Diphenylamino-oxy-carboxylic acid extracting agent, preparation method and application thereof
阅读说明：本技术 一种二苯氨基氧代羧酸萃取剂、其制备方法及应用 (Diphenylamino-oxy-carboxylic acid extracting agent, preparation method and application thereof ) 是由 王艳良 吴玉远 肖文涛 林锦池 于 2020-12-22 设计创作，主要内容包括：本发明涉及稀土资源回收技术领域,尤其涉及一种二苯氨基氧代羧酸萃取剂、其制备方法及应用。所述二苯氨基氧代羧酸萃取剂具有式(Ⅰ)所示结构；式(I)中,R-1和R-2独立的选自H或C1～C9的烷基,n为1～6的自然数。本发明提供的二苯氨基氧代羧酸萃取剂能有效地将钇与镧系元素分离,与工业应用的环烷酸萃取剂相比,该萃取剂组分单一,化学结构稳定,萃取有机相浓度不降低,萃取性能稳定；并且,所述二苯氨基氧代羧酸类萃取剂对轻稀土元素和钇分离系数明显高于环烷酸,对重稀土元素和钇分离系数同样高于环烷酸,在分离能效上能完全取代环烷酸,具有十分良好的应用前景。(The invention relates to the technical field of rare earth resource recovery, in particular to a diphenylamino-oxy-carboxylic acid extracting agent, and a preparation method and application thereof. The diphenylamino oxocarboxylic acid extractant has a structure shown in a formula (I); in the formula (I), R 1 And R 2 Independently selected from H or C1-C9 alkyl, and n is a natural number of 1-6. Compared with the naphthenic acid extracting agent applied in industry, the diphenylamino-oxy carboxylic acid extracting agent provided by the invention has the advantages that the component is single, the chemical structure is stable, the concentration of an extracted organic phase is not reduced, and the extraction performance is stable; moreover, the benzimido oxycarboxylic acid extractant has obviously higher separation coefficient for light rare earth elements and yttrium than naphthenic acid, and also has higher separation coefficient for heavy rare earth elements and yttrium than naphthenic acid, can completely replace naphthenic acid in separation energy efficiency, and has very good application prospect.)
1. A diphenylamino-oxy-carboxylic acid extractant has a structure shown in formula (I):
in the formula (I), R1And R2Independently selected from H or C1-C9 alkyl, and n is a natural number of 1-6.
2. The benziminophenoxycarboxylic acid extractant of claim 1, wherein R is1And R2Independently selected from H, methyl or n-octyl;
n is 1 or 2 or 3.
3. A preparation method of a diphenylamino-oxy carboxylic acid extractant comprises the following steps:
A) mixing dialkyl aniline, alkyl diacid monoethyl ester acyl chloride, an organic solvent and organic base, and reacting to obtain a reaction solution;
B) mixing the reaction solution with water to obtain an oil phase and a water phase;
C) carrying out reduced pressure distillation on the oil phase to obtain diphenylamino-oxy carboxylic acid monoethyl ester;
D) heating and refluxing the diphenylaminooxy carboxylic acid monoethyl ester in a sodium hydroxide solution, and obtaining the diphenylaminooxy carboxylic acid extractant after acidification and reduced pressure distillation.
4. The method according to claim 3, wherein in step A), the dialkylaniline is one or more selected from diphenylamine, 4' -dimethyldiphenylamine, 4' -diethyldiphenylamine, 4' -dibutyldiphenylamine, 4' -dioctyldiphenylamine and 4,4' -dinonyldiphenylamine.
5. The method according to claim 3, wherein in the step A), the alkyl diacid monoethyl ester acyl chloride is selected from one of malonic acid monoethyl ester acyl chloride, succinic acid monoethyl ester acyl chloride, glutaric acid monoethyl ester acyl chloride, adipic acid monoethyl ester acyl chloride, pimelic acid monoethyl ester acyl chloride and suberic acid monoethyl ester acyl chloride.
6. The preparation method according to claim 3, wherein in the step A), the organic solvent is one or more selected from toluene, xylene, heptane, octane, dichloromethane, chloroform and sulfonated kerosene;
the organic base is triethylamine.
7. The preparation method according to claim 3, wherein in the step A), the mass ratio of the dialkyl aniline to the alkyl diacid monoethyl ester acyl chloride is 16-40: 15-18;
the mass ratio of the dialkyl aniline to the organic alkali is 16-40: 14-16;
the reaction temperature is 0-20 ℃, and the reaction time is 15-60 min.
8. The method according to claim 3, wherein in step D), the solvent in the sodium hydroxide solution comprises ethanol and water;
the heating reflux temperature is 60-90 ℃, and the time is 1-4 h;
the reagent used for acidification is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-8 mol/L;
after the reduced pressure distillation, the method further comprises the following steps: and (5) washing with water.
9. A method for separating rare earth elements from a rare earth solution comprises the following steps:
a) mixing an extractant with an organic solvent to obtain an extractant solution; the extractant is the diphenylamino-oxo-carboxylic acid extractant of any one of claims 1 to 2 or the extractant prepared by the preparation method of any one of claims 3 to 8;
b) mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution;
c) and mixing the saponified extractant solution with a rare earth solution for extraction, wherein yttrium is enriched in a water phase, and yttrium-poor rare earth is enriched in an organic phase.
10. The separation process of claim 9, wherein the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium;
the total concentration of rare earth ions in the rare earth solution is 0.05-1.5 mol/L, and the pH value of the rare earth solution is 1-7.
Technical Field
The invention relates to the technical field of rare earth resource recovery, in particular to a diphenylamino-oxy-carboxylic acid extracting agent, and a preparation method and application thereof.
Background
In the field of rare earth element ion separation, naphthenic acid is mainly used as an extractant to extract and separate yttrium element from a rare earth element mixture industrially. Naphthenic acid is a byproduct of petrochemical industry, has limited source and complex components, and needs to be stripped at higher pHRare earth can be extracted under the condition, and the components of the rare earth are easy to change after long-term use, so that the concentration of an organic phase is reduced, and the stability of a separation process is influenced. Currently, researchers are eagerly looking for new carboxylic acid extractants to replace naphthenic acids, such as: chinese patent CN1084574A discloses a carboxylic acid type extractant for separating rare earth elements, the molecular formula of which is ROCH2COOH, R in the formula is C8-C20 straight chain or branched chain alkyl or substituted phenyl of C4-C16 straight chain or branched chain alkyl, and secondary octyl phenoxy is recommended to replace acetic acid, the novel extractant can effectively separate yttrium from all lanthanide elements in the extraction and separation process of rare earth elements, and can overcome the problem that the concentration of an organic phase is reduced when the yttrium is separated by naphthenic acid extraction, and in addition, the novel extractant is also suitable for separation among lanthanide elements.
Although the molecular formula is ROCH2The alkyl phenoxy carboxylic acid of COOH can separate yttrium from lanthanide, and has stable extraction performance, but the separation coefficient of heavy rare earth and yttrium in the extraction system is obviously lower than that of naphthenic acid, which causes the heavy rare earth element and yttrium to be difficult to separate, thus more stages of extraction tanks need to be designed to achieve the separation effect.
Therefore, the molecular structure of the carboxylic acid extractant needs to be regulated and controlled, and the extractant which can overcome the problem of concentration reduction of the extracted organic phase and has higher separation coefficient of heavy rare earth elements and yttrium is developed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a diphenylaminoxy carboxylic acid extractant, a preparation method thereof, and an application thereof.
The invention provides a diphenylamino-oxy carboxylic acid extracting agent, which has a structure shown in a formula (I):
in the formula (I), R1And R2Independently selected from H or C1-C9 alkyl, and n is a natural number of 1-6.
Preferably, R1And R2Independently selected from H, methyl or n-octyl;
n is 1 or 2 or 3.
The invention also provides a preparation method of the diphenylamino-oxy carboxylic acid extractant, which comprises the following steps:
A) mixing dialkyl aniline, alkyl diacid monoethyl ester acyl chloride, an organic solvent and organic base, and reacting to obtain a reaction solution;
B) mixing the reaction solution with water to obtain an oil phase and a water phase;
C) carrying out reduced pressure distillation on the oil phase to obtain diphenylamino-oxy carboxylic acid monoethyl ester;
D) heating and refluxing the diphenylaminooxy carboxylic acid monoethyl ester in a sodium hydroxide solution, and obtaining the diphenylaminooxy carboxylic acid extractant after acidification and reduced pressure distillation.
Preferably, in step a), the dialkylaniline is one or more selected from diphenylamine, 4' -dimethyldiphenylamine, 4' -diethyldiphenylamine, 4' -dibutyldiphenylamine, 4' -dioctyldiphenylamine and 4,4' -dinonyldiphenylamine.
Preferably, in the step a), the alkyl diacid monoethyl ester acyl chloride is selected from one of malonic acid monoethyl ester acyl chloride, succinic acid monoethyl ester acyl chloride, glutaric acid monoethyl ester acyl chloride, adipic acid monoethyl ester acyl chloride, pimelic acid monoethyl ester acyl chloride and suberic acid monoethyl ester acyl chloride.
Preferably, in the step a), the organic solvent is one or more selected from toluene, xylene, heptane, octane, dichloromethane, chloroform and sulfonated kerosene;
the organic base is triethylamine.
Preferably, in the step a), the mass ratio of the dialkyl aniline to the alkyl diacid monoethyl ester acyl chloride is 16-40: 15-18;
the mass ratio of the dialkyl aniline to the organic alkali is 16-40: 14-16;
the reaction temperature is 0-20 ℃, and the reaction time is 15-60 min.
Preferably, in step D), the solvent in the sodium hydroxide solution comprises ethanol and water;
the heating reflux temperature is 60-90 ℃, and the time is 1-4 h;
the reagent used for acidification is a hydrochloric acid solution, and the concentration of the hydrochloric acid solution is 1-8 mol/L;
after the reduced pressure distillation, the method further comprises the following steps: and (5) washing with water.
The invention also provides a method for separating rare earth elements from the rare earth solution, which comprises the following steps:
a) mixing an extractant with an organic solvent to obtain an extractant solution; the extractant is the diphenylamino-oxo-carboxylic acid extractant of any one of claims 1 to 2 or the extractant prepared by the preparation method of any one of claims 3 to 8;
b) mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution;
c) and mixing the saponified extractant solution with a rare earth solution for extraction, wherein yttrium is enriched in a water phase, and yttrium-poor rare earth is enriched in an organic phase.
Preferably, the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium;
the total concentration of rare earth ions in the rare earth solution is 0.05-1.5 mol/L, and the pH value of the rare earth solution is 1-7.
The invention provides a diphenylamino-oxy carboxylic acid extracting agent which has a structure shown in a formula (I); in the formula (I), R1And R2Independently selected from H or C1-C9 alkyl, and n is a natural number of 1-6. Compared with the naphthenic acid extracting agent applied in industry, the diphenylamino-oxy carboxylic acid extracting agent provided by the invention has the advantages that the component is single, the chemical structure is stable, the concentration of an extracted organic phase is not reduced, and the extraction performance is stable; moreover, the benzimido oxycarboxylic acid extractant has obviously higher separation coefficient to light rare earth elements and yttrium than naphthenic acid, and has higher separation coefficient to heavy rare earth elements and yttrium than naphthenic acid,can completely replace naphthenic acid in separation energy efficiency, and has very good application prospect.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 5-diphenylamino-5-oxopentanoic acid of example 1 of the present invention;
FIG. 2 is a NMR spectrum of 5-diphenylamino-5-oxopentanoic acid of example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a diphenylamino-oxy carboxylic acid extracting agent, which has a structure shown in a formula (I):
in the formula (I), R1And R2Independently selected from H or C1-C9 alkyl, and n is a natural number of 1-6.
In certain embodiments of the invention, the R is1And R2Independently selected from H, methyl or n-octyl.
In certain embodiments of the invention, n is 1 or 2 or 3.
In certain embodiments of the present invention, the diphenylamino-oxocarboxylic acid extractant is selected from one of the structures represented by formulas (I-1) to (I-3);
the invention also provides a preparation method of the diphenylamino-oxy carboxylic acid extractant, which comprises the following steps:
A) mixing dialkyl aniline, alkyl diacid monoethyl ester acyl chloride, an organic solvent and organic base, and reacting to obtain a reaction solution;
B) mixing the reaction solution with water to obtain an oil phase and a water phase;
C) carrying out reduced pressure distillation on the oil phase to obtain diphenylamino-oxy carboxylic acid monoethyl ester;
D) heating and refluxing the diphenylaminooxy carboxylic acid monoethyl ester in a sodium hydroxide solution, and obtaining the diphenylaminooxy carboxylic acid extractant after acidification and reduced pressure distillation.
In certain embodiments of the invention, step a) comprises:
a) mixing dialkyl aniline, organic alkali and an organic solvent to obtain a mixed solution;
b) and mixing the alkyl diacid monoethyl ester acyl chloride with the mixed solution for reaction to obtain a reaction solution.
In certain embodiments of the present invention, the dialkylaniline is selected from one or more of diphenylamine, 4' -dimethyldiphenylamine, 4' -diethyldiphenylamine, 4' -dibutyldiphenylamine, 4' -dioctyldiphenylamine and 4,4' -dinonyldiphenylamine.
In certain embodiments of the present invention, the alkyl diacid monoethyl ester acyl chloride is selected from one of malonic acid monoethyl ester acyl chloride, succinic acid monoethyl ester acyl chloride, glutaric acid monoethyl ester acyl chloride, adipic acid monoethyl ester acyl chloride, pimelic acid monoethyl ester acyl chloride, and suberic acid monoethyl ester acyl chloride.
In certain embodiments of the present invention, the organic solvent is selected from one or more of toluene, xylene, heptane, octane, methylene chloride, chloroform, and sulfonated kerosene.
In certain embodiments of the invention, the organic base is triethylamine. The organic alkali is used for neutralizing byproduct hydrogen chloride generated in the reaction, so that the product is prevented from being acidified and hydrolyzed by the hydrogen chloride.
In certain embodiments of the present invention, the mass ratio of the dialkyl aniline to the alkyl diacid monoethyl ester acyl chloride is 16-40: 15 to 18. In certain embodiments, the mass ratio of dialkylaniline to alkyl diacid monoethyl ester chloride is 16.9: 17.9 or 19.7: 15.0 or 39.3: 16.0.
in certain embodiments of the present invention, the mass ratio of the dialkylaniline to the organic base is 16 to 40: 14 to 16. In certain embodiments, the mass ratio of dialkylaniline to organic base is 16.9: 15.2 or 19.7: 15.2 or 39.3: 15.2.
in certain embodiments of the present invention, in the step a), the ratio of the organic solvent to the dialkylaniline is 30 to 50 mL: 16-40 g. In certain embodiments, the organic solvent and dialkylaniline are used in a ratio of 40 mL: 16.9 g.
In certain embodiments of the invention, in step a), the mixing is stirred.
In certain embodiments of the present invention, before mixing the alkyl diacid monoethyl chloride with the mixed solution in the step b), the method further comprises: and cooling the mixed solution to 0 ℃ by using ice water bath.
In certain embodiments of the invention, in step b), the reaction is a stirred reaction.
The stirring method and parameters for the stirring reaction are not particularly limited in the present invention, and the stirring method and parameters known to those skilled in the art may be used.
In some embodiments of the present invention, the reaction temperature is 0-20 ℃ and the reaction time is 15-60 min. In certain embodiments, the temperature of the reaction is 0 ℃. In certain embodiments, the time of the reaction is 30 min.
In certain embodiments, the temperature of the reaction is 0 ℃. In certain embodiments, the time of the reaction is 30 min.
After obtaining the reaction solution, mixing the reaction solution with water to obtain an oil phase and a water phase.
In certain embodiments of the present invention, the water is deionized water. The water can extract hydrochloride formed by reaction byproducts of hydrogen chloride and triethylamine into a water phase, and an oil phase is reserved as a target product, so that the product and the byproducts are separated. The present invention is not particularly limited in the amount ratio of the reaction solution to water, and the above separation can be achieved.
And distilling the oil phase under reduced pressure to obtain a crude product of diphenylamino-oxy carboxylic acid monoethyl ester.
The method and parameters of the reduced pressure distillation are not particularly limited in the present invention, and those known to those skilled in the art can be used.
After crude product diphenylamino-oxo-carboxylic acid monoethyl ester is obtained, the diphenylamino-oxo-carboxylic acid monoethyl ester is heated and refluxed in sodium hydroxide solution, and the diphenylamino-oxo-carboxylic acid extractant is obtained after acidification and reduced pressure distillation.
In certain embodiments of the invention, the solvent in the sodium hydroxide solution comprises ethanol and water. In certain embodiments of the present invention, the volume ratio of ethanol to water in the solvent is 0.5 to 1.5: 0.5 to 1.5. In certain embodiments, the volume ratio of ethanol to water in the solvent is 1: 1. in certain embodiments of the invention, the concentration of the sodium hydroxide solution is 0.01-0.10 g/mL. In certain embodiments, the concentration of the sodium hydroxide solution is 0.05 g/mL.
In some embodiments of the invention, the temperature of the heating reflux is 60-90 ℃ and the time is 1-4 h. In certain embodiments, the temperature of the heated reflux is 70 ℃. In certain embodiments, the heating reflux time is 4 hours.
In the invention, the process of heating and refluxing the diphenylaminooxy carboxylic acid monoethyl ester in the sodium hydroxide solution is also a hydrolysis process.
In certain embodiments of the invention, the reagent used for acidification is a hydrochloric acid solution. In some embodiments of the invention, the concentration of the hydrochloric acid solution is 1-8 mol/L. In certain embodiments, the concentration of the hydrochloric acid solution is 6 mol/L.
The method and parameters of the reduced pressure distillation after acidification are not particularly limited in the present invention, and the method and parameters of the reduced pressure distillation well known to those skilled in the art can be adopted. The reduced pressure distillation was used to remove the solvent.
In certain embodiments of the present invention, after the vacuum distillation, the method further comprises: and (5) washing with water. The method of washing with water is not particularly limited in the present invention, and a method of washing with water known to those skilled in the art may be used.
The preparation method of the diphenylamino-oxo-carboxylic acid extracting agent provided by the invention is simple to operate, and the prepared diphenylamino-oxo-carboxylic acid extracting agent has single component and better chemical stability.
The invention also provides a method for separating rare earth elements from the rare earth solution, which comprises the following steps:
a) mixing an extractant with an organic solvent to obtain an extractant solution; the extracting agent is the diphenyl amino oxo carboxylic acid extracting agent or the diphenyl amino oxo carboxylic acid extracting agent prepared by the preparation method;
b) mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution;
c) and mixing the saponified extractant solution with a rare earth solution for extraction, wherein yttrium is enriched in a water phase, and yttrium-poor rare earth is enriched in an organic phase.
In certain embodiments of the present invention, the organic solvent is selected from one or more of toluene, xylene, heptane, octane, methylene chloride, chloroform, and sulfonated kerosene.
In some embodiments of the present invention, the concentration of the extractant solution is 0.5-1.0 mol/L. In certain embodiments, the concentration of the extractant solution is 0.60 mol/L.
And after an extractant solution is obtained, mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution.
In certain embodiments of the invention, the inorganic base solution is an aqueous solution of sodium hydroxide. In some embodiments of the invention, the concentration of the inorganic alkali solution is 8-12 mol/L. In certain embodiments, the concentration of the inorganic base solution is 10.8 mol/L.
In some embodiments of the present invention, the saponification temperature is 25-65 ℃ and the saponification time is 0.5-2 h. In certain embodiments, the temperature of the saponification is 65 ℃, 45 ℃, or 25 ℃. In certain embodiments, the saponification time is 0.5h, 1h, or 2 h.
In certain embodiments of the invention, the saponified extractant solution has a saponification degree of 80% to 85%. In certain embodiments, the saponified extractant solution has a saponification degree of 83.3%.
And after obtaining the saponified extractant solution, mixing the saponified extractant solution with the rare earth solution for extraction, wherein yttrium is enriched in the water phase, and yttrium-poor rare earth is enriched in the organic phase.
In certain embodiments of the invention, the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium. In certain embodiments of the present invention, the total concentration of rare earth ions in the rare earth solution is 0.05 to 1.5 mol/L. In certain embodiments, the total concentration of rare earth ions in the rare earth solution is 1.15 mol/L. In some embodiments of the invention, the rare earth solution has a pH of 1 to 7. In certain embodiments, the rare earth solution has a pH of 5.5.
In some embodiments of the present invention, the volume ratio of the saponified extractant solution to the rare earth solution is 70-100: 20 to 40. In certain embodiments, the volume ratio of saponified extractant solution to rare earth solution is 80: 30.
in certain embodiments of the invention, the temperature at which the saponified extractant solution is mixed with the rare earth solution is room temperature.
In certain embodiments of the invention, the temperature of the extraction is room temperature. In some embodiments of the present invention, the extraction time is 0.5 to 3 hours. In certain embodiments, the time for the extraction is 2 hours.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
Compared with the naphthenic acid extracting agent applied in industry, the diphenylamino-oxy carboxylic acid extracting agent provided by the invention has the advantages that the component is single, the chemical structure is stable, the concentration of an extracted organic phase is not reduced, and the extraction performance is stable; moreover, the benzimido oxycarboxylic acid extractant has obviously higher separation coefficient for light rare earth elements and yttrium than naphthenic acid, and also has higher separation coefficient for heavy rare earth elements and yttrium than naphthenic acid, can completely replace naphthenic acid in separation energy efficiency, and has very good application prospect.
The diphenylamino-oxy-carboxylic acid extractant provided by the invention is used for separating yttrium from lanthanide, fewer stages of extraction tanks can be arranged to achieve the separation effect, and the separation method is simple and easy to implement and has lower cost.
In order to further illustrate the present invention, the following examples are provided to describe the benziminooxycarboxylic acid extractants, the preparation method and the applications thereof in detail, but the invention should not be construed as being limited by the scope of the present invention.
In the following examples and comparative examples, the content of yttrium and other rare earths in the aqueous phase was measured by inductively coupled plasma emission spectroscopy (hereinafter referred to as ICP-OES). The instrument model is JY ULTIMA 2, produced by France. ICP excitation power is 1.3kW, atomizer flow is 0.75L/min, solution lifting amount is 1.50mL/min, and observation height is 1.4 cm. The analytical method refers to the determination of the fifteen rare earth element oxide proportioning in the eighth part of the GB/T18114.8-2010 rare earth concentrate chemical analytical method. The separation effect of yttrium and other rare earth ions is measured by a separation coefficient beta, and the calculation method is as follows: let concentrations of metal ion M1 before and after extraction be Ci1 and Cr1, respectively, and concentrations of metal ion M2 before and after extraction be Ci2 and Cr2, respectively. The extraction rate E of the metal ions M1 and M2 is:
separation coefficient beta of metal ions M1 and M2M1/M2Expressed as:
example 1
5-Diphenylamino-5-oxopentanoic acid chemistryThe structure is shown as formula (I-1), namely R1And R2All are H, and n takes the value of 3;
the preparation method comprises the following steps:
(1) 16.9g of diphenylamine, 15.2g of triethylamine and 40mL of dichloromethane were mixed and stirred uniformly to obtain a mixed solution, and the mixed solution was cooled to 0 ℃ with an ice water bath.
(2) 17.9g of glutaric acid monoethyl ester acyl chloride is added into the mixed solution, and the mixture is stirred and reacted for 30min at the temperature of 0 ℃, so that reaction solution is obtained.
(3) And adding deionized water into the reaction liquid, separating the reaction liquid into an oil phase and a water phase, and distilling the oil phase under reduced pressure to obtain a crude product of the ethyl 5-diphenylamino-5-oxopentanoate.
(4) Heating 5-diphenylamino-5-oxo-pentanoic acid ethyl ester in 100mL of mixed solution (solvent comprises ethanol and water in a volume ratio of 1: 1) containing 5g of sodium hydroxide to 70 ℃, refluxing and hydrolyzing for 4h, then acidifying with 25mL of 6mol/L hydrochloric acid solution, removing the solvent by reduced pressure distillation, and washing with water to obtain 5-diphenylamino-5-oxo-pentanoic acid.
The nuclear magnetic resonance analysis of the prepared product is carried out, and the result is shown in figure 1. FIG. 1 is a NMR spectrum of 5-diphenylamino-5-oxopentanoic acid of example 1 of the present invention. Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz，CDCl3)2.08(2H，m)，2.46(4H，t)，6.9～7.5(10H，m)，8.70(1H，s)。
FIG. 2 is a NMR spectrum of 5-diphenylamino-5-oxopentanoic acid of example 1 of the present invention. Nuclear magnetic resonance carbon spectrum analysis:13C NMR(500MHz，CDCl3)20.3(1C)，33.4(1C)，34.5(1C)，77.1(CDCl3，t)，117.8(4C)，120.9(2C)，129.7(4C)，142.7(2C，d)，173.1(1C)，178.2(1C)。
from the hydrogen spectrum and carbon spectrum of nuclear magnetic resonance1H and13the C peak corresponds to the structure shown in formula (I-1), and there is no impurity peak.
Through acid-base titration and nuclear magnetic resonance detection, the purity reaches 99 percent, and the yield is more than 98 percent.
Example 2
The chemical structure of the 3- (4,4' -dimethyl diphenylamino) -3-oxo-propionic acid is shown as the formula (I-2), namely R1And R2Are all methyl, and n takes the value of 1;
the preparation method comprises the following steps:
(1) 19.7g of 4,4' -dimethyldiphenylamine, 15.2g of triethylamine and 40mL of dichloromethane are mixed and stirred uniformly to obtain a mixed solution, and the mixed solution is cooled to 0 ℃ by using an ice water bath.
(2) Adding 15.0g of malonic acid monoethyl ester acyl chloride into the mixed solution, and stirring and reacting for 30min at the temperature of 0 ℃ to obtain a reaction solution.
(3) And adding deionized water into the reaction liquid, separating the reaction liquid into an oil phase and a water phase, and distilling the oil phase under reduced pressure to obtain a crude product of the ethyl 3- (4,4' -dimethyl diphenylamino) -3-oxo propionate.
(4) Heating 3- (4,4 '-dimethyl diphenylamino) -3-oxo-propionic acid ethyl ester in 100mL of mixed solution containing 5g of sodium hydroxide (solvent comprises ethanol and water in a volume ratio of 1: 1) to 70 ℃, refluxing and hydrolyzing for 4h, then acidifying with 25mL of 6mol/L hydrochloric acid solution, removing the solvent by reduced pressure distillation, and washing with water to obtain 3- (4,4' -dimethyl diphenylamino) -3-oxo-propionic acid.
Through acid-base titration and nuclear magnetic resonance detection, the purity reaches 98 percent, and the yield is more than 97 percent.
Example 3
The chemical structure of the 4- (4,4' -di-n-octyl diphenylamino) -4-oxobutyric acid is shown as the formula (I-3), namely R1And R2Are all n-octyl groups, and the value of n is 2;
the preparation method comprises the following steps:
(1) 39.3g of 4,4' -di-n-octyldiphenylamine, 15.2g of triethylamine and 50mL of dichloromethane were mixed and stirred uniformly to obtain a mixed solution, and the mixed solution was cooled to 0 ℃ with an ice water bath.
(2) Adding 16.0g of succinic acid monoethyl ester acyl chloride into the mixed solution, and stirring and reacting for 30min at the temperature of 0 ℃ to obtain a reaction solution.
(3) Adding deionized water into the reaction solution, separating the reaction solution into an oil phase and a water phase, and distilling the oil phase under reduced pressure to obtain a crude product of ethyl 4- (4,4' -di-n-octyl diphenylamino) -4-oxo-butyrate.
(4) Heating 4- (4,4 '-di-n-octyl diphenylamino) -4-oxo-butyric acid ethyl ester in 100mL of ethanol-water mixed solution containing 5g of sodium hydroxide (solvent comprises ethanol and water with volume ratio of 1: 1) to 70 ℃, refluxing and hydrolyzing for 4h, then acidifying with 25mL of 6mol/L hydrochloric acid solution, removing the solvent by reduced pressure distillation, and washing with water to obtain 4- (4,4' -di-n-octyl diphenylamino) -4-oxo-butyric acid.
Through acid-base titration and nuclear magnetic resonance detection, the purity reaches 97%, and the yield is more than 96.5%.
Example 4
Preparing a rare earth solution:
preparing a rare earth solution with the total concentration of rare earth ions of 1.15mol/L, wherein the pH value is 5.5, and the concentrations of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are all 0.0767 mol/L.
Preparation of an extractant solution:
the extractant used was 5-diphenylamino-5-oxopentanoic acid, taken 13.6g in mass, mixed with 66.4mL of toluene to make an extractant solution, the concentration was 0.60 mol/L.
The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 65 ℃ for 0.5h to give a saponified extractant solution having a degree of saponification of 83.3%.
Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y)Ln/YMeasure and measureThe test results are shown in table 1.
Example 5
Preparing a rare earth solution:
preparing a rare earth solution with the total concentration of rare earth ions of 1.15mol/L, wherein the pH value is 5.5, and the concentrations of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are all 0.0767 mol/L.
Preparation of an extractant solution:
the used extractant is 3- (4,4' -dimethyl diphenylamino) -3-oxo-propionic acid, the mass of the extractant is 13.6g, and the extractant solution is prepared by mixing with 66.4mL of toluene, and the concentration is 0.60 mol/L.
The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 45 ℃ for 1h to give a saponified extractant solution having a degree of saponification of 83.3%.
Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y)Ln/YThe test results are shown in table 1.
Example 6
Preparing a rare earth solution:
preparing a rare earth solution with the total concentration of rare earth ions of 1.15mol/L, wherein the pH value is 5.5, and the concentrations of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are all 0.0767 mol/L.
Preparation of an extractant solution:
the used extractant is 4- (4,4' -di-n-octyl diphenylamino) -4-oxobutyric acid, 23.0g of the extractant is taken and mixed with 57mL of toluene to prepare an extractant solution with the concentration of 0.60 mol/L.
The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 25 ℃ for 2h to give a saponified extractant solution having a degree of saponification of 83.3%.
Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating each diluted solutionRelative separation coefficient beta of earth ions (Ln) relative to yttrium ions (Y)Ln/YThe test results are shown in table 1.
Comparative example 1
Preparing a rare earth solution:
preparing a rare earth solution with the total concentration of rare earth ions of 1.15mol/L, wherein the pH value is 5.5, and the concentrations of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are all 0.0767 mol/L.
Preparation of an extractant solution:
the used extractant is industrial naphthenic acid, 12g of the extractant is mixed with 68mL of toluene to prepare an extractant solution with the concentration of 0.60 mol/L.
The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified to give a saponified extractant solution having a degree of saponification of 83.3%.
Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y)Ln/YThe test results are shown in table 1.
TABLE 1 relative separation coefficient β of each rare earth ion (Ln) with respect to yttrium ion (Y)Ln/Y
βLn/Y
Example 4
Example 5
Example 6
Comparative example 1
La/Y
2.13
2.69
0.57
0.52
Ce/Y
3.29
4.33
0.95
0.94
Pr/Y
4.18
5.38
1.29
1.23
Nd/Y
4.01
5.42
2.21
1.93
Sm/Y
4.81
6.36
3.30
3.25
Eu/Y
4.27
5.65
3.21
3.18
Gd/Y
3.61
3.60
2.37
2.28
Tb/Y
3.31
3.62
2.57
2.53
Dy/Y
2.96
3.07
2.86
2.36
Ho/Y
2.37
2.39
2.78
2.13
Er/Y
2.35
2.05
3.22
2.08
Tm/Y
2.36
2.02
4.16
2.32
Yb/Y
2.99
1.93
5.04
2.93
Lu/Y
2.85
1.75
4.97
2.75
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
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