JP5522563B2 - Method and apparatus for producing radioactive molybdenum - Google Patents

Description

The present invention, radioactive molybdenum ^{99 Mo} which is the parent nuclide of a radioactive diagnostic agent radioactive technetium ^{99m Tc,} without the use of nuclear fuel material uranium, consisting essentially (e.g. strontium 90 from long broad isotope half-life high-strength Cesium 137) The present invention relates to a manufacturing method and an apparatus capable of producing a radioactive waste efficiently and inexpensively without generating a large amount and enabling a stable supply.

  At present, in the medical field, radiation and radioisotopes (hereinafter referred to as RI) are indispensable for diagnosis and treatment of diseases. Radiation emitted from RI can be reliably detected and quantified even if the amount of the substance itself is very small, and examination and diagnosis are performed by scintigraphy using this property. The pharmaceutical used for this is called a so-called “radiopharmaceutical”, and the RI used for radiopharmaceuticals and the like is suitable to emit a gamma ray having a short half-life and a large radiation penetration.

Examples of RI used for radiopharmaceuticals and examples of use thereof include, for example, ^99m Tc for brain / thyroid / bone scintigraphy, ⁶⁷ Ga for breast cancer / lung cancer / malignant lymphoma treatment, ²⁰¹ Tl for thyroid tumor scintillator, ⁶⁰ Co Is a source for gamma knife, ³² P is leukemia treatment, ³⁵ S is DNA base sequence / gene chromosome arrangement determination, ⁵¹ Cr is measurement of circulating blood volume / red blood cell volume, ⁵⁹ Fe is measuring serum total iron binding ability (TIBC) ⁸⁹ Sr, ^153m Sm, ¹⁸⁶ Re is pain relieving agent, ⁹⁰ Y is malignant lymphoma treatment, ¹⁰³ Pd is prostate cancer treatment, ¹²⁵ I is a tumor marker, ¹³¹ I is hyperthyroidism / thyroid cancer treatment, ¹³³ Xe is local Lung ventilation function test, etc.

^99m Tc which is used in more than 80% of all diagnostic nuclear medicine in these RI ^are now highly concentrated ²³⁵ U was concentrated about the ²³⁵ U 36% to 93% as a raw material, the neutron it in the reactor It is manufactured by irradiating and causing fission reaction, and extracting ⁹⁹ Mo, which is the parent nuclide of ^99m Tc, from the fission product. This method of using enriched ²³⁵ U is particularly problematic from the standpoint of non-proliferation, and the International Atomic Energy Agency (IAEA) and others are working to switch to technologies that use low enriched ²³⁵ U with a ²³⁵ U enrichment of 20% or less. It is conducted in various countries, and technology development corresponding to it is being promoted all over the world. However, despite 30 years of work, most of the world's ⁹⁹ Mo is still produced using highly enriched ²³⁵ U. On the other hand, if low-concentration ²³⁵ U with a ²³⁵ U enrichment of 20% or less is used as a raw material for ⁹⁹ Mo production, 5 times more uranium will be produced if an attempt is made to produce the same amount of ⁹⁹ Mo as using high-concentration ²³⁵ U. Therefore, a new problem arises that the amount of plutonium produced is increased by about 25 times at the same time as the amount of waste is increased by 5 times. For this reason, a method of irradiating a ⁹⁸ Mo target with thermal neutrons (0.025 eV) of a nuclear reactor and extracting the generated ⁹⁹ Mo is also used. A method of irradiating charged particles from a cyclotron is also used.

Some RIs are manufactured in Japan, but most of them rely on imports from overseas. In 2007, it became difficult to obtain radiopharmaceuticals because of a problem with a Canadian reactor. In August 2008, a Dutch reactor supplying approximately 26% of ⁹⁹ Mo to the global market stopped operation due to partial corrosion deformation of the bottom structure of the primary cooling system, and started operation in mid-February 2009. It was resumed. However, in May 2009, a heavy water leak was detected again in a Canadian reactor, and the operation was suspended. The restoration is considered to be early as of the end of March 2010. In this way, if most of RI is relied on by imports from other countries, it is expected that a stable supply system cannot be maintained due to domestic circumstances in other countries, aging of reactors, maintenance, troubles, etc., and stable supply of RI Has become an important and urgent issue. Especially in Canada, where Japan relies on imports of most RI, it has been decided that the nuclear reactors for supply will reach the operation deadline in 2011. There is no realistic plan from the point of view. In the United States and Europe, the stable supply of RI including ⁹⁹ Mo is eagerly awaited, but a realistic system that can cope with it has not been taken, and it is necessary to establish the system as soon as possible ( Non-patent document 1). In addition, if most of RI is dependent on imports from overseas, the price of RI used in medical treatments will rise, and this will cause a rise in overall medical costs. In 2007, the sales price of radiopharmaceuticals reached 44 billion yen (Non-patent Document 2: Page 5).

In addition, when ²³⁵ U is fissioned in a nuclear reactor, various nuclides are generated in addition to the desired RI as shown in FIG. 1 (Non-Patent Document 3), and storage, management, processing, etc. of unnecessary nuclear waste are generated. Became enormous and very annoying.

Such consideration of problems, the applicants have not used uranium, to produce radioactive molybdenum ^{99 Mo} which is the parent nuclide of radioactive technetium ^{99m Tc,} which is very often used as a radioactive diagnostic agent effectively A technique was proposed (Patent Document 1). In the proposed method, an aqueous Mo solution in which a Mo compound is dissolved in water is irradiated with neutrons in an irradiation capsule installed in the core of a nuclear reactor to generate ⁹⁹ Mo by a ⁹⁸ Mo (n, γ) reaction. It is intended to produce ⁹⁹ Mo efficiently by recovering Mo aqueous solution continuously or batchwise. Likewise Patent Document 2, using a ^{98 Mo,} a technique for generating radioactive molybdenum ^{99 Mo} by thermal neutron capture reaction is proposed. However, in the case of using these thermal neutron capture reactions, since the reactor is used, the production site is limited, and in addition to being largely dependent on the operation mode of the reactor, the production cost is expensive and the reaction cross section is small. The specific activity was low and there was a problem in production efficiency. In addition, considering the safety of nuclear reactors, for example, there may be a situation where it is necessary to stop the operation for half a year, for example, during periodic inspections. In order to easily and stably supplying the ^{99 Mo} facilities such as hospitals these circumstances, it was necessary further technical devices.

  On the other hand, it is also performed to generate a RI by irradiating a raw material target with a proton or heavy ion beam using an accelerator. In the case of protons, by making the accelerator used compact, it can be easily used in facilities such as hospitals. However, when generating RI using protons emitted from such a small accelerator, it can only cope with RI of light nuclides, and avoiding enlargement of the accelerator when trying to cope with RI of heavy nuclides. There was a problem that could not. That is, when generating a RI using protons, the proton has a positive charge, so to react with the target nucleus of a heavy nuclide (although it is a nucleus with many positively charged protons) Because there is a repulsive interaction between positive charges, we have to overcome this and get inside the nucleus. For that purpose, the energy of the incident protons needs to be sufficiently high. Further, when protons enter the target material, the energy of the protons in the target is greatly reduced, so that the thickness of the target that can be used is limited, and as a result, the efficiency of generating sufficient RI is often not high. On the other hand, energy loss in the target increases the temperature of the target, and the use intensity of the proton beam may be limited for a target having a low melting point. By the way, the proton beam is generated by an accelerator and transported through the vacuum pipe to a nearby location where the target is set. However, when the target is set on the atmosphere side, it is necessary to maintain the vacuum in the vacuum pipe and shut off the atmosphere side portion. The material used for blocking must be as thin as possible because it must not reduce the energy and intensity of the proton beam. However, on the other hand, since this material is continuously irradiated with a proton beam, it is destroyed as a result of radiation damage, and it becomes difficult to use a high-intensity proton beam for a long time. In order to manufacture various RIs according to the purpose, if the target material can be set in the atmosphere, the shape and material of the target can be selected flexibly, which is very convenient in practice. However, as described above, RI generation using a proton beam has a problem. These circumstances are similar for heavy ion beams. The problem is greater than the amount of positive charges more than protons.

JP 2008-102078 A Special Table 2002-504231

“Accelerating production of medical isotopes” Nature Vol 457, 29 January 2009 Science Council of Japan Basic Medical Committee / General Engineering Committee Meeting Task Review Subcommittee on Radioactive and Radioactive Utilization “Proposal: Stable Supply System of Radioisotopes in Japan” July 24, 2008 Nuclear Physics A462 (1987) 85-108 North-Holland, Amsterdam

The present invention solves the above-mentioned problems of the prior art, does not use the enrichment ²³⁵ U, does not use the nuclear reactor facility, and does not generate a large amount of fuel waste efficiently and inexpensively and easily. It is an object of the present invention to provide a method and an apparatus capable of realizing a stable supply of radioactive molybdenum.

  In order to solve the above problems, the present invention provides the following technical methods or means.

[1] A power supply for applying a voltage to accelerate a charged particle beam made of deuterium or protons, an acceleration tube for applying the voltage from the power supply and accelerating the charged particle beam, and an accelerator emitting unit In addition, a target for generating fast neutrons of titanium with occluded deuterium is disposed, and a fast neutron generating unit that emits fast neutrons when irradiated with the accelerated charged particle beam is provided, and 9.5 MeV to 25 MeV Using a small accelerator with a scale that generates fast neutrons with energy, fast neutrons generated by the charged particle beam irradiation are irradiated to a raw material target containing ¹⁰⁰ Mo as a target nucleus, and by irradiation with one neutron releasing two neutrons (n, 2n) reaction cause, of a radioactive diagnostic agent radioactive technetium ^99m Tc Method for producing a radioactive molybdenum, characterized in that to produce a radioactive molybdenum ^{99 Mo} is nuclide.

[2] In the first invention, as the target nuclei of raw material target, method of manufacturing radioactive molybdenum, which comprises using a ^{100 Mo} generated as waste fission reaction ^{235 U} in the reactor.

[3] In the first or second aspect of the invention, and characterized by irradiating the high-speed neutrons to raw material target raw material target in a state of fast neutron generator in is allowed state or spaced close contact provided to the accelerator exit section A method for producing radioactive molybdenum.

[4] A radioactive molybdenum production apparatus that generates radioactive molybdenum ⁹⁹ Mo, which is a parent nuclide of radioactive technetium ^99m Tc, which is a ^{radiodiagnostic} agent, and applies a voltage to accelerate a charged particle beam composed of deuterium or protons. A power source to be applied, a voltage applied from the power source, an accelerator tube for accelerating the charged particle beam, and an accelerator emitting unit, and a target for generating fast neutrons of titanium storing the deuterium are disposed, A small accelerator that has a fast neutron generator that emits fast neutrons when irradiated with the charged particle beam accelerated thereto and generates fast neutrons having an energy of 9.5 MeV to 25 MeV, and a target of ¹⁰⁰ Mo comprising a target support means for supporting the material target containing as a nucleus, the charged particles Bee The fast neutrons are generated by irradiation by irradiating the raw material target, by irradiation of a single neutron emitting two neutrons (n, 2n) to cause the reaction, characterized in that to produce a radioactive molybdenum ^{99 Mo} Radio molybdenum production equipment.

[5] The radioactive molybdenum production apparatus according to the fourth invention, wherein the target nucleus of the raw material target is ¹⁰⁰ Mo as waste generated in a nuclear reactor by a ²³⁵ U fission reaction.

[6] In the fourth or fifth invention, the radioactive molybdenum is characterized in that the raw material target is set in a state of being in close contact with or separated from a fast neutron generator provided in the accelerator emission part Manufacturing equipment.

[7] In any of the above aspects to fourth to sixth, fast neutron generator provided in the accelerator exit section comprises a cooling means, and fast neutron generating portion of the vacuum chamber and the atmosphere-side partition walls function Yes and, and fast neutron generator apparatus for producing radioactive molybdenum according to any one of the things to claims 4-6, characterized in that raw material target is set in a state of being state or spaced are adhered to.

According to the present invention, the fast neutrons generated by the charged particle beam irradiation from the accelerator are used to cause the (n, 2n) reaction to produce radioactive molybdenum. Therefore, without using concentrated ²³⁵ U, Without using nuclear reactor facilities, high-strength, long-lived fuel waste can be reduced, enabling stable and stable supply of radioactive molybdenum efficiently and inexpensively.

In addition, the isotopic composition ratio of natural Mo is 9.6% for ¹⁰⁰ Mo, whereas the isotopic composition ratio of reactor fuel waste Mo is about 25.5%. Generation efficiency can be improved by using ¹⁰⁰ Mo generated in a nuclear reactor by fission reaction of ²³⁵ U.

  Further, the apparatus for producing radioactive molybdenum according to the present invention does not need to be regulated by nuclear fuel materials and can be miniaturized, and thus has an advantage that it can be easily used in facilities such as hospitals.

  Further, according to the present invention, since the RI is generated by irradiating the raw material target with neutrons, the neutron has no charge compared to the case of irradiating the target with a positively charged proton beam. It is possible to irradiate a target with a weight about 100 times more than a proton beam at the same time without being bothered by energy loss due to electromagnetic interaction and the accompanying heat generation of the target, thereby increasing the amount of RI generated. Can do. Further, since the target can be arranged in the atmosphere, there is an advantage that the degree of freedom in the arrangement of the raw material target and the selection of the material is increased. This is considered to give immense convenience to various users.

It is a figure which shows the production amount distribution of the nuclide produced | generated by ²³⁵ U nuclear fission in a nuclear reactor. It is a graph which shows the reaction cross-sectional area evaluation value of ¹⁰⁰ Mo and a fast neutron. When irradiated with fast neutrons to ¹⁰⁰ Mo, it is a graph showing the relationship between the reaction cross-sectional area of the fast neutrons and ¹⁰⁰ Mo when (n, 2n) reaction takes place ⁹⁹ Mo is produced. It is a figure which shows typically the radioactive molybdenum manufacturing apparatus by one Embodiment of this invention. It is a figure which shows typically the principal part of the radioactive molybdenum manufacturing apparatus by another embodiment of this invention. It is a block diagram which shows the manufacture procedure of ⁹⁹ Mo by this invention. The fast neutrons are generated by the charged particle beam irradiation from the accelerator, by irradiating the raw material target containing the target nucleus ^{100 Mo,} a diagram showing that ^{the 99 Mo} is generated, (a) is ^{99 Mo} beta decay (B) is a measurement data of 141 keV gamma rays emitted from the state of ^99m Tc excited by the beta decay of ⁹⁹ Mo. (A), (b) shows that the molybdenum-mixed titanate gel irradiated with fast neutrons is put in a glass tube, milked with water and physiological saline, and the resulting solution is dried to change the gamma ray intensity of ^99m Tc. It is a figure which shows the result of having measured. (A), (b) takes molybdenum mixed titanate gel was irradiated with fast neutrons milking to a beaker, respectively washed with water and saline, the supernatant is dried, the change in the gamma ray intensity of ^{9 9m Tc} It is a figure which shows the measurement result.

  Hereinafter, the present invention will be described in detail based on embodiments.

In the present invention, radioactive molybdenum ⁹⁹ Mo, which is a parent nuclide of radioactive technetium ( ^99m Tc), which is a radioactive diagnostic agent, is irradiated with fast neutrons generated by irradiation with charged particle beams from an accelerator on a target containing ¹⁰⁰ Mo, It is manufactured by causing a (n, 2n) reaction that emits two neutrons by irradiation with one neutron. In the present invention, fast neutron means neutron having energy of 0.1 MeV or more.

  Mo is an element of atomic number 42, and the isotopic composition ratio of natural Mo is as shown in Table 1.

  From the above table, it can be seen that when the Mo (n, 2n) reaction is the main, the Mo (n, 2n) reaction product is mostly Mo that is stably present in nature with one neutron less than the target Mo. .

Let us focus on ¹⁰⁰ Mo. ^{When 100} Mo is irradiated with fast neutrons, (n, 2n) reaction, (n, ⁴ He) reaction, (n, p) reaction, (n, 3n) reaction, (n, np) reaction, (n, n ′) Various reactions such as γ) reaction occur. FIG. 2 is a graph showing evaluation values of neutron energy and reaction cross section when ¹⁰⁰ Mo is irradiated with fast neutrons. FIG. 2 shows that when ¹⁰⁰ Mo is irradiated with fast neutrons of about 14 MeV, the (n, 2n) reaction cross section is close to the maximum value and has a much larger reaction cross section than other reactions.

Further, in FIG. ^3, when irradiated with fast neutrons to ¹⁰⁰ Mo, showing the relationship between the reaction cross section of fast neutrons and ¹⁰⁰ Mo when (n, 2n) reaction takes place ⁹⁹ Mo is produced. From FIG. 3, it can be seen that the (n, 2n) reaction shows a very large and almost constant reaction cross-section from about 9.5 MeV to about 25 MeV, with the neutron energy rising rapidly from around 8.5 MeV. It can be seen that the (n, 2n) reaction cross-section takes a value close to the maximum value in the vicinity of 14 MeV.

Therefore, in the present invention, radioactive molybdenum ^{99 Mo,} the target containing ^{100 Mo,} irradiated with fast neutrons caused by the charged particle beam irradiation from the accelerator, emits two neutrons by the irradiation of a single neutron Produced by initiating a (n, 2n) reaction. This reaction is represented by the following formula.

¹⁰⁰ Mo + n → ⁹⁹ Mo + 2n
As described above, in order to efficiently generate radioactive molybdenum ⁹⁹ Mo from ¹⁰⁰ Mo, the energy of fast neutrons is in the range of 9.5 to 25 MeV, more preferably 12 to 17 MeV. When the energy of fast neutrons becomes smaller than 9.5 MeV, the generation efficiency of radioactive molybdenum ⁹⁹ Mo rapidly decreases, and when it exceeds 25 MeV, reactions other than the reaction gradually become more dominant, and again (n, 2n) The generation efficiency of radioactive molybdenum ^99Mo due to the reaction is lowered.

In the present invention, in order to produce ⁹⁹ Mo, ¹⁰⁰ Mo is irradiated with fast neutrons generated by charged particle beam irradiation using a small accelerator without using a nuclear reactor. In this way, compared with the case where a nuclear reactor is used, the radioactivity can be reduced without generating a large amount of fuel waste.
Further, when ¹⁰⁰ Mo of spent fuel waste of a nuclear reactor is used as a raw material target nucleus, not only the production efficiency of ⁹⁹ Mo is further improved, but also effective utilization of spent fuel waste of a nuclear reactor can be achieved.

The small accelerator generated by charged particle beam irradiation that generates fast neutrons may be, for example, a commercially available small accelerator, or the Japan Atomic Energy Agency's neutron source facility for fusion neutron engineering, which is the facility of the present applicant ( A facility such as a DT neutron source such as FNS may be used.

In the accelerator for neutron generation, for example, deuterium ( ² H) beam is irradiated to tritium ( ³ H), and fast neutrons can be generated together with helium ( ⁴ He) in the next reaction.

² H + ³ H → ⁴ He + n
The neutron energy (En) generated by this reaction is given by the following relational expression.

4 × En = Ed + 2 × {2 × Ed × En} ^1/2 × cos θ + 3 × Q
Here, Ed is deuterium energy, Q is the generated energy of the reaction, and Q = 17.6 MeV. θ is the angle between the generated neutrons and incident deuterium. From this equation, it can be seen that 14 MeV fast neutrons can be obtained by using, for example, 0.35 MeV low energy deuterium. At the International Fusion Materials Irradiation Facility (IFFIF), which is currently underway, liquid lithium (Li) is irradiated with deuterium to produce high-intensity fast neutrons. Furthermore, fast neutrons can be generated even when metal Li or metal beryllium (Be) is irradiated with protons or deuterium.

Here, the production efficiency of ⁹⁹ Mo according to the present invention will be examined. The amount of ⁹⁹ Mo produced by fission in the nuclear reactor (Y _furnace ) is given below.

²³⁵ U: Concentration 20%. The fission cross section due to the reaction between thermal neutrons and ²³⁵ U is 585 burns. Among them, the production ratio of ⁹⁹ Mo is 6% (see FIG. 1). From the above, the amount of ⁹⁹ Mo generated in this U = 0.20 × 585 × 0.06 = 7 burns.

¹⁰⁰ Mo: natural abundance ratio 9.6%. ⁹⁹ Mo production reaction cross section by fast neutron is 1.5 burn. From the above, ⁹⁹ Mo produced by natural Mo = 0.096 × 1.5 = 0.14 burn.

That is, the ratio of Y _{high speed} to Y _furnace = Y _{high speed} / Y _furnace = 0.14 / 7 = 0.02 Formula (1)
The amount of ⁹⁹ Mo produced by fast neutrons is 2% in the case of a nuclear reactor, excluding the amount of neutrons.

By the way, as for the amount of neutrons, the thermal neutron amount of the _reactor φ _Reactor : In the case of Japan Nuclear Energy Agency Research Reactor Facility JRR3, φ _Reactor = 10 ¹⁴ pieces / (cm ² · second)
Formula (2)
Amount of fast neutrons φ _Fast : In the case of IFMIF, φ _fast = 10 ¹⁴ pieces / (cm ² · sec)
Formula (3)
That is, the ratio of the fast neutron amount to the reactor amount is: φ _fast / φ _reactor = 1 formula (4)
It becomes. Above, in view of the neutron amount, the ratio of the fast neutron ^{99 Mo} production amount by utilizing a reactor ^{99 Mo} production amount by the use it is given below.

0.02 × 1 = 0.02 Formula (5)
Here, considering that a high concentration of ¹⁰⁰ Mo can be obtained relatively easily (for example, assuming 100% concentration), the ratio of equation (5) is calculated from equations (1) and (4):
0.02, 9.6 × 100 = 0.21 Formula (6)
It becomes. That is, according to the present invention, it is understood that ⁹⁹ Mo can be produced in an amount sufficiently comparable to the production amount in the nuclear reactor using fast neutrons.
On the other hand, when the spent fuel of the reactor ¹⁰⁰ Mo is used as a raw material target, the enrichment is 25.5%, which is higher than natural 9.6%, so the ratio of formula (5) is 0.02 ÷ 0.096 × 0.255 = 0.05 Formula (7)
It becomes. In other words, 2.5 times more ⁹⁹ Mo can be produced than when natural Mo is used.

FIG. 4 schematically shows an apparatus for manufacturing radioactive molybdenum ^{99Mo according} to an embodiment of the present invention.

In the figure, 1 is a high voltage power source, 2 is a power cable, 3 is an accelerator terminal, 4 is an accelerator tube, 5 is a deuteron transport line, 6 is a neutron generator, 7 is a cooling tube, 8 cooling system, and 9 is a Mo target. Reference numeral 10 denotes a target support frame or sample container, 11 denotes a target support, and 12 denotes a ⁹⁹ Mo containing container subjected to radiation shielding. 4A and 4B show a state in which the Mo target 9 is in close contact with the neutron generating unit 6 and a state in which the Mo target 9 is separated from the neutron generating unit 6, respectively.

  The generation efficiency of RI increases when the raw material target 9 is brought into close contact with the fast neutron generator 6 as shown in FIG. In this case, the raw material target 9 or the sample container 10 containing it is brought into close contact with the tips of the fast neutron generator 6 and the cooling tube 7 via a cooling member made of, for example, Cu. In this case, the cooling member provided in the fast neutron generator 6 has a partition function between the vacuum chamber of the deuteron transport line 5 and the atmosphere side where the raw material target 9 is located. In some cases, as shown in FIG. 4B, the source target 9 may be separated from the fast neutron generator 6 by about 10 mm, and this distance is not limited.

  The high voltage power supply 1 outputs a high voltage for making the deuterium beam energy of about 0.35 MeV in order to generate a large amount of neutrons by the neutron generation reaction. The power cable 2 is for applying the high voltage of the high voltage power supply 1 to the acceleration tube 4 in contact with the accelerator terminal 3. In the fast neutron generator 6, a metal plate having excellent thermal conductivity such as Cu is provided with a deposition film such as titanium occluded with deuterium, for example. It plays the role of generating a large amount of neutrons by causing the neutron generation reaction. The cooling system 8 serves to cool the metal plate by the cooling pipe 7 in order to prevent thermal diffusion of the deuterium in the metal plate irradiated with the deuterium beam. Cooling is performed by water cooling or the like. The metal plate may be a fixed type or a rotary type.

As Mo target 9 nucleus of the present invention, it is possible to use ¹⁰⁰ Mo as waste generated by fission reaction of ²³⁵ U of ¹⁰⁰ Mo or reactors natural. Further, Mo as the target 9, those that have been the ¹⁰⁰ Mo was concentrated above natural abundance of natural ¹⁰⁰ Mo or ¹⁰⁰ Mo molybdenum oxide powder such as molybdenum trioxide MoO _3, or those with the powder density The one formed by compression molding and pelletized (bulk density of 60% or more) can be used (for example, JP-A-55-22102). Moreover, when using concentrated ¹⁰⁰ Mo, it is necessary to perform an electromagnetic separation collection method etc. as the pretreatment. In the case of using a powder of molybdenum trioxide MoO ₃ , it is necessary to seal it in a quartz tube and then seal it in an aluminum metal irradiation container. When using a pellet of molybdenum trioxide MoO ₃ powder, it is directly sealed in a metal irradiation container. This metal irradiation container is the sample container 10. Furthermore, Mo metal can also be used as a target. However, in this case, dissolution with nitric acid or the like is required for Mo extraction. Furthermore, according to the present invention, as the Mo target 9, a molybdic acid mixed gel body prepared by adding a molybdic acid aqueous solution whose molybdenum is ¹⁰⁰ Mo to a titanic acid alkoxide, zirconic acid alkoxide or a mixture thereof may be used. it can.

When using pelletized Mo target 9, for example, a 10 mm diameter and 0.5 mm thickness can be used as the dimensions, but of course this is only an example and is not limited to this. Considering the irradiation energy, yield and the like of fast neutrons, the shape and size can be appropriately set. In that case, if the thickness of the Mo target 9 is too thick, a problem of neutron scattering occurs and the generation efficiency is lowered. Therefore, it is necessary to consider this point. Neutrons are emitted from the fast neutron generator 6 in all directions, and the neutron flux (pieces / cm ² · sec) decreases at 1 / r ² . For this reason, the production efficiency of ⁹⁹ Mo is maximized when the Mo target is in close contact with the fast neutron generator 6. Here, r is the distance from the neutron generator to the Mo target.

The target support frame or the sample container 10, or Mo sample ⁽¹⁰⁰ Mo) is fixed, and is housed. The target support 11 serves to fix the target support frame or the sample container 10. ^{The 99} Mo container 12 is provided with a radiation shield, and the generated radioactive molybdenum ⁹⁹ Mo is put in this, taken out from the laboratory, and transported and moved to a required place. In addition, each member other than the ⁹⁹ Mo container 12 also performs radiation shielding as necessary.

In consideration of the half-life of the generated RI, a desired amount of ⁹⁹ Mo can be obtained by irradiating the neutron of about 14 MeV for about 2 to 3 days with the apparatus configured as described above. In this case, since fast neutrons generated by charged particle beam irradiation from the accelerator are used, fission is not used, so a large amount of fuel waste is not generated, and (n, 2n) reaction with a relatively large reaction cross section. Therefore, desired ⁹⁹ Mo can be stably supplied with high efficiency. Furthermore, since the apparatus configuration can be very downsized using a commercially available accelerator, ⁹⁹ Mo can be easily and stably manufactured and used in a facility such as a hospital.

In addition, when the reaction threshold of the target target is 15 MeV or more, an apparatus having the following configuration is used. In order to generate a large amount of neutrons by the neutron generation reaction, the high voltage power supply 1 outputs a high voltage for making the proton beam energy of about 25 MeV, for example. The power cable 2 is for applying the high voltage of the high voltage power supply 1 to the acceleration tube 4 in contact with the accelerator terminal 3. The fast neutron generator 6 is set with a metallic Li thin film provided on a metal plate excellent in thermal conductivity such as Cu, and the fast neutron generator 6 causes the above neutron generation reaction, It plays a role in generating neutrons. The cooling system 8 serves to cool the metal plate by the cooling pipe 7 in order to prevent Li on the surface of the Cu metal plate irradiated with the proton beam from being thermally diffused. Cooling is performed by water cooling or the like. The metal plate may be a fixed type or a rotary type. In this case, most of the neutrons are emitted from the fast neutron generator 6 along the proton beam axis, and the neutron flux (pieces / cm ² · sec) decreases at 1 / r ² . Therefore, it is preferable that the raw material target 9 is disposed in close contact with the neutron generating portion or in close proximity (separated to about 10 mm).

  Next, another embodiment of the present invention will be described.

FIG. 5 is a diagram schematically showing a main part of a production apparatus for radioactive molybdenum ^{99Mo according} to another embodiment of the present invention, and (a) is a schematic diagram seen from a direction perpendicular to the deuterium beam traveling direction. When the neutron generating part and the raw material target are in close contact, (b) is a schematic view when the neutron generating part and the raw material target are separated from each other, and (c) is a schematic view seen from the traveling direction of the deuterium beam.

  In the figure, 21 is a deuterium beam, 22 is a rectangular parallelepiped vacuum beam tube, 33 is a copper plate having a titanium film adsorbing tritium (tritium), 24 is a target sample, and 25 is a cooling member. The cooling member 25 may be integrated with the copper plate 23. In this case, the copper plate 23 has an inner wall and an outer wall, and a titanium film adsorbing deuterium on the surface of the copper plate 23 on the inner wall (vacuum chamber side). The target sample 24 is disposed in close contact with or spaced from the surface of the copper plate on the outer wall (atmosphere side) so that a cooling medium such as water passes through the space between the inner wall and the outer wall. Yes.

The fast neutrons generated by irradiating the deuterium ( ² H ⁺ ) beam 21 to the deuterium ( ³ H) isotropically in almost the entire space regardless of the incident direction of the deuterium beam 21. Has the property of being released. Therefore, the Mo sample 24 is arranged as follows in order to make maximum use of neutrons generated in a limited neutron utilization time. As the Mo sample 24, for example, pellets obtained by compressing, solidifying and sintering natural Mo or concentrated Mo trioxide powder may be used, or metal Mo as described above may be used. You can also

  The deuterium-containing titanium plate 23 is cooled by the cooling pipe 25 in order to prevent the high-intensity deuterium beam 21 irradiated to the deuterium-containing titanium plate 23 from increasing the temperature of titanium and causing thermal diffusion of the deuterium. To do. In order to use a higher-intensity deuterium beam 21 within a given cooling capacity range, it is conceivable to reduce the heat load per unit area provided by the deuterium beam 21. Therefore, the size of the deuterium beam 21 is changed from the usual 5 mm diameter to, for example, 10 mm diameter by changing the beam transport system of the accelerator. As a result, the heat load per unit area can be reduced to ¼ and increased up to four times the intensity of the conventional deuterium beam, and the resulting neutrons can be used four times as much. Further, since fast neutrons are isotropically emitted to the entire space, the Mo sample 24 is set not only in front of the deuterium beam 21 but also on the side surface as shown in FIG.

The deuterium beam 21 is irradiated to a copper plate 23 having a tritium-containing titanium film through a beam transport system in which a vacuum is maintained by a vacuum beam tube 22 which is a rectangular parallelepiped. Then, fast neutrons generated by the ² H ⁺ + ³ H → ⁴ He + n reaction are irradiated to the Mo sample 24 embedded in the atmosphere side of the cooling tube 15 (closest distance). On the other hand, in order to efficiently use fast neutrons emitted backward with respect to the deuterium beam 21 incident at a right angle to the copper plate 23 having a tritium-containing titanium film, a vacuum beam tube (a rectangular parallelepiped) close to the fast neutron generation site. ) Four surfaces of 22 are processed and the Mo sample 24 is embedded as shown. With such a configuration, fast neutrons are isotropically emitted into the entire space, so that generation of radioactive molybdenum ⁹⁹ Mo is performed with higher efficiency.

⁹⁹ Mo produced in the present invention is used at a medical site in a state of ^99m Tc due to β decay. In this case, ^99m Tc is separated by using, for example, fast neutron as a target of a Mo sample 24 such as MoO _3. after irradiation, the alkaline solution (e.g., sodium hydroxide) dissolved ^in, 99 _MoO ^{4 2-adsorbed} onto an alumina column, ⁹⁹ TcO ₄ through saline ^- taken out, to be used by dissolving in a suitable solvent Can do. Extracting desired ^99m Tc in this way is called milking. Such a device for milking is called a generator or cow. As a generator, a PZC generator that extracts ^99m Tc through physiological saline by adsorbing ⁹⁹ Mo to a high-density zirconium compound (PZC) (for example, Japanese Patent Laid-Open Nos. 52-17199 and 08-309182). JP-A-10-30027, etc.) can also be preferably used.

In the present invention, as described above, a molybdic acid mixed gel body prepared by adding a molybdic acid aqueous solution whose molybdenum is ¹⁰⁰ Mo to a titanic acid alkoxide, zirconic acid alkoxide or a mixture thereof is used as a target sample. Can do.

  In this case, examples of the alcohol used in the titanic acid alkoxide, zirconic acid alkoxide, or a mixture thereof include monohydric alcohols such as methanol, ethanol, isopropanol and butanol, dihydric alcohols such as ethylene glycol, glycerin and polyvinyl alcohol, and the like. Can be used.

As the molybdate solution, ammonium molybdate (NH ₄ ) ₂ MoO ₄ , potassium molybdate, calcium molybdate, cobalt molybdate, sodium molybdate, lead molybdate, magnesium molybdate, manganese (II) molybdate, etc. are used. be able to.

Here, the example of a manufacturing method of a molybdic acid mixed titanic acid gel is described.
The gel body of the molybdic acid mixture was prepared by dissolving 10 ml of (titanium (IV) t-butoxide Ti (O—C ₄ H ₉ ) ₄ and 1 mol of ammonium molybdate in n-butanol C ₄ H ₅ OH [100 ml]. While stirring with a stirrer, 0.1N HNO ₃ [10 ml] was added to give a titanic acid gel containing molybdic acid by a hydrolysis reaction of butyl titanate.
The resulting titanic acid gel was collected by a centrifuge, washed with acetone, dried, and then pressure-shaped to obtain an irradiated sample.

Thus, when the molybdic acid mixed titanic acid gel is used as the raw material target, the work of mixing ⁹⁹ Mo after fast neutron irradiation into the zirconium acid gel or the titanic acid gel is unnecessary, so There is an advantage that the problem of exposure and environmental pollution can be avoided.

  Moreover, when using a faster neutron, as mentioned above, a proton etc. are irradiated to Li or Be. In this case, most of the neutron flux is emitted along the direction of the proton beam. Therefore, the arrangement of the target sample 24 is in front of the neutron generator as shown in FIGS. 5 (d) and 5 (e). FIG. 5D shows the case where the target sample 14 is brought into close contact with the neutron generator, and FIG. 5E shows the case where the target sample 24 is spaced from the neutron generator. As described above, according to the present invention, since the target sample 24 can be arranged on the atmosphere side instead of in a vacuum, there is an advantage that the shape of the target sample 24 and the degree of freedom in arrangement are increased.

Next, a method for producing ⁹⁹ Mo according to the present invention will be described.

The ⁹⁹ Mo production method according to the present invention basically irradiates a raw material target containing ¹⁰⁰ Mo as a target nucleus with fast neutrons generated by irradiation with a charged particle beam from an accelerator, and irradiates with two neutrons. A (n, 2n) reaction that emits individual neutrons is caused to generate ⁹⁹ Mo.

Hereinafter, an example of a method for producing ⁹⁹ Mo according to the present invention will be described with reference to the block diagram of the production procedure of FIG.

First, using, for example, natural Mo, a powder of molybdenum trioxide MoO ₃ is compressed, molded, and sintered to prepare a Mo target containing pellet-shaped ¹⁰⁰ Mo (step S1).

  Next, the Mo target is put in a sample container and set at a neutron irradiation position (step S2).

Next, a deuterium beam of 0.35 MeV, for example, is irradiated from the accelerator onto the titanium plate on which the deuterium is occluded provided on the cooling copper plate. Thus, for example, 14 MeV fast neutrons are generated (step S3).
In the Mo target, the (n, 2n) reaction occurs preferentially by the irradiation of fast neutrons, and ⁹⁹ Mo is generated (step S4).

After performing neutron irradiation for an appropriate time, the irradiation is stopped, the sample container containing ⁹⁹ Mo is taken out, and the desired ⁹⁹ Mo is obtained (step S5).

The obtained ⁹⁹ Mo becomes ^99m Tc due to β decay, and this ^99m Tc is separated using the above-described generator and used for a desired application (step S6).

Although an example of the manufacturing method has been described above, of course, the manufacturing method of the present invention is not limited to this example, and each step can be performed using the various methods described above. In the above, natural Mo is used. However, if Mo of nuclear fission fuel waste or isotope enriched ¹⁰⁰ Mo is used as a target nucleus of a raw material target, the production efficiency of ⁹⁹ Mo is further improved.

Next, the results of experiments conducted to confirm the above will be described.
<Experimental purpose>
* Confirmation that ⁹⁹ Mo is generated with 14 MeV fast neutrons using a natural Mo sample with the expected reaction cross section * Generated with 14 MeV neutrons using the ⁹³ Nb sample used to determine the absolute value of the above reaction cross section Measurement of ⁹² Nb radiation and confirmation that it can be used to determine the cross-sectional area * ⁹⁹ Quantitative evaluation of residual radioactive isotopes (radioactive waste) produced in association with Mo production reaction * ² H + ³ H (R) Confirmation of whether 14 MeV neutrons generated by the ⁴ He + n reaction are stably generated with the expected neutron intensity ( ³ H target performance evaluation)
* Confirmation that ² H (deuterium beam) for inducing the above reaction is supplied stably (Verification that small accelerator operates stably)
* Confirmation that Mo and Nb targets can be easily and flexibly installed and removed from the neutron irradiation site <Experiment location> Neutron Source Facility for Fusion Neutron Engineering, Japan Atomic Energy Agency (FNS)
<Experiment date>
Neutron irradiation experiment: January 27 to January 30, 2009 (6 hours of irradiation per day)
Measurement of generated Mo radioactivity: January 27 to February 5, 2009 <Sample> Natural Mo
Sample 1: Diameter: about 10 mm, thickness: 50 microns (0.05 mm), weight 40.214 mg
Sample 2: Diameter: about 10 mm, thickness: 5 microns (0.005 mm), weight 3.663 mg
Sample 1 was measured after 6 hours of irradiation.
Sample 2 was measured after neutron irradiation until the last day.
<Sample> ⁹³ Nb
Sample 3: diameter 10 mm, thickness: 0.1 mm, weight 67.196 mg
<Mo target installation location>
² Location 10 cm away from the neutron generation site in the direction of extension of the H beam axis.
<Neutral irradiation conditions>
* 14 MeV neutron production reaction
² H + ³ H (R) ⁴ He + n: ² H beam energy: 0.35 MeV
* Neutron generation amount 1.8 × 10 ¹¹ n / cm ² · sec [January 27] to 1.5 × 10 ¹¹ n / cm ² · sec [January 30]
^<99 Mo production reaction>
¹⁰⁰ Mo + n (R) ⁹⁹ Mo + 2n
< ⁹² Nb production reaction>
⁹³ Nb + n (R) ⁹² Nb + 2n
<Measurement of ⁹⁹ Mo and residual radioactivity (measured with FNS)>
* Measurement conditions: Start measurement after cooling time of approximately 1 hour after neutron irradiation * Measurer: Ge semiconductor detector * ⁹⁹ Mo sample and ⁹² Nb sample placement: Set 5 cm away from Ge detector <Result>
* Confirm that ⁹⁹ Mo is produced in the amount originally predicted * Confirm that ⁹³ Nb sample can be used to determine ⁹⁹ Mo cross-sectional area * ⁹⁹ Residual radioisotope (radioactive) generated in association with Mo formation reaction Quantitative evaluation of waste) (Check that it is a small amount compared to the amount of ⁹⁹ Mo).

* Confirmed that 14 MeV neutrons generated by the ² H + ³ H (R) ⁴ He + n reaction are stably generated at the expected neutron intensity ( ³ H target was evaluated to have high performance)
* It was confirmed that ² H (deuterium beam) for inducing the above reaction was stably supplied.

(Verification of stable operation of small accelerators)
* It was confirmed that the Mo target and Nb target can be easily and flexibly installed and removed from the neutron irradiation site.

Moreover, it was confirmed by detecting gamma rays using a high-performance germanium semiconductor detector that ⁹⁹ Mo was produced under the above conditions. The semiconductor detector was placed at a position 5 cm from the sample. The result is shown in FIG. FIG. 7 (a) shows measurement data of 739 keV gamma rays emitted with ⁹⁹ Mo beta decay, and FIG. 7 (b) shows measurement data of 141 keV gamma rays emitted from the state of ^99m Tc excited by ⁹⁹ Mo beta decay. It is. It was confirmed that ⁹⁹ Mo was generated with high-speed 14 MeV neutrons.

Next, an example in which the sample actually produced in the above-described method for producing the molybdic acid-containing titanate gel was applied to a ⁹⁹ Mo / ^99m Tc generator and subjected to milking will be described.
First, titanic acid gel irradiated with fast neutrons was placed in a beaker, washed with water 2 ml each time 4 times with water, the supernatant was dried, and the change in gamma ray intensity of ^99m Tc was examined with the semiconductor detector. The result is shown in FIG. FIG. 8B shows the result of the same measurement using physiological saline instead of water.
Next, put the same titanic acid gel irradiated with fast neutrons into a glass tube, elute ^99m Tc with water and perform milking, take 5 drops (1 drop is 0.274 mg), and dry. The change in gamma ray intensity of ^99m Tc contained was examined. The result is shown in FIG. FIG. 9B shows the result of the same measurement using physiological saline instead of water.
From the above, it was confirmed that ^99m Tc was obtained.
In the case of titanic acid gel, by arranging an alumina column in series with a generator made of a radioactive molybdenum-containing material, it is possible to prevent the influence caused by Sc that occurs when Ti is irradiated with neutrons, and a higher purity carrier-free ^99m Tc can be obtained.

^99m Tc obtained by β-decay of ⁹⁹ Mo produced according to the present invention can be used in the following forms, particularly for the following examinations and treatments in the medical field.

(1) Function test: pulmonary circulation function, cardiac output, lung blood volume Technetium human serum albumin ( ^99m Tc-HSA)
(2) Functional test: Thyroid intake rate Sodium pertechnetate (3) Brain scintigraphy Sodium pertechnetate, Technetium methylenediphosphonate ( ^99m Tc-MDP)
(4) Cerebral blood flow scintigraphy Exametadim technetium (hexamethylpropyleneamine oxime) ( ^99m Tc-HM-PAO), N, N′-ethylenedi-L-cisutenate (3) Oxotechnetium diethyl ester (5) Thyroid scinti Graphite sodium pertechnetate (6) Pulmonary blood flow scintigraphy Technetium macroaggregated human serum albumin ( ^99m Tc-MAA)
(7) Myocardial scintigraphy Hexakis (2-methoxyisobutyl isonitrile) technetium ( ^99m Tc-MIBI), ^tetrofosmin technetium, technetium pyrophosphate ( ^99m Tc-PYP)
(8) Heart pool scintigraphy technetium human serum albumin ( ^99m Tc-HSA), human serum albumin diethylenetriaminepentaacetic acid technetium ( ^99m Tc-HSA-DTPA)
(9) Liver scintigraphy technetium tin colloid, technetium phytate, galactosyl human serum albumin diethylenetriaminepentaacetic acid technetium ( ^99m Tc-GSA)
(10) Liver / biliary tract scintigraphy N- (2,6-dimethylphenylcarbamoylmethyl) iminodiacetic acid technetium ( ^99m Tc-HIDA), diethylacetanilideiminodiacetic acid technetium, pyridoxylideneisoleucine technetium ( ^99m Tc-PI) N-pyridoxyl-5-methyltryptophan technetium ( ^99m Tc-PMT)
(11) Salivary gland scintigraphy Sodium pertechnetate (12) Renal scintigraphy Technetium dimercaptosuccinate ( ^99m Tc-DMSA), Technetium diethylenetriaminepentaacetate, ( ^99m Tc-DTPA), mercaptoacetylglycylglycine technesium ( ^99m Tc- MAG ₃ )
(13) Spleen scintigraphy technetium tin colloid, technetium phytate (14) Lymph node scintigraphy technetium tin colloid, technetium phytate (15) bone scintigraphy technetium ethanehydroxydiphosphonate ( ^99m Tc-EHDP), hydroxymethylene diphosphon Technetium acid ( ^99m Tc-HMDP), technetium pyrophosphate ( ^99m Tc-PYP), technetium methylenephosphonate ( ^99m Tc-MDP)

DESCRIPTION OF SYMBOLS 1 High voltage power supply 2 Power supply cable 3 Accelerator terminal 4 Acceleration tube 5 Deuteron transport line 6 Neutron generation part 7 Cooling tube 8 Cooling system 9 Mo target 10 Target support frame 11 Target support stand or sample container 12 Target storage 21 Deuterium beam 22 Vacuum transport line 23 Copper plate with tritium-containing titanium film 24 Mo target 25 Cooling tube 26 Proton beam

Claims (7)

A power source for applying a voltage for accelerating a charged particle beam made of deuterium or protons, an accelerator tube for accelerating the charged particle beam to which the voltage from the power source is applied, and an accelerator emitting unit, and 3 A target for generating fast neutrons of titanium with occluded deuterium is disposed, and includes a fast neutron generator that emits fast neutrons when irradiated with the accelerated charged particle beam, and has an energy of 9.5 MeV to 25 MeV Using a small accelerator that generates fast neutrons,
The fast neutrons generated by the charged particle beam irradiation are irradiated to a raw material target containing ¹⁰⁰ Mo as a target nucleus, and a reaction that releases two neutrons by irradiation of one neutron is caused (n, 2n), method for producing a radioactive molybdenum, characterized in that to produce a radioactive molybdenum ^{99 Mo} which is the parent nuclide of a radioactive diagnostic agent radioactive technetium ^{99m Tc.} 2. The method for producing radioactive molybdenum according to claim 1, wherein waste ¹⁰⁰ Mo generated by a ²³⁵ U fission reaction in a nuclear reactor is used as a target nucleus. 3. Production of radioactive molybdenum according to claim 1 or 2, wherein the raw material target is irradiated with fast neutrons in a state in which the raw material target is in close contact with or separated from a fast neutron generator provided in the accelerator emission part. Method. An apparatus for producing radioactive molybdenum that generates radioactive molybdenum ⁹⁹ Mo which is a parent nuclide of radioactive technetium ^99m Tc which is a radioactive diagnostic agent,
A power source for applying a voltage for accelerating a charged particle beam made of deuterium or protons, an accelerator tube for accelerating the charged particle beam to which a voltage from the power source is applied, and an accelerator emitting unit are provided. A target for generating fast neutrons of titanium with occluded deuterium is arranged, and includes a fast neutron generator that emits fast neutrons when irradiated with the accelerated charged particle beam, and has an energy of 9.5 MeV to 25 MeV A small accelerator that generates fast neutrons,
Comprising target support means for supporting a raw material target containing ¹⁰⁰ Mo as a target nucleus,
Irradiating a raw material target with fast neutrons generated by the charged particle beam irradiation, causing (n, 2n) reaction to emit two neutrons by irradiation of one neutron, and generating radioactive molybdenum ⁹⁹ Mo; An apparatus for producing radioactive molybdenum. The apparatus for producing radioactive molybdenum according to claim 4, wherein the target nucleus of the raw material target is ¹⁰⁰ Mo as waste generated in a nuclear reactor in a fission reaction of ²³⁵ U. 6. The radioactive molybdenum production apparatus according to claim 4 or 5, wherein the raw material target is set in a state of being in close contact with or separated from a fast neutron generator provided in the accelerator emission part . Fast neutron generator provided in the accelerator exit section comprises a cooling means, and fast neutron generator has a partition wall function of the vacuum chamber and the atmosphere side, and the state or away from the raw material target to fast neutron generator is brought into close contact The apparatus for producing radioactive molybdenum according to any one of claims 4 to 6 , wherein the apparatus is set in a state of being allowed to enter.