CN113713788B - Intercalation type manganese thiophosphite material and preparation method and application thereof - Google Patents

Abstract

The application discloses insertion layer type manganese thiophosphite material, insertion layer type manganese thiophosphite material molecular formula is G _2x Mn _1‑x PS ₃ ·[H ₂ O] _y (ii) a Wherein, the object cation G is selected from at least one of ammonium ions, protonated organic amine cations and alkali metal ions; x is more than or equal to 0.2 and less than or equal to 0.3, and y is more than or equal to 0 and less than or equal to 2. In the application, the insertion type manganese thiophosphite is used as an adsorbent to treat uranium in a water body, so that the insertion type manganese thiophosphite and the adsorbent are contacted for a certain time to complete the adsorption of the uranium; mixing the intercalation manganese thiophosphite with Sm ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ The uranium solution of the plasma interference ions is mixed, so that the selective removal of uranium by the adsorbent can be realized.

Description

Intercalation type manganese thiophosphite material and preparation method and application thereof

Technical Field

The invention relates to the technical field of uranium-containing wastewater treatment, and particularly relates to an intercalation type manganese thiophosphite material as well as a preparation method and application thereof.

Background

With the increasing depletion of fossil energy, nuclear energy is receiving attention due to its characteristics of sustainability, high efficiency, cleanliness, and the like. By the end of 2019, 443 nuclear reactors were operating around the world and 54 nuclear reactors were under construction. The strategic resource uranium (U) is the primary raw material used by the nuclear industry. With the rapid development of nuclear power worldwide, the demand for uranium consumption continues to increase. This phenomenon may have two major adverse effects. On the one hand, the scarcity of uranium resources will adversely affect the development of the nuclear industry. On the other hand, a large amount of uranium-containing wastewater is generated in the whole nuclear fuel circulation and spent fuel post-treatment processes, and uranium is used as a long-life radioactive element, has high radiotoxicity and chemical toxicity, and is very easy to cause serious damage to organisms when released into the environment. It has been shown that once uranium is taken into the body, it is difficult to remove it, and the alpha rays generated by its fission can cause long-term, persistent irradiation damage to cells, dna and other biological macromolecules, inducing their malignant mutations until cell death or disease. Therefore, it is necessary to enrich, concentrate and recover uranium in uranium-containing wastewater, which is not only beneficial to the sustainable development of nuclear power and the recycling of resources, but also beneficial to environmental protection and human health.

At present, the purification treatment method of uranium-containing wastewater mainly comprises solvent extraction, chemical precipitation, membrane filtration, chemical reduction, adsorption/ion exchange and the like. Among them, the adsorption/ion exchange method has attracted much attention because of its simple operation, low cost and high efficiency. Heretofore, many adsorbents, such as clay minerals, zeolites, metal oxides, modified graphene oxides, modified activated carbons, silicon-based materials, metal organic frameworks, and the like, have been studied to enrich uranium in water bodies. However, these existing materials have more or less drawbacks, such as expensive raw materials for synthesis, low adsorption capacity, high influence of salt content, poor cyclic regeneration capability, etc. Therefore, the development of a method for enriching and recycling uranium from uranium-containing wastewater with low cost, high adsorption capacity, high selectivity and recyclable property is urgently needed.

Disclosure of Invention

According to one aspect of the present application, an intercalation-type manganese thiophosphite material is disclosed.

An insertion layer type manganese thiophosphite material, wherein the molecular formula of the insertion layer type manganese thiophosphite material is G _2x Mn _{1- x} PS ₃ ·[H ₂ O] _y ；

Wherein the guest cation G is at least one selected from ammonium ions, protonated organic amine cations and alkali metal ions; x is more than or equal to 0.2 and less than or equal to 0.3, and y is more than or equal to 0 and less than or equal to 2.

Alternatively, the guest cation G is located in MnPS ₃ Interlaminar to framework.

Optionally, G is an ammonium ion.

Alternatively, 0.22 ≦ x ≦ 0.25

Optionally, the intercalated manganese thiophosphite material is (NH) ₄ ) _0.48 Mn _0.76 PS ₃ ·H ₂ O。

According to another aspect of the application, a preparation method of the insertion-layer type manganese thiophosphite material is also provided, and comprises the following steps:

(a) Mixing manganese, phosphorus, sulfur and a chemical transport agent iodine, and heating and reacting under a vacuum condition to obtain manganese thiophosphite powder crystals;

(b) Adding the manganese thiophosphite powder crystal into a solution containing guest cations G, stirring for reaction, cleaning a reaction product, and drying to obtain the intercalation manganese thiophosphite.

Optionally, the heating reaction in the step (a) comprises the steps of heating at 650-700 ℃ for 45-55 h, cooling to 480-520 ℃ within 8-10 h, and naturally cooling to room temperature.

Optionally, the heating reaction process in the step (a) is to heat at a constant temperature of 670 ℃ for 48h, then cool to 500 ℃ within 9h, and then naturally cool to room temperature.

Optionally, the mixture containing manganese, phosphorus, sulfur and iodine as chemical transport agent contains 6-10 molar parts of manganese, 6-10 molar parts of phosphorus and 18-30 molar parts of sulfur.

Optionally, the mass ratio of manganese to iodine in the mixture containing manganese, phosphorus, sulfur and iodine as a chemical transport agent is 50-70: 1.

optionally, the solid-to-liquid ratio of the manganese thiophosphite powder crystal in the step (b) to the solution containing the guest cation G is 10-30 mg/mL, and the concentration of the guest cation G in the solution containing the guest cation G is 1-3 mol/L;

optionally, the solid-to-liquid ratio of the manganese thiophosphate powder crystal in the step (b) to the solution containing the guest cation G is 20mg/mL, and the concentration of the guest cation G in the solution containing the guest cation G is 2mol/L.

Optionally, the manganese thiophosphite powder crystal in the step b and the solution containing the guest cation G are stirred to react for 20-30 h.

Optionally, the manganese thiophosphate powder crystal in the step b is stirred and reacts with the solution containing the guest cation G for 24 hours.

According to a further aspect of the present application, there is provided the use of an intercalated manganese thiophosphite material for the enrichment and/or recovery of uranium in a body of water. The method has excellent adsorption capacity, rapid kinetic response and high selectivity for extracting uranium. The intercalation manganese thiophosphite has good acid and alkali resistance and irradiation resistance, and can elute the adsorbed uranium in an easy-to-operate and environment-friendly way, thereby realizing the recycling of the uranium and the cyclic regeneration of the adsorbent.

The application comprises the following steps:

and contacting the intercalation type manganese thiophosphite material with a uranium-containing solution, and adsorbing uranium in a water body by using the intercalation type manganese thiophosphite material.

Optionally, the uranium-containing solution comprises alkali metal ions and/or alkaline earth metal ions and/or rare earth ions;

optionally, the molar ratio of alkali metal ions and/or alkaline earth metal ions and/or rare earth ions to uranium in the uranium-containing solution is 31.48 to 1.22 × 10 ⁴ 。

Optionally, the separation factor of the uranium from alkali metal ions and/or alkaline earth metal ions and/or rare earth ions is greater than 100;

optionally, the uranium containing solution includes radioactive wastewater, uranium mine wastewater, uranium contaminated tap water and lake water.

Optionally, after the intercalation type manganese thiophosphite adsorbent is irradiated by high-dose beta rays and/or gamma rays, the uranium removal rate is not lower than 96%.

Optionally, the concentration of uranium in the uranium-containing solution is 1.03 to 1500ppm.

Optionally, the manganese thiophosphite of the intercalation type is stable in the range of pH 2.0 to 12.5, and the pH of the uranium-containing solution is 2.8 to 12.2.

Optionally, the pH of the uranium containing solution is any one of 2.8, 3, 3.5, 4, 4.5, 5, 6, 7, 8, 9, 10, 11, 12, 12.2 or a range between any two.

Optionally, the pH of the uranium-containing solution is 4 to 5;

optionally, the pH of the uranium containing solution is 4.2.

Optionally, the temperature for adsorbing uranium in the body of water is between 20 and 30 ℃.

Alternatively, the adsorption temperature is 25 ℃.

Optionally, the contacting is for a time of 3 to 24 hours.

Optionally, the time of contact is any of 3, 3.5, 4, 4.5, 5, 6, 8, 12, 16, 20, 24 or a range between any two.

Optionally, the intercalated manganese thiophosphite is contacted with a uranium containing solution to reach adsorption equilibrium within 3 hours. The method for enriching and recovering uranium in water has quick dynamic response, and can reach an equilibrium state within 3 hours when uranium is removed.

Optionally, 8-12 mg of the intercalation-type manganese thiophosphite material is added to each 10ml of uranium-containing solution.

Optionally, the application further comprises the steps of:

and (3) immersing the intercalated manganese thiophosphite material after adsorption into an inorganic salt solution, eluting uranium, and recycling the intercalated manganese thiophosphite material.

The intercalation manganese thiophosphite treated by the aqueous solution of inorganic salt is used for the enrichment and/or recovery of uranium again. The method for enriching and recycling uranium can realize the cyclic regeneration of the inserted manganese thiophosphite by an easy-to-operate and environment-friendly method, and utilizes NH ₄ And the inorganic salt solution such as Cl can completely elute and recover uranium enriched by the adsorbent.

The beneficial effect that this application can produce includes:

1) According to the method for efficiently and selectively enriching, separating and recycling uranium in the water body by using the recyclable insertion type manganese thiophosphite adsorbent, the insertion type manganese thiophosphite is used as the adsorbent to treat the uranium in the water body, and the insertion type manganese thiophosphite and the adsorbent are contacted for a certain time to complete the adsorption of the uranium; mixing the intercalation manganese thiophosphite with Sm ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ Uranium solution mixing of plasma interference ions can realize selection of uranium by the adsorbentAnd (5) sex elimination.

2) The method for enriching and recycling uranium provided by the application has high selectivity to uranium under the condition that uranium coexists with one or more ions of various ions such as alkali metal ions, alkaline earth metal ions, transition metal ions, rare earth ions and carbonate ions: under the environment of tap water and lake water polluted by uranium, the removal rate of uranium reaches 93.29 percent and 95.67 percent respectively; 31.48 to 1.22X 10 in the presence of alkali metal ions and/or alkaline earth metal ions and/or rare earth ions in excess ⁴ Selectively adsorbing uranium in Na in aqueous solution ⁺ 、Ca ²⁺ 、Eu ³⁺ The uranium removal rates of the ions existing independently are respectively as high as 95.00%, 93.68% and 90.82%, and the separation factor SF _U/Na 、SF _U/Ca 、SF _U/Eu Up to 3832, 254, 171, respectively; at 145ppm HCO ₃ ^- The uranium can be efficiently removed in the excessive water solution, and the uranium removal rate is up to 93.79%; at Sm ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ In the uranium solution with coexisting ions, the removal rate of uranium reaches up to 90.82 percent; at Sm ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ 、La ³⁺ 、Co ²⁺ 、Ni ²⁺ In the uranium solution with coexisting ions, the removal rate of uranium is as high as 74.38%.

3) The method for enriching and recovering uranium provided by the application has excellent irradiation resistance, uranium can be enriched after irradiation of high-intensity beta or gamma rays (100 kGy beta, 200kGy beta, 100kGy gamma and 200kGy gamma), and the removal rates are respectively as high as 98.47%, 97.93%, 96.98% and 96.98% when the initial concentration of the solution is 12.06 ppm.

Drawings

FIG. 1 is transmission electron microscope and selected area electron diffraction patterns of (a) manganese thiophosphite intercalation type and (b) uranium adsorption type.

FIG. 2 shows the adsorption kinetics of intercalated manganese thiophosphite on uranium.

FIG. 3 (a) shows an isothermal adsorption model of uranium by intercalated manganese thiophosphites; (b) The corresponding distribution coefficient and removal rate results for different initial uranium concentrations.

FIG. 4 shows the insertion manganese thiophosphite at different molar ratios Na/U (a), ca/U (b), eu/U (c) and 145mg/L HCO ₃ ^- (d) And (5) obtaining the distribution coefficient and the removal rate of uranium.

FIG. 5 (a) shows the result of removing uranium and various competitive ions from the intercalation manganese thiophosphite in the coexisting solution of various metal ions; (b) As a result of the removal of uranium and various competing ions in uranium contaminated tap water and lake water.

FIG. 6 shows the results of partition coefficient and removal rate of intercalated manganese thiophosphites for uranium over a wide pH range.

FIG. 7 is a comparison graph (a) of X-ray powder diffraction before and after irradiation of the insertion-type manganese thiophosphite and a comparison result (b) of the removal rate of uranium.

Fig. 8 shows the results of uranium removal rate of the intercalated manganese thiophosphite in five adsorption-elution cycles.

FIG. 9 shows the results of X-ray energy spectrum analysis after the first round (a) and the fifth round (b) of adsorption-elution cycles of intercalated manganese thiophosphites.

FIG. 10 is a scanning electron micrograph of the fifth round of adsorption-elution cycles.

Detailed Description

The present application will be described in detail with reference to examples, but the present application is not limited to these examples.

Unless otherwise specified, the raw materials and the like referred to in the examples of the present application were purchased commercially.

The analytical methods in the examples of the present application are as follows:

inductively coupled plasma mass spectrometry (ICP-MS) and inductively coupled plasma emission spectroscopy (ICP-OES) were performed on XSerise II and Thermo 7400 devices, respectively.

X-ray energy spectroscopy (EDS) and Scanning Electron Microscopy (SEM) were performed on a JEOL JSM-6700F apparatus.

Transmission Electron Microscopy (TEM) and Selected Area Electron Diffraction (SAED) were performed on a FEI Tecnai G2F 20 instrument.

MiniFlex by Rigaku corporation at 30kV and 15mA for X-ray powder diffractometer phase analysis (PXRD)On a II-ray diffractometer, cu target, ka radiation source

In the embodiment of the application, the distribution coefficient is calculated by the following method:

in the examples of the present application, the separation factor is calculated by:

in the embodiment of the application, the removal rate is calculated by the following method:

in the above formula, C ₀ And C _e Respectively representing the initial concentration and the equilibrium concentration of uranium solution, K _d ^A And K _d ^B Representing the partition coefficients of a and B ions, respectively.

Example 1 preparation and structural characterization of intercalated manganese thiophosphite

Mixing and grinding high-purity manganese powder (8 mmol), red phosphorus (8 mmol) and sublimed sulfur (24 mmol) according to a molar ratio of 1. 400mg of the material is taken, ground and sieved by a 200-mesh sieve, and then 20mL of 2mol/L NH is poured into the material ₄ And (3) stirring the mixture for 24 hours at room temperature in a Cl aqueous solution, washing the mixture for several times by using deionized water and ethanol in sequence, and drying the mixture in vacuum at the temperature of 50 ℃ to obtain the intercalation manganese thiophosphite.

FIG. 1 (a) is a transmission electron micrograph and a selected area electron diffraction pattern of the synthesized intercalated manganese thiophosphite. The intercalation type manganese thiophosphite material has two morphologies, except that the flaky morphology of the main body is maintained, the surface becomes rough and uneven, and has a typical nanorod morphology.

Example 2

400mg of the dark green manganese thiophosphite powder crystal obtained in example 1 was ground and sieved with a 200-mesh sieve, and then 20mL of 2mol/L (CH) powder was poured ₃ ) ₄ And (3) stirring the mixture for 24 hours at room temperature in an NCl aqueous solution, washing the mixture for several times by using deionized water and ethanol in sequence, and drying the mixture in vacuum at 50 ℃ to obtain the intercalation manganese thiophosphite.

Example 3

400mg of the dark green manganese thiophosphite powder crystal obtained in example 1 was ground and sieved with a 200-mesh sieve, and then 20mL of 2mol/L (C) solution was poured ₂ H ₅ ) ₄ And (3) stirring the mixture for 24 hours at room temperature in an NCl aqueous solution, washing the mixture for several times by using deionized water and ethanol in sequence, and drying the mixture in vacuum at the temperature of 50 ℃ to obtain the intercalation manganese thiophosphite.

Example 4

Taking 400mg of the dark green manganese thiophosphite powder crystal obtained in the example 1, grinding and sieving the powder crystal by a 200-mesh sieve, then pouring the powder crystal into 20mL of 2mol/L KCl aqueous solution, stirring the solution for 24 hours at room temperature, washing the solution for several times by deionized water and ethanol in turn, and drying the solution in vacuum at 50 ℃ to obtain the intercalation manganese thiophosphite.

Example 5 adsorption kinetics testing of intercalated manganese thiophosphite enrichment and uranium recovery

The manganese thiophosphite intercalation form of example 1 is mixed with an initial uranium solution concentration, in terms of V (volume of solution): m (mass of exchanger) =1000mL/g, stirring at 25 ℃. Taking a small amount of supernatant liquid at certain intervals, and measuring the ion concentration by inductively coupled plasma mass spectrometry. The test result is shown in fig. 2, and the uranium adsorption of the intercalation manganese thiophosphite can reach the balance within 3 h.

Example 6 isothermal adsorption model testing of intercalated manganese thiophosphite enrichment and uranium recovery

Will be described in example 1The intercalation type manganese thiophosphites of (b) are mixed with aqueous solutions of different initial uranium concentrations, respectively, the pH of the uranium solution having been adjusted by a dilute NaOH solution by 4.2 to avoid precipitation of peracids or uranium. According to V (volume of solution): m (mass of exchanger) =1000mL/g, stirring at 25 ℃ for 24h. And (4) taking the supernatant and the initial solution after the adsorption is finished, and measuring the concentration of the uranium by using inductively coupled plasma mass spectrometry. The experimental result is shown in figure 3, the maximum adsorption capacity of the intercalation type manganese thiophosphite to uranium is as high as 853.70mg/g, and the partition coefficients are all kept at 10 ⁴ The removal rate is about 95% when the concentration is more than mL/g.

Example 7 ability to selectively enrich and recycle uranium in intercalated manganese thiophosphite

The manganese thiophosphite of insertion type in example 1 was mixed with a uranium solution containing one or more competing ions of alkali metal ions, alkaline earth metal ions, transition metal ions, rare earth ions, and carbonate ions, and uranium-contaminated tap water and lake water in accordance with V (volume of solution): m (mass of exchanger) =1000mL/g, stirring at 25 ℃ for 24h. And taking the supernatant and the initial solution after adsorption, and respectively determining the concentration of uranium and other ions by using inductively coupled plasma mass spectrometry and inductively coupled plasma emission spectroscopy. FIG. 4 shows a reaction condition in Na ⁺ Or Ca ²⁺ Or Eu ³⁺ Or HCO ₃ ^- Graph of uranium removal capacity by intercalated manganese thiophosphites in the presence of large excess of competing ions, even at the maximum molar ratios Na/U, ca/U, eu/U and 145mg/L HCO, as shown ₃ ^- In a competitive aqueous solution, uranium can still be captured with high selectivity, and the removal rates of uranium can reach 95.00%, 93.68%, 90.82% and 99.86% respectively.

FIG. 5 (a) shows a symbol Sm ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ As shown in the figure, although the concentration of competitive ions is close to the initial concentration (367.5 ppm) of uranium, the insertion manganese thiophosphite can still effectively capture uranium, the removal rate is as high as 90.82%, and most competitive ions are still remained in the solution after adsorption. Specific data are shown in table 1:

TABLE 1

Fig. 5 (b) is a diagram of the selective removal capacity of the intercalated manganese thiophosphite for uranium in the tap water and lake water polluted by uranium, and as shown in the figure, the intercalated manganese thiophosphite still has strong selectivity for uranium in the complex environment of actual water, and the removal rates can reach 93.29% and 95.67% respectively, which are obviously higher than the removal rates of other competitive ions. Specific data for uranium contaminated tap water are shown in table 2:

TABLE 2

The method for enriching and recycling uranium in water can separate uranium from alkali metal ions, alkaline earth metal ions, transition metal ions, rare earth ions and carbonate ions in a complex environment, and enrichment and recycling of radioactive uranium are realized.

Example 8 ability of intercalated manganese thiophosphites to enrich and recover uranium at different pH

The manganese thiophosphites of the intercalated type of example 1 were mixed with uranium solutions of different pH, according to V (volume of solution): m (mass of exchanger) =1000mL/g, stirring at 25 ℃ for 24h. And taking the supernatant and the initial solution after adsorption is finished, and measuring the concentration of uranium by using inductively coupled plasma mass spectrometry. As a result, as shown in FIG. 6, the intercalated manganese thiophosphite can maintain the uranium removal activity in a pH range of 2.8 to 12.2. The method for enriching and recycling uranium in water body has strong removing capability to uranium in a wide pH activity range.

Example 9 ability test of manganese Thiophosphate intercalated form to enrich and recycle uranium before and after high intensity irradiation

The intercalation-type manganese thiophosphite of example 1 and the material irradiated with 100kGy β, 200kGy β, 100kGy γ, and 200kGy γ rays were mixed with a uranium solution according to V (solution volume): m (mass of exchanger) =1000mL/g conditions, stirring at 25 ℃ for 24h. And taking the supernatant and the initial solution after adsorption is finished, and measuring the concentration of uranium by using inductively coupled plasma mass spectrometry. The test result is shown in fig. 7, the insertion manganese thiophosphite still maintains high distribution coefficient and removal rate to uranium after irradiation, and the framework can be kept unchanged, which is verified by comparing the X-ray powder diffraction patterns of the original and irradiated samples. The adsorbent provided by the application has excellent irradiation resistance, and still has stronger removing capability to uranium after beta and gamma ray irradiation of high strength.

Example 10 cyclic regeneration Capacity testing of intercalated manganese thiophosphite enrichment and uranium recovery

Mixing a certain amount of intercalation manganese thiophosphite with a uranium-containing aqueous solution, and stirring at 25 ℃ for 24 hours to obtain a uranium-adsorbed sample. The sample was placed in 0.2mol/L NH ₄ And stirring the solution in Cl for 24 hours at the temperature of 25 ℃ to realize regeneration. The sample after the first round of elution was then adsorption-eluted under the same conditions. The adsorption-elution was repeated 5 times, and the initial solution and the supernatant after each cycle of adsorption were taken and the uranium concentration was determined by inductively coupled plasma mass spectrometry, the results being shown in fig. 8. Along with the increase of the recycling times, the adsorption capacity of the intercalation type manganese thiophosphite to uranium does not obviously decline, and the uranium can still be kept at a high removal rate after five cycles of circulation. As in FIG. 9, over NH ₄ And (4) treating with a Cl solution, wherein the adsorbed uranium of the first round and the fifth round samples is completely eluted. The adsorbent provided by the application has certain recyclable regeneration capacity.

Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (15)

1. The application of the intercalation manganese thiophosphite material in the enrichment and/or recovery of uranium in a water body is characterized by comprising the following steps:

contacting the intercalation type manganese thiophosphite material with a uranium-containing solution, wherein the intercalation type manganese thiophosphite material adsorbs uranium in a water body, and the pH value of the uranium-containing solution is 2.8 to 12.2;

the molecular formula of the intercalation type manganese thiophosphite material is G _x2 Mn _x1- PS ₃ ·[H ₂ O] _y ；

Wherein the guest cation G comprises at least one of ammonium ions, protonated organic amine cations and alkali metal ions; x is more than or equal to 0.2 and less than or equal to 0.3, and y is more than or equal to 0 and less than or equal to 2;

the preparation method of the intercalation type manganese thiophosphite material comprises the following steps:

(a) Heating a mixture containing manganese, phosphorus, sulfur and a chemical transport agent iodine under a vacuum condition for reaction to obtain manganese thiophosphite powder crystals;

(b) And reacting the manganese thiophosphite powder crystal with a solution of guest cations G to obtain the intercalation manganese thiophosphite.

2. Use according to claim 1, wherein the guest cation G is selected from at least one of ammonium, tetramethylammonium, tetraethylammonium, potassium, sodium and lithium.

3. The use according to claim 2, wherein the guest cation G is an ammonium ion, x is 0.22. Ltoreq. X.ltoreq.0.25.

4. The application of claim 1, wherein the heating reaction in the step (a) is carried out by heating at a constant temperature of 650-700 ℃ for 45-55h, cooling to 480-520 ℃ within 8-10 h, and naturally cooling to room temperature.

5. The use according to claim 4, wherein the mixture of manganese, phosphorus, sulfur and iodine as a chemical transport agent comprises 6 to 10 molar parts of manganese, 6 to 10 molar parts of phosphorus and 18 to 30 molar parts of sulfur.

6. The use according to claim 1, wherein the solid-to-liquid ratio of the manganous thiophosphite powder crystal in the step (b) to the solution containing the guest cation G is 10 to 30mg/mL, and the concentration of the guest cation G in the solution containing the guest cation G is 1 to 3mol/L.

7. The use according to claim 6, wherein the manganese thiophosphite powder crystal in the step (b) is stirred and reacted with the solution containing the guest cation G for 20 to 30h.

8. The use according to claim 1, wherein the uranium content of the uranium-containing solution is 1.03 to 1500ppm.

9. Use according to claim 8 wherein the uranium containing solution comprises at least one of alkali metal ions, alkaline earth metal ions and rare earth element ions.

10. Use according to claim 9, wherein Sm is contained in the uranium-containing solution ³⁺ 、Eu ³⁺ 、Sr ²⁺ 、Ba ²⁺ 、Na ⁺ 、Cs ⁺ 、La ³⁺ At least one of (a).

11. Use according to claim 9 wherein the molar ratio of alkali metal ions, alkaline earth metal ions and rare earth element ions to uranium in the uranium-containing solution is from 1.22 to 31.48 x 10 ⁴ 。

12. Use according to claim 1, wherein the uranium containing solution has a pH of 4 to 5.

13. Use according to claim 1, wherein the contact time is 3 to 24 hours.

14. The use as claimed in claim 1, wherein 8 to 12mg of the intercalation type manganese thiophosphite material is added to 10mL of uranium-containing solution.

15. The application according to claim 1, characterized in that it further comprises the steps of:

and (3) immersing the intercalated manganese thiophosphite material after adsorption into an inorganic salt solution, eluting uranium, and recycling the intercalated manganese thiophosphite material.

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