JP2014532855A - Thermal decontamination of graphite with reducing gas. - Google Patents

Abstract

Providing a heater operating with an inert gas, optional oxidizing gas and reducing gas at a temperature in the range of 800 ° C. to 2000 ° C., for contaminating graphite contaminated with radionuclides including tritium, carbon 14 and chlorine 36 To process. The combination of temperature and gas makes it possible to substantially limit vaporization of the bulk graphite while removing most or substantially all of the carbon 14 in the graphite.

Description

  The present invention generally relates to a graphite decontamination method for removing tritium, carbon 14, and chlorine 36 using heat treatment with a purge gas containing a reducing gas.

  Graphite consisting essentially of carbon atoms is used as a moderator in many nuclear reactor designs, such as the MAGNOX and AGR gas cooled reactors in the UK and the RBMK design in Russia. At the end of the life of the furnace, the graphite moderator, typically weighing about 200 tons, becomes a radioactive waste that requires safe disposal. Graphite is a relatively stable carbon form and is often suitable for direct disposal without treatment. However, after neutron radiation, graphite contains stored Wigner energy. In the disposal method for raw graphite, it is necessary to address this potential for energy release. Instead, the graphite is processed before disposal, allowing a safe release of the accumulated Wigner energy.

  Graphite also contains significant amounts of radionuclides from neutron-induced reactions, both in the graphite itself and in the minority impurities it contains. Due to the structure of graphite including loosely packed leaf-like layers, radioisotopes can be trapped in the graphite space or pores. Radioisotopes can be conveniently classified into the following two types: short-lived isotopes and long-lived isotopes. Short-lived isotopes (such as cobalt 60) make it difficult to handle graphite immediately after the furnace shuts down, but it decays in decades. Long-lived isotopes (mainly carbon 14 and chlorine 36) are of concern for possible disposal to the biosphere. Carbon 14 occurs in the graphite in one of two ways. One method is the activation of nitrogen gas, where carbon 14 is present in the graphite pores as carbon dioxide gas. Another method is by neutron activation of carbon 13, which is the natural stable isotope of carbon and accounts for only over 1 percent of the oxygen in graphite. The carbon 14 produced in this way is part of the graphite matrix. Chlorine 36 is similarly formed by the radiation of chlorine left in the graphite matrix during the graphite sintering process. The treatment of graphite provides an opportunity to separate the majority of the graphite mass (carbon) from long-lived radioisotopes. This treatment may facilitate disposal of graphite waste immediately after the end of the furnace life and may allow reuse.

  Due to the properties of graphite and its mass, the current most common method for decommissioning a graphite moderator is to store the core in situ for a period of decades after the reactor shuts down. . During this period, the short-lived radioisotope decays sufficiently to allow subsequent manual dismantling of the graphite moderator. As such, most programs envisage disposing of graphite in its existing chemical form, with appropriate additional packaging to prevent long-term degradation or release of carbon 14 and chlorine 36 decay. Has been.

  The custody has the following bad consequences: 1) the existence of long-term financial debt, 2) a prominent custody structure without production purpose, 3) what the future people (whatever from the original assets) to complete the later removal The demands imposed on those who do not benefit. If the storage alternative is to replace short-term management, it is important to treat the graphite in a safe and radiologically acceptable manner.

  In certain prior art techniques for treating radioactive graphite, the graphite is treated with heat and oxidizing gas to remove a sufficient proportion of long-lived radionuclides in the graphite. In such a process, heating with an inert gas such as nitrogen or argon or “roasting” can remove substantially all of the hydrogen 3 (tritium), but removes more than approximately 60 percent of the carbon 14. I know I can't. By providing a limited amount of oxygen-containing gas to the inert gas to provide oxygen that can preferentially convert carbon 14 to carbon monoxide or carbon dioxide gas (which can later be removed from graphite). Alternative processes have also been performed to improve carbon 14 removal. Tests with inert and oxygen-containing gases (water vapor, carbon dioxide, nitrous oxide, oxygen) can improve carbon 14 removal, but the presence of oxygen dramatically increases the vaporization of bulk graphite. I know that there is a tendency. To reduce this vaporization effect when combining an oxygen-containing gas with an inert gas, the operating temperature of the heating process must be reduced or limited to prevent excessive bulk graphite vaporization. Unfortunately, by reducing or limiting the heating temperature, the amount of carbon 14 removed is also significantly reduced or limited. As a result, when introducing an oxygen-containing gas with an inert gas, the concentration of the oxidizing gas must be reduced so that higher temperatures can be used. However, when the heating temperature exceeds about 1200 ° C., the amount of bulk graphite to be vaporized is excessive even though a low concentration oxygen-containing gas is used.

  The test results of these processes show that if the concentration of the oxygen-containing gas is sufficiently limited to reduce bulk graphite vaporization at temperatures above about 1200 ° C., the removal of carbon 14 is below about 60 percent. Significantly reduced, this has been shown to be inadequate. When the oxygen-containing gas concentration is increased so that the carbon 14 is sufficiently removed, excess bulk graphite is vaporized. In any case, the problem of volatilizing more than 90 percent of carbon 14 and simultaneously reducing the vaporization of bulk graphite to less than 5 percent by weight cannot be achieved with these prior art techniques.

  System and method capable of exposing graphite to a temperature range sufficient to volatilize radionuclides without vaporizing bulk graphite, vaporizing less than 5 percent bulk graphite while removing more than 90 percent carbon 14 What is needed is a system and method that can do this.

Exemplary embodiments of the present invention provide a method by which the graphite can be exposed to a temperature range sufficient to volatilize the radionuclide without substantially vaporizing the bulk graphite. One aspect of the present invention includes (1) heating a heater to a temperature between 800 ° C. and 2000 ° C., (2) introducing graphite contaminated with a radionuclide into the heater; 3) introducing an inert gas into the heater; (4) introducing a reducing gas into the heater; and (5) removing the volatilized radionuclide from the heater. Provide a method. The method may also include the following additional steps:
Adding oxidizing gas into the heater and / or
• reducing the size of the graphite before introducing the graphite into the heater.
The method may also be characterized by the following points:
• Less than 5 percent of graphite is vaporized;
The temperature of the process is between 1200 ° C and 1500 ° C;
The radionuclide comprises carbon 14 and at least 70 percent of the carbon 14 is removed from the graphite;
The radionuclide comprises carbon 14 and at least 90 percent of the carbon 14 is removed from the graphite;
The purge gas comprises at least one of nitrogen, helium, and argon and the reducing gas comprises at least one of hydrogen, hydrazine, ammonia, carbon monoxide, and hydrocarbon vapor;
The purge gas comprises one or more reducing gases capable of producing free hydrogen, carbon monoxide (CO), ammonium, or organic vapor;
The oxidizing gas is at least one of water vapor, carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), air, alcohol (having an OH group), and other oxygenated vapor Comprising:
The step of introducing the inert gas into the heater and the step of introducing the reducing gas into the heater comprise the steps of introducing the inert gas and the reducing gas at a location near the bottom of the heater; The gas and reducing gas flow through the graphite; and / or
The heater comprises a vertical moving bed heater, and the step of introducing graphite contaminated with radionuclides into the heater comprises introducing graphite near the top of the heater; Introducing the inert gas into the heater and introducing the reducing gas into the heater includes introducing a gas near the bottom of the heater.

1 shows a block diagram of a system for processing radioactive graphite according to an exemplary embodiment of the present invention. FIG. 2 shows a process flow diagram for processing radioactive graphite according to an exemplary embodiment of the present invention. 1 shows a schematic diagram of a heater for processing radioactive graphite according to an exemplary embodiment of the present invention. FIG.

  Exemplary embodiments of the present invention provide systems and methods for treating radioactive graphite contaminated with tritium, carbon 14, and chlorine 36 generated during reactor operation or other nuclear processes. The system and method includes a heater that operates at a temperature in the range of 800 ° C. to 2000 ° C. with an inert gas, optionally an oxidizing gas and a reducing gas. The combination of temperature and gas allows the vaporization of less than 5 percent bulk graphite while simultaneously removing more than 90 percent carbon 14 in the graphite.

  FIG. 1 shows a block diagram of a system 100 for processing radioactive graphite according to an exemplary embodiment of the present invention. Referring to FIG. 1, a material handling unit 110 receives graphite that is processed in the system 100. Typically, graphite has been used as a moderator for nuclear reactor cores. Other graphite sources include, but are not limited to, fuel element sleeves, braces, and other reactor components irradiated with the reactor neutron flux. The graphite is typically contaminated with radionuclides such as hydrogen 3 (tritium), carbon 14, chlorine 36, iron 55, cobalt 60, etc., and other typical fission and activation products. May also be included.

  The size of the material handling unit 110 is the size of graphite, and holds the graphite in preparation for introducing the graphite into the heater 120. The graphite received by the material handling unit 110 has been removed from the reactor by a conventional process. Such a process may include a wet process, a dry process, or a combination of both. The present invention can be applied to any size or shape of dry or wet graphite resulting from the removal process. Further, the graphite can be immersed in water or other solution before being received at the material handling section 110.

  Graphite can be processed in granular or powder form. The size reduction sub-part 112 of the material handling part 110 reduces the size of the received graphite for introduction into the heater 120. In this exemplary embodiment, the received graphite is reduced to a size of less than 20 mm. This small size enhances the radionuclide volatilization from the graphite. In order to reduce the size of the graphite, the exemplary size reduction sub-portion 112 includes a jaw crusher or a rotary crusher. Other size reduction machines can also be used. The hopper sub-section 114 of the material handling section 110 receives the reduced-size graphite and holds the graphite that is waiting to be introduced into the heater 120. The internal atmosphere of the exemplary size reduction sub-portion 112 and hopper sub-portion 114 includes an inert gas blanket such as argon, nitrogen, carbon dioxide, or other similar inert gas. As some radionuclides can be released from the graphite during the size reduction process, the internal atmosphere of the exemplary size reduction sub-part 112 and hopper sub-part 114 is connected to the degassing system of the heater 120. In an alternative embodiment, graphite can be received in a shape and size suitable for introduction into the heater 120 without the need for size reduction. Similarly, a continuous process can omit the hopper sub-section 114.

  The heater 120 includes a vessel that is used to process sized graphite. The heater 120 operates within a temperature range between 800 ° C and 2000 ° C. The capacity, shape, and size of the heater 120 can be changed according to the application. The heater 120 is made of a material suitable for high temperature operation, for example, a steel vessel lined with a heat resistant material. The operating pressure can vary from ultra-vacuum to slight pressurization. Any type of heater or apparatus can be used including fluidized bed, moving bed, batch or fixed bed heaters. One exemplary heater is a vertical moving bed heater, with the purge gas flowing upward through the graphite pile, placing fresh graphite at the top of the pile and removing the treated graphite from the bottom of the pile. (See FIG. 3 below). Graphite batch processing typically involves powdered graphite using a fluidized bed process. For graphite larger than powder, a continuous moving bed heater is preferred. In the exemplary embodiment, heater 120 is electrically heated, although other types of heating can be used. Electrical heating is preferred because it reduces the need to introduce oxidizing gas into the vessel that can vaporize bulk graphite and improves temperature control and energy efficiency. The heater 120 receives graphite from the material inlet 117. A variety of mechanical methods can be used to move material from the material handling section 110 through the material inlet 117 to the heater 120. In an exemplary system, a double valve hermetic method is used to prevent gases from inside the heater from exiting the heater and gases other than inert gases are introduced into the heater with graphite. Limit what is done.

  The heater 120 includes gas inlets 130, 140, 150 that receive one or more inert purge gases, one or more reducing gases, and optionally one or more oxidizing gases. Of course, the gas inlets 130, 140, 150 can also be a single inlet connected to three different gas sources, with the first source providing an inert purge gas and the second source providing a reducing gas. A third source provides the oxidizing gas. Typically, the gas inlet is located near the bottom of the heater 120 to allow the gas to enter the vessel and travel upward through the graphite present in the heater 120. The gas may be introduced through a flow distributor or distributor that distributes the gas through the graphite volume, but this is not essential. The heater includes an outlet 122 for volatilized radionuclide, and the volatilized radionuclide is carried out of the outlet 122 by an inert purge gas. The heater 120 also includes an outlet 124 for the treated graphite.

  Volatile radionuclides are carried out of the heater by a purge gas stream and stabilized in the processing subsystem 160 using a suitable method for processing the radionuclides. The treated graphite is further processed in the processing subsystem 170 and packaged or reused for final disposal as “clean” (non-radioactive) waste.

  Carbon 14 is more reactive and more mobile than bulk carbon 12 in the graphite matrix. Oxygen present in small amounts provides the oxygen necessary to convert carbon 14 to carbon monoxide. The reducing gas suppresses the oxidation of carbon 12 in the graphite matrix. One exemplary advantage of adding reducing gas is due to the possibility that the carbon-14 compound in the graphite contains cyanide. The introduction of hydrogen into the heater causes hydrogen atoms to bind to cyanide to produce volatile hydrogen cyanide, so that part of the carbon 14 can be removed by the presence of a reducing gas containing hydrogen.

  FIG. 2 shows a flow diagram of a process 200 for processing radioactive graphite according to an exemplary embodiment of the present invention. Referring to FIGS. 1 and 2, in step 210, graphite is introduced into the heater 120 from the hopper sub-part 114 of the material handling part 110 by mechanical transfer of the graphite into the heater. In this exemplary embodiment, the process is performed in a batch mode. Alternatively, the graphite can be processed in a continuous process, for example, graphite enters the top of the heater 120 and exits from the bottom of the heater 120, and the reaction gas enters the bottom of the heater 120 and Go out from the top. The hopper sub-section 114 can be omitted.

  Prior to introducing graphite into the heater 120, the heater 120 is brought to the processing temperature. This temperature is in the range of 800 ° C to 2000 ° C. In this exemplary embodiment, since a reducing gas is used, the preferred temperature range is 1200 ° C to 1500 ° C. In previous graphite treatment processes for removing carbon 14 from graphite, high vaporization of graphite occurs as a result of operating a heater having an oxygen-containing gas above 1200 ° C., so that the temperature is approximately 1200 ° C. It was restricted. By introducing reducing gas into the treatment process, the heater 120 can operate at a temperature in excess of 1200 ° C. Such a high operating temperature allows substantially all of the tritium, substantially all (greater than 90 percent) of chlorine 36, and most (greater than 70 percent) of carbon 14 to be released from the graphite.

In step 220, reaction gas is introduced into the heater 120. As the gas flows through the heated graphite, the gas contacts the heated graphite. The reaction gas includes at least an inert purge gas and a reducing gas. The purge gas includes one or more of nitrogen, argon, and similar non-reactive gases. Inert gases such as carbon dioxide should not be used because they provide a source of oxygen that can vaporize bulk carbon. In step 220, a reducing gas is also introduced, for example, hydrogen, hydrazine, ammonia, carbon monoxide, hydrocarbon vapor, etc., and may produce free hydrogen, carbon monoxide, ammonium, or organic vapor. Other reducing gases that can be mentioned. The amount of reducing gas introduced is between 100 ppm and 50 percent of the total gas introduced, preferably in the range of 2 percent to 20 percent, more preferably between 2 percent and 10 percent. The mixture of the inert purge gas and the reducing gas is introduced into the heater 120 near the bottom of the heater 120. The gas rises through the graphite and carries the volatilized radionuclide out of the heater 120 at the outlet 124. Even when oxidizing gas is included, the inclusion of reducing gas greatly reduces the vaporization of bulk graphite, and less than 5 percent of bulk graphite is vaporized. In addition, operation at a temperature of approximately 1200 ° C. and a mixture of inert purge gas, oxidizing gas and reducing gas results in the removal of substantially all of the carbon 14 from the majority. In an alternative embodiment, the reaction gas also includes an oxidant. The presence of oxygen converts solid carbon 14 to carbon dioxide or CO gas and promotes diffusion from the graphite matrix. Inert purge gas (preferably nitrogen), limited amount of oxygen-containing gas, water vapor, carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), air, alcohol (OH group) Or other oxygenated steam, etc., and in combination with a reducing gas such as hydrogen, enhances the removal of carbon-14 radionuclides compared to all prior art methods while limiting vaporization of bulk graphite. The A preferred oxidizing gas is water vapor and accounts for approximately 1 to 50 percent (preferably 2 to 10 percent) of the total input reaction gas. When either carbon dioxide or nitrous oxide is used as the oxidizing gas, it accounts for approximately 1 to 10 percent of the total input reaction gas. Inclusion of the reducing gas greatly reduces vaporization of the bulk graphite in the presence of the oxidant, and less than 5 percent bulk graphite is vaporized. The reducing gas shifts the reaction equilibrium of oxygen with the bulk graphite so as to substantially suppress the reaction rate of the oxygen-containing gas, thereby preventing the oxidant from reacting with the bulk graphite.

  In step 230, purge gas is collected in the processing subsystem 160 and the radionuclide is stabilized using known methods. In step 240, the graphite is removed from the heater 120 and processed in the processing subsystem 170. Typically, the treated graphite is either dumped in a landfill or reused to treat it as low level radioactive waste rather than medium level radioactive waste. The process ends at 250. If necessary, the process may be repeated.

  FIG. 3 shows a schematic diagram of an exemplary heater 300. Graphite is introduced through a supply system (not shown) such as a hopper at an inlet 310 below the inert gas blanket. As the reaction bath is introduced at the inlet 370 and the graphite descends the vessel 330, the reaction gas flows upward through the graphite and exits from the degas outlet 320. The graphite is heated (shown as heated graphite 340) as it travels through the vessel 330 (which can be a ceramic tube). The vessel 330 is surrounded by a heat source 350 such as an electric heating coil. The vessel 330 and the heat source 350 are accommodated in an outer vessel 360 (such as a metal shell lined with a heat-resistant material). Treated graphite is removed from vessel 330 through outlet port 380.

  Those skilled in the art will provide a method for treating radioactive graphite contaminated with tritium, carbon 14 and chlorine 36 and other radionuclides generated during operation of the reactor or in other nuclear processes. I want you to understand. The method includes a heater that operates at a temperature in the range of 800 ° C. to 2000 ° C. with an inert gas, optional oxidizing gas, and reducing gas. The combination of temperature and gas makes it possible to substantially limit vaporization of the bulk graphite while removing most or substantially all of the carbon 14 in the graphite.

DESCRIPTION OF SYMBOLS 100 System 110 Material handling part 112 Size reduction sub part 114 Hopper sub part 117 Material inlet 120 Heater 122 Outlet (for radionuclides)
124 Exit (for graphite)
130 Gas inlet (for inert purge gas)
140 Gas inlet (for reducing gas)
150 Gas inlet (for oxidizing gas)
160 treatment subsystem (for radionuclides)
170 Processing subsystem (for graphite)

Claims (12)

Heating the heater to a temperature between 800 ° C and 2000 ° C;
Introducing graphite contaminated with radionuclides into the heater;
Introducing an inert gas into the heater;
Introducing a reducing gas into the heater;
Removing volatilized radionuclides from the heater.   The method of claim 1, wherein less than 5 percent of the graphite is vaporized.   The method of claim 1, wherein the temperature is between 1200 ° C. and 1500 ° C.   The method of claim 1, wherein the radionuclide comprises carbon 14 and at least 70 percent of the carbon 14 is removed from the graphite.   The method of claim 1, wherein the radionuclide comprises carbon 14 and at least 90 percent of the carbon 14 is removed from the graphite.   The purge gas comprises at least one of nitrogen, helium, and argon, and the reducing gas comprises at least one of hydrogen, hydrazine, ammonia, carbon monoxide, and hydrocarbon vapor. The method described in 1.   The method of claim 1, wherein the purge gas comprises one or more reducing gases capable of producing free hydrogen, carbon monoxide (CO), ammonium, or organic vapor.   The method of claim 1, further comprising adding an oxidizing gas into the heater. The oxidizing gas is at least one of water vapor, carbon dioxide (CO ₂ ), nitrous oxide (N ₂ O), oxygen (O ₂ ), air, alcohol (having an OH group), and other oxygenated vapor. 9. The method of claim 8, comprising:   The step of introducing an inert gas into the heater and the step of introducing a reducing gas into the heater include introducing the inert gas and the reducing gas at a location near the bottom of the heater. The method of claim 1, wherein the inert gas and the reducing gas flow through the graphite.   The method of claim 1, further comprising the step of reducing the size of the graphite prior to introducing graphite into the heater.   The heater comprises a vertical moving bed heater, and introducing the graphite contaminated with radionuclides into the heater comprises introducing the graphite near a top of the heater; The method of claim 1, wherein introducing an inert gas into the heater and introducing a reducing gas into the heater comprises introducing a gas near a bottom of the heater.

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