CN103789547B - A kind of ionic liquid extration resin and methods for making and using same thereof - Google Patents
A kind of ionic liquid extration resin and methods for making and using same thereof Download PDFInfo
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Abstract
The present invention relates to a kind of can the ionic liquid extration resin of high efficiente callback rare earth and methods for making and using same thereof, this ionic liquid extration resin has programmable zwitterion constructional feature, the physicochemical property of ionic liquid extration resin can be regulated and controled by the structure or kind changing zwitterion, overcome the problem of traditional extration resin function singleness, extraction agent poor stability, the recovery that can be used for solution middle-weight rare earths be separated.The preparation method of ionic liquid extration resin of the present invention take styrene series anion exchange resin as solid support material, acted on styrene-divinylbenzene skeleton by non covalent bond and introduce acid phosphine extraction agent, obtain the ionic liquid extration resin that acid phosphine extraction agent is modified.Ionic liquid extration resin of the present invention can efficient recovery rare earth ion, and it has higher adsorption rate and adsorption selectivity to rare earth ion, can be used for separation and the recovery of complex system middle-weight rare earths.
Description
Technical field
The invention belongs to ionic liquid extration resin field, be specifically related to a kind of can the ionic liquid extration resin of high efficiente callback rare earth and methods for making and using same thereof.
Background technology
Extraction and separation technology is used widely in a lot of field, but directly adopting solvent extration to carry out recovery separation to the rare earth in dilute solution is not a kind of cost-effective method, it is large that it also also exists partial extraction agent solubleness, organic phase is easily caused to lose, the discharge of organic liquid waste can increase the problems such as environmental pressure, and the problems referred to above that develop into of extration resin isolation technique provide a new approach.Extration resin is adsorbed onto by extraction agent on macroporous polymer carrier to be prepared from, have the highly selective of solvent extration and easy, the high efficiency of ion exchange technique concurrently, also overcome partial extraction agent layering difficulty simultaneously, the advantages such as ion exchange resin and resin synthesis complexity, are more and more applied to the recovery separation field of metal ion.
At present, extration resin technology recovery separating metal ions is adopted to obtain the concern of vast researcher.Difunctional ion liquid abstraction agent [A336] [CA-100] is impregnated in Amberlite XAD-7 and has prepared extration resin by Chen Ji etc., achieves Sc
3+with Y
3+, Eu
3+, Ce
3+effective separation (X Sun, Y Ji, J Chen, J Ma, J.Rare Earth, 2009,27 (6): 932-936.); Chen etc. are by D
2eHPA is impregnated on Amberlite XAD-4, and the extration resin of preparation can from Pb
2+and Cu
2+in mixing solutions, selective separation goes out Pb
2+(J.H.Chen, Y.Y.Kao, C.H.Lin, F.R.Yang, Sep.Sci.Technol., 2004,39:2067-2090.).Although extration resin overcomes the deficiency that extraction agent exists in metal extraction process, but also there is following limitation in the application of extration resin in metal separation reclaims prepared by traditional method: first, tradition extration resin function singleness, is only determined by extraction agent the extracting power of metal ion, selectivity and extraction mechanisms; Secondly, tradition extration resin be by extraction agent by surface affinity physical adsorption in polymer support, extraction agent is stable not high, contact with strong acid, strong base substance for a long time, easily cause the loss of active ingredient, affect its working life, limit the widespread use of extration resin in extracting and separating field and development.
Summary of the invention
The object of the invention is the technical problem that there is function singleness and extraction agent poor stability for traditional extration resin, a kind of programmable zwitterion constructional feature of having is provided, can the ionic liquid extration resin of high efficiente callback rare earth and methods for making and using same thereof.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A kind of ionic liquid extration resin,
Take styrene series anion exchange resin as positively charged ion donor, with the acid phosphine extraction agent of deprotonation for anionic donor;
The concrete structure formula of described positively charged ion donor is:
The concrete structure formula of described anionic donor is:
or
R in described positively charged ion donor
1, R
2be respectively methyl, R
3for methyl or hydroxyethyl;
R in described anionic donor
4, R
5be respectively identical or different, substituent that carbonatoms is the alkyl of 8.
In technique scheme, described anionic donor is two-(2 of deprotonation, 4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), two-(2-ethylhexyl) phosphonic acids (P204) or 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507).
The preparation method of described ionic liquid extration resin, comprises the following steps:
(1) first with hydrochloric acid soln or sodium hydroxide solution washing chlorine type highly basic phenylethylene resin series, be then neutral by washed with de-ionized water to flowing liquid pH value;
Again with sodium hydroxide solution or hydrochloric acid soln washing chlorine type highly basic phenylethylene resin series, be then neutral by washed with de-ionized water to flowing liquid pH value;
Adding sodium hydroxide solution at room temperature stirring reaction, is then neutral by washed with de-ionized water to solution ph;
20 DEG C of-50 DEG C of dryings after filtration, obtain hydrogen-oxygen type highly basic phenylethylene resin series;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed in DMF, swelling 0.5-6h under room temperature, add acid phosphine extraction agent again, filter after abundant reaction, wash, dry at 20 DEG C-50 DEG C, obtain ionic liquid extration resin.
In technique scheme, the volume ratio of the chlorine type highly basic phenylethylene resin series described in step (1) and hydrochloric acid, sodium hydroxide solution is 1:1 ~ 1:4.
In technique scheme, being used for the concentration of the hydrochloric acid soln and sodium hydroxide solution that wash chlorine type highly basic phenylethylene resin series in step (1) is respectively 2-4%.
In technique scheme, in step (2), the mol ratio of hydrogen-oxygen type highly basic phenylethylene resin series and acid phosphine extraction agent is 1:1 ~ 1:2.
In technique scheme, the reaction times of the abundant reaction in step (2) is 6-48h.
The application method of described ionic liquid extration resin, this ionic liquid extration resin can be applicable to recovering rare earth ion.
In technique scheme, described rare earth ion be in trivalent rare earth ions any one or multiple.
The present invention has following beneficial effect:
Ionic liquid extration resin of the present invention take styrene series anion exchange resin as positively charged ion donor, with the acid phosphine extraction agent of deprotonation for anionic donor.Ionic liquid extration resin of the present invention has programmable zwitterion constructional feature, can by changing structure or the kind of zwitterion, and the physicochemical property of regulation and control ionic liquid extration resin, overcome the shortcoming of traditional extration resin function singleness.
Because the present invention is reacted by acid-base neutralisation, be fixed in styrene-divinylbenzene skeleton structure by acid phosphine extraction agent by non covalent bond effect, the stability of extraction agent is higher than the traditional extration resin be distributed to by physisorption in carrier.Ionic liquid extration resin of the present invention can efficient recovery rare earth ion, and it has higher adsorption rate and adsorption selectivity to rare earth ion, can be used for separation and the recovery of complex system middle-weight rare earths.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is to Lu under Application Example 1 ~ 2 different pH condition of the present invention
3+the graphic representation of adsorption rate;
Fig. 2 is to Yb under Application Example 4 ~ 5 different pH condition of the present invention
3+the graphic representation of adsorption rate;
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
Preparation embodiment 1
(1) 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 20 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:1;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 0.5h under room temperature, then add two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), after abundant reaction 6h, filter out resin, use absolute ethanol washing resin, dry at 20 DEG C, obtain the ionic liquid extration resin ([D201] [C272]) that Cyanex272 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272) is 1:1.
Preparation embodiment 2
(1) 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 50 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:4;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, then add two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), after abundant reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 50 DEG C, obtain the ionic liquid extration resin ([D201] [C272]) that Cyanex272 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272) is 1:1.2.
Preparation embodiment 3
(1) 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 40 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:2;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, then add two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), after abundant reaction 21h, filter out resin, use absolute ethanol washing resin, dry at 40 DEG C, obtain the ionic liquid extration resin ([D201] [C272]) that Cyanex272 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272) is 1:1.8.
Preparation embodiment 4
(1) 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 50 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:3;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, add two-(2-ethylhexyl) phosphonic acids (P204) again, after abundant reaction 48h, filter out resin, use absolute ethanol washing resin, dry at 50 DEG C, obtain the ionic liquid extration resin ([D201] [P204]) that P204 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2-ethylhexyl) phosphonic acids (P204) is 1:1.5.
Preparation embodiment 5
(1) 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 20 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:3.5;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 0.5h under room temperature, add two-(2-ethylhexyl) phosphonic acids (P204) again, after abundant reaction 40h, filter out resin, use absolute ethanol washing resin, dry at 20 DEG C, obtain the ionic liquid extration resin ([D201] [P204]) that P204 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2-ethylhexyl) phosphonic acids (P204) is 1:2.
Preparation embodiment 6
(1) 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 40 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:2.5;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, add two-(2-ethylhexyl) phosphonic acids (P204) again, after abundant reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 40 DEG C, obtain the ionic liquid extration resin ([D201] [P204]) that P204 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and two-(2-ethylhexyl) phosphonic acids (P204) is 1:2.
Preparation embodiment 7
(1) 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 50 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:1.5;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, add 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507) again, after abundant reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 50 DEG C, obtain the ionic liquid extration resin ([D201] [P507]) that P507 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507) is 1:1.
Preparation embodiment 8
(1) 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 20 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:3.5;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 0.5h under room temperature, add 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester again, after abundant reaction, filter out resin, use absolute ethanol washing resin, dry at 20 DEG C, obtain the ionic liquid extration resin ([D201] [P507]) that P507 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is 1:1.
Preparation embodiment 9
(1) 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type) is used respectively, and being neutrality by the deionized water pH value of repeatedly cleaning to flowing liquid, finally use sodium hydroxide solution and resin at room temperature stirring reaction, the pH value of deionized water wash solution is neutral, filter, 40 DEG C of dryings, obtain the highly basic phenylethylene resin series of hydrogen-oxygen type; The volume ratio of described chlorine type highly basic phenylethylene resin series and hydrochloric acid, sodium hydroxide solution is 1:1.5;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, add 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester again, after abundant reaction, filter out resin, use absolute ethanol washing resin, dry at 40 DEG C, obtain the ionic liquid extration resin ([D201] [P507]) that P507 modifies.
The mol ratio of described hydrogen-oxygen type highly basic phenylethylene resin series and 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester is 1:2.
Application Example 1
Take 0.3g and prepare ionic liquid extration resin that embodiment 2 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of the different acidity of 100mL preparation containing Lu
3+the feed liquid of concentration to be 0.5mmol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Lu
3+adsorption rate, adsorption rate the results are shown in Figure 1.When material liquid pH value is 5.16, the ionic liquid extration resin that preparation embodiment 2 obtains is to Lu
3+reach maximum adsorption.
Application Example 2
Take 0.3g and prepare ionic liquid extration resin that embodiment 4 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of the different acidity of 100mL preparation containing Lu
3+the feed liquid of concentration to be 0.5mmol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Lu
3+adsorption rate, adsorption rate the results are shown in Figure 1.When material liquid pH value is 1.65, the ionic liquid extration resin that preparation embodiment 4 obtains is to Lu
3+reach maximum adsorption.
Application Example 3
Take 0.3g and prepare ionic liquid extration resin that embodiment 7 obtains in triangular flask, add 100mL preparation containing Lu
3+concentration is 0.5mmol/L, H
+the feed liquid of concentration to be 1.0mol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Lu
3+adsorption rate be 55.5%.
Application Example 4
Take 0.3g and prepare ionic liquid extration resin that embodiment 1 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of the different acidity of 100mL preparation containing Yb
3+the feed liquid of concentration to be 0.5mmol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Yb
3+adsorption rate, adsorption rate the results are shown in Figure 2.When material liquid pH value is 3.89, the ionic liquid extration resin that preparation embodiment 1 obtains is to Yb
3+reach maximum adsorption.
Application Example 5
Take 0.3g and prepare ionic liquid extration resin that embodiment 5 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of the different acidity of 100mL preparation containing Yb
3+the feed liquid of concentration to be 0.5mmol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Yb
3+adsorption rate, adsorption rate the results are shown in Figure 2.When material liquid pH value is 1.65, the ionic liquid extration resin that preparation embodiment 5 obtains is to Yb
3+reach maximum adsorption.
Application Example 6
Take 0.3g and prepare ionic liquid extration resin that embodiment 8 obtains in triangular flask, add 100mL preparation containing Yb
3+concentration is 0.5mmol/L, H
+the feed liquid of concentration to be 1.0mol/L, NaCl concentration be 0.5mol/L, under 25 DEG C of conditions fully after concussion, calculates Yb
3+adsorption rate be 48.8%.
Application Example 7
Preparation is containing the feed liquid of trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein, trivalent rare earth ions concentration is 0.5mmol/L, NaCl concentration is 0.5mmol/L, the concentration of hydrochloric acid is 0.1mol/L, ionic liquid extration resin that embodiment 3 obtains is prepared to feed liquid described in 50mL with 2g, after fully shaking at 25 DEG C, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor obtaining lutetium ytterbium is 2.6.
Application Example 8
Preparation is containing the feed liquid of trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein, trivalent rare earth ions concentration is 0.5mmol/L, NaCl concentration is 0.5mmol/L, the concentration of hydrochloric acid is 0.1mol/L, ionic liquid extration resin that embodiment 6 obtains is prepared to feed liquid described in 50mL with 2g, after fully shaking at 25 DEG C, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor obtaining lutetium ytterbium is 1.5.
Application Example 9
Preparation is containing the feed liquid of trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein, trivalent rare earth ions concentration is 0.5mmol/L, NaCl concentration is 0.5mmol/L, the concentration of hydrochloric acid is 0.1mol/L, ionic liquid extration resin that embodiment 9 obtains is prepared to feed liquid described in 50mL with 2g, after fully shaking at 25 DEG C, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor obtaining lutetium ytterbium is 1.3.
Application Example 10
Stock liquid, from the sulphuric leachate of red soil nickel ore, contains the Al of 11.4g/L in stock liquid
3+, the Fe of 15.5g/L
3+, the Mg of 2.3g/L
2+, the Ca of 0.54g/L
2+, the Mn of 0.52g/L
2+, the Ni of 0.48g/L
2+, the Zn of 0.05g/L
2+, the Sc of 0.13g/L
3+, the acidity of solution is 3.7mol/L.Get 1g and prepare ionic liquid extration resin that embodiment 2 obtains in triangular flask, add 160mL above-mentioned raw materials liquid, at 25 DEG C fully after concussion, calculate Sc
3+adsorption rate be 32.4%.
Application Example 11
Stock liquid, from the sulphuric leachate of red soil nickel ore, contains the Al of 11.4g/L in stock liquid
3+, the Fe of 15.5g/L
3+, the Mg of 2.3g/L
2+, the Ca of 0.54g/L
2+, the Mn of 0.52g/L
2+, the Ni of 0.48g/L
2+, the Zn of 0.05g/L
2+, the Sc of 0.13g/L
3+, the acidity of solution is 3.7mol/L.Get 1g and prepare ionic liquid extration resin that embodiment 4 obtains in triangular flask, add 160mL above-mentioned raw materials liquid, at 25 DEG C fully after concussion, calculate Sc
3+adsorption rate be 93.9%, and all 5% is less than to the adsorption rate of other interfering ion in above-mentioned raw materials liquid.
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (9)
1. an ionic liquid extration resin, is characterized in that,
Take styrene series anion exchange resin as positively charged ion donor, with the acid phosphine extraction agent of deprotonation for anionic donor;
The concrete structure formula of described positively charged ion donor is:
The concrete structure formula of described anionic donor is:
R in described positively charged ion donor
1, R
2be respectively methyl, R
3for methyl or hydroxyethyl;
R in described anionic donor
4, R
5be respectively identical or different, substituent that carbonatoms is the alkyl of 8.
2. ionic liquid extration resin according to claim 1, is characterized in that,
Described anionic donor is two-(2 of deprotonation, 4,4-tri-methyl-amyl) phosphonic acids (Cyanex 272), two-(2-ethylhexyl) phosphonic acids (P204) or 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507).
3. the preparation method of ionic liquid extration resin according to claim 1, is characterized in that, comprise the following steps:
(1) first with hydrochloric acid soln or sodium hydroxide solution washing chlorine type highly basic phenylethylene resin series, be then neutral by washed with de-ionized water to flowing liquid pH value;
Again with sodium hydroxide solution or hydrochloric acid soln washing chlorine type highly basic phenylethylene resin series, be then neutral by washed with de-ionized water to flowing liquid pH value;
Adding sodium hydroxide solution at room temperature stirring reaction, is then neutral by washed with de-ionized water to solution ph;
20 DEG C of-50 DEG C of dryings after filtration, obtain hydrogen-oxygen type highly basic phenylethylene resin series;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) obtained is distributed in DMF, swelling 0.5-6h under room temperature, add acid phosphine extraction agent again, filter after abundant reaction, wash, dry at 20 DEG C-50 DEG C, obtain ionic liquid extration resin;
The structure of described chlorine type highly basic phenylethylene resin series is:
The structure of described acid phosphine extraction agent is:
Wherein, described R
1, R
2be respectively methyl, R
3for methyl or hydroxyethyl; Described R
4, R
5be respectively identical or different, substituent that carbonatoms is the alkyl of 8.
4. preparation method according to claim 3, is characterized in that, the volume ratio of the chlorine type highly basic phenylethylene resin series described in step (1) and hydrochloric acid, sodium hydroxide solution is 1:1 ~ 1:4.
5. preparation method according to claim 3, is characterized in that, is used for the concentration of the hydrochloric acid soln and sodium hydroxide solution that wash chlorine type highly basic phenylethylene resin series to be respectively 2-4% in step (1).
6. preparation method according to claim 3, is characterized in that, in step (2), the mol ratio of hydrogen-oxygen type highly basic phenylethylene resin series and acid phosphine extraction agent is 1:1 ~ 1:2.
7. preparation method according to claim 3, is characterized in that, the reaction times of the abundant reaction in step (2) is 6-48h.
8. the application method of ionic liquid extration resin according to claim 1, is characterized in that, this ionic liquid extration resin can be applicable to recovering rare earth ion.
9. application method according to claim 8, is characterized in that, described rare earth ion be in trivalent rare earth ions any one or multiple.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3369097A4 (en) * | 2015-10-30 | 2019-05-01 | II-VI Incorporated | Composite extractant-enhanced polymer resin, method of making the same, and its usage for extraction of valuable metal(s) |
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| CN108726555B (en) * | 2017-10-19 | 2020-02-14 | 厦门稀土材料研究所 | Method for recovering rare earth through precipitation based on ionic liquid |
| CN109735718B (en) * | 2019-03-14 | 2020-05-19 | 北京科技大学 | Method for separating praseodymium and neodymium by liquid-liquid three-phase external push-pull system |
| CN110331291B (en) * | 2019-07-19 | 2020-06-09 | 中国科学院福建物质结构研究所 | Method for separating and/or extracting lanthanide |
| CN113308603B (en) * | 2021-05-26 | 2022-08-26 | 广西银亿新材料有限公司 | Treatment method of interphase dirt in nickel-cobalt metallurgy P204 extraction system |
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