CN115677528A - Method for separating rhenium and technetium - Google Patents

Method for separating rhenium and technetium Download PDF

Info

Publication number
CN115677528A
CN115677528A CN202211371804.3A CN202211371804A CN115677528A CN 115677528 A CN115677528 A CN 115677528A CN 202211371804 A CN202211371804 A CN 202211371804A CN 115677528 A CN115677528 A CN 115677528A
Authority
CN
China
Prior art keywords
reo
compound
tco
extractant
extraction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202211371804.3A
Other languages
Chinese (zh)
Inventor
胡艳琴
杨帆
薛丽燕
谢美英
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Xiamen Institute of Rare Earth Materials
Original Assignee
Xiamen Institute of Rare Earth Materials
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Xiamen Institute of Rare Earth Materials filed Critical Xiamen Institute of Rare Earth Materials
Priority to CN202211371804.3A priority Critical patent/CN115677528A/en
Publication of CN115677528A publication Critical patent/CN115677528A/en
Pending legal-status Critical Current

Links

Images

Abstract

The invention uses ReO 4 ‑ And/or 99 TcO 4 ‑ The amide extractant with unique extraction effect is used for liquid phase extraction, has high extraction and back extraction rate, and can realize ReO 4 ‑ And/or 99 TcO 4 ‑ And (4) recycling. The extractant has good selectivity under high acid condition, such as D2EHAG extractant which is different from the prior extractant and has competitive anion NO 3 ‑ And ReO 4 ‑ Up to 1000: greater breakthrough in selectivity at 1 (D2 EHAG vs. ReO) 4 ‑ The removal rate of (2) is still close to 70%, and the extraction effect is very excellent). The extractant is under high acid condition (acid concentration)Degree is 1-6 mol/L) has good extraction effect, wherein the effect of the PELLAG extractant is best under the condition of high acid of 1 mol/L. The extractant can directly separate ReO by using an alkaline back extractant in one step 4 ‑ And/or 99 TcO 4 ‑ The method has the advantages of simple process flow, less used equipment and suitability for industrial use.

Description

Method for separating rhenium and technetium
Technical Field
The invention belongs to the technical field of separation and extraction, and particularly relates to efficient separation of ReO 4 - And 99 TcO 4 - the method of (1).
Background
Technetium-99 (a radioactive artificial nuclide) 99 Tc) is mainly produced in nuclear reactors 235 U fission occurs with high fission yield (6.13%) and long half-life (2.13X 10) 5 a) High solubility in water (11.3 mol/L) mainly based on TcO 4 - The form exists. 99 Tc exhibits high mobility in groundwater and biological systems and is extremely volatile and leaks during post-treatment. 99 Tc leaks into the environment, and is accumulated in underground water, soil, microorganisms, animals and plants, and the like, and constitutes long-term potential harm to human beings and the whole ecological system. Thus, tc is one of the most important nuclides of interest in environmental radioactive safety assessment procedures. In recent years, with the rapid development of nuclear industry, radionuclides 99 The Tc content is continuously increased, and how to effectively and selectively remove the Tc from the high-radioactivity waste liquid 99 TcO 4 - Has become one of the essential key technologies of the nuclear industry.
Disclosure of Invention
In order to solve the above technical problems, the present invention first provides a compound represented by the following formula I:
Figure BDA0003925672530000011
wherein R is selected from the following groups unsubstituted or optionally substituted by one, two or more Rs: c 1-12 Alkyl radical, C 6-20 Aryl or 5-20 membered heteroaryl;
rs is selected from halogen, -CN, C 1-12 Alkyl radical, C 1-12 Alkoxy or halo C 1-12 An alkyl group;
a. b are identical or different and are each independently selected from 1,2, 3, 4, 5 or 6.
In the present inventionIn some embodiments of the invention, R is selected from C 1-8 Alkyl or C 6-12 An aryl group; a. b are identical or different and are selected independently of one another from 1,2 or 3.
In some preferred embodiments of the invention, R is selected from phenyl or the following groups:
Figure BDA0003925672530000021
* Wherein represents a linking site; a. b is 1.
The invention also provides a preparation method of the compound shown in the formula I, which comprises the following steps:
Figure BDA0003925672530000022
wherein R, a, b are as defined above; l is a leaving group;
and reacting the compound Ia with a compound Ib to obtain a compound Ic, and reacting the compound Ic with a compound Id to obtain a compound I.
In some embodiments of the invention, L is halogen, e.g., chlorine.
In some embodiments of the invention, the molar ratio of compound Ia to compound Ib is 1.
In some embodiments of the invention, the reaction of compound Ia with compound Ib is carried out in the presence of an acid scavenger, for example triethylamine, which is an acid scavenger.
In some embodiments of the invention, the reaction of compound Ia with compound Ib is carried out at ambient temperature for a reaction time of 1 to 12h, for example 2 to 6h.
In some embodiments of the invention, the reaction of compound Ic with compound Id is carried out in sodium hydroxide in methanol.
In some embodiments of the invention, compound Ic is reacted with compound Id at a temperature of 40 to 80 ℃ for a period of 1 to 24 hours.
The invention also provides a method for separating and extracting ReO from the compound shown in the formula I or the compound shown in the formula I 4 - And/or 99 TcO 4 - The use of (a);
wherein, the compound shown in the formula I' is selected from the following structures:
Figure BDA0003925672530000023
wherein R is 1 、R 2 Identical or different, independently of one another, from the following groups, unsubstituted or optionally substituted by one, two or more Rq: c 1-12 Alkyl radical, C 6-20 Aryl or 5-20 membered heteroaryl;
rq is selected from halogen, -CN, C 1-12 Alkyl radical, C 1-12 Alkoxy or halo C 1-12 An alkyl group;
c. d is identical or different and is selected independently of one another from 1,2, 3, 4, 5 or 6.
In some embodiments of the invention, the compound of formula I' is D2EHAG.
The invention also provides a method for separating and extracting ReO from the compound shown in the formula I or the formula I 4 - And/or 99 A process for Tc comprising the steps of:
will contain ReO 4 - And/or 99 TcO 4 - And competitive anionic NO 3 - 、Cl - 、SO 4 2- Spent fuel reprocessing effluents or containing ReO 4 -and/or 99 TcO 4 -、H 2 SO 4 、HCl、HNO 3 Mixing the metal solution with high acid with the compound of formula I or formula I', shaking, centrifuging, and re O 4 - And/or 99 TcO 4 - Entering an extracting agent.
In some embodiments of the invention, the method further comprises a back extraction step, wherein a back extraction agent is added into the extractant layer during the back extraction, and the back extraction step is performed by shaking, centrifugation and ReO 4 - And/or 99 TcO 4 - Is back extracted into water phase;
the stripping agent is selected from HCl and H 2 SO 4 、HNO 3 And NH 4 One of OH solutions.
In some embodiments of the invention, the extraction is performed at room temperature.
In some embodiments of the invention, the pH of the system at the time of extraction is < 8, preferably less than 7 or 4.
In some embodiments of the invention, reO 4 - And/or 99 TcO 4 - Respectively with competitive anion SO 4 2- 、NO 3 - 、Cl - Concentration (ppm) ratio of each 1 to 10000, and ReO 4 - And/or 99 TcO 4 - With competing anions SO 4 2- 、NO 3 - 、Cl - The total concentration ratio of the mixture is 1 to 10000, wherein C is SO42- :C NO3- :C Cl- 1, for example, 1.
In some embodiments of the invention, the concentration of acid in the high acid metal solution is from 0.01 to 6M, for example from 0.1 to 3M, such as from 1 to 1.5M.
In some embodiments of the invention, the concentration of the extraction agent is from 10 to 60mmol, for example from 20 to 50mmol, such as from 30 to 40mmol.
In some preferred embodiments of the invention, the stripping agent used in stripping is selected from NH 4 And (4) OH solution.
In some embodiments of the invention, the concentration of stripping agent is 0.001 to 0.01, for example 0.05mol/L.
In some embodiments of the invention, the process further comprises using an acidic reagent, such as H, after stripping is complete 2 SO 4 Activating the extractant, and then recycling.
In one embodiment of the invention, the isolated ReO 4 - And/or 99 TcO 4 - The method comprises the following steps: d2EHAG or M2EHAG or PELLAG is used as an extracting agent, and during extraction: at room temperature, at a pH of less than 8.0 (pH of PELLAG < 8), will contain ReO 4 - And/or 99 TcO 4 - 、NO 3 - 、Cl - 、SO 4 2- (C ReO4- :C Competing anions Spent fuel post-treatment waste liquid containing a large number of competitive anions, such as =1, 10, 100, 1000, 10000), or ReO 4 - / 99 TcO 4 - 、H 2 SO 4 、HCl、HNO 3 Mixing (concentration is 0.01-6M) high acid metal solution with different concentrations (10-50 mmol) of D2EHAG or M2EHAG or PELLAG extractant, and oscillating at 150-200rpm for 1-5 min; centrifuging at 2500-5000rpm after shaking, and performing ReO 4 - And/or 99 TcO 4 - Entering an extracting agent; during back extraction: adding alkaline reagent (0.01-6M) into the extractant layer for back extraction, and oscillating in an oscillator at 150-200rpm for 1-5 min; centrifuging at 2500-5000rpm after shaking, and performing ReO 4 - And/or 99 TcO 4 - Is back extracted into the aqueous phase. The concentration of metal ions in the aqueous phase was measured using an inductively coupled plasma atomic emission spectrometer (ICP-OES).
The invention has the beneficial effects that:
(1) The invention uses ReO 4 - And/or 99 TcO 4 - The amide extractant with unique extraction effect is used for liquid phase extraction, has high extraction and back extraction rate, and can realize ReO 4 - And/or 99 TcO 4 - And (4) recycling.
(2) The extractant has unsaturated metal sites, contains four elements of C, H, O and N, has low cost, environmental friendliness and high solubility, contains different organic ligands such as oxygen, nitrogen and the like, and has different extraction performances.
(3) The extractant has good selectivity under high acid condition, for example, the D2EHAG extractant is different from the prior extractant and has good selectivity under competitive anion NO 3 - And ReO 4 - Up to 1000: greater breakthrough in selectivity at 1 (D2 EHAG vs. ReO) 4 - Is still removedNearly 70%, the extraction effect is very excellent).
(4) The extractant has good extraction effect under high acid condition (acid concentration is 1-6 mol/L), wherein the PELLAG extractant has the best extraction effect under the high acid condition of 1 mol/L.
(5) The extractant can directly separate ReO by using an alkaline stripping agent in one step 4 - And/or 99 TcO 4 - The method has the advantages of simple process flow, less used equipment and suitability for industrial use.
In conclusion, the extracting agent has high extracting speed (less than or equal to 1 min) and high selectivity, wherein the extraction rate of the D2EHAG can reach 98 percent, and the extracting agent has wide application prospect.
Definition and description of terms
Unless defined otherwise, all technical and scientific terms herein have the same meaning as commonly understood by one of ordinary skill in the art to which the claimed subject matter belongs.
Due to the fact that 99 TcO 4 - Having radioactive properties, rhenium (ReO) is commonly used in the art in a manner similar to its physicochemical properties 4 - ) The study was conducted so that although the compounds of the present application were extracted against ReO 4 - . However, it will be appreciated by those skilled in the art that the compounds are equally suitable for extraction 99 TcO 4 - And with ReO 4 - The extraction effect of (2) is equivalent.
"halogen" means fluorine, chlorine, bromine or iodine.
The term "C 1-12 Alkyl "is understood to mean a straight-chain or branched saturated monovalent hydrocarbon radical having from 1 to 12 carbon atoms. For example, "C 1-6 Alkyl "denotes straight and branched chain alkyl groups having 1,2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-ethylpropyl, 1, 2-dimethylpropyl, neopentyl, 1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3-dimethylbutyl2, 2-dimethylbutyl, 1-dimethylbutyl, 2, 3-dimethylbutyl, 1, 3-dimethylbutyl or 1, 2-dimethylbutyl, and the like, or isomers thereof.
The term "C 1-12 Alkoxy "is to be understood as meaning-O-C 1-12 Alkyl radical, wherein C 1-12 Alkyl groups have the same definitions as above.
The term "C 6-20 Aryl "is understood to mean a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partial aromaticity of 6 to 20 carbon atoms, preferably" C 6-14 Aryl ". The term "C 6-14 Aryl "is to be understood as preferably meaning a mono-, bi-or tricyclic hydrocarbon ring having a monovalent or partially aromatic character with 6, 7, 8, 9, 10, 11, 12, 13 or 14 carbon atoms (" C 6-14 Aryl "), in particular a ring having 6 carbon atoms (" C 6 Aryl "), such as phenyl; or biphenyl, or is a ring having 9 carbon atoms ("C 9 Aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 Aryl radicals), such as tetralinyl, dihydronaphthyl or naphthyl, or rings having 13 carbon atoms ("C 13 Aryl radicals), such as the fluorenyl radical, or a ring having 14 carbon atoms ("C) 14 Aryl), such as anthracenyl. When said C is 6-20 When the aryl group is substituted, it may be mono-or polysubstituted. And, the substitution site thereof is not limited, and may be, for example, ortho-, para-or meta-substitution.
The term "5-20 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5 to 20 ring atoms and containing 1 to 5 heteroatoms independently selected from N, O and S, e.g., "5-14 membered heteroaryl". The term "5-14 membered heteroaryl" is understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: which has 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, in particular 5 or 6 or 9 or 10 carbon atoms, and which comprises 1 to 5, preferably 1 to 3, heteroatoms each independently selected from N, O and S and, in addition, can in each case be benzo-fused. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl and the like and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl and the like; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl and the like, and benzo derivatives thereof, such as quinolyl, quinazolinyl, isoquinolyl and the like; or azocinyl, indolizinyl, purinyl and the like and benzo derivatives thereof; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like.
Drawings
FIG. 1 shows the structural diagrams of M2EHAG, PELLAG, and D2EHAG.
FIG. 2 is a FT-IR chart of M2EHAG, PELLAG and D2EHAG prepared by the present invention.
FIG. 3 is a graph showing the comparison of M2EHAG, PELLAG, D2EHAG against ReO at various times at a pH of the aqueous phase of 0.5 in accordance with the present invention 4 - The extraction rate of (2).
FIG. 4 shows the different acid types and concentrations of ReO in aqueous phase for M2EHAG, PELLAG, D2EHAG in the present invention 4 - The extraction rate was as follows.
FIG. 5 shows the results of M2EHAG, PELLAG, D2EHAG extraction of ReO at aqueous pH of 0.5-8 4 - The extraction rate of (2).
FIG. 6 is a graph of M2EHAG vs ReO for different ratios of competing anions in the aqueous phase in accordance with the present invention 4 - Extraction rate of (wherein, SO) 4 2- /NO 3 - /Cl - Representing the sum of the three ion concentrations).
FIG. 7 shows the ratio of PELLAG to ReO in different proportions of competing anions in the aqueous phase according to the present invention 4 - Extraction ratio of (in which, SO) 4 2- /NO 3 - /Cl - Representing the sum of the three ion concentrations).
FIG. 8 is a graph of the D2EHAG vs ReO of the present invention at different ratios of competing anions in the aqueous phase 4 - Of (2) extractionRate (wherein, SO) 4 2- /NO 3 - /Cl - Representing the sum of the three ion concentrations).
FIG. 9 shows different concentrations of D2EHAG in aqueous phase of different stripping agent pairs ReO in accordance with the present invention 4 - The stripping rate of (a).
FIG. 10 shows the cyclic extraction experiment of D2EHAG in the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The calculation of the removal and extraction rates in the following examples is:
Figure BDA0003925672530000061
wherein, C 0 And C e The initial concentration and the equilibrium concentration (mg/L) of the metal ions are indicated, respectively.
The back extraction rate is calculated in the following way:
Figure BDA0003925672530000062
wherein, C 0 And C e The initial and equilibrium concentrations (mg/L) of the metal ions are indicated, respectively.
Unless otherwise stated, inductively coupled plasma atomic emission spectrometry (ICP-OES) was used herein to measure the concentration of metal ions in the aqueous phase.
Example 1
The extracting agents (M2 EHAG, PELLAG and D2 EHAG) are synthesized by a chemical synthesis method, and the specific implementation steps are as follows:
diisooctylamine (30.5mL, 0.1mol) and triethylamine (14mL, 0.1mol) were dissolved in methylene chloride, and chloroacetyl chloride (9.6mL, 0.12mol) was slowly added thereto and stirred at room temperature for 3 hours (500 to 1000 rpm). The resulting mixture was filtered by adding a small amount of activated carbon, washed several times with about 0.1mol/L hydrochloric acid to remove unreacted amine salts, and the organic phase was washed several times with deionized water. The dichloromethane and water were removed from the solution by rotary evaporation to give CDEHAA (2-chloro-N, N-bis (2-ethylhexyl) -acetamide) as a yellow liquid. Glycine (15g, 0.2mol) and sodium hydroxide (8g, 0.2mol) were dissolved in a methanol solution, and a CDEHAA solution (12.658g, 0.04mol) was added dropwise to the mixed solution, followed by stirring at 60 ℃ for 15 hours (500 to 1000 rpm). Methanol was removed from the solution by rotary evaporation, and the mixture was dissolved by adding dichloromethane. Adding a small amount of activated carbon into the solution for filtration, washing the solution for multiple times by using 1.0mol/L sulfuric acid, and washing the organic phase by using deionized water for multiple times. The dichloromethane and water were removed from the solution by rotary evaporation to give a yellow viscous liquid D2EHAG, which was freeze dried. The synthesis method of M2EHAG and PELLAG is similar to that of D2EHAG, and the diisooctylamine is only replaced by isooctylamine or beta-phenylethylamine.
The structure of the newly obtained extractant is shown in figure 1, the extractant is characterized by Fourier infrared spectroscopy (FT-IR), the result is shown in figure 2, the existence of main functional groups in FT-IR spectrums of D2EHAG, M2EHAG and PELLAG proves the successful synthesis of the extractant, D2EHAG: FT-IR (v/cm) -1 ),1730(-C＝O),1650(N-C＝O)；M2EHAG:FT-IR(v/cm -1 ),1660(-C＝O),1560(N-C＝O),3280(-NH)；PELLAG：FT-IR(v/cm -1 ),1640(-C＝O),1540(N-C＝O),3280(-NH)。
Example 2
Several efficient separation of ReO 4 - Extraction reaction time test of the extractant
50mmol/L of the three extractants prepared in example 1 were added to a solution containing 10ppm of ReO 4 - In the metal mixed solution, the mixture was shaken in a shaker at room temperature of 200rpm, and the amount of extracted metal was measured by inductively coupled plasma atomic emission spectrometry. The results are shown in FIG. 3,3 extractants can reach extraction equilibrium rapidly within 1min, and 3 extractants can react with ReO 4 - All have good extraction ability according to PLLAG<M2EHAG<The order of D2EHAG increases.
Example 3
Several efficient separation of ReO 4 - Acid resistance test of the extractant
Acid species and acid concentration in extraction aqueous phase for extraction of ReO with 3 types of amic acid extractants 4 - The effect of (a) is shown in fig. 4, and the results show that: with H in the water phase 2 SO 4 HCl and HNO 3 The concentration of (2) is increased from 0.01mol/L to 6mol/L, and M2EHAG is used for ReO 4 - The removal rate of the catalyst is respectively reduced from 86.75% to 58.06%, from 88.07% to 29.31% and from 84.02% to 10.61%; d2EHAG vs ReO 4 - The removal rate of the catalyst is respectively reduced from 98.29 percent to 59.43 percent, from 98.7 percent to 40.31 percent and from 97.41 percent to 14.52 percent; the PELLAG is sensitive to pH, and shows a trend of rising firstly and then falling with the increase of acid concentration, generally reaches a peak value at 1mol/L and is used for ReO 4 - The removal rates of the catalyst were increased from 54.46% to 65.70% and then decreased to 55.81%, increased from 37.90% to 53.39% and then decreased to 33.64%, and decreased from 30.07% to 28.66% and then decreased to 11.85%, respectively. pH to ReO 4 - The effect of extraction is shown in figure 5. The extraction rate of PELLAG is continuously reduced along with the increase of pH, and when the pH is about =4, the extraction rate of PELLAG is reduced to ReO 4 - The extraction rate of (2) was reduced to 0%. M2EHAG and D2EHAG against ReO at pH =0.5-7.0 4 - The extraction rate of (2) is almost unchanged, and the extraction rates fluctuate from 95% to 80% respectively. When the pH is not less than 7, however, the extraction rate is abruptly reduced and ReO is hardly extracted 4 - 。
In summary, 3 types of amic acid extractants still react with ReO under high acid conditions 4 - Has good extraction ability and acidity influence as H 2 SO 4 <HCl<HNO 3 The order of (a) increases. Under the acidic condition, the extraction capability of the D2EHAG extractant is better than that of M2EHAG and PLLAG.
Example 4
Several efficient separation of ReO 4 - Extractant competitive anion test of
D2EHAG, M2EHAG and PELLAG at high strengthCompeting anion SO 4 2- 、NO 3 - 、Cl - In the presence of ReO 4 - The results of the extraction behavior (setting the pH of the aqueous phase to 0.5, since PELLAG is sensitive to pH) tests are shown in FIGS. 6-8.
The results in FIG. 6 show that: with SO in the aqueous phase 4 2- 、NO 3 - And Cl - And ReO 4 - When the concentration ratio (ppm) of M2EHAG to ReO is increased from 1 to 10000 4 - The removal rate of the catalyst is respectively reduced from 83.60 percent to 68.08 percent, from 83.60 percent to 23.47 percent and from 84.29 percent to 38.60 percent
The results in FIG. 7 show that: SO in aqueous phase with pH =0.5 4 2- 、NO 3 - And Cl - And ReO 4 - To an extreme of 10000 (ppm) from 1 to 1, PELLAGs against ReO 4 - The removal rates of the catalyst are respectively reduced from 68.43% to 65.79%, from 68.21% to 14.22% and from 66.14 to 1.63%.
The results in FIG. 8 show that: when the water phase is SO 4 2- And ReO 4 - 1 to 10000, D2EHAG to ReO (ppm) 4 - The removal rate of (2) is 90% or more, and very excellent selectivity is exhibited. When Cl is present - And ReO 4 - To 10000 from 1 4 - The removal rate of the catalyst is reduced to 72.72 percent from 98.98 percent, namely, good selectivity is shown. NO in aqueous phase 3 - And ReO 4 - When the concentration ratio of (A) to (B) is up to 1000 4 - The removal rate of (2) is still close to 70%, i.e. the selectivity is very excellent. For this purpose, we will not be able to substitute NO 3 - And ReO 4 - The concentration ratio of (a) to (b) is raised to the extreme 10000, which is the most extreme condition reported, and the results show that D2EHAG is opposite to ReO 4 - The extraction rate of the method can still reach 37.18 percent, and the extraction effect is very excellent.
In summary, 3 types of amic acid extractants are still sensitive to ReO in the presence of competing anions 4 - Has good extraction ability and extractionEnergy take according to PLLAG<M2EHAG<The order of D2EHAG increases. Extraction of ReO by competitive anion-pair amic acid extractant in aqueous phase 4 - Has the influence sequence of NO 3 - ＞Cl - ＞SO 4 2- . The extraction capability and the selectivity effect of the D2EHAG extractant are better than those of M2EHAG and PLLAG.
Example 4
D2EHAG vs ReO 4 - Extraction cycle experiment of
Specifically, in the back extraction process, the extractant in the upper layer is taken for filtration, and HCl and H with different concentrations are added 2 SO 4 、HNO 3 And NH 4 And (3) performing back extraction on the OH solution, putting the mixture in a shaking table at room temperature and 200rpm for 1min, centrifuging for 3min, filtering the aqueous phase solution, and detecting the back extraction amount of the metal by inductively coupled plasma atomic emission spectrometry. The results are shown in FIG. 9 when HCl and H are added 2 SO 4 、HNO 3 When the aqueous phase is used as stripping solution, the stripping effect is poor even at 6M HCl and H 2 SO 4 、HNO 3 Under the condition, the back extraction rates are respectively 50%,20% and 80%. When ammonia water is used as the stripping aqueous phase, the stripping rate of 98.73% can be achieved under the condition that the concentration of the ammonia water is 0.05mol/L, therefore, the ammonia water is a good stripping agent, and 0.05mol/L ammonia water solution is selected as the stripping aqueous phase in subsequent circulation experiments.
As shown in FIG. 10, the regeneration process of stripping first uses 0.05mol/L ammonia solution, and then uses 0.05M H 2 SO 4 Activation of D2EHAG was performed. Test results show that after the D2EHAG is subjected to extraction-back extraction for 5 times for recycling, the extraction rate is still maintained at about 98 percent, and the back extraction rate is slightly reduced but is always maintained at more than 95 percent. The result shows that the D2EHAG has excellent recycling performance and good industrial application prospect.
The invention selects a pair of ReO by taking M2EHAG, PELLAG and D2EHAG as extracting agents 4 - And/or 99 TcO 4 - The extractant has unique extracting effect. The extractant was subjected to successive extraction experiments, which were repeated five times without a large change in extraction capacity.Can almost completely strip out in an acid medium to realize ReO 4 - And/or 99 TcO 4 - The method has good extraction capability under the condition of high acid, and has very strong practicability and good industrial application prospect.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A compound of formula I:
Figure FDA0003925672520000011
wherein R is selected from the following groups unsubstituted or optionally substituted by one, two or more Rs: c 1-12 Alkyl radical, C 6-20 Aryl or 5-20 membered heteroaryl;
rs is selected from halogen, -CN, C 1-12 Alkyl radical, C 1-12 Alkoxy or halo C 1-12 An alkyl group;
a. b are identical or different and are selected independently of one another from 1,2, 3, 4, 5 or 6.
2. A process for the preparation of a compound of formula I according to claim 1, comprising the steps of:
Figure FDA0003925672520000012
wherein R, a, b have the definitions as set forth in claim 1; l is a leaving group;
and reacting the compound Ia with the compound Ib to obtain a compound Ic, and reacting the compound Ic with the compound Id to obtain the compound I.
3. The method of1 or separating and extracting ReO from a compound shown as the formula I or a compound shown as the formula I 4 - And/or 99 TcO 4 -the use of (a);
wherein, the compound shown in the formula I' is selected from the following structures:
Figure FDA0003925672520000013
wherein R is 1 、R 2 Identical or different, independently of one another, from the following groups, unsubstituted or optionally substituted by one, two or more Rq: c 1-12 Alkyl radical, C 6-20 Aryl or 5-20 membered heteroaryl;
rq is selected from halogen, -CN, C 1-12 Alkyl radical, C 1-12 Alkoxy or halo C 1-12 An alkyl group;
c. d are identical or different and are selected independently of one another from 1,2, 3, 4, 5 or 6.
4. ReO is separated and extracted from the compound of the formula I as claimed in claim 1 or the compound of the formula I' as claimed in claim 2 4 -and/or 99 TcO 4 - The method is characterized by comprising the following steps:
will contain ReO 4 - And/or 99 TcO 4 - And competitive anion NO 3 - 、Cl - 、SO 4 2- Spent fuel reprocessing effluents or containing ReO 4 - And/or 99 TcO 4 - 、H 2 SO 4 、HCl、HNO 3 Mixing the metal solution with high acid with the compound shown in formula I or formula I', oscillating, centrifuging, and performing ReO 4 - And/or 99 TcO 4 - And then enters an extracting agent.
5. The method according to claim 4, further comprising a back extraction step of adding a back-extracting agent to the extractant layer for back extraction, shaking, centrifuging, and ReO 4 - And/or 99 TcO 4 - Is back extracted into the water phase;
the stripping agent is selected from HCl and H 2 SO 4 、HNO 3 And NH 4 One of OH solutions.
6. A method according to claim 4 or 5, characterized in that the pH of the system during extraction is < 8.
7. The method of any one of claims 4 to 6, wherein ReO 4 - And/or 99 TcO 4 - Respectively with competing anions SO 4 2- 、NO 3 - 、Cl - Concentration (ppm) ratio of each 1 to 10000, and ReO 4 - And/or 99 TcO 4 - With competing anions SO 4 2- 、NO 3 - 、Cl - The mixing total concentration ratio is 1.
8. A process according to any one of claims 4 to 7, characterised in that the concentration of acid in the high acid metal solution is from 0.01 to 6M.
9. The process of any one of claims 4 to 8, wherein the concentration of the extractant is from 10 to 60mmol.
10. The process according to any one of claims 4-9, further comprising using an acidic reagent, such as H, after the stripping is completed 2 SO 4 Activating the extractant, and then recycling.
CN202211371804.3A 2022-11-03 2022-11-03 Method for separating rhenium and technetium Pending CN115677528A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202211371804.3A CN115677528A (en) 2022-11-03 2022-11-03 Method for separating rhenium and technetium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202211371804.3A CN115677528A (en) 2022-11-03 2022-11-03 Method for separating rhenium and technetium

Publications (1)

Publication Number Publication Date
CN115677528A true CN115677528A (en) 2023-02-03

Family

ID=85048359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202211371804.3A Pending CN115677528A (en) 2022-11-03 2022-11-03 Method for separating rhenium and technetium

Country Status (1)

Country Link
CN (1) CN115677528A (en)

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114129A (en) * 2007-11-07 2009-05-28 Japan Atomic Energy Agency N,n,n',n'-tetraoctyl-3-methyliminodiglycol amide compound and complexing extractant of specific metal comprising the compound
CN103044422A (en) * 2012-12-27 2013-04-17 威海迪之雅医药化工开发有限公司 Preparation method of praziquantel
CN103620065A (en) * 2011-11-09 2014-03-05 国立大学法人九州大学 Cobalt extraction method
CN103764857A (en) * 2012-03-13 2014-04-30 国立大学法人九州大学 Scandium extraction method
CN104583427A (en) * 2012-08-20 2015-04-29 国立大学法人九州大学 Indium extraction agent and indium extraction method
CN104583426A (en) * 2012-08-20 2015-04-29 国立大学法人九州大学 Gallium extraction agent and gallium extraction method
CN105074022A (en) * 2013-03-18 2015-11-18 国立大学法人九州大学 Method for separating impurities from an acidic solution containing nickel and cobalt and/or scandium
CN105074023A (en) * 2013-04-15 2015-11-18 国立大学法人九州大学 Extraction agent for precious metals and rhenium, and extraction method for precious metals and rhenium using same
CN107382896A (en) * 2017-08-02 2017-11-24 张建华 The epoxide phenoxy group propionyl imine compound of benzoxazole 2 and its synthetic method and application
CN111485125A (en) * 2020-03-25 2020-08-04 中国原子能科学研究院 Method for recovering technetium from spent fuel post-treatment waste liquid
CN114591244A (en) * 2022-03-24 2022-06-07 兰州大学 Material for separating technetium and preparation method thereof

Patent Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009114129A (en) * 2007-11-07 2009-05-28 Japan Atomic Energy Agency N,n,n',n'-tetraoctyl-3-methyliminodiglycol amide compound and complexing extractant of specific metal comprising the compound
CN103620065A (en) * 2011-11-09 2014-03-05 国立大学法人九州大学 Cobalt extraction method
CN103764857A (en) * 2012-03-13 2014-04-30 国立大学法人九州大学 Scandium extraction method
CN104583427A (en) * 2012-08-20 2015-04-29 国立大学法人九州大学 Indium extraction agent and indium extraction method
CN104583426A (en) * 2012-08-20 2015-04-29 国立大学法人九州大学 Gallium extraction agent and gallium extraction method
CN103044422A (en) * 2012-12-27 2013-04-17 威海迪之雅医药化工开发有限公司 Preparation method of praziquantel
CN105074022A (en) * 2013-03-18 2015-11-18 国立大学法人九州大学 Method for separating impurities from an acidic solution containing nickel and cobalt and/or scandium
CN105074023A (en) * 2013-04-15 2015-11-18 国立大学法人九州大学 Extraction agent for precious metals and rhenium, and extraction method for precious metals and rhenium using same
CN107382896A (en) * 2017-08-02 2017-11-24 张建华 The epoxide phenoxy group propionyl imine compound of benzoxazole 2 and its synthetic method and application
CN111485125A (en) * 2020-03-25 2020-08-04 中国原子能科学研究院 Method for recovering technetium from spent fuel post-treatment waste liquid
CN114591244A (en) * 2022-03-24 2022-06-07 兰州大学 Material for separating technetium and preparation method thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
BURGER KLAUS等: "Application of hexafluoroacetone as protecting and activating reagent in amino acid and peptide chemistry. N-Substituted glycine derivatives from iminodiacetic acid", ZEITSCHRIFT FUER NATURFORSCHUNG, B: CHEMICAL SCIENCES, vol. 48, no. 1, pages 107 - 120 *
CHEMICAL ABSTRACT SERVICE: "RN: 2845558-64-5等", STN REGISTRY数据库 *
宋岳等: "离子液体萃取锝和铼的研究", 北京大学学报(自然科学版), vol. 53, no. 5, pages 810 - 816 *

Similar Documents

Publication Publication Date Title
Jańczewski et al. Tripodal diglycolamides as highly efficient extractants for f-elements
CN108017632B (en) Phenanthroline-derived bispyrazole extractant and preparation method and application thereof
CN106892835A (en) Double two sweet amide ligands and preparation method thereof and the group of the lanthanides containing double two sweet amide ligands/actinium series separating and extracting system
CN110894578B (en) Extraction method of tetravalent plutonium ions
Kraus et al. Adsorption of Protactinium from Hydrochloric Acid Solutions by Anion Exchange Resins1
CN106048266A (en) Method for separating and concentrating trace amounts of uranium from large amounts of thorium
Liu et al. Unique extraction of U (VI), Pu (IV), Am (III) and Eu (III) from nitric acid medium using a phosphonium based ionic liquid consisting of novel anion, 1, 1, 1, 5, 5, 5-hexafluoro-2, 4-pentanedionate–Dual solvent behavior
JPH044983B2 (en)
CN115677528A (en) Method for separating rhenium and technetium
CN107958717B (en) Method for separating trivalent actinide and lanthanide ions based on synergistic effect
Tian et al. Synthesis and characterisation of diamide extractants for the extraction of neodymium
JP5631396B2 (en) Compounds suitable for use as actinide ligands, their synthesis and use
Sasaki et al. Studies on the extraction of soft acid metal species using MIDOA and analogous compounds
JP5497174B2 (en) Dialkyldiaza-tetraalkyloctanediamide derivatives useful for separation of trivalent actinides from lanthanides and methods for producing the same
CN114591244A (en) Material for separating technetium and preparation method thereof
CN114752783B (en) High-efficiency Sr separation 2+ And Cs + Is a method of (2)
Grdenić et al. The complexing of tetravalent uranium with dialkylpyrophosphoric acid
Zhijun et al. Liquid-liquid extraction of uranium (VI) and thorium (IV) by two open-chain crown ethers with terminal quinolyl groups in chloroform
Sopo et al. Aminoalkylbis (phenolate)[O, N, O] donor ligands for uranyl (VI) ion coordination: Syntheses, structures, and extraction studies
PT115507B (en) SYNTHESIS PROCESS OF THE IONIC LIQUID DI(2-ETHYLHEXYL)- TETRAOCTYLAMONIUM OXAMATE (IL-5), PRODUCT OBTAINED AND ITS USE IN THE SELECTIVE EXTRACTION OF METALS
CN114957146B (en) Trinuclear terbium complex and preparation method and application thereof
Miyasita et al. Separation of americium (III) from europium (III) by dioctylammonium dioctyldithiocarbamate/nitrobenzene extraction
Zeman et al. A new principle of activation-analysis separations—X: Substoichiometric determination of traces of gallium
Matsubayashi et al. Thermodynamic consideration for solvent effects in the synergistic extraction of europium (III) with pivaloyltrifluoroacetone and 1, 10-phenanthroline
Yakabe et al. Liquid-liquid extraction of hafnium complex ion from aqueous oxalic acid solution with high molecular weight amine

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination