Separation and purification method of medical isotope 67Cu

Abstract

The invention relates to the technical field of radionuclide separation and purification, and particularly discloses a separation and purification method of medical isotope 67Cu. A separation and purification method of medical isotope 67Cu comprises the following steps: adding Zn particles and Sn powder into a Cu solution, then adding mixed acid for dissolving, and adjusting the pH value of the solution through a first buffer solution to obtain a target material dissolving solution; preparing an LN resin column, introducing the target material dissolving solution to obtain a first recovery solution, and adjusting the pH value of the first recovery solution through a second buffer solution to obtain a first column loading solution; preparing a CU resin column, and sequentially introducing the first column loading liquid and the first washing liquid to obtain a second recovery liquid; introducing a first hydrochloric acid solution into the CU resin column to obtain a desorption solution; preparing an AG1-X8 resin column, and sequentially introducing the desorption liquid and the second washing liquid to obtain waste liquid; and introducing a second hydrochloric acid solution into the AG1-X8 resin column to obtain a 67Cu product solution.

Description

Technical Field

[0001] The present invention relates to the technical field of separation and purification of radioactive nuclides, and in particular to a medical isotope 67 Method for separation and purification of Cu. Background Art

[0002] 67 Cu is a β-radionuclide with a half-life of 61.8 hours. It is a medical isotope suitable for both radiodiagnosis and in vivo radiotherapy. 67 Cu can be 68 Zn(γ,p) 67 Cu reaction production, the production process uses high abundance metals 68 Zn as target, high abundance 68 Zn is expensive and usually needs to be recycled for reuse. 68 Tens to hundreds of milligrams of metal Sn are added to the Zn target as 67 The carrier of Cu is separated and recovered by vacuum distillation, taking advantage of the fact that Zn is volatile at high temperatures while Cu is non-volatile. 68 Zn target, the remaining residue contains tens to hundreds of milligrams of 68 Zn, Sn and trace amounts 67 Cu, in order to obtain the medical requirements 67 Cu, trace amounts of which must be separated and purified from the residue after vacuum distillation 67 Cu, which requires solving the separation problem of Cu, Zn and Sn.

[0003] At present, there are many methods for separating trace Cu from Zn and Sn, such as ion exchange, coprecipitation, solvent extraction, extraction chromatography and electrodeposition. Extraction chromatography is a separation technology that combines the high selectivity of solvent extraction with the high efficiency of chromatographic separation. It is easy to realize automated operation and can separate and purify trace Cu from a large amount of Zn target solution. 67 Cu, but the separation needs to be carried out under the condition of pH = 2 to 5. Under this condition, Sn 4+ Hydrolysis reaction will occur to generate precipitate, and the precipitate will be adsorbed when filtering to remove the precipitate 67 Cu will cause 67 The Cu recovery rate is reduced, and the desorption 67 The Cu product solution is a 4-7 mol / L HCl medium, and the acidity is too high to meet the requirements of nuclear medicine applications. Summary of the invention

[0004] In order to overcome the shortcomings of the prior art, the present invention aims to provide a medical isotope 67 The separation and purification method of Cu and its preparation method are used to improve 67The recovery and purity of Cu and the low acidity required for nuclear medicine applications 67 Cu product solution.

[0005] The technical solution adopted by the present invention is:

[0006] A medical isotope 67 The separation and purification method of Cu comprises the following steps:

[0007] S1, adding Zn particles and Sn powder into a Cu solution, then adding a mixed acid to dissolve, and adjusting the pH of the solution with a first buffer solution to obtain a target material solution;

[0008] S2, preparing an LN resin column and introducing the target material dissolving solution into the column to obtain a first recovery solution, and adjusting the pH of the first recovery solution by a second buffer solution to obtain a first column liquid;

[0009] S3, preparing a CU resin column and sequentially introducing the first column liquid and the first washing liquid to obtain a second recovery liquid;

[0010] S4, introducing the first hydrochloric acid solution into the CU resin column to obtain a desorption solution;

[0011] S5, preparing an AG1-X8 resin column and sequentially introducing the desorption liquid and the second washing liquid to obtain a waste liquid;

[0012] S6, introducing the second hydrochloric acid solution into the AG1-X8 resin column to obtain 67 Cu product solution.

[0013] Optionally, the mass ratio of the Zn particles to the Sn powder is 10:1, and the Cu 2+ The concentration is 500 μg / mL, and the mixed acid is a mixture of concentrated hydrochloric acid and concentrated nitric acid in a volume ratio of (3-25):1;

[0014] The target solution preparation includes the following steps: adding 1g Zn particles and 0.1g Sn powder to 0.1mL Cu solution and then adding mixed acid; after the Zn particles and Sn powder are completely dissolved, adding 1.0mol / L NH 3 ·H 2 The acidity of the O solution and the neutralization solution is 0.5-1.0 mol / L to obtain a target material solution.

[0015] Optionally, the mass of the LN resin is 2 to 3 g, the target material solution passes through the LN resin column to obtain a first effluent, the third hydrochloric acid solution passes through the LN resin column to obtain a second effluent, and the first recovered liquid is a mixture of the first effluent and the second effluent; the third hydrochloric acid solution is 10 to 50 mL of HCl solution with a molar concentration of 0.1 to 1.0 mol / L.

[0016] Optionally, the preparation steps of the LN resin column are as follows:

[0017] After LN resin was soaked in ultrapure water for 24 h, it was loaded into a 10 mL separation column;

[0018] Wash the LN resin column with a third hydrochloric acid solution;

[0019] Wherein, the volume of LN resin in the LN separation column is 8 mL.

[0020] Optionally, the second buffer solution is one of ammonium acetate and ammonia water, and the amount of the second buffer solution added is 15 to 20 mL;

[0021] The pH of the first column liquid is 2-6.

[0022] Optionally, the volume of the CU resin column is 1-2 mL, the first washing solution is 20 mL of a 0.01 mol / L HCl solution; and the first hydrochloric acid solution is 2-6 mL of a HCl solution with a molar concentration of 0.5-7.0 mol / L.

[0023] Optionally, the volume of the AG1-X8 resin is 1 to 2 mL, the second washing solution is 1 to 10 mL of a 0.01 mol / L HCl solution; and the second hydrochloric acid solution is 1 to 10 mL of a 0.2 mol / L HCl solution.

[0024] Optionally, the LN resin column, CU resin column and AG1-X8 resin column are sequentially connected in series via connecting tubes. The beneficial effects of the present invention are as follows: the present application adopts a multi-step resin column separation and purification process, and by optimizing resin selection and operating conditions, it efficiently removes impurity elements and reduces product acidity, and ultimately obtains a high-purity 67Cu solution that meets the requirements of nuclear medicine applications. LN resin has a highly selective adsorption capacity for Sn and can effectively remove Sn impurities in the solution. CU resin has a specific adsorption effect on Cu and can efficiently remove Zn impurities in the solution while maximally retaining 67 Cu. AG1-X8 resin can not only further purify 67 Cu, removes residual trace impurities, and can effectively reduce the acidity of the solution to meet the requirements of nuclear medicine applications. Through the above multi-step resin column separation and purification process, this application successfully achieved 67 Efficient recovery and purification of Cu, ultimately obtaining high purity 67 The Cu solution fully meets the standards for nuclear medicine applications. The process has the advantages of simple operation, high recovery rate, and high product purity, and is suitable for large-scale production and application.

[0025] This application uses LN resin column to separate and remove Sn, then uses CU resin column to remove Zn, and finally uses AG1-X8 resin column to further purify and reduce 67 The acidity of the Cu product solution is to obtain the required 67 Cu solution, improve 67 Cu recovery rate. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 For the present invention 67 Flow chart of the Cu solution preparation method.

[0027] Figure 2 The distribution ratio of Cu and Zn on AG1-X8 resin under different HCl concentrations of the present invention.

[0028] Figure 3 The elution curve of Cu-Zn-Sn of the present invention on a 1 mL AG1-X8 column. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] Example

[0031] Example 1

[0032] A medical isotope 67 The separation and purification method of Cu comprises the following steps:

[0033] Weigh 1.0 g Zn particles and 0.1 g Sn powder in a 100 mL beaker, add 0.10 mL of 500 μg / mL Cu solution to the beaker, slowly drop 8 mL of a mixture of concentrated hydrochloric acid and concentrated nitric acid with a volume ratio of 10:1 to the beaker to completely dissolve the Zn particles and Sn powder, and drop 50 mL of 1.0 mol / L NH 3 ·H 2 O adjusts the solution acidity to 0.5-1.0 mol / L, and stirs evenly to obtain 58 mL of target material solution;

[0034] Weigh 3g of LN resin and soak it in ultrapure water for 24h, remove the small particles floating on the upper layer, take a 10mL empty separation column, install the lower filter plate and fill it with ultrapure water, wait for the water flow to be smooth, use a dropper to absorb 8mL of the soaked LN resin and move it into the separation column, install the lower filter plate, and rinse off the excess water; use 50mL of 0.5mol / L HCl solution to rinse the LN resin column, introduce the target material solution into the LN resin column, and adsorb Sn 4+ , obtain a first effluent, use 20mL 0.5mol / L HCl solution to wash the LN resin column to obtain a second effluent, mix the first effluent and the second effluent evenly, add 18mL 5.0mol / L ammonium acetate solution, mix evenly to obtain a first column liquid;

[0035] 2 mL of CU resin was loaded into a 2 mL empty separation column, and after installing the upper and lower filter plates, it was filled with ultrapure water. A peristaltic pump was used to evacuate air from the outlet at the lower end of the CU resin column. After the water flow was smooth, the evacuation was stopped and the excess ultrapure water was poured out. After the CU resin column was rinsed with 20 mL of 0.01 mol / L HCl solution, the first column liquid and 20 mL of 0.01 mol / L HCl were introduced into the CU resin column in sequence to obtain the second recovery liquid. 5 mL of 7.0 mol / L HCl solution was introduced into the CU resin column to obtain a desorption liquid.

[0036] Transfer 2 mL of soaked AG1-X8 resin into a 2 mL separation column, install the upper and lower filter plates, and rinse off excess water. Use 10 mL of 1.0 mol / L HNO 3 , 10mL ultrapure water, and 10mL 7.0mol / L HCl solution to rinse the AG1-X8 resin column; the desorption solution was introduced into the AG1-X8 resin column to adsorb Cu 2+ and residual Zn 2+ and Sn 4+ After washing the AG1-X8 resin column with 0.5 mL of 0.2 mol / L HCl solution, 4 mL of 0.2 mol / L HCl solution was introduced into the AG1-X8 resin column to obtain 67 Cu product solution.

[0037] Comparative Example

[0038] Comparative Example 1

[0039] A medical isotope 67 The separation and purification method of Cu comprises the following steps:

[0040] The irradiated Zn metal target was placed in a corundum crucible of a vacuum distillation device. Under vacuum conditions of 0.01-100 Pa and temperature of 600-800 °C, Zn was volatilized into a graphite crucible and condensed and deposited. After running for 8 hours, the target residue in the corundum crucible entered the chemical separation process. 8 mL of concentrated HCl + concentrated HNO was slowly added to the target residue. 3 (v / v=10:1) mixed acid to dissolve it completely. After the target is completely dissolved, add 50mL 1.0mol / L NH 3 ·H 2 O is neutralized and stirred evenly to obtain a target material solution;

[0041] Weigh 3g of LN resin and soak it in ultrapure water for 24h, remove the small particles floating on the upper layer, take a 10mL empty separation column, install the lower filter plate and fill it with ultrapure water, wait for the water flow to be smooth, use a dropper to absorb 8mL of the soaked LN resin and move it into the separation column, install the lower filter plate, and rinse off the excess water; use 50mL of 0.5mol / L HCl solution to rinse the LN resin column, introduce the target material solution into the LN resin column, and adsorb Sn 4+ , obtain a first effluent, use 20mL0.5 mol / L HCl solution to wash the LN resin column to obtain a second effluent, mix the first effluent and the second effluent evenly, add 18mL5.0mol / L ammonium acetate solution, mix evenly to obtain a first column liquid;

[0042] 2 mL of CU resin was loaded into a 2 mL empty separation column, and after installing the upper and lower filter plates, it was filled with ultrapure water. A peristaltic pump was used to evacuate air from the outlet at the lower end of the CU resin column. After the water flow was smooth, the evacuation was stopped and the excess ultrapure water was poured out. After the CU resin column was rinsed with 20 mL of 0.01 mol / L HCl solution, the first column liquid and 20 mL of 0.01 mol / L HCl were introduced into the CU resin column in sequence to obtain the second recovery liquid. 5 mL of 7.0 mol / L HCl solution was introduced into the CU resin column to obtain a desorption liquid.

[0043] Transfer 2 mL of soaked AG1-X8 resin into a 2 mL separation column, install the upper and lower filter plates, and rinse off excess water. Use 10 mL of 1.0 mol / L HNO 3 , 10mL ultrapure water, and 10mL 7.0mol / L HCl solution to rinse the AG1-X8 resin column; the desorption solution was introduced into the AG1-X8 resin column to adsorb Cu 2+ and residual Zn 2+ and Sn 4+ After washing the AG1-X8 resin column with 0.5 mL of 0.2 mol / L HCl solution, 4 mL of 0.2 mol / L HCl solution was introduced into the AG1-X8 resin column to obtain67 Cu product solution.

[0044] Performance Testing

[0045] 1. Zn in desorption solution 2+ and Sn 4+ The content of is measured, the measurement steps are as follows:

[0046] Weigh 0.210g ZnCl 2 , 0.220g SnCl 4 In a 100mL beaker, add 0.10mL 500μg / mL Cu standard solution with a pipette, dissolve it with 100mL 0.2mol / L HCl, weigh 3g LN resin and soak it in ultrapure water for 24h, remove the small particles floating on the upper layer, take a 10mL empty separation column, install the lower filter plate and fill it with ultrapure water, after the water flow is smooth, use a dropper to absorb 8mL of the soaked LN resin and move it into the separation column, install the lower filter plate, and rinse off the excess water; use 50mL 0.5mol / LHCl solution to rinse the LN resin column, introduce the target material solution into the LN resin column, and adsorb Sn. 4+ , obtain the first effluent, use 20mL 0.2mol / L HCl solution to wash the LN resin column, obtain the second effluent, mix the first effluent and the second effluent evenly, and then add NH 3 ·H 2 O ammonium acetate solution, mix well to obtain a first column liquid with a volume of 130 mL;

[0047] 2mL of CU resin was loaded into a 2mL empty separation column. After installing the upper and lower filter plates, it was filled with ultrapure water. A peristaltic pump was used to extract air from the outlet at the lower end of the CU resin column. After the water flow was smooth, the air was stopped and the excess ultrapure water was poured out. 20mL of 0.01mol / L HCl solution was introduced into the CU resin column. 10mL of 0.01mol / L HCl solution was added in batches to rinse the CU resin column to obtain the eluent. 1mL was added each time. The 1st, 3rd, 5th, 7th, and 9th mL of the eluent were marked as C1 to C5. 5mL of 0.1mol / L HCl solution was added in batches to the CU resin column to obtain the eluent. 1mL was added each time. The 1st, 3rd, and 5th mL of the eluent were marked as C6 to C8. 10mL of 6.0mol / L HCl solution was introduced into the CU resin column in batches to obtain the desorption solution. 1mL was added each time. The desorption solution was marked as C9 to C18. 5.0mL was added to C1 to C9. 1.0 mol / L HCl solution, diluted 6 times; add 5.0 mL ultrapure water to each of the C9-C18 plastic centrifuge tubes and dilute 6 times.

[0048] (1) Preparation of mixed standards of Cu, Zn, and Sn: 0.05, 0.1, 0.5, 1.0, 2.0, 5.0, and 10.0 ppm, in 1.0 mol / L HCl medium, labeled B1 to B7. The data of the standard solutions measured by ICP-OES are shown in Table 1.

[0049] Table 1

[0050] serial number B0 B1 B2 B3 B4 B5 Concentration / μg / mL 0.00 0.05 0.10 1.00 5.00 10.00 Cu counting rate / cps 2 101 198 2038 10238 20654 Zn counting rate / cps 2 54 107 1049 5227 10381 Sn count rate / cps 1 7 12 120 594 1191

[0051] (2) Calculate the Cu content in the eluent based on the ICP-OES measurement data. 2+ 、Zn 2+ Sn 4+ The concentrations are shown in Table 2.

[0052] Table 2

[0053]

[0054]

[0055] No Cu flowed out during the loading process of the column liquid. Some Cu was lost when eluting with 5 mL 0.1 mol / L HCl. 4 mL 6.0 mol / L HCl was used to desorb Cu, and the recovery rate was >83.5%.

[0056] Table 2 shows that 8 mL of LN resin column can completely remove 100 mg of Sn. In 0.01 mol / L HCl medium, CU resin does not adsorb Zn. 130 mL of 100 mg Zn solution has no effect on the separation of 50 μg Cu. After the liquid is loaded on the column, elution with 10 mL of 0.01 mol / L HCl can completely remove Zn. Elution with 5 mL of 0.1 mol / L HCl will cause partial loss of Cu, so this step can be omitted. For 2 mL of CU resin column, 50 μg Cu can be completely desorbed with 2 mL of 6.0 mol / L HCl. To ensure complete reception, the process determines that 4 mL (2 column volumes) of 6.0 mol / L HCl is used to desorb Cu, and the recovery rate is > 83.5%. Desorption of Cu with analytically pure 6.0 mol / L HCl will bring in a certain amount of Zn and Sn, so high-purity HCl is required.

[0057] 2. Cu 2+ -Zn 2+ The distribution ratio is measured on AG1-X8 anion resin. The measurement steps are as follows:

[0058] Prepare the solution:

[0059] HCl solution: 40 mL each of 0.001, 0.01, 0.1, 0.5, 1.0, 2.0, 4.0, and 6.0 mol / L;

[0060] Mixed standard solution: Pipette 10.0 mL of 500 mg / L Cu standard and 10.0 mL of 500 mg / L Zn standard into a 50 mL beaker, heat on a hot plate and evaporate to dryness, dissolve in 5.0 mL of ultrapure water in batches and transfer to 10 mL plastic centrifuge tubes with lids, shake well, and set aside. The concentration of each element is 1000 mg / L.

[0061] Take 8 10mL plastic centrifuge tubes with caps, add 0.200mL of mixed standard solution to each, then add 8.0mL of 0.001, 0.01, 0.1, 0.5, 1.0, 2.0, 4.0, 6.0mol / L HCl in sequence, shake well. Mark them as b1, b2, b3, b4, b5, b6, b7, b8 respectively.

[0062] Take 8 10mL plastic centrifuge tubes with caps and label them as a1, a2, a3, a4, a5, a6, a7, and a8. Weigh the AG1-X8 anion resin respectively and record the exact weight W (g). The specific weight is as follows:

[0063] a1: 0.269, a2: 0.259, a3: 0.270, a4: 0.288, a5: 0.299, a6: 0.300, a7: 0.279, a8: 0.293;

[0064] Add 8.0mL of 0.001, 0.01, 0.1, 0.5, 1.0, 2.0, 4.0, 6.0mol / L HCl to centrifuge tubes a1, a2, a3, a4, a5, a6, a7, and a8, shake well, and soak for 12h; add 0.200mL of mixed standard solution to each centrifuge tube a1, a2, a3, a4, a5, a6, a7, and a8, cover tightly, and shake for 30min; use a 2mL medical syringe to draw the solution in each centrifuge tube, add a 0.45μm syringe filter to filter into another empty centrifuge tube; transfer 0.5mL of each filtered a1, a2, a3, a4, a5, a6, a7, and a8 solution to another empty centrifuge tube, add 5.0mL of ultrapure water to each, cover tightly, shake well, and send for measurement. Mark them as A1, A2, A3, A4, A5, A6, A7, A8 respectively; transfer 0.5 mL of solution b1, b2, b3, b4, b5, b6, b7, b8 to another empty centrifuge tube, add 5.0 mL of ultrapure water to each tube, cover the tube tightly, shake well, mark them as B1, B2, B3, B4, B5, B6, B7, B8 respectively, and send them for measurement.

[0065] ICP-OES measures the counting rate of Cu and Zn in each sample. The counting rate of samples B1, B2, B3, B4, B5, B6, B7, and B8 is C0, and the counting rate of samples A1, A2, A3, A4, A5, A6, A7, and A8 is C. The distribution ratio of each element is calculated as follows:

[0066]

[0067] Among them, C 0 is the counting rate of samples B1 to B8, C is the counting rate of samples A1 to A8, and the weight of resin used in each sample is W.

[0068] The distribution ratios calculated based on the measured data are shown in Table 3 and Figure 2 .

[0069] Table 3 Distribution ratio of Cu and Zn on AG1-X8 resin at different HCl concentrations

[0070]

[0071] When the HCl concentration is less than 4.0 mol / L, Cu 2+ The distribution ratio is less than 5. When the HCl concentration is greater than or equal to 6.0 mol / L, Cu 2+ The distribution ratio of Zn 2+ The distribution ratio increases first and then decreases. When the HCl concentration is equal to 2.0 mol / L, Zn 2+ The distribution ratio of Zn is the largest, greater than 1000; when the HCl concentration is 6.0 mol / L, 2+ The distribution ratio is 338, Cu 2+ The distribution ratio of Zn is 11. 2+ and Cu 2+ can be adsorbed by AG1-X8 resin; when the HCl concentration is 0.2 mol / L, Zn 2+ The distribution ratio is greater than 100, Cu 2+ The distribution ratio of Cu is about 1.0. 2+ It is not adsorbed and can be easily washed off, while Zn 2+ Therefore, when the HCl concentration is greater than 0.5 mol / L, the AG1-X8 anion exchange resin has no significant effect on Zn 2+ The adsorption capacity is greater than that of Cu 2+ The adsorption capacity is sufficient for further purification 67 The purpose of Cu; select 6.0~7.0mol / L HCl medium for column loading, Zn 2+ and Cu 2+ All can be adsorbed on the AG1-X8 resin column; 0.2 mol / L HCl is selected to desorb Cu2+ , Zn 2+ Still adsorbed on the AG1-X8 resin column, so that higher chemical purity can be obtained 67 Cu.

[0072] 3. Separation performance of Cu-Zn-Sn on AG1-X8 anion resin column. The specific steps are as follows:

[0073] Prepare the column solution: add 0.04 mL of 500 μg / mL Zn standard solution, 0.02 mL of 1000 μg / mL Sn standard solution, and 0.1 mL of 500 μg / mL Cu standard solution to a 10 mL plastic centrifuge tube with a lid, then add 5 mL of 6.0 mol / L HCl solution and mix well.

[0074] Transfer 2 mL of soaked AG1-X8 resin into a 1 mL separation column, install the upper and lower filter plates, and rinse off excess water. Use 10 mL of 1.0 mol / L HNO 3 , 10mL ultrapure water, 10mL 0.01mol / L HCl solution, 5mL 6.0mol / L HCl solution to wash the AG1-X8 resin column; transfer the prepared column liquid into the column to adsorb Cu 2+ 、Zn 2+ Sn 4+ ; 1mL 6.0mol / LHCl was used to wash the centrifuge tube and transferred to the separation column; 10mL 0.2mol / L HCl was used to desorb Cu, 1mL was added each time, and the mixture was collected in plastic centrifuge tubes and marked as D1 to D10; 5.0mL ultrapure water was added to each of the D1 to D10 plastic centrifuge tubes, and the mixture was diluted 6 times and shaken well.

[0075] A mixed standard of Cu, Zn and Sn was prepared: 0.05, 0.1, 0.5, 2.0, 10.0 ppm, 0.02 mol / L HCl medium, marked as E1~E5, and the measurement data of the standard solution is shown in Table 4; ICP-OES measured the counting rates of Cu, Zn and Sn in E1~E5, D1~D10, and the measurement data were linearly fitted to obtain the standard working curve equation, Cu: y=2296.02x+2.3934, correlation coefficient R=1; Zn: y=906.29x+4.3954, correlation coefficient R=1; Sn: y=132.65x-1.5011, correlation coefficient R=0.99995.

[0076] Table 4 Measurement data of standard solution

[0077] serial number E0 E1 E2 E3 E4 E5 Concentration / μg / mL 0.00 0.05 0.10 0.50 2.00 10.00 Cu counting rate / cps 7 117 231 1148 4593 22963 Zn counting rate / cps 3 49 92 457 1824 9066 Sn count rate / cps 0 8 14 67 253 1327

[0078] The concentrations of Cu, Zn and Sn in the desorption solution were calculated based on the measured data and the standard working curve equation and are listed in Table 5. The concentrations of Cu, Zn and Sn in the effluent after 5 mL of column liquid and 1 mL of 6.0 mol / L HCl washing liquid passed through the separation column were estimated based on the distribution ratio data, and the elution curve was drawn in combination with the measured data of the desorption solution. Figure 3 .

[0079] Table 5 Concentrations of Cu, Zn and Sn in the effluent

[0080]

[0081]

[0082] From the column separation experimental data, it can be seen that 20μg of Zn and Sn in 50μg Cu can be completely separated and removed by 1mL of AG1-X8 column, and 51.29μg Cu can be obtained by desorption with 2mL of 0.2mol / L HCl, with a recovery rate of 102.6%, of which the concentrations of Zn and Sn are less than 0.04μg / mL, and a small amount of Zn and Sn begin to flow out from the 5th mL; 50μg Cu (containing 20μg of Zn and Sn each) is purified and separated by 1mL of AG1-X8 column, 6mL of 6mol / L HCl is loaded on the column, and Cu, Zn, and Sn are completely adsorbed; Cu can be completely desorbed by 2mL of 0.2mol / L HCl, with a recovery rate of 102.6%. When eluted with 0.2mol / L HCl, a small amount of Zn and Sn begin to flow out from the 5th mL. From the baseline of the elution curve, it is estimated that the concentrations of Zn and Sn in the Cu product are less than 0.04μg / mL.

[0083] 3. Detection of pH value of target material solution. The detection steps are as follows:

[0084] After the target residue is dissolved, Sn is first removed with an LN resin column. The distribution ratio of Zn and Sn on LN resin at different HCl concentrations is shown in Table 6. From the data in Table 6, it can be seen that when the HCl concentration is 0.1-2.0 mol / L, LN resin adsorbs Sn but not Zn, so it is appropriate to select an HCl concentration of 0.1-2.0 mol / L in the target solution. The experimental results of the separation of 50μgCu in 100mg Zn+100mg Sn in Section 2 have proved that in a 0.2 mol / L HCl medium, 8mL LN resin column can completely remove 100mg of Sn. In order to increase the redundancy during acidity adjustment, the HCl concentration in the target solution is set to 0.5-1.0 mol / L.

[0085] Table 6 Distribution ratio of Zn and Sn on LN resin

[0086] HCl / mol / L 0.01 0.1 0.2 0.5 1.0 2.0 4.0 6.0 Sn 42483 55727 54803 26407 7015 817 31 17 Zn 72.56 3.48 1.15 0.33 0.63 1.11 1.78 4.94

[0087] (1) Weigh ~1.0 g Zn particles and ~0.1 g Sn powder in a 100 mL beaker, add 0.10 mL of 500 μg / mL Cu standard solution; add 50% concentrated HCl + concentrated HNO in batches. 3 (v / v = 25:1) mixed acid, 1.0 mL per batch, when no bubbles are generated in the beaker solution, add 2 mL more 50% concentrated HCl + concentrated HNO 3 (v / v=25:1) mixed acid; after observing that the target material is completely dissolved, add 25mL ultrapure water to dilute and stir evenly to obtain the target material solution. Accurately pipette 1.00mL of the target material solution, add ~5mL ultrapure water and a few drops of phenolphthalein solution, and titrate with 0.100mol / L standard NaOH solution to determine the acidity of the target material solution. Repeat the titration operation twice. Repeat the target material dissolution simulation experiment twice.

[0088] (2) Weigh 1.0 g Zn particles and 0.1 g Sn powder in a 100 mL beaker, add 0.10 mL 500 μg / mL Cu standard solution; slowly add 10 mL concentrated HCl + concentrated HNO 3 (v / v=10:1) mixed acid to make it completely dissolved, without heating at the beginning, observe the intensity of the reaction, and heat appropriately when the reaction is slow; after observing that the target material is completely dissolved, add 50mL 1.0mol / L NH 3 ·H 2 O for neutralization and stirring to obtain target material solution. Accurately pipette 2.00mL of target material solution, add ~5mL of ultrapure water and a few drops of phenolphthalein solution, and titrate with 0.100mol / L standard NaOH solution to determine the acidity of the target material solution. Repeat the titration operation twice. Repeat the target material dissolution simulation experiment twice.

[0089] Use 50% concentrated HCl + concentrated HNO 3 When the mixed acid (v / v = 25:1) was dissolved, a total of 7 mL of mixed acid was added to each sample, which was an excess. However, the oxide film on the surface of the Zn particles was difficult to dissolve, and a white precipitate was formed in the solution. Then, concentrated HCl + concentrated HNO 3 (v / v = 25:1) mixed acid, heated and stirred, a total of 6 mL of mixed acid was added, and the oxide film and white precipitate were completely dissolved. 3 The amount of HCl+HNO was not enough, and the oxidation ability was not strong; then concentrated HCl+HNO was added to samples 1 and 3 respectively. 3(v / v=10:1) mixed acid, 1.0mL per batch, heated and dissolved until no bubbles were generated in the beaker solution, and a total of 6mL of mixed acid was added. The solution in the beaker was yellow, the Zn particles in the beaker were completely dissolved and the white precipitate disappeared; after observing the dissolution of target samples No. 1, 2, and 3, 25mL of ultrapure water was added to dilute and stir evenly to obtain target solution, 1.00mL of target solution was transferred, 5mL of ultrapure water and a few drops of phenolphthalein solution were added, and titrated with 0.100mol / L standard NaOH solution, the amount of 0.100mol / L standard NaOH solution was recorded, and the acidity of the target solution was further calculated, and the titration experiment was repeated twice, and the results are shown in Table 7.

[0090] Table 7 Acidity of target dissolving solution

[0091]

[0092]

[0093] Where: V—50% concentrated HCl + concentrated HNO 3 (v / v = 25:1) volume; V' - concentrated HCl + concentrated HNO 3 (v / v=10:1); V1, V2, V3—the volume of 0.100mol / L standard NaOH solution.

[0094] After the target material was dissolved, it was diluted with 25 mL of ultrapure water, with a total volume of 38 mL. The acidity of the target material solution was 1.44-1.95 mol / L, which did not reach the acidity target.

[0095] Use 10mL concentrated HCl + concentrated HNO 3 (v / v=10:1) mixed acid to dissolve the target material, and then use 50mL 1.0mol / L NH 3 ·H 2 O was used for neutralization and stirred evenly to obtain a target material solution. Then, the acidity of the target material solution was titrated with a 0.0926 mol / L or 0.0943 mol / L standard NaOH solution. The results are shown in Table 8.

[0096] Table 8 Target weight and acidity of target solution

[0097] Sample No. Zn particles / g Sn powder / g V1 / mL V2 / mL V3 / mL Acidity / (mol / L) 1 1.0 0.1 21 21.2 21 0.9754 2 1.0 0.1 17.5 17.7 17.4 0.8118 3 1.0 0.1 15.8 15.6 15.7 0.7402

[0098] The experimental results show that the acidity of the target solution can be adjusted in the range of 0.5-1.0 mol / L by this method, and the solution is adjusted to 60 mL to achieve the expected goal. 3 (v / v=10:1) mixed acid dissolution, the volume is controlled at 8-10mL; after the target is dissolved, add 50mL 1.0mol / L NH3 ·H 2 O adjusts the acidity of the solution to control the acidity within the target range of 0.5 to 1.0 mol / L.

[0099] The experiment of Example 1 was repeated 3 times, and the recovery rates were 45.3%, 113%, and 111%, respectively. In the first experiment, about 55% of Cu was lost. This is because the CU resin is very hydrophobic and has a very low density. It can only be packed in a dry column, which easily causes uneven column filling, and the mobile phase will form a channeling phenomenon. When adsorbed on the column, part of the Cu is not adsorbed and is lost; 67 The removal rate of Zn and Sn in the Cu separation and purification process is very high. In the final Cu sample solution, Zn is less than 0.005μg / mL and Sn is less than 0.02μg / mL. The content is very low and the separation effect is good.

[0100] In comparative example 1 67 The Cu product solution was measured by ICP-OES, and the Cu recovery was 28.2μg, the Cu addition was 50.00μg, and the recovery rate was 56.4%. The Sn concentration in the sample solution was: 0.0000μg / mL (not measured), and the Zn concentration was 0.002μg / mL. During the vacuum distillation process, part of the Cu volatilized into the graphite crucible along with the Zn, resulting in a low recovery rate.

[0101] Finally, it should be noted that the above description is only a preferred example of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art can still modify the technical solutions described in the aforementioned embodiments or replace some of the technical features therein by equivalents. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A medical isotope 67 The method for separating and purifying Cu is characterized in that: The steps include: S1, adding Zn particles and Sn powder into a Cu solution, then adding a mixed acid to dissolve, and adjusting the pH of the solution with a first buffer solution to obtain a target material solution; S2, preparing an LN resin column and introducing the target material dissolving solution into the column to obtain a first recovery solution, and adjusting the pH of the first recovery solution by a second buffer solution to obtain a first column liquid; S3, preparing a CU resin column and sequentially introducing the first column liquid and the first washing liquid to obtain a second recovery liquid; S4, introducing the first hydrochloric acid solution into the CU resin column to obtain a desorption solution; S5, preparing an AG1-X8 resin column and sequentially introducing the desorption liquid and the second washing liquid to obtain a waste liquid; S6, introducing the second hydrochloric acid solution into the AG1-X8 resin column to obtain 67 Cu product solution.

2. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The mass ratio of Zn particles to Sn powder is 10:1, and the Cu content of the Cu solution is 2+ The concentration is 500 μg / mL, and the mixed acid is a mixture of concentrated hydrochloric acid and concentrated nitric acid in a volume ratio of (3-25):1; The preparation of the target solution includes the following steps: adding 1g Zn particles and 0.1g Sn powder into 0.1mL Cu solution and then adding mixed acid; after the Zn particles and Sn powder are completely dissolved, adding 1.0mol / L NH3·H2O solution to neutralize the solution to an acidity of 0.5-1.0mol / L, thereby obtaining a target solution.

3. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The mass of the LN resin is 2 to 3 g, the target solution passes through the LN resin column to obtain a first effluent, the third hydrochloric acid solution passes through the LN resin column to obtain a second effluent, the first recovery liquid is a mixture of the first effluent and the second effluent; the third hydrochloric acid solution is 10 to 50 mL of a HCl solution with a molar concentration of 0.1 to 1.0 mol / L.

4. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The preparation steps of the LN resin column are as follows: After LN resin was soaked in ultrapure water for 24 h, it was loaded into a 10 mL separation column; Wash the LN resin column with a third hydrochloric acid solution; Wherein, the volume of LN resin in the LN separation column is 8 mL.

5. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The second buffer solution is one of ammonium acetate and ammonia water, and the amount of the second buffer solution added is 15-20 ml; The pH of the first column liquid is 2-6.

6. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The volume of the CU resin column is 1-2 mL, the first washing liquid is 20 mL of 0.01 mol / L HCl solution; the first hydrochloric acid solution is 2-6 mL of HCl solution with a molar concentration of 0.5-7.0 mol / L.

7. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The volume of the AG1-X8 resin is 1 to 2 mL, the second washing liquid is 1 to 10 mL of a 0.01 mol / L HCl solution; and the second hydrochloric acid solution is 1 to 10 mL of a 0.2 mol / L HCl solution.

8. A medical isotope according to claim 1 67 The method for separating and purifying Cu is characterized in that: The LN resin column, the CU resin column and the AG1-X8 resin column are sequentially connected in series via connecting pipes.

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