阅读说明：本技术 一种稀土萃取材料、制备方法及应用 (Rare earth extraction material, preparation method and application ) 是由 张作州 刘强 于 2020-12-21 设计创作，主要内容包括：本发明提供一种稀土萃取材料的制备方法及应用,首先通过将4-(4-甲氧苯基)-α-溴代-2-丁基乙烯单体与DMF混合搅拌得到单体溶液,将单体溶液与将醋酸钯、配体、碱混合脱气升温反应,随后将反应液与甲醇混合,加入纳米氧化硅和6-环己基己酸,得到6-环己基己酸、氧化硅、聚乙炔混合物；将N-正丁基二乙酰亚胺与五乙烯六胺混合形成改性N-正丁基二乙酰亚胺,并加入上述6-环己基己酸、氧化硅、聚乙炔混合物,形成目标产物稀土萃取材料。本发明工艺简单,生产成本低,可有效提高萃取率,进而提高了稀土提取过程中资源利用率,操作简单,实用性强,适于工业化生产,可广泛应用于稀土元素的提取领域。(The invention provides a preparation method and application of a rare earth extraction material, firstly, mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and DMF (dimethyl formamide) to obtain a monomer solution, mixing the monomer solution with palladium acetate, a ligand and alkali, degassing, heating for reaction, then mixing the reaction solution with methanol, and adding nano silicon oxide and 6-cyclohexylhexanoic acid to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene; mixing N-N-butyl diacetyl imide and pentaethylene hexamine to form modified N-N-butyl diacetyl imide, and adding the mixture of the 6-cyclohexyl caproic acid, the silicon oxide and the polyacetylene to form the target product rare earth extraction material. The method has the advantages of simple process, low production cost, simple operation, strong practicability, suitability for industrial production and wide application in the field of extraction of rare earth elements, and can effectively improve the extraction rate and further improve the resource utilization rate in the rare earth extraction process.)

1. The preparation method of the rare earth extraction material is characterized by comprising the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N dimethylformamide solvent to obtain a monomer solution;

mixing palladium acetate, triphenylphosphine and potassium phosphate, adding the monomer solution to form a mixed solution, and degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid;

mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out;

filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexyl caproic acid into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexyl caproic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

uniformly mixing n-butylamine, trichloromethane and triethylamine to form a mixed solution;

placing the mixed solution at-18 ℃ to-15 ℃, and slowly adding acetyl chloride solution to obtain a reaction solution;

washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral;

drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; and heating the mixed powder to 70-80 ℃, preserving heat for 1-2 hours, then continuously heating to 90-95 ℃, preserving heat for 1-2 hours, and cooling to room temperature to obtain the extraction material.

2. The method for preparing a rare earth extraction material according to claim 1, wherein in S1, the weight ratio of 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer to N-N dimethylformamide solvent is (0.7-0.8): 5.

3. The method for preparing a rare earth extraction material according to claim 1, wherein in S1, the weight ratio of palladium acetate, triphenylphosphine, potassium phosphate to the monomer solution is (0.15-0.2): 0.4: 30: 100.

4. the method for preparing a rare earth extraction material according to claim 1, wherein in S1, the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10 (0.2-0.5).

5. The method for preparing a rare earth extraction material according to claim 1, wherein in S2, the volume ratio of chloroform to n-butylamine to triethylamine is: 10: (0.7-0.8): 4.

6. the method for preparing a rare earth extraction material according to claim 1, wherein in S2, the time for adding the acetyl chloride solution is 2-3 h, the concentration of the acetyl chloride solution is 0.2mol/L, and the volume ratio of the acetyl chloride solution to the trichloromethane is 1: (0.2-0.3).

7. The method for preparing a rare earth extraction material according to claim 1, wherein the weight ratio of pentaethylenehexamine to N-N-butyldiacetylimide in S2 is (0.1-0.3): 55.

8. The method for preparing a rare earth extraction material according to claim 1, wherein in S3, the weight ratio of the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene to the modified N-N-butyldiacetylimide is 0.1-0.4: 2.5.

9. A rare earth extraction material, characterized by being prepared by the preparation method according to any one of claims 1 to 8.

10. The rare earth extraction material prepared by the preparation method of any one of claims 1 to 8 is applied to the field of rare earth extraction.

Technical Field

The invention belongs to the technical field of rare earth extraction materials, and particularly relates to a rare earth extraction material, a preparation method and application thereof.

Background

The rare earth element is also called rare earth metal, and refers to a general name of 17 metal elements including lanthanide elements, scandium and yttrium. Is an important and non-renewable scarce strategic resource, in particular to an important raw material of high and new technology industry, and is widely applied to the fields of electronics, petrochemical industry, metallurgy, machinery, energy, light industry, environmental protection, agriculture and the like. China is the country with the largest reserve of rare earth resources in the world, the application of rare earth elements in various fields is gradually widened at present, but the separation efficiency of the rare earth elements is still not high because the properties of different rare earth elements are very similar. Solid phase extraction of rare earths is an emerging extraction method by which compounds dissolved or suspended in a liquid mixture are separated from other compounds in the mixture according to their physical and chemical properties. CN201910648565.3 discloses a preparation method of a solid phase extractant, in particular to a preparation method and application of a P204 doped polythiophene light rare earth solid phase extractant. However, the extraction rate is low, which results in low resource utilization rate in the rare earth extraction process. Therefore, it is necessary to design a new rare earth extractant to improve the rare earth extraction rate, improve the resource utilization rate and reduce the environmental pollution.

Disclosure of Invention

The invention aims to provide a rare earth extraction material, a preparation method and application aiming at the defects of the prior art.

The invention adopts the following technical scheme:

a preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution;

mixing palladium acetate, triphenylphosphine (ligand) and potassium phosphate (alkali), adding the monomer solution to form a mixed solution, and degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid;

mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out;

filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexyl caproic acid into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexyl caproic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

uniformly mixing n-butylamine, trichloromethane and triethylamine to form a mixed solution;

placing the mixed solution at-18 ℃ to-15 ℃, and slowly adding acetyl chloride solution to obtain a reaction solution;

washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral;

drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; and heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain the extraction material.

Furthermore, in S1, the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer to the N-N Dimethylformamide (DMF) solvent is (0.7-0.8): 5.

Further, in S1, the weight ratio of palladium acetate, triphenylphosphine, potassium phosphate to the monomer solution is (0.15-0.2): 0.4: 30: 100.

furthermore, in S1, the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexyl hexanoic acid is 10 (0.2-0.5).

Further, in S2, the volume ratio of chloroform to n-butylamine to triethylamine is: 10: (0.7-0.8): 4.

further, in S2, the time for adding the acetyl chloride solution is 2-3 hours, the concentration of the acetyl chloride solution is 0.2mol/L, and the volume ratio of the acetyl chloride solution to the trichloromethane is 1: (0.2-0.3).

Furthermore, in S2, the weight ratio of pentaethylenehexamine to N-N-butyldiacetylimide is (0.1-0.3): 55.

Furthermore, in S3, the weight ratio of the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene to the modified N-N-butyldiacetyl imide is 0.1-0.4: 2.5.

The invention also provides a rare earth extraction material prepared by the preparation method.

The invention also provides application of the rare earth extraction material prepared by the preparation method in the field of rare earth extraction.

The invention has the beneficial effects that:

(1) according to the invention, the rare earth extraction material is prepared by mixing a mixture of 6-cyclohexyl caproic acid, silicon oxide and polyacetylene with modified N-N-butyl diacetyl imide, and the microscopic electrical behavior of polyacetylene can be improved by introducing nano silicon oxide, so that the orientation of captured rare earth is improved; 6-cyclohexyl caproic acid can bring a silicon oxide polyacetylene mixture into the modified N-N-butyl diacetyl imide to improve oil solubility;

(2) according to the invention, N-N-butyl diacetyl imide and pentaethylene hexamine are mixed to form modified N-N-butyl diacetyl imide, so that functional groups can be increased, the extraction distribution ratio of the N-N-butyl diacetyl imide can be improved by pentaethylene hexamine through acidity change, the NO group of rare earth is activated and absorbed, and the orientation and extraction capacity of the N-N-butyl diacetyl imide for capturing rare earth are improved;

(3) the invention introduces inorganic substance (silicon oxide), which can greatly reduce the volatilization of organic solvent and the complexity of separation operation;

(4) the method has the advantages of easily available raw materials, wide sources, low production cost, convenient preparation, simple process, good effect and strong practicability, is suitable for industrial production, and can be widely used for extracting rare earth elements.

The specific implementation mode is as follows:

in order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.

Example 1

A preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution, wherein the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene to the N-N dimethylformamide is 0.7: 5; mixing palladium acetate, triphenylphosphine and potassium phosphate, and adding the monomer solution to form a mixed solution (the weight ratio of the palladium acetate, the triphenylphosphine and the potassium phosphate to the monomer solution is 0.15: 0.4: 30: 100); degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid; mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out; filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexylhexanoic acid (the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10: 0.2) into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

trichloromethane, n-butylamine and triethylamine in a volume ratio of 10: 0.7: 4, uniformly mixing to form a mixed solution; and (2) placing the mixed solution at-18 ℃ to-15 ℃, slowly adding 0.2mol/L of acetyl chloride solution, and adding the acetyl chloride solution for 2 hours to obtain a reaction solution, wherein the volume ratio of the acetyl chloride solution to the trichloromethane is 1: 0.2; washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral; drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide according to the weight ratio of 0.1:55, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain an extraction material; wherein the weight ratio of the 6-cyclohexylhexanoic acid silicon oxide polyacetylene mixture to the modified N-N-butyldiacetyl imide liquid is 0.15: 2.5.

Example 2

A preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution, wherein the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene to the N-N dimethylformamide is 0.8: 5; mixing palladium acetate, triphenylphosphine and potassium phosphate, and adding the monomer solution to form a mixed solution (the weight ratio of the palladium acetate, the triphenylphosphine and the potassium phosphate to the monomer solution is 0.2: 0.4: 30: 100); degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid; mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out; filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexylhexanoic acid (the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10: 0.4) into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

trichloromethane, n-butylamine and triethylamine in a volume ratio of 10: 0.75: 4, uniformly mixing to form a mixed solution; and (2) placing the mixed solution at-18 ℃ to-15 ℃, slowly adding 0.2mol/L of acetyl chloride solution, and adding the acetyl chloride solution for 3 hours to obtain a reaction solution, wherein the volume ratio of the acetyl chloride solution to the trichloromethane is 1: 0.25; washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral; drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide according to the weight ratio of 0.3:55, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain an extraction material; wherein the weight ratio of the 6-cyclohexylhexanoic acid silicon oxide polyacetylene mixture to the modified N-N-butyldiacetyl imide liquid is 0.25: 2.5.

Example 3

A preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution, wherein the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene to the N-N dimethylformamide is 0.75: 5; mixing palladium acetate, triphenylphosphine and potassium phosphate, and adding the monomer solution to form a mixed solution (the weight ratio of the palladium acetate, the triphenylphosphine and the potassium phosphate to the monomer solution is 0.18: 0.4: 30: 100); degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid; mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out; filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexylhexanoic acid (the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10: 0.5) into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

trichloromethane, n-butylamine and triethylamine in a volume ratio of 10: 0.8: 4, uniformly mixing to form a mixed solution; and (2) placing the mixed solution at-18 ℃ to-15 ℃, slowly adding 0.2mol/L of acetyl chloride solution, and adding the acetyl chloride solution for 3 hours to obtain a reaction solution, wherein the volume ratio of the acetyl chloride solution to the trichloromethane is 1: 0.3; washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral; drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide according to the weight ratio of 0.2:55, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain an extraction material; wherein the weight ratio of the 6-cyclohexylhexanoic acid silicon oxide polyacetylene mixture to the modified N-N-butyldiacetyl imide liquid is 0.10: 2.5.

Example 4

A preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution, wherein the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene to the N-N dimethylformamide is 0.8: 5; mixing palladium acetate, triphenylphosphine and potassium phosphate, and adding the monomer solution to form a mixed solution (the weight ratio of the palladium acetate, the triphenylphosphine and the potassium phosphate to the monomer solution is 0.2: 0.4: 30: 100); degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid; mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out; filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexylhexanoic acid (the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10: 0.3) into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

trichloromethane, n-butylamine and triethylamine in a volume ratio of 10: 0.8: 4, uniformly mixing to form a mixed solution; and (2) placing the mixed solution at-18 ℃ to-15 ℃, slowly adding 0.2mol/L of acetyl chloride solution, and adding the acetyl chloride solution for 3 hours to obtain a reaction solution, wherein the volume ratio of the acetyl chloride solution to the trichloromethane is 1: 0.3; washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral; drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide according to the weight ratio of 0.3:55, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain an extraction material; wherein the weight ratio of the 6-cyclohexylhexanoic acid silicon oxide polyacetylene mixture to the modified N-N-butyldiacetyl imide liquid is 0.2: 2.5.

Example 5

A preparation method of a rare earth extraction material comprises the following steps:

preparation of a mixture of S1, 6-cyclohexyl hexanoic acid, silica and polyacetylene:

mixing and stirring a 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene monomer and an N-N Dimethylformamide (DMF) solvent to obtain a monomer solution, wherein the weight ratio of the 4- (4-methoxyphenyl) -alpha-bromo-2-butylethylene to the N-N dimethylformamide is 0.7: 5; mixing palladium acetate, triphenylphosphine and potassium phosphate, and adding the monomer solution to form a mixed solution (the weight ratio of the palladium acetate, the triphenylphosphine and the potassium phosphate to the monomer solution is 0.2: 0.4: 30: 100); degassing the mixed solution; then under the protection of argon, heating the mixed solution to 90-95 ℃, and preserving heat for 10-15 hours to obtain a reaction liquid; mixing the reaction liquid with methanol for 3-10 min, then adding nano silicon oxide, stirring for 10-20 min, standing for 1-2h to form a mixture precipitate of polyacetylene and silicon oxide, and separating out; filtering, cleaning, drying and crushing a mixture of polyacetylene and silicon oxide, adding 6-cyclohexylhexanoic acid (the weight ratio of the dried mixture of silicon oxide and polyacetylene to 6-cyclohexylhexanoic acid is 10: 0.5) into the mixture, and stirring for 30-60 min to obtain a mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene;

s2, preparation of modified N-N-butyl diacetyl imide:

trichloromethane, n-butylamine and triethylamine in a volume ratio of 10: 0.8: 4, uniformly mixing to form a mixed solution; and (2) placing the mixed solution at-18 ℃ to-15 ℃, slowly adding 0.2mol/L of acetyl chloride solution, and adding the acetyl chloride solution for 3 hours to obtain a reaction solution, wherein the volume ratio of the acetyl chloride solution to the trichloromethane is 1: 0.3; washing the reaction solution with distilled water, separating out a lower organic phase, washing with 15% sodium carbonate solution, washing with 15% hydrochloric acid solution, and washing with distilled water until the washing solution is neutral; drying the washed solution with anhydrous magnesium sulfate overnight, filtering to obtain a filtrate which is a reddish brown trichloromethane solution, heating in an oil bath, and distilling under reduced pressure to remove the solvent to obtain N-N-butyl diacetyl imide; then mixing pentaethylenehexamine and N-N-butyl diacetyl imide according to the weight ratio of 0.3:55, and stirring for 1-2 hours to obtain modified N-N-butyl diacetyl imide;

s3, preparation of rare earth extraction material:

mixing the mixture of 6-cyclohexylhexanoic acid, silicon oxide and polyacetylene obtained in the step S1 with the modified N-N-butyl diacetyl imide obtained in the step S2, and uniformly stirring to obtain mixed powder; heating the mixed powder to 70-80 ℃, preserving heat for 1-2h, then continuously heating to 90-95 ℃, preserving heat for 1-2h, and cooling to room temperature to obtain an extraction material; wherein the weight ratio of the 6-cyclohexylhexanoic acid silicon oxide polyacetylene mixture to the modified N-N-butyldiacetyl imide liquid is 0.4: 2.5.

And (3) testing the extraction effect:

preparation of a catalyst containing La³⁺The rare earth chloride solution of (A) is a raw material solution of La³⁺The concentration of the rare earth is 0.01-0.09 mol/L, and the pH of the rare earth solution is adjusted to 3 by adopting inorganic acid.

The saponifier is sodium hydroxide. Adding saponifying agent into water, stirring for 20-40min, and filtering to obtain saponified clear liquid. The concentration of the saponified solution was 0.75 kg/L.

The extracting agent prepared in the embodiments 1-5 of the invention is mixed with kerosene according to the weight ratio of 1 (1-1.2) to form an extraction liquid.

Stirring and mixing the saponification liquid and the extraction liquid for 0.5-1 h, quickly saponifying the organic phase of the extraction liquid, and allowing sodium ions to enter the organic phase; adding La³⁺The rare earth chloride solution is used as a raw material solution, stirring and extracting are carried out, the extraction stirring time is 20-30 min, the extraction standing time is 20-40min, and the extraction temperature is 25-35 ℃; wherein the mass ratio of the rare earth ion enrichment raw material liquid to the extractant solution to the saponifier is 1:1 (0.03-0.06). Standing and layering after extraction, wherein an upper organic phase is a target product, and the organic phase enters a separation and extraction procedure to obtain a raw material for preparing the rare earth compound; the lower aqueous phase enters a sodium chloride recovery procedure. The concentration of the rare earth in the water phase is measured, and the extraction rate of the extracting agent prepared in the embodiments 1-5 of the invention is shown in table 1.

TABLE 1 extraction test results

	Example 1	Example 2	Example 3	Example 4	Example 5
						Extraction ratio%	76.85	77.03	76.94	76.63	76.78

As can be seen from Table 1, the extraction rate of the rare earth extraction material prepared by the method can reach 77.03%, which is significantly higher than the extraction rate (59.52-75.16%) of the extraction material of the prior art (CN 201910648565.3), so that the method can effectively improve the extraction rate, further improve the resource utilization rate in the rare earth extraction process, is simple to operate, has good effect, and can be widely applied to the field of extraction of rare earth elements.

The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention, it should be noted that, for those skilled in the art, several modifications and decorations without departing from the principle of the present invention should be regarded as the protection scope of the present invention.