CN103789547A - Ionic liquid extraction resin as well as preparation and application method thereof - Google Patents

Abstract

The invention relates to an ionic liquid extraction resin capable of efficiently recovering rare earths and its preparation and application method. The ionic liquid extraction resin has designable anion and cation structure characteristics, and the ionic liquid extraction can be regulated by changing the structure or type of anion and cation. The physical and chemical properties of the leaching resin overcome the problems of single function of the traditional leaching resin and poor stability of the extractant, and can be used for the recovery and separation of rare earths in the solution. The preparation method of the ionic liquid extraction and leaching resin of the present invention uses styrene-based anion exchange resin as the carrier material, introduces an acidic phosphine extractant on the styrene-divinylbenzene skeleton through non-covalent bonding, and obtains an acidic phosphine extractant modified ionic liquid extraction resin. The ionic liquid extraction and leaching resin of the invention can effectively recover rare earth ions, has higher adsorption rate and adsorption selectivity for rare earth ions, and can be used for separation and recovery of rare earths in complex systems.

Description

A kind of ionic liquid extraction resin and its preparation and application method

technical field

The invention belongs to the field of ionic liquid extraction and leaching resins, and in particular relates to an ionic liquid extraction and leaching resin capable of efficiently recovering rare earths and a preparation and application method thereof.

Background technique

Extraction and separation technology has been widely used in many fields, but it is not an economical and effective method to directly use solvent extraction to recover and separate rare earths in dilute solutions. It also has the high solubility of some extractants, which may easily cause the loss of organic phase. , The discharge of organic waste liquid will increase the environmental burden and other problems, and the development of extraction resin separation technology provides a new way for the above problems. The extraction resin is prepared by adsorbing the extractant onto a macroporous polymer carrier. It combines the high selectivity of the solvent extraction method with the simplicity and high efficiency of the ion exchange technology. Exchange resins and chelating resins are more and more used in the field of recovery and separation of metal ions due to their advantages such as complex synthesis.

At present, the use of extraction resin technology to recover and separate metal ions has attracted the attention of many scientific researchers. Chen Ji et al impregnated the bifunctional ionic liquid extractant [A336][CA-100] into Amberlite XAD-7 to prepare the extraction resin, which realized the effective separation of Sc ³⁺ and Y ³⁺ , Eu ³⁺ , Ce ³⁺ Separation (X Sun, Y Ji, J Chen, J Ma, J. Rare Earth, 2009, 27(6):932-936.); Chen et al impregnated D ₂ EHPA onto Amberlite XAD-4, and the prepared extraction The resin can selectively separate Pb ²⁺ from the mixed solution of Pb ²⁺ and Cu ²⁺ (JHChen, YYKao, CHLin, FYang, Sep.Sci.Technol., 2004,39:2067-2090.). Although the leaching resin overcomes the shortcomings of the extractant in the metal extraction process, the application of the leaching resin prepared by the traditional method in the metal separation and recovery still has the following limitations: First, the traditional leaching resin has a single function, and the metal ion The extraction ability, selectivity and extraction mechanism are only determined by the extraction agent; secondly, the traditional extraction resin physically adsorbs the extraction agent into the polymer carrier through surface affinity, the extraction agent is not stable, and it is in contact with strong acid and strong alkali for a long time , It is easy to cause the loss of active components, affect its working life, and limit the wide application and development of extraction resin in the field of extraction and separation.

Contents of the invention

The purpose of the present invention is to solve the technical problems of single function and poor stability of extraction agent in traditional extraction and leaching resins, to provide an ionic liquid extraction and leaching resin with designable anion and cation structure characteristics, which can efficiently recover rare earths, and its preparation and application method.

In order to solve the problems of the technologies described above, the technical solution of the present invention is specifically as follows:

An ionic liquid extraction resin,

Styrene-based anion-exchange resins are used as cation donors, and deprotonated acidic phosphine extractants are used as anion donors;

The concrete structural formula of described cation donor is:

The concrete structural formula of described anion donor is:

or

R ₁ and R ₂ in the cation donor are respectively methyl, and R ₃ is methyl or hydroxyethyl;

R ₄ and R ₅ in the anion donor are respectively the same or different substituents of alkyl groups with 8 carbon atoms.

In the above technical scheme, the anion donor is deprotonated di-(2,4,4-trimethylpentyl)phosphonic acid (Cyanex272), di-(2-ethylhexyl)phosphonic acid (P204) or 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester (P507).

The preparation method of described ionic liquid extraction resin, comprises the following steps:

(1) Wash the chlorine-type strong alkali styrene resin with hydrochloric acid solution or sodium hydroxide solution, and then wash it with deionized water until the pH value of the effluent liquid is neutral;

Wash the chlorine-type strong alkali styrene resin with sodium hydroxide solution or hydrochloric acid solution, and then clean it with deionized water until the pH value of the effluent liquid is neutral;

Add sodium hydroxide solution and stir the reaction at room temperature, then wash with deionized water until the pH value of the solution is neutral;

After filtering, dry at 20°C-50°C to obtain a hydrogen-oxygen type strong base styrene resin;

(2) Disperse the hydroxide type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 0.5-6h, then add acidic phosphine extractant, fully react and filter , washing, and drying at 20° C. to 50° C. to obtain an ionic liquid extraction resin.

In the above technical solution, the volume ratio of the chlorine-type strong base styrene resin to hydrochloric acid and sodium hydroxide solution in step (1) is 1:1-1:4.

In the above technical scheme, the concentrations of the hydrochloric acid solution and the sodium hydroxide solution used to wash the chlorine-type strong alkali styrene resin in the step (1) are 2-4% respectively.

In the above technical solution, in the step (2), the molar ratio of the hydrogen-oxygen type strong base styrene resin to the acidic phosphine extractant is 1:1-1:2.

In the above technical scheme, the reaction time for the full reaction in step (2) is 6-48h.

The application method of the ionic liquid extraction and leaching resin, the ionic liquid extraction and leaching resin can be applied to recover rare earth ions.

In the above technical solution, the rare earth ions are any one or more of trivalent rare earth ions.

The present invention has following beneficial effect:

The ionic liquid extraction resin of the present invention uses styrene-based anion exchange resin as a cation donor, and deprotonated acidic phosphine extractant as an anion donor. The ionic liquid leaching resin of the present invention has designable anion and cation structure characteristics, and can regulate the physical and chemical properties of the ionic liquid leaching resin by changing the structure or type of anion and cation, and overcomes the disadvantage of single function of the traditional leaching resin.

Since the present invention fixes the acidic phosphine extractant in the styrene-divinylbenzene skeleton structure through the acid-base neutralization reaction through non-covalent bonding, the stability of the extractant is higher than that dispersed in the carrier by physical adsorption. Traditional extraction resin. The ionic liquid extraction and leaching resin of the invention can effectively recover rare earth ions, has higher adsorption rate and adsorption selectivity for rare earth ions, and can be used for separation and recovery of rare earths in complex systems.

Description of drawings

The present invention will be described in further detail below in conjunction with the accompanying drawings and specific embodiments.

Fig. 1 is the graph of the adsorption rate of Lu under the condition of ^different pH value of application example 1～2 of the present invention;

Fig. 2 is the graph of the adsorption rate of ^Yb under the different pH value conditions of application examples 4 to 5 of the present invention;

Detailed ways

The present invention will be described in detail below in conjunction with the accompanying drawings.

Preparation Example 1

(1) Wash the strong base styrene resin (chlorine type) with 2% (wt) hydrochloric acid solution and 2% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 20°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong alkali styrene resin to hydrochloric acid and sodium hydroxide solution is 1:1;

(2) Disperse the hydroxide type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 0.5h, then add bis-(2,4,4-tris Methylpentyl)phosphonic acid (Cyanex272), after fully reacting for 6h, filter out the resin, wash the resin with absolute ethanol, and dry at 20°C to obtain the ionic liquid extraction resin modified by Cyanex272 ([D201][C272]) .

The molar ratio of the hydrogen-oxygen type strong base styrene resin to bis-(2,4,4-trimethylpentyl)phosphonic acid (Cyanex272) is 1:1.

Preparation Example 2

(1) Wash the strong base styrene resin (chlorine type) with 4% (wt) hydrochloric acid solution and 4% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 50°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:4;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell for 2 hours at room temperature, and then add bis-(2,4,4-trimethyl Amylpentyl)phosphonic acid (Cyanex272). After fully reacting for 12h, the resin was filtered out, washed with absolute ethanol, and dried at 50°C to obtain the ionic liquid extraction resin modified by Cyanex272 ([D201][C272]).

The molar ratio of the hydroxide type strong base styrene resin to bis-(2,4,4-trimethylpentyl)phosphonic acid (Cyanex272) is 1:1.2.

Preparation Example 3

(1) Wash the strong base styrene resin (chlorine type) with 3% (wt) hydrochloric acid solution and 3% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 40°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:2;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 6 hours, and then add bis-(2,4,4-trimethyl Amylpentyl)phosphonic acid (Cyanex272). After fully reacting for 21h, the resin was filtered out, washed with absolute ethanol, and dried at 40°C to obtain the ionic liquid extraction resin modified by Cyanex272 ([D201][C272]).

The molar ratio of the hydroxide type strong base styrene resin to bis-(2,4,4-trimethylpentyl)phosphonic acid (Cyanex272) is 1:1.8.

Preparation Example 4

(1) Wash the strong base styrene resin (chlorine type) with 4% (wt) hydrochloric acid solution and 4% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 50°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:3;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 2 hours, and then add di-(2-ethylhexyl)phosphonic acid (P204), after fully reacting for 48 hours, filter out the resin, wash the resin with absolute ethanol, and dry at 50°C to obtain the P204 modified ionic liquid extraction resin ([D201][P204]).

The molar ratio of the hydroxide type strong base styrene resin to bis-(2-ethylhexyl)phosphonic acid (P204) is 1:1.5.

Preparation Example 5

(1) Wash the strong base styrene resin (chlorine type) with 2% (wt) hydrochloric acid solution and 2% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 20°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:3.5;

(2) Disperse the hydroxide type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 0.5h, and then add bis-(2-ethylhexyl)phosphine acid (P204), after fully reacting for 40 hours, the resin was filtered out, washed with absolute ethanol, and dried at 20°C to obtain a P204-modified ionic liquid extraction resin ([D201][P204]).

The molar ratio of the hydroxide type strong base styrene resin to bis-(2-ethylhexyl)phosphonic acid (P204) is 1:2.

Preparation Example 6

(1) Wash the strong base styrene resin (chlorine type) with 3% (wt) hydrochloric acid solution and 3% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 40°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:2.5;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 6 hours, and then add di-(2-ethylhexyl)phosphonic acid (P204), after fully reacting for 12 hours, filter out the resin, wash the resin with absolute ethanol, and dry at 40°C to obtain the P204 modified ionic liquid extraction resin ([D201][P204]).

The molar ratio of the hydroxide type strong base styrene resin to bis-(2-ethylhexyl)phosphonic acid (P204) is 1:2.

Preparation Example 7

(1) Wash the strong base styrene resin (chlorine type) with 4% (wt) hydrochloric acid solution and 4% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 50°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:1.5;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 2 hours, and then add 2-ethylhexylphosphonic acid mono(2- Ethylhexyl) ester (P507), after fully reacting for 12 hours, filter out the resin, wash the resin with absolute ethanol, and dry at 50°C to obtain the P507 modified ionic liquid extraction resin ([D201][P507]).

The molar ratio of the hydroxide type strong base styrene resin to 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester (P507) is 1:1.

Preparation Example 8

(1) Wash the strong base styrene resin (chlorine type) with 2% (wt) hydrochloric acid solution and 2% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 20°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:3.5;

(2) Disperse the hydroxide type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 0.5h, then add 2-ethylhexylphosphonic acid mono(2 -Ethylhexyl) ester, after fully reacting, filter out the resin, wash the resin with absolute ethanol, and dry at 20°C to obtain the P507 modified ionic liquid extraction resin ([D201][P507]).

The molar ratio of the hydroxide type strong base styrene resin to 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester is 1:1.

Preparation Example 9

(1) Wash the strong base styrene resin (chlorine type) with 3% (wt) hydrochloric acid solution and 3% (wt) sodium hydroxide solution respectively, and wash repeatedly with deionized water until the pH value of the effluent liquid is neutral , and finally use sodium hydroxide solution and resin to stir and react at room temperature, the pH value of the deionized water washing solution is neutral, filter, and dry at 40°C to obtain a strong base styrene resin of the hydroxide type; the chlorine The volume ratio of type strong base styrene resin to hydrochloric acid and sodium hydroxide solution is 1:1.5;

(2) Disperse the hydroxide-type strong base styrene resin obtained in step (1) into N,N-dimethylformamide, swell at room temperature for 6 hours, and then add 2-ethylhexylphosphonic acid mono(2- Ethylhexyl) ester, after fully reacting, filter out the resin, wash the resin with absolute ethanol, and dry at 40°C to obtain the P507-modified ionic liquid extraction resin ([D201][P507]).

The molar ratio of the hydroxide type strong base styrene resin to 2-ethylhexylphosphonic acid mono(2-ethylhexyl) ester is 1:2.

Application Example 1

Weigh 0.3 g of the ionic liquid extraction resin obtained in Preparation Example 2 into an Erlenmeyer flask, add 100 mL of prepared different acidity (pH is 0.02, 1.04, 1.65, 2.82, 3.89, 5.16) containing Lu ³⁺ concentration of 0.5 mmol/L, NaCl concentration of 0.5mol/L feed solution, after fully shaking at 25°C, calculate the adsorption rate of Lu ³⁺ , the results of the adsorption rate are shown in Figure 1. When the pH value of the feed solution was 5.16, the ionic liquid extraction resin obtained in Preparation Example 2 reached the maximum adsorption on Lu ³⁺ .

Application Example 2

Weigh 0.3 g of the ionic liquid extraction resin obtained in Preparation Example 4 into an Erlenmeyer flask, add 100 mL of prepared different acidity (pH is 0.02, 1.04, 1.65, 2.82, 3.89, 5.16) containing Lu ^{3 +} concentration of 0.5 mmol/L, NaCl concentration of 0.5mol/L feed solution, after fully shaking at 25°C, calculate the adsorption rate of Lu ³⁺ , the results of the adsorption rate are shown in Figure 1. When the pH value of the feed solution was 1.65, the ionic liquid extraction resin obtained in Preparation Example 4 reached the maximum adsorption on Lu ³⁺ .

Application Example 3

Weigh 0.3g of the ionic liquid extraction resin obtained in Preparation Example 7 in a conical flask, add 100mL of prepared Lu3 ⁺ concentration of 0.5mmol/L, H ⁺ concentration of 1.0mol/L, and NaCl concentration of 0.5mol/L L feed solution, after fully shaking at 25°C, the calculated Lu ³⁺ adsorption rate is 55.5%.

Application Example 4

Weigh 0.3 g of the ionic liquid extraction resin obtained in Preparation Example 1 into an Erlenmeyer flask, add 100 mL of different acidity (pH is 0.02, 1.04, 1.65, 2.82, 3.89, 5.16) containing Yb ³⁺ concentration of 0.5 Mmol/L, NaCl concentration of 0.5mol/L feed liquid, after fully shaking at 25 °C, calculate the adsorption rate of Yb ³⁺ , the results of the adsorption rate are shown in Figure 2. When the pH value of the feed solution was 3.89, the ionic liquid extraction resin obtained in Preparation Example 1 reached the maximum adsorption on Yb ³⁺ .

Application Example 5

Weigh 0.3 g of the ionic liquid extraction resin obtained in Preparation Example 5 into an Erlenmeyer flask, add 100 mL of different acidity (pH is 0.02, 1.04, 1.65, 2.82, 3.89, 5.16) containing Yb ³⁺ concentration of 0.5 Mmol/L, NaCl concentration of 0.5mol/L feed liquid, after fully shaking at 25 °C, calculate the adsorption rate of Yb ³⁺ , the results of the adsorption rate are shown in Figure 2. When the pH value of the feed solution was 1.65, the ionic liquid extraction resin obtained in Preparation Example 5 reached the maximum adsorption on Yb ³⁺ .

Application Example 6

Weigh 0.3g of the ionic liquid extraction resin obtained in Preparation Example 8 in a conical flask, add 100mL of prepared Yb3 ⁺ concentration of 0.5mmol/L, H ⁺ concentration of 1.0mol/L, and NaCl concentration of 0.5mol/L L feed solution, after fully shaking at 25°C, the calculated adsorption rate of Yb ³⁺ is 48.8%.

Application Example 7

Prepare a feed solution containing trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein the trivalent rare earth The ion concentration is 0.5mmol/L, the NaCl concentration is 0.5mmol/L, and the concentration of hydrochloric acid is 0.1mol/L. Use 2g of the ionic liquid extraction resin obtained in Preparation Example 3 to 50mL of the feed solution at 25°C. After sufficient shaking, the adsorption rate of trivalent rare earth ions and the separation coefficient of lutetium and ytterbium were calculated, and the separation coefficient of lutetium and ytterbium was obtained as 2.6.

Application Example 8

Prepare a feed solution containing trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein the trivalent rare earth The ion concentration is 0.5mmol/L, the NaCl concentration is 0.5mmol/L, and the concentration of hydrochloric acid is 0.1mol/L. Use 2g of the ionic liquid extraction resin obtained in Preparation Example 6 to 50mL of the feed solution, at 25°C After sufficient shaking, the adsorption rate of trivalent rare earth ions and the separation coefficient of lutetium and ytterbium were calculated, and the separation coefficient of lutetium and ytterbium was obtained as 1.5.

Application Example 9

Prepare a feed solution containing trivalent rare earth ions (La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y, Er, Tm, Yb, Lu), NaCl and hydrochloric acid, wherein the trivalent rare earth The ion concentration is 0.5mmol/L, the NaCl concentration is 0.5mmol/L, and the concentration of hydrochloric acid is 0.1mol/L. Use 2g of the ionic liquid extraction resin obtained in Preparation Example 9 to 50mL of the feed solution at 25°C. After sufficient shaking, the adsorption rate of trivalent rare earth ions and the separation coefficient of lutetium and ytterbium were calculated, and the separation coefficient of lutetium and ytterbium was obtained as 1.3.

Application Example 10

The raw material solution comes from the sulfuric acid leaching solution of laterite nickel ore. The raw material solution contains 11.4g/L Al ³⁺ , 15.5g/L Fe ³⁺ , 2.3g/L Mg ²⁺ , 0.54g/L Ca ²⁺ , 0.52g/L Mn ²⁺ , 0.48g/L Ni ²⁺ , 0.05g/L Zn ²⁺ , 0.13g/L Sc ³⁺ , the acidity of the solution is 3.7mol/L. Take 1 g of the ionic liquid extraction resin obtained in Preparation Example 2 into an Erlenmeyer flask, add 160 mL of the above raw material solution, and shake fully at 25 ° C. The calculated adsorption rate of Sc ³⁺ is 32.4%.

Application Example 11

The raw material solution comes from the sulfuric acid leaching solution of laterite nickel ore. The raw material solution contains 11.4g/L Al ³⁺ , 15.5g/L Fe ³⁺ , 2.3g/L Mg ²⁺ , 0.54g/L Ca ²⁺ , 0.52g/L Mn ²⁺ , 0.48g/L Ni ²⁺ , 0.05g/L Zn ²⁺ , 0.13g/L Sc ³⁺ , the acidity of the solution is 3.7mol/L. Take 1 g of the ionic liquid extraction resin obtained in Preparation Example 4 in an Erlenmeyer flask, add 160 mL of the above-mentioned raw material solution, and after fully shaking at 25 ° C, calculate the adsorption rate of Sc ³⁺ to be 93.9%, while for the above-mentioned raw material solution The adsorption rates of other interfering ions were less than 5%.

Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. And the obvious changes or changes derived therefrom are still within the scope of protection of the present 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:

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.

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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