CN107287456B - A kind of extracting process of separating-purifying heavy rare earth - Google Patents
A kind of extracting process of separating-purifying heavy rare earth Download PDFInfo
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Abstract
A kind of extracting process of separating-purifying heavy rare earth, the method extract rare earth sulfate solution with the organic phase comprising extractant and diluent；The extractant is ether amide functional ionic liquids.The method, as strip liquor, is stripped the rare earth element being extracted in normal heptane, obtains the anti-stripping agent containing rare earth using water, realizes the extraction separation of rare earth element.The present invention improves its dissolubility in diluent and to the compatibility of rare earth ion due to the ether-oxygen bond in ether amide functional ionic liquids structure, it is obviously improved it to the separating capacity between rare earth element, heavy rare earth element is especially preferentially extracted in extraction process, the pre-treatment except iron, aluminium is not needed, and during subsequent back extraction, heavy rare earth back extraction only usually can be realized with water, reduce acid and alkali consumption.The present invention is good in extraction process Interfacial Phenomenon, it is not necessary that extractant to be saponified, can reach extraction and separation effect it is not necessary that salting-out agents are added i.e..
Description
Technical field
The present invention relates to a kind of extracting process of separating-purifying heavy rare earth, belong to rare earth extraction technical field.
Background technique
Rare earth has the characteristics such as excellent light, electricity, magnetic, is widely used in defence and military and high-tech field of new materials, has
The good reputation of " industrial vitamin ".Wherein, middle heavy rare earth (samarium~lutetium and yttrium) partition of southern ion adsorption type rare earth ore is up to
30%~80%, several high-tech sectors such as middle heavy rare earth and photoelectricity, information, the energy, metallurgy of these high values and industry join
Close, product added value with higher is fastened, the irreplaceable important application in the fields such as new and high technology and defence and military is
The development for really restricting external related fields, is the strategic resource with absolute competitive advantage.
Currently, single rare earth separation is mainly extraction using P507 (2- ethylhexyl phosphonic acid mono (2- ethylhexyl) ester)
Take the extraction separating method of agent.But there are still back extraction acidity height for P507 extraction system separation heavy rare earth, and are stripped not exclusively, acid
Alkali consumes big problem, influences separation and the High Purity of heavy rare earth.In addition, stepping up with national requirements for environmental protection, existing
The problems such as acid and alkali consumption existing for P507 extraction system is big, ammonia and nitrogen pollution becomes increasingly conspicuous, and from the angle of source prevention, develops soda acid
It is most important to the exploitation of high efficiency rare-earth clean separation new process to consume Novel Extractant and extraction system low, that selectivity is high.
In recent years, functional ionic liquids have been obtained as the research hotspot of Green Chemistry in Rare Earth Separation field wide
Concern, the method prior art discloses several functions ionic liquid as extractant rare-earth separating, publication number
CN101723975 discloses a kind of " preparation method of quaternary amine dual-functional ionic liquid " this method using quaternary ammonium base and organic
The hydrogen ion on extractant is eliminated in neutralization reaction between phosphine (carboxylic) acid extraction agent, realizes non-saponifiable extraction, this method is made
Standby soda acid coupled mode difunctionalization ion liquid abstraction agent (code name ABC-BIL) can effectively avoid phosphine (carboxylic) acid extraction agent and answer
With produced saponification waste-water pollution on the environment；Publication number CN102618736 discloses a kind of " extraction of rare earth element point
From method ", the method that extraction and separation are carried out to rare earth element using above-mentioned ionic liquid；But general use in the prior art
Functional ionic liquids in sulfuric acid medium to extract and separation trivalent rare earth element ability it is weaker, especially to iron,
The impurities removing efficiency of the divalent metals such as aluminium, zinc is low, causes to be difficult to obtain high-purity heavy rare earth product.
Summary of the invention
The object of the present invention is to which in view of the deficiencies of the prior art, the present invention provides a kind of extraction of separating-purifying heavy rare earth
Method, the ether amide functional ionic liquids of use are strong to rare earth element extracting power in sulfuric acid medium, easily anti-without saponification
Extraction.
Realize the technical scheme is that, a kind of extracting process of separating-purifying heavy rare earth, the method with include extraction
The organic phase of agent and diluent is taken to extract rare earth sulfate solution；The extractant is ether amide functional ionic liquids；
The method, as strip liquor, is stripped the rare earth element being extracted in normal heptane, obtains containing the anti-of rare earth using water
Extract liquor realizes the extraction separation of rare earth element.
The ether amide functional ionic liquids have following structure general formula:
Wherein, R1 and R2 is linear or branched alkyl group independent, at least one is the alkane at least four carbon atom
Base group, R3 are the straight chained alkyls that carbon atom number is 2~8, and X is chlorine anion, bromine anion, hexafluoro-phosphate radical, bis- (three fluothane
One of base sulfonyl) amido anion.
The preparation method step of the ether amide functional ionic liquids are as follows:
(1) anhydride diethylene glycol and dialkylamine that molar ratio is 1.1:1 are reacted into generation corresponding two in tetrahydrofuran
Alkyl diethylene glycol (DEG) amic acid；
(2) by dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyl) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzenes
And triazole carries out amide reaction in organic reagent, by being filtered, washed, silica gel column chromatography separating step obtain ether amide function
Change imidazoles；
(3) ether amide functionalization imidazoles is reacted with halide generate ether amide functionality that anion is halide ion from
Sub- liquid；
(4) ether amide functional ionic liquids and inorganic salts that anion is halogen are carried out in the presence of organic reagent
Anion exchange reaction, then be filtered, washed, be evaporated under reduced pressure step and remove inorganic salts and organic reagent and obtain corresponding ether acyl
Amine functionality ionic liquid.
The dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyl) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzenes
And triazole reaction molar ratio be 1.2:1:1.2:1.2, react using chloroform as solvent, reaction under inert gas protection into
Row；
It is 1:1.2 that the ether amide functionalization imidazoles, which reacts molar ratio with alkyl halide, is reacted using acetonitrile as solvent, reaction exists
It is carried out under inert gas shielding；
The anion is the ether amide functional ionic liquids of halogen and the molar ratio of inorganic salt reaction is 1:2.5, instead
It should be using acetonitrile as solvent.
The concentration of the n-heptane solution of the ether amide functional ionic liquids is 0.01~0.1mol/L.
The concentration of the rare earth sulfate solution is 0.2~3mmol/L.
The rare earth includes the one or more of Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Y3+.
The invention has the advantages that in the present invention, due to the ether-oxygen bond in ether amide functional ionic liquids structure
Its dissolubility in diluent and the compatibility to rare earth ion are improved, obtains it to the separating capacity between rare earth element
To being obviously improved, heavy rare earth element is especially preferentially extracted in extraction process, does not need the pre-treatment except iron, aluminium, and
During subsequent back extraction, heavy rare earth back extraction only usually can be realized with water, reduce acid and alkali consumption.In addition, side of the present invention
Method is good in extraction process Interfacial Phenomenon, it is not necessary that extractant to be saponified, can reach extraction and separation effect it is not necessary that salting-out agents are added i.e.
Fruit.
Detailed description of the invention
Fig. 1 is the structural formula figure of ether amide functional ionic liquids of the present invention；
Fig. 2 be [DGA] [PF6] as extractant when solution equilibria pH value and rare earth ion distribution coefficient scattergram；
Fig. 3 be [D2EHGA] [PF6] as extractant when solution equilibria pH value and rare earth ion distribution coefficient it is dotted
Figure.
Specific embodiment
Embodiment 1
It weighs 100g anhydride diethylene glycol to be dissolved in 1000mL tetrahydrofuran, bis- n-octyl amine of 189g is added, under protection of argon gas
Acquired solution is dissolved in 400mL chloroform by normal-temperature reaction 48h after rotating, and is distilled after being washed with dilute hydrochloric acid solution, is true
Sky is dry, obtains dioctyl diethylene glycol (DEG) amic acid；By 90g dioctyl diethylene glycol (DEG) amic acid, 37.2g aminopropyl imidazoles, 61.2g bis-
Carbodicyclo hexylimide, 40.2g I-hydroxybenzotriazole are dissolved in 1000mL chloroform, under protection of argon gas normal-temperature reaction
Solution decompression is filtered, is dissolved in 500mL ethyl acetate after distillation, washed with sodium carbonate liquor and remove remaining 1- hydroxyl by 12h
Benzotriazole screws out ethyl acetate under vacuum condition, using silica gel column chromatography, uses chloroform and methanol as mobile phase,
Obtain 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N, N- dioctyl acetamide；Weigh 102g 2- [2- (- 2 oxygen of aminopropyl imidazoles
Generation)]-N, N- dioctyl acetamide, 37.14g bromobutane are dissolved in 1000mL acetonitrile, are stirred to react 48h in 80 DEG C, use n-hexane
Washing removes excessive bromobutane, and revolving removes acetonitrile, obtains the imidazoles bromide of ether amide functionalization；By 71g ether amide functionalization
Imidazoles bromide be dissolved in 600mL acetonitrile, mixed with the acetonitrile solution of the bis- trifluoromethanesulfonimide lithiums of 85.2g, at normal temperature
Reaction for 24 hours, is washed with water and removes remaining double trifluoromethanesulfonimide lithiums, and vacuum condition backspin steams acetonitrile and water, obtains
Double trifluoromethanesulfonimide roots are the ether amide functional ionic liquids of anion, are labeled as [DGA-TSIL] [Tf2N].
Embodiment 2
It weighs 100g anhydride diethylene glycol to be dissolved in 1000mL tetrahydrofuran, 189g bis- (2- ethylhexyl) amine is added, in argon
Acquired solution is dissolved in 400mL chloroform, after being washed with dilute hydrochloric acid solution by normal-temperature reaction 48h under gas shielded after rotating
It distilled, be dried in vacuo, obtain two (2- ethylhexyl) diethylene glycol (DEG) amic acids；By 90g bis- (2- ethylhexyl) diethylene glycol (DEG) amide
Acid, 37.2g aminopropyl imidazoles, 61.2g dicyclohexylcarbodiimide, 40.2g I-hydroxybenzotriazole are dissolved in tri- chloromethane of 1000mL
In alkane, normal-temperature reaction 12h, solution decompression is filtered, is dissolved in 500mL ethyl acetate after distillation, carbonic acid is used under protection of argon gas
Sodium solution washing removes remaining I-hydroxybenzotriazole, screws out ethyl acetate under vacuum condition, using silica gel column chromatography, uses
Chloroform and methanol obtain 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N, N- bis- (2- ethylhexyl) acetyl as mobile phase
Amine；102g 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N is weighed, N- bis- (2- ethylhexyl) acetamide, 37.14g bromobutane are molten
In 1000mL acetonitrile, it is stirred to react 48h in 80 DEG C, washs the excessive bromobutane of removing with n-hexane, revolving removes acetonitrile, obtains
The imidazoles bromide of ether amide functionalization；The imidazoles bromide of 71g ether amide functionalization is dissolved in 600mL acetonitrile, with 50.12g six
The acetonitrile solution of sodium fluoro phosphate mixes, and reacts at normal temperature for 24 hours, is washed with water and removes remaining sodium hexafluoro phosphate, vacuum condition
Backspin steams acetonitrile and water, obtains the ether amide base functional ionic liquids that hexafluoro-phosphate radical is anion, is labeled as
[D2EHGA-TSIL][PF6]。
Embodiment 3
It weighs 100g anhydride diethylene glycol to be dissolved in 1000mL tetrahydrofuran, bis- n-octyl amine of 189g is added, under protection of argon gas
Acquired solution is dissolved in 400mL chloroform by normal-temperature reaction 48h after rotating, and is distilled after being washed with dilute hydrochloric acid solution, is true
Sky is dry, obtains dioctyl diethylene glycol (DEG) amic acid；By 90g dioctyl diethylene glycol (DEG) amic acid, 37.2g aminopropyl imidazoles, 61.2g bis-
Carbodicyclo hexylimide, 40.2g I-hydroxybenzotriazole are dissolved in 1000mL chloroform, under protection of argon gas normal-temperature reaction
Solution decompression is filtered, is dissolved in 500mL ethyl acetate after distillation, washed with sodium carbonate liquor and remove remaining 1- hydroxyl by 12h
Benzotriazole screws out ethyl acetate under vacuum condition, using silica gel column chromatography, uses chloroform and methanol as mobile phase,
Obtain 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N, N- dioctyl acetamide；Weigh 102g 2- [2- (- 2 oxygen of aminopropyl imidazoles
Generation)]-N, N- dioctyl acetamide, 37.14g chlorobutane are dissolved in 1000mL acetonitrile, are stirred to react 48h in 90 DEG C, use n-hexane
Washing removes excessive chlorobutane, and revolving removes acetonitrile, obtains the imidazoles villaumite of ether amide functionalization；By 65.87g ether amide function
The imidazoles villaumite of change is dissolved in 600mL acetonitrile, is mixed with the acetonitrile solution of 50.12g sodium hexafluoro phosphate, is reacted at normal temperature for 24 hours,
It is washed with water and removes remaining sodium hexafluoro phosphate, vacuum condition backspin steams acetonitrile and water, and obtaining hexafluoro-phosphate radical is anion
Ether amide base functional ionic liquids, be labeled as [DGA-TSIL] [PF6].
Embodiment 4
It weighs 100g anhydride diethylene glycol to be dissolved in 1000mL tetrahydrofuran, 189g bis- (2- ethylhexyl) amine is added, in argon
Acquired solution is dissolved in 400mL chloroform, after being washed with dilute hydrochloric acid solution by normal-temperature reaction 48h under gas shielded after rotating
It distilled, be dried in vacuo, obtain two (2- ethylhexyl) diethylene glycol (DEG) amic acids；By 90g bis- (2- ethylhexyl) diethylene glycol (DEG) amide
Acid, 37.2g aminopropyl imidazoles, 61.2g dicyclohexylcarbodiimide, 40.2g I-hydroxybenzotriazole are dissolved in tri- chloromethane of 1000mL
In alkane, normal-temperature reaction 12h, solution decompression is filtered, is dissolved in 500mL ethyl acetate after distillation, carbonic acid is used under protection of argon gas
Sodium solution washing removes remaining I-hydroxybenzotriazole, screws out ethyl acetate under vacuum condition, using silica gel column chromatography, uses
Chloroform and methanol obtain 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N, N- bis- (2- ethylhexyl) acetyl as mobile phase
Amine；102g 2- [2- (- 2 oxo of aminopropyl imidazoles)]-N is weighed, N- bis- (2- ethylhexyl) acetamide, 37.14g chlorobutane are molten
In 1000mL acetonitrile, it is stirred to react 48h in 85 DEG C, washs the excessive chlorobutane of removing with n-hexane, revolving removes acetonitrile, obtains
The imidazoles bromide of ether amide functionalization；The imidazoles villaumite of 65.87g ether amide functionalization is dissolved in 600mL acetonitrile, with 85.2g
The acetonitrile solution of double trifluoromethanesulfonimide lithiums mixes, and reacts at normal temperature for 24 hours, is washed with water and removes remaining double fluoroforms
Alkane sulfimide lithium, vacuum condition backspin steam acetonitrile and water, obtain the ether acyl that double trifluoromethanesulfonimide roots are anion
Amido functional ionic liquids are labeled as [D2EHGA-TSIL] [Tf2N].
Embodiment 5~8
Embodiment 5 use rare earth ion for Eu3+, embodiment 6 use rare earth ion for Y3+, embodiment 7 using rare earth from
Son is Yb3+, embodiment 8 uses rare earth ion to prepare earth solution respectively for Lu3+.
It is extraction organic phase with [DGA-TSIL] [PF6] n-heptane solution of 0.05mol/L, it is dense prepares rare earth ion respectively
Degree be 5.0 × 10-4mol/L, sulfuric acid concentration be 0.2mol/L earth solution, rare earth ion be respectively Eu3+, Y3+, Yb3+ and
Lu3+.The organic phase that volume ratio is 1:1 is mixed with earth solution, at room temperature concussion extraction 15 minutes, extraction series is 1 grade.
After extraction, measure water phase in rare earth ion concentration, calculate Eu3+, Y3+, Yb3+ and Lu3+ distribution ratio difference 5.59,
25.29、6.85、9.26。
Embodiment 9~12
Embodiment 9 with rare earth ion is Eu3+, embodiment 10 use rare earth ion for Y3+, embodiment 11 using rare earth from
Son is Yb3+, embodiment 12 uses rare earth ion to prepare earth solution respectively for Lu3+.
With [D2EHGA-TSIL] [PF6] n-heptane solution of 0.05mol/L be extraction organic phase, respectively prepare rare earth from
Sub- concentration be 5.0 × 10-4mol/L, sulfuric acid concentration be 0.2mol/L earth solution, rare earth ion be respectively Eu3+, Y3+,
Yb3+ and Lu3+.The organic phase that volume ratio is 1:1 is mixed with earth solution, concussion extraction 15 minutes, extracts series at room temperature
It is 1 grade.After extraction, rare earth ion concentration in water phase is measured, calculates the distribution ratio difference of Eu3+, Y3+, Yb3+ and Lu3+
1.22、7.09、3.28、5.16。
Embodiment 13~16
It is Y3+, embodiment 15 using rare earth that embodiment 13, which uses rare earth ion to use rare earth ion for Eu3+, embodiment 14,
Ion is Yb3+, embodiment 16 uses rare earth ion to prepare earth solution respectively for Lu3+.
It is extraction organic phase with [DGA-TSIL] [Tf2N] n-heptane solution of 0.05mol/L, prepares rare earth ion respectively
Concentration is 5.0 × 10-4mol/L, and sulfuric acid concentration is the earth solution of 0.2mol/L, and rare earth ion is respectively Eu3+, Y3+, Yb3+
And Lu3+.The organic phase that volume ratio is 1:1 is mixed with earth solution, at room temperature concussion extraction 15 minutes, extraction series is 1
Grade.After extraction, rare earth ion concentration in water phase is measured, the distribution ratio for calculating Eu3+, Y3+, Yb3+ and Lu3+ is respectively
2.75、12.26、5.22、6.38。
Embodiment 17~20
It is Y3+, embodiment 19 using rare earth that embodiment 17, which uses rare earth ion to use rare earth ion for Eu3+, embodiment 18,
Ion is Yb3+, embodiment 20 uses rare earth ion to prepare earth solution respectively for Lu3+.
With [D2EHGA-TSIL] [Tf2N] n-heptane solution of 0.05mol/L be extraction organic phase, respectively prepare rare earth from
Sub- concentration be 5.0 × 10-4mol/L, sulfuric acid concentration be 0.2mol/L earth solution, rare earth ion be respectively Eu3+, Y3+,
Yb3+ and Lu3+.The organic phase that volume ratio is 1:1 is mixed with earth solution, concussion extraction 15 minutes, extracts series at room temperature
It is 1 grade.After extraction, rare earth ion concentration in water phase is measured, calculates the distribution ratio difference of Eu3+, Y3+, Yb3+ and Lu3+
It is 1.50,4.54,2.71,3.95.
Embodiment 21
Influence of the solution equilibria pH value to [DGA-TSIL] [PF6] extraction single rare earth ionic distribution ratio:
It is extraction organic phase with [DGA-TSIL] [PF6] n-heptane solution of 0.05mol/L, it is dense prepares rare earth ion respectively
Degree is 5.0 × 10-4mol/L, and rare earth ion is respectively Lu3+, Y3+, Eu3+.Volume ratio is molten for the organic phase and rare earth of 1:1
Liquid mixing, concussion extraction 15 minutes at room temperature, extraction series is 1 grade.After extraction, water phase equilibrium ph and right is measured respectively
Rare earth ion concentration in water phase is answered, the distribution coefficient of rare earth ion is calculated.Fig. 2 is [DGA-TSIL] [PF6] when being extractant
The scattergram of solution equilibria pH value and rare earth extraction distribution ratio, it can be seen from the figure that when compared with highly acidity, point of rare earth ion
Proportion reduces as equilibrium ph increases, and in relatively low acidity, when equilibrium ph increases, the distribution ratio of rare earth ion increases
Greatly.
Embodiment 22
Influence of the solution equilibria pH value to [D2EHGA-TSIL] [PF6] extraction single rare earth ionic distribution ratio:
With [D2EHGA-TSIL] [PF6] n-heptane solution of 0.05mol/L be extraction organic phase, respectively prepare rare earth from
Sub- concentration is 5.0 × 10-4mol/L, and rare earth ion is respectively Lu3+, Y3+, Eu3+.By volume ratio be 1:1 organic phase with it is dilute
Native solution mixing, concussion extraction 15 minutes at room temperature, extraction series is 1 grade.After extraction, water phase equilibrium ph is measured respectively
With rare earth ion concentration in corresponding water phase, the distribution coefficient of rare earth ion is calculated.Fig. 3 is that [D2EHGA-TSIL] [PF6] is extraction
The scattergram of solution equilibria pH value and rare earth extraction distribution ratio when taking agent, it can be seen from the figure that working as balance when compared with highly acidity
When pH value increases, the distribution ratio of rare earth ion reduces, and in relatively low acidity, the distribution ratio of rare earth ion increases with equilibrium ph
And increase.
Embodiment 23
It is extraction organic phase with [DGA-TSIL] [PF6] n-heptane solution of 0.10mol/L, takes mixed aqueous solution, metal
Total ion concentration is 3.5 × 10-3mol/L, and sulfuric acid concentration is the mixed solution of 0.2mol/L, and wherein metal ion is respectively Eu3
+, Y3+, Yb3+, Lu3+, Fe3+, Al3+, Zn2+, concentration is 5.0 × 10-4mol/L.By volume ratio be 1:1 organic phase with
Mixed solution, concussion extraction 15 minutes at room temperature, extraction series is 1 grade.After extraction, it is dense to measure metal ion in water phase
Degree, the extraction yield for calculating Eu3+, Y3+, Yb3+, Lu3+ is respectively 87.52%, 97.34%, 88.95%, 91.92%, and
Al3+ and Zn2+ are not extracted, extraction yield < 5% of Fe3+, the results showed that, under the conditions of highly acidity, [DGA-TSIL] [PF6] is preferential
Extracting rare-earth element hardly extracts the impurity elements such as iron, aluminium, zinc.
Embodiment 24
It is extraction organic phase with [D2EHGA-TSIL] [PF6] n-heptane solution of 0.10mol/L, takes mixed aqueous solution, gold
Category total ion concentration is 3.5 × 10-3mol/L, and sulfuric acid concentration is the mixed solution of 0.2mol/L, and wherein metal ion is respectively
Eu3+, Y3+, Yb3+, Lu3+, Fe3+, Al3+, Zn2+, concentration are 5.0 × 10-4mol/L.It is the organic of 1:1 by volume ratio
It is mutually mixed with rare earth sulfate solution, at room temperature concussion extraction 15 minutes, extraction series is 1 grade.After extraction, measure in water phase
Concentration of metal ions, calculate Eu3+, Y3+, Yb3+, Lu3+ extraction yield difference 74.02%, 83.72%, 77.58%,
80.16%, and Fe3+, Al3+ and Zn2+ are not extracted, the results showed that, under the conditions of highly acidity, [D2EHGA-TSIL] [PF6] is excellent
First extracting rare-earth element, does not extract the impurity elements such as iron, aluminium, zinc.
The above is only a preferred embodiment of the present invention, it is noted that various modifications to these embodiments are to this
It will be apparent for the professional technician in field, the general principles defined herein can not depart from the present invention
Spirit or scope in the case where, realize in other embodiments.Therefore, the present invention be not intended to be limited to it is shown in this article this
A little embodiments, and it is to fit to the widest scope consistent with the principles and novel features disclosed herein.
Claims (5)
1. a kind of extracting process of separating-purifying heavy rare earth, which is characterized in that the method is with comprising extractant and diluent
Organic phase extracts rare earth sulfate solution；The extractant is ether amide functional ionic liquids；The ether amide function
Property ionic liquid n-heptane solution concentration be 0.01~0.1mol/L；The method uses water as strip liquor, to extraction
Rare earth element into normal heptane is stripped, and the anti-stripping agent containing rare earth is obtained, and realizes the extraction separation of rare earth element；
The ether amide functional ionic liquids have following structure general formula:
Wherein, R1 and R2 is linear or branched alkyl group independent, at least one is the alkyl base at least four carbon atom
Group, R3 are the straight chained alkyls that carbon atom number is 2~8, and X is chlorine anion, bromine anion, hexafluoro-phosphate radical, bis- (trifluoroalkyl sulphurs
One of acyl group) amido anion.
2. a kind of extracting process of separating-purifying heavy rare earth according to claim 1, which is characterized in that the ether amide function
The preparation method step of energy property ionic liquid are as follows:
(1) anhydride diethylene glycol and dialkylamine that molar ratio is 1.1:1 are reacted in tetrahydrofuran and generates corresponding dialkyl group
Diethylene glycol (DEG) amic acid；
(2) by dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyl) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzo three
Azoles carries out amide reaction in chloroform, by being filtered, washed, silica gel column chromatography separating step obtain ether amide functionalization miaow
Azoles；
(3) ether amide functionalization imidazoles is reacted to the ether amide functional ion liquid for generating that anion is halide ion with halide
Body；
(4) by ether amide functional ionic liquids and inorganic salts that anion is halogen is carried out in the presence of organic reagent it is negative from
Sub- exchange reaction, then be filtered, washed, be evaporated under reduced pressure step and remove inorganic salts and acetonitrile to obtain corresponding ether amide functional
Ionic liquid.
3. a kind of extracting process of separating-purifying heavy rare earth according to claim 2, which is characterized in that the dialkyl group two
The molar ratio that glycol amic acid is reacted with 1- (3- aminopropyl) imidazoles, dicyclohexylcarbodiimide, I-hydroxybenzotriazole is
1.2:1:1.2:1.2, reaction carry out under inert gas protection；
It is 1:1.2 that the ether amide functionalization imidazoles, which reacts molar ratio with alkyl halide, reacts using acetonitrile as solvent, reacts in inertia
It is carried out under gas shield；
The anion is the ether amide functional ionic liquids of halogen and the molar ratio of inorganic salt reaction is 1:2.5, reaction with
Acetonitrile is solvent.
4. a kind of extracting process of separating-purifying heavy rare earth according to claim 1, which is characterized in that the sulfuric acid rare earth
The concentration of solution is 0.2~3mmol/L.
5. a kind of extracting process of separating-purifying heavy rare earth according to claim 1, which is characterized in that the rare earth includes
The one or more of Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Y3+.
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| CN201710466434.4A CN107287456B (en) | 2017-06-20 | 2017-06-20 | A kind of extracting process of separating-purifying heavy rare earth |
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| CN201710466434.4A CN107287456B (en) | 2017-06-20 | 2017-06-20 | A kind of extracting process of separating-purifying heavy rare earth |
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| CN107828961B (en) * | 2017-11-02 | 2024-04-05 | 中国科学院过程工程研究所 | Extraction method of rare earth element ions and obtained rare earth enrichment liquid |
| CN109837400B (en) * | 2018-11-14 | 2021-08-06 | 中国地质科学院郑州矿产综合利用研究所 | Method for extracting rare earth and niobium from niobium-rich slag |
| CN110306059B (en) * | 2019-07-30 | 2020-12-25 | 江西省科学院应用化学研究所 | Method for recycling rare earth in cerium-doped lutetium yttrium silicate waste |
| CN110904350B (en) * | 2019-12-12 | 2021-07-20 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating tungsten and molybdenum |
| CN112574028B (en) * | 2020-12-03 | 2023-09-26 | 福建省长汀金龙稀土有限公司 | Extractant, preparation method and method for separating rare earth yttrium from lanthanide series |
| CN112501460B (en) * | 2020-12-21 | 2022-04-12 | 江苏南方永磁科技有限公司 | Rare earth extraction material, preparation method and application |
| CN113106271B (en) * | 2021-04-06 | 2022-01-14 | 中国科学院过程工程研究所 | Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid |
| CN114934178B (en) * | 2022-06-21 | 2023-03-24 | 中国地质科学院郑州矿产综合利用研究所 | Method for recovering gold from gold smelting slag chloridizing roasting leacheate |
| CN116239490A (en) * | 2022-12-20 | 2023-06-09 | 中国原子能科学研究院 | Amide extractant, preparation method and application thereof |
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| CN103451427A (en) * | 2013-09-24 | 2013-12-18 | 兰州大学 | Heavy rare earth and light rare earth separation method and extraction agent |
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