A method for preparing high-purity Ge-68 using a high-intensity proton cyclotron

Abstract

The present invention provides a method for preparing high-purity Ge-68 by using a high-intensity proton cyclotron, comprising the following steps: S1: preparing a fixed Ga4Ni alloy target, subjecting the alloy target to high-intensity proton irradiation treatment, and then performing sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni and nat Cu; S2: introducing the electrolytic solution into a series of chromatographic columns for separation and purification, the series of chromatographic columns being a hydroxamate resin separation column, a cross-linked polydivinylbenzene resin separation column, and an AG MP-50 resin separation column, and collecting the solution containing 68 Ge to complete the preparation. By means of the present invention, the problems in the prior art of cumbersome and lengthy chemical separation processes, poor preparation effects, and high preparation technical difficulties in the preparation of high-purity Ge-68 are solved, and a method for preparing high-purity Ge-68 by using a high-intensity proton cyclotron that is simple to operate and easy to automate is provided; the 68 Ge product obtained by the present invention has a high purity, is in a hydrochloric acid medium, has a suitable acidity, and can be directly used to prepare a Ge-Ga generator.

Description

Technical Field

[0001] The invention relates to the technical field of isotope production, and in particular to a method for preparing high-purity Ge-68 by using a high-current proton cyclotron. Background Art

[0002] Recommended by the International Atomic Energy Agency (IAEA) nat Ga(p,xn) 68 Ge nuclear reaction production 68 Ge, 68 The production of Ge is mainly concentrated in Brookhaven National Laboratory and Los Alamos National Laboratory in the United States, the South African National Accelerator Center and the Obninsk Cyclotron Company in Russia. Due to the special chemical properties of metal Ga, its low melting point and high chemical activity, Brookhaven National Laboratory, Los Alamos National Laboratory and the South African National Accelerator Center produce Ge. 68 Ge, usually prepared by irradiation of metal Ga target wrapped in Nb capsule 68 Ge, and then chemically separated by extraction or volatilization; while the Russian Obninsk Cyclotron Co., Ltd. has been using the Ga4Ni alloy target prepared by the melting method and using copper as the target support for irradiation production. 68 Ge. The preparation of metallic Ga targets has very strict requirements on the grain size, purity and preparation method of the encapsulating material Nb. The preparation of Ga4Ni alloy by melting method is technically difficult and the bonding with the copper target holder is not strong. Ga-Ni alloy targets can also be prepared by electroplating, which can withstand higher irradiation beams than melting method. At the same time, the chromatographic separation process is a commonly used chemical separation method for medical isotopes, which can realize continuous separation operations and is conducive to the design and control of automated separation.

[0003] In 2014, the Institute of Isotopes of the China Institute of Atomic Energy and Atom Hi-Tech Co., Ltd. reported the use of electroplating to prepare Ga-Ni alloy targets (a radioactive 68 Ge solution preparation method), and a layer of metal Ni was plated on the Ga-Ni alloy layer to prevent damage to the target during irradiation. The prepared target was also placed at the Cyclone-30 cyclotron terminal for a small dose irradiation experiment to verify the feasibility of the target. After the target was cooled, the target was electrolyzed, the electrolyte was separated and purified on a silica gel column, and desorbed with a nitric acid solution. 68 Ge. The silica gel column separation method has some disadvantages. First, after the solution is loaded on the silica gel column, it needs to be eluted with sulfuric acid to remove the impurity ions on the silica gel column. The residual sulfate ion content on the silica gel column is very high, which will lead to the preparation of 68 Ge solution cannot be used 68 Ge- 68Preparation of Ga generator. Secondly, even if concentrated nitric acid is used to elute the silica gel column, the sulfate ions on the silica gel column can be removed, but it needs to be continuously desorbed and repeatedly soaked with dilute nitric acid, and the process is time-consuming. Finally, the desorption solution containing nitric acid medium is evaporated to dryness with a polytetrafluoroethylene evaporating dish to remove nitric acid, and then the solid matter in the evaporating dish is soaked with hydrochloric acid solution for one week to prepare 68 Ge- 68 Preparation of the hydrochloric acid medium required for the Ga generator 68 Ge solution. This method changes three acidic media in the middle, and the chemical separation process is complicated and lengthy.

[0004] In 2023, the Institute of Modern Physics of the Chinese Academy of Sciences and Sichuan University used electroplating to prepare Ga-Ni alloy targets (a method based on accelerator irradiation production and preparation in China with Chinese publication number CN114937516 A) 68 Ge method), referring to the dual AG1X8 and Ge method developed by Brookhaven National Laboratory in the United States for Nb capsule-wrapped metal Ga targets. The three-column separation process of G-25 was established by Chelex100 and G-25 resin coupled with a recyclable dual-column separation process was designed and built 68 Ge automated separation device, and the device was used to achieve accelerator irradiation Ga-Ni alloy target 68 Separation of Ge, 68 Ge recovery rate is about 70%, activity is about 5mCi, The final eluent of G-25 is hydrochloric acid medium, which is very suitable for direct preparation 68 Ge- 68 Ga generator. This method also has some problems. BNL uses Nb capsule to wrap the metal Ga target process, which only requires dilute hydrochloric acid and hydrogen peroxide to dissolve the target, while the Ga-Ni alloy target needs to be dissolved with a strong acid solution and hydrogen peroxide mixed system, which takes 8-10 hours; the Ga-Ni alloy target solution is dark blue and transparent, indicating that the copper target holder is dissolved in large quantities, while the Nb capsule wrapped metal Ga target does not have this problem. And because the Cu in the target solution 2+ The concentration is too high. The Chelex 100 column needs to be reused three times to remove a large amount of Cu. 2+ If the large amount of Cu is not removed at the Chelex 100 column stage, 2+ , when the pH is adjusted to alkaline ( Before G-25 column separation), Cu 2+ Being precipitated will not only cause 68 More losses, and 68 Ge products also contain a large amount of citric acid and inorganic impurities.

[0005] ITM Germany is producing68 Ge- 68 Before the Ge-Ga generator, the Ge stock solution from BNL or LANL sources is often further finely separated (Chinese Publication No. CN 110612272 A Method for preparing high-purity Ge materials for radiopharmaceutical purposes), and a Ge-API (API = active pharmaceutical ingredient) solution meeting Good Manufacturing Practice (GMP) is produced. The radiochemical method disclosed in its patent is based on separating Ge with two different adsorption materials. First, Eichrom PreFilter resin is used to adsorb germanium tetrachloride form to purify Ge from organic and metal impurities, and then further purification is carried out through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge stock solution for further fine separation (Chinese Patent Publication No. CN 110612272 A Method for preparing high-purity Ge materials for radiopharmaceutical purposes), producing a Ge-API (API = active pharmaceutical ingredient) solution that complies with Good Manufacturing Practice (GMP). The radiochemical method disclosed in the patent is based on separating Ge with two different adsorption materials. First, Eichrom PreFilter resin is used to adsorb germanium tetrachloride form to purify Ge from organic and metal impurities, and then further purification is carried out through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge material) to produce a Ge-API (API = active pharmaceutical ingredient) solution that complies with Good Manufacturing Practice (GMP). The radiochemical method disclosed in the patent is based on separating Ge with two different adsorption materials. First, Eichrom PreFilter resin is used to adsorb germanium tetrachloride form to purify Ge from organic and metal impurities, and then further purification is carried out through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge-API (API = active pharmaceutical ingredient) solution. The radiochemical method disclosed in the patent is based on separating Ge with two different adsorption materials. First, Eichrom PreFilter resin is used to adsorb germanium tetrachloride form to purify Ge from organic and metal impurities, and then further purification is carried out through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge, first using Eichrom PreFilter resin to adsorb germanium tetrachloride form to purify Ge from organic and metal impurities, and then further purifying through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge, and then further purified through cation exchange of AG MP-50 resin, so that the final Ge-API product meets the regulatory requirements of GMP production specifications. 68 Ge-API product meets the regulatory requirements of GMP production specifications.

[0006] Currently, in the prior art for preparing high-purity GE-68, there are still a large number of problems, including the cumbersome and lengthy operation of the chemical separation process, poor preparation effect due to the large amount of dissolution of the target holder caused by the addition of strong acidic solution and hydrogen peroxide during the reaction process, and high preparation technical difficulty. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide a method for preparing high-purity Ge-68 using a high-intensity proton cyclotron to solve the problems of cumbersome and lengthy chemical separation process, poor preparation effect, and high preparation technical difficulty in the prior art for preparing high-purity Ge-68.

[0008] To solve the above problems, the present invention provides a method for preparing high-purity Ge-68 using a high-intensity proton cyclotron, including the following steps:

[0009] S1: Prepare a fixed Ga4Ni alloy target, and after irradiating the alloy target with high-intensity protons, perform sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing Ge, Ga, Co, Zn, Ni, and Cu; 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni, and nat Cu;

[0010] S2: Pass the electrolytic solution obtained in step S1 through a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamic acid ester resin separation column, cross-linked polydivinylbenzene resin separation column, and AG MP-50 resin separation column, and collect the solution containing Ge to complete the preparation. 68 Ge solution to complete the preparation.

[0011] A method for preparing high-purity Ge-68 by using a high-intensity proton cyclotron according to the present invention uses an inert metal as a substrate target holder. After preparing a solid Ga4Ni alloy target and irradiating the target with a high-intensity proton cyclotron, the target is further electrolyzed with sulfuric acid, and a tandem chromatographic column separation process of hydroxamate resin (Zr resin), cross-linked polystyrene resin (Guard resin) and AG MP-50 resin is established, so as to prepare Ge-68 with relatively high purity, solving the problems of cumbersome and lengthy operation in the chemical separation process of preparing high-purity Ge-68 in the prior art, poor preparation effect and high preparation technical difficulty.

[0012] Moreover, the present invention provides a fast and efficient electrolysis target method. Since most of the target dissolution methods in the prior art use hydrochloric acid plus hydrogen peroxide and heating to assist dissolution to generate a GeCl4 solution, and GeCl4 has a low boiling point (84°C), is easy to generate radioactive aerosol, and the process takes a long time and is cumbersome, bringing great trouble. While the present invention adopts a sulfuric acid electrolysis process, which is simple to operate, the sulfuric acid medium avoids pollution by volatile radioactive substances, and the electrolysis takes a short time. And the operation of the present invention is simple and easy to realize automation; the 68 Ge product prepared by the preparation method of the present invention has high purity, is in a hydrochloric acid medium, has a suitable acidity, and can directly prepare a Ge-Ga generator.

[0013] In a possible implementation manner, in the step S1, the conditions for the high-intensity proton irradiation treatment are: irradiating with a high-intensity proton accelerator, with an energy of 18-30 MeV, a beam current of 50-300 μA, a time of at least 3 h, and a cooling time of at least 20 days.

[0014] In a possible implementation manner, in the step S1, the structure of the solid Ga4Ni alloy target is as follows in 1) or 2):

[0015] 1) It includes at least two layers, including a metal base layer and a solid gallium-nickel alloy layer connected in sequence;

[0016] 2) It includes at least three layers, including a metal base layer, a metal protection layer and a solid gallium-nickel alloy layer connected in sequence;

[0017] In 1), the material of the metal base layer is Ta, Ti, Nb or Inconel alloy;

[0018] In 2), the material of the metal base layer is Cu or Al;

[0019] The material of the metal protection layer is Au or Pt, and the thickness is more than 5 μm.

[0020] In the above possible embodiments, in 1), the material of the metal-based bottom layer is selected as an inert metal with conductivity, heat conductivity, high hardness, and corrosion resistance, thereby improving the conductivity, heat conductivity, strength, and corrosion resistance of the target structure; in 2), the material of the metal-based bottom layer is selected as an inert metal with conductivity, heat conductivity, high hardness, and corrosion resistance, and an inert metal with strong conductivity and heat conductivity is selected as the metal protection layer, further improving the strength, thermal conductivity, electrical conductivity, and corrosion resistance of the target structure.

[0021] In a possible embodiment, in the solid gallium-nickel alloy layer, the mass content of Ga is not less than 60%, and the thickness is greater than 20 mg / cm 2 .

[0022] In a possible embodiment, the solid gallium-nickel alloy layer is prepared by electroplating, and the preparation method includes:

[0023] A1: Dissolve metallic gallium in HNO3 solution, heat and stir, and then add H2SO4 solution with a concentration of more than 98% to obtain Ga2(SO4)3 precipitate;

[0024] A2: Dissolve the Ga2(SO4)3 precipitate prepared in step A1 in water, adjust the pH value of the solution to 2 - 2.5 with ammonia solution, heat the solution to 40 - 50 °C, and add NiSO4 to prepare the final electroplating solution;

[0025] A3: Perform electrodeposition using a constant current electrolysis technique, adjust the current density to 20 - 60 mA / cm 2 , the temperature is 25 - 100 °C, maintain a rotation speed of about 300 - 800 rpm during the electroplating process, and obtain a Ga4Ni alloy target after 6 - 8 hours.

[0026] In the above possible embodiments, a method for preparing high-purity Ge-68 using a high-intensity proton cyclotron according to the present invention prepares a Ga4Ni alloy target that is easy to irradiate and separate by controlling the electroplating method. Based on a corrosion-resistant inert metal substrate, a Ga4Ni alloy target is prepared by an electroplating method with simple operation and stable process. The combination of the electroplating method and the target holder is firmer than the melting method and can withstand a larger irradiation beam current. And by using a Ta target holder substrate, inorganic impurities such as copper, aluminum, and gold can be avoided from being introduced during the dissolution of the target, which affects the effect of subsequent chromatographic separation.

[0027] In a possible embodiment, in step A1, the weight ratio of the metallic gallium to the NiSO4 is (15 - 20):(10 - 15); the concentration of the HNO3 solution is 9 - 12 M.

[0028] In a possible implementation, in the step S2, the step of passing the electrolyte solution into a series of chromatographic columns for separation and purification includes:

[0029] B1: Dilute the electrolyte solution and perform at least one separation process. The separation process includes: passing it through the hydroxamate resin separation column, eluting with H2SO4 and collecting the elution waste liquid simultaneously, then desorbing the elution waste liquid with dilute citric acid to obtain a desorbed solution, and adding H2SO4 to the desorbed solution at the same time; after the separation process is completed, add HCl to the desorbed solution for acidification;

[0030] B2: Pass it through a cross-linked polydivinylbenzene resin separation column into the desorbed solution acidified in step B1, elute with HCl and collect the elution waste liquid simultaneously, then desorb the elution waste liquid with deionized water to obtain a pure water desorbed solution; finally, pass the pure water desorbed solution into an AG MP-50 resin separation column, add HCl for further desorption, and collect the Ge-68 product to complete the preparation.

[0031] In the above possible implementation, the number of times of the separation process is 1 - 3 times. Through multiple separation processes, the treatment effect on waste impurities in the analytical solution can be improved.

[0032] In the above possible implementation, in step B1, since the elution waste liquid contains a large amount of inorganic impurities such as Ga, Ni, Co, and Zn, dilute citric acid is used to desorb the above elution waste liquid to remove a large amount of the above impurities; and further in step B2, the elution waste liquid collected after eluting with HCl contains a large amount of sulfuric acid, citric acid, and organic impurities, so it is desorbed with deionized water to remove a large amount of the above impurities; finally, through the AG MP-50 resin separation column, trace impurities such as Fe, Ni, Cu, Zn, and Pb in the solution are removed, and further desorption is performed with HCl again, thereby improving the final purity of the Ge-68 product.

[0033] In a possible implementation, in step B1, the conditions for diluting the electrolyte solution are to dilute it to a H2SO4 concentration of 5 - 8 M; in the elution with H2SO4, the concentration of H2SO4 is 4 - 5 M; the concentration of the dilute citric acid is 0.08 - 0.15 M; in adding H2SO4 to the desorbed solution, the concentration value of H2SO4 is 5 - 8 M; the concentration of HCl is 9 - 10 M.

[0034] In a possible implementation, in step B2, in the elution with HCl, the concentration of HCl is 9 - 10 M; in adding HCl for further desorption, the concentration of HCl is 0.2 - 0.5 M.

[0035] In the above possible embodiments, based on a sulfuric acid electrolyte medium, the present invention uses three resin chromatographic columns for separation and purification to prepare 68 a Ge solution, and the Zr resin 68 completely separates Ge from a large amount of inorganic impurities such as target materials, substrates, and competing nuclear reactions. The Guard resin completely separates citric acid, sulfuric acid, and organic impurities, and the AG MP-50 resin separates trace impurities, obtaining a high-purity 68 Ge solution.

[0036] In summary, a method for producing high-purity Ge-68 by a high-intensity proton cyclotron provided in the present application has the following advantages:

[0037] 1) Preparation of a Ga4Ni alloy target piece that is easy to irradiate and separate:

[0038] Based on a corrosion-resistant inert metal substrate, the present invention uses an electroplating method with simple operation and stable process to prepare a Ga4Ni alloy target piece. Compared with the traditional melting method, the target layer and the target holder in the present invention are more firmly combined and can withstand a larger irradiation beam current. And by using an inert metal such as Ta as the target holder substrate, compared with past methods, it can avoid introducing inorganic impurities such as copper, aluminum, and gold during the dissolution of the target, which affects the subsequent chromatographic separation effect.

[0039] 2) A rapid and efficient electrolytic target method:

[0040] In the past, the target dissolution method often used hydrochloric acid plus hydrogen peroxide and heating to assist in dissolution to generate a GeCl4 solution. GeCl4 has a low boiling point and is prone to generating radioactive aerosols, and the dissolution takes a long time and the operation is cumbersome. The present invention uses a sulfuric acid electrolysis process with simple operation. The sulfuric acid medium avoids pollution by volatile radioactive substances, and the electrolysis takes a short time.

[0041] 3) Preparation of a high-purity 68Ge solution:

[0042] Based on a sulfuric acid electrolyte medium, the present invention uses three resin chromatographic columns for separation and purification to prepare 68 a Ge solution. The Zr resin 68 completely separates Ge from a large amount of inorganic impurities such as target materials, substrates, and competing nuclear reactions. The Guard resin completely separates citric acid, sulfuric acid, and organic impurities, and the AG MP-50 resin separates trace impurities, obtaining a high-purity 68Ge solution that meets the standards. This invention has simple operation, avoids the operations of changing acids multiple times and the need for evaporation and concentration in past methods, and takes into account the requirements of the standards for the content of organic substances and metal ions, and uses three-stage resins to achieve high purity 68Separation of Ge, avoiding the problems of a large amount of citric acid, resin decomposition products, and copper ions in the products of previous methods. The recovery rate of the present invention is high, it is easy to realize automation, the product purity is high, it is in hydrochloric acid medium with appropriate acidity, and a Ge-Ga generator can be directly prepared. Description of the Drawings

[0043] Figure 1 It is a process flow chart for a method of preparing high-purity Ge-68 using a high-intensity proton cyclotron according to the present invention;

[0044] Figure 2 It is a schematic diagram of the structure and principle of the separation device in the embodiment of the present invention. Detailed Embodiments

[0045] First of all, those skilled in the art should understand that these embodiments are only used to explain the technical principles of the embodiments of the present application, and are not intended to limit the protection scope of the embodiments of the present application. Those skilled in the art can make adjustments according to needs to adapt to specific application scenarios.

[0046] In the description of the embodiments of the present application, it should be noted that unless otherwise clearly specified and limited, the terms "connected" and "connected" should be understood in a broad sense. For example, it can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected, or indirectly connected through an intermediate medium. For those of ordinary skill in the art, the specific meanings of the above terms in the embodiments of the present application can be understood according to specific situations.

[0047] The present invention provides a method for preparing high-purity Ge-68 using a high-intensity proton cyclotron, including the following steps:

[0048] S1: Prepare a fixed Ga4Ni alloy target, and after irradiating the alloy target with high-intensity protons, perform sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni and nat Cu;

[0049] S2: Pass the electrolytic solution obtained in step S1 into a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamic acid ester resin separation columns, cross-linked polydivinylbenzene resin separation columns, and AG MP-50 resin separation columns, and collect the solution containing 68 Ge to complete the preparation.

[0050] As a preferred solution, in the step S1, the conditions for the high-intensity proton irradiation treatment are as follows: irradiation is carried out using a high-intensity proton accelerator, the energy is 18 - 30 MeV, the beam current is 50 - 300 μA, the time is greater than or equal to 3 h, and the cooling time is greater than or equal to 20 days.

[0051] As a preferred solution, in the step S1, the structure of the solid Ga4Ni alloy target is as follows in 1) or 2):

[0052] 1) It includes at least two layers, including a metal-based bottom layer and a solid gallium-nickel alloy layer connected in sequence;

[0053] 2) It includes at least three layers, including a metal-based bottom layer, a metal protection layer and a solid gallium-nickel alloy layer connected in sequence;

[0054] In 1), the material of the metal-based bottom layer is Ta, Ti, Nb or Inconel alloy;

[0055] In 2), the material of the metal-based bottom layer is Cu or Al;

[0056] The material of the metal protection layer is Au or Pt, and the thickness is more than 5 μm.

[0057] As a preferred solution, in the solid gallium-nickel alloy layer, the mass content of Ga is not less than 60%, and the thickness is greater than 20 mg / cm 2 .

[0058] As a preferred solution, the solid gallium-nickel alloy layer is prepared by electroplating, and the preparation method includes:

[0059] A1: Dissolve metallic gallium in HNO3 solution, heat and stir, and then add H2SO4 solution with a concentration of more than 98% to obtain Ga2(SO4)3 precipitate;

[0060] A2: Dissolve the Ga2(SO4)3 precipitate prepared in the step A1 in water, adjust the pH value of the solution to 2 - 2.5 with ammonia solution, heat the solution to 40 - 50 °C, and add NiSO4 to prepare the final electroplating solution;

[0061] A3: Carry out electro-deposition using a constant current electrolysis technique, adjust the current density to 20 - 60 mA / cm 2 , the temperature is 25 - 100 °C, keep stirring at a speed of about 300 - 800 rpm during electroplating, and obtain a Ga4Ni alloy target after 6 - 8 hours.

[0062] As a preferred solution, in the step A1, the weight ratio of the gallium metal to the NiSO4 is (15 - 20):(10 - 15); the concentration of the HNO3 solution is 9 - 12M.

[0063] As a preferred solution, in the step S2, the steps of separating and purifying the electrolyte by passing it through a series of chromatographic columns include:

[0064] B1: Dilute the electrolyte and perform at least one separation process. The separation process includes: passing it through the hydroxamate resin separation column, eluting with H2SO4 and collecting the elution waste liquid simultaneously, then desorbing the elution waste liquid with dilute citric acid to obtain a desorbed solution, and adding H2SO4 to the desorbed solution at the same time; after the separation process is completed, add HCl to the desorbed solution for acidification;

[0065] B2: Pass it through a cross-linked polydivinylbenzene resin separation column into the desorbed solution acidified in the step B1, elute with HCl and collect the elution waste liquid at the same time, then desorb the elution waste liquid with deionized water to obtain a pure water desorbed solution; finally, pass the pure water desorbed solution through an AG MP - 50 resin separation column, add HCl for further desorption, and collect the Ge - 68 product to complete the preparation.

[0066] As a preferred solution, in the step B1, the conditions for diluting the electrolyte are to dilute it to an H2SO4 concentration of 5 - 8M; in the elution with H2SO4, the concentration of H2SO4 is 4 - 5M; the concentration of the dilute citric acid is 0.08 - 0.15M; in the addition of H2SO4 to the desorbed solution, the concentration value of H2SO4 is 5 - 8M; the concentration of the HCl is 9 - 10M.

[0067] As a preferred solution, in the step B2, in the elution with HCl, the concentration of the HCl is 9 - 10M; in the addition of HCl for further desorption, the concentration of the HCl is 0.2 - 0.5M.

[0068] In the above technical solution, the present invention mainly provides a method for preparing high - purity Ge - 68 using a high - intensity proton cyclotron: mainly including the following steps: Dissolve gallium salt and nickel salt in a sulfuric acid solution, and use the electroplating principle to co - deposit two metals, gallium and nickel, on a tantalum target holder to prepare a gallium - nickel alloy target; after irradiating the alloy target with ACSI - FLEX 30MeV, an alloy target containing 68 Ge is obtained, place the cooled target, and then electrolyze the target (electrolysis is the reverse process of electroplating); subsequently, separate, purify, and desorb the electrolyte on a series of chromatographic columns to achieve impurity separation and solution medium conversion, and obtain high - purity Ge - 68.

[0069] The following provides some embodiments in combination with the above data range to further explain the present invention:

[0070] Example 1:

[0071] This embodiment provides a method for producing high-purity Ge-68 using a high-intensity proton cyclotron, including:

[0072] A method for preparing high-purity Ge-68 using a high-intensity proton cyclotron includes the following steps:

[0073] S1: Prepare a fixed Ga4Ni alloy target, and irradiate the alloy target with high-intensity protons. The conditions for the high-intensity proton irradiation treatment are: irradiate using a high-intensity proton accelerator, with an energy of 18 MeV, a beam current of 50 μA, a time of 3 h, and a cooling time of 20 days;

[0074] After that, perform sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni, and nat Cu;

[0075] The structure of the solid Ga4Ni alloy target is as follows:

[0076] It includes two layers, specifically including a metal-based bottom layer and a solid gallium-nickel alloy layer connected in sequence. The material of the metal-based bottom layer is Ta metal;

[0077] The solid gallium-nickel alloy layer is prepared by electroplating. In the solid gallium-nickel alloy layer, the mass content of Ga is 60%, and the thickness is 20 mg / cm 2 , and its preparation method includes:

[0078] A1: Dissolve metallic gallium in a 9M HNO3 solution, heat and stir, and then add a 98% H2SO4 solution to obtain a Ga2(SO4)3 precipitate;

[0079] A2: Dissolve the Ga2(SO4)3 precipitate prepared in step A1 in water, adjust the pH value of the solution to 2 with an ammonia solution, heat the solution to 40 °C, and add NiSO4 to prepare the final electroplating solution. The weight ratio of NiSO4 to the metallic gallium is 10:15;

[0080] A3: Use a constant current electrolysis technique for electroplating, and adjust the current density to 20 mA / cm 2, at a temperature of 25 °C, rotate and stir at a speed of about 300 rpm during the electroplating process, and obtain a Ga4Ni alloy target after 6 hours.

[0081] S2: Pass the electrolyte obtained in the step S1 into a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamate resin separation column, cross-linked polystyrene-divinylbenzene resin separation column and AG MP-50 resin separation column, and collect the solution containing 68 Ge to complete the preparation.

[0082] The step of passing the electrolyte into the series of chromatographic columns for separation and purification includes:

[0083] B1: Dilute the electrolyte to a H2SO4 concentration of 5M and then perform a separation treatment. The separation treatment includes: passing it through the hydroxamate resin separation column, eluting with 4M H2SO4 and collecting the elution waste liquid at the same time, and then desorbing the elution waste liquid with 0.08M dilute citric acid to obtain a desorbed solution, and adding 5M H2SO4 to the desorbed solution at the same time; after the separation treatment is completed, add 9-10M HCl to the desorbed solution for acidification;

[0084] B2: Pass it into the cross-linked polystyrene-divinylbenzene resin separation column until the desorbed solution acidified in the step B1, elute with 9M HCl and collect the elution waste liquid at the same time, and then desorb the elution waste liquid with deionized water to obtain a pure water desorbed solution; finally, pass the pure water desorbed solution into the AG MP-50 resin separation column, add 0.2M HCl for further desorption, and collect the Ge-68 product to complete the preparation.

[0085] Example 2:

[0086] This example provides a method for producing high-purity Ge-68 by a high-intensity proton cyclotron, including:

[0087] A method for preparing high-purity Ge-68 using a high-intensity proton cyclotron includes the following steps:

[0088] S1: Prepare a fixed Ga4Ni alloy target, and irradiate the alloy target with high-intensity protons. The conditions for the high-intensity proton irradiation treatment are: irradiate using a high-intensity proton accelerator, with an energy of 24 MeV, a beam current of 175 μA, a time of 5 days, and a cooling time of 30 days;

[0089] Then perform sulfuric acid electrolytic dissolution to obtain a solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni and natElectrolyte for Cu;

[0090] The structure of the solid Ga4Ni alloy target is as follows:

[0091] It includes three layers, specifically a metal base layer, a metal protection layer, and a solid gallium-nickel alloy layer connected in sequence. The material of the metal base layer is Cu; the material of the metal protection layer is Au, and its thickness is 5 μm.

[0092] The solid gallium-nickel alloy layer is prepared by electroplating. In the solid gallium-nickel alloy layer, the mass content of Ga is 65%, and its thickness is 25 mg / cm 2 , and its preparation method includes:

[0093] A1: Dissolve metallic gallium in a 10.5 M HNO3 solution, heat and stir it, and then add a H2SO4 solution with a concentration of 98.5% to obtain Ga2(SO4)3 precipitate;

[0094] A2: Dissolve the Ga2(SO4)3 precipitate obtained in step A1 in water, adjust the pH value of the solution to 2.3 with an ammonia solution, heat the solution to 45 °C, and add NiSO4 to prepare the final electroplating solution. The weight ratio of NiSO4 to the metallic gallium is 12.5:17.5;

[0095] A3: Adopt the constant current electrolysis technique for electrodeposition, adjust the current density to 40 mA / cm 2 , the temperature is 62.5 °C, keep stirring at a speed of about 550 rpm during the electroplating process, and obtain the Ga4Ni alloy target after 7 hours.

[0096] S2: Pass the electrolyte obtained in step S1 into a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamate resin separation column, cross-linked polydivinylbenzene resin separation column, and AG MP-50 resin separation column, and collect the solution containing 68 Ge to complete the preparation.

[0097] The steps of passing the electrolyte into a series of chromatographic columns for separation and purification include:

[0098] B1: Dilute the electrolyte to a H2SO4 concentration of 6.5 M and then perform two separation treatments. The separation treatments include: passing it through the hydroxamate resin separation column, eluting with 4.5 M H2SO4 and collecting the elution waste liquid at the same time, then desorbing the elution waste liquid with 0.115 M dilute citric acid to obtain the desorbed solution, and adding 6.5 M H2SO4 to the desorbed solution at the same time; after the separation treatment is completed, add 9.5 M HCl to the desorbed solution for acidification;

[0099] B2: Introduce it into the cross-linked polydivinylbenzene resin separation column and into the desorbed solution acidified in step B1, wash it with 9.5 M HCl while collecting the washing waste liquid, and then desorb the washing waste liquid with deionized water to obtain a pure water desorbed solution; finally, introduce the pure water desorbed solution into the AG MP-50 resin separation column, add 0.35 M HCl for further desorption, and collect the Ge-68 product to complete the preparation.

[0100] Example 3:

[0101] This example provides a method for producing high-purity Ge-68 using a high-intensity proton cyclotron, including:

[0102] A method for preparing high-purity Ge-68 using a high-intensity proton cyclotron includes the following steps:

[0103] S1: Prepare a fixed Ga4Ni alloy target, and irradiate the alloy target with high-intensity protons. The conditions for the high-intensity proton irradiation treatment are: irradiate using a high-intensity proton accelerator, with an energy of 30 MeV, a beam current of 300 μA, a time of 15 days, and a cooling time of 40 days;

[0104] After that, perform sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni, and nat Cu;

[0105] The structure of the solid Ga4Ni alloy target is as follows:

[0106] It includes two layers, specifically including a metal-based bottom layer and a solid gallium-nickel alloy layer connected in sequence. The material of the metal-based bottom layer is Ta metal; the solid gallium-nickel alloy layer is prepared by electroplating, and in the solid gallium-nickel alloy layer, the mass content of Ga is 70%, and the thickness is 30 mg / cm 2 , and its preparation method includes:

[0107] A1: Dissolve metallic gallium in 12 M HNO3 solution, heat and stir it, and then add 99% H2SO4 solution to obtain Ga2(SO4)3 precipitate;

[0108] A2: Dissolve the Ga2(SO4)3 precipitate prepared in step A1 in water, adjust the pH value of the solution to 2.5 with ammonia solution, heat the solution to 50 °C, and add NiSO4 to prepare the final electroplating solution, and the weight ratio of NiSO4 to metallic gallium is 15:20;

[0109] A3: Electroplating is carried out using constant-current electrolysis technology. The current density is adjusted to 60 mA / cm 2 , the temperature is 100 °C, and it is rotated and stirred at a speed of about 800 rpm during the electroplating process. After 8 hours, a Ga4Ni alloy target is obtained.

[0110] S2: The electrolyte obtained in step S1 is passed into a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamate resin separation columns, cross-linked polydivinylbenzene resin separation columns, and AG MP-50 resin separation columns, and a solution containing 68 Ge is collected to complete the preparation.

[0111] The step of passing the electrolyte into the series of chromatographic columns for separation and purification includes:

[0112] B1: The electrolyte is diluted to a H2SO4 concentration of 8 M and then subjected to at least one separation treatment. The separation treatment includes: passing it through the hydroxamate resin separation column, eluting with 4 - 5 M H2SO4 and collecting the elution waste liquid simultaneously, then desorbing the elution waste liquid with 0.15 M dilute citric acid to obtain a desorbed solution, and adding 8 M H2SO4 to the desorbed solution at the same time; after the separation treatment is completed, 10 M HCl is added to the desorbed solution for acidification;

[0113] B2: Pass it into the cross-linked polydivinylbenzene resin separation column to the desorbed solution acidified in step B1, elute with 10 M HCl and collect the elution waste liquid simultaneously, then desorb the elution waste liquid with deionized water to obtain a pure water desorbed solution; finally, pass the pure water desorbed solution into the AG MP-50 resin separation column, add 0.5 M HCl for further desorption, and collect the Ge-68 product to complete the preparation.

[0114] Based on the above-mentioned method for producing high-purity Ge-68 by a high-intensity proton cyclotron, the following embodiments of the present invention provide an automatic Ge separation system solution based on a ferrule design, as 68 shown, including a liquid extraction unit, a transportation unit, a separation unit, a collection unit, and a control unit. Figure 2 The Ge nuclide separation has many steps. A disposable ferrule with 18 holes is designed, which is composed of 3 six-way three-way valves, and 16 holes are used in this process. The liquid extraction unit and the collection unit include several liquid storage containers and liquid transportation pipelines; the transportation unit includes at least 1 injection pump and 3 six-way three-way valves; the separation unit includes at least three identical or different separation columns; the collection unit includes several collection containers and liquid recovery pipelines; the control unit includes a host computer, a programmable logic controller (PLC), control software, and a communication protocol, specifically including: 68 ​

[0115] Example 4

[0116] S1: Prepare a Ga4Ni alloy target by electroplating method

[0117] A1: Dissolve 18 g of metallic gallium in 10 M HNO3, continuously heat and stir, then add concentrated H2SO4 with a concentration of 98%, and obtain the precipitate Ga2(SO4)3;

[0118] A2: Dissolve the Ga2(SO4)3 precipitate in water, and adjust the pH value of the solution to 2 with ammonia solution. Heat the solution to 45 °C, add 12 g of NiSO4 to prepare the final electroplating solution, and the final volume of the electroplating solution is 450 mL;

[0119] A3: Adjust the current density of Ga-Ni electrodeposition to 25 mA / cm by using the constant current electrolysis technology 2 , the temperature is 60 °C, keep stirring at a speed of about 500 rpm during the electroplating process, and obtain the Ga4Ni alloy target after 8 hours.

[0120] Irradiate the Ga4Ni alloy target with ACSI-FLEX 30 MeV to prepare an alloy target containing radioactive 68 Ge; electrolyze the irradiated Ga4Ni alloy target by sulfuric acid in the reverse process of electroplating.

[0121] S2: Separate and purify the electrolyte with a series of chromatographic columns, which includes the following automatic control steps:

[0122] B1:

[0123] Load the electrolyte with Zr resin: After diluting the solution after electrolysis of the solid target to a H2SO4 concentration value of 5 M, inject it into the stock solution bottle A1 of the separation device. Conduct the A1-V1-V2-P1 circuit, and the injection pump extracts the electrolytic dilution solution in the stock solution bottle A1; conduct the P1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, and the injection pump injects the electrolytic dilution solution, 68 Ge combines with the isohydroxamic acid ester group, is loaded on the Zr resin separation column, and the waste liquid flows into the waste liquid bottle A3; conduct the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, purge the liquid circuit with nitrogen, and the residual electrolytic waste liquid flows into the waste liquid bottle A3.

[0124] Sulfuric acid leaching: Connect the P1-V2-V3-B1 circuit, and the syringe pump extracts 5M H2SO4 from B1; connect the P1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, and the syringe pump injects 4M H2SO4 to leach the Zr resin separation column, and the waste liquid flows into the waste liquid bottle A3; connect the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, and nitrogen purges the liquid circuit, and the residual leaching waste liquid flows into the waste liquid bottle A3. The sulfuric acid leaching waste liquid contains a large amount of inorganic impurities such as Ga, Ni, Co, and Zn.

[0125] Citric acid desorption: Connect the P1-V2-V3-V4-B2 circuit, and the syringe pump extracts 0.1M dilute citric acid from B2; connect the P1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-desorption bottle A2 circuit, and the syringe pump injects 0.1M dilute citric acid. 68 Ge complexes with citric acid and is desorbed from the Zr resin separation column. 68 The Ge desorption liquid flows into the desorption bottle A2; connect the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-desorption bottle A2 circuit, and nitrogen purges the liquid circuit, and the residual desorption liquid flows into the desorption bottle A2.

[0126] Zr resin recycling: Connect the P1-V2-V3-B1 circuit, and the syringe pump extracts 5M H2SO4 from B1; connect the P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-desorption bottle A2 circuit, and the syringe pump injects 5M H2SO4 into the desorption bottle A2 to adjust the pH value; connect the P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-desorption bottle A2 circuit, and the syringe pump extracts the desorption liquid after adjusting the pH; connect the P1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, and the syringe pump loads the desorption liquid after adjusting the pH onto the Zr resin separation column again, and the waste liquid flows into the waste liquid bottle A3; connect the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-Zr resin-V9-V10-V11-V12-V13-waste liquid bottle A3 circuit, and nitrogen purges the liquid circuit, and the residual waste liquid flows into the waste liquid bottle A3. According to the actual situation, sulfuric acid leaching-citric acid desorption can be carried out, and the cyclic separation can be carried out 0-2 times.

[0127] B2:

[0128] Desorption liquid loading of Guard resin: Connect the loop of P1-V2-V3-V4-V5-B3, and the injection pump extracts 9M HCl from B3; Connect the loop of P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-desorption bottle A2, and the injection pump injects 9M HCl into the desorption bottle A2 to adjust the pH value; Connect the loop of P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-desorption bottle A2, and the injection pump extracts the desorption liquid after pH adjustment; Connect the loop of P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-V11-Guard resin-V12-V13-waste liquid bottle A3, and the injection pump injects the desorption liquid after adjusting the pH with hydrochloric acid onto the Guard resin separation column, and the waste liquid flows into the waste liquid bottle A3; Connect the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-V9-V10-V11-Guard resin-V12-V13-waste liquid bottle A3 loop, and nitrogen purges the liquid loop, and the remaining waste liquid flows into the waste liquid bottle A3.

[0129] Hydrochloric acid elution: Connect the loop of P1-V2-V3-V4-V5-B3, and the injection pump extracts 9M HCl from B3; Connect the loop of P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-V11-Guard resin-V12-V13-waste liquid bottle A3, and the injection pump injects 9M HCl to elute the Guard resin separation column, replace the acidic medium, wash sulfate and citric acid, and the waste liquid flows into the waste liquid bottle A3; Connect the nitrogen source-V1-V2-V3-V4-V5-V6-V7-V8-V9-V10-V11-Guard resin-V12-V13-waste liquid bottle A3 loop, and nitrogen purges the liquid loop, and the remaining eluent flows into the waste liquid bottle A3. The hydrochloric acid elution waste liquid contains a large amount of sulfuric acid, citric acid and organic impurities.

[0130] Pure water desorption and loading of AG MP-50 resin: Connect the loop of P1-V2-V3-V4-V5-V6-B4, and the injection pump extracts pure water from B4; Connect the loop of P1-V2-V3-V4-V5-V6-V7-V8-V9-V10-V11-Guard resin-V12-V13-V14-AG MP 50 resin-V15-V16-waste liquid bottle A4, and the injection pump injects pure water to make 68Ge is hydrolyzed to desorb it from the Guard resin separation column. The desorbed solution is loaded onto the AG MP-50 resin, and the waste liquid flows into the waste liquid bottle A3. The nitrogen source - V1 - V2 - V3 - V4 - V5 - V6 - V7 - V8 - V9 - V10 - V11 - Guard resin - V12 - V13 - V14 - AG MP 50 resin - V15 - V16 - waste liquid bottle A4 loop is conducted, and nitrogen is used to purge the liquid loop. The residual waste liquid flows into the waste liquid bottle A3. The pure hydrolyzed desorbed solution is introduced into the AG MP-50 resin separation column to further separate trace impurities such as Fe, Ni, Cu, Zn, and Pb.

[0131] Desorption with dilute hydrochloric acid: The P1 - V2 - V3 - V4 - V5 - V6 - V7 - B5 loop is conducted, and the injection pump extracts 0.2M HCl from B5. The P1 - V2 - V3 - V4 - V5 - V6 - V7 - V8 - V9 - V10 - V11 - V12 - V13 - V14 - AG MP 50 resin - V15 - V16 - product bottle A5 loop is conducted, and the injection pump injects the dilute hydrochloric acid to 68 acidify Ge to desorb it from the AG MP-50 resin separation column, and the product bottle collects 68 the Ge product. This product is in a hydrochloric acid medium with a suitable acidity and does not require further purification, and can be directly used to prepare a Ge-Ga generator.

[0132] After 68 the purification of Ge is completed, the 68 Ge obtained in Examples 1 / 2 / 3 is subjected to relevant determinations to determine the amounts of specific metal ions and organic compounds in the final product. As shown in Table 1 and Table 2, it can be seen that the contents of several common metal ions in the target, target holder, and mineral acid are extremely low, and the contents of possible solvents, mineral oils, resin decomposition products, or organic acids in several common extraction or column chromatography separation methods are all lower than the detection limit (D.L.) and are not detected, meeting the standard requirements.

[0133] The determination results are shown in Table 1 and Table 2 below:

[0134] Among them, Sample I, Sample II, and Sample III correspond to the finished products of Example 2, Example 1, and Example 3 of the present invention, respectively.

[0135] Table 1:

[0136]

[0137] Table 2:

[0138]

[0139] In the description of the embodiments of the present application, it should be noted that in the description of the present application, the terms "inner", "outer", etc., indicating the direction or positional relationship, are based on the direction or positional relationship shown in the drawings. This is only for the convenience of description and does not indicate or imply that the device or component must have a specific orientation, be constructed and operated in a specific orientation. Therefore, it should not be construed as a limitation to the present application.

[0140] In the description of the present application, the description with reference to terms such as "one embodiment", "some embodiments", "in this embodiment", "specific example", or "some examples", etc. means that the specific features, mechanisms, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present application. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, mechanisms, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0141] As described above, it is only the specific implementation manner of the present application, but the protection scope of the present application is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed in the present application should be covered by the protection scope of the present application. Therefore, the protection scope of the present application should be subject to the protection scope of the claims.

Claims

1. A method for preparing high-purity Ge-68 using a high-intensity proton cyclotron, characterized in that, It includes the following steps: S1: Prepare a solid Ga4Ni alloy target. After irradiating the alloy target with high-intensity proton beams, perform sulfuric acid electrolytic dissolution to obtain an electrolytic solution containing 68 Ge, 68,nat Ga, 56,57,58 Co, 65 Zn, nat Ni and nat Cu; In the step S1, the conditions of the high-intensity proton irradiation treatment are as follows: irradiation is carried out using a high-intensity proton accelerator, the energy is 18 - 30 MeV, the beam current is 50 - 300 μA, the time is greater than or equal to 3 h, and the cooling time is greater than or equal to 20 days; In the step S1, the structure of the solid Ga4Ni alloy target is as follows in 1): 1) It includes at least two layers, including a metal-based bottom layer and a solid gallium-nickel alloy layer connected in sequence; in 1), the material of the metal-based bottom layer is Ta; The solid gallium-nickel alloy layer is prepared by electroplating. In the solid gallium-nickel alloy layer, the mass content of Ga is not less than 60%, and the thickness is greater than 20 mg / cm 2 , and the preparation method includes the following steps: A1: Dissolve metallic gallium in HNO3 solution, heat and stir it, and then add H2SO4 solution with a concentration of more than 98% to obtain Ga2(SO4)3 precipitate; A2: Dissolve the Ga2(SO4)3 precipitate prepared in the step A1 in water, adjust the pH value of the solution to 2 - 2.5 with ammonia solution, heat the solution to 40 - 50 °C, and add NiSO4 to prepare the final electroplating solution; A3: Electroplating is carried out using the constant current electrolysis technique, and the current density is adjusted to 20 - 60 mA / cm 2 , the temperature is 25 - 100 °C, and it is rotated and stirred at a speed of 300 - 800 rpm during the electroplating process. After 6 - 8 hours, a Ga4Ni alloy target is obtained; S2: Pass the electrolyte solution obtained in step S1 into a series of chromatographic columns for separation and purification. The series of chromatographic columns are hydroxamate resin separation column, cross-linked polydivinylbenzene resin separation column and AG MP-50 resin separation column, and collect the solution containing 68 Ge to complete the preparation; In the step S2, the steps of separating and purifying the electrolyte by passing it through a series of chromatographic columns include: B1: Dilute the electrolyte and perform at least one separation treatment. The separation treatment includes: passing it through the hydroxamate resin separation column, eluting with H2SO4 and collecting the elution waste liquid simultaneously, then desorbing the hydroxamate resin separation column with dilute citric acid to obtain a desorbed solution, and adding H2SO4 to the desorbed solution at the same time; after the separation treatment is completed, add HCl to the desorbed solution to acidify it; B2: Pass the desorbed solution acidified in the step B1 into a cross-linked polystyrene-divinylbenzene resin separation column, elute with HCl and collect the elution waste liquid simultaneously, then desorb the cross-linked polystyrene-divinylbenzene resin separation column with deionized water to obtain a pure water desorbed solution; finally, pass the pure water desorbed solution into an AG MP-50 resin separation column, add HCl for further desorption, and collect the Ge-68 product to complete the preparation; In the step B1, the conditions for diluting the electrolyte are to dilute it to a H2SO4 concentration of 5 - 8 M; in the elution with H2SO4, the concentration of H2SO4 is 4 - 5 M; the concentration of dilute citric acid is 0.08 - 0.15 M; in adding H2SO4 to the desorbed solution, the concentration value of H2SO4 is 5 - 8 M; the concentration of HCl is 9 - 10 M.

2. The method for preparing high-purity Ge-68 by using a high-intensity proton cyclotron according to claim 1, wherein In the steps A1 and A2, the weight ratio of the metallic gallium to the NiSO4 is (15 - 20):(10 - 15); the concentration of the HNO3 solution is 9 - 12 M.

3. The method for preparing high-purity Ge-68 by using a high-intensity proton cyclotron according to claim 1, characterized in that In the step B1, the number of times of the separation treatment is 1 - 3 times.

4. The method for preparing high-purity Ge-68 using a high-intensity proton cyclotron according to claim 1, characterized in that, In the step B2, in the elution with HCl, the concentration of HCl is 9 - 10 M; in adding HCl for further desorption, the concentration of HCl is 0.2 - 0.5 M.

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