CN113718116A - Method for extracting nickel, cobalt and manganese from acidic lithium-rich solution - Google Patents
Method for extracting nickel, cobalt and manganese from acidic lithium-rich solution Download PDFInfo
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- CN113718116A CN113718116A CN202111005369.8A CN202111005369A CN113718116A CN 113718116 A CN113718116 A CN 113718116A CN 202111005369 A CN202111005369 A CN 202111005369A CN 113718116 A CN113718116 A CN 113718116A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 75
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 73
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 73
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 31
- 239000010941 cobalt Substances 0.000 title claims abstract description 28
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 27
- 239000011572 manganese Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 27
- 230000002378 acidificating effect Effects 0.000 title claims abstract description 26
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000000605 extraction Methods 0.000 claims abstract description 108
- 239000007788 liquid Substances 0.000 claims abstract description 64
- 230000001105 regulatory effect Effects 0.000 claims abstract description 23
- 239000012074 organic phase Substances 0.000 claims abstract description 20
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 11
- 239000012071 phase Substances 0.000 claims description 54
- 238000003756 stirring Methods 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 28
- 238000002156 mixing Methods 0.000 claims description 17
- 239000003085 diluting agent Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 5
- 230000007246 mechanism Effects 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims description 2
- 229920003169 water-soluble polymer Polymers 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 10
- 239000000843 powder Substances 0.000 abstract description 7
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 59
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 150000003839 salts Chemical class 0.000 description 7
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 6
- 239000006004 Quartz sand Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 229920001903 high density polyethylene Polymers 0.000 description 4
- 239000004700 high-density polyethylene Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-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
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229940081066 picolinic acid Drugs 0.000 description 2
- -1 picolinic acid ester Chemical class 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B47/00—Obtaining manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution, and relates to the technical field of waste liquid recycling. Aiming at the fact that a lithium-rich solution generated in the lithium selective extraction process of lithium battery powder contains more nickel, cobalt and manganese ions, the P204 and HBL110 are used for extracting the nickel, cobalt and manganese ions in the lithium-rich solution step by step, a loaded organic phase is used for carrying out back extraction through inorganic acid, and the obtained nickel, cobalt and manganese solution is used as a purification feed liquid; multi-stage countercurrent extraction system for lithium-rich solutionThe lithium-rich solution and the extractant are fully mixed and contacted in a countercurrent mode, and the flow is accurately regulated by the regulating valve and the booster pump, so that the Ni content is greatly improved2+、Co2+、Mn2+The extraction rate of (2).
Description
Technical Field
The invention relates to the technical field of waste liquid recycling, in particular to a method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution.
Background
Under the background of the era of advocating energy conservation and environmental protection, the new energy automobile industry in China develops rapidly, wherein the ternary power battery occupies an important market, and the problem of resource shortage is increasingly serious along with the continuous improvement of the power battery production, so that the comprehensive recycling of the power battery has important significance.
CN 106654437a discloses a method for recovering lithium from waste lithium ion batteries, in which dried positive electrode powder of waste batteries is dissolved with sulfuric acid and hydrogen peroxide, filtered to remove organic solvent, and added with sodium carbonate solid for precipitation and recrystallization to obtain lithium carbonate.
Compared with the traditional chemical precipitation method, the solvent extraction method has the advantages of high selectivity, high reaction rate, good separation effect, simple process and the like. CN 105789724A discloses a method for treating waste lithium ion batteries, which comprises the steps of dissolving waste lithium ion battery powder with alkali liquor to recover aluminum, dissolving obtained precipitates with acid liquor and hydrogen peroxide to form a mixed solution, adjusting pH to remove iron and aluminum, then using countercurrent multistage synergistic extraction to obtain lithium salt raffinate and mixed salt of nickel, cobalt and nickel, cobalt or nickel, cobalt and manganese, obtaining cobalt salt through acid back extraction, and preparing a novel anode material from the mixed salt through chemical synthesis. In conclusion, the method for extracting nickel, cobalt and manganese from the lithium-rich solution in the prior art has long process, poor extraction selectivity and low extraction rate, and needs further research and improvement.
Disclosure of Invention
The invention aims to provide a method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution, which is used for solving the technical problems of long flow, poor extraction selectivity and low extraction rate of the method for extracting nickel, cobalt and manganese from the lithium-rich solution in the prior art.
The purpose of the invention can be realized by the following technical scheme:
a method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution comprises the following steps:
s1, performing single-stage or multi-stage countercurrent extraction by using an organic phase-to-acid lithium-rich solution containing di (2-ethylhexyl) phosphate, and separating to obtain a first raffinate and a first extract phase;
s2, carrying out single-stage or multi-stage countercurrent extraction on the organic phase containing the HBL110 relative to the first raffinate, and separating to obtain a second raffinate and a second extract phase, wherein the second raffinate is a high-purity lithium-rich solution;
s3, carrying out single-stage or multi-stage countercurrent back extraction on the second extract phase by inorganic acid to obtain Ni-containing2+、Co2+、Mn2+The purified liquid of (1).
In a further preferred embodiment of the present invention, the pH value of the acidic lithium-rich solution is 1 to 5, and Ni in the acidic lithium-rich solution2+、Co2+、Mn2+The solubility of the water-soluble polymer is 2.6-3.2 g/L, 0.3-0.6 g/L, 0.1-0.3 g/L.
In a further preferred embodiment of the invention, the HBL110 is a compound of naphthalenesulfonic acid and picolinic acid ester, and the organic phase containing bis (2-ethylhexyl) phosphate is formed by mixing bis (2-ethylhexyl) phosphate and a diluent in a volume ratio of 1: 3-5; the organic phase containing the HBL110 is formed by mixing the HBL110 and a diluent according to the volume ratio of 1: 3-5.
As a further preferred embodiment of the present invention, the diluent is selected from one or more of sulfonated kerosene, No. 260 solvent oil and aviation kerosene.
In a further preferable embodiment of the present invention, the inorganic acid is selected from one or more of sulfuric acid, hydrochloric acid, and nitric acid, and the concentration of the inorganic acid is 1 to 4 mol/L.
As a further preferred aspect of the present invention, the multi-stage countercurrent extraction in steps S1 and S2 is performed by a multi-stage countercurrent extraction system for lithium-rich solution.
As a further preferable scheme of the invention, the multi-stage countercurrent extraction system for the lithium-rich solution comprises a plurality of extraction tanks and a liquid separation tank which are arranged from one side to the other side, wherein a stirring and mixing mechanism is arranged in each extraction tank, a liquid discharge valve is arranged at the bottom of each extraction tank, and a stirring layered structure is arranged in each liquid separation tank; the bottom of the first extraction tank is connected with a solution tank through a liquid inlet pipe, and a first regulating valve and a first booster pump are sequentially arranged on the path of the liquid inlet pipe; a light phase outlet is arranged at the upper part of the side wall of the extraction tank, a heavy phase outlet is arranged at the bottom of the extraction tank, a light phase inlet is arranged at the lower part of the side wall of the liquid separation tank, and a heavy phase inlet is arranged at the upper part of the side wall; the light phase outlet on the extraction tank is communicated with the light phase inlet on the adjacent liquid separation tank through a first connecting pipe, and the heavy phase outlet on the extraction tank is communicated with the heavy phase inlet on the liquid separation tank arranged at intervals through a second connecting pipe.
As a further preferable scheme of the invention, the side wall of the first liquid separation tank is connected with a material storage tank through a discharge pipe at the upper part; the bottom of the last liquid separating tank is connected with an extracting agent tank through a feeding pipe; a second regulating valve and a second booster pump are arranged on the path of the second connecting pipe; a third regulating valve is arranged on the path of the feeding pipe; the bottom of the liquid separating tank is communicated with the bottom of the adjacent extraction tank through a mixed liquid pipe, and a fourth regulating valve and a third booster pump are arranged on the mixed liquid pipe.
The invention has the following beneficial effects:
1. aiming at the fact that the lithium-rich solution generated in the lithium selective extraction process of the lithium battery powder contains more nickel, cobalt and manganese ions, the P204 and the HBL110 are used for extracting the nickel, cobalt and manganese ions in the lithium-rich solution step by step, the loaded organic phase is subjected to back extraction through inorganic acid, and the obtained nickel, cobalt and manganese solution is used as a purification feed liquid.
2. A multistage countercurrent extraction system for rich lithium solution fully mixes the rich lithium solution and extractant in countercurrent mode and is in flow accurate adjustment through an adjusting valve and a booster pump, thereby greatly improving Ni2+、Co2+、Mn2+The extraction rate of (2).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic diagram of a multi-stage counter-current extraction system for a lithium-rich solution in an embodiment of the present invention;
FIG. 2 is a schematic diagram of the structure of an extraction tank in an embodiment of the present invention;
FIG. 3 is a schematic structural view of an exhaust gas purifying chamber according to an embodiment of the present invention;
FIG. 4 is a schematic structural diagram of a liquid separation tank in an embodiment of the invention;
fig. 5 is a partial enlarged view of a portion a in fig. 4.
Reference numerals: 100. an extraction tank; 110. a stirring and mixing mechanism; 111. a first reduction motor; 112. a first stirring shaft; 113. a stirring frame; 114. a first coupling; 120. a drain valve; 130. a liquid inlet pipe; 131. a first regulating valve; 132. a first booster pump; 140. a solution tank; 150. a light phase outlet; 160. a heavy phase outlet; 170. a first connecting pipe; 180. a second connecting pipe; 181. a second regulating valve; 182. a second booster pump; 190. an exhaust pipe; 191. an exhaust gas purification chamber; 192. a purification frame; 193. a quartz sand filter layer; 194. an activated carbon filter layer; 195. a HDPE filter layer; 196. expanding the mouth; 197. an air inlet pipe; 200. liquid separating tank; 210. stirring the layered structure; 211. a second reduction motor; 212. a second stirring shaft; 213. a stirring blade; 214. a second coupling; 215. an anti-sticking plate; 216. an anti-sticking column; 220. a light phase inlet; 230. a heavy phase inlet; 240. a discharge pipe; 241. a mixed liquid pipe; 242. a fourth regulating valve; 243. a third booster pump; 250. a material storage tank; 260. a feed pipe; 261. a third regulating valve; 270. an extractant tank.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The embodiment provides a method for extracting nickel, cobalt and manganese from an acid lithium-rich solution, which comprises the following steps:
s1, performing single-stage or multi-stage countercurrent extraction by using an organic phase-to-acid lithium-rich solution containing di (2-ethylhexyl) phosphate, and separating to obtain a first raffinate and a first extract phase; wherein the pH value of the acid lithium-rich solution is 1-5, and Ni in the acid lithium-rich solution2+、Co2+、Mn2+The solubility of the water-soluble organic solvent is 2.6-3.2 g/L, 0.3-0.6 g/L and 0.1-0.3 g/L respectively;
s2, carrying out single-stage or multi-stage countercurrent extraction on the organic phase containing the HBL110 relative to the first raffinate, and separating to obtain a second raffinate and a second extract phase, wherein the second raffinate is a high-purity lithium-rich solution;
s3, carrying out single-stage or multi-stage countercurrent back extraction on the second extract phase by inorganic acid to obtain Ni-containing2+、Co2+、Mn2+The purified liquid of (1).
Wherein, the multi-stage countercurrent extraction in the steps S1 and S2 is completed by a multi-stage countercurrent extraction system for the lithium-rich solution; the HBL110 is a compound of naphthalene sulfonic acid (salt) and pyridine carboxylate, and the organic phase containing di (2-ethylhexyl) phosphate is formed by mixing di (2-ethylhexyl) phosphate and a diluent according to a volume ratio of 1: 3-5; the organic phase containing the HBL110 is formed by mixing the HBL110 and a diluent according to the volume ratio of 1: 3-5; the diluent is selected from one or a mixture of more of sulfonated kerosene, No. 260 solvent oil and aviation kerosene; the inorganic acid is selected from one or a mixture of sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the inorganic acid is 1-4 mol/L; the stage number of the countercurrent extraction is 1-10, and the stage number of the back extraction is 1-10.
Example 2
This example provides a secondary acidA method for extracting Ni, Co and Mn from acidic lithium-rich solution is characterized in that the acidic lithium-rich solution is a lithium-rich solution for selectively extracting lithium from lithium battery powder, wherein the lithium-rich solution contains Ni2+2.945g/L、Co2+0.48g/L、Mn2+0.14g/L and pH 4.2;
the organic phase is formed by mixing an extracting agent of di (2-ethylhexyl) phosphate P204 and a diluent according to the volume ratio of 1:4, wherein the diluent is selected from sulfonated kerosene;
taking the acidic lithium-rich solution as a water phase, carrying out four-stage extraction with an organic phase at a volume ratio of 1:1 to obtain an extract phase and a raffinate, adjusting the pH of the raffinate to 5-6 by sulfuric acid back extraction, wherein the extraction equilibrium time is 5-10 minutes, the extraction temperature is 20-30 ℃, and the extraction results are shown in table 1:
table 1.P204 results of nickel-cobalt-manganese extraction from lithium-rich solution
As can be seen from Table 1, the P204 extraction rates of the nickel, cobalt and manganese ions are all more than 92%, wherein the highest extraction rate of the cobalt is 99.46%, the extraction rate of the manganese is 99.14%, and the extraction rate of the nickel is 92.88%.
Example 3
This example provides a method for extracting Ni, Co, Mn from an acidic lithium-rich solution, which is a lithium-rich solution for selectively extracting Li from Li battery powders, wherein the lithium-rich solution contains Ni2+2.945g/L、Co2+0.48g/L、Mn2+0.14g/L and pH 4.2;
the organic phase is formed by mixing a compound HBL110 of naphthalene sulfonic acid (salt) and pyridine carboxylate with a diluent according to the volume ratio of 1:4, wherein the diluent is selected from sulfonated kerosene;
the acidic lithium-rich solution is used as a water phase and is subjected to single-stage extraction with an organic phase under the condition that the volume ratio of the acidic lithium-rich solution to the organic phase is 1:1 to obtain an extract phase and a raffinate, the pH of the raffinate is adjusted to 5-6 through nitric acid back extraction, the extraction equilibrium time is 5-10 minutes, the extraction temperature is 20-30 ℃, and the extraction results are shown in table 2:
TABLE 2 results of extraction of Ni, Co and Mn from Li-rich solution by complex of naphthalene sulfonate and pyridine carboxylate
As can be seen from table 2, the complex of naphthalenesulfonic acid (salt) and picolinic acid ester has an extraction rate of 94.92% for nickel, 95.71% for manganese and 68.75% for nickel in the lithium-rich solution.
Example 4
This example provides a method for extracting Ni, Co, Mn from an acidic lithium-rich solution, which is a lithium-rich solution for selectively extracting Li from Li battery powders, wherein the lithium-rich solution contains Ni2+2.945g/L、Co2+0.48g/L、Mn2+0.14g/L and pH 4.2;
extracting agent P204 and a compound HBL110 of naphthalene sulfonic acid (salt) and pyridine carboxylic ester are taken from an organic phase respectively, a diluent in the organic phase is sulfonated kerosene, and the volume ratio of the extracting agent to the sulfonated kerosene is 1: 4;
taking the acidic lithium-rich solution as an aqueous phase, performing four-stage extraction under the condition that the volume ratio of the P204 organic phase to the aqueous phase is 1:1, adjusting the pH of raffinate to 5-6, and keeping the extraction equilibrium time for 3-10 minutes at the extraction temperature of 20-30 ℃. And separating the liquid after extraction to obtain a first raffinate and a first extract phase. Performing single-stage extraction on a composite organic phase of naphthalene sulfonic acid (salt) and pyridine carboxylate and a first raffinate at a volume ratio of 1:1 to obtain a second raffinate, performing hydrochloric acid back extraction on the second raffinate to adjust the pH value to 5-6, wherein the extraction balance time is 3-10 minutes, and the extraction temperature is 20-30 ℃; the extraction results are shown in table 3:
TABLE 3 Experimental results of stepwise extraction of Ni, Co, Mn from Li-rich solution by P204 and HBL110
As can be seen from table 3, P204 and HBL110 have excellent effect of extracting nickel, cobalt and manganese from lithium-rich solution by steps, with an extraction rate of 97.89% for nickel, 99.29% for manganese and 99.01% for cobalt.
Example 4
As shown in FIG. 1, this example provides a multi-stage countercurrent extraction system for lithium-rich solution, which is used to extract Ni from acidic lithium-rich solution by means of multi-stage countercurrent extraction2+、Co2+、Mn2+The device comprises a plurality of extraction tanks 100 and a liquid separating tank 200 which are arranged from one side to the other side, wherein a stirring and mixing mechanism 110 is arranged in the extraction tank 100, a liquid discharge valve 120 is arranged at the bottom of the extraction tank 100, and a stirring and layering structure 210 is arranged in the liquid separating tank 200; the bottom of the first extraction tank 100 is connected with a solution tank 140 through a liquid inlet pipe 130, and a first regulating valve 131 and a first booster pump 132 are sequentially arranged on the path of the liquid inlet pipe 130; a light phase outlet 150 is arranged at the upper part of the side wall of the extraction tank 100, a heavy phase outlet 160 is arranged at the bottom of the extraction tank, a light phase inlet 220 is arranged at the lower part of the side wall of the liquid separation tank 200, and a heavy phase inlet 230 is arranged at the upper part of the side wall; the light phase outlet 150 on the extraction tank 100 is communicated with the light phase inlet 220 on the adjacent liquid separation tank 200 through a first connecting pipe 170, and the heavy phase outlet 160 on the extraction tank 100 is communicated with the heavy phase inlet 230 on the liquid separation tank 200 arranged at intervals through a second connecting pipe 180.
The upper part of the side wall of the first liquid separation tank 200 is connected with a material storage tank 250 through a material discharge pipe 240; the bottom of the last liquid separation tank 200 is connected with an extractant tank 270 through a feeding pipe 260; a second regulating valve 181 and a second booster pump 182 are arranged on the path of the second connecting pipe 180; a third regulating valve 261 is arranged on the path of the feeding pipe 260; the bottom of the liquid separation tank 200 is communicated with the bottom of the adjacent extraction tank 100 through a mixed liquid pipe 241, and a fourth regulating valve 242 and a third booster pump 243 are arranged on the mixed liquid pipe 241.
In the embodiment, the multi-stage countercurrent extraction system for the lithium-rich solution is adopted, the lithium-rich solution in the solution tank 140 enters the first extraction tank 100 from the liquid inlet pipe 130 after the first regulating valve 131 is opened and the first booster pump 132 is pressurized; the extractant in the extractant tank 270 enters the last liquid separation tank 200 through the feeding pipe 260 after the third regulating valve 261 is opened; the lithium-rich solution heavy phase enters the separated liquid separating tank 200 through the heavy phase outlet 160, the second connecting pipe 180 and the heavy phase inlet 230, and the light phase enters the light phase separating tank through the light phase outlet 150 and the first connecting pipe 170. The light phase inlet 220 enters the liquid separation tank 200; the extractant enters the adjacent extraction tanks 100 through the first connecting pipe 170, the mixed liquid in the extraction tanks 100 is regulated by the fourth regulating valve 242 and pressurized by the third pressurizing pump 243 and then enters the liquid separation tank 200, the lithium-rich solution and the extractant are subjected to multi-stage countercurrent extraction and extracted in the extraction tanks 100, and the liquid separation tank 200 is layered; the raffinate phase enters the storage tank 250 through the discharge pipe 240, and the extract phase is discharged after the discharge valve 120 is opened. The sizes and the quantities of the extraction tank 100 and the liquid separation tank 200 are adjusted according to the specific solution treatment capacity. The multistage countercurrent extraction system can fully mix and contact solution and an extractant in a countercurrent mode, and accurately adjust the flow rate through the regulating valve and the booster pump, so that the Ni content is greatly improved2+、Co2+、Mn2+The extraction rate of (2).
As shown in fig. 1-5, the stirring and mixing mechanism 110 includes a first speed-reducing motor 111, a first stirring shaft 112, and a stirring frame 113, the first speed-reducing motor 111 is disposed at the top of the extraction tank 100, the first speed-reducing motor 111 is connected to the first stirring shaft 112 extending into the inner cavity of the extraction tank 100 through a first coupling 114, and the stirring frame 113 is disposed at the periphery of the first stirring shaft 112. After the first speed reduction motor 111 is started, the first speed reduction motor 111 drives the first stirring shaft 112 and the stirring frame 113 to rotate, and the stirring frame 113 fully stirs the lithium-rich solution and the extractant to promote the compatibility of the component to be extracted and the extractant.
Stirring layered structure 210 includes second gear motor 211, second (mixing) shaft 212, stirring vane 213, and liquid tank 200's top is divided in second gear motor 211 locating, and second gear motor 211 passes through second shaft coupling 214 and is connected with the second (mixing) shaft 212 that stretches into liquid tank 200 inner chamber, and a plurality of stirring vane 213 symmetries set up on the radial direction of second (mixing) shaft 212, and from the size of supreme stirring vane 213 constantly reducing down. The top of the inner wall of the liquid separation tank 200 is provided with an arc-shaped anti-sticking plate 215, and a plurality of anti-sticking columns 216 are uniformly distributed on the wall of the anti-sticking plate 215 towards the center of the inner cavity of the liquid separation tank 200.
After the second speed reducing motor 211 is turned on, the second speed reducing motor 211 drives the second stirring shaft 212 and the stirring blades 213 to rotate, the plurality of stirring blades 213 promote further mixing of the extract phase and the raffinate phase, and the mixture is stood for layering after the second speed reducing motor 211 is turned off. The outer layers of the anti-sticking plate 215 and the anti-sticking column 216 are coated with smooth coatings, so that the adhesion of raffinate phases on the top of the liquid separation tank 200 can be avoided, and the extraction rate is improved.
One side of the top of the extraction tank 100 is connected with a waste gas purification chamber 191 through an exhaust pipe 190; the waste gas purification chamber 191 comprises a purification frame 192, and a quartz sand filter layer 193, an activated carbon filter layer 194 and an HDPE filter layer 195 are sequentially arranged from one side to the other side in the purification frame 192; an expansion opening 196 is arranged at the end part of the exhaust pipe 190 facing the quartz sand filter layer 193, and a plurality of air inlet pipes 197 are arranged between the quartz sand filter layer 193 and the activated carbon filter layer 194 and between the activated carbon filter layer 194 and the HDPE filter layer 195.
In the process of stirring by the stirring frame 113, a small amount of gas is generated to emulsify the solution, so that the extraction and layering efficiency is reduced, and by arranging the waste gas purification chamber 191, the gas enters the purification frame 192 through the expansion port 196 and is sequentially filtered by the quartz sand filter layer 193, the activated carbon filter layer 194 and the HDPE filter layer 195, so that the discharge of particle impurities and harmful gas in the gas is removed, the emulsification effect is weakened, and the extraction and layering efficiency is improved.
The foregoing is merely exemplary and illustrative of the present invention and various modifications, additions and substitutions may be made by those skilled in the art to the specific embodiments described without departing from the scope of the invention as defined in the following claims.
In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments are not intended to be exhaustive or to limit the invention to the precise forms disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (8)
1. A method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution is characterized by comprising the following steps:
s1, performing single-stage or multi-stage countercurrent extraction by using an organic phase-to-acid lithium-rich solution containing di (2-ethylhexyl) phosphate, and separating to obtain a first raffinate and a first extract phase;
s2, carrying out single-stage or multi-stage countercurrent extraction on the organic phase containing the HBL110 relative to the first raffinate, and separating to obtain a second raffinate and a second extract phase, wherein the second raffinate is a high-purity lithium-rich solution;
s3, carrying out single-stage or multi-stage countercurrent back extraction on the second extract phase by inorganic acid to obtain Ni-containing2+、Co2+、Mn2+The purified liquid of (1).
2. The method for extracting Ni, Co, Mn from acidic lithium-rich solution according to claim 1, wherein the pH of the acidic lithium-rich solution is 1-5, and Ni in the acidic lithium-rich solution2+、Co2+、Mn2+The solubility of the water-soluble polymer is 2.6-3.2 g/L, 0.3-0.6 g/L, 0.1-0.3 g/L.
3. The method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution according to claim 1, wherein the HBL110 is a compound of naphthalene sulfonate and pyridine carboxylate, and the organic phase containing di (2-ethylhexyl) phosphate is formed by mixing di (2-ethylhexyl) phosphate and a diluent according to a volume ratio of 1: 3-5; the organic phase containing the HBL110 is formed by mixing the HBL110 and a diluent according to the volume ratio of 1: 3-5.
4. The method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution according to claim 3, wherein the diluent is selected from one or more of sulfonated kerosene, No. 260 solvent naphtha and aviation kerosene.
5. The method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution according to claim 1, wherein the inorganic acid is one or more selected from sulfuric acid, hydrochloric acid and nitric acid, and the concentration of the inorganic acid is 1-4 mol/L.
6. The method of claim 1, wherein the multi-stage countercurrent extraction in steps S1 and S2 is performed by a multi-stage countercurrent extraction system for the lithium-rich solution.
7. The method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution according to claim 6, wherein the multi-stage countercurrent extraction system for the lithium-rich solution comprises a plurality of extraction tanks (100) and a liquid separation tank (200) which are arranged from one side to the other side, wherein a stirring and mixing mechanism (110) is arranged in each extraction tank (100), a liquid discharge valve (120) is arranged at the bottom of each extraction tank (100), and a stirring and layering structure (210) is arranged in each liquid separation tank (200); the bottom of the first extraction tank (100) is connected with a solution tank (140) through a liquid inlet pipe (130), and a first regulating valve (131) and a first booster pump (132) are sequentially arranged on the path of the liquid inlet pipe (130); a light phase outlet (150) is arranged at the upper part of the side wall of the extraction tank (100), a heavy phase outlet (160) is arranged at the bottom of the extraction tank, a light phase inlet (220) is arranged at the lower part of the side wall of the liquid separation tank (200), and a heavy phase inlet (230) is arranged at the upper part of the side wall; a light phase outlet (150) on the extraction tank (100) is communicated with a light phase inlet (220) on the adjacent liquid separation tank (200) through a first connecting pipe (170), and a heavy phase outlet (160) on the extraction tank (100) is communicated with a heavy phase inlet (230) on the liquid separation tank (200) arranged at intervals through a second connecting pipe (180).
8. The method for extracting nickel, cobalt and manganese from an acidic lithium-rich solution according to claim 7, characterized in that a storage tank (250) is connected to the upper part of the side wall of the first liquid separation tank (200) through a discharge pipe (240); the bottom of the last liquid separating tank (200) is connected with an extractant tank (270) through a feeding pipe (260); a second regulating valve (181) and a second booster pump (182) are arranged on the path of the second connecting pipe (180); a third regulating valve (261) is arranged on the path of the feeding pipe (260); the bottom of the liquid separating tank (200) is communicated with the bottom of the adjacent extraction tank (100) through a mixed liquid pipe (241), and a fourth regulating valve (242) and a third booster pump (243) are arranged on the mixed liquid pipe (241).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115818732A (en) * | 2022-10-28 | 2023-03-21 | 中南大学 | Method for directly preparing ternary precursor by jointly extracting nickel, cobalt and manganese in laterite-nickel ore high-pressure leaching solution |
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