CN106148697A - A kind of rare earth synergistic extractant system and utilize the method that this synergistic extractant system extracts separation of rare earth elements from nitric rare earth feed liquid - Google Patents
A kind of rare earth synergistic extractant system and utilize the method that this synergistic extractant system extracts separation of rare earth elements from nitric rare earth feed liquid Download PDFInfo
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Abstract
The present invention provides a kind of rare earth synergistic extractant system and the method utilizing this synergistic extractant system to extract separation of rare earth elements from nitric rare earth feed liquid, described rare earth synergistic extractant system is with the mixed liquor of quaternary phosphonium ionic liquid and neutral organophosphorus (phosphine) kind of extractants as extraction phase, and water is strip liquor.The method utilizing this synergistic extractant system to extract separation of rare earth elements from nitric rare earth feed liquid comprises the following steps: the mixed liquor of preparation quaternary phosphonium ionic liquid and neutral organophosphorus (phosphine) kind of extractants is as extraction phase, it is optionally added into salting-out agents, regulation material liquid pH, is obtained by extraction the extract containing rare earth and raffinate；Water, as strip liquor, carries out back extraction to the extract containing rare earth, obtains the anti-stripping agent containing rare earth, it is achieved the extraction of rare earth element separates.The present invention is effectively increased the separation to rare earth element, increases the extraction efficiency to rare earth.Extraction process, without saponification, eliminates ammonia nitrogen waste water and discharges problem the most up to standard from source, and in extraction system, strip liquor is water, green economy.
Description
Technical field
The invention belongs to technical field of rare-earth separation, relate to a kind of rare earth synergistic extractant system and utilize this synergistic extractant system
The method extracting separation of rare earth elements from nitric rare earth feed liquid.
Background technology
Rare earth is important mineral resources, has the good reputation of " industry vitamin ".Each developed country pair of the world
The extraction of rare earth separates and all pays much attention to, especially because the reinforcement day by day of environmental protection, the low energy consumption of rare-earth separating
Green system has obtained extensive attention.
Up to now, alkali phosphorus (phosphine) acid is the extractant that the selectivity of extracting and separating rear earth element is best.
Be widely used in the rare earth solvent extraction first generation, P204 and P507 of second filial generation flow process is this kind of extractants
Representative, the development to Hydrometallurgical Industry of Rare Earths has played very big effect.Organophosphor (phosphine) kind of extractants
Become to be applied at present the most commonly used extractant of Hydrometallurgical Industry of Rare Earths undoubtedly.Particularly ammonification P204
With P507 extraction system, it has obtained bigger raising to selectivity and the loading capacity of rare earth, but ammonification has
Machine phosphorus (phosphine) acid system is when extracting and separating rear earth, and the subject matter existed is to produce ammonia nitrogen waste water, administers
Difficulty is big, and emission of industrial pollutants is difficult to up to standard, increases the burden of factory's end treatment, and this is the dilutest
Soil extract and separate field problem demanding prompt solution.From source solve problem, be cleaning procedure flow process must
Ask.
Ionic liquid is the class fusing point organic salt less than 100 DEG C, is in a liquid state under room temperature.With conventional organic solvent
Compare, there is negligible vapour pressure, the nonflammable and feature of part Modulatory character.Based on ionic liquid
The outstanding advantages that body has, in recent years, increasing separation science man focuses more on ion liquid system and uses
Extract and separate in metal ion.Study the more hydrophobic ionic liquid for extraction system mainly sun
Ion is the ionic liquid of imidazole type and pyridine type, and what anion research was more is trifluoromethyl sulfonyl
(NTf2) and hexafluoro-phosphate radical (PF6 -).But, ionic liquid is as anion and cation solvent, in extracting gold
During belonging to ion, generally its anions and canons can be with metal ion or its complex generation exchange reaction.
This means that and can lose at extraction process intermediate ion liquid component, and this is the most disadvantageous for extraction system.
Directly result in ionic liquid and reclaim difficulty, be difficult to recycle, and the component run off can polluted-water.Such as PF6 -,
Susceptible to hydrolysis in acidic bodies of water become poisonous and corrosive PO4 3-, HF, POF3, H2PO3F and
HPO2F2.In order to avoid ionic liquid loss in extraction process, the scheme being usually taken is, design from
The extraction mechanism of sub-liquid base extraction system replaces routine for neutral complex mechanism or ion association mechanism
Ion exchanger reason.
At present, with nitrate anion (NO3 -) or chlorine root (Cl-) it is that the floride-free functionalized ion liquid of counter anion is subject to
To paying close attention to widely.Such as tricaprylylmethylammchloride chloride (Aliquat 336) and chlorination three hexyl myristyl phosphine
(Cyphos IL 101) is common business-like metal ion extraction agent, is again a class ionic liquid.?
In the extraction system research relevant with ionic liquid, they are used for synthesizing the double merit of a series of zwitterion more
The ion liquid abstraction agent of energyization, as [A336] [P204], [A336] [P507], [A336] [C272],
[A336] [C302], [A366] [CA-12] and [A336] [CA-100].But, this kind of difunctionalization ionic liquid
Extractant, viscosity is big, sometimes in semisolid, during extracting metals ion, it has to use another kind
Ionic liquid or volatile organic solvent are as diluent.If the another kind of ionic liquid of employing is as diluent,
Unavoidably there is same problem, whether i.e. whether it participates in reaction, be ion exchanger when participating in and reacting
Reason.If using volatile organic solvent as diluent, still there is the maximum of traditional liquid liquid solvent extraction
The pollution to environment of shortcoming, i.e. volatile organic solvent.Owing to the viscosity of this kind of ionic liquid is big, the most very
The rare report utilizing these ionic liquids under conditions of being not added with any diluent, metal ion to be extracted
Road.
Neutral phosphor (phosphine) oxygen extractant extracting rare-earth ion typically belongs to complex coordination mechanism, its extracting metals
During ion, it is not necessary to saponification, do not produce ammonia nitrogen waste water.Under Low acid during extracting metals ion, saltout
The impact of agent is the most notable.Salting-out agents are soluble in water, itself are not extracted, the most not with aqueous metal ion network
Closing, this is the major parameter affecting neutral phosphor (phosphine) oxygen extractant extraction ability.It is said that in general, neutral phosphor
(phosphine) oxygen extractant is at HNO3And HNO3Add the extracting power ratio in salting-out agents medium at HCl medium
In generally exceed 1-2 the order of magnitude, this is becauseAnion has the hydration energy of minimum, and Cl-Have bigger
Hydration energy,Bigger salting out can be produced.
Therefore, in the art, it is desirable to coupled ion liquid and the advantage of neutral phosphor (phosphine) oxygen kind of extractants,
Develop the extraction separation method of the rare earth element of a kind of green economy.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide a kind of rare earth synergistic extractant system；This
The two of the purpose of invention are to provide one to utilize this rare earth synergistic extractant system to extract separation from nitric rare earth feed liquid
The method of rare earth element.
For reaching this goal of the invention, the present invention by the following technical solutions:
On the one hand, the invention provides a kind of rare earth synergistic extractant system, described rare earth synergistic extractant system with season phosphonium salt from
The mixed liquor of sub-liquid and neutral organophosphorus (phosphine) kind of extractants is extraction phase, and water is strip liquor.
In rare earth synergistic extractant system of the present invention, described quaternary phosphonium ionic liquid is nitric acid root type season phosphonium salt
Ionic liquid；Described nitric acid root type quaternary phosphonium ionic liquid is the season phosphonium salt using nitrate anion as counter anion
Ionic liquid；Preferably, described quaternary phosphonium ionic liquid is three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Ionic liquid.
In rare earth synergistic extractant system of the present invention, described neutral organophosphorus (phosphine) kind of extractants is selected from phosphorus
Acid tributyl (TBP), extraction (P350) or 2-ethylhexyl phosphonic acid two (2-ethyl hexyl
Base) any one or the combination of at least two in ester (DEHEHP).
In rare earth synergistic extractant system of the present invention, described ionic liquid and neutral organophosphorus (phosphine) class extraction
The volume ratio taking agent is 1:4-4:1, such as 1:4,1:3,1:2,1:1,2:1,2:3,2:5,2:7,3:1,3:2,
3:4,3:5,3:7,3:8 or 4:1, preferably 2:3.
On the other hand, the invention provides one utilizes described rare earth synergistic extractant system to carry from nitric rare earth feed liquid
The method taking separation of rare earth elements, said method comprising the steps of:
(1) mixed liquor of preparation quaternary phosphonium ionic liquid and neutral organophosphorus (phosphine) oxygen kind of extractants is as extraction
Take phase, be optionally added into salting-out agents, the pH of regulation feed liquid, extract, obtain the extract containing rare earth and
Raffinate；
(2) adopt and use water as strip liquor, step (1) gained extract containing rare earth is carried out back extraction,
To the anti-stripping agent containing rare earth, it is achieved the extraction of rare earth element separates.
In the method extracting separation of rare earth elements from nitric rare earth feed liquid of the present invention, step (1) institute
State regulation feed liquid pH be 2-5.5, such as 2,2.2,2.5,2.7,3.0,3.2,3.4,3.6,3.8,4.0,
4.2,4.5,4.6,4.8,5.0,5.1,5.2,5.3,5.4 or 5.5, preferably 3.2-4.5；Preferably,
The volume ratio of step (1) described extraction phase and feed liquid is 1:20-10:1, such as 1:20,1:19,1:18,1:17,
1:16、1:15、1:14、1:13、1:12、1:11、1:10、1:9、1:8、1:7、1:6、1:5、1:4、1:3、
1:2、1:1、2:1、3:1、4:1、4:3、5:1、5:2、6:1、6:4、7:1、7:2、7:3、7:4、7:5、
7:6,8:1,9:1 or 10:1.
In the method extracting separation of rare earth elements from nitric rare earth feed liquid of the present invention, step (1) institute
The feed liquid stated can also add salting-out agents；Preferably, described salting-out agents are sodium nitrate and/or lithium nitrate；Institute
State the addition of salting-out agents be the concentration making it in feed liquid be 0.5-5mol/L, such as 0.5mol/L, 1mol/L,
1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L, 4mol/L, 4.5mol/L or 5mol/L,
It is preferably 3mol/L.Such as, if feed liquid Rare Earth Ion concentration is relatively low, during the most several ppm, permissible
In feed liquid, add appropriate salting-out agents, such as sodium nitrate, the beneficially formation of nitric acid rare earth complex, be beneficial to
Extraction.When aqueous phase middle rare earth concentration is higher, such as reach the tens the most hundreds of gram per liter of gram per liter, so that it may
To be not added with salting-out agents, and just can complete from salting out in solution is utilized to extract.
In the method extracting separation of rare earth elements from nitric rare earth feed liquid of the present invention, step (2) institute
Stating the volume ratio of strip liquor and the extract containing rare earth in stripping process is 1:1, back extraction 1-5 time, such as 1 time,
2 times, 3 times, 4 times or 5 times, preferably 3 times.
As optimal technical scheme, the present invention provides a kind of and extracts separation of rare earth elements from nitric rare earth feed liquid
Method, specifically include following steps:
(1) preparation nitric acid root type quaternary phosphonium ionic liquid and the mixing of neutral organophosphorus (phosphine) oxygen kind of extractants
Liquid, as extraction phase, adds salting-out agents sodium nitrate, and the pH of regulation feed liquid is 3.2-4.5, extracts, obtains
Extract containing rare earth and raffinate；
(2) adopt and use water as strip liquor, step (1) gained extract containing rare earth is carried out back extraction, instead
Extract 3 times, obtain the anti-stripping agent containing rare earth, it is achieved the extraction of rare earth element separates.
In the method extracting separation of rare earth elements from nitric rare earth feed liquid of the present invention, nitric acid rare earth
The foreign metal ion contained in feed liquid mainly includes Mn, Cu, Zn, Co, Ni and Al etc..Utilize this
Bright described method can be by the rare earth ion in nitric rare earth feed liquid and foreign metal ion isolation, the most in fact
From nitric rare earth feed liquid, now extract the purpose of separation of rare earth elements.In nitric rare earth feed liquid of the present invention
The total concentration of each metal ion species (including rare earth ion) be several ppm to hundreds of g/L, according to feed liquid
Rare Earth Ion concentration, when determining extraction, the volume ratio of aqueous phase and organic facies is 1:10-20:1, such as, work as feed liquid
When Rare Earth Ion concentration is ppm magnitude (such as 1500ppm), aqueous phase and the volume of organic facies during extraction
Ratio can be 20:1,15:1 or 10:1 etc., when feed liquid Rare Earth Ion concentration is g/L magnitude (such as 50g/L
Or 100g/L) time, can suitably reduce the consumption of aqueous phase, such as aqueous phase and the volume ratio of organic facies during extraction
Can be 1:1,2:1 or 1:2 etc..
Nitric acid root type quaternary phosphonium ionic liquid of the present invention is to utilize nitrate anion as the season phosphine of counter anion
Ionic liquid.Neutral organophosphorus of the present invention (phosphine) oxygen kind of extractants is the extraction of neutral organophosphorus oxygen class
Agent or neutral organophosphine oxygen kind of extractants.Quaternary phosphonium ionic liquid of the present invention and neutral organophosphorus (phosphine)
Oxygen kind of extractants is commercially produced product.The present invention utilizes nitric acid root type quaternary phosphonium ionic liquid and neutrality organic
Phosphorus (phosphine) oxygen kind of extractants, as synergistic extractant system, follows neutral complex mechanism or ion association during extracting rare-earth
, there is not the loss of extractant component in mechanism.Gluing of business-like neutral organophosphorus (phosphine) oxygen kind of extractants
Spending low, after its ionic liquid bigger with viscosity mixes mutually, viscosity is substantially reduced, and is conducive to accelerating extraction dynamic
Mechanics is also prone to extracting operation.Owing to being neutral complex mechanism, therefore back extraction is easy, the most only with water
Realize complete back extraction.
For prior art, the method have the advantages that
The present invention utilizes quaternary phosphonium ionic liquid and the mixed liquor conduct of neutral organophosphorus (phosphine) oxygen kind of extractants
There is obvious Association stripping effect during extract extraction, not only make the extraction efficiency of rare earth be greatly increased, Er Qieyou
Improve the separation to rare earth element to effect, it is possible to realize extracting rare-earth separating from nitric rare earth feed liquid
The purpose of element.Not using volatile organic solvent during extracting rare-earth, extraction mechanism belongs to neutral complex mechanism
Or ion association mechanism, the most there is not the loss of the component that extractant causes because participating in extractive reaction,
Organic extraction is easily recycled mutually.Extraction process, without saponification, eliminates current Rare Earth Factory from source
The ammonia nitrogen waste water existed discharges problem the most up to standard.Traditional relative to toluene as diluent of synergistic extractant system
Liquid-liquid extraction system, extraction efficiency is greatly improved.Additionally, strip liquor is water in extraction system, green economy.
Accompanying drawing explanation
Fig. 1 be the embodiment of the present invention 1 and comparative example 1 preparation different proportion synergistic extractant system with to Pr (III)
And the relation between the synergistic coefficient R of Nd (III) rare earth element, wherein vertical coordinate XA336/P6,6,6,14Represent
[P6,6,6,14][NO3] or [A336] [NO3] volume fraction；
Fig. 2 is the synergistic extractant system [P of the embodiment of the present invention 36,6,6,14][NO3]+DEHEHP and the list of comparative example 2
One ionic liquid [P6,6,6,14][NO3] comparison diagram to the extracting power of full rare earth；
Fig. 3 is the synergistic extractant system [P of the embodiment of the present invention 36,6,6,14][NO3]+DEHEHP and the list of comparative example 2
One ionic liquid [P6,6,6,14][NO3] to rare earth Lu and the block diagram of the extraction efficiency of non-rare earth.
Detailed description of the invention
Technical scheme is further illustrated below by detailed description of the invention.Those skilled in the art
It will be clearly understood that the only help of described embodiment understands the present invention, it is not construed as the concrete restriction to the present invention.
Embodiment 1
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP), water is anti-
Extraction liquid.It is extract and separate Pr and Nd the feed liquid of 700ppm from the concentration of known Pr and Nd, examines
Examine the synergistic extractant system used synergistic coefficient to rare earth element, and determine the optimal volume of extractant in synergistic extractant system
The method of ratio, extract and separate Pr and Nd specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) mixed liquor of ester (DEHEHP) as extraction phase, [P in extraction phase6,6,6,14][NO3] with
The volume ratio of DEHEHP is set as 1:4,3:7,2:3,1:1,3:2,7:3 or 4:1 (i.e. [P6,6,6,14][NO3]
The mark accounting for total extraction phase volume is 0.2,0.3,0.4,0.5,0.6,0.7 and 0.8), add in feed liquid
Lithium nitrate (lithium nitrate concentration in feed liquid is 3mol/L) is as salting-out agents, and the pH of regulation feed liquid is 3.5,
Extraction phase is 1:20 with the volume ratio of feed liquid, extracts feed liquid, obtains the extract containing rare earth and raffinate
Liquid；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 2 times, obtains the anti-stripping agent containing rare earth.
Comparative example 1
In this comparative example, rare earth synergistic extractant system is with the methyl trioctylphosphine ammonium nitrate disclosed in prior art
[A336][NO3] and 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP) mixed liquor for extraction
Taking phase, water is strip liquor.It is extract and separate Pr the feed liquid of 700ppm from the concentration of known Pr and Nd
And Nd, investigate the synergistic extractant system used synergistic coefficient to rare earth element, and determine extractant in synergistic extractant system
Optimum volume ratio, the method for extract and separate Pr and Nd specifically includes following steps:
(1) preparation methyl trioctylphosphine ammonium nitrate [A336] [NO3] and 2-ethylhexyl phosphonic acid two (2-ethylhexyl)
The mixed liquor of ester (DEHEHP) as extraction phase, [A336] [NO in extraction phase3] and the volume of DEHEHP
Ratio is set as 1:4,3:7,2:3,1:1,3:2,7:3 or 4:1 (i.e. [A336] [NO3] account for total extraction phase volume
Mark be 0.2,0.3,0.4,0.5,0.6,0.7 and 0.8), in feed liquid add lithium nitrate (lithium nitrate
Concentration in feed liquid is 3mol/L) as salting-out agents, the pH of regulation feed liquid is 3.5, extraction phase and feed liquid
Volume ratio be 1:20, feed liquid is extracted, obtains the extract containing rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 2 times, obtains the anti-stripping agent containing rare earth.
To synergistic extractant system ([P in embodiment 1 and comparative example 16,6,6,14][NO3] and DEHEHP and
[A336][NO3] and DEHEHP) shadow to the rare earth element Association stripping effect as representative with Pr (III) and Nd (III)
Ringing and be evaluated, result is as shown in Figure 1.
As seen from Figure 1, with [P6,6,6,14][NO3]+DEHEHP is synergistic extractant system, to Pr (III) and
Nd (III) is that the rare earth element of representative has obvious Association stripping effect, and when in synergistic extractant system (i.e. extraction phase)
[P6,6,6,14][NO3] volume fraction XP6,6,6,14When being 0.4, i.e. [P6,6,6,14][NO3] and the volume of DEHEHP
Than during for 2:3, synergistic coefficient R is maximum, and extraction yield is maximum, and is 0.4-0.8 in extraction phase volume fraction
Time, synergistic extractant system [P6,6,6,14][NO3]+DEHEHP to the synergistic coefficient R of rare earth element more than [A336] [NO3]
+ DEHEHP synergistic extractant system, this explanation is compared to [A336] [NO3]+DEHEHP, synergistic extractant system
[P6,6,6,14][NO3]+DEHEHP is more easy to realize separation to rare earth element.
Embodiment 2
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Mixed liquor (volume ratio is 2:3) with 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP)
For extraction phase, water is strip liquor.In nitric rare earth feed liquid, the concentration of contained full rare earth ion is about 50g/L, logical
Crossing following methods and extract the full rare earth element of separation from nitric rare earth feed liquid, described method specifically includes following step
Rapid:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) mixed liquor of ester (DEHEHP) as extraction phase, [P in extraction phase6,6,6,14][NO3] with
The volume ratio of DEHEHP is set as 2:3, and (sodium nitrate concentration in feed liquid is to add sodium nitrate in feed liquid
2mol/L) as salting-out agents, the pH of regulation feed liquid is 4.0, and extraction phase is 1:1 with the volume ratio of feed liquid,
Feed liquid is extracted, obtains the extract containing rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction three times, obtains the anti-stripping agent containing rare earth；
Synergistic extractant system [P6,6,6,14][NO3]+DEHEHP extracts system when the two volume ratio is 2:3 to the association of full rare earth
Number R is shown in Table 1.
Table 1
Z represents that rare earth element, R represent synergistic coefficient
As it can be seen from table 1 synergistic extractant system [P6,6,6,14][NO3]+DEHEHP is when volume ratio is 2:3, right
The significant synergistic enhancing effect of light rare earth La-Eu, and centering heavy rare earth positive coopertive effect relatively overly soft pulse is certain to having
Anti-synergistic effect；Therefore this synergistic extractant system is so that rare earth element is according to the La-Eu with cooperative effect
And have more weak positive cooperative effect or have anti-synergistic effect Gd-Lu packet separate, i.e. realize light rare earth
Separate with middle heavy rare earth.
(can be drawn Eu extracting power by Fig. 1 with the Eu that extracting power in light rare earth La-Eu group is the most weak
The most weak) it is representative, investigate synergistic extractant system [P6,6,6,14][NO3]+DEHEHP when volume ratio is 2:3, Eu
With middle heavy rare earth group Gd-Lu, separation between each rare earth element in Y, result is as shown in table 2.
Table 2
PD represents [P6,6,6,14][NO3]+DEHEHP system；P represents [P6,6,6,14][NO3] system；D represents DEHEHP system.
From table 2 it can be seen that synergistic extractant system [P6,6,6,14][NO3]+DEHEHP can realize rare earth element
Packet separates.
Additionally, for synergistic extractant system [P6,6,6,14][NO3] mix for 2:3 by volume with DEHEHP before and after
Viscosity under different temperatures is determined, and result is as shown in table 3.To synergistic extractant system
[P6,6,6,14][NO3]+DEHEHP and single extractant [P6,6,6,14][NO3] and under 303K, extract Pr (III),
Viscosity before and after extraction is contrasted, and result is as shown in table 4.
Table 3
Table 4
From table 3 it can be seen that single ionic liquid [P6,6,6,14][NO3] viscosity relatively big, when only applying this list
When only ionic liquid carrys out extracting rare-earth, it is relatively slow that extraction reaches balancing speed, and the viscosity of ionic liquid is with Pr
(III) load significantly increases, as shown in Table 4, when in ionic liquid, the loading concentrations of Pr (III) is
During 0.277mol/L, viscosity be up to 818.2126mPa s, well imagine when Pr (III) load capacity amount more
Gao Shi, viscosity is up to thousands of, and this extraction may need liter high-temperature just can carry out.And synergistic extractant system
[P6,6,6,14][NO3] viscosity of+DEHEHP is relative to ionic liquid [P6,6,6,14][NO3] viscosity be substantially reduced,
And lower temperature 25-45 DEG C, it is possible to relatively quick extracting rare-earth ion, and viscosity after supported rare earth
Being relatively low, as shown in table 4, when the loading concentrations of Pr (III) is 0.375mol/L, viscosity is only
171.715mPa s, therefore this system can complete extraction completely at normal temperatures.
Embodiment 3
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP), water is anti-
Extraction liquid.In nitric rare earth feed liquid, the concentration of contained various rare earth ions is respectively 9ppm, by the following method from
Extracting separation of rare earth elements in nitric rare earth feed liquid, described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) mixed liquor of ester (DEHEHP) as extraction phase, [P in extraction phase6,6,6,14][NO3] with
The volume ratio of DEHEHP is set as 2:3, and (sodium nitrate concentration in feed liquid is to add sodium nitrate in feed liquid
5mol/L) as salting-out agents, the pH of regulation feed liquid is 5.5, and extraction phase is 1:20 with the volume ratio of feed liquid,
Feed liquid is extracted, obtains the extract containing rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, obtains the anti-stripping agent containing rare earth.
Comparative example 2
This comparative example difference from Example 3 is, utilizes single ionic liquid D EHEHP as extraction
Phase, in addition, extracts remaining operating procedure and the operation bar of separation of rare earth elements from nitric rare earth feed liquid
Part is same as in Example 3.
To synergistic extractant system [P in embodiment 3 and comparative example 26,6,6,14][NO3]+DEHEHP and single ionic liquid
[P6,6,6,14][NO3] extracting power of full rare earth is compared, as shown in Figure 2.With Lu for rare earth element generation
Table, to synergistic extractant system [P6,6,6,14][NO3]+DEHEHP and single ionic liquid [P6,6,6,14][NO3] to rare earth Lu
Compare with the extraction efficiency of non-rare earth, as shown in Figure 3.Table 5 summarize corresponding with Fig. 3
The synergistic extractant system separation selectivity factor beta to rare earth Lu and non-rare earth.
Table 5
β represents separation selectivity coefficient, and PD represents synergistic extractant system [P6,6,6,14][NO3]+DEHEHP, P represent single ionic liquid
[P6,6,6,14][NO3]。
Fig. 2 shows, with [P6,6,6,14][NO3]+DEHEHP is synergistic extractant system, relative to single ionic liquid
[P6,6,6,14][NO3], the extracting power of full rare earth there are raising in various degree, the wherein extracting power to Ce
The highest, minimum to the extracting power of Lu.
As seen from Figure 3, with synergistic extractant system, its Lu with minimum extracting power is represented for rare earth element,
Synergistic extractant system [P6,6,6,14][NO3] extraction efficiency of rare earth metal Lu is noticeably greater than non-rare earth by+DEHEHP
The extraction efficiency of metal ion (such as Mn, Cu, Zn, Co, Ni and Al).
Table 5 shows synergistic extractant system [P6,6,6,14][NO3]+DEHEHP to rare earth metal Lu and non-rare earth metal from
The separation selectivity factor beta of son is far longer than single ionic liquid [P6,6,6,14][NO3] to rare earth metal Lu with non-
The separation selectivity factor beta of rare earth ion, this illustrates synergistic extractant system [P6,6,6,14][NO3]+DEHEHP can
Separating with non-rare earth ion realizing rare earth ion relatively easily, it has extraction rare-earth separating
Element the Potential performance with non-Rare Earth Separation.
Embodiment 4
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP), water is anti-
Extraction liquid.In nitric rare earth feed liquid, the concentration of contained rare earth ion is about 1.5g/L, dilute from nitric acid by the following method
Extracting separation of rare earth elements in earth material liquid, described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) mixed liquor of ester (DEHEHP) as extraction phase, [P in extraction phase6,6,6,14][NO3] with
The volume ratio of DEHEHP is set as 2:3, and (sodium nitrate concentration in feed liquid is to add sodium nitrate in feed liquid
3mol/L) as salting-out agents, the pH of regulation feed liquid is 2, and extraction phase is 1:20 with the volume ratio of feed liquid, right
Feed liquid extracts, and obtains the extract containing rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 2 times, obtains the anti-stripping agent containing rare earth.
Embodiment 5
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of 2-ethylhexyl phosphonic acid two (2-ethylhexyl) ester (DEHEHP), water is anti-
Extraction liquid.In nitric rare earth feed liquid, the concentration of contained rare earth ion is about 50g/L, dilute from nitric acid by the following method
Extracting separation of rare earth elements in earth material liquid, described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) mixed liquor of ester (DEHEHP) as extraction phase, [P in extraction phase6,6,6,14][NO3] with
The volume ratio of DEHEHP is set as 2:3, and (sodium nitrate concentration in feed liquid is to add sodium nitrate in feed liquid
0.5mol/L) as salting-out agents, the pH of regulation feed liquid is 3.0, and extraction phase is 1:1 with the volume ratio of feed liquid,
Feed liquid is extracted, obtains the extract containing rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 3 times, obtains the anti-stripping agent containing rare earth.
Embodiment 6
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of tributyl phosphate (TBP), water is strip liquor.In nitric rare earth feed liquid contained dilute
The concentration of soil ion is about 60g/L, extracts separation of rare earth elements by the following method from nitric rare earth feed liquid,
Described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and tributyl phosphate (TBP)
Mixed liquor as extraction phase, [P in extraction phase6,6,6,14][NO3] it is set as 2:3 with the volume ratio of TBP, regulation
The pH of feed liquid is 3.2, and extraction phase is 1:1 with the volume ratio of feed liquid, extracts feed liquid, obtains containing rare earth
Extract and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 3 times, obtains the anti-stripping agent containing rare earth；
Embodiment 7
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of extraction (P350), water is strip liquor.Nitric rare earth feed liquid
Contained by, the concentration of rare earth ion is about 1000ppm, extracts by the following method and divide from nitric rare earth feed liquid
From rare earth element, described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and extraction
(P350) mixed liquor as extraction phase, [P in extraction phase6,6,6,14][NO3] be set as with the volume ratio of P350
2:3, adds sodium nitrate (sodium nitrate concentration in feed liquid is 3mol/L) as salting-out agents, tune in feed liquid
The pH of joint feed liquid is 4.5, and extraction phase is 1:15 with the volume ratio of feed liquid, extracts feed liquid, is contained
The extract of rare earth and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction 1 time, obtains the anti-stripping agent containing rare earth.
Embodiment 8
In the present embodiment, rare earth synergistic extractant system is with three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Being extraction phase with the mixed liquor of extraction (P350), water is strip liquor.Nitric rare earth feed liquid
Contained by, the concentration of rare earth ion is about 100g/L, extracts by the following method and separate from nitric rare earth feed liquid
Rare earth element, described method specifically includes following steps:
(1) three hexyls (myristyl) nitric acid phosphine [P is prepared6,6,6,14][NO3] and extraction
(P350) mixed liquor is as extraction phase, [P in extraction phase6,6,6,14][NO3] it is set as 2:3 with the volume ratio of P350,
Lithium nitrate (lithium nitrate concentration in feed liquid is 4mol/L) is added as salting-out agents, regulation material in feed liquid
The pH of liquid is 5.5, and extraction phase is 10:1 with the volume ratio of feed liquid, extracts feed liquid, obtains containing rare earth
Extract and raffinate；
(2) adopting and use water as strip liquor, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, to step
Suddenly (1) gained extract containing rare earth carries out back extraction, back extraction 5 times, obtains the anti-stripping agent containing rare earth.
Applicant states, the present invention illustrates rare earth synergistic extractant system and the utilization of the present invention by above-described embodiment
This synergistic extractant system extracts the method for separation of rare earth elements from nitric rare earth feed liquid, but the invention is not limited in
Above-described embodiment, does not i.e. mean that the present invention has to rely on above-mentioned processing step and could implement.Affiliated technology neck
The technical staff in territory is it will be clearly understood that any improvement in the present invention, and the equivalence to raw material selected by the present invention is replaced
Change and the interpolation of auxiliary element, concrete way choice etc., all fall within protection scope of the present invention and open model
Within enclosing.
Claims (10)
1. a rare earth synergistic extractant system, it is characterised in that described rare earth synergistic extractant system is with quaternary phosphonium ionic liquid
Being extraction phase with the mixed liquor of neutral organophosphorus (phosphine) kind of extractants, water is strip liquor.
Rare earth synergistic extractant system the most according to claim 1, it is characterised in that described season phosphonium salt ionic liquid
Body is nitric acid root type quaternary phosphonium ionic liquid；
Preferably, described quaternary phosphonium ionic liquid is three hexyls (myristyl) nitric acid phosphine [P6,6,6,14][NO3]
Ionic liquid.
Rare earth synergistic extractant system the most according to claim 1 and 2, it is characterised in that described neutrality is organic
Phosphorus (phosphine) kind of extractants is selected from tributyl phosphate, extraction or 2-ethylhexyl phosphonic acid two (2-
Ethylhexyl) any one or the combination of at least two in ester.
4. according to the rare earth synergistic extractant system according to any one of claim 1-3, it is characterised in that described season
Phosphonium ionic liquid is 1:4-4:1, preferably 2:3 with the volume ratio of neutral organophosphorus (phosphine) kind of extractants.
5. the rare earth synergistic extractant system that a kind utilizes according to any one of claim 1-4 is from nitric rare earth feed liquid
The method extracting separation of rare earth elements, it is characterised in that said method comprising the steps of:
(1) mixed liquor of preparation quaternary phosphonium ionic liquid and neutral organophosphorus (phosphine) kind of extractants is as extraction
Phase, is optionally added into salting-out agents, the pH of regulation feed liquid, extracts, obtain the extract containing rare earth and extraction
Remaining liquid；
(2) adopt and use water as strip liquor, step (1) gained extract containing rare earth is carried out back extraction,
To the anti-stripping agent containing rare earth, it is achieved the extraction of rare earth element separates.
Method the most according to claim 5, it is characterised in that step (1) described regulation feed liquid
PH is 2-5.5, preferably 3.2-4.5.
7. according to the method described in claim 5 or 6, it is characterised in that step (1) described extraction phase
It is 1:20-10:1 with the volume ratio of feed liquid.
8. according to the method according to any one of claim 5-7, it is characterised in that step (1) is described
Feed liquid in add salting-out agents；
Preferably, described salting-out agents are sodium nitrate and/or lithium nitrate.
Method the most according to claim 8, it is characterised in that the addition of described salting-out agents is for making it
Concentration in feed liquid is 0.5-5mol/L, preferably 3mol/L.
10. according to the method according to any one of claim 5-9, it is characterised in that step (2) is described
In stripping process, strip liquor is 1:1 with the volume ratio of the extract containing rare earth, back extraction 1-5 time, preferably 3 times.
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| CN107299234A (en) * | 2017-06-14 | 2017-10-27 | 中国科学院过程工程研究所 | A kind of green method of the recovering rare earth from useless fluorescent material and application thereof |
| CN112458319A (en) * | 2020-11-23 | 2021-03-09 | 中国科学院过程工程研究所 | Method for separating heavy rare earth elements based on ionic liquid extraction system |
| CN114959264A (en) * | 2022-06-06 | 2022-08-30 | 辽宁大学 | Environment-friendly extraction system and scandium extraction method based on same |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106947876A (en) * | 2017-04-21 | 2017-07-14 | 北京工业大学 | A kind of method of the discarded CRT pickle liquor middle rare earth secondary resources of synergic solvent extraction separation and recovery |
| CN106947876B (en) * | 2017-04-21 | 2019-06-07 | 北京工业大学 | A kind of method that synergic solvent extraction separates and recovers rare earth secondary resource in discarded CRT pickle liquor |
| CN107299234A (en) * | 2017-06-14 | 2017-10-27 | 中国科学院过程工程研究所 | A kind of green method of the recovering rare earth from useless fluorescent material and application thereof |
| CN112458319A (en) * | 2020-11-23 | 2021-03-09 | 中国科学院过程工程研究所 | Method for separating heavy rare earth elements based on ionic liquid extraction system |
| CN114959264A (en) * | 2022-06-06 | 2022-08-30 | 辽宁大学 | Environment-friendly extraction system and scandium extraction method based on same |
| CN114959264B (en) * | 2022-06-06 | 2023-12-08 | 辽宁大学 | Environment-friendly extraction system and scandium extraction method based on same |
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