CN108866359B - Method for extracting actinide elements - Google Patents

Method for extracting actinide elements Download PDF

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CN108866359B
CN108866359B CN201810819009.3A CN201810819009A CN108866359B CN 108866359 B CN108866359 B CN 108866359B CN 201810819009 A CN201810819009 A CN 201810819009A CN 108866359 B CN108866359 B CN 108866359B
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actinides
solution
extracting
acid
actinide
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CN108866359A (en
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熊亮萍
吕开
古梅
杨楚汀
胡胜
李毅
吴奉承
韩军
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Institute of Nuclear Physics and Chemistry China Academy of Engineering Physics
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Institute of Nuclear Physics and Chemistry China Academy of Engineering Physics
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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
    • 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
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
    • C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
    • 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
    • C22B7/005—Separation by a physical processing technique only, e.g. by mechanical breaking
    • 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
    • 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

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Abstract

The invention discloses a method for extracting actinides, which adopts hafnium phosphate as an adsorbent to realize high-efficiency extraction of actinides in medium or strong acidity medium. The method for extracting the actinides can obviously reduce the generation amount of secondary waste, greatly simplifies the post-treatment process and obviously enhances the environmental friendliness; in addition, the adsorbent adopted by the method is easy to synthesize, has excellent acid resistance and irradiation resistance, and obviously improves the extraction efficiency of the actinide in moderate or strong acid solution. The method is within the acidity range of 0.01-5 mol/L, and the concentration of the acid in the solution is 10‑5g/mL actinide cation, the extraction efficiency is higher than 99 percent; for trace amounts239Pu and237np, the extraction efficiency can also reach more than 90%. The method for extracting the actinides has important application prospects in the fields of nuclear fuel circulation, radioactive waste liquid treatment and the like.

Description

Method for extracting actinide elements
Technical Field
The invention belongs to the technical field of nuclear fuel circulation and radioactive waste liquid treatment, and particularly relates to a method for extracting actinide elements.
Background
In the nuclear industry, it is known that,the effective extraction of actinides is a prerequisite for sustainable development of nuclear energy. At the front end of the nuclear fuel cycle, it is necessary to extract the actinides efficiently from the mineral or target in order to obtain usable nuclear fuel (for example235U、239Pu、232Th, etc.); at the back end of the nuclear fuel cycle, the actinides (such as Pu, Np, Am, etc.) in the spent fuel need to be fully recovered to reduce the radioactivity and chemical toxicity of the spent fuel and to improve the utilization rate of the nuclear fuel with limited reserves. In the treatment of radioactive waste liquids, the decontamination of actinides is essential in order to reduce the risks to the environment and to the organisms. In these processes, the medium is mostly a moderately or strongly acidic solution (acidity higher than 0.1 mol/L) in which the actinides are mainly present in cationic form.
At present, the method for extracting actinides from acidic solutions is mainly a solvent extraction method, an adopted extracting agent is an organic solvent containing P or N, for example, a typical spent fuel treatment process-PUREX (Plutonium URanium extraction) process adopts 30% of tributyl phosphate (TBP) -kerosene to recover U and Pu from a nitric acid medium, and on the basis, an improved TRUEX (TRansUranic extraction) process adds carbamyl phosphine oxide (CMPO) into the organic solvent to extract the minor actinides such as Np and Am and U, Pu at the same time. The method is mature, but still has some obvious disadvantages, such as large amount of generated secondary waste, easy formation of a third phase in an extraction system, influence on recovery efficiency, long time and high cost for post-treatment of a large amount of organic solvent, unfavorable environmental protection, poor radiation resistance of the organic solvent, and the like.
The solid phase extraction method adopts solid adsorbent to extract actinides, which can avoid the problems, the currently developed actinide solid adsorbent has functionalized zeolite, porous silicon, polymer resin, multi-walled carbon nano-tubes and the like, the adsorption of the materials on the actinides in the solution is mainly ion exchange effect, the materials have better adsorption performance on actinides cations under the weakly acidic condition (the pH value is more than or equal to 3), but with the increase of acidity, H in the solution+Increased concentration and participation in competitive adsorption, resulting in adsorption of actinide cationsCan be significantly reduced (most materials almost lose adsorption performance at pH < 2). However, the common spent fuel treatment or radioactive waste liquid is an acid solution with medium strength or strong strength, and under the condition, the adsorption performance of the adsorbents on actinide cations is poor, so that the adsorbents cannot be applied to the field.
Therefore, the development of an efficient and environment-friendly method for extracting actinides is urgently needed.
Disclosure of Invention
The invention aims to solve the technical problem of providing an extraction method of actinide elements.
The method for extracting actinides comprises the following steps:
a. adjusting the concentration range of inorganic acid in the solution containing the actinide elements to be 0.01-5 mol/L;
b. adding hafnium phosphate powder into the solution obtained in the step a, sealing, and continuously oscillating for 4-24 hours;
c. carrying out suction filtration;
d. drying for 6-48 h at 50-100 ℃.
The actinide comprises thorium, uranium, plutonium or neptunium, one or more of thorium, uranium, plutonium or neptunium, and the mass concentration of the actinide in the solution is more than or equal to 1 x 10-8g/mL。
The concentration of the inorganic acid in the step a is preferably within the range of 0.1-4 mol/L.
The inorganic acid in the step a comprises one of nitric acid, hydrochloric acid, sulfuric acid or perchloric acid.
The atomic ratio of the hafnium to the phosphorus in the hafnium phosphate powder in the step b is 1: 1-1: 5.
The ratio of the mass of the hafnium phosphate powder to the volume of the solution in the step b is 0.5-20 mg/mL.
The oscillation temperature range in the step b is 5-40 ℃.
The extraction method of actinides adopts hafnium phosphate as an adsorbent, which is a tetravalent metal-phosphonic acid framework material, wherein an inorganic metal center hafnium provides good chemical stability and radiation resistance, and three oxygen atoms in a phosphonic acid group have strong complexing ability and high selectivity on actinides cations. At different acidity, hafnium phosphate achieves adsorption of actinide cations by different mechanisms: in weak acid solution (≪ 1 mol/L), adsorption of actinides (i.e. ion exchange of protons of phosphorus hydroxyl groups P-OH with actinides) occurs mainly by the "ion exchange mechanism"; in moderately or strongly acidic solutions (> 1 mol/L), the actinides are adsorbed mainly by the "solvation mechanism" (i.e. the O atom in the P = O double bond is in coordination complex with the actinide). In addition, since the phosphonic acid groups have preferential selectivity for actinides cations, selective extraction of actinides cations can be achieved by adjusting the amount of adsorbent when other cations are present in solution at the same time.
Therefore, within the acidity range of 0.01 mol/L-5 mol/L, the method for extracting the actinides has high extraction efficiency and selectivity on the actinides: for a concentration of 10 in solution-5g/mL actinide cation, the extraction efficiency is higher than 99 percent; even at very low concentrations (trace amount,. about.10)-8g/mL) of239Pu and237np, the extraction efficiency can also reach more than 90%; and the actinide cations have a separation factor from other cations of above 200.
The method for extracting the actinides can obviously reduce the generation amount of secondary waste, greatly simplifies the post-treatment process and obviously enhances the environmental friendliness; in addition, the adsorbent adopted by the method is easy to synthesize, has excellent acid resistance and radiation resistance, and obviously improves the extraction efficiency of actinide cations in moderate or strong acid solution. The method for extracting the actinides has important application prospects in the fields of nuclear fuel circulation, radioactive waste liquid treatment and the like.
Drawings
Fig. 1 is a bar graph of the effect of selective extraction of actinides in embodiment 8 of the method for extracting actinides of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and examples.
All of the features disclosed in this specification, or all of the steps in any method or process so disclosed, may be combined in any combination, except combinations of features and/or steps that are mutually exclusive.
Any feature disclosed in this specification may be replaced by alternative features serving equivalent or similar purposes, unless expressly stated otherwise. That is, unless expressly stated otherwise, each feature is only an example of a generic series of equivalent or similar features.
The method for extracting actinides comprises the following steps:
a. adjusting the concentration range of inorganic acid in the solution containing the actinides to be 0.01-5 mol/L;
b. adding hafnium phosphate powder into the solution obtained in the step a, sealing, and continuously oscillating for 4-24 hours;
c. carrying out suction filtration;
d. drying for 6-48 h at 50-100 ℃.
The actinide comprises thorium, uranium, plutonium or neptunium, one or more of thorium, uranium, plutonium or neptunium, and the mass concentration of the actinide in the solution is more than or equal to 1 x 10-8g/mL。
The concentration of the inorganic acid in the step a is preferably within the range of 0.1-4 mol/L.
The inorganic acid in the step a comprises one of nitric acid, hydrochloric acid, sulfuric acid or perchloric acid.
The atomic ratio of the hafnium to the phosphorus in the hafnium phosphate powder in the step b is 1: 1-1: 5.
The ratio of the mass of the hafnium phosphate powder to the volume of the solution in the step b is 0.5-20 mg/mL.
The oscillation temperature range in the step b is 5-40 ℃.
Example 1
Will contain Th4+(concentration by mass is 1X 10)-5g/mL) to 0.01mol/L HNO3And adding 100 mg of hafnium phosphate HfP-1 (namely the atomic ratio of Hf to P is 1: 1) into 5 mL of the solution, sealing, continuously oscillating for 4h at 5-25 ℃, filtering, and drying for 6h at 50-70 ℃. The embodiment pairTh in solution4+The extraction efficiency of (3) was 99.4%.
Example 2
Will contain UO2 2+(concentration by mass is 1X 10)-5g/mL) to 0.1mol/L HNO3And adding 100 mg of hafnium phosphate HfP-2 (namely the atomic ratio of Hf to P is 1: 2) into 10mL of the solution, sealing, continuously oscillating for 10h at 10-30 ℃, filtering, and drying for 12h at 70-90 ℃. This example is for UO in solution2 2+The extraction efficiency of (3) was 99.9%.
Example 3
Will contain radioactivity239Pu (mass concentration of 1X 10)-8g/mL) to 4mol/L HNO3And (2) adding 20 mg of hafnium phosphate HfP-3 (namely the atomic ratio of Hf to P is 1: 3) into 5 mL of the solution, sealing, continuously oscillating for 24h at 20-30 ℃, filtering, and drying for 48h at 60-80 ℃. This example is for the amount of tracer in solution239The extraction efficiency of Pu is 92.3%.
Example 4
Will contain radioactivity237Np (mass concentration of 5X 10)-8g/mL) to 5mol/L HNO3Adding 10mg of hafnium phosphate HfP-5 (namely the atomic ratio of Hf to P is 1: 5) into 5 mL of the solution, sealing, continuously oscillating for 24h at 20-30 ℃, filtering, and drying for 24h at 50-60 ℃. This example is for the amount of tracer in solution237The extraction efficiency of Np was 90.9%.
Example 5
Will contain Th4+(the mass concentration is 3X 10)-6g/mL) of the solution is adjusted to 1mol/L of HCl medium, 10mg of hafnium phosphate HfP-4 (namely, the atomic ratio of Hf to P is 1: 4) is added into 20mL of the solution, the solution is sealed and continuously oscillated for 12 hours at the temperature of 25-40 ℃, and is filtered and dried for 12 hours at the temperature of 50-70 ℃. This example is for Th in solution4+The extraction efficiency of (3) was 97.1%.
Example 6
Will contain Th4+(the mass concentration is 2X 10)-5g/mL) was adjusted to 0.1mol/L HClO4Medium, to 10mL of this solution, 10 was addedmg hafnium phosphate HfP-4 (namely the atomic ratio of Hf to P is 1: 4), continuously oscillating for 24h at 10-25 ℃ after sealing, filtering, and drying for 24h at 80-100 ℃. This example is for Th in solution4+The extraction efficiency of (3) was 99.2%.
Example 7
Will contain Th4+(the mass concentration is 5X 10)-5g/mL) to 1mol/L H2SO4Adding 50 mg of hafnium phosphate HfP-3 (namely the atomic ratio of Hf to P is 1: 3) into 10mL of the solution, sealing, continuously oscillating for 24h at 10-30 ℃, filtering, and drying for 36 h at 50-70 ℃. This example is for Th in solution4+The extraction efficiency of (3) was 99.6%.
Example 8
Will contain Th4+、UO2 2+、Ce3+、Eu3+、Ho3+、Yb3+、Sr2+、Co2+、Cs+、Na+The solution of 10 kinds of cations is adjusted to 0.1mol/L HNO3Medium (wherein each cation has a mass concentration of 1X 10-5g/mL), adding 20 mg of hafnium phosphate HfP-4 (namely the atomic ratio of Hf to P is 1: 4) into 20mL of the solution, sealing, continuously oscillating for 10h at 15-35 ℃, filtering, and drying for 12h at 60-80 ℃. The results of this example are shown in FIG. 1 for Th in solution4+And UO2 2+The extraction efficiency of (a) was 99.3% and 99.8%, respectively.
The invention is not limited to the foregoing embodiments. The invention extends to any novel feature or any novel combination of features disclosed in this specification and any novel method or process steps or any novel combination of features disclosed.

Claims (7)

1. A method for extracting actinides, comprising the steps of:
a. adjusting the concentration range of inorganic acid in the solution containing the actinide elements to be 0.01-5 mol/L;
b. adding hafnium phosphate powder into the solution obtained in the step a, sealing, and continuously oscillating for 4-24 hours;
c. carrying out suction filtration;
d. drying for 6-48 h at 50-100 ℃.
2. The method for extracting actinides as claimed in claim 1, wherein: the actinide comprises thorium, uranium, plutonium or neptunium, one or more of thorium, uranium, plutonium or neptunium, and the mass concentration of the actinide in the solution is more than or equal to 1 x 10-8g/mL。
3. The method for extracting actinides as claimed in claim 1, wherein: the concentration range of the inorganic acid in the step a is 0.1-4 mol/L.
4. The method for extracting actinides as claimed in claim 1, wherein: the inorganic acid in the step a comprises one of nitric acid, hydrochloric acid, sulfuric acid or perchloric acid.
5. The method for extracting actinides as claimed in claim 1, wherein: the atomic ratio of the hafnium to the phosphorus in the hafnium phosphate powder in the step b is 1: 1-1: 5.
6. The method for extracting actinides as claimed in claim 1, wherein: the ratio of the mass of the hafnium phosphate powder to the volume of the solution in the step b is 0.5-20 mg/mL.
7. The method for extracting actinides as claimed in claim 1, wherein: the oscillation temperature range in the step b is 5-40 ℃.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088485A (en) * 1992-12-19 1994-06-29 布莱阿姆青年大学 Be used to remove the part on the solid carrier of being stated from that contains the aminoalkyl phosphonic acids of metal ion
CN101076868A (en) * 2003-11-20 2007-11-21 原子能委员会 Method for separating uranium (VI) and actinides (IV)and/or actinides (VI) and its application
WO2014031702A1 (en) * 2012-08-20 2014-02-27 University Of Maryland Polymers grafted with organic phosphorous compounds for extracting uranium from solutions
CN107352720A (en) * 2017-07-25 2017-11-17 西南科技大学 The processing method of uranium-bearing water body and except uranium agent

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1088485A (en) * 1992-12-19 1994-06-29 布莱阿姆青年大学 Be used to remove the part on the solid carrier of being stated from that contains the aminoalkyl phosphonic acids of metal ion
CN101076868A (en) * 2003-11-20 2007-11-21 原子能委员会 Method for separating uranium (VI) and actinides (IV)and/or actinides (VI) and its application
WO2014031702A1 (en) * 2012-08-20 2014-02-27 University Of Maryland Polymers grafted with organic phosphorous compounds for extracting uranium from solutions
CN107352720A (en) * 2017-07-25 2017-11-17 西南科技大学 The processing method of uranium-bearing water body and except uranium agent

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型吸附剂偏磷酸铈对铀酰的吸附性能研究;董韬等;《离子交换与吸附》;20161020;第32卷(第05期);461-471 *

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