Adsorbent for germanium[68Ge]-gallium[68Ga] generator and method for producing the same, and germanium[68Ge]-gallium[68Ga] generator

Abstract

germanium[ 68 Ge]-Gallium[ 68 Adsorbent for Ga generator and method for manufacturing the same, and germanium [ 68 Ge]-Gallium[ 68 A Ga generator, wherein the adsorbent is 68 Used to adsorb element Ge, it contains multiple titanium dioxide particles, each with a specific surface area of ​​30 m². 2 / g~100m 2 The titanium dioxide particles are expressed as / g and consist of multiple nanoparticles with an average particle size of 10nm to 100nm, and the nanoparticles contain mesopores with a pore size of 5nm to 30nm.

Description

[[TECHNICAL FIELD]]

[0001] The present application claims the priority of Chinese Patent Application No. 202311178638.X entitled "Germanium 68 Ge]-Gallium 68 Ga] Generator", filed on September 13, 2023, and the priority of Chinese Patent Application No. 202311178636.0 entitled "Germanium 68 Ge]-Gallium 68 Ga] Generator Adsorbent and Method for Producing the Same", filed on September 13, 2023, and the entire contents of the above two application documents are incorporated herein by reference.

[0002] The present application belongs to the technical field of adsorbents, and specifically relates to an adsorbent for germanium 68 Ge]-gallium 68 Ga] generators, a method for producing the same, and a germanium 68 Ge]-gallium 68 Ga] generator. [[BACKGROUND ART]]

[0003] Germanium 68 Ge]-gallium 68 Ga] generator ( 68 Ge- 68 Ga generator) is a device that converts a radioactive 68 Ge source into 68 Ga and supplies 68 Ga based on the principles of radioactive decay and radionuclide separation. 68 In the process of supplying Ga, how to reduce the content of 68 Ge and improve the yield of 68 Ga is an improvement direction for germanium 68 Ge]-gallium 68 Ga] generators.

[0004] Generally, 68 Ge- 68 Ga generators are commonly used 68Adsorbent materials for Ge adsorption mainly include tin dioxide, titanium dioxide, aluminum oxide, polymer matrices (e.g., polystyrene, polymethacrylate, etc.), and silica-organic resin copolymers, but each of these adsorbent materials has certain limitations.

[0005] In 1996, the Russian company Cyclotron was the first to develop a system based on modified TiO2 material. 68 Ge- 68 We supply Ga generators to the market, which have an initial elution efficiency of 60-75%. 68 The Ge leakage rate is approximately 0.001% (American Journal of Nuclear Medicine and Molecular Imaging, 2019, 9, 30-66). In recent years, companies such as Eckert & Ziegler in Germany and IRE EliT in Belgium have also been commercializing TiO2-based materials. 68 Ge- 68 Although Ga generators were successively researched and developed, their elution efficiency gradually decreased with increasing usage time, and further fell to below 55%. US Patent US10357758B2 discloses a method for manufacturing a chromatographic adsorption material for a nuclide generator, and a 33mCi class gas produced using this material 68 Ge- 68 The Ga generator is 68 The initial elution efficiency for Ga is approximately 75%, and after several elutions, the elution efficiency can be stabilized at 65% or higher. 68 The Ge leakage rate is according to the European Pharmacopoeia for gallium chloride [ 68 The solution can meet the standard (≤0.001%) for Ga.

[0006] As can be seen from the above, the prior art is disclosed 68 Ge- 68 The Ga generator is 68 The elution efficiency for Ga is generally 75% or less, which is for pharmaceutical grade materials. 68 Ge- 68 Ga generator is at least 0.001% or less 68 We must satisfy Ge's leakage rate requirements. 68 The increase in Ga elution efficiency is usually 68This is accompanied by a corresponding increase in the leakage rate of Ge, 68 This is because the elution efficiency of Ga is limited.

[0007] Based on the above analysis, in this field, lower 68 Ge leakage rate and higher, more stable 68 It has Ga elution efficiency 68 Ge- 68 A Ga generator is still necessary. [Overview of the Initiative]

[0008] This application is, 68 Along with the effect of adsorbing Ge elements, germanium [ 68 Ge]-Gallium[ 68 When eluting the adsorbent in the Ga generator 68 To better release Ga and into titanium dioxide particles 68 Germanium [ 68 Ge]-Gallium[ 68 The objective is to provide an adsorbent for a germanium [Ga] generator and a method for manufacturing the same. This application further relates to germanium [Ga] having at least the above beneficial effects. 68 Ge]-Gallium[ 68 We provide a Ga generator.

[0009] In the first embodiment, the embodiments of this application use germanium [ 68 Ge]-Gallium[ 68 We provide an adsorbent for a Ga generator, and the adsorbent is 68 This material is for the adsorption of the element Ge and contains multiple titanium dioxide particles, each consisting of multiple nanoparticles with an average particle size of 10 nm to 100 nm. The titanium dioxide particles further contain mesopores, each with a pore diameter of 5 nm to 30 nm.

[0010] In some select embodiments, the adsorbent has a specific surface area of ​​30 m². 2 / g~100m 2The value is / g. In some select embodiments, the adsorbent has a specific surface area of ​​31m². 2 / g~97m 2 The particle size is / g, and the multiple nanoparticles have an average particle size of 12nm to 96nm, while the mesopores have a pore diameter of 5.7nm to 19nm.

[0011] In some selectable embodiments, the adsorbent has an anatase-type crystalline phase.

[0012] In some selectable embodiments, the adsorbent has an average particle size of 10 μm to 300 μm.

[0013] In several select embodiments, the adsorbent has a pore volume of 0.1 cm³. 3 / g~0.5cm 3 It is / g.

[0014] In some selectable embodiments, the adsorbent comprises one or more of the following: titanium dioxide particles with an average particle size of 30-60 μm, titanium dioxide particles with an average particle size of 50-100 μm, titanium dioxide particles with an average particle size of 75-150 μm, and titanium dioxide particles with an average particle size of 90-180 μm.

[0015] In several selectable embodiments, titanium dioxide particles are treated by one or more of the following methods: vibration, vortexing, and ultrasound, to smooth the surface of the titanium dioxide particles.

[0016] In a second embodiment, according to the present application, 68 Ge- 68 This invention provides a method for producing a titanium dioxide adsorbent for Ga generators, wherein the adsorbent is produced by a sol-gel method, and the production method is as follows: The process involves dissolving a titanium source in an organic alcohol, then adding glacial acetic acid to obtain a titanium source solution, The process involves adding a titanium source solution drop by drop to a purified aqueous solution while stirring, allowing it to stand to obtain a first gel, heating and maintaining the temperature of the first gel, and recrystallizing it to obtain a second gel. The process includes the steps of forming a second gel in a first firing, then crushing it to select solid particles with a particle size of 10 to 300 μm, performing surface modification, and then performing a second firing to obtain an adsorbent.

[0017] In some selectable embodiments, the method of dispensing drop by drop while stirring has a stirring speed of 10 to 100 rpm and a dispensing speed of 1 to 100 mL / min.

[0018] In some select embodiments, the volume ratio of the titanium source solution to purified water is 1:(0.5~10).

[0019] In some preferred embodiments, heating and keeping warm are performed at a temperature of 110-180°C for a duration of 6-36 hours.

[0020] In several selectable embodiments, surface modification of solid particles is performed by ultrasonic treatment, wherein the ultrasonic output is 50-1000W and the duration is 0.5-12 hours.

[0021] In some selectable embodiments, the process of forming a second gel in a first calcination, then crushing it to separate solid particles with a particle size of 10 to 300 μm, performing surface modification, and then performing a second calcination to obtain an adsorbent includes the steps of forming a second gel in a first calcination, then crushing it to separate solid particles with particle sizes of 30 to 60 μm, 50 to 100 μm, 75 to 150 μm, and 90 to 180 μm, and then performing a second calcination to obtain an adsorbent.

[0022] In some selectable embodiments, the first firing is performed at a temperature of 300-700°C, and the second firing is performed at a temperature of 400-700°C.

[0023] In some selectable embodiments, the first firing is performed for a duration of 1 to 12 hours, and the second firing is performed for a duration of 1 to 6 hours.

[0024] In a third embodiment, the embodiment of this application includes a germanium [ filled cylinder filled with the adsorbent described in the first embodiment or the adsorbent manufactured by the manufacturing method described in the second embodiment] 68 Ge]-Gallium[ 68 It provides a Ga generator, and the adsorbent is 68 The element Ge is adsorbed onto it.

[0025] In some preferred embodiments, the material of the packing cylinder is one or more of the following: a plastic chromatography column, a glass tube, or a quartz tube.

[0026] The present invention has the following beneficial effects.

[0027] 1) In the embodiments of this application, the adsorbent, i.e., the titanium dioxide particle material, is such that any titanium dioxide particle consists of multiple nanoparticles bonded together, and the pore size of the nanoparticles is 5 nm to 30 nm, the titanium dioxide particles are relatively large and have an appropriate specific surface area. 68 The amount of adsorption to Ge can be improved. On the other hand, by ensuring that titanium dioxide particles have an appropriate pore volume or adsorption sites, 68 It can accommodate large quantities of molecules or ions containing the element Ge. 68 It can better adsorb the element Ge, and during elution, 68 To better release Ga and into titanium dioxide particles 68 This can reduce the residue of Ga element and improve elution efficiency.

[0028] 2) Multiple nanoparticles are independent small particles during the manufacturing process and possess a certain mechanical strength. Multiple nanoparticles can stably exist in an acid elution environment, and in the related technology, the embrittlement of the edges of integrally formed titanium dioxide particles is avoided, and the titanium dioxide particles have good structural stability through a configuration such as bonding between multiple nanoparticles, thereby preventing embrittlement of the edges of titanium dioxide particles. 68 This can reduce the risk of leakage of the element Ge and lower the leakage rate.

[0029] 3) In this invention, a titanium dioxide adsorbent is manufactured using an improved sol-gel method. On the one hand, the process is simple, environmentally friendly, there is no risk of introducing other metal ions, the manufacturing is efficient and convenient, and it is possible to produce it on a large scale. On the other hand, it overcomes the problem that titanium dioxide manufactured by the conventional sol-gel method is at the nanoscale and cannot be used as an adsorbent for germanium-gallium generators. The titanium dioxide particles manufactured by the sol-gel method are made at the micron level, and furthermore, when used as an adsorbent for germanium-gallium generators, they have excellent performance.

[0030] 4) The adsorbent produced in the present invention, i.e., titanium dioxide particles, consists of nanoparticles of 10 to 100 nm in size, with a specific surface area of ​​30 to 100 m². 2 It has a density of / g, a pore size of 5-30 nm, and a smooth surface. 68 Ge- 68 When used in a Ga generator, 68 Ge- 68 The performance of the Ga generator has been significantly improved, especially in the activity range of 30 mCi class and above. 68 The hotel leakage rate has decreased to approximately 0.0001% in all cases, 68 The elution efficiency of Ga is improved to over 75%, and multiple elutions can be maintained at over 70%.

[0031] To more clearly illustrate the technical solutions of the embodiments of this application, the drawings that need to be used in the embodiments of this application are briefly described below. Obviously, the drawings described below represent only a few embodiments of this application, and those skilled in the art can obtain other drawings based on these drawings without any creative effort. [Brief explanation of the drawing]

[0032] [Figure 1] The X-ray diffraction pattern of the modified TiO2 particle material of the embodiment of this application is shown. [Figure 2] Scanning electron microscope (SEM) images of the modified TiO2 particle material of the embodiment of this application are shown. [Figure 3] Scanning electron microscope (SEM) images of the modified TiO2 particle material of the embodiment of this application are shown. [Figure 4] Scanning electron microscope (SEM) images of the modified TiO2 particle material of the embodiment of this application are shown. [Figure 5] The changes in elution efficiency and linear fitting diagrams over 200 days for the 50mCi68Ge-68Ga generator of the embodiment of this application are shown. [Figure 6] This diagram shows the change in long-term elution efficiency of the 85mCi68Ge-68Ga generator according to the embodiment of this application. [Modes for carrying out the invention]

[0033] In drawings, the proportions are not always accurate to the actual values.

[0034] The germanium of this application is described below with reference to the drawings as appropriate. 68 Ge]-Gallium[ 68 Adsorbent for Ga generator and method for manufacturing the same, and germanium [ 68 Ge]-Gallium[ 68 Embodiments specifically disclosing the Ga generator will be described in detail. However, descriptions that are unnecessarily detailed may be omitted. For example, detailed descriptions of already well-known matters or redundant descriptions of substantially identical configurations may be omitted. This is to avoid the following description becoming unnecessarily verbose and to facilitate understanding for those skilled in the art. The accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter described in the claims.

[0035] The “ranges” disclosed in this application are limited in the form of lower and upper limits, and a given range is limited by selecting one lower limit and one upper limit, and the selected lower and upper limits define the boundaries of a special range. Ranges defined in this way may or may not include end values ​​and can be combined arbitrarily, that is, any lower limit and any upper limit can be combined to form a single range. For example, if the ranges 60-120 and 80-110 are listed for a particular parameter, the ranges 60-110 and 80-120 can also be expected. Also, if the minimum range values ​​1 and 2 and the maximum range values ​​3, 4 and 5 are listed, all ranges 1-3, 1-4, 1-5, 2-3, 2-4, and 2-5 can also be expected. In this application, unless otherwise stated, the numerical range “a-b” indicates an abbreviation of any combination of real numbers between a and b, where a and b are both real numbers. For example, the numerical range "0 to 5" indicates that the text lists all real numbers between "0 to 5," while "0 to 5" simply omits combinations of these numbers. Similarly, when a parameter is described as an integer greater than or equal to 2, it is equivalent to disclosing that the parameter is an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12.

[0036] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions, and such technical solutions should be considered to be included in the disclosures of this application.

[0037] Unless otherwise specified, all technical features and selectable technical features of this application can be combined to form new technical solutions, and such technical solutions should be considered to be included in the disclosures of this application.

[0038] Unless otherwise specifically stated, all steps in the present application may be performed sequentially or randomly, and are preferably performed sequentially. For example, the statement that a method comprises steps (a) and (b) indicates that the method may comprise the steps performed in the order of step (a) and (b), or may comprise the steps performed in the order of step (b) and (a). For example, when the method further comprises step (c), step (c) may be added to the method in any order; for example, the method may comprise steps (a), (b) and (c), may comprise steps (a), (c) and (b), or may comprise steps (c), (a) and (b), etc.

[0039] As used in the present application, the term "plurality" means two or more (including two). As used in the present application, the terms "plurality of types" and "several types" mean two or more types (including two types). As used in the present application, the terms "plurality of items" and "several" mean two or more items (including two items).

[0040] The term "elution efficiency" refers to the parent nuclide 68 Ge is the daughter nuclide 68 after decay to Ga, it means the ratio of the actual amount of 68 Ga collected by elution with an eluent to the theoretical amount thereof.

[0041] The term "leakage rate" refers to that during elution with an eluent, 68 the leakage rate of Ge, that is, the 68 activity of Ge in liquid / 68 it means the activity of Ga.

[0042] The term "specific surface area" means the total area possessed by an adsorbent material per unit mass, and can be measured by a gas adsorption method.

[0043] The term "size of titanium dioxide particles" means the size or diameter of titanium dioxide particles, which can be measured using a laser particle size analyzer. It should be understood that titanium dioxide micron particles are formed by aggregation of nanoparticles.

[0044] The term "nanoparticles" refers to nano-titanium dioxide microparticles that form titanium dioxide micron particles through aggregation.

[0045] The term "pore size" refers to the diameter or width of a pore, which can be used to evaluate the size of the pore and can be measured using instruments such as specific surface area and porosity analyzers. For example, it refers to the size of the internal voids in micron-level titanium dioxide (micron-level titanium dioxide is formed by the aggregation of nano-level titanium dioxide nanoparticles, and the pore size is the size of the voids between nano-level titanium dioxide nanoparticles and the internal voids of the nanoparticles).

[0046] In the first embodiment, the embodiments of this application use germanium [ 68 Ge]-Gallium[ 68 We provide an adsorbent for a Ga generator, and the adsorbent is 68 Used for adsorbing the element Ge, it contains multiple titanium dioxide particles, each consisting of multiple nanoparticles with an average particle size of 10 nm to 100 nm, and the titanium dioxide particles further contain mesopores, each with a pore diameter of 5 nm to 30 nm.

[0047] The mesopores may have a pore diameter of 5 nm, 10 nm, 15 nm, 20 nm, 25 nm, or 30 nm, or a configuration range thereof.

[0048] In the embodiments of this application, the adsorbent, i.e., the titanium dioxide particle material, is composed of titanium dioxide particles formed by the bonding of multiple nanoparticles together, where the multiple nanoparticles are independent small particles during the manufacturing process, possess a certain mechanical strength, and can stably exist in an acid elution environment. In related technologies, the brittleness of the edges of integrally formed titanium dioxide particles is avoided, and the titanium dioxide particles have good structural stability through a configuration such as the bonding of multiple nanoparticles together, thereby preventing the brittleness of the edges of the titanium dioxide particles. 68 This can reduce the risk of leakage of the element Ge.

[0049] If the average diameter of the nanoparticles is too small, in the process of producing titanium dioxide particles, the nanoparticles with an excessively small particle size are relatively soft and have small inner pore diameters, so they are likely to be tightly bonded with a plurality of other nanoparticles, making it difficult to obtain titanium dioxide particles having a constant specific surface area and appropriate pore diameters. If the average particle diameter of the nanoparticles is too large, in the process of producing and using the titanium dioxide particles, the nanoparticles with an excessively large particle size are prone to deformation or breakage and have low aggregation strength, making it difficult to form titanium dioxide particles having a constant mechanical strength and an appropriate specific surface area. Therefore, the nanoparticles in the titanium dioxide particles have an average particle diameter of 10 nm to 100 nm. The size of the nanoparticles may be 10 nm, 20 nm, 50 nm, 60 nm, 80 nm, 100 nm, or may be within the range of 10 to 30 nm, 20 to 60 nm, 50 to 100 nm; the pore diameter may be 5 nm, 10 nm, 15 nm, 20 nm, 30 nm, or may be within the range of 5 to 10 nm, 10 to 25 nm, 20 to 30 nm. In some alternative embodiments, the average particle diameter of the plurality of nanoparticles is 50 nm to 80 nm.

[0050] Unless otherwise specified, the average particle diameter of the nanoparticles in the titanium dioxide particles referred to in the present application means the average value of the particle diameters of the nanoparticles calculated by performing statistical analysis on 200 nanoparticles sampled when the produced titanium dioxide particles are observed with a scanning electron microscope (SEM).

[0051] Studies have shown that when titanium dioxide particles composed of nanoparticles are applied to germanium 68 Ge]-gallium 68 Ga] generators, when the pore diameter of the nanoparticles is 5 nm to 30 nm, the titanium dioxide particles can be provided with a relatively large and appropriate specific surface area, 68 while the adsorption capacity for Ge can be improved, and the titanium dioxide particles can be provided with a relatively large pore volume or adsorption sites, 68 which can accommodate a large amount of Ge element-containing molecules or ions, 68 can better adsorb Ge elements, and during elution, 68To better release Ga and into titanium dioxide particles 68 We found that this method can reduce the residue of Ga element and improve elution efficiency.

[0052] In several select embodiments, multiple titanium dioxide particles have a specific surface area of ​​30 m². 2 / g~100m 2 It is / g.

[0053] For example, the specific surface area is 30m². 2 / g, 40m 2 / g, 70m 2 / g, 85m 2 / g, 100m 2 It may also be / g, 30-50m 2 / g, 50-100m 2 / g, 80-100m 2 It may be within the range of the specific surface area per g.

[0054] In the embodiments of this application, when the specific surface area of ​​the titanium dioxide particles is within the above range, 68 It can better adsorb the element Ge.

[0055] In some select embodiments, the specific surface area of ​​the adsorbent is 31 m². 2 / g~97m 2 The particle size is 12 nm to 96 nm, and the average particle size of the multiple nanoparticles is 12 nm to 96 nm, with a mesopore diameter of 5.7 nm to 19 nm. Therefore, the above adsorbent can further improve elution efficiency and reduce leakage rate.

[0056] In some selectable embodiments, the crystalline phase type of the adsorbent is anatase. In embodiments of this application, anatase-type titanium dioxide particles have a relatively large specific surface area and a more suitable pore structure. 68 Adsorption of Ge elements and 68 To improve the effect of Ga release.

[0057] In some selectable embodiments, the adsorbent has an average particle size of 10 μm to 300 μm.

[0058] Furthermore, when the particle size of the adsorbent described in this application is 10 to 300 μm, it means titanium dioxide particles within the particle size range of 10 to 300 μm. The specific particle sizes may be, for example, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, or 300 μm, or any range within 10 to 300 μm, for example, 10 to 50 μm, 30 to 60 μm, 50 to 150 μm, 20 to 200 μm, 130 to 260 μm, or 200 to 300 μm, preferably within the particle size ranges of 30 to 60 μm, 50 to 100 μm, 75 to 150 μm, and 90 to 180 μm.

[0059] In this embodiment, particulate titanium dioxide of the 10-300 μm class is 68 This can reduce the rate of data leaks in Ge.

[0060] In several select embodiments, the adsorbent has a pore volume of 0.1 cm³. 3 / g~0.5cm 3 It is / g.

[0061] Selectively, the pore volume of titanium dioxide particles is 0.1 cm³. 3 / g, 0.2cm 3 / g, 0.3cm 3 / g, 0.4cm 3 / g, 0.5cm 3 The value may be any of the values ​​per g or their constituent range. Therefore, if the pore volume of multiple titanium dioxide particles is within the above range, sufficient sites and 68 It is advantageous for providing bonding with the element Ge, and in the elution process, 68 Even if the element Ge is eluted, the titanium dioxide particles provide sufficient sites. 68 Ge adsorption can be re-achieved. When the pore volume of multiple titanium dioxide particles is within the above range, the adsorption of multiple regions can be performed under appropriate elution conditions during elution. 68 By releasing Ga element, 68 This improves the yield of Ga and enhances elution efficiency.

[0062] In some selectable embodiments, the adsorbent comprises one or more of the following: titanium dioxide particles with an average particle size of 30-60 μm, titanium dioxide particles with an average particle size of 50-100 μm, titanium dioxide particles with an average particle size of 75-150 μm, and titanium dioxide particles with an average particle size of 90-180 μm. Therefore, the adsorbent comprises 68 Ge- 68 Further improve the elution efficiency of the Ga generator, 68 This can reduce the leakage phenomenon of [Ge].

[0063] In several selectable embodiments, titanium dioxide particles are treated by one or more of the following methods: vibration, vortexing, or ultrasound, to smooth the surface of the titanium dioxide particles. Any combination or single treatment method such as vibration, vortexing, or ultrasound can further smooth the surface of the titanium dioxide particles, i.e., the particles typically have smooth edges and fewer sharp corners. Generally, the sharp corner portions of titanium dioxide particles are present in a certain amount. 68 Because it contains Ge, and the sharp edges are broken down and washed away during the elution process of the adsorbent, smoothing the surface of the titanium dioxide particles is important. 68 Reduction of Ge leakage phenomenon and 68 Ge- 68 This is advantageous for improving the elution efficiency of the Ga generator.

[0064] In a second embodiment, according to the present application, 68 Ge- 68 This invention provides a method for producing a titanium dioxide adsorbent for Ga generators, wherein the adsorbent is produced by a sol-gel method, and the production method is as follows: The process involves dissolving a titanium source in an organic alcohol, then adding glacial acetic acid to obtain a titanium source solution, The process involves adding a titanium source solution drop by drop to a purified aqueous solution while stirring, allowing it to stand to obtain a first gel, heating and maintaining the temperature of the first gel, and recrystallizing it to obtain a second gel. The process includes the steps of forming a second gel in a first firing, then crushing it to select solid particles with a particle size of 10 to 300 μm, performing surface modification, and then performing a second firing to obtain an adsorbent.

[0065] In this embodiment, the method for producing titanium dioxide is a sol-gel method, and includes the steps of: dissolving a titanium source in an organic alcohol, then adding glacial acetic acid to obtain a titanium source solution; adding the titanium source solution drop by drop to a purified aqueous solution while stirring, allowing it to stand to obtain a first gel; heating and maintaining the temperature of the first gel, and recrystallizing it to obtain a second gel; and shaping the second gel by first calcination, then pulverizing it to select solid particles with a particle size of 10 to 300 μm, performing surface modification, and further performing a second calcination to obtain an adsorbent.

[0066] In the embodiments of this application, the second gel can be understood as a dry gel, i.e., crystalline particles, obtained by gradually concentrating and recrystallizing the gel under heating conditions, and finally removing a large amount of solvent.

[0067] In this embodiment, the specific method for producing the titanium source solution is a conventional sol-gel method, that is, a titanium source (e.g., tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, etc.) is dissolved in an organic alcohol solution, and then an inhibitor (e.g., glacial acetic acid, etc.) is added to suppress its hydrolysis and form the titanium source solution. This application is not particularly limited and only preferred embodiments are provided.

[0068] In some of the selectable embodiments, the method for producing the titanium source solution is as follows:

[0069] In step S1, a titanium source (e.g., tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate, tetrahexyl titanate, etc.) is dissolved in a C2-C5 alcohol solution and mixed uniformly to obtain a clear, transparent solution. The purpose of this step is to dissolve the titanium source. Here, the volume ratio of the titanium source to the C2-C5 alcohol solution is preferably in the range of 2:(0.5~20), the titanium source is more preferably tetraisopropyl titanate or tetrabutyl titanate, the alcohol solution is more preferably isopropanol, and if the alcohol solution is isopropanol, the volume ratio of the titanium source to isopropanol is more preferably in the range of 1:(3~6).

[0070] In step S2, the obtained clear transparent solution is added dropwise to glacial acetic acid while stirring to obtain a cloudy solution, which is then left to stand for a while to obtain a clear transparent solution, i.e., the titanium source solution. This step is intended to suppress the hydrolysis of the titanium source. Here, the volume ratio of the titanium source to glacial acetic acid is preferably in the range of 1:(0.5~10), and more preferably 1:1.

[0071] Conventional technologies generally produce titanium dioxide using methods such as the sulfuric acid method and chlorination method, but these processes are complex, energy-intensive, produce a lot of waste, have a high content of metal impurities in the produced titanium dioxide, and have complex crystal structures. 68 Ge- 68 It cannot be used as an adsorption packing material for Ga generators. Disclosed in US10357758B2 68 Ge- 68 Titanium dioxide used as an adsorption packing material for Ga generators has an initial adsorption efficiency of 75%, and its long-term elution efficiency stabilizes at approximately 65%. At the same time, as can be seen from the data disclosed in the prior art, 68 The leakage rate of Ge is according to the European Pharmacopoeia for gallium chloride [ 68 Assuming the solution conforms to the standard (≤0.001%) of Ga, 68The elution efficiency of Ga is generally below 75%, and a problem arises where the elution efficiency decreases significantly after multiple elutions. The sol-gel method is simple, rapid, environmentally friendly, and does not carry the risk of introducing other metal ions, making it a point of interest for engineers. However, titanium dioxide produced by conventional sol-gel methods is generally nanoscale. This is because, after the titanium source forms a titanium source solution through the action of organic alcohol and an inhibitor, it aggregates in purified water to form sol particles of about 1 nm. These sol particles further grow during the standing process to form a gel, but this gel is merely an overlap between the sol particles, and its essence remains nanoscale titanium dioxide hydrate. Therefore, after directly drying, calcining, and pulverizing the gel, more than 80% of the obtained material is nanoscale titanium dioxide. Because the particle size of this titanium dioxide is too small, it is easy to increase the column pressure too much after packing it into the column, resulting in a high elution flow rate loss and 68 This increases the Ge leakage rate. When glacial acetic acid is used as an inhibitor, it is possible to selectively obtain some micron-level titanium dioxide particles (formed by aggregation of nano-level titanium dioxide), but the yield is generally less than 20%, and the yield is unstable. At the same time, the adsorption performance and leakage rate of the micron-level titanium dioxide particles do not meet the requirements.

[0072] Based on this, the present application describes a method in which secondary gelation is performed during the gelation stage of the titanium source, and the first gel is heated and kept warm to recrystallize, thereby agglomerating and growing nano-level sol particles in the first gel. After secondary heating and warming, the particle size of the sol particles aggregates to form a second gel, thereby allowing titanium dioxide to exist at the micron level particle size after calcination and pulverization.

[0073] Furthermore, in order to obtain titanium dioxide particles at the micron level, the inhibitor used to prepare the titanium source solution must be limited to glacial acetic acid. In the prior art, inhibitors generally include glacial acetic acid, ethanolamine, aqueous ammonia, acetylacetone, etc. However, the applicant has found that when other inhibitors are added, it is not possible to select titanium dioxide at the required micron level even after secondary gelation, and that the above requirement can only be met when the inhibitor is glacial acetic acid.

[0074] The applicant further found that, assuming glacial acetic acid as the inhibitor, the leakage rate and elution efficiency of the micron-level titanium dioxide sorted after primary calcination were neither ideal, regardless of whether it was primary or secondary gelation.

[0075] This is because the micron-level titanium dioxide obtained in the primary calcination is further aggregated with nano-level titanium dioxide during secondary gelation. Under the conditions of primary calcination, nano-titanium dioxide that aggregates to form micron-level titanium dioxide has crystal particles that are too small, resulting in a large specific surface area and too many surface-active sites. Therefore, the material has high adsorption capacity for both germanium and gallium, making it difficult to achieve separation. On the other hand, many ultrafine particles adhere to the surface of the titanium dioxide obtained after primary calcination, roughening the surface of the crystal particles and increasing the specific surface area. Furthermore, the adhesion of the ultrafine particles is not strong, and during elution, along with the washing of the eluent, 68 Ge leaks have increased significantly. 68 This affects the elution efficiency of Ga and its stability after multiple elutions.

[0076] In response to the above problem, the applicant, assuming the formation of micron-level titanium dioxide, has titanium dioxide particles with a size of 10 to 300 μm, consisting of nanoscale titanium dioxide nanoparticles in the range of 10 to 100 nm, and a specific surface area of ​​30 to 100 m². 2 If the pore size is 5-30 nm, the surface is smooth, and it exhibits an anatase phase, then 68 Ge- 68We found that using it as an adsorbent in a Ga generator significantly improves its performance.

[0077] Based on this, in this application, after the first firing, the obtained titanium dioxide is surface modified to smooth the surface of the titanium dioxide particles and remove the ultrafine particles on the surface. Subsequently, a second firing is performed, and in the micron-level titanium dioxide obtained from the second firing, the size range of nanoscale titanium dioxide particles that aggregate to form micron-level titanium dioxide is set to 10 to 100 nm, the pore diameter of the nanoscale titanium dioxide is set to 5 to 30 nm, and the specific surface area is set to 30 to 100 m². 2 The amount is set to / g, and the surface is smoothed to exhibit the anatase phase, and titanium dioxide 68 Ge- 68 When used as an adsorbent for Ga generators, different 68 In terms of Ge loading activity, 68 The leakage rate for Ge has decreased to approximately 0.0001% in all cases, and the initial 68 The elution efficiency of Ga is improved to over 75%, and the energy required for multiple washes is maintained at over 70%.

[0078] In the above embodiment, the size range of the nano-titanium dioxide particles that aggregate to form micron-level titanium dioxide is controlled to 10-100 nm because titanium dioxide nanoparticles in this size range contain many grain boundaries, and these grain boundaries can eliminate crystal defects, resulting in greater radiation resistance compared to crystal grains larger than 100 nm, thus improving the performance of micron-level titanium dioxide. However, the above titanium dioxide is 68 Ge and 68 Both have adsorption capabilities for Ga, and therefore, the pore size range of nanoscale titanium dioxide can be controlled to 5-30 nm, and the specific surface area can be increased to 30-100 m². 2 / g 68 Ge and 68 It is necessary to improve the adsorption selectivity for Ga. The titanium dioxide adsorbent in question is 68 To improve the adsorption capacity for Ge, 68To minimize adsorption to Ga, and therefore, 68 Ga elution efficiency is improved, and 68 It exhibits the characteristic of a reduced Ge leakage rate.

[0079] As a result, the manufactured titanium dioxide adsorbent has a particle size of 10-300 μm, consists of titanium dioxide nanoparticles of 10-100 nm, and has a specific surface area of ​​30-100 m². 2 The titanium dioxide is specified as having a density of / g, a pore size of 5-30 nm, a smooth surface, and exhibiting the characteristics of the anatase phase standard. 68 Ge- 68 When used as an adsorbent for a Ga generator, different 68 In terms of Ge loading activity, 68 The hotel leakage rate has decreased to approximately 0.0001% in all cases, 68 Ga elution efficiency improved to over 75%, and was maintained at over 70% after multiple elutions (within a 200-day elution cycle).

[0080] In some selectable embodiments, during the titanium source gelation process, the titanium source solution is added dropwise to a purified aqueous solution while stirring, with the stirring speed controlled to 10-100 rpm and the dropping acceleration controlled to 1-100 mL / min. This is because the stirring speed and dropping time have a certain effect on the particle size of the sol particles. Rationally controlling the stirring speed and dropping time is advantageous in increasing the particle size of the sol particles that form the first gel, shortening the time it takes for the sol particles to grow from the nano-level to the micron-level when forming the second gel, and increasing the number of micron-level titanium dioxide particles after grinding. In this embodiment, the amounts of titanium source solution and purified water added can be selected by those skilled in the art, and in this application, a volume ratio of 1:(0.5-10) is preferred.

[0081] In some selectable embodiments, the heating and holding time for forming the second gel is 110-180°C and 6-36 hours. The heating and holding temperatures and times affect the rate and size at which the sol particles grow from the nanoscale to the micronscale, and can usually be selected by those skilled in the art after understanding the technical principles of this application, depending on the size of the sol particles to be obtained. In this application, since it is necessary to obtain more titanium dioxide of the 10-300 μm class, the holding temperature is preferably 110-180°C and the holding time is preferably 6-36 hours.

[0082] In several selectable embodiments, surface modification aims to smooth the surface and remove ultrafine titanium dioxide particles from the surface, and can be carried out by methods such as vibration, vortexing, or ultrasound. In this application, ultrasound is preferred, with an output of 50 to 1000 W and a duration of 0.5 to 12 hours.

[0083] In embodiments of this application, titanium dioxide particles, which are adsorbents manufactured by methods such as vibration, vortexing, and ultrasound, have a smooth surface, indicating that there are few or no fine particles adsorbed on their surface and that they have a certain degree of acid-resistant cleaning properties. The adsorbent is germanium [ 68 Ge]-Gallium[ 68 When used in a Ga generator, it has good elution efficiency and obtained 68 In Ga-containing solution 68 The Ge content is extremely low. 68 To improve the reliability of Ga-containing solutions.

[0084] In several selectable embodiments, the material is ground to separate solid particles with particle sizes of 30-60 μm, 50-100 μm, 75-150 μm, and 90-180 μm, because the applicant has found that the above particle size combinations further improve the performance as a titanium dioxide adsorbent.

[0085] In several selectable embodiments, the titanium dioxide particles are smoothed by methods such as vibration, vortexing, or ultrasound.

[0086] In several selectable embodiments, the first firing is performed at a temperature of 300–700°C, and the second firing is performed at a temperature of 400–700°C. The applicant found that the firing temperature and firing time affect the specific surface area of ​​titanium dioxide. The firing temperature is 30–100°C. 2 To obtain the maximum specific surface area of ​​titanium dioxide per gram, it is preferable that the firing time is 1 to 12 hours for the first firing and 1 to 6 hours for the second firing.

[0087] Furthermore, after the second gel is formed, the process further includes a step, as disclosed in conventional sol-gel methods, of placing the second gel in an oven and heating it further to remove any residual solvent from the gel surface. The drying temperature is preferably 110 to 180°C, and its purpose is to remove any organic alcohol and glacial acetic acid remaining on the surface.

[0088] Furthermore, during surface modification, it is necessary to place the solid particles in a purified aqueous solution. To facilitate the removal of ultrafine particles by vibration and smooth the surface, and to improve the effect, purified water may be replaced with a 0.1 mol / L hydrochloric acid solution. At the same time, it is necessary to dry the surface after surface modification, and the drying temperature is preferably 110 to 180°C.

[0089] In a third embodiment, the embodiment of the present application includes a germanium [ filled cylinder filled with the adsorbent described in the first embodiment or the adsorbent manufactured by the manufacturing method described in the second embodiment] 68 Ge]-Gallium[ 68 It provides a Ga generator, and the adsorbent is 68 The element Ge is adsorbed onto it.

[0090] The adsorbent and manufacturing method of any of the above embodiments are described in the embodiments of this application. 68 Ge- 68It can be used in Ga generators, but the explanation is omitted here.

[0091] In some preferred embodiments, the adsorbent has a particle size of 10 to 300 μm, consists of nanoparticles of 10 to 100 nm, and has a specific surface area of ​​30 to 100 m². 2 This is particulate titanium dioxide with a density of / g, a pore size of 5-30 nm, a smooth surface, and exhibiting anatase phase.

[0092] The applicant claims that the titanium dioxide adsorbent meeting the above performance criteria has better adsorption performance. 68 Ge- 68 Ga generator 68 The Ge leakage rate can be reduced to approximately 0.0001%, and in the activity range of 30-85 mCi class or higher, 68 We found that the Ga elution efficiency improved to over 75%, reaching a maximum of 86%, and that the elution efficiency could be maintained at over 70% even after multiple elutions.

[0093] Furthermore, when the particle size of the adsorbent described in this application is stated to be 10 to 300 μm, it means that the particle size range is titanium dioxide particles within 10 to 300 μm. The specific particle size may be, for example, 10 μm, 50 μm, 100 μm, 150 μm, 200 μm, 250 μm, or 300 μm, or it may be any range within 10 to 300 μm, for example, 10 to 50 μm, 30 to 60 μm, 50 to 150 μm, 20 to 200 μm, 130 to 260 μm, or 200 to 300 μm, preferably within the particle size ranges of 30 to 60 μm, 50 to 100 μm, 75 to 150 μm, or 90 to 180 μm.

[0094] The specific surface area, nanoparticle size, and pore diameter are as described above; for example, the specific surface area is 30 m². 2 / g, 40m 2 / g, 70m 2 / g, 85m 2 / g, 100m 2 It may also be / g, 30-50m 2 / g, 50-100m 2 / g, 80-100m 2It may be within the range of the specific surface area per g.

[0095] The size of the nanoparticles may be 10 nm, 20 nm, 50 nm, 60 nm, 80 nm, or 100 nm, or within the range of 10-30 nm, 20-60 nm, or 50-100 nm, and the pore size may be 5 nm, 10 nm, 15 nm, 20 nm, or 30 nm, or within the range of 5-10 nm, 10-25 nm, or 20-30 nm.

[0096] In this embodiment, particulate titanium dioxide of the 10-300 μm class is 68 By reducing the Ge leakage rate and influencing the specific surface area through its crystal structure, it affects the yield, pore size, and surface smoothness of the titanium dioxide anatase phase. 68 This affects the Ga elution efficiency, and only if titanium dioxide meets the above criteria, 68 Ge- 68 Ga generator 68 Reduce the Ge leakage rate, 68 This can improve Ga elution efficiency and elution stability.

[0097] In some select embodiments, germanium [ 68 Ge]-Gallium[ 68 The Ga generator is, Housing and A lead shield is provided inside the housing and fitted onto the outside of the filling cylinder, The filling cylinder is eluted and gallium [ 68 It is used to obtain the element Ga, and includes an elution channel that penetrates the housing and lead shield and communicates with the filling cylinder.

[0098] In some preferred embodiments, the packing tube is made of a material such as a plastic chromatography column, a glass tube, or a quartz tube.

[0099] In some of the selectable embodiments, 68 Ge- 68 The Ga generator further includes an elution pipeline and a lead shield.

[0100] In some select embodiments, loaded 68 Depending on the difference in Ge activity, 68 Ge- 68 Ga generators can be divided into different levels. For example, loaded 68 Depending on the Ge activity level, there are 30mCi, 50mCi, and 80mCi class 68 Ge- 68 A Ga generator can be obtained.

[0101] Furthermore, the loading activity described above is only the preferred loading activity of this application and should not be interpreted as a limitation on loading activity. The titanium dioxide produced in this application has superior performance and can be used with different loading activity levels such as microcurie, millicurie, and 100 millicurie. 68 Ge- 68 It can be manufactured into a Ga generator.

[0102] To further clarify the purpose, technical solutions, and advantages of this application, the application will be described in more detail below in combination with examples. Note that the specific examples described herein are for interpretation purposes only and do not limit the scope of this application. [Examples]

[0103] Unless otherwise specified, the reagents, methods, and apparatus used in this application are those of the ordinary in the art.

[0104] Example 1 Manufacturing of titanium dioxide adsorbent

[0105] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isopropanol, mix uniformly to obtain a clear solution, and add the clear solution dropwise to 50 mL of glacial acetic acid, leave at room temperature for 24 hours to obtain a titanium source solution.

[0106] 2) Add the titanium source solution dropwise to 200 mL of purified water at a stirring speed of 55 rpm and a dropping rate of 5 mL / min while stirring, one drop at a time, and leave at room temperature for 24 hours to convert to the first gel. Place the first gel in an air-circulating oven and heat to 150°C, then maintain the temperature for 24 hours to obtain the second gel.

[0107] 3) Place the second gel in a muffle furnace and heat it to 400°C at a heating rate of 5°C / min, bake for 4 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 50-180 μm.

[0108] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to ultrasonic treatment for 2 hours at an ultrasonic output of 200 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 150°C. The dried solid particles are then placed in a muffle oven and heated to 500°C at a heating rate of 5°C / min, baked for 3 hours, allowed to cool naturally at room temperature, and removed to obtain titanium dioxide adsorbent.

[0109] Example 2 Manufacturing of titanium dioxide adsorbent

[0110] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of anhydrous ethanol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0111] 2) The titanium source solution is added dropwise to 1500 mL of purified water at a stirring speed of 10 rpm and a dropping rate of 50 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven, heated to 110°C, and kept warm for 26 hours to obtain the second gel.

[0112] 3) Place the second gel in a muffle furnace and heat it to 300°C at a heating rate of 5°C / min, bake for 1 hour, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 10-300 μm.

[0113] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to sonication for 6 hours at an ultrasonic output of 50 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 150°C. The dried solid particles are then placed in a muffle oven and heated to 400°C at a heating rate of 5°C / min, baked for 1 hour, allowed to cool naturally at room temperature, and removed to obtain a titanium dioxide adsorbent.

[0114] Example 3 Manufacturing of titanium dioxide adsorbent

[0115] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of n-butanol, mixing uniformly to obtain a clear solution. Add this clear solution dropwise to 50 mL of glacial acetic acid and leave at room temperature for 24 hours to obtain a titanium source solution.

[0116] 2) The titanium source solution is added dropwise to 3000 mL of purified water at a stirring speed of 100 rpm and a dropping rate of 100 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven, heated to 180°C, and kept warm for 36 hours to obtain the second gel.

[0117] 3) Place the second gel in a muffle furnace and heat it to 700°C at a heating rate of 5°C / min, bake for 12 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 75-150 μm.

[0118] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to ultrasonic treatment for 12 hours at an ultrasonic output of 1000 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 150°C. The dried solid particles are then placed in a muffle oven and heated to 700°C at a heating rate of 5°C / min, baked for 6 hours, allowed to cool naturally at room temperature, and removed to obtain titanium dioxide adsorbent.

[0119] Example 4 Manufacturing of titanium dioxide adsorbent

[0120] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0121] 2) The titanium source solution is added dropwise to 800 mL of purified water at a stirring speed of 80 rpm and a dropping rate of 20 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven and heated to 165°C, where it is kept warm for 35 hours to obtain the second gel.

[0122] 3) Place the second gel in a muffle furnace and heat it to 550°C at a heating rate of 5°C / min, bake for 4.5 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 50-100 μm.

[0123] 4) The selected solid particles are placed in a 0.1 M HCl solution and ultrasonically treated for 8 hours at an ultrasonic output of 120 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 150°C. The dried solid particles are then placed in a muffle oven and heated to 550°C at a heating rate of 5°C / min, calcined for 2 hours, allowed to cool naturally at room temperature, and removed to obtain titanium dioxide adsorbent.

[0124] Example 5 Manufacturing of titanium dioxide adsorbent

[0125] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0126] 2) The titanium source solution is added dropwise to 2200 mL of purified water at a stirring speed of 30 rpm and a dropping rate of 70 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven and heated to 170°C, and kept warm for 30 hours to obtain the second gel.

[0127] 3) Place the second gel in a muffle furnace and heat it to 600°C at a heating rate of 5°C / min, bake for 8 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 90-180 μm.

[0128] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to ultrasonic treatment for 1 hour at an ultrasonic output of 800 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 150°C. After drying, the solid particles are placed in a muffle oven and heated to 650°C at a heating rate of 5°C / min, and fired for 5 hours. After being allowed to cool naturally at room temperature and removed, a titanium dioxide adsorbent is obtained.

[0129] Example 6 Manufacturing of titanium dioxide adsorbent

[0130] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0131] 2) The titanium source solution is added dropwise to 1000 mL of purified water at a stirring speed of 100 rpm and a dropping rate of 100 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven, heated to 180°C, and kept warm for 30 hours to obtain the second gel.

[0132] 3) Place the second gel in a muffle furnace and heat it to 300°C at a heating rate of 5°C / min, bake for 12 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 75-150 μm.

[0133] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to ultrasonic treatment for 5 hours at an ultrasonic output of 50 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 120°C. The dried solid particles are then placed in a muffle oven and heated to 500°C at a heating rate of 5°C / min, fired for 5 hours, allowed to cool naturally at room temperature, and removed to obtain a titanium dioxide adsorbent.

[0134] Example 7 Manufacturing of titanium dioxide adsorbent

[0135] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0136] 2) Add the titanium source solution dropwise to 500 mL of purified water at a stirring speed of 10 rpm and a dropping rate of 5 mL / min while stirring, one drop at a time, and leave at room temperature for 24 hours to convert to the first gel. Place the first gel in an air-circulating oven and heat to 120°C, then maintain the temperature for 30 hours to obtain the second gel.

[0137] 3) Place the second gel in a muffle furnace and heat it to 500°C at a heating rate of 5°C / min, bake for 3 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 50-150 μm.

[0138] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to ultrasonic treatment for 1 hour at an ultrasonic output of 100 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 130°C. The dried solid particles are placed in a muffle oven and heated to 550°C at a heating rate of 5°C / min, and fired for 2 hours. After being allowed to cool naturally at room temperature and removed, a titanium dioxide adsorbent is obtained.

[0139] Example 8 Manufacturing of titanium dioxide adsorbent

[0140] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of anhydrous ethanol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0141] 2) The titanium source solution is added dropwise to 1200 mL of purified water at a stirring speed of 13 rpm and a dropping rate of 55 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven, heated to 130°C, and kept warm for 26 hours to obtain the second gel.

[0142] 3) Place the second gel in a muffle furnace and heat it to 380°C at a heating rate of 5°C / min, bake for 2 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 50-300 μm.

[0143] 4) The selected solid particles are placed in a 0.1 M HCl solution and ultrasonically treated for 6 hours at an ultrasonic output of 50 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 130°C. The dried solid particles are placed in a muffle oven and heated to 400°C at a heating rate of 5°C / min, baked for 1 hour, allowed to cool naturally at room temperature, and then removed to obtain a titanium dioxide adsorbent.

[0144] Example 9 Manufacturing of titanium dioxide adsorbent

[0145] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0146] 2) The titanium source solution is added dropwise to 2000 mL of purified water at a stirring speed of 38 rpm and a dropping rate of 95 mL / min while stirring, one drop at a time. The mixture is left at room temperature for 24 hours to convert to the first gel. The first gel is then placed in an air-circulating oven, heated to 170°C, and kept warm for 30 hours to obtain the second gel.

[0147] 3) Place the second gel in a muffle furnace and heat it to 570°C at a heating rate of 5°C / min, bake for 8 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 75-180 μm.

[0148] 4) The selected solid particles are placed in a 0.1 M HCl solution and ultrasonically treated for 2 hours at an ultrasonic output of 800 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 170°C. The dried solid particles are placed in a muffle oven and heated to 670°C at a heating rate of 5°C / min, and fired for 5 hours. After being allowed to cool naturally at room temperature and removed, the titanium dioxide adsorbent is obtained.

[0149] Comparative Example 1 Manufacturing of titanium dioxide adsorbent

[0150] The product was manufactured using the conventional sol-gel method, with aqueous ammonia (30%) selected as the inhibitor, specifically as follows:

[0151] 1) Add 50 mL of tetraisopropyl titanate dropwise to 200 mL of isopropanol and mix uniformly to obtain a clear, transparent solution.

[0152] 2) The clear, transparent solution described above is added dropwise to 30% ammonia water while stirring to adjust the pH to ≥ 7, and left at room temperature for 24 hours to obtain the titanium source solution.

[0153] 3) Add the titanium source solution dropwise to 200 mL of purified water while stirring, and leave at room temperature for 24 hours to convert to the first gel. Remove the solvent by rotating and evaporating the gel in a rotary evaporator at 90°C.

[0154] 4) Place the first gel in a muffle furnace and heat it to 400°C at a heating rate of 5°C / min, bake for 4 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar and pestle, and sieve it to obtain a yellowish-white solid powder.

[0155] Mesh-based sorting results: In Comparative Example 1, titanium dioxide produced by the conventional sol-gel method was used, and the inhibitor was limited to aqueous ammonia (30%). After pulverization, it was not possible to screen for dense titanium dioxide particles in the range of 10-300 μm, making it difficult to use as an adsorption packing material for a radionuclide generator.

[0156] Comparative Example 2 Manufacturing of titanium dioxide adsorbent

[0157] The product was manufactured using the conventional sol-gel method, with glacial acetic acid selected as the inhibitor, specifically as follows:

[0158] 1) Add 50 mL of tetraisopropyl titanate dropwise to 200 mL of isopropanol and mix uniformly to obtain a clear, transparent solution.

[0159] 2) Add the above clear transparent solution dropwise to 50 mL of glacial acetic acid while stirring, one drop at a time, and leave at room temperature for 24 hours to obtain the titanium source solution.

[0160] 3) Add the titanium source solution dropwise to 200 mL of purified water while stirring, and leave at room temperature for 24 hours to convert to the first gel. Remove the solvent by rotating and evaporating the gel in a rotary evaporator at 90°C.

[0161] 4) Place the first gel in a muffle furnace and heat it to 400°C at a heating rate of 5°C / min, bake for 4 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar and pestle, and sieve it to obtain a black or yellowish-white solid powder.

[0162] Mesh sorting results: In Comparative Example 2, titanium dioxide produced by the conventional sol-gel method was used, and the inhibitor was limited to glacial acetic acid. After grinding, titanium dioxide particles in the range of 10-300 μm were screened, and the yield was 18%, which is too low and contains many impurities. 68 Ge- 68 It is difficult to use as an adsorbent for Ga generators.

[0163] Comparative Example 3 Manufacturing of titanium dioxide adsorbent

[0164] The manufacturing method is the same as in Example 1. The difference is that in Comparative Example 3, the titanium dioxide particles obtained after sorting (step 3) following the first firing are used as is, and the process in step 4 is omitted.

[0165] Comparative Example 4 Manufacturing of titanium dioxide adsorbent

[0166] The manufacturing method is the same as in Example 1; the difference is that in Comparative Example 4, the titanium dioxide particles used after ultrasonic cleaning and drying in step 4 are used as is, and the subsequent secondary firing process is omitted.

[0167] Comparative Example 5 Manufacturing of titanium dioxide adsorbent

[0168] The manufacturing method is the same as in Example 1; the difference is that in Comparative Example 5, the ultrasonic cleaning process is omitted, and the titanium dioxide particles obtained after sorting (step 3) following the first firing are subjected to secondary firing as is.

[0169] Comparative Example 6 Manufacturing of titanium dioxide adsorbent

[0170] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isoamyl alcohol, mix uniformly to obtain a clear, transparent solution, add the clear, transparent solution dropwise to 50 mL of glacial acetic acid, and leave at room temperature for 24 hours to obtain a titanium source solution.

[0171] 2) Pour the titanium source solution directly into 300 mL of purified water and leave it at room temperature for 24 hours to convert into the first gel. Place the first gel in an air-circulating oven, heat it to 180°C, and keep it warm for 30 hours to obtain the second gel.

[0172] 3) Place the second gel in a muffle furnace and heat it to 700°C at a heating rate of 5°C / min, bake for 12 hours, and allow it to cool naturally at room temperature. Remove it, grind it in a mortar, and sieve it to separate solid particles in the range of 50-150 μm.

[0173] 4) The selected solid particles are placed in a 0.1 M HCl solution and subjected to sonication for 5 hours at an ultrasonic output of 1000 watts. The ultrafine particles are rinsed off, washed multiple times, and dried in an oven at a drying temperature of 160°C. After drying, a titanium dioxide adsorbent is obtained.

[0174] Comparative Example 7 Manufacturing of titanium dioxide adsorbent

[0175] 1) Add 50 mL of tetrabutyl titanate dropwise to 200 mL of isopropanol, mix uniformly to obtain a clear solution, and add the clear solution dropwise to 50 mL of glacial acetic acid, leave at room temperature for 24 hours to obtain a titanium source solution.

[0176] 2) The titanium source solution is added dropwise drop by drop into 200 mL of purified water while stirring at a stirring speed of 55 rpm and a dropping rate of 5 mL / min, then left to stand at room temperature for 24 hours to convert into a first gel. The first gel is placed in an air-circulating oven, heated to 120°C and kept warm for 24 hours to obtain a second gel.

[0177] 3) The second gel is placed in a muffle furnace, heated to 700°C at a heating rate of 5°C / min, calcined for 14 hours, and allowed to cool naturally to room temperature. After being taken out, it is placed in a mortar, crushed, passed through a mesh, and solid particles in the range of 50 to 180 μm are sorted out.

[0178] 4) The sorted solid particles are placed in a 0.1 M HCl solution, subjected to ultrasound for 2 hours with an ultrasound output of 500 W to rinse off ultrafine particles, washed multiple times and dried in an oven at a drying temperature of 120°C. The solid particles after drying are placed in a muffle furnace, heated to 700°C at a heating rate of 5°C / min, calcined for 6 hours, allowed to cool naturally to room temperature and taken out, whereby a titanium dioxide adsorbent is obtained.

[0179] Application Example 1 For a 2 mCi grade 68 Ge- 68 Ga generator

[0180] First, 5 g of the adsorbents prepared in the examples and comparative examples are weighed and placed into a glass tube with a sand core, glass wool and a sieve plate are added, the mixture is compacted and assembled into a generator column, then the column is washed with 250 mL of 0.1 M hydrochloric acid solution. Further, the TiO₂ cold column is placed in a lead shield, the lead shield, generator housing and components are assembled to form a cold generator. 2 mCi of 68 Ge solution is placed into a vial, and by means of a syringe positive pressure injection method, the 68 Ge solution is injected into the cold generator, air continues to be injected under pressure to discharge the liquid remaining in the empty column, the column is further slowly rinsed with 250 mL of 0.1 M hydrochloric acid solution, air is injected under pressure to discharge the liquid remaining in the empty column, whereby a 2 mCi grade 68 Ge- 68 Ga generator is obtained.

[0181] Application Example 2 30mCi class and above 68 Ge- 68 Ga generator

[0182] First, weigh 5 g of the adsorbent produced in Example 1 and place it in a glass tube with a sand core. Add glass wool and a sieve plate, compact it, and assemble it into a generator column. Then, wash the column with 250 mL of 0.1 M hydrochloric acid solution. Next, place the TiO2 cold column on a lead shield, assemble the lead shield, generator housing and components, and assemble it into a cold generator. 30~85 mCi 68 Place the Ge solution in a vial and inject it using a syringe under positive pressure. 68 The Ge solution is injected into the cooling generator, and air is continuously injected under pressure to drain any remaining liquid from the empty column. Then, the column is slowly washed with 250 mL of 0.1 M hydrochloric acid solution, air is injected under pressure, and any remaining liquid from the empty column is drained. 68 Ge- 68 Each Ga generator will be manufactured, and its relevant performance indicators will be evaluated over the long term.

[0183] Test Example 1 2mCi class 68 Ge- 68 Performance investigation of Ga generators

[0184] 68 Ge- 68 Elution using a Ga generator: Take 2 mL of 0.1 M hydrochloric acid solution into a 10 mL sterile syringe, slowly elute the generator using a positive pressure injection method, inject air under pressure to drain the liquid remaining in the empty column, collect the eluent in a sterile vial, and gallium chloride [ 68 A Ga solution was obtained. The activity of the eluent was measured and found to be of the 2mCi class. 68 Ge- 68 Ga generator elution efficiency, 68 The Ge leakage rate and elution efficiency after multiple elutions can be obtained.

[0185] Test Example 2 30mCi class or higher 68Ge- 68 Performance investigation of Ga generators

[0186] 68 Ge- 68 Elution using a Ga generator: Take 5 mL of 0.1 M hydrochloric acid solution into a 10 mL sterile syringe, slowly elute the generator using a positive pressure injection method, inject air under pressure to drain the liquid remaining in the empty column, collect the eluent in a sterile vial, and gallium chloride [ 68 Ga solution was obtained. The activity of the eluent was measured, and activity levels of 30 mCi, 50 mCi, and 85 mCi were found. 68 Ge- 68 Ga generator elution efficiency, 68 The Ge leakage rate and elution efficiency after multiple elutions can be obtained.

[0187] Experimental results: Table 1-1: 2mCi class for application example 1 68 Ge- 68 Performance testing of Ga generator Table 1-2: 2mCi class for application example 1 68 Ge- 68 Performance testing of Ga generator Table 2: Class 30mCi and above in Application Example 1 68 Ge- 68 Elution efficiency of Ga generator Table 3: Application Example 1: 30 mCi class or higher 68 Ge- 68 Ga generator 68 Microsoft leakage rate Table 4: Common commercially available products 68 Ge- 68 Ga generator performance

[0188] [Table 1-1]

[0189] Results Analysis: As can be seen from Table 1-1, the amount of 2mCi produced by the adsorbents used in Examples 1-5 68 Ge- 68 The Ga generator is 68 The Ge leakage rate is ≤0.0001% in all cases.68 Ge- 68 Meeting the basic performance and quality requirements for Ga generators, 68 Ge- 68 It can be used in the commercial development of Ga generators. 68 Ge- 68 Compared to the performance of the Ga generator, 2mCi 68 Ge- 68 The initial elution efficiency of the Ga generator is consistent with that of conventional technology. 68 Ge- 68 The elution efficiency of the Ga generator 68 It has a certain relationship with Ge loading activity and is in the range of 2-30 mCi. 68 Due to low Ge loading activity and an unsaturated state, no difference in elution efficiency is observed, or no clear improvement is seen. 68 The Ge leakage rate is clearly reduced, and the performance of titanium dioxide produced using the manufacturing method of this application is clearly improved compared to the prior art. On the other hand, the manufacturing methods of Comparative Example 1 (replacing the inhibitor with aqueous ammonia) or Comparative Example 2 (not performing secondary gelation) are unable to produce titanium dioxide at the micron level or the yield is too low, and the adsorbents produced in Comparative Examples 3, 4, and 5 68 Ge- 68 The performance used in the Ga generator is too low, and its elution efficiency is low, 68 The Ge leakage rate is much higher than 0.001%, making it difficult to use in commercial development. When titanium dioxide is produced by the sol-gel method, the inhibitor is glacial acetic acid, and it is necessary to calcine and wash it in a secondary gel state. By controlling the specific calcination temperature and time, it is possible to produce particles with a size of 10-300 μm, a nanoparticle size range of 10-100 nm for titanium dioxide, a pore size of 5-30 nm, and a specific surface area of ​​30-100 m². 2 Titanium dioxide can be produced that is of a certain density ( / g), has a smooth surface, and exhibits the anatase phase. This titanium dioxide can be used as an adsorbent. 68 Ge- 68 This demonstrates that the performance of Ga generators can be improved.

[0190] Furthermore, none of the titanium dioxides produced in Comparative Examples 1 to 5 have prospects for commercial development, and there is no significant difference in performance between the titanium dioxide adsorbents produced in Examples 1 to 5. Therefore, subsequent tests compare Example 1 with the prior art.

[0191]

Table 1-2

[0192] As can be seen from the above table, the adsorbents of Example 1 and Examples 6 to 9 are anatase-type, and the specific surface area of the adsorbent is 30 m 2 / g to 100 m 2 / g, the average particle diameter of the nanoparticles is 10 nm to 100 nm, and the pore diameter of the mesopores is 5 nm to 30 nm. The produced 2 mCi 68 Ge- 68 Ga generator, 68 the Ge leakage rate is all ≤0.0001%, and the initial elution efficiency is 71% or more, 68 Ge- 68 meets the basic performance and quality requirements of Ga generators, 68 Ge- 68 can be used for commercial development of Ga generators. Compared with other adsorbents, the specific surface area, average nanoparticle size and pore diameter of other adsorbents 68 Ge- 68 affect the elution efficiency and leakage rate of Ga generators, 68 Ge- 68 reduce the quality of Ga generators, indicating that the above-mentioned titanium dioxide of the examples as an adsorbent 68 Ge- 68 can improve the performance of Ga generators.

[0193]

Table 2

[0194]

Table 3

[0195] [Table 4]

[0196] Results Analysis: As can be seen from Tables 2 to 4, in the loading activity range of 30 to 85 mCi, the initial elution efficiency was always 80% or higher, reaching a maximum of 86%, and the elution efficiency after long-term elution (average elution time of 6 months) was still maintained at 70% or higher, compared to several conventional commercially available products. 68 Ge- 68 Compared to a Ga generator (Table 4), 68 Assuming a decrease in the Ge leakage rate (approximately 0.0001%), the initial elution efficiency improves to over 80%, and the elution efficiency after 200 days of elution can still be maintained at over 70%. Therefore, titanium dioxide produced by the manufacturing method of this application is 68 Ge- 68 When used in Ga generators, it has been shown to significantly improve performance.

[0197] Explanation of long-term elution efficiency time based on data in Table 4: Conventional technology does not have clear specifications for long-term elution efficiency, and different manufacturers have different specifications for long-term elution. Commonly seen publicly available long-term elution data is 200 days of elution time or 200 elutions. Pharmaceutical grade 68 Ge- 68 The lifespan of a Ga generator is generally up to 12 months, and it is of chemical industrial grade. 68 Ge- 68 Ga generators last 3 years (based on different performance indicators, for example, in Russia) 68 Ge- 68 The Ga generator has an elution efficiency of ≥45%. 68 The Ge leakage rate reaches ≤0.005% (the fixed validity period can be set to 3 years), and therefore, this application uses 200 days as the comparison time for long-term elution efficiency.

[0198] Commercially available titanium dioxide 68 Ge- 68The long-term elution efficiency over one year or the elution efficiency over 200 elution cycles reported by Ga generators, such as those from Cyclotron (Russia), EZAG (Germany), IRE ELiT (Belgium), and Nordion (Canada), is in the range of 55% to 65%, and it is generally difficult to reach 70% or higher.

[0199] Elute with 5 mL of 0.1 M HCl solution to obtain 85 mCi 68 Ge- 68 We manufactured a Ga generator. (85mCi) 68 Ge- 68 The Ga generator was manufactured using the adsorbent of Example 1. As shown in Figure 6, the change in elution efficiency during the long-term elution test was high initially at 86%, indicating very high elution efficiency. The elution efficiency gradually decreased with increasing elution days, showing a tendency to fluctuate up and down, reaching a minimum value of approximately 73% on day 245. This is because the elution efficiency decreases at low temperatures and then gradually increases. The long-term elution efficiency after one year rose to 81%, which is comparable to the titanium dioxide group reported in commercially available and literature products. 68 Ge- 68 This is clearly higher than the long-term elution efficiency of the Ga generator.

[0200] Furthermore, Figure 5 shows a 50 mCi class 68 Ge- 68 This graph shows the change in elution efficiency of the Ga generator over 200 days. The elution efficiency gradually decreased with increasing elution cycles and showed a tendency to fluctuate up and down. Based on the above trend, the change equation (y = (-2.06 × 10)) was obtained by linear fitting. -4 The result obtained was (x + 0.798), and calculations show that the elution efficiency can be maintained at over 70% even after 12 months (based on the formula, the number of elution days x = 365 was substituted into the formula to calculate y = 72%). Furthermore, multiple elutions were performed. 68 The leakage rate of Ge is stable at approximately 0.0001%, and according to the European Pharmacopoeia, gallium chloride [ 68 Ga] Solution Standard 68 This is far smaller than the leakage rate for Ge, which is ≤0.001%.

[0201] This application is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea and produces similar effects within the technical scope of this application is included. In addition, various modifications to the embodiments that a person skilled in the art could conceive, as long as they do not depart from the spirit of this application, and other forms constructed by combining some of the components of the embodiments are also included within the scope of this application.

Claims

1. germanium[ ６８ Ge]-Gallium[ ６８ Adsorbent for Ga generator, The adsorbent, ６８ For the adsorption of element Ge, the adsorbent contains a plurality of titanium dioxide particles, and the adsorbent is 1) The specific surface area of ​​the adsorbent is 30 m² ２ / g to 100m ２ / g 2) The titanium dioxide particles consist of a plurality of nanoparticles having an average particle size of 10 nm to 100 nm, and the nanoparticles contain mesopores with a pore size of 5 nm to 30 nm. An adsorbent that satisfies the requirements.

2. The adsorbent has a specific surface area of ​​31 m². ２ / g ~ 97m ２ The amount is / g, and the plurality of nanoparticles have an average particle size of 12 nm to 96 nm, and the mesopores have a pore diameter of 5.7 nm to 19 nm. The adsorbent according to claim 1.

3. The adsorbent has an anatase type crystalline phase. The adsorbent according to claim 1 or 2.

4. The adsorbent has an average particle size of 10 μm to 300 μm. The adsorbent according to any one of claims 1 to 3.

5. Said adsorbent has a pore volume of 0.1 cm ３ / g to 0.5 cm ３ / g, The adsorbent according to any one of claims 1 to 4.

6. The titanium dioxide particles include one or more of the following: titanium dioxide particles with an average particle size of 30 to 60 μm, titanium dioxide particles with an average particle size of 50 to 100 μm, titanium dioxide particles with an average particle size of 75 to 150 μm, and titanium dioxide particles with an average particle size of 90 to 180 μm. The adsorbent according to any one of claims 1 to 5.

7. The titanium dioxide particles are treated by one or more of the following methods: vibration, vortexing, and ultrasound, to smooth the surface of the titanium dioxide particles. The adsorbent according to any one of claims 1 to 6.

8. ６８ Ge- ６８ A method for producing a titanium dioxide adsorbent for a Ga generator, The adsorbent is manufactured by the sol-gel method. The aforementioned manufacturing method is The process involves dissolving a titanium source in an organic alcohol, then adding glacial acetic acid to obtain a titanium source solution, The process involves adding the titanium source solution drop by drop to a purified aqueous solution while stirring, allowing it to stand to obtain a first gel, heating and maintaining the temperature of the first gel, and recrystallizing it to obtain a second gel. The process involves forming the second gel in the first firing, then crushing it to select solid particles with a particle size of 10 to 300 μm, performing surface modification, and then performing a second firing to obtain an adsorbent. A manufacturing method that includes this.

9. 1) The method of dispensing one drop at a time while stirring involves a stirring speed of 10 to 100 rpm and a dispensing speed of 1 to 100 mL / min. 2) The volume ratio of the titanium source solution to purified water is 1:(0.5 to 10). 3) The heating and keeping warm shall be at a temperature of 110 to 180°C for a period of 6 to 36 hours. 4) Surface modification of solid particles is performed by ultrasonic treatment, wherein the ultrasonic output is 50 to 1000 W and the duration is 0.5 to 12 hours. 5) Grind the material and select solid particles with particle sizes of 30-60 μm, 50-100 μm, 75-150 μm, and 90-180 μm. 6) The first firing is performed at a temperature of 300 to 700°C, and the second firing is performed at a temperature of 400 to 700°C. 7) The first firing is performed for 1 to 12 hours, and the second firing is performed for 1 to 6 hours. The manufacturing method according to claim 8, which satisfies one or more of the following conditions.

10. germanium[ ６８ Ge]-Gallium[ ６８ A Ga generator, The filling cylinder includes an adsorbent according to any one of claims 1 to 7 or an adsorbent manufactured by the manufacturing method described in claim 8 or 9, The adsorbent includes ６８ Ge element is adsorbed. germanium[ ６８ Ge]-Gallium[ ６８ Ga generator.

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