CN112226632B - Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent - Google Patents
Method for selectively extracting and precipitating lithium in lithium mother liquor by using hydrophobic eutectic solvent Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 62
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 230000005496 eutectics Effects 0.000 title claims abstract description 53
- 239000002904 solvent Substances 0.000 title claims abstract description 53
- 230000002209 hydrophobic effect Effects 0.000 title claims abstract description 44
- 239000012452 mother liquor Substances 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims abstract description 18
- 230000001376 precipitating effect Effects 0.000 title abstract 2
- 238000000605 extraction Methods 0.000 claims abstract description 40
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims abstract description 20
- 238000001556 precipitation Methods 0.000 claims abstract description 18
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005642 Oleic acid Substances 0.000 claims abstract description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- ODTSDWCGLRVBHJ-UHFFFAOYSA-M tetrahexylazanium;chloride Chemical compound [Cl-].CCCCCC[N+](CCCCCC)(CCCCCC)CCCCCC ODTSDWCGLRVBHJ-UHFFFAOYSA-M 0.000 claims abstract description 3
- SNNIPOQLGBPXPS-UHFFFAOYSA-M tetraoctylazanium;chloride Chemical compound [Cl-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC SNNIPOQLGBPXPS-UHFFFAOYSA-M 0.000 claims abstract description 3
- 239000008346 aqueous phase Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000012071 phase Substances 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000010828 elution Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 5
- 150000003242 quaternary ammonium salts Chemical group 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000013517 stratification Methods 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 229910001416 lithium ion Inorganic materials 0.000 description 6
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000000638 solvent extraction Methods 0.000 description 4
- 150000003983 crown ethers Chemical class 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 2
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- -1 CO 3 2- Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000000658 coextraction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000374 eutectic mixture Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002433 hydrophilic molecules Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
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- 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
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- 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
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3846—Phosphoric acid, e.g. (O)P(OH)3
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Abstract
Description
技术领域technical field
本发明涉及一种疏水性低共熔溶剂选择性萃取沉锂母液中锂的方法。The invention relates to a method for selectively extracting lithium in a precipitation lithium mother liquor with a hydrophobic low eutectic solvent.
背景技术Background technique
锂作为新能源金属和战略资源，广泛应用于陶瓷、锂电池、核能、玻璃等领域。随着全球新能源的不断发展，用于动力和储能的锂离子电池产业迅速发展，对电池级碳酸锂(Li2CO3)的需求不断增加。目前，制备碳酸锂通常采用碳酸钠作为沉淀剂，但在这一过程中，产生了大量高钠锂比的沉锂母液。沉锂母液组成较为复杂，其中Li+浓度较高(1.42g/L)，且含有大量Na+(55.62g/L)、CO3 2-、Cl-或SO4 2-。而对于沉锂母液的处理方法则是直接将其排放回盐湖卤水或回收系统中，这不仅会导致CO3 2-、Cl-或SO4 2-等杂质的富集，而且会降低锂盐产品的质量。因此，高效的沉锂母液锂离子回收工艺对于整个锂产品工业发展具有十分重要的意义。As a new energy metal and strategic resource, lithium is widely used in ceramics, lithium batteries, nuclear energy, glass and other fields. With the continuous development of new energy around the world, the lithium-ion battery industry for power and energy storage has developed rapidly, and the demand for battery-grade lithium carbonate (Li 2 CO 3 ) has continued to increase. At present, sodium carbonate is usually used as a precipitant for the preparation of lithium carbonate, but in this process, a large amount of precipitation mother liquor with high sodium-to-lithium ratio is produced. The composition of the precipitation lithium mother liquor is relatively complex, in which the Li + concentration is relatively high (1.42g/L), and contains a large amount of Na + (55.62g/L), CO 3 2- , Cl - or SO 4 2- . The treatment method for the precipitation mother liquor is to directly discharge it back to the salt lake brine or recovery system, which will not only lead to the enrichment of impurities such as CO 3 2- , Cl - or SO 4 2- , but also reduce the production of lithium salts. the quality of. Therefore, an efficient lithium ion recovery process from the precipitation mother liquor is of great significance for the development of the entire lithium product industry.
溶剂萃取法具有连续萃取能耗低、易于工业化、操作简单、萃取剂用量少等优点。溶剂萃取法从盐湖卤水中提取锂离子目前应用研究最广泛。常用的萃取剂和萃取体系有β-双酮、冠醚、有机膦和离子液体。然而，酮类萃取剂溶损较为严重，且成本较高。冠醚价格昂贵，冠醚环上的氧原子易于与水形成氢键，从而产生溶损。传统萃取体系通常采用挥发性有机溶剂作为稀释剂，不仅影响萃取系统的循环寿命，而且会造成环境污染。有研究人员提出采用具有低蒸汽压、高热化学稳定性的离子液体代替传统有机溶剂，但是其提纯困难、合成复杂、成本高，极大地限制了实际应用。The solvent extraction method has the advantages of low energy consumption for continuous extraction, easy industrialization, simple operation, and less amount of extractant. Solvent extraction is the most widely used method to extract lithium ions from salt lake brine. Commonly used extractants and extraction systems are β-diketones, crown ethers, organic phosphines and ionic liquids. However, the ketone extractant has serious dissolution loss and high cost. Crown ethers are expensive, and the oxygen atoms on the crown ether ring are prone to form hydrogen bonds with water, resulting in dissolution loss. Traditional extraction systems usually use volatile organic solvents as diluents, which not only affect the cycle life of the extraction system, but also cause environmental pollution. Some researchers have proposed to use ionic liquids with low vapor pressure and high thermochemical stability to replace traditional organic solvents, but their purification, complex synthesis, and high cost greatly limit practical applications.
低共熔溶剂(DES)是一类新型的离子液体类似物，由两组分或三组分共晶混合物通过氢键相互作用自缔合而成。DES因其挥发性低、成本低、可生物降解、毒性低而被认为是绿色溶剂，具有广阔的应用前景。低共熔溶剂一般是由亲水化合物组成，易与水形成氢键，进而破坏低共熔溶剂组分间的氢键。因此，将DES的应用范围从有机相扩展至水相显得尤为重要。构建疏水性低共熔溶剂(HDESs)用于含水体系，不仅避免了使用挥发性有机溶剂所导致的环境污染，而且降低了以昂贵离子液体作为萃取剂的使用成本，在溶剂萃取中具有广泛的应用潜力。Deep eutectic solvents (DES) are a new class of ionic liquid analogs formed by self-association of two- or three-component eutectic mixtures through hydrogen bonding interactions. DES is considered as a green solvent due to its low volatility, low cost, biodegradability, and low toxicity, and has broad application prospects. Deep eutectic solvents are generally composed of hydrophilic compounds, which are easy to form hydrogen bonds with water, thereby breaking the hydrogen bonds between the deep eutectic solvent components. Therefore, it is particularly important to extend the application range of DES from organic to aqueous phases. The construction of hydrophobic deep eutectic solvents (HDESs) for aqueous systems not only avoids the environmental pollution caused by the use of volatile organic solvents, but also reduces the cost of using expensive ionic liquids as extractants, and has a wide range of applications in solvent extraction. application potential.
发明内容SUMMARY OF THE INVENTION
针对现有技术中存在不足，本发明提供了一种基于疏水性低共熔溶剂的选择性萃取沉锂母液中锂的方法，该萃取体系以磷酸三丁酯作为萃取剂，疏水性低共熔溶剂作为共萃取剂和稀释剂，具有效率高、选择性好、操作方便、绿色无污染等优点。In view of the deficiencies in the prior art, the present invention provides a method for selectively extracting lithium from a mother liquor of precipitation lithium based on a hydrophobic eutectic solvent. The extraction system uses tributyl phosphate as an extractant, and the hydrophobic eutectic As a co-extractant and diluent, the solvent has the advantages of high efficiency, good selectivity, convenient operation, green and pollution-free.
本发明是通过以下技术方案实现上述技术目的的。The present invention achieves the above technical purpose through the following technical solutions.
一种基于疏水性低共熔溶剂选择性萃取沉锂母液中锂的方法，包括如下步骤：A method for selectively extracting lithium in a precipitation lithium mother liquor based on a hydrophobic eutectic solvent, comprising the steps of:
(1)制备疏水性低共熔溶剂：(1) Preparation of hydrophobic deep eutectic solvent:
按照摩尔比将氢键供体和氢键受体混合，在50℃-80℃的加热条件下搅拌4～12小时，得到澄清透明溶液；即疏水性低共熔溶剂；所述氢键供体为油酸，氢键受体为季铵盐；Mix the hydrogen bond donor and the hydrogen bond acceptor according to the molar ratio, and stir for 4-12 hours under the heating condition of 50°C-80°C to obtain a clear and transparent solution; that is, a hydrophobic deep eutectic solvent; the hydrogen bond donor It is oleic acid, and the hydrogen bond acceptor is quaternary ammonium salt;
(2)萃取：(2) Extraction:
以步骤(1)制备的疏水性低共熔溶剂和萃取剂磷酸三丁酯构成有机相，将该有机相与氨水调控pH值的含锂水相混合，剧烈震荡下萃取一段时间，离心分层，得到萃取相和萃余液；The organic phase is formed with the hydrophobic deep eutectic solvent prepared in step (1) and the extractant tributyl phosphate, the organic phase is mixed with the lithium-containing water phase of which the pH value is regulated by ammonia water, extracted for a period of time under vigorous shaking, and centrifuged for layering. , to obtain the extract phase and the raffinate;
(3)洗脱：(3) Elution:
将步骤(2)所得的萃取相用盐酸洗脱，洗脱后，离心分层，得到富锂溶液。The extract phase obtained in step (2) is eluted with hydrochloric acid, and after elution, centrifuged and separated to obtain a lithium-rich solution.
步骤(1)中，所述的氢键供体和氢键受体的摩尔比为(1～3)：1。In step (1), the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is (1-3):1.
进一步地，所述的氢键供体和氢键受体的摩尔比为3：1，搅拌时间为6小时。Further, the molar ratio of the hydrogen bond donor and the hydrogen bond acceptor is 3:1, and the stirring time is 6 hours.
步骤(1)中，所述的季铵盐为四丁基氯化铵、四己基氯化铵、四辛基氯化铵中的至少一种。In step (1), the quaternary ammonium salt is at least one of tetrabutylammonium chloride, tetrahexylammonium chloride and tetraoctylammonium chloride.
步骤(2)中，所述有机相中，疏水性低共熔溶剂在有机相中体积分数为10～40％。In step (2), in the organic phase, the volume fraction of the hydrophobic deep eutectic solvent in the organic phase is 10-40%.
步骤(2)中，含锂水相中氨水的浓度为0.5～2.5mol/L。In step (2), the concentration of ammonia water in the lithium-containing aqueous phase is 0.5-2.5 mol/L.
步骤(2)中，有机相与含锂水相体积比为0.4～1.2。In step (2), the volume ratio of the organic phase to the lithium-containing aqueous phase is 0.4-1.2.
步骤(2)中，剧烈震荡的震荡速度为130rpm～200rpm。In step (2), the shaking speed of the violent shaking is 130 rpm to 200 rpm.
步骤(3)中，所述盐酸浓度为0.5～2.5mol/L，洗脱时间为20～40分钟。In step (3), the concentration of hydrochloric acid is 0.5-2.5 mol/L, and the elution time is 20-40 minutes.
本发明的有益效果：Beneficial effects of the present invention:
1)本发明首次提出了基于疏水性低共熔溶剂的萃取体系用于沉锂母液中锂的选择性萃取。低共熔溶剂具有合成简单、价格低廉、环境友好等优点，本发明制备的基于疏水性低共熔溶剂的萃取体系可以选择性萃取锂。1) The present invention proposes for the first time an extraction system based on a hydrophobic deep eutectic solvent for the selective extraction of lithium in the precipitation mother liquor. The deep eutectic solvent has the advantages of simple synthesis, low price, environmental friendliness, etc. The extraction system based on the hydrophobic deep eutectic solvent prepared by the present invention can selectively extract lithium.
2)本发明所述的基于疏水性低共熔溶剂的萃取体系具有较好的萃取率。2) The extraction system based on the hydrophobic deep eutectic solvent according to the present invention has a better extraction rate.
3)本发明所述的基于疏水性低共熔溶剂的萃取体系具有操作简单、安全性好等优点。且低共熔溶剂易于分离，不会造成水体二次污染，具有较好的经济和社会效益。3) The extraction system based on the hydrophobic low eutectic solvent of the present invention has the advantages of simple operation, good safety and the like. In addition, the low eutectic solvent is easy to separate, does not cause secondary pollution of the water body, and has good economic and social benefits.
附图说明Description of drawings
图1为本发明实施例所依据的沉锂母液中锂萃取的方法流程图。Fig. 1 is the method flow chart of lithium extraction in the lithium precipitation mother liquor on which the embodiment of the present invention is based.
图2为萃取体系下有机相-含锂水相两相界面的实拍图。Figure 2 is a real shot of the organic phase-lithium-containing aqueous phase two-phase interface under the extraction system.
具体实施方式Detailed ways
下面结合具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。The present invention will be further described below with reference to specific embodiments, but the protection scope of the present invention is not limited thereto.
实施例1Example 1
(1)疏水性低共熔溶剂的制备：将四丁基氯化铵和油酸按照摩尔比1：(1～3)混合，于50℃～80℃的加热条件下搅拌4～12小时，得到澄清透明溶液，即疏水性低共熔溶剂。(1) Preparation of hydrophobic deep eutectic solvent: Mix tetrabutylammonium chloride and oleic acid in a molar ratio of 1: (1-3), and stir for 4-12 hours under heating conditions of 50°C to 80°C, A clear transparent solution, a hydrophobic deep eutectic solvent, was obtained.
(2)有机相制备：磷酸三丁酯作为萃取剂，疏水性低共熔溶剂作为共萃剂和稀释剂，疏水性低共熔溶剂的体积分数变化为10～40％。(2) Preparation of organic phase: tributyl phosphate is used as extractant, hydrophobic deep eutectic solvent is used as co-extraction agent and diluent, and the volume fraction of hydrophobic deep eutectic solvent varies from 10 to 40%.
(3)含锂水相制备：配置浓度为0.1g/L的水合氯化锂溶液，通过调控氨水浓度(0.5～2.5mol/L)进而调节含锂水相pH值。(3) Preparation of lithium-containing aqueous phase: configure a hydrated lithium chloride solution with a concentration of 0.1 g/L, and adjust the pH value of the lithium-containing aqueous phase by adjusting the ammonia concentration (0.5-2.5 mol/L).
(4)将步骤1中的有机相与步骤2中的含锂水相混合，剧烈震荡下萃取一段时间，离心分层，得到萃取相和萃余液。(4) Mix the organic phase in step 1 with the lithium-containing aqueous phase in step 2, extract under vigorous shaking for a period of time, and centrifuge for stratification to obtain an extraction phase and a raffinate.
(5)将所得的萃取相用盐酸洗脱，洗脱后，离心分层，得到富锂溶液。(5) The obtained extract phase is eluted with hydrochloric acid, and after the elution, centrifuged and separated to obtain a lithium-rich solution.
实施例2Example 2
萃取步骤同实施例1步骤4。The extraction step is the same as that of step 4 in Example 1.
其中，有机相与含锂水相体积相同，在有机相中疏水性低共熔溶剂体积分数为10％，氨水浓度为1mol/L的含锂溶液条件下，实施例1步骤1中所制备的不同摩尔比的疏水性低共熔溶剂对锂离子都具有萃取效果。其中当四丁基氯化铵和油酸摩尔比为1：1、1：2和1：3时，对应的萃取率分别为45％、52.4％和63.1％。当疏水性低共熔溶剂中四丁基氯化铵和油酸的摩尔比为1：3时，其对含锂溶液中锂的萃取率最大。Among them, the organic phase and the lithium-containing aqueous phase have the same volume, and under the condition that the volume fraction of the hydrophobic eutectic solvent in the organic phase is 10%, and the ammonia concentration is 1 mol/L of the lithium-containing solution, the prepared in step 1 of Example 1 Different molar ratios of hydrophobic deep eutectic solvents can extract lithium ions. When the molar ratios of tetrabutylammonium chloride and oleic acid were 1:1, 1:2 and 1:3, the corresponding extraction rates were 45%, 52.4% and 63.1%, respectively. When the molar ratio of tetrabutylammonium chloride and oleic acid in the hydrophobic deep eutectic solvent was 1:3, the extraction rate of lithium from the lithium-containing solution was the highest.
实施例3Example 3
萃取步骤同实施例1步骤4。The extraction step is the same as that of step 4 in Example 1.
其中，有机相与含锂水相体积相同，疏水性低共熔溶剂中四丁基氯化铵和油酸的摩尔比为1：3。在有机相中疏水性低共熔溶剂体积分数为10％的条件下，疏水性低共熔溶剂对不同氨水浓度配置的含锂水相中的锂离子都具有萃取效果。当氨水浓度大于1.5mol/L时，该疏水性低共熔溶剂对含锂溶液中锂的萃取率均在70％以上。Wherein, the organic phase and the lithium-containing aqueous phase have the same volume, and the molar ratio of tetrabutylammonium chloride and oleic acid in the hydrophobic deep eutectic solvent is 1:3. Under the condition that the volume fraction of the hydrophobic deep eutectic solvent in the organic phase is 10%, the hydrophobic deep eutectic solvent has an extraction effect on lithium ions in the lithium-containing aqueous phase prepared with different ammonia concentrations. When the concentration of ammonia water is greater than 1.5 mol/L, the extraction rate of lithium in the lithium-containing solution by the hydrophobic deep eutectic solvent is all above 70%.
实施例4Example 4
萃取步骤同实施例1步骤4。The extraction step is the same as that of step 4 in Example 1.
其中，有机相与含锂水相体积相同，疏水性低共熔溶剂中四丁基氯化铵和油酸的摩尔比为1：3。在水相中氨水浓度为1.5mol/L的含锂溶液条件下，疏水性低共熔溶剂体积分数为10～40％时，其对含锂溶液中的锂离子都具有萃取效果。当低共熔溶剂的体积分数大于10％时，该疏水性低共熔溶剂对含锂溶液中锂的萃取率均在70％以上。随着低共熔溶剂用量的增大，其分配系数也随之增大，在低共熔溶剂用量为30％时，分配系数达到最大。继续增大低共熔溶剂的体积分数会稀释磷酸三丁酯萃取剂浓度，将导致萃取率降低。Wherein, the organic phase and the lithium-containing aqueous phase have the same volume, and the molar ratio of tetrabutylammonium chloride and oleic acid in the hydrophobic deep eutectic solvent is 1:3. Under the condition of a lithium-containing solution with an ammonia concentration of 1.5 mol/L in the aqueous phase, when the volume fraction of the hydrophobic deep eutectic solvent is 10-40%, it has an extraction effect on lithium ions in the lithium-containing solution. When the volume fraction of the deep eutectic solvent is greater than 10%, the extraction rate of lithium in the lithium-containing solution by the hydrophobic deep eutectic solvent is above 70%. With the increase of the amount of deep eutectic solvent, the distribution coefficient also increases, and the distribution coefficient reaches the maximum when the amount of deep eutectic solvent is 30%. Continuing to increase the volume fraction of deep eutectic solvent will dilute the concentration of the tributyl phosphate extractant, which will result in lower extraction yields.
实施例5Example 5
萃取步骤同实施例1步骤4。The extraction step is the same as that of step 4 in Example 1.
其中，疏水性低共熔溶剂中四丁基氯化铵和油酸的摩尔比为1：3，有机相中疏水性低共熔溶剂的体积分数为30％。在水相中氨水浓度为1.5mol/L的含锂溶液条件下，改变有机相和水相的体积比(0.4～1.2)进行萃取实验。随着有机相和水相比值的增大，锂的萃取率随之增大。当相比为1时，该疏水性低共熔溶剂对含锂溶液中锂的萃取率均在70％以上。当相比继续增大时，锂的萃取率继续增大，但其分配比降低。Wherein, the molar ratio of tetrabutylammonium chloride and oleic acid in the hydrophobic deep eutectic solvent is 1:3, and the volume fraction of the hydrophobic deep eutectic solvent in the organic phase is 30%. The extraction experiment was carried out by changing the volume ratio (0.4-1.2) of the organic phase to the aqueous phase under the condition of a lithium-containing solution with an ammonia concentration of 1.5 mol/L in the aqueous phase. With the increase of the ratio of organic phase to water, the extraction rate of lithium increases. When the ratio is 1, the extraction rate of lithium in the lithium-containing solution by the hydrophobic deep eutectic solvent is all above 70%. When the ratio continues to increase, the extraction rate of lithium continues to increase, but its distribution ratio decreases.
实施例6Example 6
萃取步骤同实施例1步骤4。The extraction step is the same as that of step 4 in Example 1.
其中，疏水性低共熔溶剂中四丁基氯化铵和油酸的摩尔比为1：3，有机相中疏水性低共熔溶剂的体积分数为30％。将有机相与等体积的沉锂母液混合，用于沉锂母液中锂的提取。在钠锂比为11.3的沉锂母液条件下，调节沉锂母液中氨水浓度为1.5mol/L，并与无氨水添加的沉锂母液进行比较，相关萃取数据列于表1。Wherein, the molar ratio of tetrabutylammonium chloride and oleic acid in the hydrophobic deep eutectic solvent is 1:3, and the volume fraction of the hydrophobic deep eutectic solvent in the organic phase is 30%. The organic phase is mixed with an equal volume of the precipitation mother liquor for lithium extraction from the precipitation mother liquor. Under the conditions of the precipitation lithium mother liquor with the sodium-to-lithium ratio of 11.3, the concentration of ammonia water in the precipitation lithium mother liquor was adjusted to 1.5 mol/L, and compared with the precipitation lithium mother liquor without the addition of ammonia water. The relevant extraction data are listed in Table 1.
表1基于疏水性低共熔溶剂萃取体系萃取沉锂母液中的锂Table 1 Extraction of lithium in lithium precipitation mother liquor based on hydrophobic deep eutectic solvent extraction system
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。The described embodiment is the preferred embodiment of the present invention, but the present invention is not limited to the above-mentioned embodiment, without departing from the essence of the present invention, any obvious improvement, replacement or All modifications belong to the protection scope of the present invention.
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