CN114107662B - Phosphate extractant and method for extracting and separating lithium manganese leaching solution by using same - Google Patents
Phosphate extractant and method for extracting and separating lithium manganese leaching solution by using same Download PDFInfo
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- CN114107662B CN114107662B CN202111423619.XA CN202111423619A CN114107662B CN 114107662 B CN114107662 B CN 114107662B CN 202111423619 A CN202111423619 A CN 202111423619A CN 114107662 B CN114107662 B CN 114107662B
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000002386 leaching Methods 0.000 title claims abstract description 33
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 title claims abstract description 27
- 229910019142 PO4 Inorganic materials 0.000 title claims abstract description 25
- 239000010452 phosphate Substances 0.000 title claims abstract description 25
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000605 extraction Methods 0.000 claims abstract description 122
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 93
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 93
- 239000011572 manganese Substances 0.000 claims abstract description 93
- 239000012074 organic phase Substances 0.000 claims abstract description 66
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 65
- 238000005406 washing Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 239000003085 diluting agent Substances 0.000 claims abstract description 18
- 239000003607 modifier Substances 0.000 claims abstract description 16
- 239000012071 phase Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 8
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 8
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 12
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims description 8
- 159000000002 lithium salts Chemical class 0.000 claims description 8
- 239000003350 kerosene Substances 0.000 claims description 7
- 239000002699 waste material Substances 0.000 abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract description 8
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract description 6
- 238000007127 saponification reaction Methods 0.000 abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract description 4
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 abstract description 4
- 235000011130 ammonium sulphate Nutrition 0.000 abstract description 4
- 238000009388 chemical precipitation Methods 0.000 abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 4
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 4
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 4
- 235000011132 calcium sulphate Nutrition 0.000 abstract description 3
- 229910001437 manganese ion Inorganic materials 0.000 abstract 1
- -1 phosphate ester Chemical class 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 41
- 238000001514 detection method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 150000002739 metals Chemical class 0.000 description 6
- 238000000658 coextraction Methods 0.000 description 4
- 239000003599 detergent Substances 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000000638 solvent extraction Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 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 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000002440 industrial waste Substances 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
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001180 sulfating effect Effects 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention provides a phosphate extractant and a method for extracting and separating lithium manganese leaching liquid by using the same, belonging to the technical field of hydrometallurgical separation. The invention obtains an extracted organic phase by mixing a phosphate ester extractant, a modifier and a diluent, and then carries out multistage extraction under the conditions of preset O/A ratio, temperature and time, so that manganese ions are extracted into the organic phase, and lithium ions are reserved in raffinate; and (3) carrying out multistage washing on the organic phase loaded with manganese by pure water, and then carrying out multistage back extraction on the manganese in the organic phase by sulfuric acid to enable the manganese to enter a water phase, so as to produce a pure manganese sulfate solution. Compared with the chemical precipitation manganese separation process, the method can avoid the generation of waste residues such as sodium sulfate, ammonium sulfate, calcium sulfate and the like, and also eliminates saponification waste liquid generated in the saponification process in the traditional process of extracting manganese by the phosphoric acid extractant, thereby realizing the efficient separation and green extraction of lithium and manganese in solution.
Description
Technical Field
The invention relates to the technical field of hydrometallurgical separation, in particular to a phosphate extractant and a method for extracting and separating lithium manganese leaching liquid by using the same.
Background
The waste lithium ion battery is rich in valuable resources such as lithium, nickel, cobalt, manganese, copper, aluminum, graphite and the like. In order to relieve the pressure of key energy metal resource supply and eliminate the potential risk of the environment, the recycling of valuable metals in waste lithium ion batteries has become a focus of attention in the lithium battery industry. The recycling process of the waste lithium batteries comprises a fire method and a wet method, and most domestic lithium battery recycling enterprises adopt wet treatment processes. Patent CN107181014a discloses a method for recovering waste lithium manganate batteries, which comprises the steps of firstly disassembling and washing the lithium manganate batteries to obtain a positive electrode material, leaching valuable metals in the positive electrode material by using organic acid after high-temperature treatment, and then separating lithium and manganese in the leaching solution by using a solvent extraction method. CN111254294a discloses a method for selectively extracting lithium from waste lithium ion battery powder and electrolyzing, separating and recovering manganese dioxide, which mainly adopts a sulfating roasting-calcine water leaching technology route to selectively enrich lithium in water leaching liquid, so as to realize efficient extraction of lithium source. In order to obtain higher lithium leaching rate, the process needs to increase the proportion of concentrated sulfuric acid, so that a small amount of manganese enters into an aqueous solution along with lithium, and the problem of lithium and manganese separation exists in the follow-up process.
The separation method of lithium and manganese in the solution mainly comprises chemical precipitation, electrochemical deposition, solvent extraction and the like. Although the chemical precipitation method (neutralization hydrolysis precipitation and sulfuration precipitation) can rapidly precipitate manganese, new impurity ions are easy to introduce, and not only can have adverse effects on the subsequent separation and recovery of lithium and the purity of lithium salt products, but also can generate wastes such as sodium sulfate, ammonium sulfate, calcium sulfate and the like. The electrochemical deposition technology can recycle manganese dioxide powder, but has the defects of low current efficiency, high power consumption and incomplete separation of lithium and manganese. The organic phosphoric acid solvent extraction method (P204, P507) has the characteristics of high separation efficiency and easiness in realizing automatic and continuous operation, and can realize complete separation of lithium and manganese. In order to maintain the stable pH value of the feed liquid in the extraction process to obtain higher extraction rate, the extractant needs to be subjected to saponification pretreatment so as to lead Na in the raffinate + 、NH 4 + With Li + Separation is difficult and a large amount of industrial waste salts such as sodium sulfate, ammonium sulfate and the like are produced.
Therefore, how to obtain a process for efficiently separating and extracting lithium and manganese in leaching liquid without generating industrial salt waste is a technical problem which needs to be solved at present.
Disclosure of Invention
The invention aims to provide a phosphate extractant and a method for extracting and separating lithium-manganese leaching liquid, and the extraction and separation method provided by the invention realizes the effects of efficiently separating lithium and manganese and avoiding industrial salt waste.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a phosphate extractant, which comprises one or two of the following structural formulas,
the invention provides a method for extracting and separating lithium manganese leaching liquid by using a phosphate extractant, which comprises the following steps:
1) Preparing an extracted organic phase: mixing a modifier, a diluent and a phosphate extractant to obtain an extracted organic phase;
2) And (3) manganese extraction: taking the lithium manganese leaching solution as an extraction liquid, mixing an extraction organic phase with the extraction liquid, and performing multistage extraction to obtain a manganese loaded organic phase and a lithium-containing raffinate;
3) Manganese loaded organic phase wash: carrying out multistage washing on the manganese loaded organic phase to remove lithium mixed in the organic phase, and combining the obtained washing liquid and lithium-containing raffinate to prepare a feed liquid as lithium salt;
4) Back extraction of manganese: and 3) carrying out multistage back extraction on the manganese loaded organic phase washed in the step 3) by adopting sulfuric acid solution, so that manganese in the organic phase enters into a water phase to obtain manganese sulfate solution, and returning the organic phase after back extraction to the manganese extraction step.
Further, the modifier is n-butanol and/or isobutanol;
the diluent comprises sulfonated kerosene.
Further, the volume ratio of the phosphate extractant, the modifier and the diluent is 20-50: 5-15: 35 to 75.
Further, in the step 2), the pH value of the lithium manganese leaching solution is 0.5-6, the lithium content is 3-35 g/L, and the manganese content is 5-85 g/L.
Further, in step 2), the conditions of the multistage extraction are: the O/A ratio is 1: 3-3: 1, the extraction temperature is 20-60 ℃, the extraction time is 5-15 min, and the extraction stage number is 2-10.
Further, in step 3), the conditions of the multistage washing are: the ratio of O/A is 1:1-4:1, the washing temperature is 25-60 ℃, the washing time is 5-15 min, and the washing stage number is 2-4.
Further, in step 4), the conditions of the multistage back extraction are: the ratio of O/A is 1:1-3:1, the concentration of sulfuric acid solution is 4-6 mol/L, the back extraction temperature is 20-60 ℃, the back extraction time is 5-15 min, and the back extraction stage number is 2-6.
Further, the extraction, washing and back extraction equipment is one of a centrifugal extractor, a mixer-settler and an extraction tower.
The invention has the beneficial effects that:
compared with the chemical precipitation manganese separation process, the invention can avoid the generation of waste residues such as sodium sulfate, ammonium sulfate, calcium sulfate and the like, and also eliminates the saponification waste liquid generated in the saponification process of the traditional phosphoric acid extractant; and the difficult problem of separation of lithium and impurity ions in the demanganized waste liquid is avoided, the recovery rate of lithium is greatly improved, and the efficient separation and green extraction of lithium and manganese in the solution are realized.
Detailed Description
The invention provides a phosphate extractant, which comprises one or two of the following structural formulas,
in the present invention, the phosphate extractant is preferably
The invention provides a method for extracting and separating lithium manganese leaching liquid by using a phosphate extractant, which comprises the following steps:
1) Preparing an extracted organic phase: mixing a modifier, a diluent and a phosphate extractant to obtain an extracted organic phase;
2) And (3) manganese extraction: taking the lithium manganese leaching solution as an extraction liquid, mixing an extraction organic phase with the extraction liquid, and performing multistage extraction to obtain a manganese loaded organic phase and a lithium-containing raffinate;
3) Manganese loaded organic phase wash: carrying out multistage washing on the manganese loaded organic phase to remove lithium mixed in the organic phase, and combining the obtained washing liquid and lithium-containing raffinate to prepare a feed liquid as lithium salt;
4) Back extraction of manganese: and 3) carrying out multistage back extraction on the manganese loaded organic phase washed in the step 3) by adopting sulfuric acid solution, so that manganese in the organic phase enters into a water phase to obtain manganese sulfate solution, and returning the organic phase after back extraction to the manganese extraction step.
In the present invention, the modifier is n-butanol and/or isobutanol, preferably n-butanol.
In the present invention, the diluent is preferably sulfonated kerosene.
In the invention, the volume ratio of the phosphate extractant, the modifier and the diluent is 20-50: 5-15: 35 to 75, preferably 25 to 45: 8-12: 40 to 70, more preferably 30 to 40:15: 45-65.
In the invention, in the step 2), the pH value of the lithium manganese leaching solution is 0.5-6, the lithium content is 3-35 g/L, and the manganese content is 5-85 g/L; preferably, the pH value of the lithium manganese leaching solution is 1-5, the lithium content is 5-30 g/L, and the manganese content is 20-70 g/L; further preferably, the pH value of the lithium manganese leaching solution is 2-4, the lithium content is 10-20 g/L, and the manganese content is 30-60 g/L.
In the present invention, in step 2), the conditions of the multistage extraction are: the O/A ratio is 1: 3-3: 1, the extraction temperature is 20-60 ℃, the extraction time is 5-15 min, and the extraction stage number is 2-10; preferably, the O/A ratio is 1: 2-2: 1, the extraction temperature is 30-50 ℃, the extraction time is 8-12 min, and the extraction stage number is 3-7; further preferably, the O/a ratio is 1:1 to 4:3, the extraction temperature is 35-45 ℃, the extraction time is 10min, and the extraction stage number is 4-6.
In the present invention, in step 3), the conditions of the multistage washing are: the ratio of O/A is 1:1-4:1, the washing temperature is 25-60 ℃, the washing time is 5-15 min, and the washing stage number is 2-4; preferably, the O/A ratio is 2:1 to 3:1, the washing temperature is 30-50 ℃, the washing time is 8-12 min, and the washing stage number is 3-4; further preferably, the O/a ratio is 3:1, the washing temperature is 40 ℃, the washing time is 10min, and the washing grade is 4.
In the present invention, in step 4), the conditions of the multistage stripping are: the O/A ratio is 1:1-3:1, the concentration of sulfuric acid solution is 4-6 mol/L, the back extraction temperature is 20-60 ℃, the back extraction time is 5-15 min, and the back extraction stage number is 2-6; preferably, the O/A ratio is 3:2 to 5:2, the concentration of the sulfuric acid solution is 5-6 mol/L, the back extraction temperature is 30-50 ℃, the back extraction time is 8-12 min, and the back extraction stage number is 3-4; more preferably, the O/A ratio is 2:1, the concentration of sulfuric acid solution is 5.5mol/L, the back extraction temperature is 40 ℃, the back extraction time is 10min, and the back extraction stage number is 4.
In the present invention, the extraction, washing and stripping equipment is one of a centrifugal extractor, a mixer-settler and an extraction tower, preferably a centrifugal extractor.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
The initial pH value of the lithium manganese leaching solution is 3, and the content of valuable metals is 20g/L, mn g/L of Li respectively. The clean and efficient extraction and separation of lithium and manganese are carried out in a mixer-settler according to the following steps:
(1) Preparing an extracted organic phase: the dialkyl phosphate (II) is selected as an extractant, n-butanol is used as a modifier and sulfonated kerosene is used as a diluent, and an organic phase is extracted according to the volume ratio of '40% of extractant + 10% of modifier + 50% of diluent'.
(2) And (3) manganese extraction: and (2) adopting the extracted organic phase prepared in the step (1), and carrying out 8-stage extraction on the lithium-containing manganese leaching solution under the process conditions of an O/A ratio of 1:2, an extraction temperature of 40 ℃ and an extraction time of 10min to obtain a manganese-loaded organic phase and a lithium-containing raffinate. Through detection calculation, the extraction rate of manganese can reach 99.89%, and the co-extraction rate of lithium is only 2.25%.
(3) Manganese loaded organic phase wash: pure water is used as a detergent, 3-level washing is carried out on the manganese loaded organic phase under the process conditions of O/A phase ratio of 3:1, washing temperature of 40 ℃ and washing time of 8min, lithium carried in the organic phase is removed, and the washing liquid is combined with the lithium-containing raffinate after multiple circulation to prepare a feed liquid as lithium salt. Through detection calculation, the lithium removal rate is 99.39%, and the manganese removal rate is less than 1%.
(4) Back extraction of manganese: and (3) carrying out 4-stage back extraction on the washed manganese-loaded organic phase under the process conditions of an O/A phase ratio of 1:1, a back extraction temperature of 40 ℃ and a back extraction time of 10min by adopting a 5mol/L sulfuric acid solution to obtain a pure manganese sulfate solution. Through detection calculation, the manganese back extraction rate is 99.50%.
Example 2
The initial pH value of the lithium manganese leaching solution is 4, and the content of valuable metals is Li 18g/L, mn g/L respectively. The clean and efficient extraction and separation of lithium and manganese are carried out in a mixer-settler according to the following steps:
(1) Preparing an extracted organic phase: the organic phase is extracted by taking the phosphoric acid monoalkyl ester (I) as an extracting agent, n-butanol as a modifying agent and sulfonated kerosene as a diluting agent according to the volume ratio of '35% of the extracting agent + 15% of the modifying agent + 50% of the diluting agent'.
(2) And (3) manganese extraction: and (3) extracting manganese from the lithium-containing manganese leaching solution by adopting the extracted organic phase prepared in the step (1) under the process conditions of an O/A ratio of 1:3, an extraction temperature of 45 ℃ and an extraction time of 6min to obtain a manganese-loaded organic phase and a lithium-containing raffinate. Through detection calculation, the extraction rate of manganese can reach 99.94%, and the co-extraction rate of lithium is only 1.53%.
(3) Manganese loaded organic phase wash: pure water is used as a detergent, the manganese loaded organic phase is subjected to 2-level washing under the process conditions of O/A phase ratio of 4:1, washing temperature of 45 ℃ and washing time of 8min, lithium carried in the organic phase is removed, and the washing solution is combined with the lithium-containing raffinate after multiple circulation to prepare a feed liquid as lithium salt. The detection calculation shows that the lithium removal rate is 99.62% and the manganese removal rate is less than 1%.
(4) Back extraction of manganese: and (3) carrying out 3-stage back extraction on the washed manganese loaded organic phase under the process conditions of 2.5:1O/A phase ratio, 40 ℃ back extraction temperature and 10min back extraction time by adopting a 4mol/L sulfuric acid solution to obtain a pure manganese sulfate solution. Through detection calculation, the manganese back extraction rate is 99.61%.
Example 3
The initial pH value of the lithium manganese leaching solution is 2, and the content of valuable metals is Li 10g/L, mn g/L respectively. The clean and efficient extraction and separation of lithium and manganese are carried out in a mixer-settler according to the following steps:
(1) Preparing an extracted organic phase: the organic phase is extracted by selecting '20wt% of monoalkyl phosphate (I) +80wt% of dialkyl phosphate (II)' as an extracting agent, isobutanol as a modifier and sulfonated kerosene as a diluent according to the volume ratio of '40% of the extracting agent + 15% of the modifier + 45% of the diluent'.
(2) And (3) manganese extraction: and (3) adopting the extracted organic phase prepared in the step (1), and carrying out 4-stage extraction on the lithium-containing manganese leaching solution under the process conditions of O/A phase ratio of 1:1, extraction temperature of 40 ℃ and extraction time of 10min to obtain a manganese-loaded organic phase and a lithium-containing raffinate. Through detection calculation, the extraction rate of manganese can reach 99.81%, and the co-extraction rate of lithium is only 1.81%.
(3) Manganese loaded organic phase wash: pure water is used as a detergent, the manganese loaded organic phase is subjected to 2-level washing under the process conditions of O/A ratio of 2:1, washing temperature of 40 ℃ and washing time of 10min, lithium carried in the organic phase is removed, and the washing liquid is combined with the lithium-containing raffinate after multiple circulation to prepare a feed liquid as lithium salt. Through detection calculation, the lithium removal rate is 99.56%, and the manganese removal rate is less than 1%.
(4) Back extraction of manganese: and (3) carrying out 4-stage back extraction on the washed manganese-loaded organic phase under the process conditions of 2:1O/A phase ratio, 40 ℃ back extraction temperature and 10min back extraction time by adopting a 6mol/L sulfuric acid solution to obtain a pure manganese sulfate solution. Through detection calculation, the manganese back extraction rate is 99.77%.
Example 4
The initial pH value of the lithium manganese leaching solution is 4, and the content of valuable metals is Li 15g/L, mn g/L respectively. The clean and efficient extraction and separation of lithium and manganese are carried out in a mixer-settler according to the following steps:
(1) Preparing an extracted organic phase: the organic phase is extracted by selecting 10wt% of monoalkyl phosphate (I) +90wt% of dialkyl phosphate (II) as an extractant, isobutanol as a modifier and sulfonated kerosene as a diluent according to the volume ratio of 25% of the extractant to 5% of the modifier to 60% of the diluent.
(2) And (3) manganese extraction: and (2) extracting manganese from the lithium-containing manganese leaching solution by adopting the extracted organic phase prepared in the step (1) under the process conditions of an O/A ratio of 1:2.5, an extraction temperature of 35 ℃ and an extraction time of 8min to obtain a manganese-loaded organic phase and a lithium-containing raffinate. Through detection calculation, the extraction rate of manganese can reach 99.35%, and the co-extraction rate of lithium is only 1.19%.
(3) Manganese loaded organic phase wash: pure water is used as a detergent, the manganese loaded organic phase is subjected to 2-level washing under the process conditions of O/A phase ratio of 2.5:1, washing temperature of 35 ℃ and washing time of 8min, lithium carried in the organic phase is removed, and the washing solution is combined with the lithium-containing raffinate after repeated circulation to prepare a feed liquid as lithium salt. Through detection calculation, the lithium removal rate is 99.37%, and the manganese removal rate is less than 1%.
(4) Back extraction of manganese: and carrying out 2-stage back extraction on the washed manganese loaded organic phase by adopting a 5mol/L sulfuric acid solution under the process conditions of an O/A phase ratio of 2:1, a back extraction temperature of 35 ℃ and a back extraction time of 8min to obtain a pure manganese sulfate solution. Through detection calculation, the manganese back extraction rate is 99.83%.
According to the embodiment, the invention provides the phosphate extractant and the method for extracting and separating the lithium-manganese leaching solution, and the extraction and separation method can be used for efficiently extracting and separating lithium and manganese in the lithium-manganese leaching solution, the back extraction rate of manganese is up to 99.83%, the separation rate of lithium is up to 99.62%, the efficient, green and waste-free extraction and separation effects are realized, and a more economical and feasible method is provided for comprehensive treatment of the lithium-manganese leaching solution.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (6)
1. The method for extracting and separating the lithium manganese leaching solution by using the phosphate extractant is characterized by comprising the following steps of:
1) Preparing an extracted organic phase: mixing a modifier, a diluent and a phosphate extractant to obtain an extracted organic phase;
2) And (3) manganese extraction: taking the lithium manganese leaching solution as an extraction liquid, mixing an extraction organic phase with the extraction liquid, and performing multistage extraction to obtain a manganese loaded organic phase and a lithium-containing raffinate;
3) Manganese loaded organic phase wash: carrying out multistage washing on the manganese loaded organic phase to remove lithium mixed in the organic phase, and combining the obtained washing liquid and lithium-containing raffinate to prepare a feed liquid as lithium salt;
4) Back extraction of manganese: carrying out multistage back extraction on the manganese-loaded organic phase washed in the step 3) by adopting sulfuric acid solution, so that manganese in the organic phase enters a water phase to obtain manganese sulfate solution, and returning the organic phase after back extraction to the manganese extraction step;
the phosphate extractant comprises one or two of the following structural formulas,
the conditions of the multistage extraction are as follows: the O/A ratio is 1: 2-1: 3, extracting at 20-60 ℃ for 5-15 min with 2-10 extraction stages;
the conditions of the multistage back extraction are as follows: the ratio of O/A is 1:1-3:1, the concentration of sulfuric acid solution is 4-6 mol/L, the back extraction temperature is 20-60 ℃, the back extraction time is 5-15 min, and the back extraction stage number is 2-6.
2. The method for extraction separation according to claim 1, wherein the modifier is n-butanol and/or isobutanol;
the diluent comprises sulfonated kerosene.
3. The method for extraction separation according to claim 1 or 2, wherein the volume ratio of the phosphate extractant, the modifier and the diluent is 20-50: 5-15: 35 to 75.
4. The method according to claim 3, wherein in the step 2), the pH value of the lithium manganese leaching solution is 0.5-6, the lithium content is 3-35 g/L, and the manganese content is 5-85 g/L.
5. The method of claim 1, wherein in step 3), the conditions of the multistage washing are: the ratio of O/A is 1:1-4:1, the washing temperature is 25-60 ℃, the washing time is 5-15 min, and the washing stage number is 2-4.
6. The method according to claim 4 or 5, wherein the extraction, washing and stripping equipment is one of a centrifugal extractor, a mixer-settler and an extraction column.
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