CN113106271B - Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid - Google Patents
Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid Download PDFInfo
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Abstract
The invention relates to a method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid, belonging to ionic liquid extractionThe field of rare earth separation. It is characterized by utilizing 5 functionalized ionic liquids ([ (CH) with carboxylic acid functional groups2)nCOOHpyr][NTf2]N-3, 4, 5, 6, 7) is used as extractant and ionic liquid [ C ] is used4mim][NTf2]、[C4pyr][NTf2]、[C4mim][PF6]Is a diluent and forms an ionic liquid phase with high selectivity separation on rare earth gadolinium. The method is characterized in that hydrochloric acid aqueous solution containing rare earth gadolinium and aluminum impurity is used as raw material liquid, and high-purity purification of the rare earth gadolinium is realized through an extraction separation technology. The ionic liquid phase of the invention replaces the traditional organic solvents such as naphthenic acid, P507, toluene and the like, and avoids the pollution to the environment. The method has good selectivity on rare earth gadolinium, the separation coefficient of aluminum/gadolinium is as high as 253, the removal rate of aluminum is 99.9%, and the ionic liquid phase can be recycled.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to a method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid, belonging to the field of extraction and separation of rare earth by using ionic liquid.
[ background of the invention ]
Rare earth elements are national important strategic resources and high-tech materials, and are called industrial vitamins. Rare earth elements consist of scandium, yttrium and lanthanides which are very similar in their physicochemical properties. Due to the particularity of the electronic layer structure, the rare earth elements have unique optical, electrical, magnetic and other characteristics, play an irreplaceable role in practical application, and are widely used for various functional materials, such as rare earth permanent magnetic materials, rare earth luminescent materials, rare earth catalytic materials, rare earth hydrogen storage materials, rare earth polishing materials and the like, and cover the fields of chemical industry, metallurgy, superconduction, national defense and the like.
Gadolinium, the largest number of unpaired electrons in rare earth elements, has unique physicochemical properties. Such as strong magnetic moment, strong attraction to thermal neutrons, etc., and are widely used in neutron absorbers, magnetic resonance imaging, magnetic memories, nuclear reaction masking agents, etc. However, these applications require a particularly high purity of gadolinium, generally greater than 99.995%. At present, extraction method CN101979680A and precipitation method CN105624440A are mainly used for removing impurity aluminum in rare earth solution, and the precipitation method has high cost, high rare earth loss rate and low aluminum removal efficiency, so that solvent extraction method is generally adopted in industry to purify rare earth gadolinium with high purity. In a typical rare earth extraction separation process of a P507-HCl system, the separation coefficient of aluminum ions and rare earth gadolinium is low, the situation that aluminum exceeds the standard often exists in gadolinium products, performance parameters of high-purity gadolinium are greatly influenced, and in addition, organic solvents used in the traditional solvent extraction process, such as toluene, kerosene, n-heptane and the like, are generally volatile and toxic. Therefore, the development of a novel method for purifying the rare earth gadolinium efficiently, cleanly and highly has important significance.
The ionic liquid is a kind of room temperature molten salt composed of organic cation and organic and inorganic anions. Compared with the traditional organic solvent, the ionic liquid has the advantages of low toxicity, non-volatility, designability and the like, and is widely applied to the field of rare earth extraction separation. For example, Chinese patent CN106048221A discloses a method for preparing a liquid crystal by using an ionic liquid OMIM]BF4Extracting light rare earth elements of lanthanum, cerium, praseodymium and neodymium from the acid solution; chinese patent CN111440945A discloses a method for refining rare earth gadolinium by an ionic liquid method to remove aluminum, but no article and patent for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid are reported.
[ summary of the invention ]
Aiming at the problems that the separation coefficient of aluminum/gadolinium in the industry is low, the high-purity purification of rare earth gadolinium is difficult to realize, and the traditional organic solvent used in the daily extraction separation process is volatile and toxic, the invention aims to provide the method for purifying the rare earth element gadolinium by using the carboxylic acid functionalized ionic liquid, wherein the adopted carboxylic acid functionalized ionic liquid has stable chemical property and is non-volatile, the separation coefficient of aluminum/gadolinium is as high as 253, the extraction time is short, the aluminum removal efficiency is high, and the ionic liquid phase can be recycled.
The technical scheme of the invention is as follows:
the method utilizes 5 functionalized ionic liquids [ (CH) with carboxylic acid functional groups2)nCOOHpyr][NTf2]N-3, 4, 5, 6, 7 is an extracting agent, and an ionic liquid [ C ] is adopted4mim][NTf2]、[C4pyr][NTf2]、[C4mim][PF6]The ionic liquid phase is used as a diluent and has high selectivity separation on rare earth gadolinium, hydrochloric acid aqueous solution containing rare earth gadolinium and aluminum impurity is used as raw material liquid, the ionic liquid phase and the raw material liquid are mixed and extracted, then dilute hydrochloric acid is used as a stripping agent to carry out stripping on the rare earth-loaded ionic liquid phase to realize high-purity purification of the rare earth gadolinium, and the stripped ionic liquid phase can be recycled after alkali addition regeneration treatment.
The functionalized ionic liquid with carboxylic acid functional group [ (CH)2)nCOOHpyr][NTf2]N-3, 4, 5, 6, 7 has the following general structural formula:
the ionic liquid [ C4mim][NTf2]、[C4pry][NTf2]、[C4mim][PF6]The structural formula is as follows:
the ionic liquid phase is formed by compounding an extracting agent and a diluent, and the concentration of the extracting agent in the ionic liquid phase is 0.1-0.3 mol/L.
The raw material liquid contains 0.01-0.03 mol/L of gadolinium, 0.01-0.03 mol/L of aluminum and 1.45-1.97 of pH.
And mixing and extracting the ionic liquid phase and the raw material liquid in a constant-temperature water bath oscillator, wherein the extraction ratio is 1:1, the extraction temperature is 20-45 ℃, the extraction time is 10-20 min, the rotation speed in the extraction process is 200-450 r/min, the extracted mixed solution is separated after centrifugation, the upper layer is raffinate, and the lower layer is an ionic liquid phase loaded with rare earth.
The rare earth-loaded ionic liquid phase is subjected to back extraction by using 0.04-0.08 mol/L dilute hydrochloric acid as a back extractant, then 0.035-0.105 mmol NaOH is added into the ionic liquid phase to realize regeneration, and the regenerated ionic liquid phase is used in the process of removing aluminum by purifying rare earth gadolinium with high purity.
The invention has the beneficial effects that:
the invention designs and synthesizes 5 novel carboxylic acid functionalized ionic liquids, the selectivity to rare earth gadolinium is good, the separation coefficient of aluminum/gadolinium is as high as 253, the removal rate of aluminum is 99.9%, the rare earth-loaded ionic liquid phase can be recycled after low-acid back extraction, and the extraction separation performance to aluminum/gadolinium is basically kept unchanged. The invention provides a feasible method for purifying the rare earth element gadolinium with high purity.
[ detailed description ] embodiments
In the process of the specific embodiment, after the extraction and stripping processes of the present invention are completed, the metal ion concentration in the raffinate in the upper layer is measured by the ICP method, and the metal ion concentration in the ionic liquid phase is obtained by the subtraction method.
The extraction rate of the metal ions is calculated according to formula 1:
the distribution ratio of the metal ions is calculated by equation 2:
the separation coefficient of the metal ions is calculated according to equation 3:
in the formula: [ M ] A]iAnd [ M]fRepresents the concentration of metal ions in the aqueous phase before and after extraction, [ V ]]aAnd [ V ]]oRespectively representing the volumes of the aqueous phase and the ionic liquid phase; d1And D2The partition ratios of metal ions 1 and 2, respectively.
The present invention is described by the following examples, but the present invention is not limited to the following examples, and all modifications and variations based on the basic idea of the present invention are within the technical scope of the present invention claimed in the claims without departing from the spirit of the present invention.
Example 1
Ionic liquid [ (CH)2)nCOOHpyr][Br]Preparation of, n-3, 4, 5, 6, 7
0.2mol of 4-bromobutyric acid, 5-bromovaleric acid, 6-bromohexanoic acid, 7-bromoheptanoic acid and 8-bromooctanoic acid are respectively dissolved in 50ml of ethanol, then are respectively dropwise added into a three-neck flask containing equimolar pyridine, are magnetically stirred for 48 hours at 70 ℃, and are subjected to condensation and reflux. After the reaction was complete, a precipitate was formed and excess ethanol was removed by rotary evaporation. The product was washed 10 more times with ethyl acetate and then with P2O5Drying with desiccant under vacuum at 65 deg.C for 48h to obtain 5 powdered solids [ (CH)2)nCOOHpyr][Br]When n is 3, 4, 5, 6, 7, the yields are 89.8%, 90.6%, 93.3%, 94.9%, and 93.8%, respectively.
Example 2
Ionic liquid [ (CH)2)nCOOHpyr][NTf2]Preparation of, n-3, 4, 5, 6, 7
Reacting LiNTf2Are each equimolar to [ (CH) in example 12)nCOOHpyr][Br]And n is 3, 4, 5, 6 and 7, performing ion exchange reaction in deionized water, magnetically stirring at room temperature for 12 hours, standing for layering, and obtaining a lower layer as a reaction product. Washing the product with deionized water for several times until no white precipitate is formed by detection with saturated silver bromide solution, and then using P2O5Drying with desiccant under vacuum at 65 deg.C for 24 hr to obtain 5 kinds of viscous ionic liquid [ (CH)2)nCOOHpyr][NTf2]When n is 3, 4, 5, 6, 7, the yields are 88.7%, 91.3%, 89.4.8%, 93.7%, 95.5%, respectively.
Example 3
Carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]From aluminium, gadoliniumMedium selective separation of gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) is 0.019mol/L and the pH value is 1.45.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.2 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator for 10min at the temperature of 20 ℃ at the rotating speed of 200r/min in the extraction process, and measuring the concentration of metal ions in the raffinate by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)3COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 213, and the removal rate of aluminum was 98.5%.
4) And (2) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.05mol/L dilute hydrochloric acid, adding 0.07mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 215, and the removal rate of aluminum was 98.7%.
Example 4
Carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.013mol/L, and the pH was 1.55.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]As an extractant, [ C ] is selected4pyr][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.15 mol/L.
3) Mixing raw material liquid and ionic liquid phase in a constant temperature water bath oscillator for extraction at 25 deg.C for 15min at 300r/min, the concentration of metal ions in the raffinate was determined by ICP. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)3COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 202, and the removal rate of aluminum was 97.3%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.04mol/L dilute hydrochloric acid, adding 0.052mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 205, and the removal rate of aluminum was 97.5%.
Example 5
Carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (2) was 0.015mol/L, and the pH was 1.68.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][PF6]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.3 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 13min, the temperature is 40 ℃, the rotating speed in the extraction process is 250r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 234, and the removal rate of aluminum was 98.9%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.045mol/L dilute hydrochloric acid, adding 0.105mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)3COOHpyr][NTf2]Has a separation coefficient of aluminum/gadolinium of223, the removal rate of aluminum was 98.8%.
Example 6
Carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.028mol/L, and the pH was 1.87.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.25 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 17min, the temperature is 45 ℃, the rotating speed in the extraction process is 400r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 226, and the removal rate of aluminum was 98.8%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.07mol/L dilute hydrochloric acid, adding 0.087mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 213, and the removal rate of aluminum was 98.3%.
Example 7
Carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+Has a concentration of 0.023mol/L and a pH value of 1.68.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]As an extractant, [ C ] is selected4pyr][NTf2]As a diluent, an ionic liquid phaseThe concentration of the reagent is 0.18 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 20min, the temperature is 35 ℃, the rotating speed in the extraction process is 250r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)4COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 215, and the removal rate of aluminum was 98.4%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.055mol/L dilute hydrochloric acid, adding 0.063mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 219, and the removal rate of aluminum was 98.7%.
Example 8
Carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.02mol/L, and the pH was 1.92.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][PF6]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.3 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator for 19min at the temperature of 30 ℃ at the rotating speed of 350r/min in the extraction process, and measuring the concentration of metal ions in the raffinate by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 237, and the removal rate of aluminum was 99.1%.
4) Adopting 0.065mol/L dilute hydrochloric acid to carry out back extraction on the rare earth-loaded ionic liquid phase, and adding 0.105mmol of NaOH into the back-extracted ionic liquid phaseAnd (4) regenerating, wherein the regenerated ionic liquid phase is used for purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)4COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 236 and the removal rate of aluminum was 99%.
Example 9
Carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.025mol/L and the pH was 1.97.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.2 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator for 10min at the temperature of 20 ℃ at the rotating speed of 200r/min in the extraction process, and measuring the concentration of metal ions in the raffinate by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)5COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 212, and the removal rate of aluminum was 97.9%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.08mol/L dilute hydrochloric acid, adding 0.07mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 221, and the removal rate of aluminum was 98.6%.
Example 10
Carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (2) was 0.018mol/L, and the pH was 1.5.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]As an extractant, [ C ] is selected4pyr][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.15 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 8min, the temperature is 25 ℃, the rotating speed in the extraction process is 300r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)5COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 225, and the removal rate of aluminum was 98.8%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.06mol/L dilute hydrochloric acid, adding 0.052mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 220, and the removal rate of aluminum was 98.4%.
Example 11
Carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (2) was 0.015mol/L and the pH was 1.6.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][PF6]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.2 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator for 10min at the temperature of 20 ℃ at the rotating speed of 250r/min in the extraction process, and measuring the concentration of metal ions in the raffinate by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)5COOHpyr][NTf2]Separation system for aluminum/gadoliniumThe number was 232, and the removal rate of aluminum was 99.2%.
4) And (2) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.065mol/L dilute hydrochloric acid, adding 0.07mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)5COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 230, and the removal rate of aluminum was 99.1%.
Example 12
Carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.01mol/L and the pH was 1.75.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.23 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator for 10min at the temperature of 20 ℃ at the rotating speed of 200r/min in the extraction process, and measuring the concentration of metal ions in the raffinate by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)6COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 250, and the removal rate of aluminum was 99.7%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.075mol/L dilute hydrochloric acid, adding 0.08mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 243, and the removal rate of aluminum was 99.4%.
Example 13
Carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.03mol/L, and the pH was 1.77.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]As an extractant, [ C ] is selected4pyr][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.16 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 17min, the temperature is 35 ℃, the rotating speed in the extraction process is 350r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)6COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 246 and the removal rate of aluminum was 99.5%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.045mol/L dilute hydrochloric acid, adding 0.056mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 236 and the removal rate of aluminum was 98.9%.
Example 14
Carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) is 0.026mol/L, and the pH value is 1.79.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][PF6]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.1 mol/L.
3) Mixing raw material liquid and ionic liquid phase in a constant temperature water bath oscillator for extraction at 40 deg.C for 11min, transferring during extraction processThe rate was 400r/min and the concentration of metal ions in the raffinate was determined by ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)6COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 249, and the removal rate of aluminum was 99.7%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.06mol/L dilute hydrochloric acid, adding 0.035mmol NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)6COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 240, and the removal rate of aluminum was 99.3%.
Example 15
Carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.025mol/L and the pH was 1.88.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.3 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 16min, the temperature is 45 ℃, the rotating speed in the extraction process is 400r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)7COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 253 and the removal rate of aluminum was 99.9%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.07mol/L dilute hydrochloric acid, adding 0.105mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]To aluminium/gadoliniumThe separation coefficient was 245, and the removal rate of aluminum was 99.2%.
Example 16
Carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.02mol/L, and the pH was 1.91.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]As an extractant, [ C ] is selected4pyr][NTf2]As a diluent, the concentration of the extractant in the ionic liquid phase was 0.15 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 15min, the temperature is 25 ℃, the rotating speed in the extraction process is 350r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)7COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 245, and the removal rate of aluminum was 99.2%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.05mol/L dilute hydrochloric acid, adding 0.052mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]The separation coefficient of aluminum/gadolinium was 242, and the removal rate of aluminum was 99%.
Example 17
Carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]Selective separation of gadolinium from aluminum and gadolinium
1) Preparing a raw material liquid containing Al3+、Gd3+The concentration of (A) was 0.01mol/L and the pH was 1.8.
2) Preparing ionic liquid phase, selecting carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]As an extractant, [ C ] is selected4mim][PF6]As a diluent, an ionic liquid phaseThe concentration of the medium extractant is 0.3 mol/L.
3) Mixing and extracting the raw material liquid and the ionic liquid phase in a constant-temperature water bath oscillator, wherein the extraction time is 19min, the temperature is 40 ℃, the rotating speed in the extraction process is 300r/min, and the concentration of metal ions in the raffinate is measured by an ICP method. The results show that the carboxylic acid functionalized ionic liquid [ (CH) in the extraction system2)7COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 251, and the removal rate of aluminum was 99.7%.
4) And (3) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.08mol/L dilute hydrochloric acid, adding 0.105mmol of NaOH into the back-extracted ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of purifying rare earth gadolinium to remove aluminum. The result shows that the regenerated carboxylic acid functionalized ionic liquid [ (CH)2)7COOHpyr][NTf2]The separation coefficient for aluminum/gadolinium was 252, and the removal rate of aluminum was 99.8%.
The embodiment result shows that the method for purifying the rare earth element gadolinium by using the carboxylic acid functionalized ionic liquid has the following advantages: the selectivity to rare earth gadolinium is good, the separation coefficient of aluminum/gadolinium is as high as 253, the removal rate of aluminum is 99.9%, and the ionic liquid phase can be recycled.
Claims (7)
1. The method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid is characterized by using 5 functionalized ionic liquids [ (CH) with carboxylic acid functional groups2)nCOOHpyr][NTf2]N-3, 4, 5, 6, 7 is an extracting agent, and an ionic liquid [ C ] is adopted4mim][NTf2]、[C4pyr][NTf2]、[C4mim][PF6]The ionic liquid phase is used as a diluent and has high selectivity separation on rare earth gadolinium, hydrochloric acid aqueous solution containing rare earth gadolinium and aluminum impurity is used as raw material liquid, the ionic liquid phase and the raw material liquid are mixed and extracted, then dilute hydrochloric acid is used as a stripping agent to carry out stripping on the rare earth-loaded ionic liquid phase to realize high-purity purification of the rare earth gadolinium, and the stripped ionic liquid phase can be recycled after alkali adding regeneration treatment.
2. The method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: the functionalized ionic liquid with carboxylic acid functional group [ (CH)2)nCOOHpyr][NTf2]N-3, 4, 5, 6, 7 has the following general structural formula:
3. the method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: the ionic liquid [ C4mim][NTf2]、[C4pyr][NTf2]、[C4mim][PF6]The structural formula is as follows:
4. the method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: the ionic liquid phase is formed by compounding an extracting agent and a diluent, and the concentration of the extracting agent in the ionic liquid phase is 0.1-0.3 mol/L.
5. The method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: the content of gadolinium in the raw material liquid is 0.01-0.03 mol/L, the content of impurity aluminum is 0.01-0.03 mol/L, and the pH value is 1.45-1.97.
6. The method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: and mixing and extracting the ionic liquid phase and the raw material liquid in a constant-temperature water bath oscillator, wherein the extraction ratio is 1:1, the extraction temperature is 20-45 ℃, the extraction time is 10-20 min, the rotating speed is 200-450 r/min in the extraction process, the extracted mixed solution is separated after centrifugation, the upper layer is raffinate, and the lower layer is the rare earth-loaded ionic liquid phase.
7. The method for purifying the rare earth element gadolinium with high purity by using the carboxylic acid functionalized ionic liquid according to claim 1, wherein the method comprises the following steps: and (2) performing back extraction on the rare earth-loaded ionic liquid phase by using 0.04-0.08 mol/L dilute hydrochloric acid as a back extractant, then adding 0.035-0.105 mmol NaOH into the ionic liquid phase to realize regeneration, and using the regenerated ionic liquid phase in the process of removing aluminum by purifying rare earth gadolinium with high purity.
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