CN108517406B - Solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, and preparation method and application thereof - Google Patents
Solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, and preparation method and application thereof Download PDFInfo
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/385—Thiophosphoric acids, or esters thereof
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids R2P(=O)(OH); Thiophosphinic acids, i.e. R2P(=X)(XH) (X = S, Se)
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- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
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Abstract
The invention discloses a solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides, a preparation method and application thereof, wherein the solid phase extractant comprises a magnetic mesoporous material and a dithiophosphinic acid compound, and the dithiophosphinic acid compound is grafted on the magnetic mesoporous material through a coupling agent; the dithiophosphinic acid compound is bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, and the structural formula is shown as a formula (1):the preparation method comprises the following steps: (1) connecting a coupling agent on the magnetic mesoporous material; (2) under the action of an alkaline catalyst, bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid is grafted on the magnetic mesoporous material through a coupling agent. The solid phase extractant can selectively separate trivalent minor actinides and trivalent lanthanides, and has the advantages of environment-friendly separation process and simple operation.
Description
Technical Field
The invention relates to the technical field of organic compounds and preparation thereof, in particular to a solid phase extracting agent for selectively separating trivalent minor actinides and trivalent lanthanides, and a preparation method and application thereof.
Background
Trivalent minor actinidesThe effective separation of the element and the trivalent lanthanide is one of the key steps of 'separation-transmutation' of the high-level radioactive waste liquid, and is also an effective means for further reducing the volume of the alpha waste. The separation of trivalent series elements from trivalent lanthanides has been a challenging problem. Bis (o-trifluoromethylphenyl) dithiophosphinic acid and diluent toluene or FS-13 (trifluoromethylphenyl sulfone) to Am3+Has good extraction ability and high selectivity, Am3+With Eu3+The separation factor between them is up to-105The extraction separation performance is better than that of the purified Cyanex 301. Although bis (o-trifluoromethylphenyl) dithiophosphinic acid can be used at a low pH, the diluents used (such as toluene or FS-13) are volatile and have some toxicity, and thus are harmful to the human body and cause environmental pollution.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a solid phase extracting agent for selectively separating trivalent minor actinides and trivalent lanthanides, which is environment-friendly and simple in separation operation, and also correspondingly provides a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
a solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides comprises a magnetic mesoporous material and a dithiophosphinic acid compound, wherein the dithiophosphinic acid compound is grafted on the magnetic mesoporous material through a coupling agent; the dithiophosphinic acid compound is di (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, and the structural formula is shown as a formula (1):
preferably, the magnetic mesoporous material comprises magnetic nanoparticles and mesoporous SiO2The mesoporous SiO2Coating on the surface of the magnetic nanoparticles.
The aboveA solid phase extractant for selectively separating trivalent minor actinides from trivalent lanthanides, preferably, the coupling agent has the general formula YSiX3Wherein X is an alkyl group or an alkoxy group, and Y is a hydrocarbon group having Cl at the terminal.
Preferably, the coupling agent is 3-chloropropyltriethoxysilane.
Preferably, the synthesis concept of the dithiophosphinic acid compound is as follows: phosphorus trichloride is taken as a raw material, and is reacted with a Grignard reagent protected by hydroxyl, and then bis (2-trifluoromethyl-4-hydroxyphenyl) dithiophosphinic acid is obtained through the steps of sulfuration, acidification, hydroxyl deprotection, purification and the like. The synthetic route is as formula (2):
the method specifically comprises the following steps:
1) dissolving tert-butyldimethylsilyl chloride in a first organic solvent to obtain a tert-butyldimethylsilyl chloride organic solution; dropwise adding a tert-butyldimethylsilyl chloride organic solution into a mixed solution of 3-trifluoromethyl-4-bromophenol, imidazole and a first organic solvent to perform a first nucleophilic substitution reaction to prepare 3-trifluoromethyl-4-bromophenyl tert-butyldimethylsilyl ether; imidazole has weak alkalinity and is used as a basic catalyst in the first nucleophilic substitution reaction;
2) dissolving the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether prepared in the step (1) in a second organic solvent to obtain a 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether organic solution; under the action of an initiator, dropwise adding the 3-trifluoromethyl-4-bromophenyl tert-butyldimethylsilyl ether organic solution into a mixture of magnesium and a second organic solvent to perform a Grignard reaction to generate (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl magnesium bromide;
3) dissolving phosphorus trichloride in a third organic solvent to obtain a phosphorus trichloride organic solution; under the protective atmosphere, (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenylmagnesium bromide is dripped into the phosphorus trichloride organic solutionCarrying out a second nucleophilic substitution reaction to prepare bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl phosphorus chloride; the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl phosphorus chloride, sulfur powder and sodium hydrosulfide are subjected to a third nucleophilic substitution reaction to generate di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid, and the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid and Ni are subjected to a third nucleophilic substitution reaction2SO4Mixing the aqueous solutions to generate bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl nickel dithiophosphate, wherein the structural formula is shown as a formula (3):
4) after the nickel bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinate is subjected to a complex reaction with an ammonia solution of ethylene diamine tetraacetic acid, acidifying an obtained organic phase to obtain bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinate, wherein the structural formula is shown as a formula (4):
5) in a fourth organic solvent, the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid and tetrabutylammonium fluoride are subjected to a fourth nucleophilic substitution reaction to generate the di (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid.
Preferably, in the step (1), the first organic solvent is dichloromethane; the molar ratio of the 3-trifluoromethyl-4-bromophenol, the imidazole and the tert-butyldimethylsilyl chloride is 1: 1.0-1.2: 1.0-2.0, the reaction temperature of the first nucleophilic substitution is room temperature, the reaction time is 2-7 h, and the reaction process is continuously stirred; and after the first nucleophilic substitution reaction is finished, extracting the obtained reaction liquid by using dichloromethane, washing, drying, carrying out reduced pressure rotary evaporation, and purifying the obtained oily substance by using a column chromatography method to obtain the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon-based ether.
Preferably, in the step (2), the second organic solvent is tetrahydrofuran; in the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether organic solution, the ratio of the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether to the second organic solvent is 1 g: 2-8 mL; the initiator is iodine particles; the magnesium source is a magnesium strip, and the mass ratio of the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether to the magnesium strip is 1: 1-2.
Preferably, in the step (3), the third organic solvent is tetrahydrofuran; in the phosphorus trichloride organic solution, the volume ratio of phosphorus trichloride to a third organic solvent is 1: 6-12, the molar ratio of phosphorus trichloride to (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenylmagnesium bromide is 1: 2-3, the temperature of the second nucleophilic substitution reaction is room temperature, the reaction time is 12-30 h, and the reaction process is continuously stirred.
Preferably, in the step (3), the third nucleophilic substitution reaction is performed by the following specific process: adding sulfur powder into a reaction liquid after a second nucleophilic substitution reaction with phosphorus trichloride, stirring for 15-30 h at room temperature, adding NaSH, stirring for 16-30 h at room temperature to obtain a solid-liquid mixture, centrifuging, removing a solvent in a supernatant, dissolving the obtained reactant with ethyl acetate, acidifying with HCl, standing for layering, washing the obtained organic phase with saturated saline water, and adding anhydrous Na2SO4Drying and removing ethyl acetate to obtain bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid; the molar ratio of the phosphorus trichloride to the sulfur powder to the NaSH is 1: 1-2: 2-6.
Preferably, the specific process of step (4) is as follows: dissolving nickel bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinate in ethyl acetate, adding an ammonia solution of ethylene diamine tetraacetic acid, mixing, standing for layering, acidifying the separated organic phase with hydrochloric acid, standing for layering, washing the separated organic phase with saturated saline solution, and washing with anhydrous Na2SO4Drying and removing the ethyl acetate to obtain the bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid.
Preferably, in the step (5), the fourth organic solvent is tetrahydrofuran; the molar ratio of the bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid to tetrabutylammonium fluoride is 1: 1-1.5, the temperature of the fourth nucleophilic substitution reaction is room temperature, the reaction time is 3-6 h, and the reaction process is continuously stirred; and after the reaction is finished, adding methanol to terminate the reaction, removing the fourth organic solvent, recrystallizing, filtering, drying and carrying out column chromatography to obtain the bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid.
As a general inventive concept, the present invention also provides a method for preparing the above solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides, comprising the steps of:
(1) taking a magnetic mesoporous material and a coupling agent as raw materials, and carrying out an ester exchange reaction to obtain the magnetic mesoporous material connected with the coupling agent;
(2) the solid phase extracting agent is prepared by taking bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid and a magnetic mesoporous material connected with a coupling agent as raw materials and carrying out affinity substitution reaction under the action of an alkaline catalyst.
In the above preparation method of the solid-phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides, preferably, the specific process of the step (1) is as follows: mixing the magnetic mesoporous material with a reflux solvent, heating and refluxing, adding a coupling agent, continuing heating and refluxing for carrying out an ester exchange reaction, and filtering, washing and drying after the reaction is finished to obtain the magnetic mesoporous material connected with the coupling agent.
Preferably, the refluxing solvent is toluene.
Preferably, the heating reflux temperature is 50-120 ℃, and the heating reflux time is 10-48 h.
In the above preparation method of the solid-phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides, preferably, the specific process of the step (2) is as follows: dissolving bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid and an alkaline catalyst in dimethyl sulfoxide, adding a magnetic mesoporous material connected with a coupling agent, carrying out affinity substitution reaction under the stirring condition, and filtering, washing and drying after the reaction is finished to obtain the solid-phase extracting agent.
Preferably, the basic catalyst is imidazole.
Preferably, the stirring temperature is 10-100 ℃ and the stirring time is 1-36 h.
Preferably, the dosage ratio of the bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, the alkaline catalyst, the magnetic mesoporous material connected with the coupling agent and the dimethyl sulfoxide is 1 g: 0.1-100 g: 1-100 mL.
As a general inventive concept, the invention also provides an application of the solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, or the solid phase extracting agent for selectively separating trivalent minor actinide and trivalent lanthanide, which is prepared by the preparation method, in selectively separating trivalent minor actinide and trivalent lanthanide.
The above application, preferably, comprises the following steps:
and mixing the solution containing trivalent minor actinide metal ions and trivalent lanthanide metal ions with a solid phase extracting agent to enable the trivalent lanthanide metal ions to be adsorbed on the solid phase extracting agent, and centrifuging to finish the selective separation of the trivalent minor actinide and the trivalent lanthanide.
In the application, the pH value of the solution containing trivalent minor actinide metal ions and trivalent lanthanide metal ions is preferably 2-6.
In the above application, preferably, the trivalent actinide metal is one or more of Am and Cm; the trivalent lanthanide metal is one or more of La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu.
Compared with the prior art, the invention has the advantages that:
1. the invention firstly proposes to prepare the hydroxyl-introduced dithiophosphinic acid, and then grafts the dithiophosphinic acid with the magnetic mesoporous material to obtain the solid-phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides, and practice shows that the solid-phase extractant can realize the separation of trivalent actinides and lanthanides by utilizing the difference of the coordination capacity of soft coordination atoms S and trivalent actinides and lanthanides, and the separation coefficient is more than 100 under the condition of proper pH. Compared with the conventional liquid phase extracting agent, the method has the advantages of environmental protection, simple separation operation and the like.
2. The invention firstly provides a method for preparing hydroxyl-introduced dithiophosphinic acid, namely bis (2-trifluoromethyl-4-hydroxyphenyl) dithiophosphinic acid, by taking phosphorus trichloride as a raw material, reacting the phosphorus trichloride with a Grignard reagent protected by hydroxyl, and then carrying out the steps of vulcanization, acidification, hydroxyl deprotection, purification and the like. The method has the advantages of simple operation, low toxicity, simple product purification and the like.
Drawings
FIG. 1 shows the IR spectrum of bis (4-hydroxy-2-trifluoromethyl) phenyl dithiophosphinic acid obtained in example 1 of the present invention.
FIG. 2 shows bis (4-hydroxy-2-trifluoromethyl) phenyl dithiophosphinic acid prepared in example 1 of the present invention31P NMR spectrum.
FIG. 3 shows bis (4-hydroxy-2-trifluoromethyl) phenyl dithiophosphinic acid prepared by example 1 of the present invention1H NMR spectrum.
FIG. 4 is a scheme showing the preparation of a solid phase extractant according to example 1 of the present invention.
FIG. 5 shows the solid phase extractant Fe obtained in example 13O4@SiO2@C9H21ClO3Si@C14PS2F6O2H9Wherein b is an enlarged view of a.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
Example 1:
the invention relates to a solid phase extracting agent for selectively separating trivalent minor actinides and trivalent lanthanides, which comprises a magnetic mesoporous material Fe3O4@SiO2And a dithiophosphinic acid compound by a coupling agent C9H21ClO3Si grafted on magnetic mesoporous material Fe3O4@SiO2The above.
Wherein the dithiophosphinic acid compound is bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, and the structural formula is shown as a formula (1):
the structural formula of bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid in the formula (1) is shown in the specification.
The preparation method of the solid phase extracting agent of the embodiment comprises the following steps:
(1) preparation of bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid:
1.1) protection of hydroxyl groups: 24g (0.1mol) of 3-trifluoromethyl-4-bromophenol and 7.48g (0.11mol) of imidazole are dissolved in 48mL of dichloromethane, the dichloromethane solution is dropwise added into 33mL of dichloromethane solution containing 16.6g (0.11mol) of tert-butyl-dichloromethylchlorosilane, after stirring for 4 hours at room temperature, the reactant mixture is poured into 100mL of deionized water, extraction is carried out for 3 times by dichloromethane, organic phases are combined, the solution is washed for 3 times by saturated saline, drying and rotary evaporation is carried out under reduced pressure, the obtained product is oily matter, and purification is carried out by column chromatography to obtain 34.5g (0.097mol) of 2-trifluoromethyl-4-tert-butyldimethylsilyloxybromobenzene with the yield of 97.6%.
1.2) preparation of Grignard reagent: to a three-necked flask equipped with a constant pressure funnel and a reflux condenser equipped with a drying tube were placed 3.0g (0.12mol) of magnesium strips and 4.8mL of anhydrous tetrahydrofuran, and then 2 iodine pellets were added, and to the constant pressure funnel were placed 34.5g (0.097mol) of hydroxy-protected 3-trifluoromethyl-4-bromophenol and 250mL of anhydrous tetrahydrofuran. Dropwise adding 4mL of the hydroxyl-protected 3-trifluoromethyl-4-bromophenol solution in the constant-pressure separating funnel into a three-necked bottle to initiate a reaction, and then dropwise adding the rest of the hydroxyl-protected 3-trifluoromethyl-4-bromophenol solution while stirring at a proper dropwise adding speed to keep the mild reflux of the reaction mixed solution; and after the dropwise addition of the hydroxyl protected 3-trifluoromethyl-4-bromophenol is finished, heating and mixing the reaction solution until the magnesium strip basically reacts completely, and cooling at room temperature to obtain a brown clear liquid, namely the Grignard reagent.
1.3) bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl bisSynthesis of nickel thiophosphinate: at room temperature under the protection of argon, the newly prepared Grignard reagent 3-trifluoromethyl-4-magnesium bromide phenol is dripped into 3.7mL (0.042mol) of phosphorus trichloride solution of 35mL tetrahydrofuran, and the mixture is stirred overnight after the dripping is finished, so as to obtain a brown liquid mixture. 1.85g (0.058mol) of sulfur powder is directly added for reaction, and the mixture is stirred for 24 hours at room temperature to obtain a brown yellow reaction mixture. Adding 19.0g (0.17mol) NaSH directly, stirring at room temperature for 22h, centrifuging, removing solvent from supernatant by rotary evaporation, dissolving with ethyl acetate, acidifying with 2mol/LHCl, standing for layering, washing organic phase with saturated saline, drying, removing ethyl acetate by rotary evaporation under reduced pressure, and mixing with excessive Ni2SO4Mixing the water solutions, and filtering to obtain a purple solid. The purple solid was purified by recrystallization to give a pink solid, i.e., pure nickel bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinate.
1.4) preparation of bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyldithiophosphinic acid: 5.2g (0.0038mol) of nickel bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinate are dissolved in 100mL of ethyl acetate, 100mL of an ammonia solution of LEDTA are added, mixed, allowed to stand for separation, and the organic phase is acidified with 2mol/L hydrochloric acid. The organic phase was washed with saturated brine, dried and evaporated under reduced pressure to remove ether, giving 4.8g (0.0074mol) of a beige solid in 97.4% yield.
1.5) deprotection of phenolic hydroxyl groups: 4.8g (0.0074mol) of bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyldithiophosphinic acid are diluted directly into 80mL of anhydrous THF, 22.4mL of tetrabutylammonium fluoride tetrahydrofuran solution are added, the reaction mixture is stirred for 4 hours, 50mL of methanol are added to stop the reaction, the solvent is removed by rotary evaporation under reduced pressure, and drying and recrystallization are carried out to obtain 2.8g of crude white nickel bis (2-trifluoromethyl-4-hydroxy) phenyldithiophosphinate. The crude product was subjected to column chromatography to give 2.3g (0.0055mol) of pure bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, and the structure thereof was characterized by IR and NMR.
The IR spectrum is shown in FIG. 1, and the specific results are as follows:
IR(cm-1):3084.4(w,νAr-H) 1606.4,1561.3,1481.0(w, benzene ring v)C＝C),1312.7(vs,δCF3),541.9,533.5(m,νP＝S),427.3(s,νP-SH).
31The P NMR spectrum is shown in FIG. 2, with the following specific results:
31P NMR(200MHz,DMSO):δppm＝62.70(4J(P,F)＝16Hz).
1the H NMR spectrum is shown in FIG. 3, and the specific results are as follows:
1H NMR(500MHz,DMSO):δppm＝10.03(s,2H,-OH),6.87(m,4J(H3,F)＝5.0Hz,2H,2H3),6.98(dd,3J(H5,H6)＝10Hz,4J(H5,P)＝5Hz,2H,2H5),8.91(dd,3J(H6,P)＝25Hz,3J(H6,H5)＝10Hz,2H,2H6)。
(2) preparation of Fe3O4@SiO2：
(2.1) cetyl trimethylammonium bromide (CTAB) was slowly added to an ethanol-water solution (ethanol/water volume ratio 1.2/1.0), the pH of the solution was adjusted to about 10 with NaOH solution, and then nano Fe was added3O40.1g of particles and 30min of ultrasound.
(2.2) slowly dripping 4.04g of tetraethoxysilane-ethanol solution into the nano Fe subjected to ultrasonic treatment3O4Stirring the mixed solution at room temperature for 5h, aging at room temperature for 24h, washing with water, washing precipitate particles with absolute ethyl alcohol, and performing suction filtration to obtain solid magnetic particles.
(2.3) adding the obtained solid magnetic particles into absolute ethyl alcohol, stirring at the constant temperature of 80 ℃ for 72h, removing redundant CTAB, separating by utilizing magnetism, and drying the obtained solid magnetic particles in vacuum at the temperature of 60 ℃ for 24h to obtain SiO2Coated with Fe3O4Magnetic core-shell type mesoporous silica microsphere Fe on surface3O4@SiO2。
In other embodiments, the magnetic mesoporous material may also be Fe2O3@SiO2。
In other embodiments, the magnetic mesoporous material can also be prepared by a microemulsion method, a sol-gel method, a hydrothermal method, and the like.
(3) The magnetic core-shell mesoporous silica microspheres are functionally modified by bis (4-hydroxy-2-trifluoromethylphenyl) dithiophosphinic acid, as shown in figure 4:
(3.1)Fe3O4@SiO2@C9H21ClO3preparation of Si: mixing Fe3O4@SiO2Adding into 5% methane sulfonic acid solution, stirring and activating at 90 deg.C for 8 hr, filtering, washing with water, and vacuum drying. Activated Fe3O4@SiO2Adding into anhydrous toluene, heating and refluxing at 80 deg.C, rapidly adding 3-chloropropyltriethoxysilane, and heating and refluxing at 80 deg.C for 24 hr. Cooling to room temperature after the reaction is finished, performing suction filtration, washing with toluene, diethyl ether, ethyl acetate and methanol in sequence, and performing vacuum drying at room temperature for 24 hours to obtain Fe3O4@SiO2@C9H21ClO3Si。
(3.2)Fe3O4@SiO2@C9H21ClO3Si@C14H9F6O2PS2The preparation of (1): 0.4g of bis (4-hydroxy-2-trifluoromethyl) phenyl dithiophosphinic acid and 0.08g of imidazole were dissolved in 15mL of dimethyl sulfoxide (DMSO), and then 0.4g of Fe was added3O4@SiO2@C9H21ClO3Si, stirring for 12 hours at the constant temperature of 30 ℃. Suction filtration, washing by DMSO, water and methanol in sequence, drying at 85 ℃ to obtain a solid phase extractant Fe for selectively separating trivalent minor actinides and trivalent lanthanides3O4@SiO2@C9H21ClO3Si@C14PS2F6O2H9. As shown in FIG. 5, mesoporous SiO2Coated with Fe3O4Surface, functional molecule di (4-hydroxy-2-trifluoromethylphenyl) dithio phosphinic acid passes through coupling agent C9H21ClO3Si bonded to SiO2A surface.
The prepared solid phase extracting agent is applied to selectively separating trivalent minor actinides and trivalent lanthanides, and in the embodiment, the actinides are Am3+(due to Am)3+Has radioactivity due to its radius and Nd3+Close, therefore, Nd for this embodiment3+Am instead of radioactivity3+Experiment was conducted) the lanthanoid element was Eu3+The specific separation process is as follows:
(a) preparing a standard solution: 0.2380g of Nd (NO) were weighed out3)3·6H2Dissolving O in a small amount of deionized water, then fixing the volume in a 1000mL volumetric flask, diluting the solution by 10 times, and preparing Nd3+A solution with a concentration of 10 mg/L.
Weighing 0.2920g Eu (NO)3)3·6H2Dissolving O in a small amount of deionized water, then fixing the volume in a 1000mL volumetric flask, diluting the solution by 10 times to prepare Eu3+A solution with a concentration of 10 mg/L.
(b) 10mg of Fe are weighed3O4@SiO2@C9H21ClO3Si@C14PS2F6O2H9Adding 50mL of Nd respectively3+、Eu3+Adjusting the pH of the solution to 4.00, oscillating at constant temperature of 25 ℃ for 150min, centrifuging, measuring the pH of the supernatant, and simultaneously measuring the absorbance of the supernatant by using an ultraviolet-visible spectrophotometer. The results are shown in table 1:
TABLE 1 Nd in solution before and after adsorption3+And Eu3+Absorbance of (A)
| Absorbance A before adsorption0 | Absorbance A after adsorptione | |
| Nd3+ | 0.330725 | 0.324826 |
| Eu3+ | 0.353484 | 0.133611 |
The separation coefficient was calculated as follows:
after adsorption, Nd3+Distribution ratio in solid adsorbent and solution:
after adsorption, Eu3+Distribution ratio in solid adsorbent and solution:
coefficient of separation
It can be seen that trivalent lanthanides are adsorbed on the solid phase extractant of the present invention, while trivalent minor actinides are adsorbed at a very low rate. The solid phase extraction agent can successfully separate trivalent minor actinides and trivalent lanthanides, and compared with the traditional liquid phase extraction method, the solid phase extraction method is environment-friendly, simple to operate and wide in application prospect.
In other embodiments, the trivalent minor actinide may be one or more of Am, Cm; the trivalent lanthanide may be one or more of La, Ce, Pr, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, but is not limited thereto.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (10)
1. A solid phase extracting agent for selectively separating trivalent minor actinides and trivalent lanthanides is characterized by comprising a magnetic mesoporous material and a dithiophosphinic acid compound, wherein the dithiophosphinic acid compound is grafted on the magnetic mesoporous material through a coupling agent; the dithiophosphinic acid compound is di (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid, and the structural formula is shown as a formula (1):
2. the solid-phase extractant for selectively separating trivalent minor actinides from trivalent lanthanides as claimed in claim 1, wherein the magnetic mesoporous material comprises magnetic nanoparticles and mesoporous SiO2The mesoporous SiO2Coating on the surface of the magnetic nanoparticles.
3. The solid phase extractant for selectively separating trivalent minor actinides from trivalent lanthanides as claimed in claim 2, characterized in that the coupling agent has the general formula YSiX3Wherein X is an alkyl group or an alkoxy group, and Y is a hydrocarbon group having Cl at the terminal.
4. A solid phase extractant for selective separation of trivalent minor actinides and trivalent lanthanides according to any one of claims 1 to 3, characterized in that the dithiophosphinic acid compound is prepared by a method comprising:
a) dissolving tert-butyldimethylsilyl chloride in a first organic solvent to obtain a tert-butyldimethylsilyl chloride organic solution; dropwise adding a tert-butyldimethylsilyl chloride organic solution into a mixed solution of 3-trifluoromethyl-4-bromophenol, imidazole and a first organic solvent to perform a first nucleophilic substitution reaction to prepare 3-trifluoromethyl-4-bromophenyl tert-butyldimethylsilyl ether;
b) dissolving the 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether prepared in the step (a) in a second organic solvent to obtain a 3-trifluoromethyl-4-bromophenyl tert-butyl dimethyl silicon ether organic solution; under the action of an initiator, dropwise adding the 3-trifluoromethyl-4-bromophenyl tert-butyldimethylsilyl ether organic solution into a mixture of magnesium and a second organic solvent to perform a Grignard reaction to generate (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl magnesium bromide;
c) dissolving phosphorus trichloride in a third organic solvent to obtain a phosphorus trichloride organic solution; under the protective atmosphere, dropwise adding (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl magnesium bromide into a phosphorus trichloride organic solution to perform a second nucleophilic substitution reaction to prepare bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl phosphorus chloride; the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl phosphorus chloride, sulfur powder and sodium hydrosulfide are subjected to a third nucleophilic substitution reaction to generate di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid, and the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid and Ni are subjected to a third nucleophilic substitution reaction2SO4Mixing the aqueous solutions to generate bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl nickel dithiophosphinate;
d) performing complex reaction on bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid nickel and an ammonia solution of ethylene diamine tetraacetic acid, and acidifying the obtained organic phase to obtain bis (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid;
e) in a fourth organic solvent, the di (2-trifluoromethyl-4-tert-butyldimethylsilyloxy) phenyl dithiophosphinic acid and tetrabutylammonium fluoride are subjected to a fourth nucleophilic substitution reaction to generate the di (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid.
5. A method of preparing a solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides as claimed in any one of claims 1 to 4, comprising the steps of:
(1) taking a magnetic mesoporous material and a coupling agent as raw materials, and carrying out an ester exchange reaction to obtain the magnetic mesoporous material connected with the coupling agent;
(2) the solid phase extracting agent is prepared by taking bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid and a magnetic mesoporous material connected with a coupling agent as raw materials and carrying out affinity substitution reaction under the action of an alkaline catalyst.
6. The method for preparing a solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides according to claim 5, wherein the specific process of the step (1) is as follows: mixing the magnetic mesoporous material with a reflux solvent, heating and refluxing, adding a coupling agent, continuing heating and refluxing, filtering, washing and drying after the reaction is finished to obtain the magnetic mesoporous material connected with the coupling agent.
7. The method for preparing a solid phase extractant for selectively separating trivalent minor actinides from trivalent lanthanides according to claim 5 or 6, wherein the specific process of the step (2) is as follows: dissolving bis (2-trifluoromethyl-4-hydroxy) phenyl dithiophosphinic acid and an alkaline catalyst in dimethyl sulfoxide, adding a magnetic mesoporous material connected with a coupling agent, stirring for reaction, and then filtering, washing and drying to obtain the solid-phase extracting agent.
8. The solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides as claimed in any one of claims 1 to 4 or the solid phase extractant for selectively separating trivalent minor actinides and trivalent lanthanides as prepared by the preparation method as claimed in any one of claims 5 to 7 is applied to selectively separating trivalent minor actinides and trivalent lanthanides.
9. Use according to claim 8, characterized in that it comprises the following steps:
and mixing the solution containing trivalent minor actinide metal ions and trivalent lanthanide metal ions with a solid phase extracting agent to enable the trivalent lanthanide metal ions to be adsorbed on the solid phase extracting agent, and centrifuging to finish the selective separation of the trivalent minor actinide and the trivalent lanthanide.
10. Use according to claim 9, wherein the solution containing trivalent minor actinide metal ions and trivalent lanthanide metal ions has a pH of 2 to 6.
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| TW218895B (en) * | 1993-09-03 | 1994-01-11 | Ind Tech Res Inst | An extraction agent composition suitable for separating aluminum,cobalt, and nickle ions in sulfuric aqueous solution and its separation method |
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| CA2550557C (en) * | 2006-06-14 | 2011-03-29 | Cytec Canada, Inc. | Novel phosphinic acids and their sulfur derivatives and methods for their preparation |
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