阅读说明：本技术 一种基于酮基功能化离子液体萃取分离锂的方法 (A method of based on ketone group functionalized ion liquid extraction and separation lithium ) 是由 王均凤 杨事成 王道广 李维超 张锁江 于 2019-10-08 设计创作，主要内容包括：本发明涉及一种基于酮基功能化离子液体萃取分离锂的方法。该方法以由季铵盐或季磷盐与β-双酮经两步法工艺合成的酮基功能化离子液体作为萃取剂,以酮基功能化离子液体的环己烷或三烃基膦氧化物溶液为萃取有机相,以含锂离子的卤水作为原料液,经萃取后分离得负载有机相和萃余液,使用反萃剂对负载有机相进行反萃取,离心后得到纯化的锂溶液与可回收的离子液体。本发明合成的离子液体与水不互溶,对锂的萃取效率高、分离效果好,可再生重复利用。(The present invention relates to a kind of methods based on ketone group functionalized ion liquid extraction and separation lithium.This method is using the ketone group functionalized ion liquid that is synthesized by quaternary ammonium salt or quaternary alkylphosphonium salt and β-diketone through two-step process as extractant, it is extraction organic phase with the hexamethylene of ketone group functionalized ion liquid or trihydrocarbyl phosphine oxide solution, using the brine containing lithium ion as material liquid, load organic phases and raffinate are separated to obtain after extracting, load organic phases are stripped using stripping agent, the lithium solution purified after centrifugation and recyclable ionic liquid.The ionic liquid that the present invention synthesizes and water are immiscible, good separating effect high to the extraction efficiency of lithium, renewable recycling.)

1. a kind of method based on ketone group functionalized ion liquid extraction and separation lithium, which is characterized in that this method is according to following step It is rapid to carry out:

1) synthesize ketone group functionalized ion liquid: the first step is that β-diketone and ammonia pass through acid-base neutralization reaction generation ketone ammonium salt；The Two steps are that ion-exchange reactions occurs for ketone ammonium salt and quaternary ammonium salt or quaternary alkylphosphonium salt, obtain ketone group functionalized ion liquid；

β-the diketone is hexafluoroacetylacetone, benzoyltrifluoroacetone, 2- thioyl trifluoroacetone, the fluoro- 1- of 4,4,4- tri- Any one in (2- furyl) -1,3- diacetyl, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl；

The ammonia is methanol solution, ammonia or the ammonium hydroxide of ammonia；

The quaternary ammonium salt is methyl tricapryl ammonium chloride or tetrabutylammonium chloride；The quaternary alkylphosphonium salt is tetrabutyl phosphorus chloride；

Contain β-diketone functional group in the ketone group functionalized ion liquid；

2) configuration extraction organic phase: ketone group functionalized ion liquid is dissolved in hexamethylene by a certain concentration or trihydrocarbyl phosphine aoxidizes Extraction organic phase is obtained in object；

The concentration of ketone group functionalized ion liquid is 0.1~1.2mol/L in the extraction organic phase；

3) extract: using brine containing lithium as material liquid, pH value is 1~14, and lithium concentration is 0.05~10g/L；By step 2) Obtained extraction organic phase is that 3:1~1:10 is mixed with material liquid by volume, under conditions of temperature is 10~70 DEG C, stirring Extract 5~360min, isolated raffinate and load organic phases after centrifugation or stratification；

4) be stripped: under conditions of temperature is 10~70 DEG C, the load organic phases that step 3) is obtained are with 0.01~12mol/L's Hydrochloric acid or sulfuric acid solution are stripped as stripping agent, wherein and load organic phases and the volume ratio of stripping agent are 10:1~1:1, The lithium solution and extraction organic phase for separating to purify after centrifugation or stratification；Gained extract organic phase return step 3) circulation make With.

2. the method according to claim 1, wherein the quaternary ammonium salt can also be tetrabutylammonium bromide or methyl three Octyl ammonium bromide；The quaternary alkylphosphonium salt can also be tetrabutyl phosphonium bromide phosphorus.

3. the method according to claim 1, wherein the cation in the ketone group functionalized ion liquid is season Ammonium ion or quaternary phosphonium radical ion, preferably methyl trioctylammonium radical ion, tetrabutylammonium radical ion, in tetrabutyl phosphorus radical ion Any one, structural formula respectively is:

4. the method according to claim 1, wherein β-diketone function in the ketone group functionalized ion liquid Group's anion, preferably hexafluoroacetylacetone ion, benzoyltrifluoroacetone ion, 2- thioyl trifluoroacetone ion, 4, In fluoro- 1- (2- the furyl) -1,3- diacetyl of 4,4- tri- ion, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl ion Any one, structural formula respectively is:

Technical field

The present invention relates to it is a kind of using ketone group functionalized ion liquid extraction brine in lithium method, belong to metal separation and Ion liquid abstraction technical field.

Background technique

Due to application of the lithium battery in terms of the consumer electronics and electric car in industry, so that lithium resource demand is shown The promotion of work, wherein, lithium carbonate can be not only used for positive electrode and electrolyte in lithium battery, and produce other positive electrodes Basic raw material.Still containing the lithium of higher concentration in a large amount of sinker mother liquors caused by lithium carbonate production technology, if directly arranging Putting will cause to waste.However, there is energy consumption is high, complex process, Yi Yin for the processing techniques such as existing freezing analysis sodium, precipitating analysis lithium The disadvantages of entering foreign ion is not suitable for industrial applications.And solvent extraction is recognized because of the advantages that easy to operate, output is big To be expected to become the High efficiency recovery of lithium resource in sinker mother liquor.But since sinker mother liquor is alkaline system, TBP- is not achieved FeCl₃The acidity of the tradition such as kerosene salt lake extraction lithium system, it is therefore desirable to seek a kind of suitable extracting system and be returned from the salt water Receive lithium.

To Li under β-diketone kind of extractants alkaline condition⁺Extraction have extraordinary effect.Chinese patent (publication number CN107779612A a kind of technique for extracting lithium from alkaline brine using β-diketone as extractant) is disclosed.But it is traditional Solvent-extraction system usually requires kerosene, chloroform, toluene etc. as solvent and accelerates phase point to reduce the viscosity of extraction organic phase From etc..But these solvents have very strong volatility, cause the increase of production cost and can cause environmental pollution.

The features such as high stability of ionic liquid, low-steam pressure, liquid journey is wide, becomes a kind of novel green solvent, It is expected to replace traditional volatile organic solvent.Chinese patent (publication number CN107673435A) utilizes hydroxy functionalized ion Liquid extracts aromatic compound as extractant from aqueous solution.But it is commonly used for the extraction of the glyoxaline ion liquid of extraction system Mechanism is usually cation exchange, causes glyoxaline cation to be switched in raffinate, causes the loss of ionic liquid and to ring The pollution in border.Therefore need a kind of more environmentally protective ionic liquid, make its both can under alkaline condition to lithium ion have compared with High extraction efficiency, while avoiding cation exchange mechanism.

Summary of the invention

In order to solve the above-mentioned problems of the prior art, ketone group functionalized ion liquid is utilized the present invention provides a kind of The method of extraction and separation lithium ion.Non-volatile first with ionic liquid, the advantages that stability is good, selects strong-hydrophobicity quaternary ammonium salt Or quaternary alkylphosphonium salt is introduced into ionic liquid anion and ketone is prepared as ionic liquid cation, while by β-diketone functional group Base functionalized ion liquid.Use ketone group functionalized ion liquid as extractant, the lithium ion in alkaline brine is extracted Separation is taken, the extraction system extraction efficiency is high and avoids the loss of ionic liquid cation.

What the purpose of the present invention was realized particular by following technical scheme:

Step 1) synthesizes ketone group functionalized ion liquid: using two-step process；The first step is that β-diketone and ammonia pass through acid Alkali neutralization reaction generates ketone ammonium salt；Second step is that ion-exchange reactions occurs for ketone ammonium salt and quaternary ammonium salt or quaternary alkylphosphonium salt, obtains ketone group Functionalized ion liquid.

β-the diketone is selected from hexafluoroacetylacetone, benzoyltrifluoroacetone, 2- thioyl trifluoroacetone, 4,4,4- Any one in three fluoro- 1- (2- furyl) -1,3- diacetyl, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl.

The ammonia is methanol solution, ammonia or the ammonium hydroxide of ammonia.

The quaternary ammonium salt is methyl tricapryl ammonium chloride or tetrabutylammonium chloride, and the quaternary alkylphosphonium salt is tetrabutyl chlorination Phosphorus.

Contain β-diketone functional group anion in the ketone group functionalized ion liquid, it is preferred that the β-diketone functional group Anion is hexafluoroacetylacetone ion, benzoyltrifluoroacetone ion, 2- thioyl trifluoroacetone ion, 4,4,4- tri- Fluoro- 1- (2- furyl) -1,3- diacetyl ion, 4,4,4- tri- fluoro- 1- (p-methylphenyl) -1,3- diacetyl ion it is any one Kind, structural formula respectively is:

Cation in the ketone group functionalized ion liquid is quaternary ammonium radical ion or quaternary phosphonium radical ion；Preferably, described Quaternary ammonium radical ion is any one of methyl trioctylphosphine ammonium root cation, tetrabutyl ammonium root cation, and the quaternary phosphonium radical ion is Tetrabutyl phosphorus root cation, structural formula respectively are:

Step 2) configuration extraction organic phase: ketone group functionalized ion liquid is dissolved in hexamethylene or three hydrocarbon by a certain concentration Extraction organic phase is obtained in base phosphine oxide；

Preferably, the concentration of ketone group functionalized ion liquid is 0.1~1.2mol/L in the extraction organic phase.

Preferably, the trihydrocarbyl phosphine oxide is liquid oxidatively phosphine Cyanex923 or trialkyl phosphine TRPO.

Step 3) extraction: using brine containing lithium as material liquid, pH is 1~14, and lithium concentration is 0.05~10g/L；It will The extraction organic phase that step 2) obtains is that 3:1~1:10 is mixed with material liquid by volume, the condition for being 10~70 DEG C in temperature Under, stirring extracts 5~360min, isolated raffinate and load organic phases after stratification.

Preferably, the material liquid is sinker mother liquor or salt lake bittern.

Step 4) back extraction: under conditions of temperature is 10~70 DEG C, load organic phases that step 3) is obtained with 0.01~ The hydrochloric acid or sulfuric acid solution of 12mol/L is stripped as stripping agent, wherein load organic phases and the volume ratio of stripping agent are 10:1~1:1, after stratification the chloride containing lithium of isolated purifying or the lithium solution of lithium sulfate and ketone group containing functionalization from The extraction organic phase of sub- liquid；Gained extracts organic phase return step 3) it is recycled.

Further, the quaternary ammonium salt can also be methyl trioctylphosphine ammonium bromide or tetrabutylammonium bromide, the quaternary alkylphosphonium salt It can be tetrabutyl phosphonium bromide phosphorus.

Further, lithium solution and extraction are organic in the separation and step 4) of raffinate and load organic phases in step 3) Centrifuge separation may be selected in the separation of phase, it is preferred that centrifugal rotational speed 2000-8000r/min, centrifugation time 2-10min.

β-double ketone structure with excellent extraction ability is introduced into ionic liquid anion by the present invention, simultaneous selection tool There is hydrophobic quaternary ammonium salt/quaternary alkylphosphonium salt as ionic liquid cation, has synthesized ketone group functionalization ionic liquid through two-step process Body, and be dissolved in hexamethylene or trihydrocarbyl phosphine oxide as extraction organic phase, hybrid extraction is carried out to brine containing lithium, Load organic phases and raffinate containing lithium are isolated to, lithium is stripped using stripping agent, is isolated to purifying Lithium solution and the extraction organic phase that can be recycled.

The beneficial effects of the present invention are as follows:

(1) a kind of method based on ketone group functionalized ion liquid extraction and separation lithium of the present invention, realizes from brine containing lithium The extraction organic phase of ketone group containing functionalized ion liquid can be recycled while isolating and purifying the target of lithium, technical performance is excellent More.

(2) present invention has the advantages that designability using ionic liquid, and the ketone group functional group of lithium extraction will be promoted to draw Enter into its anion, not only can guarantee the environmentally protective advantage of ionic liquid, but also have both high extraction ability.

(3) extraction efficiency of the present invention is high, and good separating effect, ionic liquid will not have loss after extraction, has wide answer Use prospect.

Specific embodiment

In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to the present invention It is further elaborated, but the present invention is not restricted to following example.