CN113667843A - Method for separating thorium by using eutectic solvent - Google Patents
Method for separating thorium by using eutectic solvent Download PDFInfo
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- CN113667843A CN113667843A CN202010403860.5A CN202010403860A CN113667843A CN 113667843 A CN113667843 A CN 113667843A CN 202010403860 A CN202010403860 A CN 202010403860A CN 113667843 A CN113667843 A CN 113667843A
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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
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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 with 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. 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 from 1:10 to 10:1, for example from 1:5 to 5:1, exemplarily 1: 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 2 to 5, such as 2 to 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 in the stripping in the 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 an exemplary concentration is 0.5 mol/L.
According to an embodiment of the present invention, the temperature during 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 1:1 at 50 deg.C until a clear transparent liquid is obtained, and cooling to room temperature. The oil-water ratio is 1:1, the extraction rate of thorium is 96.4% after single-stage extraction separation, a loaded organic phase is subjected to 1-stage washing by using a nitric acid aqueous solution with the pH value of 2, then, the loaded organic phase is subjected to back extraction by using a nitric acid aqueous solution with the concentration of 0.5mol/L, the oil-water ratio is 1:1, the back extraction rate is 99.8% after single-stage back extraction, and the thorium solution with the purity of 94.2% is obtained and only contains a small amount of calcium, magnesium and aluminum impurity elements. 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 (10)
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): and performing back extraction on the organic phase containing the thorium ions to obtain an extracting solution containing the thorium ions.
2. The method according to claim 1, wherein the organic acid in step (1) is a fatty acid, such as a medium or long chain saturated or unsaturated fatty acid, such as 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.
3. The method according to claim 1 or 2, wherein the hydroxyl compound in step (1) is one, two or more of menthol, thymol, terpineol, decanol, lauryl alcohol, tetradecanol, cetyl alcohol, stearyl alcohol.
4. A process according to any one of claims 1 to 3, wherein the molar ratio of the organic acid to the hydroxy compound in step (1) is from 1:10 to 10:1, such as from 1:5 to 5: 1;
preferably, the mixing temperature in the mixing in step (1) is 40 to 80 ℃, for example 50 to 60 ℃.
5. A process according to any one of claims 1 to 4, wherein the thorium-containing solution in step (2) is a thorium-containing rare earth ore leachate, such as a thorium-containing radioactive waste residue leachate;
preferably, the leachate is obtained by leaching with acid;
preferably, the acid is one, two or more of hydrochloric acid, nitric acid or sulfuric acid.
6. A process according to any one of claims 1 to 5, characterized in that the pH of said thorium containing solution in step (2) is comprised between 2 and 5, such as between 2 and 4;
preferably, the method of separation in step (2) is extraction; the extraction temperature is 25-50 ℃, for example 30-40 ℃.
7. The process according to any one of claims 1 to 6, wherein the organic phase obtained in step (2) is washed before the stripping in step (3);
preferably, 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.
8. The process according to any one of claims 1 to 7, wherein the pH of the acid solution in step (3) is 1 to 3, preferably 2;
preferably, the back extraction in the step (3) is performed by 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.
9. The process according to any one of claims 1 to 8, wherein the concentration of the acid solution used in the stripping in step (3) is 0.5 to 12mol/L, such as 0.5 to 6mol/L or 0.5 to 2 mol/L;
preferably, the temperature during the back extraction in step (3) is 25-100 ℃, for example, 25-50 ℃ or 25-30 ℃.
10. The method according to any one of claims 1 to 9, wherein step (3) further obtains a regenerated eutectic solvent; the obtained regenerated eutectic solvent can be recycled and used in the step (2).
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