CN113667843B - Method for separating thorium by using eutectic solvent - Google Patents
Method for separating thorium by using eutectic solvent Download PDFInfo
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- CN113667843B CN113667843B CN202010403860.5A CN202010403860A CN113667843B CN 113667843 B CN113667843 B CN 113667843B CN 202010403860 A CN202010403860 A CN 202010403860A CN 113667843 B CN113667843 B CN 113667843B
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- thorium
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- eutectic solvent
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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
- C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
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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 the field of separation of thorium and rare earth elements, and discloses a method for extracting and separating thorium by using a eutectic solvent. Comprises the following steps: step (1): mixing organic acid and hydroxyl compound to prepare a eutectic solvent; step (2): mixing the eutectic solvent and the thorium-containing solution, and separating to obtain an organic phase containing thorium ions; and (3): and performing back extraction on the organic phase containing the thorium ions to obtain an extracting solution containing the thorium ions. The eutectic solvent synthesized by the method has the advantages of wide raw material source, no toxicity, low viscosity, no need of using volatile toxic organic solvent in the extraction process, low acidity in thorium extraction, easy back extraction, great reduction in acid consumption, high extraction selectivity and stable property.
Description
Technical Field
The invention belongs to the field of rare earth separation, and particularly relates to a method for separating thorium by using a eutectic solvent.
Background
Thorium belongs to actinides, has radioactivity, and is one of the important elements developing in nuclear energy. Thorium is applied to nuclear reaction and nuclear industry, has the advantage of lower radioactivity than uranium, has higher radiation steric hindrance, is more stable in chemical property, is more abundant than uranium in reserve, develops and utilizes thorium resources, even uses thorium to replace uranium, and is regarded as a new choice for future civil nuclear energy development by many countries. Therefore, the development of thorium-based energy has become an urgent and important task. The thorium resource reserves of baotobaiyuneboite in China are rich, the thorium resource reserves of Sichuan crown and Shandong Weishan are also quite rich, and the reserves of thorium in bastnaesite are about 5 percent. A certain amount of thorium resources are also associated in the ionic rare earth ore in south China. Liquid-liquid extraction is commonly used for separating thorium from other rare earth elements, and has the main advantages of continuous operation, low cost, good separation effect and easy automatic control. Researchers have developed extractants with different structures and different functional groups for extracting and separating thorium and rare earth, such as organic phosphonic (phosphorus) acid, neutral phosphine and primary amine extractants. However, there are many disadvantages, such as the need for organic phosphonic (phosphoric) acid, the need for neutral extractant to achieve effective separation of thorium from rare earth at higher acidity, the weak loading capacity of neutral extractant and the tendency to produce emulsification, and the need for dilution with volatile organic solvent such as kerosene in the conventional extractant, which increases the production cost undoubtedly, and the toxic volatile organic solvent is harmful to the body of the production personnel.
Disclosure of Invention
In order to improve the technical problem, the invention provides a method for separating thorium by using a eutectic solvent, which comprises the following steps:
step (1): mixing organic acid and hydroxyl compound to prepare a eutectic solvent;
step (2): mixing the deep eutectic solvent and a thorium-containing solution, and separating to obtain a thorium ion-containing organic phase;
and (3): and performing back extraction on the organic phase containing the thorium ions to obtain an extracting solution containing the thorium ions.
According to an embodiment of the present invention, the organic acid in step (1) may be a fatty acid, such as may be a medium or long chain saturated or unsaturated fatty acid, such as may be one, two or more of capric acid, oleic acid, caprylic acid, lauric acid, myristic acid, linoleic acid, linolenic acid, arachidonic acid, palmitic acid, stearic acid.
According to an embodiment of the present invention, the hydroxyl compound in step (1) may be one, two or more of menthol, thymol, terpineol, decanol, lauryl alcohol, tetradecanol, cetyl alcohol, and stearyl alcohol.
According to an embodiment of the invention, the molar ratio of the organic acid to the hydroxy compound in step (1) may be 1.
According to an embodiment of the present invention, the mixing temperature at the mixing in step (1) may be 40 to 80 ℃, for example 50 to 60 ℃, exemplary 50 ℃.
According to an embodiment of the present invention, the thorium-containing solution in step (2) may be a thorium-containing rare earth ore leachate, for example, a leachate of thorium-containing radioactive waste residues; the leachate can be obtained by leaching with acid; the acid may be one, two or more of hydrochloric acid, nitric acid or sulfuric acid;
according to an embodiment of the invention, the pH of the thorium containing solution in step (2) may be between 2 and 5, for example between 2 and 4, exemplarily 3;
according to an embodiment of the present invention, the method of separating in step (2) may be extraction; the extraction temperature may be 25 to 50 ℃, for example 30 to 40 ℃.
According to an embodiment of the present invention, the organic phase obtained in step (2) is washed in step (3) before stripping. The washing may be performed with an acid solution; the acid may be one, two or more of hydrochloric acid, nitric acid, formic acid, acetic acid and lactic acid.
According to an embodiment of the present invention, the pH of the acid solution in step (3) may be 1 to 3, preferably 2.
According to an embodiment of the present invention, the stripping in the step (3) may be performed using an acid solution; the acid may be selected from one, two or more of hydrochloric acid, nitric acid, formic acid, acetic acid and lactic acid.
According to an embodiment of the present invention, the concentration of the acid solution used for the stripping in step (3) may be 0.5 to 12mol/L, such as 0.5 to 6mol/L, further such as 0.5 to 2mol/L, and is exemplary 0.5mol/L.
According to an embodiment of the present invention, the temperature at the time of the stripping in the step (3) may be 25 to 100 ℃, for example, 25 to 50 ℃, and further for example, 25 to 30 ℃.
According to an embodiment of the present invention, step (3) may also obtain a regenerated eutectic solvent. The obtained regenerated eutectic solvent can be recycled and used in the step (2).
Advantageous effects
The method has the advantages of no need of using volatile toxic organic solvent in the extraction process, raw material saving, low cost, low acidity in thorium extraction, easy back extraction, greatly reduced acid consumption, high extraction selectivity, stable property, recycling use, higher extraction rate and high purity of the obtained thorium solution.
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.
Examples
The thorium-containing radioactive waste residues are taken from a rare earth mine of certain ionic type in Jiangxi Ganzhou, leaching is carried out by using nitric acid to obtain a leaching solution, the pH value is adjusted to 3, and the content of each element in the thorium-containing radioactive waste residue leaching solution is shown in a table 1. Stirring capric acid and menthol at a molar ratio of 1. By adopting an oil-water ratio of 1. The separation coefficient of thorium and rare earth reaches 3223, and the separation effect of thorium and other elements is good. The regenerated eutectic solvent decanoic acid-menthol can still keep good stability after being recycled for 5 times.
TABLE 1 elemental composition (mg/L) of thorium-containing radioactive waste leachate
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 (25)
1. A process for the separation of thorium using a eutectic solvent, comprising the steps of:
step (1): mixing organic acid and hydroxyl compound to prepare a eutectic solvent;
step (2): mixing the deep eutectic solvent and a thorium-containing solution, and separating to obtain a thorium ion-containing organic phase;
and (3): performing back extraction on the organic phase containing thorium ions to obtain an extracting solution containing thorium ions;
the organic acid in the step (1) is one or two or more of capric acid, oleic acid, caprylic acid, lauric acid, myristic acid, linoleic acid, linolenic acid, arachidonic acid, palmitic acid and stearic acid;
the hydroxyl compound in the step (1) is one or two or more of menthol, thymol, terpineol, decanol, lauryl alcohol, tetradecanol, hexadecanol and stearyl alcohol.
2. The method according to claim 1, wherein the molar ratio of the organic acid to the hydroxy compound in step (1) is 1.
3. The method according to claim 1, wherein the molar ratio of the organic acid to the hydroxyl compound in step (1) is 1.
4. The method according to claim 1, wherein the mixing temperature in the mixing in the step (1) is 40 to 80 ℃.
5. The method according to claim 1, wherein the mixing temperature in the mixing in the step (1) is 50 to 60 ℃.
6. The process according to claim 1, wherein the thorium-containing solution in step (2) is a thorium-containing rare earth ore leachate.
7. A process according to claim 1, characterized in that said thorium-containing solution in step (2) is a leachate of radioactive thorium-containing waste residues.
8. A method according to claim 6, wherein the leach solution is a leach solution obtained by leaching with acid.
9. The method of claim 8, wherein the acid is one, two or more of hydrochloric acid, nitric acid, or sulfuric acid.
10. The method as claimed in claim 1, wherein the pH value of the thorium-containing solution in the step (2) is 2 to 5.
11. The process according to claim 1, characterized in that the pH value of the thorium-containing solution in step (2) is between 2 and 4.
12. The method according to claim 1, wherein the separation method in step (2) is extraction; the extraction temperature is 25 to 50 ℃.
13. The method according to claim 1, wherein the separation method in step (2) is extraction; the extraction temperature is 30 to 40 ℃.
14. The method according to claim 1, wherein the organic phase obtained in step (2) is washed before the stripping in step (3).
15. The method of claim 14, wherein the washing is performed with an acid solution; the acid is one, two or more of hydrochloric acid, nitric acid, formic acid, acetic acid and lactic acid.
16. The method of claim 15, wherein the acid solution has a pH of 1 to 3.
17. The method of claim 15, wherein the acid solution has a pH of 2.
18. The method according to claim 1, wherein the back extraction in step (3) is performed using an acid solution; the acid is selected from one, two or more of hydrochloric acid, nitric acid, formic acid, acetic acid and lactic acid.
19. The method as claimed in claim 18, wherein the concentration of the acid solution is 0.5 to 12 mol/L.
20. The method of claim 18, wherein the acid solution has a concentration of 0.5 to 6 mol/L.
21. The method of claim 18, wherein the acid solution has a concentration of 0.5 to 2 mol/L.
22. The process according to claim 1, wherein the temperature at the stripping in the step (3) is 25 to 100 ℃.
23. The method according to claim 1, wherein the temperature of the back extraction in the step (3) is 25 to 50 ℃.
24. The method according to claim 1, wherein the temperature of the back extraction in the step (3) is 25 to 30 ℃.
25. The method according to claim 1, characterized in that said step (3) also obtains a regenerated eutectic solvent; the obtained regenerated eutectic solvent can be recycled and used in the step (2).
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| Publication number | Priority date | Publication date | Assignee | Title |
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| GB968202A (en) * | 1960-04-04 | 1964-08-26 | Diamond Alkali Co | Improvements in or relating to metal oxide sols and silica sols |
| FR1337006A (en) * | 1961-10-11 | 1963-09-06 | Europ Pour Le Traitement Chimi | Process for the separation of pure plutonium, pure uranium and pure thorium from their impurities |
| DE1592415C3 (en) * | 1965-09-25 | 1976-01-02 | Gesellschaft Fuer Kernforschung Mbh, 7500 Karlsruhe | Process for the processing of irradiated nuclear fissile materials from the group uranium, plutonium, thorium |
| AU2001247956A1 (en) * | 2000-02-04 | 2001-08-14 | Commodore Separation Technologies, Inc. | Combined supported liquid membrane/strip dispersion processes and extractants |
| US7157061B2 (en) * | 2004-09-24 | 2007-01-02 | Battelle Energy Alliance, Llc | Process for radioisotope recovery and system for implementing same |
| CN101231899B (en) * | 2008-02-25 | 2012-07-04 | 中国疾病预防控制中心辐射防护与核安全医学所 | Magnetic particle extractive agent and method for isolating radionuclide |
| CN102994781B (en) * | 2012-12-18 | 2014-07-16 | 中国科学院长春应用化学研究所 | Method for separation and purification of thorium |
| CN106555054B (en) * | 2015-09-29 | 2019-08-13 | 中国科学院上海应用物理研究所 | A kind of separation and recovery method of thorium and uranium |
| JP6573115B2 (en) * | 2015-11-25 | 2019-09-11 | 国立研究開発法人日本原子力研究開発機構 | Amidated phosphate ester compound, extractant, and extraction method |
| CN106957966B (en) * | 2016-01-12 | 2019-03-26 | 厦门稀土材料研究所 | A method of recycling thorium and rare earth element from rare earth waste |
| EP3375895A1 (en) * | 2017-03-15 | 2018-09-19 | Fundación Tecnalia Research & Innovation | Extraction of rare earth elements with deep eutectic solvents |
| WO2019099859A1 (en) * | 2017-11-17 | 2019-05-23 | Ii-Vi Delaware, Inc. | Selective recovery of rare earth metals from an acidic slurry or acidic solution |
| KR101923384B1 (en) * | 2018-05-18 | 2018-11-29 | 한국지질자원연구원 | Selective extraction method of thorium using polymer alcohol and making method of thorium oxide therefrom |
| CN110184464B (en) * | 2019-04-30 | 2021-02-26 | 厦门稀土材料研究所 | Extraction separation method of thorium |
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