A high-efficiency separation method of barium and strontium based on solid phase leaching resin

Abstract

The present invention belongs to the technical field of metal separation, and specifically relates to a method for efficiently separating barium and strontium based on a solid phase leaching resin; the solid phase leaching resin is loaded with an amide pod ether extractant L on a solid phase carrier material. I ~L VII , and separation chromatography was used to achieve Sr 2+ and Ba 2+ Separation can not only efficiently separate Sr 2+ and Ba 2+ , and can also effectively recycle Sr 2+ In addition, the solid phase extraction resin can be regenerated and recycled. It has been proven that it can be recycled at least 10 times, which is highly economical.

Description

Technical Field

[0001] The invention belongs to the technical field of metal separation, and in particular relates to a method for efficiently separating barium and strontium based on solid phase leaching resin. Background Art

[0002] The fission of uranium-235 in a reactor produces nine strontium (Sr) isotopes with mass numbers ranging from 89 to 97. Most of these Sr isotopes have a half-life of less than 10 hours. 90 Sr has the longest half-life (28.8 years); therefore, it can be obtained from high-level liquid waste with a longer cooling time. 90 Sr.

[0003] 90 Sr can not only be used to prepare beta irradiation sources, nuclear batteries, static eliminators, transmission instruments, backscattering instruments, etc., but also can be made into medical applicators for the treatment of superficial diseases (such as scars, skin cancer, ophthalmic malignancies, etc.). 90 After Sr decays, its daughter can be obtained 90 Y, due to 90 Y has a shorter half-life (64.1 h) and higher energy (E avg =934keV), the maximum range in human tissue is 11 mm, so 90 Y can be labeled on monoclonal antibodies, peptides and macromolecules for the treatment of tumors. 90 Y-ibritumomab in the treatment of non-Hodgkin's lymphoma 90 Y resin microspheres in the treatment of liver cancer.

[0004] In high-level liquid waste, due to 90 Sr has different chemical properties from other metal ions (rare earth, technetium, cesium, super plutonium, etc.), and is easy to separate from each other. However, Sr and Ba are similar in chemical structure and belong to the second main group in the periodic table. They show the same oxidation state (+2 valence), similar chemical properties and very similar ionic radius, which greatly increases the Sr 2+ and Ba 2+ The difficulty of separation. And in the high-level waste liquid Ba 2+ The concentration of Sr 2+ , which will inevitably affect Sr 2+ The separation and purification of

[0005] Currently, for Sr 2+ and Ba 2+ There are few solid phase adsorbents for separation. Commercial SR resin is a kind of Sr 2+ Crown ether resin, in 0.01~3.0mol / L HNO3 solution, SR resin has a strong affinity for Sr 2+ The selectivity is slightly higher than that of Ba2+ , but it is impossible to achieve efficient separation of the two. Wu Yan et al. published a paper on the separation of silane-based crown ether resins in Toxics in 2023. 90 The dynamic column separation behavior and complexation mechanism of Sr were studied, which disclosed that the silicon-based crown ether resin can be used to separate and extract Sr from simulated high-level radioactive waste liquid. 2+ , except Ba 2+ In addition, the resin can effectively achieve Sr 2+ Separation from other impurity ions. Although Na-DTPA was used as eluent to elute Sr adsorbed on the resin, 2+ and Ba 2+ , nor can the two be completely separated. 2+ The eluent still contains impurities Ba 2+ Therefore, Sr 2+ with Ba 2+ The separation problem between Sr and 2+ and Ba 2+ A new type of leaching resin solid phase adsorbent with higher separation ability. Summary of the invention

[0006] The object of the present invention is to provide a method for efficiently separating barium and strontium based on solid phase leaching resin, wherein the method is to first load an amide pod ether extractant on a solid phase carrier material, and then use a separation chromatography method to efficiently separate Sr 2+ and Ba 2+ .

[0007] To achieve the above object, the present invention adopts the following technical solution:

[0008] A method for efficiently separating barium and strontium based on solid phase leaching resin comprises the following steps:

[0009] Step 1: treatment of solid support material;

[0010] The solid phase support material is rotated and shaken at room temperature at a speed of 10-100 rpm for 1-2 hours, and the air in the pores of the solid phase support material is removed by decompression;

[0011] Wherein, the solid phase carrier material is a silicon-based material or a polyacrylate resin;

[0012] Step 2: Preparation of solid phase extraction resin;

[0013] Firstly, an amide pod ether extractant is dissolved in an organic solvent to obtain an extractant solution with a concentration of 38-60 mmol / L, and a diluent is dissolved in an organic solvent to obtain a diluent solution with a concentration of 52-220 mmol / L;

[0014] Then, the extractant solution and the diluent solution are mixed in a mass ratio of 1 to 2:1 and then absorbed into the pores of the solid support material under negative pressure conditions; wherein the mass ratio of the solid support material to the amide pod extractant is 2 to 10:1;

[0015] Finally, the organic solvent was removed by rotary oscillation at room temperature at a speed of 10-100 rpm for 4-8 h;

[0016] Step 3: Preparation of leaching resin column;

[0017] The solid phase leaching resin prepared in step 2 is loaded into a chromatography column to obtain a leaching resin column, and the leaching resin column is pretreated with a nitric acid solution;

[0018] Step 4: Efficient separation of barium and strontium;

[0019] Containing Sr 2+ and Ba 2+ The feed liquid flows into the pretreated leaching resin column at a flow rate of 0.1~1.0mL / min. 2+ and Ba 2+ The Ba adsorbed on the solid phase leaching resin is then eluted with nitric acid solution. 2+ Finally, the Sr adsorbed on the solid phase extraction resin is eluted with an eluent. 2+ ;

[0020] Wherein, the eluent is α-hydroxyisobutyric acid or formic acid.

[0021] Furthermore, the silicon-based material in step 1 is SiO2 or SiO2-P.

[0022] Furthermore, the polyacrylate resin in step 1 is Amberchrom CG-71M resin or Amberlite XAD-7 resin.

[0023] Furthermore, the organic solvent in step 2 is methanol, chloroform or dichloromethane.

[0024] Further, the amide pod ether extractant in step 2 is formula L I ~L VII Any one of the compounds,

[0025] .

[0026] Furthermore, the diluent in step 2 is n-octanol, nitrobenzene, m-nitrotrifluorotoluene, toluene, xylene, or 1,1,2,2-tetrachloroethane.

[0027] Furthermore, the concentration of the nitric acid solution in step 3 is 0.1-6.0 mol / L.

[0028] The present invention has the following beneficial effects:

[0029] (1) Compared with commercial SR resin, the solid phase extraction resin has the advantages of low synthesis cost, low synthesis difficulty, easy purification, etc., and the preparation cost is lower than that of SR resin; and the preparation method is simple and mature, and it is easy to industrialize and realize.

[0030] (2) The solid phase extraction resin has a wide range of application acidity and high universality, and is very suitable for Sr under low and high acid conditions. 2+ / Ba 2+ Therefore, there is no need to adjust the acidity of the feed solution. Only the leaching resin column needs to be pretreated with nitric acid solution to quickly separate Sr 2+ / Ba 2+ It is adsorbed on solid phase extraction resin and is easy to use.

[0031] (3) Since the solid phase extraction resin has a great influence on Sr 2+ The affinity is much higher than that of Ba 2+ Ba adsorbed on the resin can be removed by using HNO3 solution. 2+ Elute and at the same time Sr 2+ Remain on the resin, thus enabling Sr 2+ / Ba 2+ Efficient separation.

[0032] (4) Sr can be removed by using common eluents 2+ After elution from the resin, Sr 2+ The solid phase extraction resin can be fully recovered; and the solid phase extraction resin can be regenerated and recycled. It has been proven that it can be recycled at least 10 times, which has high economic efficiency.

[0033] (5) The solid phase extraction resin mainly contains four elements: C, H, O, and N. The generated solid waste is easy to handle and is green and environmentally friendly. BRIEF DESCRIPTION OF THE DRAWINGS

[0034] Figure 1 This is a field emission scanning electron microscope image of the solid phase leaching resin prepared in Example 1 of the present invention.

[0035] Figure 2 The solid phase extraction resin prepared in Example 1 of the present invention is 2+ and Ba 2+ Adsorption-desorption elution curves.

[0036] Figure 3 The solid phase leaching resin prepared in Example 2 of the present invention is 2+ and Ba 2+ Adsorption-desorption elution curves. DETAILED DESCRIPTION

[0037] Example 1

[0038] 5 g of solid phase carrier material SiO2 was placed in a round bottom flask and placed on a rotary evaporator. The evaporator was rotated and oscillated at room temperature for 1 h at a speed of 10 rpm. At the same time, the air in the pores of SiO2 was removed by decompression. 1 g of amide pod extractant L I Dissolve in 50mL methanol to obtain an extractant solution with a concentration of 49mmol / L, then dissolve 1g of n-octanol in 50mL methanol to obtain a diluent solution with a concentration of 153mmol / L, then evenly mix the extractant solution and the diluent solution and suck them into the round-bottom flask through the exhaust hole of the rotary evaporator under negative pressure conditions to mix with the solid phase carrier material; at room temperature, rotate and oscillate for 4h to allow the extractant and the diluent to completely immerse in the pores of the solid phase carrier material; then, remove the organic solvent by drying to obtain 6.5g (93%) of solid phase leaching resin, the surface morphology of which is shown in Figure 1 As shown, the resin is spherical and the particle size is uniform.

[0039] Example 2

[0040] 5 g of solid phase carrier material SiO2 was placed in a round-bottom flask and placed on a rotary evaporator. The evaporator was rotated and oscillated at room temperature for 2 h at a speed of 50 rpm. At the same time, the air in the pores of SiO2 was removed by decompression. 1 g of amide pod extractant L VII Dissolve in 50 mL of dichloromethane to obtain an extractant solution with a concentration of 43 mmol / L, then dissolve 0.5 g of toluene in 50 mL of dichloromethane to obtain a diluent solution with a concentration of 108 mmol / L, and then evenly mix the two solutions and suck them into the round-bottom flask through the exhaust hole of the rotary evaporator under negative pressure conditions to mix with the solid phase carrier material; at room temperature, rotate and oscillate for 8 hours to allow the extractant and diluent to completely immerse in the pores of the solid phase carrier material; then, remove the organic solvent by drying to obtain 6.1 g (94%) of solid phase extraction resin.

[0041] Example 3

[0042] 5 g of solid phase carrier material SiO2-P was placed in a round-bottom flask and placed on a rotary evaporator. The evaporator was rotated and oscillated at room temperature for 1.5 h at a speed of 100 rpm. At the same time, the air in the pores of SiO2-P was removed by decompression. 1 g of amide pod extractant L was added. IIDissolve in 50 mL of chloroform to obtain an extractant solution with a concentration of 57 mmol / L, then dissolve 0.5 g of m-nitrotrifluorotoluene in 50 mL of chloroform to obtain a diluent solution with a concentration of 52 mmol / L, and then evenly mix the two solutions and suck them into the round-bottom flask through the exhaust hole of the rotary evaporator under negative pressure conditions to mix with the solid phase carrier material; at room temperature, rotate and oscillate for 6 hours to allow the extractant and diluent to completely immerse in the pores of the solid phase carrier material; then, remove the organic solvent by drying to obtain 6.1 g (94%) of solid phase leaching resin.

[0043] Example 4

[0044] 5 g of solid phase support material Amberchrom CG-71M was placed in a round-bottom flask and placed on a rotary evaporator. The evaporator was rotated and shaken at room temperature for 1.5 h at a speed of 80 rpm. At the same time, the air in the pores of Amberchrom CG-71M was removed by decompression. 1 g of amide pod extractant L V Dissolve in 50 mL of methanol to obtain an extractant solution with a concentration of 57 mmol / L, then dissolve 1 g of nitrobenzene in 50 mL of methanol to obtain a diluent solution with a concentration of 162 mmol / L, and then evenly mix the two solutions and suck them into the round-bottom flask through the exhaust hole of the rotary evaporator under negative pressure conditions to mix with the solid phase carrier material; at room temperature, rotate and oscillate for 4 hours to allow the extractant and diluent to completely immerse in the pores of the solid phase carrier material; then, remove the organic solvent by drying to obtain 6.3 g (90%) of solid phase extraction resin.

[0045] The solid phase extraction resin prepared in Examples 1 to 4 was applied to Sr 2+ and Ba 2+ of separation.

[0046] Application Example 1

[0047] (1) Accurately weigh 0.4 g of the eluting resin prepared in Example 1 and load it into a chromatography column (the ratio of effective column height to column diameter is 5) to obtain an eluting resin column;

[0048] (2) flowing 10 mL of 3.0 mol / L nitric acid solution into the leaching resin column at a flow rate of 0.1 mL / min to obtain a pretreated leaching resin column;

[0049] (3) Then add 1.0 mL of the feed solution (Ba 2+ With Sr 2+ The concentration ratio was 2:1) and flowed into the pretreated leaching resin column at a flow rate of 0.2 mL / min. 2+ and Ba 2+ Adsorbed by leaching resin;

[0050] (4) Use 29 mL of 3.0 mol / L nitric acid solution to remove the Ba adsorbed on the leaching resin. 2+ Wash off, Sr 2+ Retained on the resin column, achieving Sr 2+ / Ba 2+ Complete separation of

[0051] (5) Use 80 mL of 1.0 mol / L formic acid (HCOOH) solution to elute the Sr adsorbed on the leaching resin. 2+ , realizing Sr 2+ of recycling.

[0052] During the adsorption and elution process, the column effluent was collected in equal volumes and the Sr 2+ and Ba 2+ Perform concentration analysis and draw concentration curves such as Figure 2 As shown in the figure, the horizontal axis is the volume of column effluent (mL), and the vertical axis is the column effluent Sr 2+ Or Ba 2+ The concentration (mg / L) of Sr 2+ and Ba 2+ Can be completely separated, Sr 2+ The yield is greater than 99%. After ten cycles, Sr 2+ The yield is still greater than 90%.

[0053] Application Example 2

[0054] (1) Accurately weigh 0.4 g of the eluting resin prepared in Example 2 and load it into a chromatography column (the ratio of effective column height to column diameter is 5) to obtain an eluting resin column;

[0055] (2) 10 mL of 1.0 mol / L nitric acid solution was flowed into the leaching resin column at a flow rate of 0.2 mL / min to obtain a pretreated leaching resin column;

[0056] (3) Then add 1.0 mL of the feed solution (Ba 2+ With Sr 2+ The concentration ratio was 2:1) and flowed into the pretreated leaching resin column at a flow rate of 0.1 mL / min. 2+ and Ba 2+ Adsorbed by leaching resin;

[0057] (4) Use 29 mL of 1.0 mol / L nitric acid solution to remove the Ba adsorbed on the leaching resin. 2+ Washed off, Sr 2+ Retained on the resin column, thereby achieving Sr 2+ / Ba 2+ Complete separation of

[0058] (5) Use 110 mL of 1.0 mol / L α-HIBA solution to elute the Sr adsorbed on the leaching resin. 2+ , thereby achieving Sr 2+ of recycling.

[0059] During the adsorption and elution process, the column effluent was collected in equal volumes and the Sr 2+ and Ba 2+ Conduct concentration analysis and draw concentration curves, such as Figure 3 As shown. After calculation, Sr 2+ The yield is greater than 99%. After ten cycles, Sr 2+ The yield is still greater than 95%.

[0060] Application Example 3

[0061] (1) Accurately weigh 0.4 g of the eluting resin prepared in Example 3 and load it into a chromatography column (the ratio of effective column height to column diameter is 5) to obtain an eluting resin column;

[0062] (2) flowing 20 mL of 0.1 mol / L nitric acid solution into the leaching resin column at a flow rate of 1.0 mL / min to obtain a pretreated leaching resin column;

[0063] (3) Then add 1.0 mL of the feed solution (Ba 2+ With Sr 2+ The concentration ratio was 5:1) and flowed into the pretreated leaching resin column at a flow rate of 0.2 mL / min. 2+ and Ba 2+ Adsorbed by leaching resin;

[0064] (4) Use 29 mL of 3. mol / L nitric acid solution to remove the Ba adsorbed on the leaching resin. 2+ Washed off, Sr 2+ Retained on the resin column, thereby achieving Sr 2+ / Ba 2+ Complete separation of

[0065] (5) Use 110 mL of 0.5 mol / L α-HIBA solution to elute the Sr adsorbed on the leaching resin. 2+ , thereby achieving Sr 2+ of recycling.

[0066] Application Example 4

[0067] (1) Accurately weigh 0.5 g of the eluting resin prepared in Example 4 and load it into a chromatography column (the ratio of effective column height to column diameter is 10) to obtain an eluting resin column;

[0068] (2) flowing 20 mL of 3.0 mol / L nitric acid solution into the leaching resin column at a flow rate of 0.5 mL / min to obtain a pretreated leaching resin column;

[0069] (3) Then add 1.0 mL of the feed solution (Ba 2+ With Sr 2+ The concentration ratio was 10:1) and flowed into the pretreated elution resin column at a flow rate of 0.2 mL / min. 2+ and Ba 2+ Adsorbed by leaching resin;

[0070] (4) Use 29 mL of 6.0 mol / L nitric acid solution to remove the Ba adsorbed on the leaching resin. 2+ Washed off, Sr 2+ Retained on the resin column, thereby achieving Sr 2+ / Ba 2+ Complete separation of

[0071] (5) Use 110 mL of 1.0 mol / L α-HIBA solution to elute the Sr adsorbed on the leaching resin. 2+ , thereby achieving Sr 2+ of recycling.

[0072] The above description is only a preferred implementation manner of the present invention, but the protection scope of the present invention is not limited thereto, and any modification and replacement based on the technical solution and inventive concept provided by the present invention should be included in the protection scope of the present invention.

Claims

1. A high-efficiency separation method of barium and strontium based on solid phase leaching resin, It is characterized in that The steps include: Step 1: treatment of solid support material; The solid phase support material is rotated and shaken at room temperature at a speed of 10-100 rpm for 1-2 hours, and the air in the pores of the solid phase support material is removed by decompression; Wherein, the solid phase carrier material is a silicon-based material or a polyacrylate resin; Step 2: Preparation of solid phase extraction resin; Firstly, an amide pod ether extractant is dissolved in an organic solvent to obtain an extractant solution with a concentration of 38-60 mmol / L, and a diluent is dissolved in an organic solvent to obtain a diluent solution with a concentration of 52-220 mmol / L; Then, the extractant solution and the diluent solution are mixed in a mass ratio of 1 to 2:1 and then absorbed into the pores of the solid support material under negative pressure conditions; wherein the mass ratio of the solid support material to the amide pod extractant is 2 to 10:1; Finally, the organic solvent was removed by rotary oscillation at room temperature at a speed of 10-100 rpm for 4-8 h; Step 3: Preparation of leaching resin column; The solid phase leaching resin prepared in step 2 is loaded into a chromatography column to obtain a leaching resin column, and the leaching resin column is pretreated with a nitric acid solution; Step 4: Efficient separation of barium and strontium; Containing Sr 2+ and Ba 2+ The feed liquid flows into the pretreated leaching resin column at a flow rate of 0.1~1.0mL / min. 2+ and Ba 2+ The Ba adsorbed on the solid phase leaching resin is then eluted with nitric acid solution. 2+ Finally, α-hydroxyisobutyric acid or formic acid was used to elute the Sr adsorbed on the solid phase leaching resin. 2+ ; Wherein, the amide pod ether extractant is formula L I , L II , L V , L VII Any one of the compounds, 。 2. A method for efficiently separating barium and strontium based on solid phase leaching resin according to claim 1, It is characterized in that The silicon-based material in step 1 is SiO 2 or SiO 2 -P.

3. A method for efficiently separating barium and strontium based on solid phase leaching resin according to claim 1, It is characterized in that The polyacrylate resin in step 1 is Amberchrom CG-71M resin or Amberlite XAD-7 resin.

4. The method for efficiently separating barium and strontium based on solid phase leaching resin according to claim 1, It is characterized in that The organic solvent in step 2 is methanol, chloroform or dichloromethane.

5. The method for efficiently separating barium and strontium based on solid phase leaching resin according to claim 1, It is characterized in that The diluent in step 2 is n-octanol, nitrobenzene, m-nitrotrifluorotoluene, toluene, xylene, or 1,1,2,2-tetrachloroethane.

6. The method for efficiently separating barium and strontium based on solid phase leaching resin according to claim 1, It is characterized in that The concentration of the nitric acid solution in step 3 is 0.1-6.0 mol / L.

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