CN107287456A - 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
- Publication number
- CN107287456A CN107287456A CN201710466434.4A CN201710466434A CN107287456A CN 107287456 A CN107287456 A CN 107287456A CN 201710466434 A CN201710466434 A CN 201710466434A CN 107287456 A CN107287456 A CN 107287456A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- ether amide
- separating
- extraction
- heavy rare
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/36—Heterocyclic compounds
- C22B3/362—Heterocyclic compounds of a single type
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
A kind of extracting process of separating-purifying heavy rare earth, methods described is extracted with the organic phase comprising extractant and diluent to rare earth sulfate solution；The extractant is ether amide functional ionic liquids.Methods described, as strip liquor, is stripped to the rare earth element being extracted in normal heptane using water, obtains the anti-stripping agent containing rare earth, realizes the extraction separation of rare earth element.The present invention improves its dissolubility in diluent and the compatibility to rare earth ion due to the ether-oxygen bond in ether amide functional ionic liquids structure, it is set to be obviously improved the separating capacity between rare earth element, the preferential extraction heavy rare earth element particularly in extraction process, iron, the pre-treatment of aluminium need not be removed, and during follow-up back extraction, usual is only that heavy rare earth can be achieved to be stripped with water, reduces acid and alkali consumption.The present invention is good in extraction process Interfacial Phenomenon, without by extractant saponification, extract and separate effect is can reach without adding salting-out agents.
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 technology
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%, some high-tech sectors such as middle heavy rare earth and photoelectricity, information, the energy, metallurgy of these high values and industry join
Tie-down is close, and product has higher added value, and the irreplaceable important application in the field such as new and high technology and defence and military is
The development of the real external association area of restriction, is the strategic resource with absolute competitive advantage.
At present, the main P507 (2- ethylhexyl phosphonic acid monos (2- ethylhexyls) ester) that uses of single rare earth separation is extraction
Take the extraction separating method of agent.But P507 extraction systems separation heavy rare earth still suffers from back extraction acidity height, and back extraction is incomplete, acid
The problem of alkali consumption is big, influences separation and the High Purity of heavy rare earth.In addition, stepping up with national requirements for environmental protection, existing
Acid and alkali consumption that P507 extraction systems are present is big, ammonia and nitrogen pollution the problems such as become increasingly conspicuous, from the angle of source prevention, develop soda acid
Exploitation of the Novel Extractant and extraction system that consumption is low, selectivity is high to high efficiency rare-earth clean separation new technology is most important.
In recent years, functional ionic liquids have obtained wide as the study hotspot of Green Chemistry in Rare Earth Separation field
Concern, prior art discloses method of the several functions ionic liquid as extractant rare-earth separating, publication number
CN101723975 is disclosed《A kind of preparation method of quaternary amine dual-functional ionic liquid》This method uses quaternary ammonium base and organic
Neutralization reaction between phosphine (carboxylic) acid extraction agent eliminates the hydrogen ion on extractant, realizes non-saponifiable extraction, this method is made
Standby soda acid coupled mode difunctionalization ion liquid abstraction agent (code name is ABC-BIL) can be prevented effectively from phosphine (carboxylic) acid extraction agent should
With produced saponification waste-water pollution on the environment；Publication number CN102618736 discloses one kind《The extraction of rare earth element point
From method》, the method for carrying out extract and separate to rare earth element using above-mentioned ionic liquid；But, it is general in the prior art to use
Functional ionic liquids in sulfuric acid medium to extract and separate trivalent rare earth element ability it is weaker, particularly 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.
The content of the invention
The purpose of the present invention is that in view of the shortcomings 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, easily anti-in sulfuric acid medium without saponification
Extraction.
Realize the technical scheme is that, a kind of extracting process of separating-purifying heavy rare earth, methods described is to 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；
Methods described, as strip liquor, is stripped to the rare earth element being extracted in normal heptane, obtained containing the anti-of rare earth using water
Extract, realizes the extraction separation of rare earth element.
The ether amide functional ionic liquids have following general structure：
Wherein, R1 and R2 is each independent straight or branched alkyl, and at least one is the alkane with least four carbon atom
Base group, R3 is the straight chained alkyl that carbon number is 2~8, and X is chlorine anion, bromine anion, hexafluoro-phosphate radical, double (three fluothane
Base sulfonyl) one kind in amido anion.
The preparation method step of the ether amide functional ionic liquids is：
(1) it is 1.1 by mol ratio:1 anhydride diethylene glycol and dialkylamine reacts generation corresponding two in tetrahydrofuran
Alkyl diethylene glycol (DEG) amic acid；
(2) by dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyls) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzenes
And triazole carries out acid amides reaction in organic reagent, ether amide function is obtained by filtering, washing, silica gel column chromatography separating step
Change imidazoles；
(3) by ether amide functionalization imidazoles and halide react generation anion for halide ion ether amide feature from
Sub- liquid；
(4) anion is carried out for the ether amide functional ionic liquids of halogen with inorganic salts in the presence of organic reagent
Anion exchange reaction, then corresponding ether acyl is obtained by filtering, washing, vacuum distillation step removing inorganic salts and organic reagent
Amine functionality ionic liquid.
The dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyls) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzenes
And the mol ratio of triazole reaction is 1.2:1:1.2:1.2, react using chloroform as solvent, reaction is entered under inert gas shielding
OK；
The ether amide functionalization imidazoles is 1 with alkyl halide reaction mol ratio:1.2, react using acetonitrile as solvent, reaction exists
Carried out under inert gas shielding；
The anion is the ether amide functional ionic liquids of halogen and the mol ratio of inorganic salt reaction is 1:2.5, instead
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 Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Y3+ one or more.
The beneficial effects of the invention are as follows 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, it is obtained the separating capacity between rare earth element
To being obviously improved, the preferential extraction heavy rare earth element particularly in extraction process, it is not necessary to except the pre-treatment of iron, aluminium, and
During follow-up back extraction, usual is only that heavy rare earth can be achieved to be stripped with water, reduces acid and alkali consumption.In addition, present invention side
Method is good in extraction process Interfacial Phenomenon, without by extractant saponification, extract and separate effect is can reach without adding salting-out agents
Really.
Brief description of the drawings
Fig. 1 is the structural formula figure of ether amide functional ionic liquids of the present invention；
Fig. 2 is [DGA] [PF6] as solution equilibria pH value during extractant and the scattergram of rare earth ion distribution coefficient；
Fig. 3 is [D2EHGA] [PF6] as solution equilibria pH value during extractant and the point-like of rare earth ion distribution coefficient
Figure.
Embodiment
Embodiment 1
Weigh 100g anhydride diethylene glycols to be dissolved in 1000mL tetrahydrofurans, add the n-octyl amines of 189g bis-, under argon gas protection
Normal-temperature reaction 48h, resulting solution is dissolved in 400mL chloroforms after revolving, through distillation, true after being washed with dilute hydrochloric acid solution
Sky is dried, and obtains dioctyl diethylene glycol (DEG) amic acid；By 90g dioctyl diethylene glycol (DEG)s amic acid, 37.2g aminopropyls imidazoles, 61.2g bis-
Carbodicyclo hexylimide, 40.2g I-hydroxybenzotriazoles are dissolved in 1000mL chloroforms, the normal-temperature reaction under argon gas protection
12h, will be dissolved in 500mL ethyl acetate after solution decompression suction filtration, distillation, the 1- hydroxyls for removing residual is washed with sodium carbonate liquor
Ethyl acetate is screwed out under BTA, vacuum condition, using silica gel column chromatography, with chloroform and methanol as mobile phase,
Obtain 2- [2- (oxo of aminopropyl imidazoles -2)]-N, N- dioctyl acetamides；Weigh the 102g 2- [2- (oxygen of aminopropyl imidazoles -2
Generation)]-N, N- dioctyls acetamide, 37.14g NBBs be dissolved in 1000mL acetonitriles, in 80 DEG C of stirring reaction 48h, uses n-hexane
Washing removes excessive NBB, and revolving removes acetonitrile, obtains the imidazoles bromide of ether amide functionalization；By 71g ether amide functionalization
Imidazoles bromide be dissolved in 600mL acetonitriles, mixed with the acetonitrile solution of the double trifluoromethanesulfonimide lithiums of 85.2g, at normal temperatures
24h is reacted, the double trifluoromethanesulfonimide lithiums for removing residual are washed with water, vacuum condition backspin steams acetonitrile and water, obtained
Double trifluoromethanesulfonimide roots are the ether amide functional ionic liquids of anion, labeled as [DGA-TSIL] [Tf2N].
Embodiment 2
Weigh 100g anhydride diethylene glycols to be dissolved in 1000mL tetrahydrofurans, 189g bis- (2- ethylhexyls) amine is added, in argon
Normal-temperature reaction 48h under gas shielded, resulting solution is dissolved in 400mL chloroforms after revolving, after being washed with dilute hydrochloric acid solution
Through distillation, vacuum drying, two (2- ethylhexyls) diethylene glycol (DEG) amic acids are obtained；By 90g bis- (2- ethylhexyls) diethylene glycol (DEG) acid amides
Acid, 37.2g aminopropyls imidazoles, 61.2g dicyclohexylcarbodiimides, 40.2g I-hydroxybenzotriazoles are dissolved in the chloromethanes of 1000mL tri-
In alkane, the normal-temperature reaction 12h under argon gas protection will be dissolved in 500mL ethyl acetate after solution decompression suction filtration, distillation, use carbonic acid
Sodium solution washing removes and screws out ethyl acetate under the I-hydroxybenzotriazole of residual, vacuum condition, using silica gel column chromatography, uses
Chloroform and methanol obtain 2- [2- (oxo of aminopropyl imidazoles -2)]-N, N- bis- (2- ethylhexyls) acetyl as mobile phase
Amine；102g 2- [2- (oxo of aminopropyl imidazoles -2)]-N is weighed, N- bis- (2- ethylhexyls) acetamide, 37.14g NBBs are molten
In 1000mL acetonitriles, in 80 DEG C of stirring reaction 48h, the excessive NBB of removing is washed with n-hexane, revolving removes acetonitrile, obtained
The imidazoles bromide of ether amide functionalization；The imidazoles bromide of 71g ether amide functionalization is dissolved in 600mL acetonitriles, with 50.12g six
The acetonitrile solution mixing of sodium fluoro phosphate, reacts 24h, the sodium hexafluoro phosphate for removing residual, vacuum condition is washed with water at normal temperatures
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
Weigh 100g anhydride diethylene glycols to be dissolved in 1000mL tetrahydrofurans, add the n-octyl amines of 189g bis-, under argon gas protection
Normal-temperature reaction 48h, resulting solution is dissolved in 400mL chloroforms after revolving, through distillation, true after being washed with dilute hydrochloric acid solution
Sky is dried, and obtains dioctyl diethylene glycol (DEG) amic acid；By 90g dioctyl diethylene glycol (DEG)s amic acid, 37.2g aminopropyls imidazoles, 61.2g bis-
Carbodicyclo hexylimide, 40.2g I-hydroxybenzotriazoles are dissolved in 1000mL chloroforms, the normal-temperature reaction under argon gas protection
12h, will be dissolved in 500mL ethyl acetate after solution decompression suction filtration, distillation, the 1- hydroxyls for removing residual is washed with sodium carbonate liquor
Ethyl acetate is screwed out under BTA, vacuum condition, using silica gel column chromatography, with chloroform and methanol as mobile phase,
Obtain 2- [2- (oxo of aminopropyl imidazoles -2)]-N, N- dioctyl acetamides；Weigh the 102g 2- [2- (oxygen of aminopropyl imidazoles -2
Generation)]-N, N- dioctyls acetamide, 37.14g chlorobutanes be dissolved in 1000mL acetonitriles, in 90 DEG C of stirring reaction 48h, uses n-hexane
Washing removes excessive chlorobutane, and revolving removes acetonitrile, obtains the imidazoles villaumite of ether amide functionalization；By 65.87g ether amide functions
The imidazoles villaumite of change is dissolved in 600mL acetonitriles, is mixed with the acetonitrile solution of 50.12g sodium hexafluoro phosphates, 24h is reacted at normal temperatures,
The sodium hexafluoro phosphate for removing residual is washed with water, vacuum condition backspin steams acetonitrile and water, obtains hexafluoro-phosphate radical for anion
Ether amide base functional ionic liquids, labeled as [DGA-TSIL] [PF6].
Embodiment 4
Weigh 100g anhydride diethylene glycols to be dissolved in 1000mL tetrahydrofurans, 189g bis- (2- ethylhexyls) amine is added, in argon
Normal-temperature reaction 48h under gas shielded, resulting solution is dissolved in 400mL chloroforms after revolving, after being washed with dilute hydrochloric acid solution
Through distillation, vacuum drying, two (2- ethylhexyls) diethylene glycol (DEG) amic acids are obtained；By 90g bis- (2- ethylhexyls) diethylene glycol (DEG) acid amides
Acid, 37.2g aminopropyls imidazoles, 61.2g dicyclohexylcarbodiimides, 40.2g I-hydroxybenzotriazoles are dissolved in the chloromethanes of 1000mL tri-
In alkane, the normal-temperature reaction 12h under argon gas protection will be dissolved in 500mL ethyl acetate after solution decompression suction filtration, distillation, use carbonic acid
Sodium solution washing removes and screws out ethyl acetate under the I-hydroxybenzotriazole of residual, vacuum condition, using silica gel column chromatography, uses
Chloroform and methanol obtain 2- [2- (oxo of aminopropyl imidazoles -2)]-N, N- bis- (2- ethylhexyls) acetyl as mobile phase
Amine；102g 2- [2- (oxo of aminopropyl imidazoles -2)]-N is weighed, N- bis- (2- ethylhexyls) acetamide, 37.14g chlorobutanes are molten
In 1000mL acetonitriles, in 85 DEG C of stirring reaction 48h, the excessive chlorobutane of removing is washed with n-hexane, revolving removes acetonitrile, obtained
The imidazoles bromide of ether amide functionalization；The imidazoles villaumite of 65.87g ether amide functionalization is dissolved in 600mL acetonitriles, with 85.2g
The acetonitrile solution mixing of double trifluoromethanesulfonimide lithiums, reacts 24h, the double fluoroforms for removing residual is washed with water at normal temperatures
Alkane sulfimide lithium, vacuum condition backspin steams acetonitrile and water, obtains the ether acyl that double trifluoromethanesulfonimide roots are anion
Amido functional ionic liquids, labeled as [D2EHGA-TSIL] [Tf2N].
Embodiment 5~8
Embodiment 5 use rare earth ion used for Eu3+, embodiment 6 rare earth ion for Y3+, embodiment 7 using rare earth from
Son is that Yb3+, embodiment 8 use rare earth ion to prepare earth solution respectively for Lu3+.
Using 0.05mol/L [DGA-TSIL] [PF6] n-heptane solution as extraction organic phase, rare earth ion is prepared respectively dense
Spend for 5.0 × 10-4mol/L, sulfuric acid concentration is 0.2mol/L earth solution, rare earth ion be respectively Eu3+, Y3+, Yb3+ and
Lu3+.It is 1 by volume ratio:1 organic phase is mixed with earth solution, at room temperature concussion extraction 15 minutes, and extraction series is 1 grade.
Extraction finish after, determine aqueous phase 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 be Eu3+, embodiment 10 use rare earth ion for Y3+, embodiment 11 using rare earth from
Son is that Yb3+, embodiment 12 use rare earth ion to prepare earth solution respectively for Lu3+.
Using 0.05mol/L [D2EHGA-TSIL] [PF6] n-heptane solution as 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+.It is 1 by volume ratio:1 organic phase is mixed with earth solution, and concussion extraction 15 minutes, extracts series at room temperature
For 1 grade.After extraction is finished, aqueous phase Rare Earth Ion concentration is determined, Eu3+, Y3+, Yb3+ and Lu3+ distribution ratio difference is calculated
1.22、7.09、3.28、5.16。
Embodiment 13~16
Embodiment 13 uses rare earth ion to use rare earth ion to use rare earth for Y3+, embodiment 15 for Eu3+, embodiment 14
Ion is that Yb3+, embodiment 16 use rare earth ion to prepare earth solution respectively for Lu3+.
Using 0.05mol/L [DGA-TSIL] [Tf2N] n-heptane solution as extraction organic phase, rare earth ion is prepared respectively
Concentration is 5.0 × 10-4mol/L, and sulfuric acid concentration is 0.2mol/L earth solution, and rare earth ion is respectively Eu3+, Y3+, Yb3+
And Lu3+.It is 1 by volume ratio:1 organic phase is mixed with earth solution, at room temperature concussion extraction 15 minutes, and extraction series is 1
Level.After extraction is finished, aqueous phase Rare Earth Ion concentration is determined, the distribution ratio for calculating Eu3+, Y3+, Yb3+ and Lu3+ is respectively
2.75、12.26、5.22、6.38。
Embodiment 17~20
Embodiment 17 uses rare earth ion to use rare earth ion to use rare earth for Y3+, embodiment 19 for Eu3+, embodiment 18
Ion is that Yb3+, embodiment 20 use rare earth ion to prepare earth solution respectively for Lu3+.
Using 0.05mol/L [D2EHGA-TSIL] [Tf2N] n-heptane solution as 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+.It is 1 by volume ratio:1 organic phase is mixed with earth solution, and concussion extraction 15 minutes, extracts series at room temperature
For 1 grade.After extraction is finished, aqueous phase Rare Earth Ion concentration is determined, Eu3+, Y3+, Yb3+ and Lu3+ distribution ratio difference is calculated
For 1.50,4.54,2.71,3.95.
Embodiment 21
Solution equilibria pH value to [DGA-TSIL] [PF6] extract single rare earth ionic distribution than influence：
Using 0.05mol/L [DGA-TSIL] [PF6] n-heptane solution as extraction organic phase, rare earth ion is prepared respectively dense
Spend for 5.0 × 10-4mol/L, rare earth ion is respectively Lu3+, Y3+, Eu3+.It is 1 by volume ratio:1 organic phase and rare earth are molten
Liquid is mixed, at room temperature concussion extraction 15 minutes, and extraction series is 1 grade.After extraction is finished, aqueous phase equilibrium ph is determined respectively and right
Aqueous phase Rare Earth Ion concentration is answered, the distribution coefficient of rare earth ion is calculated.When Fig. 2 is extractant for [DGA-TSIL] [PF6]
The scattergram of solution equilibria pH value and rare earth extraction distribution ratio, it can be seen that when compared with highly acidity, point of rare earth ion
Proportioning reduces as equilibrium ph increases, in relatively low acidity, when equilibrium ph increases, and the distribution ratio of rare earth ion increases
Greatly.
Embodiment 22
Solution equilibria pH value to [D2EHGA-TSIL] [PF6] extract single rare earth ionic distribution than influence：
Using 0.05mol/L [D2EHGA-TSIL] [PF6] n-heptane solution as 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+.It is 1 by volume ratio:1 organic phase with it is dilute
Native solution mixing, concussion extraction 15 minutes at room temperature, extraction series is 1 grade.After extraction is finished, aqueous phase equilibrium ph is determined respectively
With correspondence aqueous phase Rare Earth Ion concentration, 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 that when compared with highly acidity, working as balance
When pH value increases, the distribution ratio of rare earth ion reduces, in relatively low acidity, and the distribution ratio of rare earth ion increases with equilibrium ph
And increase.
Embodiment 23
Using 0.10mol/L [DGA-TSIL] [PF6] n-heptane solution as extraction organic phase, mixed aqueous solution, metal are taken
Total ion concentration is 3.5 × 10-3mol/L, and sulfuric acid concentration is 0.2mol/L mixed solution, and wherein metal ion is respectively Eu3
+, Y3+, Yb3+, Lu3+, Fe3+, Al3+, Zn2+, concentration is 5.0 × 10-4mol/L.It is 1 by volume ratio:1 organic phase with
Mixed solution, concussion extraction 15 minutes at room temperature, extraction series is 1 grade.After extraction is finished, metal ion in aqueous phase is determined dense
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, Fe3+ extraction yield<5%, as a result show, under the conditions of highly acidity, [DGA-TSIL] [PF6] is preferential
Extracting rare-earth element, is hardly extracted to impurity elements such as iron, aluminium, zinc.
Embodiment 24
Using 0.10mol/L [D2EHGA-TSIL] [PF6] n-heptane solution as extraction organic phase, mixed aqueous solution is taken, gold
Category total ion concentration is 3.5 × 10-3mol/L, and sulfuric acid concentration is 0.2mol/L mixed solution, and wherein metal ion is respectively
Eu3+, Y3+, Yb3+, Lu3+, Fe3+, Al3+, Zn2+, concentration are 5.0 × 10-4mol/L.It is 1 by volume ratio:1 it is organic
Mixed with rare earth sulfate solution, at room temperature concussion extraction 15 minutes, extraction series is 1 grade.After extraction is finished, determine in aqueous 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, and are as a result shown, under the conditions of highly acidity, [D2EHGA-TSIL] [PF6] is excellent
First extracting rare-earth element, is not extracted to impurity elements such as iron, aluminium, zinc.
Described above is only the preferred embodiment of the present invention, it is noted that to a variety of modifications of these embodiments to this
It will be apparent for the professional and technical personnel in field, generic principles defined herein can not depart from the present invention
Spirit or scope in the case of, 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 most wide scope consistent with features of novelty with principles disclosed herein.
Claims (7)
1. a kind of extracting process of separating-purifying heavy rare earth, it is characterised in that methods described is with comprising extractant and diluent
Organic phase is extracted to rare earth sulfate solution；The extractant is ether amide functional ionic liquids；Methods described uses water
As strip liquor, the rare earth element being extracted in normal heptane is stripped, the anti-stripping agent containing rare earth is obtained, realizes rare earth
The extraction separation of element.
2. a kind of extracting process of separating-purifying heavy rare earth according to claim 1, it is characterised in that the ether amide work(
Energy property ionic liquid has following general structure：
Wherein, R1 and R2 is each independent straight or branched alkyl, and at least one is the alkyl base with least four carbon atom
Group, R3 is the straight chained alkyl that carbon number is 2~8, and X is chlorine anion, bromine anion, hexafluoro-phosphate radical, double (trifluoroalkyl sulphurs
Acyl group) one kind in amido anion.
3. a kind of extracting process of separating-purifying heavy rare earth according to claim 2, it is characterised in that the ether amide work(
Can the preparation method step of property ionic liquid be：
(1) it is 1.1 by mol ratio:1 anhydride diethylene glycol and dialkylamine reacts the corresponding dialkyl group of generation in tetrahydrofuran
Diethylene glycol (DEG) amic acid；
(2) by dialkyl group diethylene glycol (DEG) amic acid and 1- (3- aminopropyls) imidazoles, dicyclohexylcarbodiimide, 1- hydroxy benzos three
Azoles carries out acid amides reaction in organic reagent, and ether amide functionalization miaow is obtained by filtering, washing, silica gel column chromatography separating step
Azoles；
(3) ether amide functionalization imidazoles and halide are reacted into the ether amide functional ion liquid that generation anion is halide ion
Body；
(4) by anion for ether amide functional ionic liquids and the inorganic salts of halogen is carried out in the presence of organic reagent the moon from
Sub- exchange reaction, then corresponding ether amide work(is obtained by filtering, washing, vacuum distillation step removing inorganic salts and organic reagent
Can property ionic liquid.
4. a kind of extracting process of separating-purifying heavy rare earth according to claim 3, it is characterised in that the dialkyl group two
Glycol amic acid and the mol ratio of 1- (3- aminopropyls) imidazoles, dicyclohexylcarbodiimide, I-hydroxybenzotriazole reaction are
1.2:1:1.2:1.2, react using chloroform as solvent, reaction is carried out under inert gas shielding；
The ether amide functionalization imidazoles is 1 with alkyl halide reaction mol ratio:1.2, react using acetonitrile as solvent, react in inertia
Carried out under gas shield；
The anion is the ether amide functional ionic liquids of halogen and the mol ratio of inorganic salt reaction is 1:2.5, reaction with
Acetonitrile is solvent.
5. a kind of extracting process of separating-purifying heavy rare earth according to claim 2, the ether amide functional ion liquid
The concentration of the n-heptane solution of body is 0.01~0.1mol/L.
6. a kind of extracting process of separating-purifying heavy rare earth according to claim 1, it is characterised in that the sulfuric acid rare earth
The concentration of solution is 0.2~3mmol/L.
7. the extracting process of a kind of separating-purifying heavy rare earth according to claim 1, it is characterised in that the rare earth includes
Eu3+, Tb3+, Dy3+, Ho3+, Er3+, Tm3+, Yb3+, Lu3+, Y3+ one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710466434.4A CN107287456B (en) | 2017-06-20 | 2017-06-20 | A kind of extracting process of separating-purifying heavy rare earth |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710466434.4A CN107287456B (en) | 2017-06-20 | 2017-06-20 | A kind of extracting process of separating-purifying heavy rare earth |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107287456A true CN107287456A (en) | 2017-10-24 |
| CN107287456B CN107287456B (en) | 2019-01-18 |
Family
ID=60097339
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710466434.4A Active CN107287456B (en) | 2017-06-20 | 2017-06-20 | A kind of extracting process of separating-purifying heavy rare earth |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107287456B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828961A (en) * | 2017-11-02 | 2018-03-23 | 中国科学院过程工程研究所 | A kind of extracting process of rare earth element ion and obtained rare-earth enrichment liquid |
| CN109837400A (en) * | 2018-11-14 | 2019-06-04 | 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 |
| CN110306059A (en) * | 2019-07-30 | 2019-10-08 | 江西省科学院应用化学研究所 | A method of rare earth in recycling cerium dopping yttrium luetcium silicate waste material |
| CN110904350A (en) * | 2019-12-12 | 2020-03-24 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating tungsten and molybdenum |
| CN112501460A (en) * | 2020-12-21 | 2021-03-16 | 江苏南方永磁科技有限公司 | Rare earth extraction material, preparation method and application |
| CN112574028A (en) * | 2020-12-03 | 2021-03-30 | 厦门钨业股份有限公司 | Extracting agent, preparation method thereof and method for separating rare earth element yttrium from lanthanide |
| CN113106271A (en) * | 2021-04-06 | 2021-07-13 | 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 |
| CN114934178A (en) * | 2022-06-21 | 2022-08-23 | 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 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382982A (en) * | 2011-11-10 | 2012-03-21 | 中国科学院过程工程研究所 | Method for separating rare earth ions by extraction of liquid-liquid-liquid three-phase system |
| CN103451427A (en) * | 2013-09-24 | 2013-12-18 | 兰州大学 | Heavy rare earth and light rare earth separation method and extraction agent |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
| WO2017096470A1 (en) * | 2015-12-10 | 2017-06-15 | Université de Montréal | Ionic liquids and their use in the extraction of rare earth elements and/or gallium |
-
2017
- 2017-06-20 CN CN201710466434.4A patent/CN107287456B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102382982A (en) * | 2011-11-10 | 2012-03-21 | 中国科学院过程工程研究所 | Method for separating rare earth ions by extraction of liquid-liquid-liquid three-phase system |
| CN103451427A (en) * | 2013-09-24 | 2013-12-18 | 兰州大学 | Heavy rare earth and light rare earth separation method and extraction agent |
| WO2017096470A1 (en) * | 2015-12-10 | 2017-06-15 | Université de Montréal | Ionic liquids and their use in the extraction of rare earth elements and/or gallium |
| CN106399686A (en) * | 2016-09-05 | 2017-02-15 | 厦门稀土材料研究所 | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107828961A (en) * | 2017-11-02 | 2018-03-23 | 中国科学院过程工程研究所 | A kind of extracting process of rare earth element ion 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 |
| CN109837400A (en) * | 2018-11-14 | 2019-06-04 | 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 |
| CN110306059A (en) * | 2019-07-30 | 2019-10-08 | 江西省科学院应用化学研究所 | A method of rare earth in recycling cerium dopping yttrium luetcium silicate waste material |
| 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 |
| CN110904350A (en) * | 2019-12-12 | 2020-03-24 | 中国地质科学院郑州矿产综合利用研究所 | Method for separating tungsten and molybdenum |
| CN112574028A (en) * | 2020-12-03 | 2021-03-30 | 厦门钨业股份有限公司 | Extracting agent, preparation method thereof and method for separating rare earth element yttrium from lanthanide |
| 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 |
| CN112501460A (en) * | 2020-12-21 | 2021-03-16 | 江苏南方永磁科技有限公司 | Rare earth extraction material, preparation method and application |
| CN113106271A (en) * | 2021-04-06 | 2021-07-13 | 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 |
| CN114934178A (en) * | 2022-06-21 | 2022-08-23 | 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107287456B (en) | 2019-01-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107287456B (en) | A kind of extracting process of separating-purifying heavy rare earth | |
| CN108384970B (en) | The extraction agent solution and extracting process of titanium and iron are extracted from containing the more metal chloride acid solutions of ferrotianium | |
| Sun et al. | The adjustable synergistic effects between acid–base coupling bifunctional ionic liquid extractants for rare earth separation | |
| CN104894372B (en) | Method for extracting and separating trivalent lanthanum and trivalent actinium ion | |
| CN103272554B (en) | The preparation method of lithium manganese oxide-type lithium adsorbent | |
| CN105016368A (en) | Iron-containing aluminum chloride solution iron removal method | |
| JP2014531415A (en) | Bisquaternary ammonium salt ionic liquid having two centers, process for its preparation and use | |
| CN106399686A (en) | Acidic ionic liquid and method for separating and purifying rare earth or rare and precious metals by solvent extraction coupling electrolytic process | |
| WO2007071028A1 (en) | Compounds, complexes and uses thereof | |
| CN105536707A (en) | Material for separating lithium isotope, preparation method and application thereof | |
| CN110563653A (en) | asymmetric alkyl pyrazole ionic liquid, preparation method thereof and application of ionic liquid as metal corrosion inhibitor | |
| CN101638722A (en) | Method for extracting and separating uranyl ions from aqueous phase | |
| CN103449480A (en) | Battery-grade high-purity lithium fluoride and preparation method thereof | |
| CN108676029B (en) | Benzyl triphenyl phosphonium bis (trifluoromethane) sulfonyl imide ionic liquid, synthetic method and application thereof as metal corrosion inhibitor | |
| CN112981139A (en) | Hydrophobic eutectic solvent for separating nickel and cobalt ions, preparation method thereof and method for separating nickel and cobalt ions | |
| CN106669538A (en) | Composite surfactant with excellent surface activity and spumescence | |
| CN110306059B (en) | Method for recycling rare earth in cerium-doped lutetium yttrium silicate waste | |
| CN114934178B (en) | Method for recovering gold from gold smelting slag chloridizing roasting leacheate | |
| Li et al. | Separation of valuable metals from mixed cathode materials of spent lithium-ion batteries by single-stage extraction | |
| CN106532123A (en) | Electrolyte for lithium-ion battery and battery containing electrolyte | |
| CN103601240B (en) | Preparation method of silver hexafluoroantimonate | |
| CN114150159B (en) | Temperature-controlled noble metal separation and extraction agent, preparation method thereof and homogeneous extraction method | |
| CN109830772A (en) | A kind of regeneration method of LiFePO4 waste material | |
| JPH03291332A (en) | Separation of rare earth element | |
| CN104399364B (en) | A kind of ionic liquid containing nitro is for the method for sulfur dioxide absorption gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |