CN113981253A - Recovery method of americium-containing waste material - Google Patents
Recovery method of americium-containing waste material Download PDFInfo
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- CN113981253A CN113981253A CN202111273570.4A CN202111273570A CN113981253A CN 113981253 A CN113981253 A CN 113981253A CN 202111273570 A CN202111273570 A CN 202111273570A CN 113981253 A CN113981253 A CN 113981253A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0295—Obtaining thorium, uranium, or other actinides obtaining other actinides except plutonium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/08—Processing by evaporation; by distillation
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- G—PHYSICS
- G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
- G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
- G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
- G21F9/04—Treating liquids
- G21F9/06—Processing
- G21F9/12—Processing by absorption; by adsorption; by ion-exchange
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for recovering americium-containing waste. In the method for recovering americium-containing waste, firstly, the americium-containing waste is dissolved in hydrochloric acid liquor to obtain an americium-containing solution, and the americium-containing waste contains americium elements and complexes thereof; evaporating and drying the americium-containing solution, and adding a nitric acid solution to obtain an americium-containing nitric acid solution; adsorbing nitric acid solution containing americium by using ion exchange resin, and desorbing to obtain americium ion solution, wherein the active group of the ion exchange resin comprises any one of sulfonic group, phosphonic group or amide group. The method can separate and recover americium from americium-containing wastes with complex components, has high separation efficiency and mild conditions, and the obtained high-purity americium ion solution can be used for a radioactive experiment to realize the reutilization of wastes, so that the treatment capacity and the treatment cost of radioactive wastes in a laboratory are reduced, and the pressure of radioactive waste treatment is greatly relieved.
Description
Technical Field
The invention relates to the technical field of radioactive metal treatment, in particular to a method for recovering americium-containing waste.
Background
With the gradual implementation of carbon peak reaching, carbon neutralization and commitment in China, the proportion of clean energy in the energy structure of China is getting heavier. The nuclear energy is used as clean energy, has the advantages of high energy density, low carbon emission, large uranium resource reserve and the like, and plays an important role in realizing the carbon neutralization target process. Nuclear power operation can generate a large amount of spent fuel, and the spent fuel contains a large amount of recyclable resources such as uranium and plutonium and minor actinides such as americium with long-term radioactivity. In the prior art, a closed cycle nuclear energy utilization strategy is adopted, uranium and plutonium in spent fuel are separated, recycled and reused, and meanwhile, long-life nuclides such as americium and minor actinides are separated, so that the amount of radioactive wastes needing to be treated by a geological disposal method is reduced.
Americium (Am) is taken as an important minor actinide of spent fuel, and technical personnel carry out extensive research on physicochemical property analysis and separation behaviors of americium (Am) in order to solve the separation problem of the americium (Am) in the post-treatment of the spent fuel. In a radiochemical experiment, when an Am element is utilized to carry out researches such as oxidation, separation, solid chemistry and the like, a large amount of Am-containing waste can be generated, including Am-containing waste liquid and Am-containing solid waste, and due to the inherent toxicity and strong radioactivity of the Am element, the Am-containing radioactive waste is difficult to treat by a traditional separation and purification technology to reach the standard of direct discharge. In order to minimize Am-containing radioactive wastes and reduce the storage burden of the Am-containing radioactive wastes, technicians try to separate and recover Am from the Am-containing radioactive wastes in the conventional technology, however, the conventional spent fuel post-processing technology still stays at the stage of separating and recovering uranium and plutonium, but minor actinides such as americium (Am) are difficult to separate and recover effectively. And Am-containing waste generated in radiochemical experiments is generally a solid-liquid mixture, the components are complex, the properties of the solid components are stable, Am, various ligands capable of complexing or coordinating with Am and complexes formed by the Am and the ligands are contained, and effective separation and recovery of americium (Am) from the Am-containing waste is difficult through the traditional separation technology.
Thus, the prior art remains to be improved.
Disclosure of Invention
Based on the method, the method can separate and recover americium from americium-containing wastes with complex components and has high separation efficiency.
The technical scheme of the invention is as follows.
In one aspect of the present invention, a method for recovering americium-containing waste is provided, comprising the steps of:
dissolving americium-containing waste in a hydrochloric acid liquor to obtain an americium-containing solution, said americium-containing waste containing americium elements and complexes thereof;
evaporating and drying the americium-containing solution, and adding a nitric acid solution to obtain an americium-containing nitric acid solution;
adsorbing the nitric acid solution containing americium by using ion exchange resin, and desorbing to obtain an americium ion solution; the active group of the ion exchange resin comprises any one of sulfonic acid group, phosphonic acid group or amide group.
In some of these embodiments, the active group of the ion exchange resin is a sulfonic acid group.
In some of these embodiments, the ion exchange resin is a styrene-divinylbenzene copolymer containing sulfonic acid groups.
In some of these embodiments, the step of subjecting the mixture to adsorption treatment employs dynamic adsorption; in the step of adsorption treatment, the flow rate of the americium-containing nitric acid solution is 0.5mL/min to 1.5 mL/min.
In some of these embodiments, the dynamic adsorptive contact time of the americium-containing nitric acid solution with the ion exchange resin is between 3 minutes and 10 minutes.
In some embodiments, the desorbing step uses a hydrochloric acid solution with a concentration of 4mol/L to 7mol/L as an eluent with a flow rate of 0.3mL/min to 0.7 mL/min.
In some embodiments, after the step of adsorbing and before the step of desorbing, the method further comprises the steps of:
and pre-eluting the ion exchange resin after adsorption treatment by adopting hydrochloric acid solution with the concentration of 0.5-1.5 mol/L.
In some of these embodiments, the desorbing step is repeated 3-6 times; and/or
And repeating the pre-elution step for 3-6 times.
In some of these embodiments, the method further comprises the steps of:
evaporating the americium ion solution to dryness, and adding nitric acid solution to obtain Am (NO)3)3And (3) solution.
In some of these examples, the hydrochloric acid liquor used in the step of dissolving americium-containing waste in hydrochloric acid liquor has a concentration of 4 to 7 mol/L; the volume ratio of the americium-containing waste to the hydrochloric acid solution is 1 (0.1-1); and/or
The temperature of the step of dissolving americium-containing waste in hydrochloric acid liquor is between 180 and 210 ℃.
In some of the embodiments, the concentration of the nitric acid solution is 1mol/L to 3 mol/L.
In some embodiments, before the step of performing the adsorption treatment, the method further comprises the following steps:
adopting hydrochloric acid solution with the concentration of 0.3-0.7 mol/L to carry out pre-washing treatment on the ion exchange resin.
In the method for recovering americium-containing waste, firstly, the americium-containing waste is dissolved in a hydrochloric acid solution, the hydrochloric acid solution fully dissociates americium-containing complexes in the americium-containing solution, solid substances such as americium complexes in the americium-containing waste are dissolved in the hydrochloric acid solution, so that americium elements in the americium-containing nitric acid solution exist in the form of americium ions, and a uniform americium-containing solution is obtained; then evaporating and drying the americium-containing solution, and adding a nitric acid solution to obtain an americium-containing nitric acid solution; adsorbing the nitric acid liquid containing americium by using a specific ion exchange resin, wherein in the process, the nitric acid liquid containing americium provides an acidic system which is favorable for separating americium ions from other impurities, so that the americium ions in the nitric acid liquid containing americium are favorably and fully adsorbed by the ion exchange resin, and other impurities flow out along with the effluent liquid; and then, the americium ions absorbed by the ion exchange resin are recovered through desorption to obtain a high-purity americium ion solution. So, can follow the complex americium waste that contains of composition separation and retrieve americium, separation efficiency is high, and the condition is mild, obtains high-purity americium ion solution and can be used for the radiochemical experiment, realizes recycling of waste material, has so reduced the handling capacity and the treatment cost of laboratory radioactive waste, greatly has relieved radioactive waste treatment's pressure.
Detailed Description
In order that the invention may be more fully understood, a more particular description of the invention will now be rendered by reference to specific embodiments thereof that are illustrated in the appended drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
One embodiment of the present invention provides a method for preparing ultrapure ceria, comprising the following steps S10 to S40.
Step S10, dissolving americium-containing waste in a hydrochloric acid solution to obtain an americium-containing solution, the americium-containing waste containing americium elements and complexes thereof.
And step S20, evaporating and drying the americium-containing solution obtained in the step S10, and adding a nitric acid solution to obtain an americium-containing nitric acid solution.
And step S30, subjecting the americium-containing nitric acid solution obtained in the step S20 to adsorption treatment by using ion exchange resin, and desorbing to obtain an americium ion solution.
The active group of the ion exchange resin includes any one of a sulfonic acid group, a phosphonic acid group, or an amide group.
In the method for recovering americium-containing waste, firstly, the americium-containing waste is dissolved in hydrochloric acid liquor, the americium-containing complex in the americium-containing solution is fully dissociated, and solid substances such as americium complex in the americium-containing waste are completely dissolved, so that americium elements in the americium-containing nitric acid liquor exist in the form of americium ions, and uniform americium-containing solution is obtained; then evaporating and drying the americium-containing solution, and adding a nitric acid solution to obtain an americium-containing nitric acid solution; adsorbing the nitric acid liquid containing americium by using a specific ion exchange resin, wherein in the process, the nitric acid liquid containing americium provides an acidic system which is favorable for separating americium ions from other impurities, so that the americium ions in the nitric acid liquid containing americium are favorably and fully adsorbed by the ion exchange resin, and other impurities flow out along with the effluent liquid; and then, the americium ions absorbed by the ion exchange resin are recovered through desorption to obtain a high-purity americium ion solution. So, can follow the complex americium waste that contains of composition separation and retrieve americium, separation efficiency is high, and the condition is mild, obtains high-purity americium ion solution and can be used for the radiochemical experiment, realizes recycling of waste material, has so reduced the handling capacity and the treatment cost of laboratory radioactive waste, greatly has relieved radioactive waste treatment's pressure.
It is understood that the above americium-containing wastes contain americium elements, ligands capable of complexing or coordinating with Am and complexes of both.
Furthermore, the americium-containing waste also contains other impurities, such as other metal salts and the like.
The americium-containing waste is a solid-liquid mixture, has complex components, contains Am, various ligands capable of complexing or coordinating with Am and complex solid components formed by the Am and the ligands, has stable properties, can obtain a uniform americium-containing solution by adopting hydrochloric acid solution, lays a foundation for the subsequent separation and recovery steps, and cannot be well dissolved by other acids.
In some of these examples, the americium-containing waste contains Am (NO)3)3Mellitic acid ligand (mel) and Am-mel solid crystals.
In a specific example, the aforementioned americium-containing waste is radioactive waste generated during the synthesis of Am metal-organic framework material.
In some of these examples, in step S10, the hydrochloric acid solution used in the step of dissolving americium-containing waste in hydrochloric acid solution described above has a concentration of 4mol/L to 7 mol/L;
further, the volume ratio of the americium-containing waste to the hydrochloric acid solution is 1 (0.1-1).
In some of these embodiments, the temperature of the step of dissolving americium-containing waste in hydrochloric acid liquor in step S10 is between 180 ℃ and 210 ℃; further, the time is 1d to 3 d. In a specific example, in step S10, the conditions of the step of dissolving americium-containing waste in hydrochloric acid are: the temperature is kept at 180 ℃ for 3 d.
By controlling the concentration, the dosage and the dissolving condition of the hydrochloric acid solution, solid substances in the americium-containing waste are further completely dissolved, so that a uniform americium-containing solution is obtained, a foundation is laid for the subsequent steps, and the recovery efficiency is further improved.
In some embodiments, in step S20, the concentration of the nitric acid solution is 1mol/L to 3 mol/L.
By controlling the concentration of the nitric acid solution, the obtained americium-containing nitric acid solution has a specific acidic system, and the full adsorption of americium ions in the americium-containing nitric acid solution by ion exchange resin in the subsequent steps is further promoted, so that the recovery efficiency is further improved.
In some of these embodiments, in step S20, the ratio by volume of the americium-containing solution to the nitric acid solution is 1: 0.1 to 1.
Further, in step S20, the evaporation drying step is performed under heating conditions, and the heating is performed to a temperature at which the liquid in the americium-containing solution can evaporate, without any particular limitation. Specifically, the temperature is raised to a temperature at which the liquid in the americium-containing solution flows back, and the heating is carried out.
Preferably, in step S30, the active group of the ion exchange resin is a sulfonic acid group.
After a lot of experiments, the technicians of the invention find that: when sulfonic group, phosphonic group or amide group is used as active group of ion exchange resin, americium ion is adsorbed by ion action. Among them, when a sulfonic acid group is used as an active group of an ion exchange resin, the adsorption and separation effects on americium ions are particularly excellent.
Further, the ion exchange resin is a styrene-divinylbenzene copolymer containing sulfonic acid groups.
This type of ion exchange resin further improves the adsorptive separation effect on americium ions.
Specifically, the ion exchange resin is AG 50W-X8.
It is understood that the ion exchange resin may be any one of styrene-divinylbenzene copolymer resins containing sulfonic acid groups, and is not limited to the specific commercial types described above.
In some of these embodiments, the step of subjecting to adsorption treatment employs dynamic adsorption.
Further, in the step of adsorption treatment, the flow rate of the americium-containing nitric acid solution is 0.5mL/min to 1.5 mL/min.
In some embodiments, the dynamic adsorption contact time of the americium-containing nitric acid solution with the ion exchange resin is 3 to 10 minutes.
Furthermore, the volume mass ratio of the nitric acid solution containing americium to the ion exchange resin is (1 mL-50 mL):1 g.
The breakthrough adsorption capacity in the adsorption treatment step is 50 mg/g-100 mg/g by controlling the specific adsorption treatment conditions; the adsorption rate of Am reaches 98 percent or more.
Further, the particle size unit of the ion exchange resin is 100 to 200 meshes.
In some of these embodiments, the adsorption step is performed in an exchange column; specifically, an ion exchange resin is packed into an ion exchange column to form the ion exchange column.
Furthermore, the material of the exchange column is polytetrafluoroethylene.
In some embodiments, before the step of the adsorption treatment, the method further comprises the following steps:
adopting hydrochloric acid solution with the concentration of 0.3-0.7 mol/L to carry out pre-washing treatment on the ion exchange resin.
Through a specific pre-leaching step, the ion exchange resin can be activated, and the adsorption capacity of the ion exchange resin is further improved.
Further, the pre-rinsing treatment was repeated a plurality of times. Specifically, the pre-rinsing treatment was repeated 3 times.
In some embodiments, in step S30, in the desorption step, a hydrochloric acid solution with a concentration of 4mol/L to 7mol/L is used as an eluent, and the flow rate of the eluent is 0.3mL/min to 0.7 mL/min.
By adopting hydrochloric acid solution with specific concentration as eluent and controlling the flow rate of the eluent, the americium ions absorbed by the ion exchange resin are desorbed, thereby recovering and obtaining high-purity americium ion solution.
In some embodiments, the desorbing step is repeated 3-6 times in step S30.
So as to further make the americium ions adsorbed by the ion exchange resin fully desorbed.
In a specific example, in step S30, the desorption step is repeated 5 times.
It will be appreciated that the adsorption-desorption steps described above may be carried out in the same column.
In some embodiments, after the step of adsorbing and before the step of desorbing, the step of adsorbing and desorbing in step S30 further includes the steps of:
pre-eluting the ion exchange resin after adsorption treatment by adopting hydrochloric acid solution with the concentration of 0.5-1.5 mol/L.
In some of these embodiments, the use of a specific pre-elution step can further increase the efficiency of desorption.
Further, the pre-elution step is repeated for 3 to 6 times.
Specifically, the above-mentioned pre-elution step was repeated 6 times.
The desorption rate in the desorption step reaches 88 to 99 percent through specific desorption treatment conditions. Furthermore, the recovery rate of Am in americium-containing waste reaches 86.24% -97.02%, and the purity of the americium ion solution obtained by recovery is high.
In some of these embodiments, the following step S40 is further included.
Step S40: evaporating and drying the americium ion solution obtained in step S30, and then adding a nitric acid solution to obtain Am (NO)3)3And (3) solution.
Thus, the obtained high-purity americium ion solution is converted into Am (NO) with higher purity3)3The solution can be continuously used for the radioactive experiment, the reutilization of wastes is realized, the treatment capacity and the treatment cost of radioactive wastes in a laboratory are reduced, and the pressure of radioactive waste treatment is greatly relieved.
Specifically, the concentration of the nitric acid solution used in step S40 was 0.1 mol/L.
While the present invention will be described with respect to particular embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but is intended to cover by the appended claims the scope of the invention, and that certain changes in the embodiments of the invention will be suggested to those skilled in the art and are intended to be covered by the appended claims.
DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION
Example 1
(1) Providing americium-containing waste: radioactive waste solid-liquid mixture generated in the process of synthesizing metal organic framework material of Am. The Am (NO) contained in the americium-containing waste3)3Mellitic acid ligand (mel) and Am-mel solid crystals.
(2) Adding 1.5mL of 5mol/L hydrochloric acid solution into 2mL of the americium-containing waste, heating to 180 ℃ in a reaction kettle, and carrying out heat preservation treatment for 3 days to obtain a uniform americium-containing solution.
(3) And then putting the americium-containing solution into a reflux device, heating and evaporating until the solution is dried, and then adding 5mL of 1mol/L nitric acid solution to obtain an americium-containing nitric acid solution.
(4) Filling a cation exchange resin AG50W-X8(2 g; 100-200 meshes) into a 10mL polytetrafluoroethylene adsorption column to form a cation exchange column; using 30mL of HCl solution with the concentration of 0.5mol/L as eluent, dividing the HCl solution into 3 parts equally, and pre-leaching the cation exchange resin in the cation exchange column for three times; then, a dynamic adsorption experiment is carried out, when in adsorption treatment, the flow rate of nitric acid liquid containing americium is controlled to be 1mL/min, and the dynamic adsorption contact time of the nitric acid liquid containing americium and cation exchange resin is controlled to be 5 minutes; then using 30mL of HCl solution with the concentration of 1mol/L as eluent, dividing the HCl solution into 6 parts, and pre-eluting the cation exchange resin adsorbed with Am for 6 times; and finally, 5mL of hydrochloric acid solution with the concentration of 5mol/L is used as eluent and is divided into 5 parts, the cation exchange resin after pre-elution is subjected to desorption for 5 times, and the flow rate of the eluent is controlled to be 0.5mL/min in the desorption process, so that the pure hydrochloric acid solution of Am ions is obtained.
(5) Placing the obtained hydrochloric acid solution of Am ions in a reflux device for heating and evaporation until the solution is dried, and then adding 1mL of nitric acid solution with the concentration of 0.1mol/L into the system to obtain Am (NO) for subsequent experiments3)3And (3) solution.
(6) Further detection of Am (NO)3)3Am (NO) in solution3)3The molar quantity of the Am element recovered is obtained, and the percentage of the molar quantity of the Am element recovered to the molar quantity of the Am element in the americium-containing waste is the recovery rate of the Am element. Specifically, the recovery rate of Am element in example 1 is 93% by detection calculation.
By UV-VIS absorption spectrum method to Am (NO)3)3The purity of the solution was checked, Am (NO)3)3Am (NO3)3The mass percentage of solute in the solution is Am (NO) obtained by recovery3)3Purity, results show: am (NO)3)3The mass percentage of the solute in the Am (NO3)3 solution is 99.9%.
Example 2
(1) Providing americium-containing waste: radioactive waste solid-liquid mixture generated in the process of synthesizing metal organic framework material of Am. The Am (NO) contained in the americium-containing waste3)3Mellitic acid ligand (mel) and Am-mel solid crystals.
(2) Adding 1.5mL of 5mol/L hydrochloric acid solution into 2mL of the americium-containing waste, heating to 180 ℃ in a reaction kettle, and carrying out heat preservation treatment for 3 days to obtain a uniform americium-containing solution.
(3) And then putting the americium-containing solution into a reflux device, heating and evaporating until the solution is dried, and then adding 5mL of 1mol/L nitric acid solution to obtain an americium-containing nitric acid solution.
(4) Filling cation exchange resin HDEHP extraction resin (2 g; 100-200 meshes) into 10mL of polytetrafluoroethylene adsorption column to form a cation exchange column; using 30mL of HCl solution with the concentration of 0.5mol/L as eluent, dividing the HCl solution into 3 parts equally, and pre-leaching the cation exchange resin in the cation exchange column for three times; then, a dynamic adsorption experiment is carried out, when in adsorption treatment, the flow rate of nitric acid liquid containing americium is controlled to be 1mL/min, and the dynamic adsorption contact time of the nitric acid liquid containing americium and cation exchange resin is controlled to be 5 minutes; then using 30mL of HCl solution with the concentration of 1mol/L as eluent, dividing the HCl solution into 6 parts, and pre-eluting the cation exchange resin adsorbed with Am for 6 times; and finally, 5mL of hydrochloric acid solution with the concentration of 5mol/L is used as eluent and is divided into 5 parts, the cation exchange resin after pre-elution is subjected to desorption for 5 times, and the flow rate of the eluent is controlled to be 0.5mL/min in the desorption process, so that the pure hydrochloric acid solution of Am ions is obtained.
(5) Placing the obtained hydrochloric acid solution of Am ions in a reflux device for heating and evaporation until the solution is dried, and then adding 1mL of nitric acid solution with the concentration of 0.1mol/L into the system to obtain Am (NO) for subsequent experiments3)3And (3) solution.
(6) Similar to step (6) of example 1, the recovery rate of Am element in example 2 was 90% by detection calculation. Am (NO) obtained3)3Am (NO) in solution3)3Am (NO3)3The mass percentage of the solute in the solution was 99.9%.
Example 3
(1) Providing americium-containing waste: radioactive waste solid-liquid mixture generated in the process of synthesizing metal organic framework material of Am. The Am (NO) contained in the americium-containing waste3)3Mellitic acid ligand (mel) and Am-mel solid crystals.
(2) Adding 1.5mL of 5mol/L hydrochloric acid solution into 2mL of the americium-containing waste, heating to 180 ℃ in a reaction kettle, and carrying out heat preservation treatment for 3 days to obtain a uniform americium-containing solution.
(3) And then putting the americium-containing solution into a reflux device, heating and evaporating until the solution is dried, and then adding 5mL of 1mol/L nitric acid solution to obtain an americium-containing nitric acid solution.
(4) Filling cation exchange resin amide (DGA) resin (2 g; 100-200 meshes) into 10mL of polytetrafluoroethylene adsorption column to form a cation exchange column; using 30mL of HCl solution with the concentration of 0.5mol/L as eluent, dividing the HCl solution into 3 parts equally, and pre-leaching the cation exchange resin in the cation exchange column for three times; then, a dynamic adsorption experiment is carried out, when in adsorption treatment, the flow rate of nitric acid liquid containing americium is controlled to be 1mL/min, and the dynamic adsorption contact time of the nitric acid liquid containing americium and cation exchange resin is controlled to be 5 minutes; then using 30mL of HCl solution with the concentration of 1mol/L as eluent, dividing the HCl solution into 6 parts, and pre-eluting the cation exchange resin adsorbed with Am for 6 times; and finally, 5mL of hydrochloric acid solution with the concentration of 5mol/L is used as eluent and is divided into 5 parts, the cation exchange resin after pre-elution is subjected to desorption for 5 times, and the flow rate of the eluent is controlled to be 0.5mL/min in the desorption process, so that the pure hydrochloric acid solution of Am ions is obtained.
(5) Placing the obtained hydrochloric acid solution of Am ions in a reflux device for heating and evaporation until the solution is dried, and then adding 1mL of nitric acid solution with the concentration of 0.1mol/L into the system to obtain Am (NO) for subsequent experiments3)3And (3) solution.
(6) Similar to step (6) of example 1, the recovery rate of Am element in example 3 was 88% by detection calculation. Am (NO) obtained3)3Am (NO) in solution3)3Am (NO)3)3The mass percentage of the solute in the solution was 99.9%.
Example 4
Example 4 is the same as example 1, except that: and (3) heating and evaporating the americium-containing solution in a reflux device until the solution is dried, and then adding 5mL of nitric acid solution with the concentration of 3 mol/L.
The remaining steps and conditions were the same as in example 1.
The recovery rate of Am element in example 4 is 91% by detection calculation. Am (NO) obtained3)3Am (NO) in solution3)3Am (NO)3)3The mass percentage of the solute in the solution was 99.9%.
Example 5
Example 5 is the same as example 1, except that: in the desorption step in the step (4), a hydrochloric acid solution of 7mol/L is used as an eluent.
The remaining steps and conditions were the same as in example 1.
The recovery rate of Am element in example 5 is 89% by detection calculation. Am (NO) obtained3)3Am (NO) in solution3)3Am (NO)3)3The mass percentage of solute in the solution is99.9％。
Comparative example 1
(1) Providing americium-containing waste: radioactive waste solid-liquid mixture generated in the process of synthesizing metal organic framework material of Am. The Am (NO) contained in the americium-containing waste3)3Mellitic acid ligand (mel) and Am-mel solid crystals.
(2) Adding 1.5mL of 5mol/L hydrochloric acid solution into 2mL of the americium-containing waste, heating to 180 ℃ in a reaction kettle, and carrying out heat preservation treatment for 3 days to obtain a uniform americium-containing solution.
(3) And then putting the americium-containing solution into a reflux device, heating and evaporating until the solution is dried, and then adding 5mL of 1mol/L nitric acid solution to obtain an americium-containing nitric acid solution.
(4) Filling ion exchange resin D113 resin (2 g; 100-200 meshes) into a 10mL adsorption column made of polytetrafluoroethylene to form a cation exchange column; using 30mL of HCl solution with the concentration of 0.5mol/L as eluent, dividing the HCl solution into 3 parts equally, and pre-leaching the cation exchange resin in the cation exchange column for three times; then, a dynamic adsorption experiment is carried out, when in adsorption treatment, the flow rate of nitric acid liquid containing americium is controlled to be 1mL/min, and the dynamic adsorption contact time of the nitric acid liquid containing americium and cation exchange resin is controlled to be 5 minutes; then using 30mL of HCl solution with the concentration of 1mol/L as eluent, dividing the HCl solution into 6 parts, and pre-eluting the cation exchange resin adsorbed with Am for 6 times; and finally, 5mL of hydrochloric acid solution with the concentration of 5mol/L is used as eluent and is divided into 5 parts, the cation exchange resin after pre-elution is subjected to desorption for 5 times, and the flow rate of the eluent is controlled to be 0.5mL/min in the desorption treatment process, so that the pure hydrochloric acid solution of Am ions is obtained.
(5) Placing the obtained hydrochloric acid solution of Am ions in a reflux device for heating and evaporation until the solution is dried, and then adding 1mL of nitric acid solution with the concentration of 0.1mol/L into the system to obtain Am (NO) for subsequent experiments3)3And (3) solution.
(6) Further detection of Am (NO)3)3Am (NO) in solution3)3To obtain the molar amount of the recovered Am element, and the recovered Am elementThe percentage of the molar quantity of Am element in the americium-containing waste is the recovery rate of Am element. Specifically, the recovery rate of Am element in comparative example 1 is 30% by detection calculation.
Comparative example 2
Comparative example 2 in step (2), a 5mol/L hydrochloric acid solution was replaced with a 5mol/L sulfuric acid solution, and then the mixture was heated to 180 ℃ in a reaction vessel and heat-preserved for 3 days, as a result, it was found that: the residue is present at the bottom of the reaction kettle, the solid waste cannot be completely dissolved, the dissolution efficiency is below 50%, and the subsequent steps are difficult to perform.
The above examples only show some embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. A method for recovering americium-containing waste, characterized by comprising the steps of:
dissolving americium-containing waste in a hydrochloric acid liquor to obtain an americium-containing solution, said americium-containing waste containing americium elements and complexes thereof;
evaporating and drying the americium-containing solution, and adding a nitric acid solution to obtain an americium-containing nitric acid solution;
and adsorbing the nitric acid solution containing americium by using ion exchange resin, and desorbing to obtain an americium ion solution, wherein an active group of the ion exchange resin comprises any one of a sulfonic group, a phosphonic group or an amide group.
2. A process as claimed in claim 1, characterised in that the active groups of the ion-exchange resin are sulphonic acid groups.
3. The method of recovering americium-containing waste of claim 1, wherein said ion exchange resin is a styrene-divinylbenzene copolymer containing sulfonic acid groups.
4. A method for recovering americium-containing waste as defined in any one of claims 1 to 3, wherein the step of adsorption treatment employs dynamic adsorption; in the step of adsorption treatment, the flow rate of the americium-containing nitric acid solution is 0.5mL/min to 1.5 mL/min.
5. The method of recovering americium-containing waste of claim 4, wherein the dynamic adsorption contact time of the americium-containing nitric acid solution with the ion exchange resin is between 3 minutes and 10 minutes.
6. A method as claimed in any one of claims 1 to 3, wherein, in the desorption step, a hydrochloric acid solution having a concentration of 4mol/L to 7mol/L is used as the eluent, and the flow rate of the eluent is 0.3mL/min to 0.7 mL/min.
7. A process for the recovery of americium-containing waste as claimed in claim 6, further comprising, after said step of adsorption treatment and before said step of desorption, the steps of:
and pre-eluting the ion exchange resin after adsorption treatment by adopting hydrochloric acid solution with the concentration of 0.5-1.5 mol/L.
8. The method for recovering americium-containing waste of claim 7, wherein the desorption step is repeated 3-6 times; and/or
And repeating the pre-elution step for 3-6 times.
9. A method for recovering americium-containing waste as defined in any one of claims 1 to 3, further comprising the steps of:
evaporating the americium ion solution to dryness, and adding nitric acid solution to obtain Am (NO)3)3And (3) solution.
10. A method for recovering americium-containing waste as defined in any one of claims 1 to 3, wherein a hydrochloric acid solution used in the step of dissolving the americium-containing waste in a hydrochloric acid solution has a concentration of 4mol/L to 7 mol/L; the volume ratio of the americium-containing waste to the hydrochloric acid solution is 1 (0.1-1); and/or
The temperature of the step of dissolving americium-containing waste in hydrochloric acid liquor is between 180 and 210 ℃.
11. A method for recovering americium-containing waste as defined in any one of claims 1 to 3, wherein the concentration of the nitric acid solution is between 1mol/L and 3 mol/L.
12. A method of recovering americium-containing waste as defined in any one of claims 1 to 3, further comprising, before the step of adsorption treatment, the step of:
adopting hydrochloric acid solution with the concentration of 0.3-0.7 mol/L to carry out pre-washing treatment on the ion exchange resin.
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