CN103045869A - Method for enriching uranium and thorium from water phase by using cloud point extraction technology - Google Patents

Method for enriching uranium and thorium from water phase by using cloud point extraction technology Download PDF

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CN103045869A
CN103045869A CN2012105816394A CN201210581639A CN103045869A CN 103045869 A CN103045869 A CN 103045869A CN 2012105816394 A CN2012105816394 A CN 2012105816394A CN 201210581639 A CN201210581639 A CN 201210581639A CN 103045869 A CN103045869 A CN 103045869A
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mimntf
extraction
concentration
cloud point
thorium
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CN103045869B (en
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沈兴海
高嵩
孙涛祥
陈庆德
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Peking University
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Abstract

本发明公开了一种利用浊点萃取从水相中富集U(VI)或Th(IV)的方法。该方法以三烷基氧膦为萃取剂、TX-114为表面活性剂、CnmimNTf2类疏水性离子液体为添加剂,从不同条件的含铀酰离子或钍离子的水溶液中将UO2 2+或Th4+高效地萃取分离出来;其中,萃取体系的离子强度≥0.05mol/L。本发明方法适用的水相酸度范围大,从中性条件到2mol/L HNO3均可显著萃取铀、钍离子。浊点萃取过程绿色环保,本发明方法在铀酰的富集、检测等领域前景广阔。The invention discloses a method for enriching U(VI) or Th(IV) from water phase by cloud point extraction. In this method, trialkylphosphine oxide is used as extractant, TX-114 is used as surfactant, C n mimNTf 2 type hydrophobic ionic liquid is used as additive, and UO 2 2 + or Th 4+ are efficiently extracted and separated; wherein, the ionic strength of the extraction system is ≥0.05mol/L. The method of the invention is applicable to a wide range of aqueous phase acidity, and can significantly extract uranium and thorium ions from neutral conditions to 2mol/L HNO3 . The cloud point extraction process is green and environmentally friendly, and the method of the invention has broad prospects in the fields of enrichment and detection of uranyl.

Description

A kind of Cloud-Point Extraction Technique of utilizing is from the method for aqueous phase enriched uranium, thorium
Technical field
The invention belongs to the nuclear fuel cycle field, be specifically related to a kind of cloud point extraction that utilizes from the method for aqueous phase enriched uranium, thorium.
Background technology
Uranium is a kind of topmost nuclear fuel in the present Nuclear energy uses, and thorium is the potential resources of Nuclear energy uses.Simultaneously, both all have biological pathogenic.Based on application prospect and the toxicity of uranium, thorium, uranium, thorium in effectively enrichment, separation, testing environment and the biological sample are very important.
Cloud point extraction (cloud point extraction, be called for short CPE) technology is a kind of novel separation and concentration technology that developed recently gets up, the solubilising that mainly utilizes nonionic surfactant solution and phase-splitting realize to the enrichment of solute with separate.To nonionic surfactant solution, when temperature was higher than certain value, solution becomes was muddy, is separated; One is the very little rich tensio-active agent phase of volume mutually, and another is that surfactant concentration is the water of micelle-forming concentration mutually.This phenomenon is the cloud point phenomenon, and corresponding temperature is called cloud point.Utilize this character, in cloud point extraction, metal ion and extraction agent form in the nonpolar nuclear that hydrophobic title complex enters micella; When temperature is higher than the cloud point of nonionogenic tenside, be separated, the metal ion that is solubilized in the micella is separated out with tensio-active agent, thereby realizes the extracting and separating of metal ion.Compare with conventional solvent extraction, this technology need not be used a large amount of poisonous and hazardous organic solvents, having the remarkable advantages such as coefficient of concentration is high, simple to operate, low-cost, the safety of being separated, high speed, is a kind of novel eco-friendly isolation technique, has good industrial application potentiality.
Adopt more existing reports of enrichment U (VI), Th (IV) of Cloud-Point Extraction Technique, such as (Draye M. such as Draye, et al, J.Chem.Technol.Biotechnol., 2006,81,1872) adopting oxine (8-HQ) is extraction agent, the extraction UO take TX-114 as tensio-active agent 2 2+When pH>4, extraction efficiency can reach 100%, but is reduced to gradually pH<2 with pH, and extraction efficiency levels off to 0.Dibenzoyl (DBM), 1-(pyridylazo)-acidic extractants such as beta naphthal (PAN) also are used to cloud point extraction UO 2 2+, Th 4+In, but all have substantially unfruitful problem under the acidic conditions.And in practical application, in nuclear fuel reprocessing, the acidity of solution often is in a higher level, thereby has limited the application of cloud point extraction.Neutral-neutral Extractants such as tributyl phosphate (TBP), has preferably effect of extracting under acidic conditions in the conventional solvent extraction, but relatively poor (Pashalidis I., et al., J.Radioanal.Nucl.Chem. of effect in cloud point extraction, 2010,286,461).
Summary of the invention
The purpose of this invention is to provide a kind of method of utilizing Cloud-Point Extraction Technique to extract U (VI) or Th (IV) from aqueous phase.
Method from aqueous phase extraction U (VI) or Th (IV) provided by the present invention is to adopt the cloud point extraction method, take trialkylphosphine oxide (TRPO) as extraction agent, Diethylene Glycol list [(1,1,3, the 3-tetramethyl butyl) phenyl] ether (TX-114) is tensio-active agent, C nMimNTf 2Class (be 1-alkyl-3-Methylimidazole two trifluoromethane sulfimides) ionic liquid is additive, from the aqueous solution that contains uranyl ion or thorium ion of different condition with certain ionic strength with UO 2 2+Or Th 4+Extracting and separating out efficiently.
C involved in the present invention nMimNTf 2The specific examples of class ionic liquid comprises: C 2MimNTf 2, C 4MimNTf 2, C 6MimNTf 2, C 8MimNTf 2, C 10MimNTf 2, C 12MimNTf 2Deng, these ionic liquids can use separately, also one or more can be mixed together.
Ionic liquid is the organic compound that a class fully is comprised of zwitterion and is in a liquid state under room temperature or close temperature, have nontoxic, without remarkable vapour pressure, environmentally friendly, without flammable, fusing point is low and liquid zone between the advantages such as wide, Heat stability is good, solubilized gas chromatography and inorganics, be described as " green solvent ".Ionic liquid can change the physicochemical property of surfactant soln as additive.The present invention uses C nMimNTf 2The class ionic liquid is additive, has greatly improved the accumulation ability of extraction system to uranium, thorium ion.
TRPO of the present invention both can be single material, such as trioctylphosphine oxide (TOPO) (TOPO), triheptylphosphine oxide, trihexylphosphine oxide etc.; Also can be the mixture of two or more trialkylphosphine oxides; Certainly also can be the trialkylphosphine oxide compound that contains different alkyl chain lengths; Or be the mixture of above-mentioned various materials.The extraction ability of trialkyl (mixing) phosphine oxide is similar to TOPO.
It is tensio-active agent that the present invention adopts TX-114, and the concentration of TX-114 in the aqueous solution is generally 0.008-0.02mol/L, preferred 0.01-0.02mol/L; Adopt TRPO as extraction agent, the concentration of TRPO in the aqueous solution is generally 0-0.005mol/L (but not comprising 0mol/L), preferred 0.0002-0.002 mol/L; Adopt C nMimNTf 2The class ionic liquid is as additive, C nMimNTf 2Concentration in the aqueous solution is generally 0-0.004mol/L (but not comprising 0mol/L), preferred 0.0002-0.003mol/L.Generally speaking, extracted aqueous phase UO 2 2+Or Th 4+Concentration be 0-0.0001mol/L, preferred 0-0.00005mol/L.
When the ionic strength of extraction system does not reach 0.05mol/L, can be by in extraction system, adding salt (such as NaNO 3, NaCl) regulate.The ionic strength of described extraction system is preferred 〉=0.5mol/L.
Among the present invention, water condition to be extracted is variable, and this aqueous phase can also comprise the acid (HNO for example of different concns except the uranyl ion or thorium ion that contain different concns 3, HCl) and salt (NaNO for example 3, NaCl) etc. impurity.Utilize TRPO-C nMimNTf 2Using cloud point extraction system can be from the efficient extracting and enriching U of the aqueous phase of above various different conditions (VI), Th (IV).
The present invention is with the two trifluoromethane sulfimide (C of 1-alkyl-3-Methylimidazole nMimNTf 2) class ionic liquid, tensio-active agent TX-114 and Neutral-neutral Extractants trialkylphosphine oxide (TRPO) be combined, obtained that U (VI), Th (IV) are had the extraction system of efficient extraction ability, usually o'clock all significantly Extraction of Uranium, thorium ion in pH value≤6 have better application prospect.
Description of drawings
Fig. 1 be the adding of different ionic liquid on the histogram of the impact of cloud point extraction uranium, Extraction of thorium rate (1: without ionic liquid, 2:C 2MimNTf 2, 3:C 4MimNTf 2, 4:C 6MimNTf 2, 5:C 8MimNTf 2, 6:C 10MimNTf 2, 7:C 12MimNTf 2); Wherein, [TX-114]=0.01mol/L, [TOPO]=0.0005mol/L, [UO 2 2+]=0.00005mol/L or [Th 4+]=0.00005mol/L, [NaNO 3]=0.1mol/L, [ILs]=0.001mol/L.
Fig. 2 is TOPO-C 4MimNTf 2The cloud point system is to the schematic diagram that concerns of the percentage extraction of uranium and TX-114 concentration; Wherein, [TOPO]=0.0005mol/L, [UO 2 2+]=0.00005mol/L, [NaNO 3]=0.1mol/L, [C 4MimNTf 2]=0.001mol/L.
Fig. 3 is TOPO-C 4MimNTf 2The cloud point system is to the schematic diagram that concerns of the percentage extraction of uranium and TOPO concentration; Wherein, [TX-114]=0.01mol/L, [UO 2 2+]=0.00005mol/L, [NaNO 3]=0.1mol/L, [C 4MimNTf 2]=0.001mol/L.
Fig. 4 is TOPO-C 4MimNTf 2The cloud point system is to percentage extraction and the C of uranium 4MimNTf 2Concentration concern schematic diagram; Wherein, [TX-114]=0.01mol/L, [TOPO]=0.0005mol/L, [UO 2 2+]=0.00005mol/L, [NaNO 3]=0.1mol/L.
Fig. 5 is the schematic diagram that concerns of cloud point extraction uranium, Extraction of thorium rate and aqueous phase acidity; Wherein, [TX-114]=0.01mol/L, [TOPO]=0.0005mol/L, [UO 2 2+]=0.00005mol/L or [Th 4+]=0.00005mol/L, [NaNO 3]=0.1mol/L, [ILs]=0.001mol/L.
Fig. 6 is the schematic diagram that concerns of the percentage extraction of cloud point extraction uranium and water salinity; Wherein, [TX-114]=0.01mol/L, [TOPO]=0.0005mol/L, [UO 2 2+]=0.00005mol/L, [ILs]=0.001mol/L.
Embodiment
The present invention will be described below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Embodiment 1, utilize cloud point extraction to extract UO from aqueous phase 2 2+Or Th 4+
When carrying out extraction experiments, in the 10mL centrifuge tube, add successively quantitative tensio-active agent TX-114, extraction agent TOPO, ionic liquid, uranyl ion (UO 2 2+) or thorium ion (Th 4+) solution and NaNO 3Solution is settled to 10mL with three distilled water.Shake up rear 70 ℃ of constant temperature 2h, while hot centrifugation, the concentration (measuring method: ICP-AES is inductively coupled plasma atomic emission) of getting upper water facies analysis U (VI) or Th (IV).Extraction enters the U (VI) of tensio-active agent phase or the concentration of Th (IV) is tried to achieve with minusing, tries to achieve thus percentage extraction E.
TX-114 concentration is not that 0.01mol/L, TOPO concentration are 0.0005mol/L, NaNO in acid adding and the aqueous solution outside 3Concentration is under the condition of 0.1mol/L, does not add or add different C nMimNTf 2Ionic liquid is to containing uranyl ion ([UO 2 2+]=0.00005mol/L) or thorium ion ([Th 4+Uranyl ion or thorium ion extract in the aqueous solution of]=0.00005mol/L), measure percentage extraction.The results are shown in Figure 1 (1: without ionic liquid, 2:C 2MimNTf 2, 3:C 4MimNTf 2, 4:C 6MimNTf 2, 5:C 8MimNTf 2, 6:C 10MimNTf 2, 7:C 12MimNTf 2).
As shown in Figure 1, outside, under the condition of acid adding, when TX-114 concentration is 0.01mol/L in the aqueous solution, do not adopt separately the UO of the TOPO cloud point extraction 0.00005mol/L of 0.0005mol/L 2 2+And Th 4+, extraction efficiency is~36% and 30%.In system, add 0.001mol/L C 2MimNTf 2The time, extraction efficiency all increases to~and 75% and~66%.With C 2MimNTf 2Replace with respectively C 4MimNTf 2, C 6MimNTf 2, C 8MimNTf 2, C 10MimNTf 2Or C 12MimNTf 2The time, the extraction efficiency of the extraction system of U and C 2MimNTf 2System is basic identical; For the extraction system of Th, add C 4MimNTf 2, C 6MimNTf 2, C 8MimNTf 2System extraction efficiency with add C 2MimNTf 2System is basic identical, and adds C 10MimNTf 2And C 12MimNTf 2The system extraction efficiency decrease.
With C 4MimNTf 2-CPE system extraction U (VI) is example, investigates the impact that various conditions change.Under the condition of acid adding, keeping TOPO concentration is not 0.0005mol/L, NaNO outside 3Concentration is 0.1mol/L, C 4MimNTf 2Concentration is 0.001mol/L, changes TX-114 concentration extraction U (VI) (concentration 0.00005mol/L), measures percentage extraction.As shown in Figure 2, increase with TX-114 concentration, system increases the extraction efficiency of uranyl ion, but lower phase volume increases.So, preferred 0.01-0.02mol/L.
Fig. 3 is under the condition of acid adding outside not, and keeping TX-114 concentration is 0.01mol/L, NaNO 3Concentration is 0.1mol/L, C 4MimNTf 2Concentration is 0.001mol/L, the variation of percentage extraction when changing TOPO extraction U (VI) (concentration 0.00005mol/L).Increase with TOPO concentration, system increases the extraction efficiency of uranyl ion.When TOPO concentration reached 0.002mol/L, extraction efficiency reached 100%.
Under the condition of acid adding, TX-114 concentration is not that 0.01mol/L, TOPO concentration are that 0.0005mol/L extracts U (VI) (concentration 0.00005mol/L) in the aqueous solution outside, measures percentage extraction.With uranyl ion percentage extraction (E) and C 4MimNTf 2The concentration mapping the results are shown in Figure 4.As shown in Figure 4, outside not under the condition of acid adding, when TX-114 concentration in the aqueous solution is that 0.01mol/L, TOPO concentration are when being 0.0005mol/L extraction 0.00005mol/L U (VI), with C in the water 4MimNTf 2Concentration increases, and system increases the extraction efficiency of uranyl ion, works as C 4MimNTf 2When concentration reached 0.003mol/L, extraction efficiency was near 90%.
Adopting TX-114 concentration is that 0.01mol/L, TOPO concentration are 0.0005mol/L, C 4MimNTf 2When concentration was system extraction 0.00005mol/L U (VI), the Th (IV) of 0.001mol/L, extraction efficiency changed with the variation of concentrations of aqueous nitric acid, as shown in Figure 5.With extraction UO 2 2+Be example, when existing without other acid, the pH of solution is about 6.Separately TOPO exists down, increases with acidity, the percentage extraction of U (VI) is improved, when acidity greater than 1moldm -3The time, the percentage extraction of uranyl ion reduces.Work as C 4MimNTf 2Add (TOPT-IL-U curve among the figure) after the extraction system, with not contain ion liquid system identical, but percentage extraction all remains on more than 60% with the variation tendency of acidity variation extraction rate.In general, the TOPO using cloud point extraction system of ionic liquid participation can extract U (VI), Th (IV) in a larger Acidity Range.
When adopting the inventive method, need in the extraction system to guarantee that certain ionic strength is separated with realization.Adopting TX-114 concentration is that 0.01mol/L, TOPO concentration are 0.0005mol/L, C 4MimNTf 2When concentration was the system extraction 0.00005mol/L U (VI) of 0.001mol/L, extraction efficiency changed with the variation of water sodium nitrate concentration, as shown in Figure 6.With the increase of water salinity, the uranyl ion extraction efficiency increases, and works as NaNO 3Concentration is 0.05mol/L (ionic strength is about 0.05mol/L), and U (VI) percentage extraction is 60%, works as NaNO 3Concentration is during greater than 0.5mol/L (ionic strength is greater than 0.5mol/L), and percentage extraction is substantially constant.

Claims (8)

1. method from aqueous phase extraction uranyl ion or thorium ion, comprise the steps: take trialkylphosphine oxide as extraction agent, Diethylene Glycol list [(1,1,3, the 3-tetramethyl butyl) phenyl] ether is that the two trifluoromethane sulfimide ionic liquids of tensio-active agent, 1-alkyl-3-Methylimidazole are additive, extracting and separating obtains uranyl ion or thorium ion from the aqueous solution that contains uranyl ion or thorium ion; Wherein, the ionic strength 〉=0.05mol/L of extraction system.
2. method according to claim 1 is characterized in that: the two trifluoromethane sulfimide ionic liquids of described 1-alkyl-3-Methylimidazole are selected from following at least a: C 2MimNTf 2, C 4MimNTf 2, C 6MimNTf 2, C 8MimNTf 2, C 10MimNTf 2And C 12MimNTf 2
3. method according to claim 1 and 2, it is characterized in that: the concentration of described trialkylphosphine oxide in the described aqueous solution is 0-0.005mol/L, but does not comprise 0mol/L; Preferred 0.0002-0.002mol/L.
4. each described method according to claim 1-3 is characterized in that: described Diethylene Glycol list [(1,1,3, the 3-tetramethyl butyl) phenyl] concentration of ether in the described aqueous solution is 0.005-0.02mol/L, preferred 0.01-0.02mol/L.
5. each described method according to claim 1-4 is characterized in that: the two concentration of trifluoromethane sulfimide ionic liquid in the described aqueous solution of described 1-alkyl-3-Methylimidazole are 0-0.004mol/L, but do not comprise 0mol/L; Preferred 0.0002-0.003mol/L.
6. each described method according to claim 1-5 is characterized in that: the ionic strength 〉=0.5mol/L of described extraction system.
7. each described method according to claim 1-6 is characterized in that: the pH of the described aqueous solution≤6.
8. each described method according to claim 1-7 is characterized in that: UO in the described aqueous solution 2 2+Or Th 4+Concentration be 0-0.0001mol/L, preferred 0-0.00005mol/L, but do not comprise 0mol/L.
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CN103760141A (en) * 2014-01-14 2014-04-30 昆明理工大学 Method for rapid detection of residual amount of sulfanilamide in food
CN106591604A (en) * 2016-12-02 2017-04-26 燕山大学 Method for extracting and separating molybdenum (VI) in aqueous solution
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CN112342380A (en) * 2020-10-27 2021-02-09 北京大学 Application method of hydrophobic extractant in cloud point extraction system
CN114686708A (en) * 2021-10-25 2022-07-01 核工业北京化工冶金研究院 Method for extremely reducing neutralized sediment slag

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CN103760141A (en) * 2014-01-14 2014-04-30 昆明理工大学 Method for rapid detection of residual amount of sulfanilamide in food
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CN112226635A (en) * 2020-10-12 2021-01-15 中国工程物理研究院核物理与化学研究所 Uranyl ion separation method based on carboxyl functional ionic liquid
CN112342380A (en) * 2020-10-27 2021-02-09 北京大学 Application method of hydrophobic extractant in cloud point extraction system
CN114686708A (en) * 2021-10-25 2022-07-01 核工业北京化工冶金研究院 Method for extremely reducing neutralized sediment slag

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