, -a combination of CONH 2 and-NH or a combination of three of ≡N, -C-NH and-C-N.
Preferably, the sodium removing treatment of step (3) includes sequentially performing an evaporation treatment and a cooling treatment.
The temperature of the evaporation treatment is preferably 95 to 105 ℃, and may be, for example, 95 ℃, 96 ℃, 98 ℃,100 ℃, 103 ℃, 105 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are applicable.
The control of the evaporation temperature in the invention is related to the ion concentration of the solution, the ion concentration is high, the boiling point of the solution is increased, the energy consumption is correspondingly changed, and comprehensive consideration is carried out in the process design.
The temperature of the cooling treatment is preferably 30 to 40 ℃, and may be, for example, 30 ℃, 32 ℃, 35 ℃, 37 ℃, 39 ℃,40 ℃, or the like, but is not limited to the values listed, and other values not listed in the range are equally applicable.
The cooling temperature is controlled at the same ion concentration, and as the solubility of sodium chloride is lower than that of lithium chloride, the same ion effect is utilized to separate out sodium chloride, so that the content of sodium chloride substances in a lithium chloride solution is further reduced, and the subsequent preparation of lithium chloride products is facilitated.
Preferably, after the sodium removal treatment, centrifugation is also performed.
The invention also comprises washing and pulping the filter cake according to the content of lithium in the filter cake sodium chloride obtained by centrifugal separation and the requirement of the required lithium yield, returning to the sodium removal treatment step, recovering lithium again and improving the lithium yield.
The invention can fully utilize the waste heat and the refrigerant of the sodium removal treatment system through the process design.
As a preferred technical scheme of the invention, the method comprises the following steps:
(1) Crushing the lithium-containing ore until the particle size is less than or equal to 8mm, and acidizing at 45-60 ℃ to obtain lithium-containing acidizing fluid with the pH value less than or equal to 1.6;
The lithium-containing ore comprises aluminosilicate lithium ore or aluminosilicate lithium-containing tailings; the acid liquor adopted in the acidification treatment comprises hydrochloric acid;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment comprises chelate resin taking N as a coordination atom;
The primary filtration treatment comprises that the lithium-containing acidizing fluid is filtered by a microfiltration membrane with the aperture of 0.1-10 mu m and an ultrafiltration membrane with the aperture of 2-10 nm in sequence; the pollution index SDI of the lithium-containing acidized solution after the primary filtration treatment is less than or equal to 5, and the mineralization degree is 20-50 g/L; controlling the temperature of the lithium-containing acidizing fluid after the primary filtration treatment to be 25-28 ℃; adjusting the pH value of the lithium-containing acidized solution after the primary filtration treatment to 2.5-3.5, and then carrying out nanofiltration treatment;
The aperture of the acid-resistant nanofiltration membrane adopted in the nanofiltration treatment is 0.5-2 nm; the operation pressure of the nanofiltration treatment is 3-4 MPa; adjusting the pH value of the water produced after the nanofiltration treatment to 8.5-9.5, and then carrying out ion exchange treatment; the chelate resin taking N as a coordination atom comprises a chelate resin with a coordination group of-NH 2、-NH、≡N、-C-NH、-C-N、-C-N-OH、-CONHNH2、-CONH2, -N-N or nitrogen-containing heterocyclic compound resin;
(3) The lithium-containing concentrated solution is subjected to sodium removal treatment to obtain a lithium chloride product;
The sodium removing treatment comprises the steps of sequentially carrying out evaporation treatment at the temperature of 95-105 ℃ and cooling treatment at the temperature of 30-40 ℃.
The present invention will be described in further detail below. The following examples are merely illustrative of the present invention and are not intended to represent or limit the scope of the invention as defined in the claims.
Example 1
The present embodiment provides a method of extracting lithium from a lithium-containing ore, the method comprising the steps of:
(1) Crushing the lithium aluminosilicate ore until the particle size is less than or equal to 8mm, and acidizing at 45 ℃ for 5 hours to obtain lithium-containing acidizing fluid with the pH value of 1.6;
the acid liquor adopted in the acidification treatment is hydrochloric acid with the mass concentration of 15%;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment is a resin with a coordination group of-N-N;
the primary filtration treatment comprises that the lithium-containing acidizing fluid is filtered by a microfiltration membrane with the aperture of 0.1-10 mu m and an ultrafiltration membrane with the aperture of 2-10 nm in sequence; the pollution index SDI of the lithium-containing acidized solution after the primary filtration treatment is less than or equal to 5, and the mineralization degree is 35g/L; controlling the temperature of the lithium-containing acidizing fluid after the primary filtration treatment to be 28 ℃; adjusting the pH value of the lithium-containing acidized solution after the primary filtration treatment to be 2.6, and then carrying out nanofiltration treatment;
The aperture of the acid-resistant nanofiltration membrane adopted in the nanofiltration treatment is 0.5-2 nm; the operation pressure of the nanofiltration treatment is 3.5MPa; adjusting the pH value of the water produced after the nanofiltration treatment to 9, and then carrying out ion exchange treatment;
(3) The lithium-containing concentrated solution is subjected to sodium removal treatment to obtain a lithium chloride product; the sodium removing treatment comprises evaporation treatment at 95 ℃ and cooling treatment at 40 ℃ in sequence.
Example 2
The present embodiment provides a method of extracting lithium from a lithium-containing ore, the method comprising the steps of:
(1) Crushing the lithium-containing associated iron aluminate ore to a particle size less than or equal to 8mm, and acidizing at 60 ℃ for 6 hours to obtain a lithium-containing acidizing fluid with a pH value of 1.0;
the acid liquor adopted in the acidification treatment comprises hydrochloric acid with the mass concentration of 20%;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment is a resin with-C-N coordination groups;
the primary filtration treatment comprises that the lithium-containing acidizing fluid is filtered by a microfiltration membrane with the aperture of 0.1-10 mu m and an ultrafiltration membrane with the aperture of 2-10 nm in sequence; the pollution index SDI of the lithium-containing acidized solution after the primary filtration treatment is less than or equal to 5, and the mineralization degree is 20g/L; controlling the temperature of the lithium-containing acidizing fluid after the primary filtration treatment to be 25 ℃; adjusting the pH value of the lithium-containing acidized solution after the primary filtration treatment to 3.5, and then carrying out nanofiltration treatment;
The aperture of the acid-resistant nanofiltration membrane adopted in the nanofiltration treatment is 0.5-2 nm; the operating pressure of the nanofiltration treatment is 30MKPa; adjusting the pH value of the water produced after the nanofiltration treatment to 9.5, and then carrying out ion exchange treatment;
(3) The lithium-containing concentrated solution is subjected to sodium removal treatment to obtain a lithium chloride product;
The sodium removal treatment includes sequentially performing an evaporation treatment at a temperature of 105 ℃ and a cooling treatment at a temperature of 40 ℃.
Example 3
The present embodiment provides a method of extracting lithium from a lithium-containing ore, the method comprising the steps of:
(1) Crushing the aluminosilicate lithium-containing tailings until the particle size is less than or equal to 8mm, and acidizing at 50 ℃ for 7 hours to obtain a lithium-containing acidizing fluid with the pH value of 1.4;
the acid liquor adopted in the acidification treatment comprises hydrochloric acid with the mass concentration of 17%;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment is-CONHNH 2 ligand group resin;
the primary filtration treatment comprises that the lithium-containing acidizing fluid is filtered by a microfiltration membrane with the aperture of 0.1-10 mu m and an ultrafiltration membrane with the aperture of 2-10 nm in sequence; the pollution index SDI of the lithium-containing acidized solution after the primary filtration treatment is less than or equal to 5, and the mineralization degree is 50g/L; controlling the temperature of the lithium-containing acidizing fluid after the primary filtration treatment to be 27 ℃; adjusting the pH value of the lithium-containing acidized solution after the primary filtration treatment to be 2.5, and then carrying out nanofiltration treatment;
The aperture of the acid-resistant nanofiltration membrane adopted in the nanofiltration treatment is 0.5-2 nm; the operation pressure of the nanofiltration treatment is 40MKPa; adjusting the pH value of the water produced after the nanofiltration treatment to 8.5, and then carrying out ion exchange treatment;
(3) The lithium-containing concentrated solution is subjected to sodium removal treatment to obtain a lithium chloride product;
The sodium removal treatment comprises evaporation treatment at a temperature of 100 ℃ and cooling treatment at a temperature of 32 ℃ in sequence.
Example 4
This example provides a process for extracting lithium from lithium-containing ore, which is the same as example 2 except that the pH of the acidification reaction is replaced with 2.
Example 5
This example provides a method for extracting lithium from a lithium-containing ore, which is the same as in example 2, except that the mineralization degree of the lithium-containing acidified solution after the primary filtration treatment is replaced with 10 g/L.
Example 6
This example provides a method for extracting lithium from a lithium-containing ore, which is the same as in example 2, except that the mineralization degree of the lithium-containing acidified solution after the primary filtration treatment is replaced with 60 g/L.
Comparative example 1
This comparative example provides a process for extracting lithium from lithium-containing ores except that the ion exchange resin employed in the ion exchange treatment is a macroporous strongly acidic styrenic cation exchange resin. The resin was prepared in the same manner as in example 1 except that the styrene-divinylbenzene copolymer having a macroporous structure had sulfonic acid groups [ -SO 3 - ] thereon and that the resin was operated under acidic conditions.
The lithium ion and heavy metal ion concentrations of the lithium chloride products obtained in the above examples and comparative examples were measured, and the lithium yields were calculated, and the results are shown in table 1.
TABLE 1
| Yield of lithium (%) | Heavy metal ion concentration (ppb) | |
| Example 1 | 58.5 | 20 |
| Example 2 | 88.5 | 1 |
| Example 3 | 76.8 | 10 |
| Example 4 | 76.5 | 20 |
| Example 5 | 59.5 | 20 |
| Example 6 | 52.5 | 20 |
| Comparative example 1 | 58 | 185000 |
As can be seen from table 1:
(1) It can be seen from a combination of example 2 and example 4 that, under the same conditions and acidification time, the lower the pH of the acidification reaction is, the more complete the reaction is, the lower the lithium loss carried by slag is, the higher the lithium yield is, but the lower the pH is, the higher the requirement for the type selection of the materials of the process equipment is.
(2) It can be seen from the combination of examples 2 and examples 5 to 6 that the mineralization degree of the lithium-containing acidified solution after the primary filtration treatment in example 5 is only 10g/L, and the lithium ion content is also low, so that the final lithium yield is low; in example 6, under the same pressure of nanofiltration, the higher the mineralization degree of the lithium-containing acidized solution subjected to nanofiltration treatment, the lower the yield of the nanofiltration process section, the higher the content of heavy metal ions in produced water, and the ion exchange load is increased, so that the resin is frequently regenerated, and the system lithium yield is affected.
(3) As can be seen from the combination of example 1 and comparative example 1, the use of chelate resin with N as the coordinating atom in the resin selection of example 1 is superior to that of comparative example 1 because the active group of the styrenic cation exchange resin is in hydrogen form during operation, which is disadvantageous in alkaline environment for exchange with other cations in solution and also reduces adsorption of higher ion.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (19)
1. A method of extracting lithium from a lithium-containing ore, the method comprising the steps of:
(1) Acidizing the lithium-containing ore at 45-60 ℃ to obtain lithium-containing acidizing fluid with pH less than or equal to 1.6; the acid liquor adopted in the acidification treatment is hydrochloric acid; the lithium-containing ore comprises aluminosilicate lithium ore or aluminosilicate lithium-containing tailings; the lithium-containing ore does not need roasting treatment;
(2) The lithium-containing acidizing fluid is subjected to primary filtration treatment, nanofiltration treatment and ion exchange treatment in sequence to obtain lithium-containing concentrated solution; the ion exchange resin adopted in the ion exchange treatment comprises chelate resin taking N as a coordination atom;
(3) And the lithium-containing concentrated solution is sequentially subjected to evaporation treatment and cooling treatment to obtain a lithium chloride product.
2. The method of claim 1, wherein the lithium-containing ore of step (1) is crushed prior to the acidification treatment.
3. The method according to claim 2, wherein the particle size of the crushed lithium-containing ore is less than or equal to 8mm.
4. The method of claim 1, wherein the primary filtration treatment of step (2) comprises filtration of the lithium-containing acidified solution through a microfiltration membrane and an ultrafiltration membrane in that order.
5. The method according to claim 4, wherein the micro-filtration membrane has a pore size of 0.1-10 μm.
6. The method of claim 4, wherein the operating pressure of the lithium-containing acidified solution filtered through the microfiltration membrane is between 0.2 mpa and 0.7mpa.
7. The method of claim 4, wherein the ultrafiltration membrane has a pore size of 2-10 nm.
8. The method of claim 4, wherein the operating pressure of the lithium-containing acidified solution filtered through the ultrafiltration membrane is 0.2 to 0.7mpa.
9. The method according to claim 1, wherein the pollution index SDI of the lithium-containing acidified solution after the primary filtration treatment is less than or equal to 5.
10. The method according to claim 1, wherein the mineralization degree of the lithium-containing acidified solution after the primary filtration treatment is 20-50 g/L.
11. The method according to claim 1, wherein the nanofiltration treatment is performed after the pH of the lithium-containing acidified solution after the primary filtration treatment is adjusted to 2.5 to 3.5.
12. The method according to claim 1, wherein the temperature of the lithium-containing acidified solution after the primary filtration treatment is controlled to be 25-28 ℃.
13. The method of claim 1, wherein the nanofiltration membrane used in the nanofiltration treatment in step (2) has a pore size of 0.5-2 nm.
14. The method of claim 13, wherein the nanofiltration membrane comprises an acid-resistant nanofiltration membrane.
15. The method according to claim 1, wherein the nanofiltration process is operated at a pressure of 3 to 4mpa.
16. The method according to claim 1, wherein the pH of the nanofiltration treated product water is adjusted to 8.5-9.5, and then ion exchange treatment is performed.
17. The method of claim 1, wherein the chelate resin having N as a coordinating atom in step (2) comprises a resin having-NH 2、-NH、≡N、-C-NH、-C-N、-C-N-OH、-CONHNH2、-CONH2, -N, or a nitrogen-containing heterocyclic compound as a coordinating group.
18. The method of claim 1, wherein the temperature of the evaporation process is 95 ℃ to 105 ℃.
19. The method of claim 1, wherein the temperature of the cooling treatment is 30 ℃ to 40 ℃.
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| AR102366A1 (en) * | 2015-08-28 | 2017-02-22 | Albemarle Corp | PROCESSES TO RECOVER VALUES OF SALMUERAS LITHIUM WITH LITHIUM CONTENT |
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