CN103789547A - Ionic liquid extraction resin as well as preparation and application method thereof - Google Patents
Ionic liquid extraction resin as well as preparation and application method thereof Download PDFInfo
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Abstract
The invention relates to ionic liquid extraction resin capable of realizing high-efficiency recycling of rare earth as well as preparation and an application method of the ionic liquid extraction resin. The ionic liquid extraction resin has a designable zwitterion structural characteristic; the physical and chemical property of the ionic liquid extraction resin can be regulated and controlled by changing the structure or the type of zwitterions, so that the problems of the conventional extraction resin has a single function and the conventional extraction agent is low in stability are solved; and the ionic liquid extraction resin can be used for recycling and separation of rare earth in a solution. According to the preparation method of the ionic liquid extraction resin, syrene anion exchange resin is used as a carrier material, and an acidic phosphine extraction agent is introduced into a syrene-divinylbenzene framework under the action of a non-covalent bond, so that the ionic liquid extraction resin modified by the acidic phosphine extraction agent is obtained. The ionic liquid extraction resin provided by the invention can effectively recycle rare earth ions, is high in adsorption rate and adsorption selectivity to the rare earth ions and can be used for the separation and the recycling of the rare earth in a complicated system.
Description
Technical field
The invention belongs to ionic liquid extration resin field, be specifically related to a kind of ionic liquid extration resin and methods for making and using same thereof that can high efficiente callback rare earth.
Background technology
Extraction and separation technology is used widely in a lot of fields, but directly adopting solvent extration to reclaim separation to the rare earth in dilute solution is not a kind of cost-effective method, it is large that it also exists part extraction agent solubleness, easily cause organic phase loss, 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 that extraction agent is adsorbed onto on macroporous polymer carrier and is prepared from, have the highly selective of solvent extration and easy, the high efficiency of ion exchange technique concurrently, also overcome part extraction agent layering difficulty simultaneously, ion exchange resin and resin synthesize the advantages such as complicated, are more and more applied to the recovery separation field of metal ion.
At present, adopt extration resin technology recovery separating metal ion to obtain the concern of vast researcher.Chen Ji etc. are impregnated into difunctional ion liquid abstraction agent [A336] [CA-100] in Amberlite XAD-7 and have prepared extration resin, have realized 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 be 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 has overcome the deficiency that extraction agent exists in metal extraction process, limitation below but extration resin prepared by the traditional method application in metal separation reclaims also exists: first, tradition extration resin function singleness, extracting power, selectivity and extraction mechanisms to metal ion are only determined by extraction agent; Secondly, tradition extration resin is that extraction agent is passed through to surface affinity physical adsorption in polymer support, extraction agent is stable not high, contact with strong acid, highly basic material for a long time, easily cause the loss of active ingredient, affect its working life, limited widespread use and the development of extration resin in extracting and separating field.
Summary of the invention
The object of the invention is to exist for traditional extration resin the technical problem of function singleness and extraction agent poor stability, provide a kind of programmable zwitterion constructional feature that has, ionic liquid extration resin and methods for making and using same thereof that can high efficiente callback rare earth.
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, take the acid phosphine extraction agent of deprotonation as negatively charged ion donor;
The concrete structure formula of described positively charged ion donor is:
The concrete structure formula of described negatively charged ion donor is:
or
R in described positively charged ion donor
1, R
2be respectively methyl, R
3for methyl or hydroxyethyl;
R in described negatively charged ion donor
4, R
5be respectively the substituent of alkyl identical or different, that carbonatoms is 8.
In technique scheme, described negatively charged ion donor is deprotonation two-(2,4,4-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;
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 again;
Adding at room temperature stirring reaction of sodium hydroxide solution, is then neutral with washed with de-ionized water to pH;
After filtration, be dried at 20 ℃-50 ℃, obtain hydrogen-oxygen type highly basic phenylethylene resin series;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) being obtained is distributed in DMF, swelling 0.5-6h under room temperature, add again acid phosphine extraction agent, fully after reaction, filter, wash, dry at 20 ℃-50 ℃, 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, in step (1), be used for washing the hydrochloric acid soln of chlorine type highly basic phenylethylene resin series and the concentration of sodium hydroxide solution 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 is take styrene series anion exchange resin as positively charged ion donor, take the acid phosphine extraction agent of deprotonation as negatively charged ion donor.Ionic liquid extration resin of the present invention has programmable zwitterion constructional feature, can, by changing structure or the kind of zwitterion, regulate and control the physicochemical property of ionic liquid extration resin, has overcome the shortcoming of traditional extration resin function singleness.
Because the present invention reacts by acid-base neutralisation, acid phosphine extraction agent is fixed in vinylbenzene-divinylbenzene skeleton structure by non covalent bond effect, the stability of extraction agent is higher than the traditional extration resin being 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 Example 1
(1) use respectively 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 20 ℃, 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) being 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), fully, after reaction 6h, filter out resin, use absolute ethanol washing resin, dry at 20 ℃, 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 Example 2
(1) use respectively 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 50 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, then add two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), fully, after reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 50 ℃, 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 Example 3
(1) use respectively 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 40 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, then add two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), fully, after reaction 21h, filter out resin, use absolute ethanol washing resin, dry at 40 ℃, 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 Example 4
(1) use respectively 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 50 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, add again two-(2-ethylhexyl) phosphonic acids (P204), fully, after reaction 48h, filter out resin, use absolute ethanol washing resin, dry at 50 ℃, 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 Example 5
(1) use respectively 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 20 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 0.5h under room temperature, add again two-(2-ethylhexyl) phosphonic acids (P204), fully, after reaction 40h, filter out resin, use absolute ethanol washing resin, dry at 20 ℃, 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 Example 6
(1) use respectively 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 40 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, add again two-(2-ethylhexyl) phosphonic acids (P204), fully, after reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 40 ℃, 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 Example 7
(1) use respectively 4% (wt) hydrochloric acid soln and 4% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 50 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 2h under room temperature, add again 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507), fully, after reaction 12h, filter out resin, use absolute ethanol washing resin, dry at 50 ℃, obtain the ionic liquid extration resin ([D201] [P507]) that P507 modifies.
Described hydrogen-oxygen type highly basic phenylethylene resin series and the mol ratio of 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester (P507) are 1:1.
Preparation Example 8
(1) use respectively 2% (wt) hydrochloric acid soln and 2% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 20 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 0.5h under room temperature, add again 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester, fully, after reaction, filter out resin, use absolute ethanol washing resin, dry at 20 ℃, 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 Example 9
(1) use respectively 3% (wt) hydrochloric acid soln and 3% (wt) sodium hydroxide solution washing highly basic phenylethylene resin series (chlorine type), and till repeatedly cleaning and be neutrality to the pH value of flowing liquid with deionized water, finally use at room temperature stirring reaction of sodium hydroxide solution and resin, the pH value of deionized water wash solution is neutral, filter, be dried at 40 ℃, 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) being obtained is distributed to N, in dinethylformamide, swelling 6h under room temperature, add again 2-ethylhexyl phosphonic acid list (2-ethylhexyl) ester, fully, after reaction, filter out resin, use absolute ethanol washing resin, dry at 40 ℃, 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 ionic liquid extration resin that 0.3g Preparation Example 2 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of different acidity of 100mL preparation containing Lu
3+concentration is 0.5mmol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated Lu
3+adsorption rate, adsorption rate the results are shown in Figure 1.In the time that material liquid pH value is 5.16, the ionic liquid extration resin that Preparation Example 2 obtains is to Lu
3+reach maximum adsorption.
Application Example 2
Take ionic liquid extration resin that 0.3g Preparation Example 4 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of different acidity of 100mL preparation containing Lu
3+concentration is 0.5mmol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated Lu
3+adsorption rate, adsorption rate the results are shown in Figure 1.In the time that material liquid pH value is 1.65, the ionic liquid extration resin that Preparation Example 4 obtains is to Lu
3+reach maximum adsorption.
Application Example 3
Take ionic liquid extration resin that 0.3g Preparation Example 7 obtains in triangular flask, add 100mL preparation containing Lu
3+concentration is 0.5mmol/L, H
+concentration is 1.0mol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated Lu
3+adsorption rate be 55.5%.
Application Example 4
Take ionic liquid extration resin that 0.3g Preparation Example 1 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of different acidity of 100mL preparation containing Yb
3+concentration is 0.5mmol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated Yb
3+adsorption rate, adsorption rate the results are shown in Figure 2.In the time that material liquid pH value is 3.89, the ionic liquid extration resin that Preparation Example 1 obtains is to Yb
3+reach maximum adsorption.
Application Example 5
Take ionic liquid extration resin that 0.3g Preparation Example 5 obtains in triangular flask, add (pH is respectively 0.02,1.04,1.65,2.82,3.89,5.16) of different acidity of 100mL preparation containing Yb
3+concentration is 0.5mmol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated Yb
3+adsorption rate, adsorption rate the results are shown in Figure 2.In the time that material liquid pH value is 1.65, the ionic liquid extration resin that Preparation Example 5 obtains is to Yb
3+reach maximum adsorption.
Application Example 6
Take ionic liquid extration resin that 0.3g Preparation Example 8 obtains in triangular flask, add 100mL preparation containing Yb
3+concentration is 0.5mmol/L, H
+concentration is 1.0mol/L, and the feed liquid that NaCl concentration is 0.5mol/L, after fully shaking under 25 ℃ of conditions, is calculated 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, the ionic liquid extration resin obtaining by 2g Preparation Example 3 is to feed liquid described in 50mL, after fully shaking at 25 ℃, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor that obtains 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, the ionic liquid extration resin obtaining by 2g Preparation Example 6 is to feed liquid described in 50mL, after fully shaking at 25 ℃, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor that obtains 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, the ionic liquid extration resin obtaining by 2g Preparation Example 9 is to feed liquid described in 50mL, after fully shaking at 25 ℃, calculate the adsorption rate of trivalent rare earth ions and the separation factor of lutetium ytterbium, the separation factor that obtains 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 ionic liquid extration resin that 1g Preparation Example 2 obtains in triangular flask, add 160mL above-mentioned raw materials liquid, at 25 ℃, 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 ionic liquid extration resin that 1g Preparation Example 4 obtains in triangular flask, add 160mL above-mentioned raw materials liquid, at 25 ℃, fully after concussion, calculate Sc
3+adsorption rate be 93.9%, and the adsorption rate of other interfering ion in above-mentioned raw materials liquid is all less than to 5%.
Obviously, above-described embodiment is only for example is clearly described, and the not restriction 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 without also giving exhaustive to all embodiments.And the apparent variation of being extended out thus or variation are still among the protection domain in 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, take the acid phosphine extraction agent of deprotonation as negatively charged ion donor;
The concrete structure formula of described positively charged ion donor is:
The concrete structure formula of described negatively charged ion donor is:
R in described positively charged ion donor
1, R
2be respectively methyl, R
3for methyl or hydroxyethyl;
R in described negatively charged ion donor
4, R
5be respectively the substituent of alkyl identical or different, that carbonatoms is 8.
2. ionic liquid extration resin according to claim 1, is characterized in that,
Described negatively charged ion donor is deprotonation two-(2,4,4-tri-methyl-amyl) phosphonic acids (Cyanex272), 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 claimed in claim 1, is characterized in that, 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;
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 again;
Adding at room temperature stirring reaction of sodium hydroxide solution, is then neutral with washed with de-ionized water to pH;
After filtration, be dried at 20 ℃-50 ℃, obtain hydrogen-oxygen type highly basic phenylethylene resin series;
(2) hydrogen-oxygen type highly basic phenylethylene resin series step (1) being obtained is distributed in DMF, swelling 0.5-6h under room temperature, add again acid phosphine extraction agent, fully after reaction, filter, wash, dry at 20 ℃-50 ℃, obtain ionic liquid extration resin.
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 washing the hydrochloric acid soln of chlorine type highly basic phenylethylene resin series and the concentration of sodium hydroxide solution is 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 claimed in 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 (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104087750A (en) * | 2014-07-14 | 2014-10-08 | 厦门稀土材料研究所 | Rare earth extraction and separation method |
| CN105348129A (en) * | 2015-09-30 | 2016-02-24 | 北京科技大学 | [A336][BDGA] ionic liquid and preparation method therefor |
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| US10808296B2 (en) | 2015-10-30 | 2020-10-20 | Ii-Vi Delaware, Inc. | Selective recovery of rare earth metals from an acidic slurry or acidic solution |
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