A gadolinium-enriched recovery system and recovery method

Abstract

The application discloses a gadolinium-enriched recovery system, which comprises a multi-way valve, a cation resin exchange column, an amide resin exchange column, a precipitation container, a filter, a heating and evaporation device and a burning device, the multi-way valve is provided with multiple inlets and one outlet, the inlet of the cation resin exchange column is communicated with the outlet of the multi-way valve through a pump, the outlet of the cation resin exchange column is provided with a first blowdown pipe, the inlet of the amide resin exchange column is communicated with the outlet of the cation resin exchange column, the outlet of the amide resin exchange column is provided with a second blowdown pipe, the inlet of the precipitation container is communicated with the outlet of the amide resin exchange column, the filter is used for filtering the mixture in the precipitation container to obtain gadolinium oxalate precipitation, the heating and evaporation device is used for removing hydrochloric acid attached to the gadolinium oxalate precipitation, and the burning device is used for converting the gadolinium oxalate precipitation into gadolinium oxide powder. The recovery system can solve the problems that the existing recovery system has a large amount of waste liquid and a large volume of solution needing to be filtered.

Description

Technical Field

[0001] This invention relates to the field of radioactive isotope preparation technology, specifically to a gadolinium enrichment and recovery system and method. Background Technology

[0002] Terbium-161 161 Terbium (Tb) possesses suitable decay characteristics, with a half-life of 6.9 days. During decay, it emits beta rays with an average energy of 154 keV, gamma rays with energies of 48.92 keV (17%), 57.19 keV (1.8%), and 74.57 keV (10%), and a large number of Auger electrons. Due to its relatively low gamma-ray energy, moderate beta-ray energy, and the production of Auger electrons during decay, it is particularly suitable for the treatment of small tumors. 161 Radiolabeled drugs using Tb as a raw material have begun clinical trials, with promising results.

[0003] Production of high specific activity 161 The only economically viable method for preparing Tb is through reactor irradiation, using enriched target materials. 160 Gd is expensive, therefore the efficiency of target recovery directly determines the production of targeted radiotherapy materials. 161 The economic benefits of Tb nuclides, therefore, enrichment in the eluent after radiochemical separation. 160 The recycling of Gd is imperative.

[0004] Currently, the main method for radiochemical separation of irradiated products after irradiation is ion chromatography. This method uses organic acids for elution separation. However, if the general rare earth recovery method of adding oxalic acid is used for precipitation recovery, there will be disadvantages such as large waste liquid volume and large volume of solution to be filtered. In addition, the recovery process involves radioactive handling operations, and it is quite troublesome to carry out complex radioactive operations in a shielded glove box. Summary of the Invention

[0005] The purpose of this invention is to provide a gadolinium enrichment and recovery system that solves the problems of large waste liquid volume and large solution volume that need to be filtered during the recovery of existing recovery systems.

[0006] This invention is achieved through the following technical solution:

[0007] A gadolinium enrichment and recovery system includes: a multi-port valve having multiple inlets and one outlet, the multiple inlets of which are respectively connected to a gadolinium-containing organic acid source, a deionized water source, a concentrated hydrochloric acid source, a dilute hydrochloric acid source, and an oxalic acid source; a cation exchange resin column, the inlet of which is connected to the outlet of the multi-port valve via a pump, and the outlet of which is provided with a first drain pipe; an amide resin exchange column, the inlet of which is connected to the outlet of the cation exchange resin column, and the outlet of which is provided with a second drain pipe; a precipitation container, the inlet of which is connected to the outlet of the amide resin exchange column; a filter for filtering the mixture in the precipitation container to obtain gadolinium oxalate precipitate; a heating and drying device for removing hydrochloric acid adhering to the gadolinium oxalate precipitate; and an ignition device for converting the gadolinium oxalate precipitate into gadolinium oxide powder.

[0008] Optionally, the pump outlet is connected to the inlet of the cation exchange column and the inlet of the amide exchange column via a two-way valve.

[0009] Optionally, the pump outlet is connected to the inlet of the cation exchange column, the inlet of the amide exchange column, and the precipitation container via a three-way valve.

[0010] Optionally, the outlet of the cation exchange column is connected to the first drain pipe and the inlet of the amide resin exchange column via a two-way valve.

[0011] Optionally, the outlet of the amide resin exchange column is connected to the second drain pipe and the sedimentation container respectively via a two-way valve.

[0012] Optionally, both the first drain pipe and the second drain pipe are connected to the waste liquid container.

[0013] Optionally, the filtrate outlet of the filter is connected to the waste liquid container.

[0014] Optionally, it also includes a fume hood, wherein the multi-way valve, the cation exchange column, the amide exchange column, the precipitation container, the filter, the heating and drying device, and the incineration device are all disposed inside the fume hood.

[0015] A method for recovering enriched gadolinium, using any of the above-mentioned gadolinium enrichment and recovery systems, includes the following steps:

[0016] Adjust the multi-way valve to connect to the gadolinium-containing organic acid source, so that the gadolinium-containing organic acid source is introduced into the cation exchange column, so that gadolinium is adsorbed on the cation exchange column to obtain the first adsorbate;

[0017] Adjust the multi-way valve to connect to the deionized water source, and perform a first rinse on the first adsorbent to obtain deacidified adsorbent;

[0018] The multi-way valve is adjusted to connect to a concentrated hydrochloric acid source to perform a second rinsing and a first desorption on the acid-desorbed adsorbent to obtain a mixed solution. The mixed solution is then passed into the amide resin exchange column to obtain a second adsorbent.

[0019] Adjust the multi-way valve to connect to the dilute hydrochloric acid source, perform a third rinsing and a second desorption on the second adsorbent to obtain a treatment solution, and then pass the treatment solution into the precipitation container;

[0020] The multi-way valve is adjusted to connect to the oxalic acid source, allowing the oxalic acid to flow into the precipitation container and mix with the treatment solution. The mixture is then stirred and allowed to stand, and finally filtered through the filter to obtain gadolinium oxalate precipitate.

[0021] The gadolinium oxalate precipitate is heated and evaporated by the heating and evaporation device, and then calcined by the calcination device to obtain gadolinium oxide powder.

[0022] Optionally, the concentration of the dilute hydrochloric acid source is 0.01-0.1 mol / L; the concentration of the concentrated hydrochloric acid source is 2-5 mol / L; the concentration of the oxalic acid source is 0.1-3 mol / L; the particle size of the cation exchange column is 50-100 mesh; the particle size of the amide resin exchange column is 50-100 mesh; the height-to-diameter ratio of the cation exchange column and the amide resin exchange column is 15-30:1; and the calcination temperature is ≥1000℃.

[0023] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0024] This invention provides a gadolinium enrichment and recovery system. By using a multi-port valve, multiple inlets are connected to different liquid sources, allowing for the introduction of various liquids. A pump is used to pump these liquids. A cation exchange column is then used to initially separate and adsorb gadolinium from the gadolinium-containing organic acid source, significantly removing organic acids and avoiding the problems of large waste liquid volumes and large filtration solution volumes during recovery. After adsorption, deionized water is circulated through the multi-port valve to rinse the adsorbed gadolinium, effectively removing any remaining organic acids. Then, concentrated hydrochloric acid is circulated through the multi-port valve to rinse the deposits on the cation exchange column, transferring them to an amide resin exchange column for further separation and adsorption. Gadolinium is first extracted, and then dilute hydrochloric acid is introduced through a multi-way valve to wash the deposits on the amide resin exchange column, transferring them to a precipitation container. Oxalic acid is then introduced through the multi-way valve, flowing into the precipitation container where it is stirred, allowed to stand, and filtered. The precipitate is then obtained by filtering through a filter. A heating and drying device is then installed to heat and dry the gadolinium oxalate precipitate, removing the hydrochloric acid from its surface. Finally, a calcination device is installed to calcify the gadolinium oxalate precipitate, transforming it into usable gadolinium oxide powder. Through the synergy of these features, this gadolinium enrichment and recovery system effectively solves the problems of large wastewater volumes and large filtration volumes required by existing recovery systems. Attached Figure Description

[0025] The accompanying drawings, which are included to provide a further understanding of embodiments of the invention and form part of this application, do not constitute a limitation thereof. In the drawings:

[0026] Figure 1 This is a schematic diagram of the gadolinium enrichment and recovery system provided in Embodiment 1 of the present invention;

[0027] Figure 2 This is a schematic diagram of the gadolinium enrichment and recovery system provided in Embodiment 2 of the present invention;

[0028] Figure 3 This is a schematic diagram of the gadolinium enrichment and recovery system provided in Embodiment 3 of the present invention;

[0029] Figure 4 This is a flowchart of the gadolinium enrichment and recovery method provided in Embodiment 1 of the present invention.

[0030] The markings and corresponding component names in the attached diagram are as follows:

[0031] 10-Multi-port valve; 11-Pump; 12-First liquid tank; 13-Second liquid tank; 14-Third liquid tank; 15-Fourth liquid tank; 16-Fifth liquid tank; 20-Cation resin exchange column; 21-First drain pipe; 30-Amide resin exchange column; 31-Second drain pipe; 40-Sedimentation container; 50-Filter; 60-Heating and drying device; 70-Incineration device; 80-Waste liquid container; 90-Fume hood. Detailed Implementation

[0032] To make the objectives, technical solutions, and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the embodiments and accompanying drawings. The illustrative embodiments and descriptions of the present invention are only used to explain the present invention and are not intended to limit the present invention.

[0033] Example 1

[0034] Please refer to Figure 1 This invention provides a gadolinium enrichment and recovery system, including a multi-port valve 10 with multiple inlets and one outlet. The multiple inlets of the multi-port valve 10 are respectively connected to a gadolinium-containing organic acid source, a deionized water source, a concentrated hydrochloric acid source, a dilute hydrochloric acid source, and an oxalic acid source. The system also includes a cation exchange column 20, whose inlet is connected to the outlet of the multi-port valve 10 via a pump 11. The outlet of the cation exchange column 20 is provided with a first drain pipe 21. Finally, the system includes an amide resin exchange column 30, whose inlet is connected to the... The outlet of the cation exchange column 20 is connected, and the outlet of the amide resin exchange column 30 is provided with a second drain pipe 31; the fourth includes a precipitation container 40, the inlet of which is connected to the outlet of the amide resin exchange column 30; the fifth includes a filter 50, which is used to filter the mixture in the precipitation container 40 to obtain gadolinium oxalate precipitate; the sixth includes a heating and drying device 60, which is used to remove hydrochloric acid adhering to the gadolinium oxalate precipitate; the seventh includes an ignition device 70, which is used to convert the gadolinium oxalate precipitate into gadolinium oxide powder. The outlet of the pump 11 is connected to the inlet of the cation exchange column 20, the inlet of the amide resin exchange column 30, and the precipitation container 40 respectively through a three-way valve.

[0035] The gadolinium enrichment and recovery system provided in this embodiment uses a multi-way valve 10, whose multiple inlets are connected to different liquid sources to allow for the introduction of different liquid sources. A pump 11 pumps the liquid sources. Based on this, a cation exchange column 20 is used to separate and adsorb gadolinium from the gadolinium-containing organic acid source, significantly removing organic acids and avoiding the problems of large waste liquid volume and large filtration solution volume during recovery. After adsorption, deionized water is circulated through the multi-way valve 10 to rinse the adsorbed gadolinium, effectively removing any remaining organic acids. Then, concentrated hydrochloric acid is circulated through the multi-way valve 10 to rinse the adsorbed substances, transferring them to an amide resin exchange column 30 for further separation and adsorption of gadolinium. Finally, dilute hydrochloric acid is circulated through the multi-way valve 10 to rinse the adsorbed substances on the amide resin exchange column 30. The gadolinium oxalate is transferred to the precipitation container 40, and then oxalic acid is introduced through the multi-way valve 10. The oxalic acid flows into the precipitation container 40, is stirred, allowed to stand, and filtered. After filtration through the filter 50, gadolinium oxalate precipitate is obtained. The gadolinium oxalate precipitate is heated and dried by the heating and drying device 60 to remove hydrochloric acid from its surface. The gadolinium oxalate precipitate is then ignited by the ignition device 70 to convert it into gadolinium oxide powder that can be effectively utilized. With the above settings, the dilute hydrochloric acid source can bypass the cation exchange column 20 and be directly introduced into the amide resin exchange column 30. The oxalic acid source can also be directly introduced into the precipitation container 40. Through the combination of the above features, this gadolinium enrichment and recovery system can effectively solve the problems of large waste liquid volume and large solution volume that need to be filtered during the recovery of existing recovery systems.

[0036] It should be noted that, in this embodiment, the gadolinium-containing organic acid source is contained in the first liquid tank 12, the deionized water source is contained in the second liquid tank 13, the concentrated hydrochloric acid source is contained in the third liquid tank 14, the dilute hydrochloric acid source is contained in the fourth liquid tank 15, and the oxalic acid source is contained in the fifth liquid tank 16.

[0037] It should be noted that in this embodiment, the filter 50 is a sand core funnel.

[0038] It should be noted that the heating and drying device 60 and the burning device 70 mentioned above can be any similar product in the prior art, as long as they can achieve the corresponding functions. For example, the heating and drying device 60 can be a crucible with a heating plate.

[0039] Example 2

[0040] Please refer to Figure 2 This invention provides a gadolinium enrichment and recovery system, which is a further improvement on embodiment 1, the difference being:

[0041] To facilitate switching the flow direction between the first drain pipe 21 and the amide resin exchange column 30, the outlet of the cation resin exchange column 20 is connected to the inlet of the first drain pipe 21 and the inlet of the amide resin exchange column 30 respectively via a two-way valve.

[0042] To facilitate switching the liquid flow direction between the second drain pipe 31 and the sedimentation container 40, the outlet of the amide resin exchange column 30 is connected to the second drain pipe 31 and the sedimentation container 40 respectively through a two-way valve.

[0043] In order to collect the waste liquid, both the first drain pipe 21 and the second drain pipe 31 are connected to the waste liquid container 80.

[0044] To further collect the waste liquid, the filtrate outlet of the filter 50 is connected to the waste liquid container 80.

[0045] Example 3

[0046] Please refer to Figure 3 This invention provides a gadolinium enrichment and recovery system, which is a further improvement on embodiment 2, the difference being:

[0047] To isolate radioactive aerosols and hydrochloric acid mist and protect operators from radioactive contamination and the effects of hydrochloric acid mist, the gadolinium enrichment and recovery system also includes a fume hood 90. The multi-port valve 10, the cation exchange column 20, the amide exchange column 30, the precipitation container 40, the filter 50, the heating and drying device 60, and the incineration device 70 are all located inside the fume hood 90.

[0048] The aforementioned fume hood 90 has a three-layer structure, consisting of two layers of plexiglass and one layer of lead glass sandwiched between the two layers of plexiglass, with the lead glass having a thickness of ≥5mm.

[0049] Example 4

[0050] This embodiment provides a method for recovering enriched gadolinium, using the gadolinium enrichment and recovery system provided in Embodiment 1, and includes the following steps:

[0051] S1. Adjust the multi-way valve 10 to connect to the gadolinium-containing organic acid source, so that the gadolinium-containing organic acid source is introduced into the cation exchange column 20, so that gadolinium is adsorbed on the cation exchange column 20 to obtain the first adsorbate;

[0052] S2. Adjust the multi-way valve 10 to connect to the deionized water source, and perform a first rinse on the first adsorbent to obtain deacidified adsorbent;

[0053] S3. Adjust the multi-way valve 10 to connect to the concentrated hydrochloric acid source, perform a second rinsing and a first desorption on the acid-removing adsorbent to obtain a mixed solution, and pass the mixed solution into the amide resin exchange column 30 to obtain a second adsorbent in the amide resin exchange column 30.

[0054] S4. Adjust the multi-way valve 10 to connect to the dilute hydrochloric acid source, perform a third rinsing and a second desorption on the second adsorbent to obtain a treatment solution, and then pass the treatment solution into the precipitation container 40.

[0055] S5. Adjust the multi-way valve 10 to connect to the oxalic acid source, so that the oxalic acid flows into the precipitation container 40 and mixes, stirs and stands with the treatment liquid, and then filters through the filter 50 to obtain gadolinium oxalate precipitate.

[0056] S6. The gadolinium oxalate precipitate is heated and dried by the heating and drying device 60, and then calcined by the calcination device 70 to obtain gadolinium oxide powder.

[0057] It should be noted that the concentration of the dilute hydrochloric acid source is 0.01-0.1 mol / L; the concentration of the concentrated hydrochloric acid source is 2-5 mol / L; the concentration of the oxalic acid source is 0.1-3 mol / L; the particle size of the cation exchange column 20 is 50-100 mesh; the particle size of the amide resin exchange column 30 is 50-100 mesh; the height-to-diameter ratio of the cation exchange column 20 and the amide resin exchange column 30 is 15-30:1; and the calcination temperature is ≥1000℃.

[0058] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A gadolinium enrichment and recovery system, characterized in that, include: A multi-port valve (10) is provided with multiple inlets and one outlet. The multiple inlets of the multi-port valve (10) are respectively connected to a gadolinium-containing organic acid source, a deionized water source, a concentrated hydrochloric acid source, a dilute hydrochloric acid source, and an oxalic acid source. A cation exchange column (20) is provided with its inlet connected to the outlet of the multi-way valve (10) via a pump (11), and its outlet is provided with a first drain pipe (21). An amide resin exchange column (30) is provided with its inlet connected to the outlet of the cation resin exchange column (20), and the outlet of the amide resin exchange column (30) is provided with a second drain pipe (31). A precipitation container (40) having its inlet connected to the outlet of the amide resin exchange column (30); A filter (50) is used to filter the mixture in the precipitation container (40) to obtain gadolinium oxalate precipitate; A heating and drying apparatus (60) is used to remove hydrochloric acid adhering to gadolinium oxalate precipitate; A calcination apparatus (70) is used to convert gadolinium oxalate precipitate into gadolinium oxide powder; The outlet of the pump (11) is connected to the inlet of the cation exchange column (20), the inlet of the amide exchange column (30) and the precipitation container (40) respectively through a three-way valve.

2. The gadolinium enrichment and recovery system according to claim 1, characterized in that, The outlet of the cation exchange column (20) is connected to the first drain pipe (21) and the inlet of the amide resin exchange column (30) respectively through a two-way valve.

3. The gadolinium enrichment and recovery system according to claim 2, characterized in that, The outlet of the amide resin exchange column (30) is connected to the second drain pipe (31) and the sedimentation container (40) respectively through a two-way valve.

4. The gadolinium enrichment and recovery system according to claim 3, characterized in that, Both the first drain pipe (21) and the second drain pipe (31) are connected to the waste liquid container (80).

5. The gadolinium enrichment and recovery system according to claim 4, characterized in that, The filtrate outlet of the filter (50) is connected to the waste liquid container (80).

6. The gadolinium enrichment and recovery system according to any one of claims 1-5, characterized in that, It also includes a fume hood (90), in which the multi-way valve (10), the cation exchange column (20), the amide exchange column (30), the precipitation container (40), the filter (50), the heating and drying device (60), and the burning device (70) are all located.

7. A method for enriching and recovering gadolinium, characterized in that, The process, performed using the gadolinium enrichment and recovery system according to any one of claims 1-6, includes the following steps: Adjust the multi-way valve (10) to connect to the gadolinium-containing organic acid source, so that the gadolinium-containing organic acid source is introduced into the cation exchange column (20), so that gadolinium is adsorbed on the cation exchange column (20) to obtain the first adsorbate; Adjust the multi-way valve (10) to connect to the deionized water source, and perform a first rinse on the first adsorbent to obtain deacidified adsorbent; Adjust the multi-way valve (10) to connect to the concentrated hydrochloric acid source, perform a second rinsing and a first desorption on the deacidified adsorbent to obtain a mixed solution, and pass the mixed solution into the amide resin exchange column (30) to obtain a second adsorbent in the amide resin exchange column (30); Adjust the multi-way valve (10) to connect to the dilute hydrochloric acid source, perform a third rinsing and a second desorption on the second adsorbent to obtain a treatment solution, and pass the treatment solution into the precipitation container (40). Adjust the multi-way valve (10) to connect to the oxalic acid source, so that the oxalic acid flows into the precipitation container (40) and mixes, stirs and stands with the treatment liquid, and then filters through the filter (50) to obtain gadolinium oxalate precipitate; The gadolinium oxalate precipitate is heated and dried by the heating and drying device (60), and then calcined by the calcination device (70) to obtain gadolinium oxide powder.

8. The method for recovering enriched gadolinium according to claim 7, characterized in that: The concentration of the dilute hydrochloric acid source is 0.01-0.1 mol / L; The concentration of the concentrated hydrochloric acid source is 2-5 mol / L; The concentration of the oxalic acid source is 0.1-3 mol / L; The particle size of the cation exchange column (20) is 50-100 mesh; The particle size of the amide resin exchange column (30) is 50-100 mesh; The height-to-diameter ratio of the cation exchange column (20) and the amide exchange column (30) is 15-30:1; The burning temperature is ≥1000℃.

Images