CN116623009A - Method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution - Google Patents
Method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution Download PDFInfo
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- CN116623009A CN116623009A CN202310585803.7A CN202310585803A CN116623009A CN 116623009 A CN116623009 A CN 116623009A CN 202310585803 A CN202310585803 A CN 202310585803A CN 116623009 A CN116623009 A CN 116623009A
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- rubidium
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 139
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 139
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052792 caesium Inorganic materials 0.000 title claims abstract description 93
- 229910052701 rubidium Inorganic materials 0.000 title claims abstract description 86
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 238000000034 method Methods 0.000 title claims abstract description 56
- 238000002386 leaching Methods 0.000 title claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 149
- 238000005406 washing Methods 0.000 claims abstract description 104
- 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 24
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 24
- 239000011591 potassium Substances 0.000 claims abstract description 24
- 239000011734 sodium Substances 0.000 claims abstract description 24
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- 238000001556 precipitation Methods 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 238000000909 electrodialysis Methods 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 11
- 150000003297 rubidium Chemical class 0.000 claims abstract description 11
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011575 calcium Substances 0.000 claims abstract description 9
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 9
- 239000000284 extract Substances 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims description 118
- 239000007788 liquid Substances 0.000 claims description 62
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 50
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 29
- 238000005191 phase separation Methods 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 239000003350 kerosene Substances 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 claims description 9
- JVJMRLZNFIEHGR-UHFFFAOYSA-N 4-tert-butyl-2-(1-phenylethyl)phenol Chemical compound C=1C(C(C)(C)C)=CC=C(O)C=1C(C)C1=CC=CC=C1 JVJMRLZNFIEHGR-UHFFFAOYSA-N 0.000 claims description 8
- 230000001105 regulatory effect Effects 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 125000005594 diketone group Chemical group 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- 239000012071 phase Substances 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000013505 freshwater Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 150000002903 organophosphorus compounds Chemical class 0.000 claims description 2
- 238000010979 pH adjustment Methods 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 1
- 230000008569 process Effects 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 12
- 239000002184 metal Substances 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 6
- 230000008020 evaporation Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052784 alkaline earth metal Inorganic materials 0.000 abstract description 2
- 150000001342 alkaline earth metals Chemical class 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract description 2
- 150000003839 salts Chemical class 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 79
- 238000005352 clarification Methods 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052629 lepidolite Inorganic materials 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 7
- 239000000126 substance Substances 0.000 description 6
- 238000000926 separation method Methods 0.000 description 5
- XPEDTFKKQLEOPL-UHFFFAOYSA-N C(CCC)C=1C(=C(C=CC=1)O)C(C1=CC=CC=C1)C Chemical group C(CCC)C=1C(=C(C=CC=1)O)C(C1=CC=CC=C1)C XPEDTFKKQLEOPL-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- FAWNVSNJFDIJRM-UHFFFAOYSA-N [Rb].[Cs] Chemical compound [Rb].[Cs] FAWNVSNJFDIJRM-UHFFFAOYSA-N 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 229910003002 lithium salt Inorganic materials 0.000 description 3
- 159000000002 lithium salts Chemical class 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000009388 chemical precipitation Methods 0.000 description 2
- 238000000658 coextraction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004137 mechanical activation Methods 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- FGDZQCVHDSGLHJ-UHFFFAOYSA-M rubidium chloride Chemical compound [Cl-].[Rb+] FGDZQCVHDSGLHJ-UHFFFAOYSA-M 0.000 description 2
- 229910052604 silicate mineral Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229940037003 alum Drugs 0.000 description 1
- CNLWCVNCHLKFHK-UHFFFAOYSA-N aluminum;lithium;dioxido(oxo)silane Chemical compound [Li+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O CNLWCVNCHLKFHK-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- -1 compound salt Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000012297 crystallization seed Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229940102127 rubidium chloride Drugs 0.000 description 1
- 229910000344 rubidium sulfate Inorganic materials 0.000 description 1
- GANPIEKBSASAOC-UHFFFAOYSA-L rubidium(1+);sulfate Chemical compound [Rb+].[Rb+].[O-]S([O-])(=O)=O GANPIEKBSASAOC-UHFFFAOYSA-L 0.000 description 1
- 238000005185 salting out Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 229910052642 spodumene Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
-
- 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution, which adopts a process combining cascade extraction, washing, back extraction and electrodialysis, not only efficiently separates valuable metals such as lithium, rubidium and cesium from alkaline earth metals such as sodium, potassium and calcium in the lithium ore leaching solution, but also greatly reduces the water inflow of rubidium and cesium extraction sections by preliminarily concentrating raffinate compared with a single extraction system. According to the invention, lithium is enriched in the leaching solution by adopting a cascade extraction-washing-back extraction mode after calcium removal through sodium carbonate precipitation, so that the defect of low lithium recovery rate caused by lithium entrainment of crystalline salt in the traditional evaporation concentration process is avoided. The invention extracts rubidium and cesium step by step, adopts a cascade washing mode to wash most of impurity ions, and then carries out back extraction enrichment to obtain high-purity cesium-enriched and rubidium-enriched solutions, thereby preparing high-purity rubidium salt and cesium salt products. The method has simple process operation and no environmental hazard, and is suitable for recovering valuable metals of lithium, rubidium and cesium in most lithium ores.
Description
Technical Field
The invention relates to the field of nonferrous metal smelting and environmental protection, in particular to a method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution.
Background
Lithium has unique physicochemical properties as the lightest and least dense metal, and along with the rapid development of electrochemical energy storage and electric automobiles in recent years, the application of lithium in the field of novel energy materials is increasingly apparent, and the development and utilization of lithium are also receiving high attention. Rubidium and cesium often coexist with similar lithium, sodium, potassium and the like in chemical properties, mainly exist in a compound state in nature, and have relatively low concentration. Rubidium and cesium have basically similar physical and chemical properties, have extremely active chemical properties and excellent photoelectric properties, and are widely applied to the fields of electronics, chemical industry, energy, medicine and the like, such as ion rocket propellers for aerospace national defense, photoelectric materials, special glass and the like.
However, as the current lithium demand is greatly increased, most of the processes mainly aim at extracting lithium from salt lake brine or lithium ore, and research on recovery of rubidium and cesium is not much, after the solution after extracting lithium is recovered to other economic metal elements, the solution is generally treated in a solid waste form, so that great waste of rare metals such as rubidium and cesium is caused. Lithium, rubidium and cesium resources mainly exist in ores and salt lake brine resources, wherein the process for comprehensively extracting valuable metals from lithium ores mainly comprises a limestone sintering method, a sulfate method, a chloridizing roasting method and a compound salt roasting method combined with chemical leaching, and lithium, rubidium and cesium in minerals are transferred into a solution for further processing to prepare lithium salt, rubidium salt and cesium salt. The extraction process of lithium in the lithium ore leaching solution is mature, and most of the industry adopts a chemical precipitation method to prepare lithium carbonate by adding sodium carbonate for lithium precipitation after evaporating and concentrating the leaching solution. The existing rubidium and cesium extraction processes mainly comprise a precipitation method, an ion exchange method and a solvent extraction method. The precipitation method is a method for extracting rubidium and cesium by crystallization, precipitation and separation of the solution after lithium extraction for multiple times, and the method has the advantages of complex process, low recovery rate, possibility of bringing in micro impurities and increased impurity removal process difficulty. The organic ion exchanger adopted in the ion exchange method has the ion exchange effect when the high-valence ions coexist under the restriction of factors such as temperature, and the inorganic ion exchanger has high solubility in water. Compared with the ion exchange method, the solvent extraction method has the advantages of simple process, less equipment, high extraction efficiency, suitability for mass production and current common method for extracting rubidium and cesium.
Patent CN113174480a discloses a method for extracting lithium, rubidium and cesium from silicate minerals containing lithium, rubidium and cesium, which comprises mixing finely ground mineral powder with calcium chloride and chlorine fixing agent in proportion, roasting at high temperature, and transferring metals such as lithium, rubidium and cesium into solution through chemical leaching of roasted calcine. The leaching solution is subjected to chemical precipitation to obtain lithium salt, and the solution after lithium precipitation is subjected to extraction-back extraction to obtain rubidium salt and cesium salt. The patent increases the utilization rate of calcium chloride by adding a chlorine fixing agent, no chlorine tail gas is generated in the roasting process, and solves the problem of chlorine in the traditional chloridized roasting flue gas, but the technical scheme only relates to a principle process flow for recovering lithium, rubidium and cesium from silicate mineral powder, and the problems of impurity removal, impurity co-extraction and removal in an extraction-back extraction section, residual extraction solution removal and the like of the leaching solution are not mentioned, so that the process integrity is insufficient, and the results of low metal recovery rate and lower purity of products of lithium, rubidium and cesium are caused; meanwhile, the technical scheme adopts chloridizing roasting, leaching extraction is also equivalent to a chloride system, and wastewater treatment is more complex than that of a sulfuric acid system.
Patent CN107475537a discloses a method for extracting lithium, rubidium and cesium from lepidolite raw materials, wherein lithium salt, rubidium salt and cesium salt are respectively obtained by taking lepidolite as a raw material through mechanical activation treatment, roasting, autoclaving acid leaching, adding a alum precipitation crystallization agent, removing impurities, neutralizing, concentrating, separating and extracting. According to the patent, through controlling the combination of low-temperature roasting and plasma high-temperature roasting for defluorination and mechanical activation treatment on calcine, metal elements in lepidolite ore can be separated and extracted to the greatest extent, residual fluorine is deeply removed, and the utilization rate of lithium, rubidium and cesium in lepidolite ore is greatly improved. According to the technical scheme, although the rubidium and cesium in the lithium-precipitating mother liquor are recovered in a stepwise extraction mode, the entrainment loss of rubidium in the cesium extraction process is reduced, the problem that sodium and potassium co-extraction influences the purity of cesium salt and rubidium salt products is not considered; meanwhile, the technical scheme adopts crystallization seed precipitation to recycle lithium, and the lithium precipitation mother liquor still contains a considerable part of lithium (1.5-2 g/L) due to the limit of solubility, so that the separation and extraction rate of lithium is lower.
Patent CN115180640A discloses a method for extracting rubidium and cesium salts from a solution after lithium extraction from lepidolite, which adopts freezing impurity removal and purification processes, fills high-purity carbon dioxide gas in the back extraction process, realizes the extraction of rubidium and cesium under weak acidity, continuously completes the extraction and back extraction in a pipeline manner, and simultaneously realizes the separation and extraction of rubidium and cesium. However, the technical proposal does not extract cesium rubidium step by step, and the organic phase carrying cesium rubidium adopts washing to elute most of sodium and potassium, but cesium and rubidium can not be thoroughly separated, and only cesium-rubidium salt mixed products can be obtained. In addition, the technical scheme adopts pure water and carbon dioxide to wash and strip the rubidium and cesium-carrying organic phase, so that the corrosiveness of strong acid to equipment is avoided, but part of cesium and rubidium still remains in the organic phase, so that the recovery rate is low, the utilization rate of carbonic acid with weak acidity formed by the carbon dioxide and the water is low, and the purpose of enriching rubidium and cesium can be realized by more strip extraction stages.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution comprises the following steps:
s1, adding sodium carbonate into the lithium ore leaching solution after impurity removal to remove calcium;
s2, mixing the decalcified liquid obtained in the step S1 with an extractant, performing 1-10-level countercurrent extraction, and separating phases after extraction balance to obtain a raffinate and a lithium-loaded organic phase; the lithium-loaded organic phase is transferred to the step S2, and the lithium extraction residual liquid is transferred to the step S6;
s3, mixing the lithium-loaded organic phase obtained in the step S2 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a washing liquid containing sodium and potassium and a washing lithium-loaded organic phase, wherein the washing liquid containing sodium and potassium returns to the step S2 for extracting lithium;
s4, mixing the washed lithium-loaded organic phase obtained in the step S3 with the strip liquor, carrying out 1-10-level countercurrent or cross-current strip extraction, and carrying out phase separation after extraction balance to obtain a lithium-rich strip liquor and an empty organic phase, wherein the empty organic phase returns to the step S2 as an extractant to participate in extraction;
s5, adding sodium carbonate into the lithium-rich strip liquor obtained in the step S4 to carry out lithium precipitation to obtain a lithium precipitation mother liquor and a lithium carbonate product, and returning the lithium precipitation mother liquor to the step S1 for decalcification of the lithium ore leaching solution;
s6, carrying out electrodialysis concentration on the lithium raffinate obtained in the step S2 to obtain fresh water and concentrated water;
s7, mixing the concentrated water obtained in the step S6 with an extractant to perform 1-10-level countercurrent extraction after regulating the pH value, and separating phases after extraction balance to obtain cesium-carrying organic phase and cesium-extracting residual liquid; the cesium-loaded organic phase is transferred to step S8, and the cesium extraction residual liquid is transferred to step S11;
s8, mixing the cesium-carrying organic phase obtained in the step S7 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a rubidium-containing washing liquid and a washing cesium-carrying organic phase, wherein the rubidium-containing washing liquid returns to the step S7 to continuously extract cesium;
s9, mixing the cesium-loaded organic phase obtained in the step S8 with the strip liquor to perform 1-10-level countercurrent or cross-current strip extraction, and separating phases after extraction balance to obtain cesium-enriched strip liquor and empty organic phase, wherein the empty organic phase returns to the step S7 to be used as an extractant to participate in extraction;
s10, evaporating and crystallizing the cesium-rich strip liquor obtained in the step S9 to obtain cesium salt products;
s11, regulating the pH value of the cesium extraction raffinate obtained in the step S7, mixing the cesium extraction raffinate with an extractant, carrying out 1-10-level countercurrent extraction, carrying out phase separation after extraction balance, obtaining rubidium extraction raffinate and a rubidium-carrying organic phase, and carrying out evaporative crystallization on the rubidium extraction raffinate to open a sodium potassium salt circuit;
s12, mixing the rubidium-carrying organic phase obtained in the step S11 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a washing liquid containing sodium and potassium and a washing rubidium-carrying organic phase, wherein the washing liquid containing sodium and potassium returns to the step S11 for rubidium extraction;
s13, mixing the washing rubidium-carrying organic phase obtained in the step S12 with the strip liquor for carrying out 1-10-level countercurrent or cross-current strip extraction, and carrying out phase separation after extraction balance to obtain rubidium-rich strip liquor and an empty organic phase, wherein the empty organic phase returns to the step S11 as an extracting agent to participate in extraction;
s14, evaporating and crystallizing the rubidium-rich strip liquor obtained in the step S13 to obtain a rubidium salt product.
Further, in the step S2, the extractant and the decalcified liquid are mixed according to the volume ratio of 1:10-10:1, and the single-stage extraction time is 1-30 min; the extractant is a combination of diketone compounds, organic phosphorus compounds and kerosene.
Further, in the step S3, the lithium-loaded organic phase and the washing liquid are mixed according to the volume ratio of 1:1-20:1, and the single-stage washing time is 1-30 min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.05-0.5 mol/L.
Further, in the step S4, the washing lithium-loaded organic phase and the back extraction solution are mixed according to the volume ratio of 1:1-50:1, and the single-stage back extraction time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 5-15 mol/L.
Further, in the step S7, the pH of the concentrated water is adjusted to 9-13 by adding alkali; mixing the extractant and the concentrated water with the pH adjusted according to the volume ratio of 1:10-10:1, wherein the single-stage extraction time is 1-30 min; the extractant is a mixture of 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, and the concentration of the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol is 0.1-1 mol/L.
Further, in the step S8, cesium-carrying organic phase and washing liquid are mixed according to the volume ratio of 1:1-20:1, and the single-stage washing time is 1-30 min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with the acid concentration of 0.5-2 mol/L.
Further, in the step S9, the organic phase carrying cesium is washed and the back extraction liquid is mixed according to the volume ratio of 1:1-50:1, and the single-stage back extraction time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.1-1 mol/L.
Further, in the step S11, adding alkali into the cesium extraction raffinate to adjust the pH to 11-14; the extractant is a mixture of 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, and the concentration of the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol is 1-5mol/L; the extractant and the cesium raffinate after pH adjustment are mixed according to the volume ratio of 1:10-10:1, and the single-stage extraction time is 1-30 min.
Further, in the step S12, the rubidium-carrying organic phase and the washing liquid are mixed according to the volume ratio of 1:1-20:1, and the single-stage washing time is 1-30 min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.5-5 mol/L.
Further, in the step S13, the washing rubidium-carrying organic phase and the stripping solution are mixed according to the volume ratio of 1:1-50:1, and the single-stage stripping time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.3-2 mol/L.
The invention has the beneficial effects that:
1) The invention adopts the process of combining cascade extraction, washing, back extraction and electrodialysis, not only efficiently separates valuable metals such as lithium, rubidium, cesium and the like from alkaline earth metals such as sodium, potassium, calcium and the like in the lithium ore leaching solution, but also greatly reduces the water inflow of rubidium and cesium extraction sections by initially concentrating the raffinate lithium compared with a single extraction system.
2) Unlike available lithium extracting process, the present invention has the leaching solution concentrated by evaporation and the sodium carbonate precipitation to eliminate calcium, and the leaching solution is concentrated by cascade extraction, washing and back extraction to avoid the lithium recovering rate caused by lithium entrainment in the crystallization salt during the traditional evaporating and concentrating process.
3) Aiming at the problem that the traditional lithium extraction tail liquid rubidium and cesium are difficult to separate and the purity of rubidium salt and cesium salt products is low due to the fact that the traditional lithium extraction tail liquid rubidium and cesium are extracted together, the process is optimized to be used for extracting rubidium and cesium step by step, and aiming at the problem of entrainment of cesium-carrying and rubidium-carrying organic phases and other impurity ions, a cascade washing mode is adopted to wash most of impurity ions, and then back extraction and enrichment are carried out to obtain high-purity cesium-enriched and rubidium-enriched solutions, so that high-purity rubidium salt and cesium salt products are prepared.
4) The lithium precipitation mother liquor obtained after the lithium carbonate is prepared from the lithium-rich back extraction liquid is returned to the leaching liquid calcium removal section, so that the medicament cost is reduced, and the utilization of alkali and the recovery of residual lithium are realized.
5) The method has simple process operation and no environmental hazard, and is suitable for recovering valuable metals of lithium, rubidium and cesium in most lithium ores.
Drawings
FIG. 1 is a flow chart of a method according to various embodiments of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, and it should be noted that, while the present embodiment provides a detailed implementation and a specific operation process on the premise of the present technical solution, the protection scope of the present invention is not limited to the present embodiment.
Example 1
The flow of the method for comprehensively recovering lithium, rubidium and cesium from the lepidolite ore leaching solution provided in the embodiment is shown in fig. 1, and a lepidolite ore calcine leaching solution is used as a raw material, and the main components are shown in table 1.
TABLE 1 content of elements of leaching solution of certain lepidolite calcine g/L
| Element(s) | Li | Rb | Cs | K | Na | Ca | SO 4 2- | pH |
| Content of | 2.21 | 1.64 | 0.12 | 18.4 | 10.8 | 0.64 | 63.64 | 8.5 |
Removing calcium from leaching liquid: adding 60% of lithium equivalent sodium carbonate into the leaching solution for decalcification, wherein the decalcification rate is over 99.5%, and allowing the decalcified solution to enter a lithium extraction section.
Lithium extraction: the decalcified liquid adopts a diketone combined organic phosphorus and kerosene extraction system, the organic phase and decalcified liquid are mixed according to the volume ratio of 1.5:1 to carry out 3-level countercurrent extraction, the raffinate and the lithium-loaded organic phase are respectively obtained after phase separation and clarification, and the raffinate enters an electrodialysis concentration section. The diketone extractant does not extract rubidium and cesium basically, and the extraction rates of lithium, sodium and potassium are 97.2%, 0.8% and 0.25% respectively.
Washing a lithium-loaded organic phase: and (3) carrying out 3-stage countercurrent washing on the lithium-carrying organic phase by using 0.05mol/L hydrochloric acid solution, mixing the lithium-carrying organic phase with the hydrochloric acid solution according to the volume ratio of 10:1, and respectively obtaining sodium-potassium-containing solution and washing lithium-carrying organic phase after phase separation and clarification. The washing rates of sodium and potassium are 98.2% and 99.8%, respectively, and the lithium loss rate is 5.3%.
Washing and carrying lithium organic back extraction: and carrying out 3-stage countercurrent stripping on the washed lithium-loaded organic phase by using 5mol/L hydrochloric acid solution, mixing the washed lithium-loaded organic phase and the hydrochloric acid solution according to the volume ratio of 20:1, and respectively obtaining a lithium-rich stripping solution and an empty organic phase after phase separation and clarification, wherein the empty organic phase is returned to the lithium extraction section to be used as an extractant.
Precipitating lithium: adding sodium carbonate with the molar weight of 1.5 times of that of lithium into the lithium-rich back extraction solution to carry out lithium precipitation to produce lithium carbonate, and returning the lithium precipitation mother solution to decalcification of the leaching solution.
Electrodialysis concentration section: and carrying out primary concentration on the lithium raffinate by electrodialysis, returning produced fresh water to the leaching pulp washing after the ore calcine water leaching, and enabling the concentrated water to enter the cesium extraction section.
Cesium extraction: the pH of the concentrated raffinate is regulated to about 12 by adopting sodium hydroxide, then a 0.5 mol/L4-tertiary butyl-2 (alpha-methylbenzyl) phenol (i.e. t-bambp) -sulfonated kerosene extraction system is adopted, the organic phase and concentrated water (i.e. the concentrated raffinate) are mixed according to the volume ratio of 1:5 to carry out 3-level countercurrent extraction, the cesium raffinate and the cesium-carrying organic phase are respectively obtained after phase separation and clarification, and the cesium raffinate enters a rubidium extraction section. the t-bambp does not extract lithium basically, and the extraction rates of cesium, rubidium, sodium and potassium are 98%, 6.3%, 0.54% and 1.0%, respectively.
Washing cesium-loaded organic phase: and (3) carrying out 5-stage countercurrent washing on the cesium-carrying organic phase by using 1.10mol/L hydrochloric acid solution, mixing the cesium-carrying organic phase and the hydrochloric acid solution according to the volume ratio of 10:1, and respectively obtaining rubidium-containing washing liquid and washing cesium-carrying organic phase after phase separation and clarification. The washing rate of rubidium and sodium is about 98%, the washing rate of potassium is more than 99%, and the cesium loss rate is 15%.
Washing cesium-carrying organic phase extraction: 3-stage countercurrent stripping is carried out on the washing cesium-carrying organic phase by using 0.40mol/L hydrochloric acid solution, the washing cesium-carrying organic phase and the hydrochloric acid solution are mixed according to the volume ratio of 30:1, the cesium-rich stripping solution and the empty organic phase are respectively obtained after phase separation and clarification, and the empty organic phase is returned to the cesium extraction section to be used as an extracting agent.
Cesium salt product preparation: and evaporating and concentrating the cesium-rich back extraction liquid by adopting MVR to obtain a cesium chloride product.
Rubidium extraction: the pH of the cesium extraction raffinate is regulated to about 14 by sodium hydroxide, then a 1 mol/L4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene extraction system is adopted, the organic phase and the cesium extraction raffinate are mixed according to the volume ratio of 1:1 for 3-stage countercurrent extraction, the rubidium extraction raffinate and the rubidium-carrying organic phase are respectively obtained after phase separation and clarification, and the rubidium extraction raffinate is subjected to evaporation concentration by MVR to open the sodium and potassium. The extraction rates of rubidium, sodium and potassium are 99%, 5.3% and 7.1%, respectively.
Washing a rubidium-carrying organic phase: and (3) carrying out 3-stage countercurrent washing on the rubidium-carrying organic phase by using 2.60mol/L hydrochloric acid solution, mixing the rubidium-carrying organic phase with the hydrochloric acid solution according to the volume ratio of 15:1, and respectively obtaining sodium-potassium-containing solution and washing rubidium-carrying organic phase after phase separation and clarification. The sodium-potassium washing rate is 98% and 99%, respectively, and the rubidium loss rate is 15%.
Washing rubidium-carrying organic reverse extraction: 4-stage countercurrent stripping is carried out on the washing rubidium-carrying organic phase by using 0.60mol/L hydrochloric acid solution, the washing rubidium-carrying organic phase and the hydrochloric acid solution are mixed according to the volume ratio of 15:1, the rubidium-rich stripping solution and the empty organic phase are respectively obtained after phase separation and clarification, and the empty organic phase is returned to the rubidium extraction section for use.
Rubidium salt product preparation: and evaporating and concentrating the rubidium-rich strip liquor by adopting MVR to obtain a rubidium chloride product.
The results of the elemental analysis of the solution during the separation process for the cascade extraction-wash-strip-electrodialysis concentration process described above are shown in table 2.
TABLE 2
Example 2
The flow of the method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution provided in this example is shown in fig. 1, and a spodumene calcine leaching solution is used as a raw material, and the main components are shown in table 3.
TABLE 3 Table 3
| Element(s) | Li | Rb | Cs | K | Na | Ca | SO 4 2- | pH |
| Content of | 3.53 | 2.46 | 0.38 | 9.43 | 15.66 | 0.86 | 70.68 | 9.8 |
Removing calcium from leaching liquid: adding sodium carbonate with lithium equivalent of 80% into the leaching solution for decalcification, wherein the decalcification rate is more than 99.5%, and allowing the decalcified solution to enter a lithium extraction section.
Lithium extraction: the decalcified liquid adopts a diketone combined organic phosphorus and kerosene extraction system, the organic phase and decalcified liquid are mixed according to the volume ratio of 1:1 to carry out 3-level countercurrent extraction, the lithium raffinate and the lithium-loaded organic phase are respectively obtained after phase separation and clarification, and the lithium raffinate enters an electrodialysis concentration section. The diketone extractant does not extract rubidium and cesium basically, and the extraction rates of lithium, sodium and potassium are 95.2%, 0.55% and 0.17%, respectively.
Washing a lithium-loaded organic phase: and (3) carrying out 3-stage countercurrent washing on the lithium-carrying organic phase by using 0.05mol/L sulfuric acid solution, mixing the lithium-carrying organic phase with hydrochloric acid solution according to the volume ratio of 7:1, and respectively obtaining sodium-potassium-containing solution and washing lithium-carrying organic phase after phase separation and clarification. The sodium-potassium washing rates were 99.5% and 99.8%, respectively, and the lithium loss rate was 3.0%.
Washing and carrying lithium organic back extraction: and carrying out 3-level countercurrent stripping on the washed lithium-loaded organic phase by using 5mol/L sulfuric acid solution, mixing the washed lithium-loaded organic phase and the sulfuric acid solution according to the volume ratio of 9:1, and respectively obtaining a lithium-rich stripping solution and an empty organic phase after phase separation and clarification, wherein the empty organic phase is returned to a lithium extraction section for use.
Precipitating lithium: adding sodium carbonate with the molar weight of 2 times to the lithium-rich back extraction solution to carry out lithium precipitation to produce lithium carbonate, and returning the lithium precipitation mother solution to decalcification of the leaching solution.
Electrodialysis concentration section: and carrying out primary concentration on the lithium raffinate by electrodialysis, returning produced fresh water to the leaching pulp washing after the ore calcine water leaching, and enabling the concentrated water to enter the cesium extraction section.
Cesium extraction: the pH of concentrated water (i.e. concentrated lithium raffinate) is firstly regulated to about 12.5 by adopting sodium hydroxide, then an extraction system of 0.8 mol/L4-tertiary butyl-2 (alpha-methylbenzyl) phenol (i.e. t-bambp) and sulfonated kerosene is adopted, organic phase and concentrated water are mixed according to the volume ratio of 1:3 for 4-level countercurrent extraction, cesium raffinate and cesium-carrying organic phase are respectively obtained after phase separation and clarification, and the cesium raffinate enters a rubidium extraction section. the t-bambp does not extract lithium basically, and the extraction rates of cesium, rubidium, sodium and potassium are 97%, 3.7%, 0.68% and 1.5%, respectively.
Washing cesium-loaded organic phase: and (3) carrying out 8-stage countercurrent washing on the cesium-carrying organic phase by using 0.5mol/L sulfuric acid solution, mixing the cesium-carrying organic phase with the sulfuric acid solution according to the volume ratio of 5:1, and respectively obtaining rubidium-containing washing liquid and washing cesium-carrying organic phase after phase separation and clarification. The washing rate of rubidium and sodium is about 98%, the washing rate of potassium is more than 99%, and the loss rate of cesium is 13%.
Washing cesium-carrying organic phase extraction: 4-stage countercurrent stripping is carried out on the washing cesium-carrying organic phase by using 0.20mol/L sulfuric acid solution, the washing cesium-carrying organic phase and the sulfuric acid solution are mixed according to the volume ratio of 20:1, the cesium-rich stripping solution and the empty organic phase are respectively obtained after phase separation and clarification, and the empty organic phase is returned to the cesium extraction section for use.
Cesium salt product preparation: and evaporating and concentrating the cesium-rich back extraction liquid by adopting MVR to obtain a cesium sulfate product.
Rubidium extraction: the pH of the cesium extraction raffinate is regulated to about 13.5 by adopting sodium hydroxide, then a 2 mol/L4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene extraction system is adopted, the organic phase and the cesium extraction raffinate are mixed according to the volume ratio of 2:1 for 3-stage countercurrent extraction, the rubidium extraction raffinate and the rubidium-carrying organic phase are respectively obtained after phase separation and clarification, and the rubidium extraction raffinate is subjected to evaporation concentration by adopting MVR to open the path of sodium and potassium. The extraction rates of rubidium, sodium and potassium are 99%, 7.5% and 10%, respectively.
Washing a rubidium-carrying organic phase: 4-level countercurrent washing is carried out on the rubidium-carrying organic phase by using 0.74mol/L sulfuric acid solution, the rubidium-carrying organic phase and the sulfuric acid solution are mixed according to the volume ratio of 10:1, and the sodium-potassium-containing solution and the washing rubidium-carrying organic phase are respectively obtained after phase separation and clarification. The sodium-potassium washing rate is 98% and 99%, respectively, and the rubidium loss rate is 15%.
Washing rubidium-carrying organic reverse extraction: and carrying out 3-stage countercurrent stripping on the washing rubidium-carrying organic phase by using 0.42mol/L sulfuric acid solution, mixing the washing rubidium-carrying organic phase with the sulfuric acid solution according to the volume ratio of 20:1, and respectively obtaining rubidium-rich stripping liquid and an empty organic phase after phase separation and clarification, wherein the empty organic phase is returned to the rubidium extraction section for use.
Rubidium salt product preparation: and evaporating and concentrating the rubidium-rich strip liquor by adopting MVR to obtain a rubidium sulfate product.
The results of the elemental analysis of the solution during the separation process for the cascade extraction-wash-strip-electrodialysis concentration process described above are shown in table 4.
TABLE 4 Table 4
Various modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing teachings and are intended to be included within the scope of the following claims.
Claims (10)
1. A method for comprehensively recovering lithium, rubidium and cesium from lithium ore leaching solution, which is characterized by comprising the following steps:
s1, adding sodium carbonate into the lithium ore leaching solution after impurity removal to remove calcium;
s2, mixing the decalcified liquid obtained in the step S1 with an extractant, performing 1-10-level countercurrent extraction, and separating phases after extraction balance to obtain a raffinate and a lithium-loaded organic phase; the lithium-loaded organic phase is transferred to the step S2, and the lithium extraction residual liquid is transferred to the step S6;
s3, mixing the lithium-loaded organic phase obtained in the step S2 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a washing liquid containing sodium and potassium and a washing lithium-loaded organic phase, wherein the washing liquid containing sodium and potassium returns to the step S2 for extracting lithium;
s4, mixing the washed lithium-loaded organic phase obtained in the step S3 with the strip liquor, carrying out 1-10-level countercurrent or cross-current strip extraction, and carrying out phase separation after extraction balance to obtain a lithium-rich strip liquor and an empty organic phase, wherein the empty organic phase returns to the step S2 as an extractant to participate in extraction;
s5, adding sodium carbonate into the lithium-rich strip liquor obtained in the step S4 to carry out lithium precipitation to obtain a lithium precipitation mother liquor and a lithium carbonate product, and returning the lithium precipitation mother liquor to the step S1 for decalcification of the lithium ore leaching solution;
s6, carrying out electrodialysis concentration on the lithium raffinate obtained in the step S2 to obtain fresh water and concentrated water;
s7, mixing the concentrated water obtained in the step S6 with an extractant to perform 1-10-level countercurrent extraction after regulating the pH value, and separating phases after extraction balance to obtain cesium-carrying organic phase and cesium-extracting residual liquid; the cesium-loaded organic phase is transferred to step S8, and the cesium extraction residual liquid is transferred to step S11;
s8, mixing the cesium-carrying organic phase obtained in the step S7 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a rubidium-containing washing liquid and a washing cesium-carrying organic phase, wherein the rubidium-containing washing liquid returns to the step S7 to continuously extract cesium;
s9, mixing the cesium-loaded organic phase obtained in the step S8 with the strip liquor to perform 1-10-level countercurrent or cross-current strip extraction, and separating phases after extraction balance to obtain cesium-enriched strip liquor and empty organic phase, wherein the empty organic phase returns to the step S7 to be used as an extractant to participate in extraction;
s10, evaporating and crystallizing the cesium-rich strip liquor obtained in the step S9 to obtain cesium salt products;
s11, regulating the pH value of the cesium extraction raffinate obtained in the step S7, mixing the cesium extraction raffinate with an extractant, carrying out 1-10-level countercurrent extraction, carrying out phase separation after extraction balance, obtaining rubidium extraction raffinate and a rubidium-carrying organic phase, and carrying out evaporative crystallization on the rubidium extraction raffinate to open a sodium potassium salt circuit;
s12, mixing the rubidium-carrying organic phase obtained in the step S11 with a washing liquid, and then carrying out 1-10-level countercurrent or cross-current washing to obtain a washing liquid containing sodium and potassium and a washing rubidium-carrying organic phase, wherein the washing liquid containing sodium and potassium returns to the step S11 for rubidium extraction;
s13, mixing the washing rubidium-carrying organic phase obtained in the step S12 with the strip liquor for carrying out 1-10-level countercurrent or cross-current strip extraction, and carrying out phase separation after extraction balance to obtain rubidium-rich strip liquor and an empty organic phase, wherein the empty organic phase returns to the step S11 as an extracting agent to participate in extraction;
s14, evaporating and crystallizing the rubidium-rich strip liquor obtained in the step S13 to obtain a rubidium salt product.
2. The method according to claim 1, wherein in the step S2, the extracting agent and the decalcified liquid are mixed according to a volume ratio of 1:10-10:1, and the single-stage extraction time is 1-30 min; the extractant is a combination of diketone compounds, organic phosphorus compounds and kerosene.
3. The method according to claim 1, wherein in step S3, the lithium-loaded organic phase and the washing liquid are mixed in a volume ratio of 1:1 to 20:1, and the single-stage washing time is 1 to 30min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.05-0.5 mol/L.
4. The method according to claim 1, wherein in step S4, the washing lithium-loaded organic phase and the stripping solution are mixed in a volume ratio of 1:1-50:1, and the single-stage stripping time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 5-15 mol/L.
5. The method according to claim 1, wherein in step S7, the concentrated water is adjusted to pH 9-13 by adding alkali; mixing the extractant and the concentrated water with the pH adjusted according to the volume ratio of 1:10-10:1, wherein the single-stage extraction time is 1-30 min; the extractant is a mixture of 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, and the concentration of the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol is 0.1-1 mol/L.
6. The method according to claim 1, wherein in step S8, the cesium-loaded organic phase and the washing liquid are mixed in a volume ratio of 1:1 to 20:1, and the single-stage washing time is 1 to 30min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with the acid concentration of 0.5-2 mol/L.
7. The method according to claim 1, wherein in step S9, the organic phase loaded with cesium is washed and the stripping solution is mixed according to a volume ratio of 1:1-50:1, and the single-stage stripping time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.1-1 mol/L.
8. The method according to claim 1, wherein in step S11, the pH of the cesium raffinate is adjusted to 11 to 14 by adding a base; the extractant is a mixture of 4-tertiary butyl-2 (alpha-methylbenzyl) phenol and sulfonated kerosene, and the concentration of the 4-tertiary butyl-2 (alpha-methylbenzyl) phenol is 1-5mol/L; the extractant and the cesium raffinate after pH adjustment are mixed according to the volume ratio of 1:10-10:1, and the single-stage extraction time is 1-30 min.
9. The method according to claim 1, wherein in step S12, the rubidium-carrying organic phase and the washing liquid are mixed in a volume ratio of 1:1-20:1, and the single-stage washing time is 1-30 min; the washing liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.5-5 mol/L.
10. The method of claim 1, wherein in step S13, the washing rubidium-carrying organic phase and the stripping solution are mixed in a volume ratio of 1:1-50:1, and the single-stage stripping time is 1-30 min; the back extraction liquid is one or more of hydrochloric acid, sulfuric acid or nitric acid solution with acid concentration of 0.3-2 mol/L.
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