CN116803907A - Method for preparing lithium hydroxide by extracting lithium from raw halogen - Google Patents
Method for preparing lithium hydroxide by extracting lithium from raw halogen Download PDFInfo
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- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 title claims abstract description 165
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 56
- 229910052736 halogen Inorganic materials 0.000 title claims description 25
- 150000002367 halogens Chemical class 0.000 title claims description 25
- 238000000605 extraction Methods 0.000 claims abstract description 167
- 239000000243 solution Substances 0.000 claims abstract description 165
- 239000012074 organic phase Substances 0.000 claims abstract description 104
- 239000012071 phase Substances 0.000 claims abstract description 97
- 239000011734 sodium Substances 0.000 claims abstract description 95
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 90
- 229910001868 water Inorganic materials 0.000 claims abstract description 90
- 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 82
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 78
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 78
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 70
- 239000002994 raw material Substances 0.000 claims abstract description 67
- 238000005406 washing Methods 0.000 claims abstract description 37
- 230000002378 acidificating effect Effects 0.000 claims abstract description 30
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- 239000011780 sodium chloride Substances 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims abstract description 16
- 239000012267 brine Substances 0.000 claims abstract description 15
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000003085 diluting agent Substances 0.000 claims abstract description 12
- 150000002825 nitriles Chemical class 0.000 claims abstract description 12
- 150000001408 amides Chemical class 0.000 claims abstract description 11
- 239000012528 membrane Substances 0.000 claims abstract description 11
- 238000001728 nano-filtration Methods 0.000 claims abstract description 10
- 238000001704 evaporation Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 49
- 239000007788 liquid Substances 0.000 claims description 44
- 239000011259 mixed solution Substances 0.000 claims description 20
- 239000008346 aqueous phase Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 239000012530 fluid Substances 0.000 claims description 7
- 239000012466 permeate Substances 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000003350 kerosene Substances 0.000 claims description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000007791 liquid phase Substances 0.000 claims description 3
- RTTCFFTVCUNXLX-UHFFFAOYSA-N n,n-di(octan-2-yl)acetamide Chemical compound CCCCCCC(C)N(C(C)=O)C(C)CCCCCC RTTCFFTVCUNXLX-UHFFFAOYSA-N 0.000 claims description 3
- YKGBNAGNNUEZQC-UHFFFAOYSA-N 6-methyl-n,n-bis(6-methylheptyl)heptan-1-amine Chemical compound CC(C)CCCCCN(CCCCCC(C)C)CCCCCC(C)C YKGBNAGNNUEZQC-UHFFFAOYSA-N 0.000 claims description 2
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 31
- 239000011777 magnesium Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- OOIOHEBTXPTBBE-UHFFFAOYSA-N [Na].[Fe] Chemical compound [Na].[Fe] OOIOHEBTXPTBBE-UHFFFAOYSA-N 0.000 description 12
- 229910052742 iron Inorganic materials 0.000 description 11
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 6
- 229910052749 magnesium Inorganic materials 0.000 description 6
- 239000011591 potassium Substances 0.000 description 6
- 229910052700 potassium Inorganic materials 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- -1 li 2 SO 4 Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
- C01D15/00—Lithium compounds
- C01D15/02—Oxides; Hydroxides
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The application relates to the technical field of extracting lithium hydroxide from salt lake brine, and particularly discloses a method for preparing lithium hydroxide by extracting lithium from raw brine, which comprises the following steps: filtering salt lake brine to remove impurities, evaporating and concentrating, performing three-stage extraction by adopting an iron-carrying sodium extractant, washing, performing three-stage back extraction by adopting a sulfuric acid solution, adding sodium hydroxide, and then performing purification and concentration treatment by adopting a nanofiltration membrane to obtain a lithium hydroxide solution; evaporating, concentrating, cooling, crystallizing, filtering, separating and drying to obtain lithium hydroxide; the iron-carrying sodium extractant is prepared from a blank organic phase, an acidic iron-carrying water phase and a sodium hydroxide solution, wherein the blank organic phase is mainly prepared from the following raw materials: diethyl nitrile phosphate, tetrabenzyl phosphate, amide regulator and diluent; the acidic iron-carrying water phase is mainly prepared from the following raw materials: hydrochloric acid solution, sodium chloride and ferric trichloride. The method of the application is matched with the iron-carrying sodium extractant, so that the lithium extraction rate is more than 99%, thereby increasing the lithium recovery rate and meeting the requirement of higher requirements.
Description
Technical Field
The application relates to the technical field of extracting lithium hydroxide from salt lake brine, in particular to a method for preparing lithium hydroxide by extracting lithium from raw brine.
Background
Lithium hydroxide is an inorganic compound and is mainly used for preparing lithium salt, lithium-based lubricating grease, electrolyte of alkaline storage batteries, absorption liquid of lithium bromide refrigerators and the like. The lithium resource in the lithium hydroxide is mainly derived from ores and salt lakes, and the lithium resource in the salt lake accounts for more than 60% of the lithium reserves.
The salt lake brine contains metal elements such as sodium, potassium, magnesium and the like, and nonmetallic elements such as chlorine, sulfur and the like, in addition to lithium. At present, methods for extracting lithium hydroxide from salt lake brine mainly comprise an extraction method, a precipitation method, an ion exchange adsorption method, a carbonization method, an electrodialysis membrane method and the like. The extraction method has the advantages of good selectivity and high extraction rate, and is widely concerned and studied. For the extraction method, salt lake brine is evaporated and concentrated, and then acid is added to adjust the pH value to be 1-3, so as to obtain raw material liquid. Then adding a compound extractant into the raw material liquid for extraction, and then adding a hydrochloric acid solution for back extraction to obtain an acidic lithium chloride solution. Then adding sodium hydroxide into the acidic lithium chloride solution to convert the lithium chloride into lithium hydroxide and sodium chloride, and then separating the lithium hydroxide from the sodium chloride to further obtain the lithium hydroxide. The compound extractant usually selects phosphotriester as a main extractant, ferric trichloride as a co-extractant and kerosene as a diluent, and when the extractant is used for extracting raw material liquid, the lithium extraction rate is about 85% at most, so that the lithium recovery rate is influenced, and the requirement of higher requirements cannot be met.
Disclosure of Invention
In order to improve the lithium extraction rate, the application provides a method for preparing lithium hydroxide by extracting lithium by raw halogen, which adopts the following technical scheme:
the method for preparing lithium hydroxide by extracting lithium by using raw halogen comprises the following steps:
s1, filtering and impurity removing is carried out on salt lake brine, and evaporation concentration is carried out to obtain raw material liquid;
s2, dropwise adding a raw material liquid into the iron-carrying sodium extractant under continuous stirring to perform primary extraction to obtain a primary extraction water phase and a primary extraction organic phase; then dripping the primary extraction water phase into the iron-carrying sodium extractant under continuous stirring to perform secondary extraction to obtain a secondary extraction water phase and a secondary extraction organic phase; then, dropwise adding the second-stage extraction water phase into the iron-carrying sodium extractant under continuous stirring to perform third-stage extraction to obtain a third-stage extraction water phase and a third-stage extraction organic phase; then mixing the first-stage extraction organic phase, the second-stage extraction organic phase and the third-stage extraction organic phase to obtain an extraction organic solution;
s3, washing the extracted organic solution by adopting a sodium chloride solution to obtain an organic mixed solution;
s4, adding sulfuric acid solution into the organic mixed solution under continuous stirring to perform primary stripping, so as to obtain a primary stripping water phase and a primary stripping organic phase; then adding sulfuric acid solution into the first-stage back extraction organic phase under continuous stirring to carry out second-stage back extraction, thereby obtaining a second-stage back extraction aqueous phase and a second-stage back extraction organic phase; adding sulfuric acid solution into the second-stage back extraction organic phase under continuous stirring to perform third-stage back extraction to obtain a third-stage back extraction aqueous phase and a third-stage back extraction organic phase; mixing the first-stage back extraction water phase, the second-stage back extraction water phase and the third-stage back extraction water phase to obtain a lithium-rich solution;
s5, adding sodium hydroxide into the lithium-rich solution for mixing to obtain a pretreatment solution, and then purifying and concentrating the pretreatment solution by adopting a nanofiltration membrane to obtain trapped fluid and a permeate, wherein the trapped fluid is a sodium sulfate solution, and the permeate is a lithium hydroxide solution;
s6, evaporating and concentrating the lithium hydroxide solution, cooling and crystallizing, filtering and separating, and drying to obtain lithium hydroxide;
the iron-carrying sodium extractant is prepared from a blank organic phase, an acidic iron-carrying water phase and a sodium hydroxide solution, wherein the volume ratio of the blank organic phase to the acidic iron-carrying water phase to the sodium hydroxide solution is 1 (0.5-1.5);
the blank organic phase is mainly prepared from the following raw materials in parts by weight: 30-40 parts of diethyl nitrile phosphate, 10-20 parts of tetrabenzyl phosphate, 5-15 parts of amide regulator and 35-45 parts of diluent;
the acidic iron-carrying water phase is mainly prepared from the following raw materials in parts by weight: 100 parts of hydrochloric acid solution, 20-30 parts of sodium chloride and 10-30 parts of ferric trichloride.
By adopting the technical scheme, the salt lake brine is firstly evaporated and concentrated, and the lithium content in the salt lake brine is increased. Then extracting by adopting an iron-carrying sodium extractant which contains NaFeCl 4 Diethyl nitrile phosphate, tetrabenzyl phosphate. The diethyl nitrilophosphate contains P (≡ N, P) and two P-O, the tetrabenzyl phosphate contains four benzene rings, five P-O and two P=O, and the synergy between the two is utilized, so that the separation of the water phase and the oil phase is facilitated, the lithium extraction rate is improved, and the raw material liquid contains Li + 、Na + 、K + 、Mg 2+ ，FeCl 4 - The extraction sequence of the cations is H + ＞Li + ＞Na + ＞Mg 2+ ＞K + At this time, H in the raw material liquid + 、Li + Transferring to an extraction organic solution which mainly contains LiFeCl 4 Residual NaFeCl 4 Small amount of HFeCl 4 Not only ensures that the lithium extraction rate is more than 99 percent, but also reduces Mg 2+ 、K + Transferring to the extraction organic solution, reducing the influence of impurities and meeting the requirement of higher requirements.
The organic solution for extraction is washed by sodium chloride solution to obtain organic mixed solution, so that K in the organic solution for extraction can be effectively reduced + 、Mg 2+ And due to the Cl contained in the sodium chloride solution - Reducing LiFeCl in extracted organic solution 4 Also reduces lithium loss during washing, and the lithium loss rate is less than 0.15%. Then the sulfuric acid solution is adopted to carry out back extraction on the organic mixed solution, liFeCl in the organic mixed solution 4 、NaFeCl 4 Conversion to HFeCl 4 、Li 2 SO 4 、Na 2 SO 4 ，HFeCl 4 Into the organic phase, li 2 SO 4 、Na 2 SO 4 Enters into a water phase to obtain a lithium-rich solution, wherein the lithium-rich solution mainly contains Li 2 SO 4 、Na 2 SO 4 Residual H 2 SO 4 And the lithium back extraction rate is more than 93 percent. Then adding sodium hydroxide into the lithium-rich solution to convert lithium sulfate and sulfuric acid into lithium hydroxide, sodium sulfate and water, and intercepting the sodium sulfate by a nanofiltration membrane to obtain a lithium hydroxide solution, and further obtaining the lithium hydroxide.
Due to NaFeCl in the iron-sodium-loaded extractant 4 When entering the water phase, decomposition may occur, followed by Fe 3+ The use effect of the iron-carrying sodium extractant is affected by hydrolysis. In the prior art, the pH value is regulated to be 1-3 by adding acid into raw material liquid to reduce Fe 3+ And (5) hydrolyzing. In the application, the raw material liquid is directly adopted for extraction, the pH value is not regulated by adding acid, the raw material liquid is synchronously added into the sodium iron carrier extractant in a dropwise manner, when the raw material liquid enters the sodium iron carrier extractant, the raw material liquid is rapidly wrapped by the sodium iron carrier extractant, lithium in the raw material liquid rapidly enters the sodium iron carrier extractant, and NaFeCl is reduced 4 Enters into the water phase to decompose, and also effectively reduces Fe 3+ And (5) hydrolyzing. The method of the application directly adopts the raw material liquid for extraction, does not add acid to adjust the pH value, is matched with the raw material liquid to be dripped into the sodium iron carrier extractant, the first extraction water phase is dripped into the sodium iron carrier extractant, the second extraction water phase is dripped into the sodium iron carrier extractant, and the Fe is effectively reduced 3+ On the basis of the influence of hydrolysis on the extraction effect of the iron-carrying sodium extractant, H in the raw material liquid is reduced + The content is excessive so as to increase the use amount of the sodium iron-carrying extractant.
Optionally, the mass concentration of the hydrochloric acid solution is 1-5%; the mass concentration of the sodium hydroxide solution is 10-20%.
By adopting the technical scheme, the mass concentration of the hydrochloric acid solution is optimized, so that the pH value of the acidic molten iron-carrying phase is kept low, and Fe is reduced 3+ Is also reduced due to Fe 3+ And the effect on the iron loading in the sodium iron-loading extractant.In addition, the mass concentration of the sodium hydroxide solution is optimized to ensure that the HFeCl 4 Complete conversion to NaFeCl 4 Reduces the factor HFeCl in the factor-carried sodium extraction agent 4 The use effect of the iron-carrying sodium extractant is affected due to excessive content.
In one or more embodiments, the mass concentration of the hydrochloric acid solution is 3.5%, which may also be set to 1%, 2%, 3%, 4%, 5%, etc., as desired.
Optionally, the amide regulator is one or more of N, N-bis (1-methylheptyl) acetamide, triisooctylamine and secondary primary carbon amine;
the diluent is one or more of sulfonated kerosene, isooctyl alcohol and n-hexane.
Through adopting above-mentioned technical scheme, optimize the selection of amide regulator, diluent, not only be convenient for the selection of amide regulator, diluent, the extraction of lithium ion is convenient for moreover, promotes the lithium ion extraction rate, simultaneously, the layering of being convenient for aqueous phase and oil phase is convenient for, the separation of aqueous phase and oil phase.
Optionally, the iron-carrying sodium extractant is prepared by the following method:
t1, adding diethyl nitrile phosphate, tetrabenzyl phosphate and an amide regulator into a diluent, and mixing to obtain a blank organic phase;
adding sodium chloride and ferric trichloride into a hydrochloric acid solution, and mixing to obtain an acidic iron-carrying water phase;
t3, adding a blank organic phase into the acidic iron-carrying liquid phase under continuous stirring, standing for layering, and separating and discarding the water phase to obtain an iron-carrying organic phase;
adding sodium hydroxide solution into the iron-carrying organic phase under continuous stirring, standing for layering, and separating and discarding the water phase to obtain the iron-carrying sodium organic phase;
and T5, washing the iron-carrying sodium organic phase by adopting a sodium chloride solution to obtain the iron-carrying sodium extractant.
By adopting the technical scheme, the blank organic phase and the acidic iron-carrying water phase are prepared in advance, and then the blank organic phase and the acidic iron-carrying water phase are mixed, so that iron is transferred from the acidic iron-carrying water phase to the blank organic phase, and the carrier is obtainedAn iron organic phase, wherein iron in the iron-carrying organic phase is in HFeCl 4 Is present in the form of (c). Then adding sodium hydroxide solution into the iron-carrying organic phase, and carrying out neutralization reaction to obtain the iron-carrying sodium organic phase, wherein the iron in the iron-carrying sodium organic phase is NaFeCl 4 Is present in the form of (c). The preparation method of the iron-carrying sodium extractant provided by the application has the advantages of simplicity, convenience and stability in preparation by carrying iron and sodium in the extractant in steps. Meanwhile, as the raw materials of the acidic iron-carrying water phase contain hydrochloric acid, the Fe is reduced 3+ So that the iron is smoothly transferred into the iron-carrying organic phase, and the Fe is reduced 3+ The hydrolysis affects the iron carrying amount in the iron-carrying sodium extractant, thereby reducing Fe 3+ The use effect of the iron-carrying sodium extractant is affected by hydrolysis.
In the step T4, the sodium chloride solution is saturated sodium chloride solution, the washing times of the iron-carrying sodium organic phase are 1-3 times, and the volume ratio of the sodium chloride solution to the iron-carrying sodium organic phase used in each washing is (1-3): 1. Preferably, the washing times of the organic phase of the sodium iron carrier are 2 times, and the volume ratio of the sodium chloride solution to the organic phase of the sodium iron carrier used for each washing is 2:1.
Preferably, the washing of the iron-sodium loaded organic phase is carried out by the following method: adding sodium chloride solution into the iron-carrying sodium organic phase under continuous stirring, standing for layering, separating and discarding the water phase to obtain a washing organic phase. Still more preferably, the stirring treatment time is 5-15min. More preferably, the stirring treatment time is 10 minutes.
Optionally, in step S2, the volume ratio of the iron-carrying sodium extractant used in the primary extraction to the iron-carrying sodium extractant used in the secondary extraction to the iron-carrying sodium extractant used in the tertiary extraction to the raw material liquid is (1.5-2.5): (1.5-2.5): (1.5-2.5): 1.
By adopting the technical scheme, the volume ratio of the iron-carrying sodium extractant used for primary extraction, the iron-carrying sodium extractant used for secondary extraction and the iron-carrying sodium extractant used for tertiary extraction to the raw material liquid is optimized, so that the extraction of lithium in the raw material liquid by the iron-carrying sodium extractant is facilitated.
Optionally, in step S2, the dripping time of the raw material liquid is 10-20min; the dripping time of the primary extraction water phase is 10-20min; the dripping time of the secondary extraction water phase is 10-20min.
By adopting the technical scheme, when the dripping time of the raw material liquid, the primary extraction water phase and the secondary extraction water phase is 10-20min, the iron-sodium-loaded extractant has good lithium extraction rate on the basis of keeping good extraction efficiency.
In one or more embodiments, in step S2, the dropping time of the raw material liquid is 15min; the dripping time of the primary extraction water phase is 15min; the dripping time of the secondary extraction water phase is 15min. The dripping time of the raw material liquid can be set to 10min, 20min and the like according to the requirement. The dripping time of the primary extraction water phase can be set to 10min, 20min and the like according to the requirement. The dripping time of the secondary extraction water phase can be set to 10min, 20min and the like according to the requirement.
Further, in step S2, the primary extraction stirring treatment time is 5-15min, preferably 10min. The second-stage extraction stirring treatment time is 5-15min, preferably 10min. The three-stage extraction stirring treatment time is 5-15min, preferably 10min.
Optionally, the mass concentration of the sulfuric acid solution is 10-40%.
By adopting the technical scheme, the mass concentration of the sulfuric acid solution is optimized, so that LiFeCl in the organic mixed solution 4 Complete conversion to HFeCl 4 、Li 2 SO 4 ，HFeCl 4 Into the stripping organic phase, li 2 SO 4 And the solution enters a back extraction water phase to obtain a lithium-rich solution, and the lithium back extraction rate of the sulfuric acid solution to the organic mixed solution is improved.
Optionally, in step S5, the volume ratio of the sulfuric acid solution used for the primary stripping to the sulfuric acid solution used for the secondary stripping to the sulfuric acid solution used for the tertiary stripping to the organic mixed solution is (5-15): 1.
By adopting the technical scheme, the volume ratio of the sulfuric acid solution used for primary back extraction, the sulfuric acid solution used for secondary back extraction, the sulfuric acid solution used for tertiary back extraction and the organic mixed solution is optimized, so that the back extraction of lithium in the organic mixed solution is facilitated.
Further, in step S5, the primary stripping stirring treatment time is 5-15min, preferably, the primary stripping stirring treatment time is 10min. The secondary back extraction stirring treatment time is 5-15min, preferably 10min. The three-stage back extraction stirring treatment time is 5-15min, preferably 10min.
Optionally, in step S3, the sodium chloride solution is saturated sodium chloride solution, the washing times of the extracted organic solution are 3-8 times, and the volume ratio of the sodium chloride solution used in each washing to the extracted organic solvent is (5-15): 1.
By adopting the technical scheme, the saturated sodium chloride solution is adopted to wash the extracted organic solution, so that the K in the extracted organic solution can be effectively reduced + 、Mg 2+ In addition, as the organic solution is saturated solution, liFeCl in the extracted organic solution is reduced 4 Thereby reducing lithium loss in the washing process and improving lithium recovery rate.
In one or more embodiments, in step S3, the number of washes of the extracted organic solution is 5, and the volume ratio of sodium chloride solution to extracted organic solvent used for each wash is 10:1.
Further, the following method is adopted for washing the extracted organic solution: adding saturated sodium chloride solution into the extracted organic solution under continuous stirring, standing for layering, separating and discarding the water phase to obtain a washed organic phase. Preferably, the stirring treatment time is 5-15min. More preferably, the stirring treatment time is 10 minutes.
Further, in step S5, the cutoff molecular weight of the nanofiltration membrane is 100-5000. Preferably, the nanofiltration membrane has a cut-off molecular weight of 100-1000. The operating pressure is 1-5MPa. Preferably, the operating pressure is 2-3MPa.
Optionally, the raw material liquid mainly comprises the following components in mass concentration: li (Li) + 0.5-3.5g/L、Na + 70-100g/L、K + 10-30g/L、Mg 2+ 5-20g/L。
By taking outBy adopting the technical scheme, the method for preparing the lithium ion battery material solution + 、Na + 、K + 、Mg 2+ The content is optimized, so that the evaporation and concentration of salt lake brine are facilitated, the stability of a method for preparing lithium hydroxide by extracting lithium from raw brine is enhanced, and the control is facilitated.
In one or more embodiments, the feed solution consists essentially of the following components in mass concentration: li (Li) + 2.34g/L、Na + 85.67g/L、K + 22.35g/L、Mg 2+ 11.42g/L. It is also possible to mix Li in the raw material liquid as needed + The content is set to 0.5g/L, 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, etc. Na in the raw material liquid can also be added according to the need + The content is set to 70g/L, 80g/L, 90g/L, 100g/L, etc. K in the raw material liquid can also be added according to the need + The content is set to 10g/L, 20g/L, 30g/L, etc. The Mg in the raw material liquid can be mixed according to the need 2+ The content is set to 5g/L, 10g/L, 15g/L, 20g/L, etc.
In summary, the application has at least the following advantages:
1. the method for preparing lithium hydroxide by extracting lithium by using raw halogen adopts an iron-carrying sodium extractant to extract, wherein the iron-carrying sodium extractant contains NaFeCl 4 Diethyl nitrile phosphate, tetrabenzyl phosphate. The diethyl nitrilophosphate contains P (≡ N, P) and two P-O, the tetrabenzyl phosphate contains four benzene rings, five P-O and two P=O, and the synergistic effect between the two is utilized, so that the separation of the water phase and the oil phase is facilitated, the lithium extraction rate is improved, and FeCl is utilized 4 - The extraction sequence of the cations is H + ＞Li + ＞Na + ＞Mg 2+ ＞K + Li in the raw material liquid + Transferring to the extracted organic solution, not only ensures that the lithium extraction rate is more than 99 percent, but also reduces Mg 2+ 、K + Transferring to the extraction organic solution, reducing the influence of impurities and meeting the requirement of higher requirements.
2. In the preparation method of the iron-carrying sodium extractant, firstly, iron is transferred from an acidic iron-carrying aqueous phase to a blank organic phase, and then sodium hydroxide solution is added to make the iron in the iron-carrying sodium organic phase take the form of NaFeCl 4 The form of the formula (I) is that the extraction agent is loaded with iron and sodium in steps, and the preparation is simple and stable.
Detailed Description
In order that the application may be more readily understood, the application will be further described in detail with reference to the following examples, which are given by way of illustration only and are not limiting in scope of application. The starting materials or components used in the present application may be prepared by commercial or conventional methods unless specifically indicated.
Preparation example
TABLE 1 raw material content of blank organic phase (unit: kg)
TABLE 2 raw material content of acidic iron-carrying aqueous phase (unit: kg)
Preparation example 1
The iron-carrying sodium extractant is prepared from a blank organic phase, an acidic iron-carrying water phase and a sodium hydroxide solution, wherein the volume ratio of the blank organic phase to the acidic iron-carrying water phase to the sodium hydroxide solution is 1:1:1, the raw materials and the proportions of the blank organic phase are shown in table 1, and the raw materials and the proportions of the acidic iron-carrying water phase are shown in table 2. The mass concentration of the sodium hydroxide solution is 15%.
Wherein the amide regulator is N, N-bis (1-methylheptyl) acetamide; the diluent is sulfonated kerosene and is selected from 260# kerosene; the mass concentration of the hydrochloric acid solution was 3.5%.
A preparation method of an iron-carrying sodium extractant comprises the following steps:
and T1, adding diethyl nitrile phosphate, tetrabenzyl phosphate and an amide regulator into the diluent at the rotating speed of 200r/min, and stirring for 10min to obtain a blank organic phase.
And T2, adding sodium chloride and ferric trichloride into the hydrochloric acid solution at the rotating speed of 200r/min, and stirring for 10min to obtain an acidic iron-carrying water phase.
And T3, adding a blank organic phase into the acidic iron-carrying liquid phase at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain the iron-carrying organic phase.
And T4, adding a sodium hydroxide solution into the iron-carrying organic phase at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain the iron-carrying sodium organic phase.
And T5, washing the iron-carrying sodium organic phase for 2 times by adopting a saturated sodium chloride solution, wherein the volume ratio of the saturated sodium chloride solution to the iron-carrying sodium organic phase used for each washing is 2:1, and thus the iron-carrying sodium extractant is obtained.
Specifically, the following method is adopted for 2 times of washing: at the rotating speed of 100r/min, adding saturated sodium chloride solution into the iron-carrying organic phase, stirring for 10min, standing for layering, separating and discarding the water phase to obtain a primary washing organic phase. Then adding saturated sodium chloride solution into the primary washing organic phase at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain a secondary washing organic phase, wherein the secondary washing organic phase is the iron-carrying sodium extractant.
Preparation example 2
The difference between the extractant and the preparation example 1 is that the volume ratio of the blank organic phase to the acidic iron-carrying aqueous phase to the sodium hydroxide solution is 1:0.5:1.5, the raw materials and the proportion of the blank organic phase are shown in table 1, the raw materials and the proportion of the acidic iron-carrying aqueous phase are shown in table 2, and the mass concentration of the sodium hydroxide solution is 20%.
Preparation example 3
The difference between the extractant and the preparation example 1 is that the volume ratio of the blank organic phase to the acidic iron-carrying aqueous phase to the sodium hydroxide solution is 1:1.5:0.5, the raw materials and the proportion of the blank organic phase are shown in table 1, the raw materials and the proportion of the acidic iron-carrying aqueous phase are shown in table 2, and the mass concentration of the sodium hydroxide solution is 10%.
Examples
Example 1
The method for preparing lithium hydroxide by extracting lithium by using raw halogen comprises the following steps:
s1, filtering and impurity removing the salt lake brine, and sun-drying, evaporating and concentrating to obtain raw material liquid.
For Li in raw material liquid + 、Na + 、K + 、Mg 2+ The content is detected, and Li in the raw material liquid + 2.34g/L、Na + 85.67g/L、K + 22.35g/L、Mg 2+ 11.42g/L。
S2, taking 1000mL of raw material liquid, dropwise adding the raw material liquid into the iron-carrying sodium extractant at the rotating speed of 100r/min, wherein the dropwise adding time of the raw material liquid is 15min, carrying out primary extraction stirring treatment for 10min after the dropwise adding is finished, standing for layering, and separating a water phase and an oil phase to obtain a primary extraction water phase and a primary extraction organic phase. And then dripping the primary extraction water phase into the iron-carrying sodium extractant at the rotating speed of 100r/min for 15min, stirring for 10min after dripping, standing for layering, and separating the water phase and the oil phase to obtain a secondary extraction water phase and a secondary extraction organic phase. And then dripping the secondary extraction water phase into the iron-carrying sodium extractant at the rotating speed of 100r/min for 15min, stirring for 10min after dripping, standing for layering, and separating the water phase and the oil phase to obtain a three-extraction water phase and a three-extraction organic phase. And then adding the second extraction organic phase and the third extraction organic phase into the first extraction organic phase at the rotating speed of 100r/min, and stirring for 10min to obtain an extraction organic solution.
Wherein, the volume ratio of the iron-carrying sodium extractant used in the primary extraction to the iron-carrying sodium extractant used in the secondary extraction to the iron-carrying sodium extractant used in the tertiary extraction to the raw material liquid is 2:2:2:1; the iron-carrying sodium extractant is prepared by adopting a preparation example 1.
And S3, washing the extracted organic solution for 5 times by adopting a saturated sodium chloride solution, wherein the volume ratio of the saturated sodium chloride solution to the extracted organic solution used for each washing is 10:1, and thus obtaining an organic mixed solution.
Specifically, the following method is adopted for 5 times of washing: at the rotating speed of 100r/min, adding saturated sodium chloride solution into the extracted organic solution, stirring for 10min, standing for layering, separating and discarding the water phase to obtain a primary washing organic phase. Then adding saturated sodium chloride solution into the primary washing organic phase at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain a secondary washing organic phase. And then adding saturated sodium chloride solution into the secondary washing organic phase at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain a tertiary washing organic phase. And then adding saturated sodium chloride solution into the organic phase of the three times of washing at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain the organic phase of the four times of washing. And then adding saturated sodium chloride solution into the four washing organic phases at the rotating speed of 100r/min, stirring for 10min, standing for layering, separating and discarding the water phase to obtain the five washing organic phases. The organic phase is washed for five times to obtain the organic mixed solution.
S4, adding sulfuric acid solution into the organic mixed solution at the rotating speed of 100r/min, carrying out primary stripping and stirring treatment for 10min, standing for layering, and separating the water phase and the oil phase to obtain a primary stripping water phase and a primary stripping organic phase. And then adding sulfuric acid solution into the first-stage back extraction organic phase at the rotating speed of 100r/min, carrying out second-stage back extraction stirring treatment for 10min, standing for layering, and separating the water phase and the oil phase to obtain a second-stage back extraction water phase and a second-stage back extraction organic phase. And adding sulfuric acid solution into the second-stage back extraction organic phase at the rotating speed of 100r/min, carrying out three-stage back extraction stirring treatment for 10min, standing for layering, and separating the water phase and the oil phase to obtain a three-stage back extraction water phase and a three-stage back extraction organic phase. And then adding a second-stage back extraction water phase and a third-stage back extraction water phase into the first-stage back extraction water phase at the rotating speed of 100r/min, and stirring for 10min to obtain a lithium-rich solution.
Wherein, the volume ratio of the sulfuric acid solution used in the primary stripping to the sulfuric acid solution used in the secondary stripping to the sulfuric acid solution used in the tertiary stripping to the organic mixed solution is 10:10:10:1; the mass concentration of the sulfuric acid solution was 24%.
S5, adding sodium hydroxide into the lithium-rich solution at the rotating speed of 100r/min, and stirring for 20min to convert lithium sulfate and sulfuric acid into lithium hydroxide, sodium sulfate and water to obtain a pretreatment solution. And purifying and concentrating the pretreatment solution by adopting a nanofiltration membrane to obtain trapped fluid and permeate. The cut-off molecular weight of the nanofiltration membrane is 100-1000, and the operating pressure is 2.5MPa. At this time, the molecular weight of sodium sulfate was 142, which could not pass through the nanofiltration membrane, and was accumulated in the trapped fluid, i.e., the trapped fluid was sodium sulfate solution. The molecular weight of lithium hydroxide is 24, and the lithium hydroxide can pass through the nanofiltration membrane and is gathered in the permeate, namely the permeate is lithium hydroxide solution.
S6, evaporating and concentrating the lithium hydroxide solution, cooling and crystallizing, filtering and separating, and drying to obtain lithium hydroxide.
Example 2
A method for preparing lithium hydroxide by extracting lithium by using raw halogen is different from the method in the embodiment 1 in that in the step S2, an iron-carrying sodium extractant is prepared by adopting the preparation example 2. In step S4, the mass concentration of the sulfuric acid solution is 40%.
Example 3
A method for preparing lithium hydroxide by extracting lithium by using raw halogen is different from the method in the embodiment 1 in that in the step S2, an iron-carrying sodium extractant is prepared by adopting the preparation example 3. In step S4, the mass concentration of the sulfuric acid solution is 10%.
Example 4
The difference between the method for preparing lithium hydroxide by extracting lithium with raw halogen and the method for preparing lithium hydroxide in the embodiment 1 is that in the step S2, the volume ratio of the iron-carrying sodium extractant used in the primary extraction to the iron-carrying sodium extractant used in the secondary extraction to the iron-carrying sodium extractant used in the tertiary extraction to the raw material liquid is 2.5:2.5:1.5:1. In the step S4, the volume ratio of the sulfuric acid solution used for the primary stripping to the sulfuric acid solution used for the secondary stripping to the sulfuric acid solution used for the tertiary stripping to the organic mixed solution is 15:15:5:1.
Example 5
The difference between the method for preparing lithium hydroxide by extracting lithium with raw halogen and the method for preparing lithium hydroxide in the embodiment 1 is that in the step S2, the volume ratio of the iron-carrying sodium extractant used in the primary extraction to the iron-carrying sodium extractant used in the secondary extraction to the iron-carrying sodium extractant used in the tertiary extraction to the raw material liquid is 1.5:1.5:2.5:1. In the step S4, the volume ratio of the sulfuric acid solution used for the primary stripping to the sulfuric acid solution used for the secondary stripping to the sulfuric acid solution used for the tertiary stripping to the organic mixed solution is 5:5:15:1.
Comparative example
Comparative example 1
A method for preparing lithium hydroxide by extracting lithium by using raw halogen is different from example 1 in that in the raw material of the sodium iron-carrying extractant of the step S2, the same amount of tributyl phosphate is used for replacing diethyl nitrile phosphate and tetrabenzyl phosphate.
Comparative example 2
A method for preparing lithium hydroxide by extracting lithium by using raw halogen is different from example 1 in that in the raw material of the sodium iron-carrying extractant of the step S2, the equal amount of diethyl nitrile phosphate is used for replacing tetrabenzyl phosphate.
Comparative example 3
A method for preparing lithium hydroxide by extracting lithium by using raw halogen is different from example 1 in that in the raw material of the sodium iron-carrying extractant of the step S2, the diethyl nitrile phosphate is replaced by an equivalent amount of tetrabenzyl phosphate.
Comparative example 4
A method for preparing lithium hydroxide by extracting lithium with raw halogen differs from example 1 in that in step S3, the sodium chloride solution is replaced with an equal amount of water.
Performance detection
(1) The extracted organic solutions obtained after the treatment in step S2 of examples 1 to 5 and comparative examples 1 to 3 were taken as samples, and the lithium content, potassium content and magnesium content in the samples were detected, and the lithium extraction rate, potassium extraction rate and magnesium extraction rate were calculated, and the detection results are shown in table 3.
(2) The organic mixed solutions obtained after the treatment in step S3 of examples 1 to 5 and comparative examples 1 to 4 were taken as samples, respectively, and the lithium content in the samples was detected, and the lithium loss rate was calculated, and the detection results are shown in table 3.
(3) The lithium-rich solutions obtained after the treatment in step S4 of examples 1 to 5 and comparative examples 1 to 4 were taken as samples, respectively, and the lithium content in the samples was detected, and the lithium stripping rate was calculated, and the detection results are shown in table 3.
TABLE 3 detection results
As can be seen from Table 3, the method for preparing lithium hydroxide by extracting lithium by using raw halogen of the application adopts three-stage extraction of the iron-carrying sodium extractant, and combines the interaction of the iron-carrying sodium extractant raw materials, the lithium extraction rate is 99.11-99.73%, the potassium extraction rate is 0.13-0.15%, and the magnesium extraction rate is 0.11-0.13%, thus not only remarkably increasing the lithium extraction rate, but also maintaining lower potassium extraction rate and magnesium extraction rate and reducing the potassium and magnesium content in the extracted organic solution. And the lithium loss rate is 1.31-1.33% when the extraction organic solvent is washed by the sodium chloride solution, so that the lithium loss rate is low. Meanwhile, the three-stage back extraction of sulfuric acid solution is matched, the lithium back extraction rate is 93.32-97.85%, the good lithium back extraction rate is maintained, the lithium recovery rate is further increased, and the market demand is met.
Tributyl phosphate is added into the raw material of the iron-carrying sodium extractant of the comparative example 1; adding diethyl nitrilophosphate into the iron-carrying sodium extractant raw material of comparative example 2; the iron-carrying sodium extractant raw material of comparative example 3 is added with tetrabenzyl phosphate; the raw materials of the iron-sodium-carrying extractant of example 1 were added diethyl nitrilophosphate and tetrabenzyl phosphate. Comparing example 1 with comparative example 1, it can be seen that the addition of diethyl nitrile phosphate and tetrabenzyl phosphate simultaneously to the sodium iron-carrying extractant raw material significantly increases the lithium extraction rate by utilizing the synergy between the two.
In step S3 of comparative example 4, the extracted organic solution was washed with water; the extracted organic solution was washed with sodium chloride solution in step S3 of example 1. Comparing example 1 with comparative example 4, it can be seen that the extraction organic solution is washed with sodium chloride solution, significantly reducing the lithium loss rate.
It should be noted that the above-described embodiments are only for explaining the present application and do not constitute any limitation of the present application. The application has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the application as defined in the appended claims, and the application may be modified without departing from the scope and spirit of the application. Although the application is described herein with reference to particular means, materials and embodiments, the application is not intended to be limited to the particulars disclosed herein, as the application extends to all other means and applications which perform the same function.
Claims (10)
1. A method for preparing lithium hydroxide by extracting lithium from raw halogen is characterized by comprising the following steps: the method comprises the following steps:
s1, filtering and impurity removing is carried out on salt lake brine, and evaporation concentration is carried out to obtain raw material liquid;
s2, dropwise adding a raw material liquid into the iron-carrying sodium extractant under continuous stirring to perform primary extraction to obtain a primary extraction water phase and a primary extraction organic phase; then dripping the primary extraction water phase into the iron-carrying sodium extractant under continuous stirring to perform secondary extraction to obtain a secondary extraction water phase and a secondary extraction organic phase; then, dropwise adding the second-stage extraction water phase into the iron-carrying sodium extractant under continuous stirring to perform third-stage extraction to obtain a third-stage extraction water phase and a third-stage extraction organic phase; then mixing the first-stage extraction organic phase, the second-stage extraction organic phase and the third-stage extraction organic phase to obtain an extraction organic solution;
s3, washing the extracted organic solution by adopting a sodium chloride solution to obtain an organic mixed solution;
s4, adding sulfuric acid solution into the organic mixed solution under continuous stirring to perform primary stripping, so as to obtain a primary stripping water phase and a primary stripping organic phase; then adding sulfuric acid solution into the first-stage back extraction organic phase under continuous stirring to carry out second-stage back extraction, thereby obtaining a second-stage back extraction aqueous phase and a second-stage back extraction organic phase; adding sulfuric acid solution into the second-stage back extraction organic phase under continuous stirring to perform third-stage back extraction to obtain a third-stage back extraction aqueous phase and a third-stage back extraction organic phase; mixing the first-stage back extraction water phase, the second-stage back extraction water phase and the third-stage back extraction water phase to obtain a lithium-rich solution;
s5, adding sodium hydroxide into the lithium-rich solution for mixing to obtain a pretreatment solution, and then purifying and concentrating the pretreatment solution by adopting a nanofiltration membrane to obtain trapped fluid and a permeate, wherein the trapped fluid is a sodium sulfate solution, and the permeate is a lithium hydroxide solution;
s6, evaporating and concentrating the lithium hydroxide solution, cooling and crystallizing, filtering and separating, and drying to obtain lithium hydroxide;
the iron-carrying sodium extractant is prepared from a blank organic phase, an acidic iron-carrying water phase and a sodium hydroxide solution, wherein the volume ratio of the blank organic phase to the acidic iron-carrying water phase to the sodium hydroxide solution is 1 (0.5-1.5);
the blank organic phase is mainly prepared from the following raw materials in parts by weight: 30-40 parts of diethyl nitrile phosphate, 10-20 parts of tetrabenzyl phosphate, 5-15 parts of amide regulator and 35-45 parts of diluent;
the acidic iron-carrying water phase is mainly prepared from the following raw materials in parts by weight: 100 parts of hydrochloric acid solution, 20-30 parts of sodium chloride and 10-30 parts of ferric trichloride.
2. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: the mass concentration of the hydrochloric acid solution is 1-5%; the mass concentration of the sodium hydroxide solution is 10-20%.
3. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: the amide regulator is one or more of N, N-bis (1-methylheptyl) acetamide, triisooctyl amine and secondary primary amine;
the diluent is one or more of sulfonated kerosene, isooctyl alcohol and n-hexane.
4. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: the iron-carrying sodium extractant is prepared by the following method:
t1, adding diethyl nitrile phosphate, tetrabenzyl phosphate and an amide regulator into a diluent, and mixing to obtain a blank organic phase;
adding sodium chloride and ferric trichloride into a hydrochloric acid solution, and mixing to obtain an acidic iron-carrying water phase;
t3, adding a blank organic phase into the acidic iron-carrying liquid phase under continuous stirring, standing for layering, and separating and discarding the water phase to obtain an iron-carrying organic phase;
adding sodium hydroxide solution into the iron-carrying organic phase under continuous stirring, standing for layering, and separating and discarding the water phase to obtain the iron-carrying sodium organic phase;
and T5, washing the iron-carrying sodium organic phase by adopting a sodium chloride solution to obtain the iron-carrying sodium extractant.
5. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: in the step S2, the volume ratio of the iron-carrying sodium extractant used in the primary extraction to the iron-carrying sodium extractant used in the secondary extraction to the iron-carrying sodium extractant used in the tertiary extraction to the raw material liquid is (1.5-2.5): (1.5-2.5): (1.5-2.5): 1.
6. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: in the step S2, the dripping time of the raw material liquid is 10-20min; the dripping time of the primary extraction water phase is 10-20min; the dripping time of the secondary extraction water phase is 10-20min.
7. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: the mass concentration of the sulfuric acid solution is 10-40%.
8. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: in the step S5, the volume ratio of the sulfuric acid solution used for the primary stripping to the sulfuric acid solution used for the secondary stripping to the sulfuric acid solution used for the tertiary stripping to the organic mixed solution is (5-15): 1.
9. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: in the step S3, the sodium chloride solution is saturated sodium chloride solution, the washing times of the extracted organic solution are 3-8 times, and the volume ratio of the sodium chloride solution used for each washing to the extracted organic solvent is (5-15): 1.
10. The method for preparing lithium hydroxide by extracting lithium by raw halogen according to claim 1, wherein the method comprises the following steps: the raw material liquid mainly comprises the following components in mass concentration: li (Li) + 0.5-3.5g/L、Na + 70-100g/L、K + 10-30g/L、Mg 2+ 5-20g/L。
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